P 246 NATIONAL SYMPOSIUM IN CHEMISTRY
Design, Synthesis and Evaluation of New Bis Pyridinium Oxime:
Reactivators for Human Acetylcholinesterase Inhibited by Nerve Agent
Sarin
Jyotiranjan Acharya, Arvind Kumar Gupta and Devendra Kumar Dubey
Process Technology Development Division, Defence Research & Development Establishment,
Jhansi Road, Gwalior, 474002.
The extensive use of neurotoxic organophosphorus (OP) compounds as pesticides in the agriculture, as well
as their potential use as mass destruction agents in chemical warfare (nerve agents) during military conflicts and
terrorism, has attracted attention to the development of effective medical counter measures for such type of poisoning.
The acute toxic effects of nerve agents such as sarin, soman, tabun, cyclosarin and VX are due to inhibition of
activity of acetylcholinesterase (AChE), an enzyme that plays an important role in the nervous system by hydrolyzing
acetylcholine, a neurotransmitter. This leads to a variety of cholinergic effects such as myosis, salivation, hypotension,
bradycardia, muscle tremors, convulsions, and respiratory depression culminating in death due to respiratory failure.
Current medical protection against the toxicity of OP poisoning consists of a regimen of anti-cholinergic
drugs, such as atropine, to counteract the accumulations of acetylcholine and oximes viz. 2-PAM, TMB-4, HI-6 and
Obidoxime to reactivate OP-inhibited AChE. However the currently used reactivators are associated with limitations
like poor lipid solubility and unstable in solution as well. Further an effective therapy by a single oxime for all the
known nerve agents is still lacking. In view of the above a search is being continued to find out a universal reactivator
which would be active against a broad spectrum of nerve agents.
In this regard we have synthesized a novel series of bis-pyridinium oximes connected by xylene linker and
their in-vitro reactivation efficacy was evaluated for sarin inhibited human AChE. Reactivation efficacy of synthesized
compounds was compared with 2-PAM and obidoxime. Among the synthesized compounds, the bis-pyridinium
oxime N,N’-p-xylene-bis[(2,2-hydroxyiminomethyl)-pyridinium] dibromide (2P-pX) exhibited 45% reactivation
of human AChE inhibited by sarin as against 34% and 24% reactivation exhibited respectively by 2-PAM and
obidoxime at a concentration of 10
-4
M within 10 minutes. The time dependent reactivation profile of the new
oximes indicated that the oxime 2P-pX was able to reactivate 56% of the sarin inhibited human AChE after 30
minutes.
348

NATIONAL SYMPOSIUM IN CHEMISTRY P 247
Aqueous-Ionic Liquid Mixtures As Effective Reaction Media
Nageshwar Khupse
a
, Shraeddha Tiwari, Sumit Turkar, Shabana Kurolikar, Anil Kumar
b
*
Physical Chemistry Division, National Chemical Laboratory, Pune – 411008.
The use of ionic liquids (ILs) as “green” alternatives to the conventional organic solvents has been increasing
over the last few years. With the ever increasing interest in the use of ILs as reaction media, there is a growing
awareness about their shortcomings. The high viscosity of ionic liquids is believed to be one of the important
detrimental factors affecting chemical transformations [1].
Water is known to reduce the viscosity of ILs to a great extent [2, 3]. The addition of water to ILs also affects
other characteristic properties of ILs like the polarity parameters. In this work we have analyzed the various
physicochemical properties (e.g. polarity, viscosity etc.) for a range of aqueous mixtures of ILs at several temperatures.
We have then examined the effect of addition of water as a co-solvent on the progress of different C-C bond-forming
organic reactions, including the Diels-Alder reaction. The correlation of the reactivities with the properties of binary
mixtures leads to an in depth understanding of the solute-solvent interactions at the molecular level. The analysis
indicates that use of water as a “viscosity-reducer” in ILs leads to highly-enhanced rates of reactions, but the other
effects of change in polarity cannot be excluded. The binary mixture when used for organic reactions gives higher
rates (as compared to ILs) and should be considered as a viable option in the scale-up stage of ILs.
References
1. S. Tiwari, A. Kumar Angew. Chem. Int. Ed. (2006) 45, 4824
2. M. J. Earle, K. R. Seddon, Pure Appl. Chem. (2000) 72, 1391
3. E. Gomez, B. Gonzalez, A. Dominguez, E. Tojo, J. Tojo. J. Chem. Eng. Data (2006) 51, 696
349

NATIONAL SYMPOSIUM IN CHEMISTRY P 241
Triphase Catalytic Activity Of A New Insoluble Multi-Site Phase Transfer
Catalyst In Etherification Of Methyl Salicylate
P.Gopinath and E.Murugan*
Department of Physical Chemistry, School of Chemical Sciences,
University of Madras, Guindy Campus, Chennai 600 025, Tamil Nadu.
Phase transfer catalysis emerged as an indispensable organic technique to carry out the reactions between two
immiscible reagents. It is an environmentally friendly and economically profitable method to synthesize wide range
of organic chemicals [1,2]. However, the removal and recovery of catalyst was found to be expensive and difficult
process in the case of soluble PTCs. This problem can be overcome by immobilizing the PTC on a solid polymeric
support i.e. insoluble polymer-supported PTC (PS-PTC) as introduced by Regen [3] and hence it can be easily
separated by filtration and recycled. So far, numerous studies have been reported on the use of soluble and insoluble
single-site PTCs for various organic reactions, but their activity was very poor due to the presence of single active-
site. The important considerations in the selection of the catalyst are economy of scale and efficiency of the phase
transfer catalysts specifically on the industrial-scale preparation of organic compounds. In order to fulfill these
requirements, multi-site PTCs (MPTCs) containing more than one active-site were developed by Idoux et al. Further,
there are only few reports available on the synthesis of polymer-supported MPTCs. In the present study, a new
polymer-supported MPTC containing three active-sites has been synthesized, characterized and its catalytic activity
was determined through etherification of methyl salicylate.
Initially, the polystyrene bound polymer beads were prepared by suspension copolymerization of styrene
(73%), divinylbenzene (2%), and vinylbenzylchloride (25%) using AIBN as a free radical initiator. The resulting
co-polymer beads containing pendant chloromethyl groups was condensed with triethyl methanetricarboxylate
followed by reduction with LiAlH
4
. The obtained condensed product was chlorinated using thionylchloride and then
quaternized with triethylamine to form a new insoluble tri-site PS-MPTC. The new PS-MPTC was characterized by
FT-IR technique, [chloride ion], and SEM analyses. The catalytic efficiency was ascertained through etherification
of methyl salicylate using epichlorohydrin under pseudo-first order reaction conditions and compared the same with
single-site PS-PTC. The rate constants were calculated by following the disappearance of substrate (methyl slaicylate)
through Gas Chromatography. It was found that the tri-site PS-MPTC was » three-fold more active than single-site
PS-PTC in terms of rate constant. The kinetic study was performed by varying the experimental parameters, viz.,
stirring speed, [substrate], [NaOH], [catalyst], and temperature. The observed results reveal that all the kinetic
parameters are dependency of the rate of reaction. The activation energy and thermodynamic parameters viz. enthalpy,
entropy and free energy change were also calculated. Based on the observed kinetic and thermodynamic results, an
interfacial mechanism was proposed for the etherification reaction.
References
1. C. M. Starks, J. Am. Chem. Soc., 93, 195 (1971).
2. E.V.Dehmlow, Angew. Chem., Int. Ed. Eng., 16, 493 (1977).
3. S.L.Regen, J. Am. Chem. Soc., 97, 5956 (1975).
343

P 242 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Antibacterial Activity of Chalcone Dendritic Architectures
Sebastian Raja and Perumal Rajakumar*
Department of Organic Chemistry, University of Madras, Chennai- 600 025
Dendrimers are a new class of spherical polymeric materials. They are highly branched, monodisperse
macromolecules. Dendrimers occupies prominent role in macromolecules because of its various applications in the
field of biology and material sciences.[1,2] In the recent years, biological applications of dendrimers have been of
growing interest.[3] In view of this, chalcone nucleus an important precursor for many potentially bioactive compounds
abundantly present in plants. Chalcone derivatives find application as antioxidant, antibiotic and antibacterial agents.
However the synthesis of biological active chalcone based dendritic architecture are yet to be investigated. We
describe herein the synthesis and antibacterial activity of chalcone based dendritic architectures 1a, 1b and 2a, 2b.
References
1. Stiriba,S.E.; Frey,H.; Haag,R. Angew.Chem., Int.Ed. 2002, 41, 1329.
2. Gillies, E.R.; Jonsson, T.B.; Fréchet, J.M.J.J.Am.Chem.Soc.2004, 126,11936.
3. Cloninger, M.J. Curr. Opin. Chem. Biol. 2002, 6, 742.
344

NATIONAL SYMPOSIUM IN CHEMISTRY P 243
New Ursane-Type Antiplasmodial Triterpenes from Tarenna Zeylanica
Leaf
Venkata Siva Satyanarayana Kantamreddi* and Colin W. Wright
The School of Pharmacy, University of Bradford, Bradford, United Kingdom – BD7
Malaria, a leading cause of death continues to challenge the world [1]. Resistance of Plasmodium falciparum
to chloroquine and some other antimalarial drugs continues to increase. In the present study, the phytochemical
investigation was carried out on an active leaf extract of Tarenna zeylanica collected from forest in the locality of
Bhubaneswar, Orissa, aimed at identifying the active antiplasmodials for further research.
Antiplasmodial activities were assessed using the parasite lactate dehydrogenase assay [2] and chloroquine
and artemether were used as positive controls. Flash chromatography was performed using TLC grade silica gel
(60G, 45ì) and for TLC studies, analytical silica gel 60F254 plates (Merck) were used. Spectra were acquired using
NMR (Jeol ECA 600MHz), IR Spectroscopy (Digilab UMA 400) and EI-MS (Finnigan MAT 90 spectrometer) &
Micromass Quattro Ultima HPLC- MSMS.
The leaf methanolic extract of T. zeylanica possessed antiplasmodial activity with low IC
50
values, 14.2 and
31.4 µg/ml against chloroquine sensitive (3D7) and resistant (K1) strains of P. falciparum respectively. A Literature
search revealed that no phytochemical studies have been reported on T. zeylanica. In the present study, seven
constituents were isolated viz. ZAL1, ZAL3A, ZAL3B, ZAL7, ZAL15 and ZAL16. The activity of ZAL3A, ZAL3B
and ZAL7 against strain K1 (IC
50
= 6.12, 0.72 and 0.67 µg/ml respectively) confirms the activity of T. zeylanica seen
in this study. The structural identification of these active compounds ZAL3A, ZAL3B and ZAL7 were established
by IR, UV, EI & ES-MS and advanced NMR (1H, 13C, Dept, DQF Cosy, HMQC & HMBC) techniques. Compound
ZAL 3A was identified as ursa-11, 13(18)-dien-3b, 28-diol and is reported for the first time. The identification of
ZAL3B and ZAL7 is in progress and preliminary spectral analysis suggests that these compounds also ursane type
of triterpenes.
References
[1] WHO (2003) World Health Organisation Fact Sheet No. 94: WHO information.
[2] Makler, M.T. et al (1993) Am J Trop Med Hyg 48: 205-210.
345

P 244 NATIONAL SYMPOSIUM IN CHEMISTRY
Click Chemistry On Sugar-Derived Alkynes And Azido-Alkynes
Palanichamy Kalanidhi and Krishna P. Kaliappan
*
Department of Chemistry, IIT Bombay, Mumbai-400 076
Click reaction is a reaction that is modular, wide in scope, gives very high yields, generates only inoffensive
byproducts that can be removed by nonchromatographic methods, and be stereospecific. Its salient features are
simple reaction conditions, the use of readily available starting materials and reagents, and water such solvent, and
simple product isolation as well.[1,2] The word “click” was coined to describe the guiding principle. Among the
various classes of click chemistry, Huisgen dipolar cycloaddition of azides and alkynes [3] to afford 1,4-triazoles in
a regioselective manner, is extensively explored because of its pharmaceutical applications.
Single click chemistry: While click chemistry of sugar-derived azides is well known, that of sugar-derived
alkynes is not much explored. We have studied Huisgen 1,3-dipolar cycloaddition of various sugar-derived alkynes
with several alkyl and aryl azides using CuI, DIPEA and acetonitrile as the co-solvent to synthesize a number of 1,4-
triazoles in excellent yields.
Double click in one pot: By a sequential addition of sugar-derived azido-alkynes and an azide in a proper time
lag to a copper metalated alkyne, using CuI, DIPEA and acetonitrile, we have accomplished a double click in one
pot to synthesize a number of bis-triazoles.
Our future plan, triple click in one pot, and the details of our single and double click work will elaborately be
discussed in the poster.
References
1. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 2004-2021.
2. Rostovstev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed. 2002, 41, 2596-2599.
3. Huisgen, R. Pure Appl. Chem. 1989, 61, 613-628.
346

NATIONAL SYMPOSIUM IN CHEMISTRY P 245
Metal Nanoparticles: A New Generation Catalyst For Organic Synthesis
Vikas Bansal, Neeraj Kumar Mishra, Mazaahir Kidwai*
Green Chemistry Research Laboratory, Department of Chemistry,
University of Delhi, Delhi-110007
Nanoscience is a combination of “nano”, from the Greek “nano” or Latin “nanus” meaning dwarf and the word
“science”. The word nano means 10
-9
, so nanometer is one billionth of a meter. Two principal factors causes the
properties of nanomaterials to differ from other materials are increased relative surface area and quantum effects.
Nanoparticles are core base materials for implementing nanotechnology and have attracted researchers not only in
field of chemistry but also in other fields such as physics, medicine, biology and material science, due to their
current and promosing applications in organic synthesis, magnetic storage media, cell and DNA separation, drug
delivery. In the growing field of metal nanoparticles they can also be used for the preparation of porous metallic
ensembles and as filters for polymers. Metal nanoparticles provide an immense potential in organic synthesis and
various organic transformations due to their characteristic, high surface to volume ratio and a higher concentration
of partially co-coordinated surface sites than the corresponding bulk materials. The metal nanoparticles are supposed
to environmentally benign as they can be readily recovered and reused, and thus economically acceptable.
Our research group has carried out several organic transformations [1] and synthesis of biological active
moieties using various metal nanoparticles [2]. One of the recent work include A
3
coupling of aldehyde, amines and
alkynes using Au(0) of 10-15 nm. nanoparticles to give propargylamines. We had also carried out Ulmann coupling
to form diaryl ether from phenol and aryl halide using Cu(0) metal nanoparticles. Ni- metal Nanoparticle has immense
potential for reduction and can perform reduction chemoselectively.
Reference
[1] (a) M. Kidwai, V. Bansal, N. K. Mishra, A. Kumar, and S. Mozumdar, SYNLETT, 2007, 1581–1584., (b) M. Kidwai,
V. Bansal, A. Saxena, S. Aerry and S. Mozumdar, Tetrahedron Lett., 2006, 47, 8049–8053.
[2] M. Kidwai, V. Bansal, A. Kumar, and S. Mozumdar, Green Chem., 2007, 9, 742–745.
347

P 236 NATIONAL SYMPOSIUM IN CHEMISTRY
A First One-Pot Synthesis, Isomerization And Synthetic Utility Of Mono
And Bis Morita-Baylis-Hillman Adducts Of 1,1’-Ferrocenedialdehyde
Suchithra Madhavan, Kodirajan Selvakumar, Vadivel Vaithiyanathan, Baby Viswambharan,
and Ponnusamy Shanmugam
*
Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science
and Technology (NIIST), Thiruvananthapuram-695 019, Kerala
The chemistry of ferrocene is still an important research area due to its applications in the area of novel
materials development,

asymmetric catalysts, nonlinear optics, biological properties and electrochemistry [1]. Amongst
various C-C bond forming reactions, the Baylis-Hillman reaction is an important reaction giving rise to densely
functionalized molecules and is considered to be atom economic. Functionalisation of ferrocene under mild conditions
is difficult task as it requires multi-step rigorous reaction condition. To address the problem and in continuation of
our research in the area of novel synthetic applications of Baylis-Hillman adducts [2], particularly with ferrocene
derivative, we have recently examined the reaction of Baylis-Hillman adduct of ferrocenealdehyde 2 with various
oxygen and carbon nucleophiles in presence of montmorillonite K10 clay catalyst. The reaction was found to afford
highly functionalised excellent yield of E- and Z-trisubstituted alkene derivatives of ferrocenealdehyde. This poster
aims to explain on our recent findings of a novel and first one-pot synthesis of mono- and bis- adduct of Morita-
Baylis-Hillman adduct of 1,1’-ferrocenedialdehyde. These adducts undergone a facile stereoselective isomerization
reaction with a number of saturated, unsaturated, aromatic alcohols to yield highly functionalised trisubstituted
alkene derivatives in excellent yield. Synthetic utility of mono and bis- propargyl derivative of 1.1-ferrocenedialdeyde
has been demonstrated in the synthesis of novel macrocycles. The study is shown in Scheme 1. The results will be
discussed in detail.
References
1. Gan, K.S-.; Hor, T.S.A. in Ferrocenes Homogeneous Catalysis, Organic Synthesis, Materials Science (Eds.: A.Togani, T.
Hayashi), VCH, Weinheim, 1995, pp.3-104;
2. Shanmugam, P.; Vaithiyanathan, V.; Baby, V. Tetrahedron 2006, 62, 4342-4347;
338

NATIONAL SYMPOSIUM IN CHEMISTRY P 237
Synthesis Of Aminoethyl-aaaaa,bbbbb-Diaminopropionyl (Aedap) PNA - Strategic
Modification To Reduce Hydrophobicity
Roopa Mitra
1
and K. N. Ganesh
2*
1
Division of Organic Chemistry, National Chemical Laboratory, Pune ;
2
Indian Institute of
Science Education and Research (IISER), Pune
The astonishing discovery of Peptide nucleic acids (PNAs) by Nielsen et. al. [1] that bind with higher affinity
to complementary nucleic acids than their natural counterparts, and obey the Watson-Crick base pairing rules resulted
in the rapid establishment of a new branch of research focused on the diagnostic and therapeutic applications of this
highly interesting class of compounds. PNA is a neutral DNA mimic derived by replacement of sugar-phosphate
backbone with N-(1-aminoethyl)glycine units carrying natural nucleobases A, T, G and C with a carbonyl linker
having a great potential to act as antisense agents.
Despite advantages offered by the achiral PNA, it has
been of interest to replace the glycine moiety of the
backbone with chiral amino acids as mentioned by Corradini
et. al.[2]. The side chains of the amino acids were envisaged
to be valuable for controlling binding affinity, specificity,
hydrophobicity and attachment of ligands to PNA. PNA
oligomers incorporating chiral monomers retained the
hybridization properties with tolerance for small and
medium substituents at the glycine-
a position. The lysine-
modified oligomers (I) as reported by Haaima et al [3], are
known to be more readily soluble in aqueous systems.
We aimed to synthesize PNA monomers having b-aminoalanine moiety in the backbone to get a modified
PNA, aminoethyl a,b-diaminopropionyl ) PNA (II), with a chiral backbone. This is expected to be stable due to the
presence of intramolecular hydrogen bonding. In addition, due to the presence of hanging amine functionality, the
low solubility and cellular penetration problems found in classical PNAs might be overcome.
The strategy towards the synthesis of target monomer used asparagine as the starting material. The a,b-
diaminopropionic acid was synthesized from it, which after reductive alkylation gave the backbone of desired PNA.
Later on, attachment of nucleobase (Thymine) via a methylene carbonyl linker to the backbone gave the desired
monomer (II). All the intermediates and the final molecule have been characterized using
1
H,
13
C-NMR and MS
analyses. The syntheses of oligomers were performed following Merrifield Solid Phase Oligomer Synthesis using
Boc-strategy and MBHA resin. Sequential combination of the aeg-T monomer with our desired monomer were
done at different positions of the oligomers e.g. N-terminal, C-terminal, middle modification etc. This was followed
by their cleavage from the resin, purification and characterization using rp-HPLC and MALDI-TOF MS techniques
respectively. The comparative biophysical studies with DNA/RNA that includes study of duplex and triplex stability
by UV-T
m
experiments are in the future plans.
References
1. Nielsen, P. E.; Egholm, M.; Berg, R. H.; Buchardt, O. Science. 1991, 254, 1497
2. Corradini, R.; Sforza, S.; Tedeschi, T.; Totsingan, F.; Marchelli, R.; Curr. Top. Med. Chem., 2007, 7, 681
3. Haaima, G.; Lohse, A.; Buchardt, O.; Nielson, P. E.; Angew.Chem. Int. Ed. Engl., 1996, 35, 1939
339

P 238 NATIONAL SYMPOSIUM IN CHEMISTRY
Un-symmetrical polyaza [N
12
] macrocycle as a potential encapsulating
agent: Spectroscopic and Electro–chemical characterization of homo–
bimetallic complexes
S. Kumar and Zafar Ahmad Siddiqi*
Inorganic Chemistry Division, Chemistry Department
Aligarh Muslin University, Aligarh 202002, U.P.
Email: [email protected]
Coordination chemistry of polyaza macrocyclic ligands has been a fascinating area of investigations to
coordination and bio-inorganic chemists. Macrocyclic ligands capable to bind two or more metal ions giving discrete
homo or hetero–bimetallic / polymetallic complexes have received much attentions. However, un–symmetrical
polyaza macrocycles which contain non – equivalent coordination sites to bind metal ions have attracted chemists
only recently [1]. The polymetallic complexes of such macrocycles can be used as suitable models to elaborate the
asymmetrical binding of various metal ions in the metallo–biosites. The individual metal ions exhibits different role
in the functioning of the polnuclear metallo – enzyme. Recently, we have reported [2–3] that use of protected two
armed reactive substrate, N,N’–bis(N-ethylaniline)propane,1,3-diimine generated from condensation of 1,3-
diamionopropane with N-acetylaniline (1:2 mole ratio) induces (in–situ) cyclo–addition reactions with a mixture of
amine and HCHO (1:3 mole ratio). This in turn results in stable dihydroperchlorate salt of big size 20–membered
[N
8
] or 32–membered [N
12
] un-symmetrical dinucleating macrocycles as stable solid product. An analogous reactive
substrate N,N’–bis(N-ethylaniline)–hydrazine-1,3-diimine obtained from reaction of N-acetylaniline and hydrazine
(2:1 mole ration) also undergoes an in–situ cyclization process with mixture of 1,3-diaminopropane and HCHO (1:3
mole ratio) which in the presence of HClO
4
produces stable solid product identified as dihydroperchlorate salt of
26–membered un–symmetrical [N
12
] macrocycle, 8,14,24,30 tetramethyl-
7,15,23,31tetraphenyl[1,5,7,9,13,15,17,21,23,25,29,31] dodecaazacyclodotri aconta-8,14,24,30-
tetraene.dihydroperchlorate. Here-in we report reactions of this macrocyclic ligand towards metal salts and their
derivative complexes which afford affording stable solid metal encapsulated products. The products have been
characterized using elemental analyses, FTIR, UV–visible (ligand field), FAB–mass spectral and magnetic moment
measurements. The cyclic voltametric studies indicate formation of quasi–reversible redox couples M
III/II
and M
II/I
compatible with the flexible nature of the macrocyclic cavity.
References:
1. S. Brooker, T.J. Simpson, J. Chem. Soc., Dalton Trans., 1151 (1998); S. Brooker, J.S. Danwar, J.B. Johnson, Polyhedron.
18, 679 (1999).
2. Z.A. Siddiqi, M.M. Khan, Syn. React. Inorg. – Org. Chem., 34, 894 (2004).
3. Z.A. Siddiqi, M.M. Khan, M. Khaid and S. Kumar, Tran. Metal Chem., 32, 913 (2007).
340

NATIONAL SYMPOSIUM IN CHEMISTRY P 239
Time Resolved Resonance Raman Spectroscopy: A Journey from
Nanosecond to Femtosecond Time Domain
S. K. Sahoo, B. Mallick, Adithya L. Y., R. Pandey, S. Umapathy
*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore-560012
Time resolved resonance Raman (TR3) spectroscopy, a pump-probe technique in fast and ultrafast time
domain, provides information directly about vibrational structure, reactivity and dynamics in the excited state [1].
The pump beam excites the molecule to the higher excited state and the probe beam detects the transient species thus
formed after a certain delay time, governed either electronically or optically.
In presence of suitable hydrogen donor, aromatic ketones undergo hydrogen abstraction reaction in their
excited triplet state. The triplet state thus formed, via intersystem crossing from singlet state, interacts with the
ground state hydrogen donor to form a ketyl radical, which may undergo further photoreaction. The triplet state
structure and reactivity of isomeric benzoylpyridines, heterocyclic analogues of benzophenone were studied using
nanosecond TR3 spectroscopy. The shortening of triplet state lifetime and decrease in intersystem crossing yield is
explained on the basis of position of the heteroatom that affects the charge density of carbonyl group and determines
the characteristics of the excited state and its efficiency for the hydrogen abstraction reaction.
It is well known that solvent polarity brings out changes in the structure and dynamics of excited triplet
state. Xanthone is structurally similar to benzophenone and well known for its solvatochromic behavior [2]. In the
present study, effect of solvent polarity on structure in both ground and excited triplet state of xanthone will be
discussed.
TR3 spectroscopy has its own limitations of interference from fluorescence background and due to transform
limit it can’t further be extended to subpicosecond time domain. Femtosecond stimulated Raman spectroscopy
(FSRS) [3] can overcome all the above obstacles. FSRS produces good quality vibrational spectra, free from strong
background fluorescence and provides quality information in femtosecond time domain. This technique uses two
NIR-pulses, one picosecond narrow-bandwidth (5-20 cm
-1
) Raman pump pulse centered at 787 nm and a broadband
continuum Raman probe pulse (800-1050 nm). When the two fields overlap spatially and temporally on the sample,
one observes gain features on top of the Probe beam. The ratio of the probe spectrum for Raman pump ON and
Raman pump OFF, gives the gain spectrum. Recently FSRS set up is designed and developed in our research group.
The preliminary SRS spectrum obtained from various solvents like benzene, CCl
4
and cyclohexane will be presented.
Also the SRS spectra of b-carotene in two different solvents are reproduced to validate the setup.
References
1. Phillips, D. L.; Kwok, W. M.; Ma, C. in Reviews of Reactive Intermediate Chemistry; Platz, M. S.,
Moss, R. A. Jones, M., Jr., Eds.; John Wiley and Sons, 2007; pp 123.
2. Heinz, B.; Schmidt, B.; Root C.; Satzger H.; Milota F.; Fierz B.; Kiefhaber T.; Zinth W.; Gilch P. Phys. Chem. Chem.
Phys. 2006, 8, 3432.
3. McCamant, David W.; Kukura, Phillip; Mathies, Richard. A. J. Phys. Chem. A 2003, 107, 8208.
341

P 240 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis Of Biscoumarins From 4-Hydroxycoumarin And Aaromatic
Aldehydes–A Comparative Assessment Of Percent Yield Under Thermal
And Microwave-Assisted Conditions
Saima Qadir, Khaliquz Zaman Khan*, Aijaz Ahmad Dar.
Department of Chemistry, University of Kashmir, Hazratbal, 190006, Srinagar, Kashmir
Coumarins form an important group of organic compounds possessing enormous pharmacological, industrial
and biological value. 4-Hydroxycoumarin and its derivatives are known for their anticoagulant,

spasmolytic,
antibacterial and antifungal

activity [1]. In addition to this, certain derivatives have also been reported as antitumor
and anti-HIV agents [2]. Besides, coumarins find diverse applications as food additives, cosmetics, laser media,
non-linear optical chromophores,

agrochemicals

as well as analytical reagents [3].
In this backdrop, efforts are being made to synthesize as many derivatives of 4-hydroxycoumarin and dicoumarols
as possible using microwave eco-friendly methods. Herein, we report convenient syntheses of various biscoumarins
by condensing a series of aldehydes with 4-hydroxycoumarin under microwave irradiation for the first time along
with a comparative account of their syntheses under conventional conditions. Under microwave, the reaction time
has been reduced considerably with improvement in yields in comparison to thermal conditions. Reactions have
been carried out both under solvent as well as in solvent-free environment and the adopted procedure provides an
energy and time-saving protocol.
References 1. Chohan, Z.H.; Shaikh, A.U.; Rauf,A.; Supuran, C.T. J. Enzym. Inhibition. Med. Chem. 2006, 21, 6, 744-748 and references
cited therein.
2. Jung, J.C.; Lee, J.H.; Oh, S., Lee J.G.; Park, O.S. Bioorg. Med. Chem. Lett. 2004, 14, 22, 5527-5531 and references cited
therein.
3. Chen,R.F.; Anal. Lett. 1968, 1, 423-428.
342

NATIONAL SYMPOSIUM IN CHEMISTRY P 231
Aqueous-Mediated Synthesis Of Heterocyclic Ketene Aminals
L. Gellina Chanu, N. Sushuma, S. Joychandra Singh, Okram Mukherjee Singh*
Department of Chemistry, Manipur University, Canchipur, Imphal- 795003, Manipur.
Heterocyclic ketene aminals are versatile ambident synthetic intermediates, which combine the nucleophilicity
of enamines and the electrophilicity of enones. They have been utilized as building blocks for the synthesis of a wide
range of heterocycles and natural products [1].

We wish to report herein an easy and green method for the synthesis
of the heterocyclic ketene aminals 1, 2, 3 (Scheme-1). Our method involves the reactions of á-oxoketene dithioacetals
[2] with various diamines and refluxing in ordinary water.
References 1. Review: (a) Huang, Z. –T., and Wang, M, -X., The Chemistry of Enamines , ed. Z Rappoport , Wiley Interscience , London
1994, p. 1303. (b) Stanovnik, B.; Svete, J., Chem. Rev. 2004, 104, 2433-2480. (c) Greenhill, J. V., Advances in Heterocyclic
Chemistry, 1996, 67, 207-343. (d) Rajappa, S., Tetrahedron 1981, 37, 1453-1480, Tetrahedron Report Number 107.
2. Review: (a) Junjappa, H.; Ila, H.; Asokan, C. V. Tetrahedron 1990, 46, 5423-5506, Tetrahedron Report No. 278. (b) Dieter,
R. K. Tetrahedron 1986, 42, 3029-3096, Tetrahedron Report No. 202.
333

P 232 NATIONAL SYMPOSIUM IN CHEMISTRY
A Short, Enantioselective Synthesis Of 2-Hydroxy Piperidine Dderivatives
From ddddd-Hydroxy Lactones
Lourdusamy Emmanuvel, Arumugam Sudalai*
Chemical Engineering & Process Development Division, National Chemical Laboratory,
Dr. Homi Bhabha Road, Pune-411008, Maharastra.
Substituted piperdine is often encountered in the biologically active alkaloids and possess diverse biological
activities. The plant enzymes readily synthesize piperidine from amino acids. However, the construction of six-
membered heterocycle of piperidine nucleus in the laboratory with fixed stereochemistry is challenging to chemists.
Here, we present the synthesis of 2-hydroxypiperidine derivatives i.e (+)-L-733, 060 and epiquinamide. (+) L-733,
060 is a synthetic NK1 receptor antagonist to show clinical utility in a variety of disorders including migraine,
rheumatoid arthritis and pains. Epiquinamide has been found to be highly selective for b2 nicotinic acetylcholine
receptors (nAChRs), as such representing a new structural class of nicotinic agonists and could be considered a lead
compound for the development of nAChR therapeutic agents. The synthesis of (+) L-733, 060 involves the Shi’
epoxidation of g,d-alkenoate to get the d-hydroxy lactone with trans selectivity while the latter make use of asymmetric
dihydroxylation to obtain the syn selectivity. Both the synthesis involve similar reaction sequences such as Johnson-
Claisen rearrangement, formation of hydroxy lactone, inversion of hydroxyl group with azide, reductive cyclization
of azidolactone to give the hydroxy piperidine. This route is practical and high yielding to construct the piperidine
rings.
334

NATIONAL SYMPOSIUM IN CHEMISTRY P 233
Synthesis Of Homoallylic Alcohols Using Cui As Catalyst
Arun Jyoti Borah, Hima Rani Kalita, Biswapran Kashyap, Pabitra kumar kalita and Prodeep
Phukan*
Department of Chemistry, Gauhati University, Guwahati -781014, Assam
The addition of allyl metal reagents to aldehydes is an important method for carbon –carbon bond formation.
In recent years, several Lewis acids, especially metal Lewis acids or transition metal complexes have been utilized
extensively to catalyze this transformation. Most of these methodologies are fraught with limitations such as excess
use of catalyst (or co-catalyst), moisture sensitive conditions, stoichiometric amount of promoter and poor substrate
selectivity. There has been increasing interest in the development of new catalysts, which are cheap, air-stable and
easily available commercially. Recently CuI has emerged as a very effective catalyst for various organic
transformations. We have developed a simple methodology for the synthesis of homoallylic alcohols using allyl
tributyl stannane as allylating agent in presence of CuI as catalyst (Scheme -1) [1].
Scheme-1
The reaction was carried out by stirring a mixture of an aldehyde (1 mmol), allyl tributylstannane (1.05 mmol)
CuI (0.15 mmol) in DMF (2 ml) at room temperature. Both aromatic and aliphatic aldehydes underwent homoallylation
efficiently to produce homoallylic alcohols in good yield (69-86%).
References
1. Kalita, H. R., Borah, A. J.; Phukan, Tetrahedron Lett., 2007, 48, 5047-5049.
335

P 234 NATIONAL SYMPOSIUM IN CHEMISTRY
Deoximation By Phase Transfer Oxidants Under Microwave Irradiation In
Solvent Less System
A.Dewan and D. K. Kakati*
Department of Chemistry, Gauhati Universuty, Guwahati-781014, Assam
The protection of certain functional groups and the deprotection of the protected derivatives constitute important
processes in the multistep synthesis of polyfunctional molecules. Regeneration of ketone and aldehyde from their
oximes is an important reaction in synthetic organic chemistry as the oxime serves as an efficient protecting group
for carbonyl compounds
[1, 2]
. Further, as the oxime can also be prepared from non-carbonyl compounds, the formation
of carbonyl compounds from oximes represents a potential route for the synthesis of aldehyde and ketone
[3]
.
Thus
there has been continuing interest in the development of new reagents and methodologies for the regeneration of
carbonyl compounds from their oximes and several deoximation reagents have so far been developed.
Solvent less reactions under microwave irradiation is gaining ground in organic synthesis, because of the
increased emphasis on eliminating and if not possible minimizing the use of organic solvents. Further the use of
microwave irradiation results in manifold reduction of reaction time. We have been investigating the use of cerium
based phase transfer oxidants in the oxidation of alcohol as well as the oxidative deoximation of oximes to their
parent carbonyl compounds both in homogeneous and heterogeneous systems. It has been observed that reactions
under microwave irradiation take much less time, but give good yields. The reaction also involves easy work up
procedures for the recovery of the products. Here in we report the use of two phase transfer oxidants cetyl dimethyl
benzyl ammonium cerium nitrate and cetyl trimethyl ammonium cerium nitrate in the regeneration of carbonyl
compounds from their oximes.
The carbonyl compounds were characterized by their spectroscopic analysis and the comparison of the data
with authentic samples. Of the two reagents, cetyl trimethyl ammonium cerium nitrate was found to be a better and
more effective deoximation reagent. Further, the nature of the other functional groups present in the neighbourhood
was found to influence the efficiency of the deoximation reagents.
References
1. Sander S.R, Karow, Organic Functional Group Preparation, 2
nd
ed., A.P, London, 1989, 413.
2. Green T.W, Wuts P.G.M, Protective group in Organic Synthesis, Wiley N.Y, 1919, 2
nd
ed., 214.
3. Barton D.H.R, Beaton J.M, Geller, J. Am. Ch. Soc., 1961, 83, 4076.
336

NATIONAL SYMPOSIUM IN CHEMISTRY P 235
Isolation Of Bioinsecticides From The Striped Tiger Butterfly, Danaus
Genutia (Lepidoptera: Nymphalidae)
Arunava Das,
a,b
Chandan Mithra
b
, R.Revanna,
b
A.R.V. Kumar,
b
K. Chandrashekara*
b
a
CMR Institute of Management Studies, Kalyannagar, Bangalore- 43.
b
Department of Entomology, College of Agriculture (South Block), University of Agriculture
Sciences, Gandhi Krishi Vigyana Kendra, Hebbal, Bangalore-65.
Most of the attempts have centered on the idea of isolating and charecterizing the cardenolides derived from
these insects or plants, however this is the first such attempt to study and analyze the effect of cardenolide containing
extract as a source of potential bio-insecticides. We wish to analyse the possible effects of toxic alkaloids isolated
from these butterflies as bio-insecticides.
All works reported here have been carried out under strict laboratory conditions at the Department of
Entomology, College of Agriculture, UAS, GKVK with permission from respective departments. We took extracts
from wholebody Striped Tiger butterflies, with 95% pre chilled ethanol, filtered and concentrated by HPLC and
then spraying the extract on pre-trimmed mustard leaf (each concentration having a set of three petriplates with one
leaf each having 10 Diamond Black Moth larvae released) with corresponding concentrations of the concentrated
and diluted extracts. Then, we checked the mortality rate for each concentration every 24 hours for seven continuous
days and reported the same.
At the end of 168 hours, i.e., after 7 days, 2% Extract showed a maximum of 68.99% of Corrected Mortality
and a minimum of 41.11% of Corrected Mortality. 0.25% Extract showed a maximum of 42.91% of Corrected
Mortality and a minimum of 14.44% of Corrected Mortality. This clearly shows that 2% Extract has given the best
results followed by 0.25% Extract.
Thus, we showed that the Butterfly Extract contains toxic alkaloids & cardenolides that have the capacity to
kill the larvae of the DBM, the pest of spinach. As expected results were interpreted and calculated and it was seen
that the 2% concentration of extract showed the best results i.e., 68.99% mortality followed by 0.25% concentration
of extract which showed 42.91% mortality. The data obtained from the graph shows the best results in 2% Extract,
but the 3% extract has shown a diminished mortality rate because the larvae did not feed on such a higher concentration
of extract sprayed leaf. Our next step is to procure more of 2% and 0.25% Extracts on a large scale basis and subject
them to purification procedures of Dialysis and HPLC for separation at a highly concentrated manner, concentrating
and characterization of the toxic alkaloids such that we can proceed to Field Trials on a broader axis.
337

Lecture
Index

Special Lectures
LECTURE INDEXCRSI-Medal Lectures
Page No.
Mark Ratner CNR Rao Award lecture .... 33
Keiji Morokuma Mizhushima-Raman lecture ... 52
Edward I. Solomon A. Chakravarty Endowment lecture .... 54
C.N.R. Rao 10th Anniversary Special Lecture ... 42
Richard N. Zare CRSI-SL1 ... 56
Chi-Huey Wong CRSI-SL1 ... 58
K. Weighart CRSI-SL3 ... 82
D.K.Chattoraj CRSI-ML_G1 ... 78
S.K. Rangrajan CRSI-ML_G1 ... 80
Deevi Basavaiah CRSI-ML-S1 .... 34
N. Chandrakumar CRSI-ML-S2 .... 36
T. K. Chandrashekar CRSI-ML-S3 .... 44
Ganesh Pandey CRSI-ML-S4 .... 68
S. Ramasesha CRSI-ML-S5 .... 84
E. Arunan CRSI-ML-B12 ... 38
Maravanji S. Balakrishna CRSI-ML-B1 .... 40
Sundarababu Baskaran CRSI-ML-B2 .... 46
Prasad V. Bharatam CRSI-ML-B3 .... 48
N. Jayaraman CRSI-ML-B4 ... 50
Faiz Ahmed Khan CRSI-ML-B5 .... 70
Samudranil Pal CRSI-ML-B6 .... 72
Parimal Paul CRSI-ML-B7 .... 74
H. Surya Prakash Rao CRSI-ML-B8 .... 76
Debashis Ray CRSI-ML-B9 .... 86
Subhas C. Roy CRSI-ML-B10 .... 88
V. Subramanian CRSI-ML-B11 .... 90
CRSI-Special Symposium Lectures
Pavel Hobza CRSI-SSL1 .... 60
Ashwini Nangia CRSI-SSL2 .... 62
Shridhar R. Gadre CRSI-SSL3 .... 64
Sanjay Wategaonkar CRSI-SSL4 .... 66
T.N. Guru Row CRSI-SSL5 ... 92
Pinak Chakrabarti CRSI-SSL6 .... 94
G.U. Kulkarni CRSI-SSL7 ... 96
P.Venugopalan CRSI-SSL8 .... 98
i

Poster
Index

Poster Author Index
A
Abaji, G. G. P267
Abdul, R. A. S. P102
Abhimanew, D. P132
Abhinaba, B. P88
Abhinav, K. P43
Abhisek, S. P17
Abhishek, C. P88
Abhishek, K. P34
Abraham, S. P186
Abraham, J. S. P6
Achintesh, N. B. P17
Adinarayana R. S. P175
Aditya, L. Y. R. P. P239
Agarwalla, U. S. P17
Aijaz, A. D. P240
Aiswarya, L. P. P203
Aiyagari, R. P54
Ajayaghosh, A. P60
Ajayakumar, G. P158
Ajaykumar, S. K. P102
Ajeesh, M. P89
Ajit Kumar P144
Ajnesh, S. P10
Akanksha P149
Alamsetti, S. K. P260
Alok, K. R. P204
Amit, J. P115
Amit, K. S. P109
Amit, S. P228
Amit, S. S. B. P93
Amita, S. P27
Amitabha Sarkar P217
Amit Kumar P108
Amol, R. D. P268
Ananda Kumar, C. S. P141
Ananthi, N. P76
Anbalagan, K. P86
Anbarasu, K. P261
Anil Kumar P247
Anil, J. E. P28
Animesh, S. P114
Aninda, J. B. P80
Anirudhan, T. S. P5
Anish Kumar P200
Anita, C. P150
Anjali, P. P67
Anjali, S. P109
Anju Das, M. P257
Ankita, S. P225
Ankita Rao P170
Ankur, B. P202
Anubhuti, A. P29
Anumita, P. P54
Anunidhi, S. P98
Anup Paul, P178
Anupa, A. K. P20
Anupa, A. K. P66
Aravindhan, R. P14
Archana, G. P109
Archana, M. P178
Archana, S. P273
Arindam, B. P183
Arlin, J. A. A. P96
Arnab, B. P87
Arora, M. P155
Arumugam, S. P232
Arun Jyoti, B. P233
Arun, C. P54
Arun, K. S. P138
Arun, K. T. P169
Aruna, D. P229
Arunan, E. P203
Arunava Das, P235
Arvind, K. G. P246
Arvind, M. P143
Asaithambi, M. P112
Ashim, J. T. P130
Ashis, K. P. P107
Ashis, K. P. P50
Ashish, K. S. P30
Ashish, V. P195
Ashish Kumar, T. P121
B
Bablee, M. P262
Babu, V. P35
Bajaj, H. C. P7
Balakrishna, M. S. P45
Balakrishnan, U. P76
Balamurugan, M. P23
Balaram, P. P156
Balasubramanian, S. P192
Ballav, M. B. P259
Bardhan, M. P193POSTER INDEX
ii

Basu Baul, T. S. P178
Basudeb, B. P262
Benaka Prasad, S. B. P141
Bhabesh, C. G. P125
Bhakiaraj, D. P. P113
Bhargava, B. L. P192
Bharti, B. P109
Bhaskar, J. S. P33
Bhattacharya, S. P153
Bhattacharya, S. P193
Bhattacharyya, K. P220
Bhuwan, B. M. P273
Bijoli, M. P67
Bijoy, K. P251
Bilgaiyan, P. P257
Biman B. P181
Binoj, K.K. P89
Bipin, P. P115
Bipul, B. P55
Birinchi, K. D. P26
Bisaria, C. S. P161
Bishan, L. K. P34
Bishwajit, G. P72
Biswajit, D. P33
Biswajit, M. P81
Biswapran, K. P233
Biswarup, P. P50
Biswas, A. N. P17
Bizzotto, D. P215
Bony, S. P274
Brahmachari, G. P255
Brijesh Kumar, S. P115
Brindaban, C. R. P93
Bulumoni, K. P201
Butcher, R. J. P221
Butoliya, S. S. P264
C
Campbell, S. A. P215
Carlo, G. P188
Carlos, J. G. G. P49
Chaitali, B. P49
Chakraborti, A. K. P230
Chakraborti, A. K. P225
Chakravarty, A. R. P50
Chakravarty, M. P163
Chandan M. P235
Chandan, S. P145
Chandra, A. S. P182
Chandrabhas, N. P92
Chandrasekaran, S. P224
Chandrasekhar, V. P46
Chandrashekara, K. P235
Chankeshwara, S. V. P230
Chary, K. V. R. P73
Chawla, H. M. P172
Chawla, S. K. P155
Chetana, P. R. P107
Chhama, A. P133
Chhavi, A. P82
Chincholkar, P. M. P102
Chokhare, R. P44
Churala, P. P120
D
Damanjit, K. P74
Damodara Reddy P131
Darshna, M. P135
Daya, S. P. P30
Dayananda, S. P41
Debabrata, B. P146
Debasree, S. P93
Debendra, K. M. P146
Deb Kumar, N. P120
Debojyoti, L. P50
Deepak, K. P257
Deshmukh P102
Deshpande, R. M. P249
Deshmukh, M. M. P188
Devaraj Stephen, L. P86
Devdutt, C. P140
Devendra, K. D. P246
Dewan, A. P234
Dhara D. P. P167
Dhaval, P. P274
Dhenadhayalan, N P196
Dhillon, R. S. P253
Dhiman, K. S P9
Dhrubo, J. S. P274
Dibakar Chandra, D. P136
Dilip, G. R. P268
Dimple P84
Dinesh, B. P150
Dinesh, S. B. P250
Dipak, K. D. P33
Dipankar, M. P214
Dipankar, S. P217
Dipika P. D. P167
Divya, A. P228
Divya Jyothi P126
POSTER INDEX
iii

Dubey, S. P. P159
E
Eknath, V. B. P250
Emmanuvel, L. P232
F
Farukh, A. P15
Fateh, V. S. P108
Fathima, N. N. P14
G
Ganesamoorthy, C. P45
Ganesamoorthy, S. P157
Ganesan, T.K. P39
Ganesh, K. N. P237
Gangopadhyay, A. P255
Ganguly, T P193
Gautam, P. P 185
Gautam, P. P134
Geetha, R. P35
Genwa, K. R. P212
George, E. P37
Giridhar, M. P65
Gopal Das P259
Gopal, K. P159
Gopidas, K. R. P158
Gopinath, C. S. P211
Gopinath, P. P241
Gorelsky, S. I. P214
Goswami, D. P197
Goswami, S. P111
Goutam, K. L. P25
Govindaraju, M. P112
Gumaste, V. K. P102
Gunanathan, C. P47
Gunasundari, T. P224
Gurjaspreet, S. P18
Gurnule, W. B. P264
Guru Row, T. N. P69
Guru Row, T.N. P65
H
Halligudi, S. B. P202
Hanumant, B. B. P267
Hardev, S. P117
Hariharan, M. P169
Hari Prasad, S. P126
Hementha, H. P. P266
Hima Rani, K. P233
Himanshu A. P3
Himanshu, M. P135
Hitendra, K. P103
Hitendra, S. P37
Hussain Reddy, K. P41
I
Ismail, A. A. P85
J
Jagadeesh, M. P150
Jagtap, S. V. P249
Jagirdar, B. R. P19
Jai, D. S. P34
Janardhan Reddy, K. P175
Jashmini, D. P54
Jasra, R. V. P7
Jatinder, K. P116
Jaya Pal, M. R. P194
Jaya Kumar, R. P198
Jayaraman, N. P147
Jayashree, N. P148
Jayendra, Z. P. P115
Jemmis, E. D. P160
Jemmis, E. D. P50
Jisha, V. S. P169
Jitendra Singh P179
Jitendra, K. B. P176
Jitendra, S. P179
Joshi, S P257
Jothivenkatachalam, K. P52
Joychandra Singh, S. P231
Joykrishna, D. P207
Jubaraj, B. B. P171
Jugal, K. P. P18
Jyoti, S. P166
Jyoti,P. S. P269
Jyotiranjan, A. P246
Jyotsna, C. P153
K
Kadia, M. V. P167
Kakati, D. K. P234
Kalanidhi, P. P244
Kalicharan, C. P93
Kalidhasan, S. P110
Kalsi, P. C. P82
Kalyan, J. B. P106
Kasthuri, J. P97
Kaushik, M. P. P103
Kawaljit, S. P228
Khaliquz, Z. K. P240
Khan, M. I. P100
Khare, S. P44
Khushbu, K. P109
POSTER INDEX
iv

Kieran, C. M. P43
Kiran, B. M. P147
Kiran, B. U. P127
Kiran, M. P272
Kiran, S. P274
Kirandeep, K. P104
Kirthika Rani, B. P39
Kishor, R. H. P105
Koena, G. P124
Komal, M. P18
Krishna, P. P274
Krishna, P. B. P137
Krishna, P. K. P244
Krishnacharya, G. A. P250
Krishnan, K. S. P156
Kuljit, K. P75
Kulkarni, G. U. P58
Kulkarni, G. U. P57
Kumar, A. R. V. P235
Kumar, R. S. P248
Kumar, S. P238
Kumaraguru, N. P1
Kumari, S. P136
Kushwaha, A. P189
L
Lakshmanan, M. P229
Lakshminarayanan, P. S. P2
Laksmikanta, A. P93
Laxmipathi, R. P95
Lloret, F. P3
M
Madan Gopal, B. P123
Mahasweta, N. P94
Maity, S. K. P119
Mala, C. P15
Mala, N. P37
Malathi, M. P154
Malhotra, N. P152
Mallick, B. P239
Mamata, S. P221
Manas, K. G. P124
Mandal, K. D. P204
Mandal, L. C. P255
Mangala, S. K. P68
Manikannan, R. P256
Manikrao, M. S. P268
Manisha, S. P103
Manoj, K. K. P72
Manoj Kumar P132
Manoj Kumar, S. P118
Manorama P210
Manoranjan, K. P70
Manu, V. P7
Marek, K. P120
Marek, Z. P120
Mary, F.M. P43
Mashhood Ali, S. P208
Mathesan, J. P254
Maulik, P. P274
Maya, K. P34
Maya, S. S. P269
Mayilmurugan, R. P23
Mazaahir, K. P245
Medhi, C. P55
Meena, R.C. P51
Meenakshia, S. P36
Meenal, B. P22
Meenal, G. P135
Meera, P. P100
Megha, M. P166
Megha, S. D. P20
Megha, S. D. P66
Mehta, B. K. P135
Menon, S. K. P200
Michael, G. B. D. P49
Mihir, K. C. P148
Minal, B. P101
Mishra, L. P174
Mitchell, K. A. R. P215
Moazzam, A. P64
Mody, H. M. P7
Mohamad, A. A. P68
Mohammad, H. P145
Mohammad, S. P143
Mohammed, S. P100
Mohan Das, T. P252
Mohan, P. S. P154
Mohan, R. P177
Mohan Rao, K. P168
Mridula, P. P106
Mugesh, G. P137
Mukesh, K. P. P109
Mukherjee, P.S. P151
Mukherjee, R. N. P3
Mukul, R. J. P115
Mukund, K. G. P146
Mulla, I. S. P100
Murali Krishna, P. P41
POSTER INDEX
v

Murugan, E. P241
Muthusamy, S. P47
Muthusubramanian, S. P256
N
Nabakrushna, B. P28
Nabanita, S. P176
Nabin, Ch. B. P77
Nagarajan, S. P211
Nagarajan, R. P227
Nageshwar, K. P247
Nageswara Reddy, C. P194
Namboothiri, I. N. N. P226
Namrata D. P174
Nanhai, S. P43
Narasimha Murthy, B. P147
Narasimhaswamy, T. P62
Narendra, N. P266
Naresh P. G. P203
Nasar, A. S. P62
Nashiour, R. P92
Natarajan, P. P52
Natarajan, P. P95
Natrayasamy, V. P36
Navneet, K. P75
Nayak, M. S. P194
Neeraj, K. M. P245
Neeta, S. P98
Neetu, S. P153
Nethaji, M. P153
Nethaji, M. P50
Nidhi G. P165
Nidhi, P75
Nidhi, J. L. P109
Nidhi, K. P274
Nidhi, R. G. P8
Nisha, S. P115
Nitin, B. D. P268
Niyati, S. P205
Nusrat, J. P109
P
Pabitra, K. K. P233
Padma malar, E. J. P198
Pallavi, S. P269
Paloth, V. P10
Palwinder, S. P116
Pampa, M. P49
Panda, D. P177
Panda, M. P111
Pande, U. C. P265
Pandey, J. P. P41
Pankaj, C. P101
Pankaj, K. P109
Pankaj, R. P79
Pankaj, R. P. P115
Paramjit, K. P213
Parasuraman, J. P120
Parbati, B. P87
Parikshit, C. M. P9
Parsons, P. R. P215
Partha Sarathi, S. P209
Partha, R. P40
Parveen, S. P182
Patel, D. S. P225
Pavan Kumar, G.V. P92
Penumaka, N. P21
Peerzada, G. M. P184
Periakaruppan, A. P95
Perumal, S. P248
Pethe, A.M. P101
Phani, P. M. P163
Pinak, M. P102
Pinaki, B.Y P17
Pitchai, P. P154
Pitre, K. S. P205
Prabal, D. P223
Prabhakaran, E. N. P131
Prabir Pal P218
Pradeep, K. P170
Pradeep, T. P71
Pradeep Kumar, P139
Pradeepta, K. P. P16
Pradhan, T. P222
Pradyot, B. P40
Pradyut, G. P2
Pramod, P. P191
Pramod, S. P226
Prasad V. B. P225
Prasad, K. L. P189
Prasanna S. G. P206
Prasanta Kumar, D. P128
Prasenjit, G. P177
Prasenjit, M. P115
Prathapa, S. J. P69
Pratibha, D. P143
Pratibha, S. P179
Pratik Sen P220
Praveen, V. K. P60
POSTER INDEX
vi

Preeti, R. P115
Priyabrata, P. P88
Priyabrata, S. P88
Prodeep P. P233
Purak, D. P17
Puranik, V. G. P102
Puspendra, S. P42
Puspendu, K. D. P53
Puspesh, K. U. P139
R
Rafiquee, M. Z. A. P27
Raghubir, S. P18
Raghunathan, R. P254
Rahul, S. P172
Rahul, D. S. P101
Rahul, J. P104
Rahul, P. P274
Rai, A. P133
Rai, V. K. P133
Raj, P.S. P10
Rajabhushan Reddy, S. P118
Raja Kumar, P. P242
Rajasekaran, T. P47
Rajeev, S. P109
Rajeev, G. P166
Rajendiran, N. P97
Rajesh, C. P26
Rajesh, Ch. P230
Rajesh, N. P110
Rajesh Kumar, P132
Rajeswara Rao. M. P38
Rajib, L. S. P55
Rajiv, K. V. P269
Rajkannan, R. P198
Raj Kumar, R. P114
Raju, D. P93
Raju, R. K. P273
Rakesh, K. M. P144
Rakesh, T. P269
Rakshit, S. P187
Ram, B. P. P51
Rama Kant P199
Rama, K. P79
Ramachandraiah, C. P175
Ramaiah, D. P169
Ramakrishnan, S. P114
Ramakrishna Rao P107
Rama Kumar, K. L. P170
Ramamurthy, P. P31
Raman, N. P216
Ramana Rao, R. V. P266
Ramaraj, R. P190
Ramarao, G. P103
Ramasesha, S. P70
Ramesh, A. P259
Ramesh, C. D. P201
Ramesh, C. S. P42
Ramesh, Ch. D. P77
Ramesha, G. K. P59
Rangappa, K. S. P141
Ranjan, P. P4
Ranjit, B. P222
Rao, C. N. R. P58
Rao, J. R. P14
Rao, K. N. P204
Rashid, M. P258
Ratti, R. P61
Ravi, P. B. P73
Ravikanth, M. P38
Ravi Kumar, I. P2
Ravindran, P.V. P56
Reena, P. K. P127
Reji, T. P57
Revanna, R. P235
Rew, D. P42
Rina, G. P119
Rina, S. P115
Ripal, C. P274
Rishikesh P. P174
Rita, M. P195
Ritu, M. P109
Rohini, O. P135
Rohit, K. R. P96
Romesh Chandra, B. P123
Roopa, M. P237
Roychoudhuary, P.K. P144
Ruchi, J. P270
Ruchi, K. P74
Ruli, B. P106
Rumila, M. P125
Rupam, S. P171
S
Sabyasachi, S. P83
Sachin, K. P150
Sachin, V. B. P268
Sahoo, S. K. P239
Saikat, D. P19
POSTER INDEX
vii

Saima, Q. P240
Sairam, S. C. P36
Sairam, S. M. P78
Sajal, D. P262
Sajal, K. P119
Sajal Kumar, D. P134
Sakthivel, A. P216
Samal, A. K. P71
Samantaray, M. K. P177
Samar, K. D. P164
Samaresh, B. P32
Samir, P. P274
Samit G. P183
Sampa, G. P53
Sampath, S. P59
Samuelson, A.G. P12
Sandeep, K. P213
Sangeeta, D. P12
Sangita S. P167
Sangita, D. K. P56
Sangita, M. P262
Sangita, R. P128
Sangmeshwer, P. S. P267
Sanjay, B. P271
Sanjay, K. S. P30
Sanjeev, P. M. P16
Sanjeev, S. P30
Sankar, P.R. P4
Sankeerth, H. P63
Santha Kumar, K. P1
Santhosh, B. S. P60
Santosh, J. G. P118
Santosh, K. U. P208
Sappanimuthu, T. P113
Saravanan, T. P113
Sarika M. B. P181
Sarkar, S. P255
Satveer K. P253
Satyanarayan, S. P172
Satyanarayana, S. P21
Saurabh, p. P265
Saurabh, S. P207
Saurin, R. P115
Savita, S. P166
Sawant, D. P251
Saxena, A. K. P161
Saxena, K. P161
Sayanti, D. P32
Sebastian, K. L. P90
Sebastian, R. P242
Seema, R. P98
Sekar, G. P260
Sekar, K.G. P261
Sekhar, K. P262
Selva Kumar, K. P236
Selvaraju, P196
Senthil, K. M. P28
Shabana, K. P34
Shabana, K. P247
Shailendra K. J. P199
Shalini, U. P144
Shameema, O. P160
Shanavas, A. P62
Shanbhag, P. P226
Shanmugam, P. P236
Shanmuga, S. K. P157
Sharma, P. P219
Sharma, V.K. P84
Shibi, I. G. P5
Shibli, S.M.A. P89
Shilpi, K. P109
Shinto, V. P186
Shiva Kumar, C. P162
Shraeddha, T. P247
Shridhar R. G. P188
Shrikant, P. N. P127
Shubhangi, B. P150
Shubhankar, K. B. P35
Shweta, S. P122
Shyamal Kumar C. P214
Shyamal, K. D. P80
Shyamal, K. J. P255
Siddhartha, De. P150
Siddhartha, P. S. P156
Siddiqi, Z. A. P238
Sinan, M. P111
Singh, A. K. P165
Singh, A. K. P259
Singh, J. K. P177
Singh, K.C. P84
Singh, N. K. P221
Singh, O. M. P231
Singh, U. P. P165
Siva, S. P. P109
Sivanesan, A. P6
Smriti, R. P24
Sneha E. A. P181
POSTER INDEX
viii

Sode, A. P215
Somnath, M. P25
Somnath, N. P271
Soni, A. S. P127
Soni, R. P24
Sonika P152
Sreedevi, M. P260
Sreedhar, N. Y. P194
Sreeprasad, T. S. P71
Srinivasa Raju, G. P192
Srinivasa Rao, A. P164
Srinivasan, K. V. P142
Srinivasan, N. P99
Srinivasa Reddy, B. P150
Sriparna, R. P177
Sripriya, S. P131
Srivastava, V. P122
Subash, P. C. P105
Subba Reddy, B.V. P270
Subhadip, G. P220
Subhash, C. J. P109
Subhendu, N. P214
Subodh, K. P75
Subodh, K. P8
Subrata, D. P130
Subrata, G. P272
Suchithra, M. P236
Sudarshan, M. P65
Sudeshna, S. P217
Sudip, K.G. P4
Suhail S. P258
Suheel, K. P. P118
Sujata, K. P11
Sujata, V. B. P127
Sujatha, D. P194
Sujit, K. S. P156
Sukhdeep, S. P228
Sukunath, N. P113
Sulekh, C. P24
Suleman, R. M. P267
Suman, S. P202
Sumit, D. P120
Sumit, K. S. P83
Sumit, T. P247
Sumita, H. P214
Sundargopal, G. P35
Sunil, K. P. P145
Sunita, B. P109
Suresh Das P186
Suresh, E. P23
Suresh, P. P85
Suresh, S. P. P142
Sureshbabu, V. V. P266
Surojit, P. P91
Suryaprakash, N. P63
Susac, D. P215
Susanta, K. N. P69
Susheel, K. M. P8
Sushobhan, G. P151
Sushuma, N. P231
Susmita, P. P262
Swapan, K. P. P78
Swapan, K. S. P64
Swarnalatha, K. P173
Swarupananda, M. P119
Swathi, R. S. P90
T
Talapatra, G. B. P218
Tarasankar, P. P91
Tejal, V. N. P129
Teo, M. P215
Thangavel, S. P190
Thankachan, P.P. P48
Thimmegowda, N. R. P141
Thirumala, K. P. P168
Thirumoorthi, R. P46
Thirunavukkarasu, K. P 211
Thomas, D. P142
Thomas, K. G. P191
Tiwari, I. P210
U
Udai, P. S. P11
Uday, S. A. P17
Uday Maitra P263
Uma, S. P29
Umapathy, S. P239
Upadhyay, K. K. P144
Uttam, R. K. P105
V
Vaithiyanathan, V. P236
Valarmathy, D. P112
Vandana, B. P117
Varada Reddy, A. P175
Varshney, K. G. P27
Vasudevan, S. P187
Vasundhara, S. P61
Vaultier, M. P61
Ved, V. A. P58
POSTER INDEX
ix

Vedprakash, S. P121
Veeraraghava, S. P113
Velmathi, S. P76
Velu, M. P185
Venkata, P. P. P150
Venkatachalam, S. G. P120
Venkatesan, K. P142
Venkatesan, R. P256
Venkateswaran, V. P112
Vibha, K. P48
Vijay, K. P51
Vijayamohanan, K. P100
Vijayaraghavan, R. K. P186
Vijayasree, V. P118
Vijay Luxami P75
Vikas P180
Vikas, B. P245
Vikas, N. T. P129
Vikas Kumar, P138
Vikram, G. P227
Vimal, P. P274
Vinita S. P179
Vinod K. K. S. P185
Vinod, K. T. P273
Vinoth Kumar P204
Vishnu, S. P79
Viswambharan, B. P236
Vitor, F. P10
W
Wong, K. C. P215
Wong, P. C. P215
Wright, C. W. P243
X
Xueqing, S. P37
Y
Yadav, J. S. P270
Yadav, J. S. P84
Yadav, L. D. S. P133
Yogesh, W. P150
Z
Zade, A. B. P264
Zhu, L. P215
Luwang M.N. P275
Srivastava S.K. P275
POSTER INDEX
x

The conference has been supported by generous
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Printed at : Uma Prints, B’lore. 9448046893

P 226 NATIONAL SYMPOSIUM IN CHEMISTRY
Rauhut-Currier Reaction of Conjugated Nitroalkenes
Pramod Shanbhag, Irishi N. N. Namboothiri*
Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076
The self-coupling reaction of activated alkenes, commonly known as Rauhut-Currier reaction, is reported only
with acrylates [1] and acrylonitriles.[2]

While similar coupling between the a-position of activated alkenes with
other electrophiles, the Morita-Baylis-Hillman (MBH) reaction, has received tremendous attention over the past
decade, Rauhut-Currier reaction is less known because it suffered from limited substrate scope. This is not only
because the reaction is a dimerization but also because the reactive intermediate involved is highly sensitive towards
electronic and steric factors and readily undergoes oligomerization and/or polymerization.
As part of our programme towards highly efficient synthesis of multifunctional molecules that exhibit interesting
properties including bioactivity,[3]

we have investigated the Rauhut-Currier reaction of nitroalkenes.

Extensive
optimization of the reaction conditions by screening various nucleophilic Lewis bases and solvents enabled us to
obtain the dimerization products from a variety of aromatic and heteroaromatic nitroalkenes in satisfactory yield.
Efforts are currently underway towards the synthesis of heterodimers using mixture of two nitroalkenes as well as
development of diastereo- and enantioselective versions of this reaction.
References
1. Rauhut, M. M.; Currier, H. U. S. Patent 1963, 3074999; Chem. Abstr. 1963, 58, 11224a.
2. Balzer, M. M.; Anderson, J. D. J. Org. Chem. 1965, 30, 1357.
3. Rastogi, N.; Mohan, R.; Panda, D.; Mobin, S.M.; Namboothiri, I. N. N. Org. Biomol. Chem. 2006, 4, 3211
328

NATIONAL SYMPOSIUM IN CHEMISTRY P 227
Synthesis of New Isoellipticine Derivatives through
Imino-Diels-Alder reaction
G.Vikram and R.Nagarajan*
School of Chemistry, University of Hyderabad, Central University (P.O.),
Hyderabad-500 046, INDIA
Ellipticine is a naturally occurring alkaloid of the 6H-pyridocarbazole family; this compound and its derivatives
are endowed with antitumor and anticancer properties. They are DNA intercalating molecules and their high DNA
binding affinity is thought to be responsible in part for this pharmacological properties.
[1-2]
14-chloro-6,7,7,16-
tetramethyl-5,7,7a,8,14b,15-hexahydrobenzo[5',6']pyrrolizino[2',1':5,6]pyrido[3,2-b]car-bazole derivatives, which
are structurally similar to isomeric ellipticine fused with pyrroloindole moiety, have been synthesized.
References:
1. Wang J. C., Annu. Rev. Biochem. 1996, 65, 635-692.
2.Monks N. R., Blankey D. C., East S. J., Dowell R. I., Caluete J. A., Curtin N. J., Arris C. E., Newell D. R., Eur. J.
Cancer. 2002, 11, 1543-1552.
329

P 228 NATIONAL SYMPOSIUM IN CHEMISTRY
Site-Selective Functionalization Of Medicinally Potent Heterocycles
Amit Sharma, Kawaljit Singh, Divya Arora, Sukhdeep Singh and Kamaljit Singh*
Organic Synthesis Laboratory, Department of Applied Chemical Sciences & Technology,
Guru Nanak Dev University, Amritsar – 143 005
Heterocyclic chemistry continues to be in the focus of life science oriented research. Structural functionalisation
is a unique tool for fine-tuning biological properties and offers extra bonus in this context. This poster presentation
shall feature two pertinent issues. First, demonstration of lithiation – substitution sequence [1] in the field of some
interesting bisheterocyclyl methanes 1, intermediates for a variety of important (medicinally and otherwise)
macrocyclic systems such as meso-porphyrins, calix[4]pyrroles etc. Second, novel and dependable routes to structural
elaboration of dihydropyrimidinones 2 – potent cardiovascular agents and special emphasis shall be laid on the
merit of the functionalisation approach [2].
References: [1] Kamaljit Singh and Amit Sharma Tetrahedron Lett. 2007, 48, 227.
[2] Kamaljit Singh, Divya Arora and Sukhdeep Singh, Tetrahedron Lett. 2007, 48, 1349
330

NATIONAL SYMPOSIUM IN CHEMISTRY P 229
Trehalose – Does It Entrap Or Replace Coupled Water In Amino Acid
Solutions?
Muthuselvi Lakshmanan, Aruna Dhathathreyan*
Chemical Lab., CLRI, Adyar, Chennai 600 020, India
Trehalose is known to stabilize protein structures in aqueous solutions. The molecular level understanding of
such mechanism could be explained either by one of the two hypotheses; wherein the coupled water is either entrapped
by trehalose in proteins or is replaced. The results from the present study on aqueous solutions of amino acids with
trehalose demonstrate the partial replacement of water molecules in the near vicinity of amino acids resulting in
enhancement of structural ordering of hydrated amino acids. This is reflected in the increased values of experimentally
determined hydrodynamically coupled water using quartz crystal microbalance (QCM) and solid/liquid interfacial
tension of aqueous solutions of amino acids with trehalose. The study suggests a Kosmotropic role of trehalose in
Protein stabilization.
331

P 230 NATIONAL SYMPOSIUM IN CHEMISTRY
A Novel Organo-Catalyst For Chemo-Selective
O-Tert -Butoxycarbonylation Of Phenols
Rajesh Chebolu, Sunay V. Chankeshwara and Asit K. Chakraborti*
Department of Medicinal Chemistry,
National Institute of Pharmaceutical Education and Research (NIPER),
Sector 67, S. A. S. Nagar 160 062, Punjab, India.
The occurrence (30% frequency) of hydroxyl groups [1] in the preparation of drug candidates makes their
protection/deprotection an important and frequently needed exercise.[2] A common approach to protect hydroxyl
groups is acylation [2,3] but the regeneration requires hydrolytic cleavage under strong alkaline conditions [2] and
is detrimental to other functional groups. Chemoselective deacylation is achievable under neutral or virtually neutral
and non-aqueous conditions following ‘demand-based thiolate anion generation’ protocols but these require elevated
temperature and high boiling solvent.
The inertness of tert-butyl carbonates (O-t-Boc) for routinely adopted experimental conditions in organic
synthesis, and the ease of removal under mild acidic environment, [2]

makes O-tert-butoxycarbonylation an efficient
alternative. However, the drawbacks of the limited methodologies for O-t-Boc formation of phenols necessitate the
development of a better methodology. Although Lewis acid catalysed N-tert-butoxycarbonylation

has recently
gained importance, phenols forms the tert-butyl ethers with (Boc)
2
O in the presence of a strong Lewis acid

highlighting
the need for organo-catalyst for which DMAP is the only choice available. However, DMAP induces formation of
symmetrical carbonates and carbonic-carbonic anhydrides and is toxic.
The present work will demonstrate a novel organo-catalyst for chemo-selective O-tert-butoxycarbonylation of
phenols.
References
1. J. S. Carey, D. Laffan, C. Thomson and M. T. Williams Org. Biomol. Chem., 2006, 4, 2337.
2. T. W. Greene and P. G. M. Wuts Protecting Group in Organic Synthesis, John Wiley and Sons, New York, ed.3,
1999.
3. a) Shivani, R. Gulhane and A. K. Chakraborti J. Mol. Catal. A: Chem. 2007, 264, 208; b) A. K. Chakraborti and
Shivani, J. Org. Chem., 2006, 71, 5785; c) A. K. Chakraborti and R. Gulhane Synlett, 2004, 627; d) A. K.
Chakraborti and R. Gulhane Synthesis, 2004, 111; e) A. K. Chakraborti, R. Gulhane and Shivani Synlett, 2003,
1805; f) A. K. Chakraborti, L. Sharma, R. Gulhane and Shivani Tetrahedron, 2003, 59, 7661; g) A. K. Chakraborti
and R. Gulhane J. Chem. Soc. Chem. Commun., 2003, 1896; h) A. K. Chakraborti and R. Gulhane Tetrahedron
Lett., 2003, 44, 3521.
332

NATIONAL SYMPOSIUM IN CHEMISTRY P 221
Synthesis, spectroscopic and DFT study of potential ligands of N’-(2-
methoxy-benzoyl)-hydrazine carbodithioate ester
Mamata Singh
#
, R.J.Butcher* and N.K.Singh
#a
a#
Department of Chemistry, Banaras Hindu University, Varanasi-221005, India.
*Department of Chemistry, Howard University, 525 college street NW,
Washington DC, 20059, USA.
In the present work synthesis and spectroscopy studies of two new ligands, N’-(2-methoxy-benzoyl)-hydrazine
carbodithioic acid benzyl ester (1) and N’-(2-methoxy-benzoyl)-hydrazine carbodithioic acid ethyl ester (2) are
reported. The compounds (1) and (2) were synthesized by stirring a CHCl
3
/ MeOH suspension of potassium [N’-(2-
methoxy-benzoyl)-hydrazine]-carbodithioate with benzyl chloride / ethyl iodide for 3-4 h, respectively. On slow
evaporation of the solution solid product were obtained. These compounds have been characterized by I.R., NMR
and single crystal X-ray spectroscopy. The white single crystal obtained by slow evaporation of (1) after 1 day
crystallizes in triclinic crystal system with space group P -1 which has unit cell parameters : a = 7.493(2), b =
10.230(3) , c = 11.212(4) 74.56(3), a = 81.49(3) , b = 77.61(2) , g = 805.3(4) and Z = 2. The molecular packing
show intermolecular C-H…S and N-H…O (carbonyl oxygen) hydrogen bonding and N-H…O (2-methoxy group)
intramolecular hydrogen bonding which have stabilized the molecular packing (Figure 1). A correlation of experimental
and theoretical results concerning the geometric and electronic structure description of both ligands has been made.
The theoretical investigation based on the density functional theory (DFT) was performed for these molecules. The
theoretical results are in good agreement with the experimental data. The topological analysis of electron density
(AIM theory) was applied to confirm the existence of intermolecular H-bond in the molecule. The molecular orbital
diagrams of (1) and (2) have been calculated on the basis of DFT.
Figure 1. The molecular packing of 1 indicating intermolecular or intramolecular hydrogen bonding
323

P 222 NATIONAL SYMPOSIUM IN CHEMISTRY
Twisted Intramolecular Charge Transfer (TICT) Reaction in
(Alkylamino)benzonitriles in Electrolyte Solutions: Concentration and Ion
Size Dependences
Tuhin Pradhan and Ranjit Biswas*
Department of Chemical, Biological & Macromolecular Sciences, S. N. Bose National Centre
for Basic Sciences, JD Block, Sector III, Salt Lake, Kolkata 700 098, INDIA
Steady state [1] and time resolved [2] spectroscopic studies have been performed with three intramolecular
charge transfer molecules, 4-(1-azetidinyl) benzonitrile (P4C), 4-(1-pyrrolidinyl) benzonitrile (P5C) and 4-(1-
piperidinyl) benzonitrile (P6C), in ethyl acetate and acetonitrile in presence of several perchlorate salts at room
temperature to investigate the effects of electrolytes on the equilibrium constants and reaction rates in these TICT
molecules. Electrolyte concentration and ion-size dependences of several spectroscopic properties such as quantum
yield, absorption and emission transition moments, radiative and nonradiative rates, and changes in reaction free
energies associated with LE®CT conversion have been determined for these molecules. Quantum yields have been
found to decrease significantly upon addition of electrolyte for all these molecules. Formation of charge transfer
(CT) state is found to be strongly favored over the locally excited (LE) state as the electrolyte concentration is
increased, electrolyte effects being more pronounced in ethyl acetate than in acetonitrile. Changes in reaction free
energies (– DG
r
) for the LE®CT conversion reaction in presence of electrolyte are more pronounced in ethyl acetate
than in acetonitrile. While quantum yield is found to decrease with the increase in ion-size, DG
r
remains largely
insensitive to the variation in ion diameter. Time resolved studies with these molecules in ethyl acetate in presence
of LiClO
4
indicate that the average reaction time for LE®CT conversion increases at low electrolyte concentration
and then decreases to become comparable and even lower than that in the pure solvent. Except for Mg
+2
, the average
reaction time decreases linearly with the ion-size in 0.5(M) LiClO
4
solution of ethyl acetate. The observed electrolyte
concentration dependence of the average reaction time for both the molecules agrees well with the calculated values
from the theory of Zwan and Hynes [3] in the broad barrier over damped limit with barrier frequency, w
b
»2x10
12
s
-1
.
References
1. Pradhan, T.; Biswas, A. J. Phys. Chem. A. 2007, 111 (in press).
2. Pradhan, T.; Biswas, A. J. Phys. Chem. A. 2007, 111 (in press).
3. Zwan, G.; Hynes, J. T. Chem. Phys. 1991, 152, 169.
324

NATIONAL SYMPOSIUM IN CHEMISTRY P 223
Ferromagnetic carbons derived from low molecular weight organic
compounds
Prabal Dasgupta
Department of central scientific services Indian Association for the Cultivation of Science,
Kolkata-700032
That ferromagnetism may occur in carbonaceous compounds has been predicted long ago, Mataga [1]. Only
recently Esquinazi et al [2] observed ferromagnetic signals in highly oriented pyrolytic graphite. Here we report that
combustion product of small organic molecules like toluene and naphthalene clearly shows ferromagnetic signals at
300K with saturation magnetization as high as 1X10
-3
emu/g, measured in a SQUID magnetometer. FTIR Studies
showSp
2
CH (arom) and sp
3
CH
2
(sym&asym) stretching modes suggesting these are hydrogenated amorphous carbon.
Electron diffraction diagram of these materials show essentially two rings, one corresponding to d
002
of graphite and
another at a still lower angle. Interplanner spacings (d values) increase as the carbon content of the parent material
increases. TEM & SEM studies reveal that these are present in one phase and depicts 3-dimensional carbon network
made up of nearly spherical globules of 50-80nm diameter. EDS study confirms absence of any magnetic contaminants.
Hence the origin of ferromagnetism is intrinsic in nature and plausible reasons were discussed in details.
References:
[1] Mataga, N. Theor. Chem. Acta (Berlin), 1968, 10,372.
[2] Esquinazi, P. et al Phys.Rev. B, 2002, 66, 024429.
325

P 224 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis Of Thio-Sugar Based Amino Acids
Thanikachalam Gunasundari and Srinivasan Chandrasekaran*
Department of Organic Chemistry, Indian Institute of Science, Bangalore.
Synthesis of thio-sugar is of continuing interest in contemporary organic synthesis due to their importance in
the glycosidase inhibition.[1] Additionally, sugar based amino acids are interesting and important class of templates
in the area of peptidomimetic[2] and supramolecular studies.[3] So, the challenge lies in the synthesis of thio-sugars
and thio-sugar based amino acids in an elegant manner. In our laboratory, we have demonstrated earlier the efficacy
of sulfur transfer reagent, Benzyltriethylammonium tetrathiomolybdate [BnNEt
3
]
2
MoS
4
. Herein, we present the
synthesis of various thio-sugar based amino acids derived from a-D-glucoheptonic-g-lactone utilizing [BnNEt
3
]
2
MoS
4
as the sulfur transfer reagent.
References
1. a) Witczak, Z. J.; Culhane, J. M. Appl. Microbiol. Biotechnol. 2005, 69, 237; b) Le Merrer, Y.; Fuzier, M.; Dosba, I.;
Foglietti, M. –J.; Depezay, J. –C. Tetrahedron 1997, 53, 16731.
2. Chakraborty, T. K.; Srinivasu, P.; Tapadar, S.; Mohan, B. K. J. Chem. Sci. 2004, 116, 187 and references cited therein.
3. a) Hartgerink, J. D.; Granja, J. R.; Milligan, R. A.; Ghadiri, M. R. J. Am. Chem. Soc. 1996, 118, 43; b) Amorin, M.;
Brea, R. J.; Castedo, L.; Granja, J. R. Org. Lett. 2005, 7, 4681.
326

NATIONAL SYMPOSIUM IN CHEMISTRY P 225
Modelling and Synthesis of GSK-3 Inhibitors,
Targeting Substrate Binding Site
Ankita Sharma, Dhilon S. Patel, Asit K. Chakraborti and Prasad V. Bharatam*
Department of Medicinal Chemistry,
National Institute of Pharmaceutical Education and Research (NIPER),
S.A.S. Nagar (Mohali) - 160 062, Punjab, India.
Glycogen Synthase Kinase-3 (GSK-3), a serine/threonine kinase, is an important target for anti-diabetic agent
design [1]. Inhibition of GSK-3 activity can be achieved through three distinct mechanisms i) Metal-ion competitive
approach at Mg
2+
binding site, ii) ATP competitive manner in ATP binding pocket and iii) ATP non-competitive
manner in substrate interaction domain. It is important to inhibit GSK-3 selectively over other phylogenitically
related kinases, in order to achieve the net effect of inhibitors. In order to solve the problem of selectivity in ATP
competitive inhibitors several rational approaches have been employed by different research groups [2, 3]. However,
there are some possible problems with the ATP competitive GSK-3 inhibitors that have been developed so far. Here
we report 2-substituted 1-Oxo-1l
4
-isothiazolidin-3-one as ATP Non-competitive GSK-3 inhibitors which bind GSK-
3 at substrate binding site and consequently inhibit the activity of the enzyme. FlexX based molecular docking
studies and virtual screening of the newly designed ligands was carried out to understand the interactions of these
ligands in substrate binding site. Higher scored ligands have been screened for TOPKAT based in silico toxicity
prediction. Ligands selected from this virtual screening exercise have been taken up for synthesis.
References
1. Bharatam, P. V., Patel, D. S., Iqbal, P. J. Med. Chem. 48, 2005, 7615.
2. Patel, D. S., Bharatam, P. V. J. Comput. Aided-Mol. Des., 20, 2006, 55.
3. Dessalew, N., Patel, D. S. Bharatam, P. V. J. Mol. Graph. Model. 25, 2007, 885.
327

P 216 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis, Structural Elucidation, Electrochemical, DNA And
Antimicrobial Studies Of Transition Metal Complexes Derived From A
Tetradentate Schiff Base
N. Raman* and A.Sakthivel
Research Centre in Chemistry, VHNSN College, Virudhunagar-626 001, India
A new tetraaza macrocyclic Schiff base, synthesised from 3-hydroxy-4- nitrobenzylideneaceto-toluidide and
o-phenylenediamine, acts as a tetradentate ligand and forms solid cationic complexes with Cu
II
, Ni
II
, Co
II
, Zn
II
, Mn
II
,
VO
IV
and Cd
II
salts in ethanol. Microanalytical data, magnetic moment, electronic, IR , Mass and ESR techniques
were used to characterize the structures of the synthesised Schiff base ligand and its complexes. Electronic absorption
and IR spectra of the complexes suggest that all the complexes exhibit square-planar geometry while the oxovanadium
complex shows square-pyramidal geometry. Elemental analysis and mass spectral data of the Schiff base and their
complexes suggest that the general formula of the complexes is [ML]X where L=Ligand, X= 2Cl
–
or SO
4
2-
. Electrolytic
behaviour of the chelates was assessed from their higher conductance data. Monomeric nature of the chelates was
confirmed from their magnetic susceptibility values. Electrochemical studies of copper complex in DMF using
cyclic voltammetry technique indicate the existence of unusual oxidation states such as Cu(III), Cu(I) which are
stabilized by the ligand system. Antimicrobial study of the ligand and its complexes (MIC values) indicates that the
complexes exhibit higher antimicrobial activity than the free ligand. The nuclease activity of the above metal complexes
shows that the complexes cleave DNA through redox chemistry. In the presence of H
2
O
2
, all the complexes are
capable of cleaving Lambda DNA.
318

NATIONAL SYMPOSIUM IN CHEMISTRY P 217
A Convenient synthesis of Palladium nanoparticles and Catalysis of
Hiyama Coupling Reaction in Water
Dipankar Srimani, Sudeshna Sawoo and Amitabha Sarkar*
Department of Organic Chemistry, Indian Association for the Cultivation of Science,
Kolkata 700032, India
Transition-metal-catalyzed reactions have become an important tool of modern organic synthesis due to their
high efficiency, selectivity and wide diversity of possible transformations.
In homogeneous metal-catalyzed reactions,
each metal complex molecule in solution functions as the catalyst or as a precatalyst. The ligand environment
around the metal atom controls its reactivity and protects it from competitive decomposition pathways. In
heterogeneous catalysis, the catalytic surface offers a limited number of ‘active’ sites for catalysis, often necessitating
harsher reaction conditions for optimum catalytic efficiency. Of late, nanoparticles emerged as useful and unique
catalysts whose efficacy is attributed to their characteristic high surface-to-volume ratio that translates into more
number of active sites per unit area compared to standard heterogeneous catalysts.
We developed a mild synthetic method for the generation of colloidal palladium in water utilizing the reducing
property of a Fisher carbene complex
1
of tungsten [(CO)
5
W=C(CH
3
)O(-) NEt
4
(+)] and PEG as capping agent. The
colloidal palladium (1 mol%) efficiently catalyzes Hiyama Cross coupling reactions
2
performed in air. The major
advantage of the protocol is three-fold: all operations are performed in water, no additive other than a small amount
of PEG is required and temperture of reaction is usually lower than 100 °C. A range of substituted aryl bromides
were used as substrates. Both electron withdrawing and electron donating substituents yielded excellent results. It
was observed that the size of the nanoparticles decreases with increasing amount of the stabilizer PEG-6000 and
the catalytic activity and stability of the nanoparticles were found to be inversely correlated. Encourage by these
results we applied our catalytic system in other C-C cross-coupling reaction such as Suzuki, Stille, Heck and
Sonogashira coupling reaction also. The present procedure is superior to several earlier methods in that it does not
use any organic solvent except for work up, nanoparticles can be used straight after preparation without any
purification step, and the entire operation is fluoride-free.
References
1. Samanta, D.; Sawoo, S.; Sarkar, A. Chem. Commun. 2006, 3438.
2. Srimani, D.; Sawoo S.; Sarkar, A. Org. Lett. 2007, 9, 3639.
319

P 218 NATIONAL SYMPOSIUM IN CHEMISTRY
The effect of salts on alcohol dehydrogenease Langmuir-Blodgett film
Tapanendu Kamilya, Prabir Pal and G. B. Talapatra*
Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur,
Kolkata-700 032, India.
Studies of proteins have emerged considerable interest due to their prospective application in nanobioscience.
Immobilization of protein/enzyme with minimum denaturation on a solid support has been found extensively valuable
for various technological applications. Langmuir-Blodgett (LB) method is a tool among various developed techniques
to study the monolayer and to immobilize biomaterials on solid surfaces. The fundamental points associated with
protein/enzyme monolayer are, the structural and conformational regulation of protein monolayer, stability, surface
coverage, biological activity and effects of salts/ions etc. We have studied here the basic property of alcohol
dehydrogenease (ADH) monolayer and the effect of salts in the subphase on the surface activity of ADH. The ADH
was purchased from Sigma. The interfacial surface activity of ADH in presence and in absence of salts was studied
by monitoring the surface pressure (p)-area (A) isotherm measurement (Fig. 1) on a LB trough. The results show that
the surface activity of ADH increases in salt containing subphase. A detail compressibility study was done to
characterize the states of ADH monolayer and to select the optimum surface pressure to transfer a well-organized
film onto a substrate surface. The conformational change of ADH in different media was studied by circular dichroism
(CD) and FTIR spectroscopy. The peak at 215 nm in the CD spectra of LB monolayers (Fig. 2) confirms the
formation of
b-structure. CD and FTIR studies show that uses of salt perturb the protein monolayer. Therefore, a
larger unfolding of ADH molecule is expected by using salt in subphase. The surface morphology of deposited
ADH films at different conditions was analyzed by atomic force microscopy (AFM). Fig. 3A shows aggregated
structure of ADH (20-30 nm in diameter) at lower pressure. However, at higher surface pressure, ADH is squeezed
out from the monolayer and forms fibrillar networks (Fig. 3B). Micro and nano fibrils (Fig. 3C and 3D) are observed
in LB-films lifted from salt containing subphases.
Fig.1. (p)-(A) isotherm Fig.2. CD spectra
Area / molecule (nm
2
)
320

NATIONAL SYMPOSIUM IN CHEMISTRY P 219
Voltammetric Ultra Trace Determination of Gallium and Indium
P. Sharma
Electroanalytical Laboratory, Department of Chemistry
J N V University, Jodhpur-342003, India
Indium is usually present with gallium in industrial processes using compounds of In and Ga for their
semiconductor properties [1]. Further the electrochemical characteristics of In (III) are also considered very close to
trivalent gallium [2]. Therefore in present study optimum conditions for the determination of indium and gallium
and gallium down to 0.10 ìg/ml by adopting differential pulse polarography (DPP) were developed.
In the presence of 1 M sodium thiocyanate, In (III) and Ga (III) gave distinguishable DP peaks at -0.62 V and
–0.77V, respectively. The possibility of interference from aluminate was examined and ruled out [3]. The calibration
characteristics in both the cases showed a coefficient of Correlation (r) of 0.99. The DPP procedure was applied
successfully for the determination of sub mg level indium and gallium in aqueous matrices where results were found
quantitative in terms of recovery of 97.8°/8 and precision (SD
+0.02).
Reference:
[1] J. Emsley, The Elements, Oxford University Press, Oxford (1988).
[2] A. J. Bard, R. Parson and J. Jordan (Eds.) Standard Potentials in Aqueous Solutions, Marcel Dekker Inc.,
New York (1985).
[3] I.M. Kolthoff and J.J. Lingane Polarography, 2
nd
edn. Interscience Publishers, New York (1955).
321

P 220 NATIONAL SYMPOSIUM IN CHEMISTRY
Excitation wavelength dependence of solvation dynamics in the micelle and
the gel phase of a PEO-PPO-PEO triblock copolymer
Subhadip Ghosh, Pratik Sen, and Kankan Bhattacharyya*
Physical Chemistry Department, Indian Association for the Cultivation of Science, Jadavpur,
Kolkata 700 032, India.
Excitation wavelength (l
ex
) dependence is used to spatially resolve the solvation dynamics in different regions
of the micellar and gel phase of a water soluble triblock copolymer, PEO
20
-PPO
70
-PEO
20
(Pluronic P123). This is
studied by femtosecond and Pico second time resolved emission spectroscopy [1-2]. In the gel, the micelles associate
to form an interconnected network with inter-micellar distance (140 Å) less than the sum (160 Å) of the radii of the
micelles. Both the P123 micelle and gel, exhibits a large (~24 nm) red edge excitation shift (REES) due to heterogeneity
in the environment. Solvation dynamics in the interior of P123 micelle and gel are found to depend strongly on the
excitation wavelength. With increase in
l
ex
, the contribution of the bulk-like exposed region having an ultrafast
component (
£2 ps) increases more than 10 times. There is concomitant decrease in the contribution of the ultraslow
component arising from the buried region.
References
1. Sen, P.; Ghosh, S.; Sahu, K.; Mondal, S. K.; Roy, D.; Bhattacharyya, K. J. Chem. Phys. 2006, 124, 204905.
2. Ghosh, S.; Adhikari, A.; Mandal, U.; Dey, S.; Bhattacharyya, K. J. Phys. Chem. C 2007, 111, 2085.
322

NATIONAL SYMPOSIUM IN CHEMISTRY P 211
Influence of Subsurface Oxygen on Palladium Surfaces Towards
CO-Oxidation at High Temperatures
S. Nagarajan, K. Thirunavukkarasu, and Chinnakonda S. Gopinath*
Catalysis Division, National Chemical Laboratory, Dr. Homi Bhabha Road,
Pune 411 008, India
Noble metals are known for high oxidation capacity of carbon monoxide (CO) and they are essential ingredients
in three-way catalytic converters employed in automobiles for emission control. In general, the rate of CO oxidation
decreases above 550 K on metal surfaces and high rate of CO-desorption becomes a limiting factor in the CO
oxidation[1-2] Recent reports [3] indicates oxygen-diffusion into the sub-surface/bulk of Pd-surfaces under ultra
high vacuum (UHV) and >500 K, and Pd
x
O
y
formation at relatively high oxygen pressure (>10
-3
mbar). Variations in
the catalytic activity of oxidation reactions with Pd catalysts are reported and generally it is attributed to differences
in activity between Pd and PdO. However, the interactions between oxygen and Pd-surfaces have important
implications, especially towards oxidation reactions, and seldom detailed reports are available in the literature on
the influence of sub-surface oxygen to oxidation reactions. In our efforts to understand the above aspect, we carried
out CO oxidation reactions, by allowing a mixed molecular beam (MB) made of CO+O
2
on Pd(111) surfaces under
a wide variety of conditions (T = 450 to 900 K, CO:O
2
= 7:1 to 1:10). A set of data is given in Figure 1 which shows
the delay in CO
2
desorption in spite of large oxygen adsorption and presence of CO. Above studies provide the
direct proof for CO-adsorption with significant sticking coefficient (s
CO
) at high temperatures on Pd surfaces that
contains significant sub-surface O-coverage. Indeed our results are highly relevant to the present generation catalytic
converters employed under air-rich conditions, in which Pd is increasingly used as an active metal or the only active
metal. More results will be presented in the poster.
Figure 1: Temporal evolution of the partial pressure of CO, O
2
, and CO
2
during the CO + O
2
reaction at 700 K on
Pd(111) surfaces for different CO:O
2
ratios between 7:1 and 1:4. Dashed arrows indicate the shutter opening and
dotted arrow indicates the onset of simultaneous CO adsorption and CO
2
desorption. Beam oscillation was carried
out between t = 190-210 s to measure the steady state rate.
References:
1. Engel, T.; Ertl, G. J. Chem. Phys. 1978, 69, 1267.
2. Szanyi, J.; Kuhn, W. K.; Goodman, D. W. J. Phys. Chem. 1994, 98, 2978.
3. Leisenberger, F. P. et al., Surf. Sci. 2000, 445, 380.
313

P 212 NATIONAL SYMPOSIUM IN CHEMISTRY
Feasibility of Photogalvanic Solar Cells in Present Scenario of Energy
Crisis
K.R. Genwa
Department of Chemistry, Jai Narain Vyas University,
Jodhpur, 342 005 (Rajastan)
There are not many people now days that need to remind the energy crisis all over the world. As we run out of
the all the energy recourses we find a heavy stress due to earths limited energy resources. All the energy sources
available as coal, Petroleum and Natural gases are quite low to serve all over the world for all energy requirements
and these sources also increase the pollution and global warming. The day is not far on which all the stored energy
resources will ends. So there is an urgent need to search a renewable energy source like solar energy. Photogalvanic
conversion of solar energy in to electrical energy has attracted attention of scientists with bright future prospect. The
photogalvanic effect reported first of all by Rideal and Williams [1]. The photogalvanic solar cells are based on
some such chemical photochemical reaction, which give rise to high energy products on excitation by a photon.
These energy rich products loose energy electrochemically. Recently we reported some photogalvanic solar systems
by using some efficient dyes as photosensitizers [2-3]. The performance and conversion efficiency of photogalvanic
cell composed of dye in presence of anionic surfactant has been studied and analyzed. The performance and conversion
efficiency cell is observed. The effects of various parameters like pH, concentration of dye, concentration of surfactant,
diffusion length and electrode area on cell’s power generation was also observed. Finally feasibility of solar cells
checked.
References:
1. Rideal, E, K; Williams, D.C. J. Chem. Soc. 1925, 258.
2. Genwa, K, R.; Chouhan, A. J. Chem. Sci. 2004, 116, 339.
3. Genwa, K, R.; Mahaveer.; Inderprakesh. J. Indian Chem. Soc. 2006, 84, 165.
314

NATIONAL SYMPOSIUM IN CHEMISTRY P 213
Non-Covalent Charge Transfer Assemblies for Selective Sensing Of Anions
in Water
Sandeep Kaur, Kamaljit Singh and Paramjit Kaur*
Department of Chemistry, Guru Nanak Dev University, Amritsar – 143 005
The development of new chemosensors for ions is an important area of investigation in supramolecular chemistry
due to their fundamental roles in medical diagnostics, physiology and environmental applications. A number of
examples of sensors based on mass changes, electrochemical devices, biosensors, chromogenic and fluorescent
chemosensors have been reported over the past few years. Colorimetric sensing events have gained more importance
owing to the ease in monitoring of the process without resorting to sophisticated techniques. A great effort has been
invested in developing simple-to-make and use naked-eye diagnostic tools for sensing of metal ions.
Anions are ubiquitous in nature. Fluoride is the smallest nucleophilic anion, which is administered in the
treatment of osteoporosis and is often added in dental pastes and water because of its beneficial effects. However, its
excess may lead to the emergence of dental caries, fluorosis, urolithiasis etc. For these reasons, the development of
probes that can sense this anion in water has become a topical objective.
In this poster presentation, synthesis and use of charge transfer assemblies such as dipyrromethane-7, 7’, 8, 8’-
tetracyanoquinodimethane (TCNQ) 1 as a selective receptor for fluoride ion (as Na
+
salt) in aqueous solutions shall
be presented. Since the sensing process invokes a visible color change, this process can be described as “Naked eye”
sensing [1]. Conceptually the present assembly utilises N-methylated pyrrole and thus does not rely on hydrogen
bonding with fluoride but senses it through perturbation of the assembly due to weak
p-interactions.
Changes in the absorption spectrum of 1, upon
addition of F
-
(Visual change: Blue to Pink).
Reference:
[1] (a) Paramjit Kaur, Sandeep Kaur and Kamaljit Singh Tetrahedron Lett. 2007, 48, 7191.
(b) Paramjit Kaur, Sandeep Kaur and Kamaljit Singh (Communicated)
1
315

P 214 NATIONAL SYMPOSIUM IN CHEMISTRY
Ruthenium(II) complexes of some thiosemicarbazones: Structural and
DFT study
Sumita Hazra
a
, Dipankar Mishra
a
, Subhendu Naskar
a
, S. I. Gorelsky
b
and Shyamal Kumar
Chattopadhyay
a*
a
Department of Chemistry, Bengal Engineering and Science University, Shibpur,
Howrah 711 103, India,
b
Centre for Catalysis Research and Innovation, Department of Chemistry,
University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
Six new thiosemicarbazones have been prepared by reacting six different (4-aryl)thiosemicarbazides with
thiophen-2-aldehyde. Reaction of the thiosemicarbazones with Ru(PPh)
3
Cl
2
afforded compounds of formula cis-
[Ru(PPh
3
)
2
(L)
2
] (L = deprtonated thiosemicarbazone ligand). X-ray single crystal structure determination of four of
these complexes reveal that thiosemicarbazone ligands coordinate to the ruthenium center through the hydrazinic
nitrogen and sulfur forming four-membered chelate rings with ruthenium in cis-N
2
trans-S
2
cis-P
2
coordination
environment. The complexes undergo quasi-reversible one electron oxidation at ~0.5 V vs Ag/AgCl electrode. DFT
calculations on these complexes indicate that HOMO has ~35% metal character and there is substantial delocalization
of the electrons over ligand backbone. Thus assignment of the oxidation state of the metal ion for such molecules
must be made with caution, as during the one electron oxidation of the complexes the electron is lost from a molecular
orbital, having appreciable ligand contribution, rather than from a pure metal centered orbital.
316

NATIONAL SYMPOSIUM IN CHEMISTRY P 215
Study of Catalysts Based On Non-Precious Metals for Applications in PEM
Fuel Cells
K.A.R. Mitchell*, D. Bizzotto, S.A. Campbell, R.R. Parsons, A. Sode, D. Susac, M. Teo,
K.C. Wong , P.C. Wong , L. Zhu
Department of Chemistry, University of British Columbia, Vancouver, Canada; Ballard Power
Systems, Burnaby, Canada; Department of Physics & Astronomy, University of British
Columbia, Canada.
The search continues for catalysts, based on non-precious metals that can act as cathodes in proton exchange
membrane (PEM) fuel cells. This is motivated by the cost of Pt for the mass production of automobiles using
currently available technology. Key challenges for the development of new catalytic materials for this application
concern activity for oxygen reduction, stability in acidic environment, and open circuit potential (OCP). Our research
focuses on thin-film materials prepared by magnetron sputtering, and formed from Fe, Co and/or Ni in combination
with S or Se. A fundamental approach is emphasized in which performances of the model catalysts are evaluated
against a Pt standard. This paper will review the new information gained so far by characterizing these catalysts
with such techniques as scanning Auger microscopy, X-ray photoelectron spectroscopy, micro-Raman spectroscopy
and X-ray diffraction, before and after application of electrochemical tests. Thin films have been produced with
OCP values approaching 0.9 V (vs. reversible hydrogen electrode).
317

P 206 NATIONAL SYMPOSIUM IN CHEMISTRY
Correlating Weak Hydrogen Bonding and Electron Donor-acceptor
Properties for Novel molecular Materials
Prasanna S. Ghalsasi*
Department of Chemistry, Faculty of Science, The MS University of Baroda,
Vadodara- 390 002.
Two most ubiquitous non-covalent interactions are hydrogen (H)-bonding and electron donor acceptor (EDA)
interaction. It is well know that, normally, the earlier interaction plays important role in stabilizing structure while
later in transmitting signals. To understand such interactions at solid state level and make them work for the practical
applications is a challenging task. Strong H-bonding and EDA interactions are studied at solid state level and were
of increasing interest from late 1980’s. But collectively both weak H-boding and weak EDA interactions are rarely
studied at solid state level. My preliminary experiments show that, with the correct balance between these two non-
covalent interactions one can tune various technologically important properties such as, molecular magnetism,
newer sensors in such compounds.
1, 2, 4, 5-tetracyanobenzene (TCNB), an electron acceptor (with reversible ionization potential of –0.65 eV in
acetonitrile at room temperature versus SCE), exist in dimeric form with weak CN
…
HAr hydrogen bonding, but
when treated with weak electron donor molecules, such as Phenol, it not only form expected charge transfer complex
but also extend its dimeric CN
…
HAr hydrogen bond to the ribbon like network, akin to host assembly. The single
crystal X-ray diffraction study clearly shows that these ribbon-like networks generate cavities (Fig 1), where Phenol
is incorporated as a guest molecule. The presence of CN
…
HAr interaction is also evident from the spectroscopic
(FT-IR and Raman, Fig 1) studies. Thus, it is evident that such a structure gets built using both charge-transfer as
well as hydrogen bonding motif in the form of flexible host-guest assembly. On the contorollary this host formation
becomes loose when stronger electron donor molecules such as TMPD (N,N,N
¢,N¢-tetramethyl-p-phenylenediamine,
a strong electron donor) is used instead of Phenol. The structure of later complex do not seem to show the usual
p-
p interaction between the two aromatic rings, but indicates the presence of n- p interaction localized between the
nitrogen atom of TMPD and the cyano groups of TCNB. Magnetic measurements using SQUID magnetometer (5-
20K) on powdered sample showed decrease in
cT values with lowering temperature, weakly antiferromagnetic
(
q=-0.85K). Thus I will present some interesting results, which show presence of weak H-bonding, and EDA
interaction, and their interplay for generating new molecular materials.
Figure1: Showing Presence of Stacking of EDA complex (X-ray, left) and CN…H Hydrogen bonding
(Raman Scattering, right).
308

NATIONAL SYMPOSIUM IN CHEMISTRY P 207
Interactions of Amino Acid Based Hydrophobically Modified Water-
Soluble Polymer with Oppositely Charged Surfactants: Fluorescence
Probe, Dynamic Light Scattering, and Calorimetric Studies
Saurabh Shrivastava and Joykrishna Dey*
Department of Chemistry, Indian Institute of Technology, Kharagpur-721 302, India
T
he formation of complexes between the cationic surfactants (CTAB and DTAB) and hydrophobically modified
polymer, poly(sodium N-acryloylglycinate-co-N-n-dodecyl-acrylamide), was investigated in dilute aqueous solutions
by means of surface tension, turbidimetry, fluorescence, isothermal titration microcalorimetry, and dynamic light
scattering. Surface tension studies resulted critical aggregation concentration (cac) values for the surfactants in
presence of a given amount of polymer, which was found to be much lower than cmc of surfactant itself. The
decrease in cmc value is much larger compared to that obtained in the presence of corresponding homopolymer,
poly(sodium N-acryoyl-glycinate). Effect of salt concentration on the complex formation was investigated. Pyrene
fluorescence studies suggest complexes formed have very compact structure due to their increased hydrophobicity.
Decrease in anisotropy observed from fluorescence depolarization studies using DPH probe suggests morphological
changes in complex upon addition of surfactant. Optical density measurements showed that upon addition of surfactant
polymer/surfactant complex formed becomes water insoluble and the solution turns turbid and accompanied by the
formation of large complex precipitates. The precipitate forms a stable dispersion in the presence of a large
concentration of surfactant. The microcalorimetry results for the mixed systems characterize systematically the
thermodynamics of their interaction and phase behavior was observed. The size of the water soluble complexes
formed was determined by dynamic light scattering measurements.
309

P 208 NATIONAL SYMPOSIUM IN CHEMISTRY
NMR Investigation on the Interaction of bbbbb-Cyclodextrin and
Ampicillin
Santosh Kumar Upadhyay, Syed Mashhood Ali*
Department of Chemistry, Aligarh Muslim University, Aligarh-202 002, UP
Cyclodextrins (CDs) are cyclic oligosaccharides of a-(1>4)-linked glucopyranose, which have a hydrophilic
exterior and a hydrophobic cavity [1]. This structural feature allows CDs to encapsulate a variety of hydrophobic
molecule, or part of it, inside their cavity through non-covalent interactions to form inclusion complexes [1]. CDs
possess a special ability to complex with drugs enabling them to increase solubility, reduce bitterness, enhance
stability, and decrease tissue irritation upon dosing [1, 2]. In this work, we used b-cyclodextrin (b-CD), which has 7
units of glucose to interact with ampicillin (AMP). AMP is a penicillin-like antibiotic drug currently used to treat
infections, including gonorrhea and meningitis. NMR spectroscopy has become the most important tool for the
structural elucidation of organic compounds, particularly in solution state [3]. The 2D ROESY (Rotating-frame
Overhauser Effect SpectroscopY) has been found very helpful for the investigation of the interaction between CD
and guest molecule and it gives the information about the mode of penetration i.e. narrower or wider rim side, the
depth of penetration and orientation of the guest [3].
1
H NMR spectroscopic study of varying ratios of b-CD and
AMP in D
2
O suggests the formation of a 1:1 inclusion complex. The assignment of resonances of guest (AMP)
protons was made with the help of 2D COSY (Correlation Spectroscopy) spectral data. The stoichiometry and
association constant were determined using the continuous variation (Job’s Plot) method by the treatment of
1
H
NMR titration data. 2D ROESY spectrum showed interaction between b-CD cavity protons (H-3’ and H-5’) and
phenyl ring protons of AMP, suggests the complexation between b-CD and AMP. The structure for the b-CD-AMP
inclusion complexes has been proposed taking into consideration the stoichiometry,
1
H NMR titration results and
ROESY spectral data.
References: 1. Szejtli, J. Chem. Rev. 1998, 98, 1743.
2. Loftsson, T.; Duchêne, D. Int. J. Pharm. 2007, 329, 1.
3. Schneider, H.-J.; Hacket, F.; Rudiger, V.; Ikeda, H. Chem. Rev. 1998, 98, 1755.
310

NATIONAL SYMPOSIUM IN CHEMISTRY P 209
Time Dependent Density Functional Theory Study of Charge Transfer
Transition of [PtBr
6
]2
-
Partha Sarathi Sengupta
Department of Chemistry, Vivekananda Mahavidyalaya,
At & P.O. Burdwan, PIN 713103
Ligand to Metal charge transfer transition of [PtBr
6
]
2-
has been investigated computationally by time dependent
Density Functional Theory in polarized continuum model . To calibrate the theoretical data, different extent of
mixing of HF calculation was made in the exchange part of exchange –correlation functional. The hybrid exchange-
correlation functional with different basis set gives a covalent ground state description. The excited state Geometry
is optimized with a significant decrease in bond length which is indicative of Charge Transfer transition from Bromine
to Pt(IV).
Excessive negative charge accumulation on [PtBr
6
]
2-
in both the ground and excited state supports LMCT type
transition.
Potential energy scan was done on to describe the bonding description of PtBr
6
2
. The calculated ligand to
metal charge transfer transition are shifted to lower energies compared to the experimental values.
Vertical excitation energies with different oscillator strength were computed for the first 60 singlet excited
states, to reproduce the UV-visible spectra. The low lying excited states were supposed to be adiabatically connected
which give rise to single expression for the exchange-correlation functional.
Partial molecular diagram of [PtBr
6
]
2-
depict four type of transitions namely i. n1 corresponding to p®p*
transition, ii. n2 Corresponding to p®s* transition, iii. n3 Corresponding to s®p* transition and iv. n4
Corresponding to s®s* transition. Each of these transitions is a group of transitions since excited orbital
configuration gives rise to several different states of similar but not identical energies.
Transitions of
n1 and n3 are absent in [PtBr
6
]
2-
due to the t
2g
6
ground state configuration.
The experimental transitions of [PtBr
6
]
2-
are at 370.37 -303.03nm and at 226.24 nm. As TDDFT requires both
excitation and de-excitation operators and Gaussian 03 offers only the excitation operator, the relative oscillator
strengths are not reliable, the lowest energy CT band is mainly from a nonbonding level to antibonding one, they
should be broad. This is reflected by a third, low intensity vertical transition in all the theoretical methods. Comparison
of the data revealed that the theoretical vertical excitation match closely with the experimental spectral data for
BP86 method protocol with Stuttgart/Dresden effective core potential basis for Pt and 6-31+G(D) basis for Br. This
6-31+G(D) is specially designed for the calculation of anions. The experimental Pt-Br bond length is 2.5 Å in
[Pt(en)Br
3]
. The B3lyp/LANL2dz optimized bond distance is 2.6163 Å.
311

P 210 NATIONAL SYMPOSIUM IN CHEMISTRY
A Novel Amperometric Hydrogen peroxide Biosensor based on HRP
incorporated in Organically modified Sol-Gel glass matrix with
multiwalled carbon nonotube
Manorama, Ida Tiwari*,
Department Of Chemistry, Faculty of Science, Banaras Hindu University,
Varanasi-221005
We herein report a novel hydrogen peroxide biosensor which has been constructed by immobilizing ferricyanide
[hexacyanoferrate(III)] and horseradish peroxidase (HRP) in ormosil with multiwalled carbon nanotube modified
within grapite paste electrode. Ferricyanide moieties have been chosen to serve as redox mediator for enzymatic
peroxide reduction in ormosil network to maintain biosensor activity because it has an ideal electrochemistry and
high electron transfer efficiency. Multiwalled carbon nanotubes (MWNTS) have been used because of having its
unique electronic, chemical and structural features that make them very attractive for electrochemical studies. For
example, they have distinct electrochemical activities and capabilities for facilitating mediated electrochemistry of
enzymes/proteins from other carbon materials. Excellent electrochemical performance was exhibited using multiwalled
carbon nanotubes (MWNTS) with redox mediator ferricyanide. In the present work, the effect of the electron transfer
efficiency of the ferricyanide was expected to be promoted by adding multiwalled carbon nanotubes into the ormosil
modified electrode. Preparation of graphite paste electrode by incorporating ormosil matrix encapsulated with enzyme
and mediator/mwnts has been done to avoid their leaching under the operational conditions. Sensor was characterized
by cyclic voltammetry and amperometry. Sensor without HRP showed no or little response whereas significant
response signal enhancement could be obtained in presence of ferricyanide and ferricyanide/MWNTS with HRP
respectively. In addition, the effect of solution pH on the response of peroxide biosensor was also investigated.
Linear relationship is observed for hydrogen peroxide reduction at an applied potential of -0.2 V vs Ag/AgCl in
phosphate buffer solution of 0.1M, pH 7.0 and detection limit is .20mM. Diffusion controlled redox process is
proved by Randel-sevick plot (peak current vs scan rate
1/2
) which obey the Randel-sevick equation. Performance of
the sensor was evaluated with respect to response time, sensitivity as well as operational stability. The HRP/MWNTS
encapsulated in ormosil modified graphite paste electrode is easy to prepare and achieved 95% of the steady state
current within <10s. It has good reproducibility, wide linear range up to 550 mM and high storage stability of 4
months stored at 4
0
C when not in use.
312

P 226 NATIONAL SYMPOSIUM IN CHEMISTRY
Rauhut-Currier Reaction of Conjugated Nitroalkenes
Pramod Shanbhag, Irishi N. N. Namboothiri*
Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076
The self-coupling reaction of activated alkenes, commonly known as Rauhut-Currier reaction, is reported only
with acrylates [1] and acrylonitriles.[2]

While similar coupling between the a-position of activated alkenes with
other electrophiles, the Morita-Baylis-Hillman (MBH) reaction, has received tremendous attention over the past
decade, Rauhut-Currier reaction is less known because it suffered from limited substrate scope. This is not only
because the reaction is a dimerization but also because the reactive intermediate involved is highly sensitive towards
electronic and steric factors and readily undergoes oligomerization and/or polymerization.
As part of our programme towards highly efficient synthesis of multifunctional molecules that exhibit interesting
properties including bioactivity,[3]

we have investigated the Rauhut-Currier reaction of nitroalkenes.

Extensive
optimization of the reaction conditions by screening various nucleophilic Lewis bases and solvents enabled us to
obtain the dimerization products from a variety of aromatic and heteroaromatic nitroalkenes in satisfactory yield.
Efforts are currently underway towards the synthesis of heterodimers using mixture of two nitroalkenes as well as
development of diastereo- and enantioselective versions of this reaction.
References
1. Rauhut, M. M.; Currier, H. U. S. Patent 1963, 3074999; Chem. Abstr. 1963, 58, 11224a.
2. Balzer, M. M.; Anderson, J. D. J. Org. Chem. 1965, 30, 1357.
3. Rastogi, N.; Mohan, R.; Panda, D.; Mobin, S.M.; Namboothiri, I. N. N. Org. Biomol. Chem. 2006, 4, 3211
328

NATIONAL SYMPOSIUM IN CHEMISTRY P 227
Synthesis of New Isoellipticine Derivatives through
Imino-Diels-Alder reaction
G.Vikram and R.Nagarajan*
School of Chemistry, University of Hyderabad, Central University (P.O.),
Hyderabad-500 046, INDIA
Ellipticine is a naturally occurring alkaloid of the 6H-pyridocarbazole family; this compound and its derivatives
are endowed with antitumor and anticancer properties. They are DNA intercalating molecules and their high DNA
binding affinity is thought to be responsible in part for this pharmacological properties.
[1-2]
14-chloro-6,7,7,16-
tetramethyl-5,7,7a,8,14b,15-hexahydrobenzo[5',6']pyrrolizino[2',1':5,6]pyrido[3,2-b]car-bazole derivatives, which
are structurally similar to isomeric ellipticine fused with pyrroloindole moiety, have been synthesized.
References:
1. Wang J. C., Annu. Rev. Biochem. 1996, 65, 635-692.
2.Monks N. R., Blankey D. C., East S. J., Dowell R. I., Caluete J. A., Curtin N. J., Arris C. E., Newell D. R., Eur. J.
Cancer. 2002, 11, 1543-1552.
329

P 228 NATIONAL SYMPOSIUM IN CHEMISTRY
Site-Selective Functionalization Of Medicinally Potent Heterocycles
Amit Sharma, Kawaljit Singh, Divya Arora, Sukhdeep Singh and Kamaljit Singh*
Organic Synthesis Laboratory, Department of Applied Chemical Sciences & Technology,
Guru Nanak Dev University, Amritsar – 143 005
Heterocyclic chemistry continues to be in the focus of life science oriented research. Structural functionalisation
is a unique tool for fine-tuning biological properties and offers extra bonus in this context. This poster presentation
shall feature two pertinent issues. First, demonstration of lithiation – substitution sequence [1] in the field of some
interesting bisheterocyclyl methanes 1, intermediates for a variety of important (medicinally and otherwise)
macrocyclic systems such as meso-porphyrins, calix[4]pyrroles etc. Second, novel and dependable routes to structural
elaboration of dihydropyrimidinones 2 – potent cardiovascular agents and special emphasis shall be laid on the
merit of the functionalisation approach [2].
References: [1] Kamaljit Singh and Amit Sharma Tetrahedron Lett. 2007, 48, 227.
[2] Kamaljit Singh, Divya Arora and Sukhdeep Singh, Tetrahedron Lett. 2007, 48, 1349
330

NATIONAL SYMPOSIUM IN CHEMISTRY P 229
Trehalose – Does It Entrap Or Replace Coupled Water In Amino Acid
Solutions?
Muthuselvi Lakshmanan, Aruna Dhathathreyan*
Chemical Lab., CLRI, Adyar, Chennai 600 020, India
Trehalose is known to stabilize protein structures in aqueous solutions. The molecular level understanding of
such mechanism could be explained either by one of the two hypotheses; wherein the coupled water is either entrapped
by trehalose in proteins or is replaced. The results from the present study on aqueous solutions of amino acids with
trehalose demonstrate the partial replacement of water molecules in the near vicinity of amino acids resulting in
enhancement of structural ordering of hydrated amino acids. This is reflected in the increased values of experimentally
determined hydrodynamically coupled water using quartz crystal microbalance (QCM) and solid/liquid interfacial
tension of aqueous solutions of amino acids with trehalose. The study suggests a Kosmotropic role of trehalose in
Protein stabilization.
331

P 230 NATIONAL SYMPOSIUM IN CHEMISTRY
A Novel Organo-Catalyst For Chemo-Selective
O-Tert -Butoxycarbonylation Of Phenols
Rajesh Chebolu, Sunay V. Chankeshwara and Asit K. Chakraborti*
Department of Medicinal Chemistry,
National Institute of Pharmaceutical Education and Research (NIPER),
Sector 67, S. A. S. Nagar 160 062, Punjab, India.
The occurrence (30% frequency) of hydroxyl groups [1] in the preparation of drug candidates makes their
protection/deprotection an important and frequently needed exercise.[2] A common approach to protect hydroxyl
groups is acylation [2,3] but the regeneration requires hydrolytic cleavage under strong alkaline conditions [2] and
is detrimental to other functional groups. Chemoselective deacylation is achievable under neutral or virtually neutral
and non-aqueous conditions following ‘demand-based thiolate anion generation’ protocols but these require elevated
temperature and high boiling solvent.
The inertness of tert-butyl carbonates (O-t-Boc) for routinely adopted experimental conditions in organic
synthesis, and the ease of removal under mild acidic environment, [2]

makes O-tert-butoxycarbonylation an efficient
alternative. However, the drawbacks of the limited methodologies for O-t-Boc formation of phenols necessitate the
development of a better methodology. Although Lewis acid catalysed N-tert-butoxycarbonylation

has recently
gained importance, phenols forms the tert-butyl ethers with (Boc)
2
O in the presence of a strong Lewis acid

highlighting
the need for organo-catalyst for which DMAP is the only choice available. However, DMAP induces formation of
symmetrical carbonates and carbonic-carbonic anhydrides and is toxic.
The present work will demonstrate a novel organo-catalyst for chemo-selective O-tert-butoxycarbonylation of
phenols.
References
1. J. S. Carey, D. Laffan, C. Thomson and M. T. Williams Org. Biomol. Chem., 2006, 4, 2337.
2. T. W. Greene and P. G. M. Wuts Protecting Group in Organic Synthesis, John Wiley and Sons, New York, ed.3,
1999.
3. a) Shivani, R. Gulhane and A. K. Chakraborti J. Mol. Catal. A: Chem. 2007, 264, 208; b) A. K. Chakraborti and
Shivani, J. Org. Chem., 2006, 71, 5785; c) A. K. Chakraborti and R. Gulhane Synlett, 2004, 627; d) A. K.
Chakraborti and R. Gulhane Synthesis, 2004, 111; e) A. K. Chakraborti, R. Gulhane and Shivani Synlett, 2003,
1805; f) A. K. Chakraborti, L. Sharma, R. Gulhane and Shivani Tetrahedron, 2003, 59, 7661; g) A. K. Chakraborti
and R. Gulhane J. Chem. Soc. Chem. Commun., 2003, 1896; h) A. K. Chakraborti and R. Gulhane Tetrahedron
Lett., 2003, 44, 3521.
332

NATIONAL SYMPOSIUM IN CHEMISTRY P 231
Aqueous-Mediated Synthesis Of Heterocyclic Ketene Aminals
L. Gellina Chanu, N. Sushuma, S. Joychandra Singh, Okram Mukherjee Singh*
Department of Chemistry, Manipur University, Canchipur, Imphal- 795003, Manipur.
Heterocyclic ketene aminals are versatile ambident synthetic intermediates, which combine the nucleophilicity
of enamines and the electrophilicity of enones. They have been utilized as building blocks for the synthesis of a wide
range of heterocycles and natural products [1].

We wish to report herein an easy and green method for the synthesis
of the heterocyclic ketene aminals 1, 2, 3 (Scheme-1). Our method involves the reactions of á-oxoketene dithioacetals
[2] with various diamines and refluxing in ordinary water.
References 1. Review: (a) Huang, Z. –T., and Wang, M, -X., The Chemistry of Enamines , ed. Z Rappoport , Wiley Interscience , London
1994, p. 1303. (b) Stanovnik, B.; Svete, J., Chem. Rev. 2004, 104, 2433-2480. (c) Greenhill, J. V., Advances in Heterocyclic
Chemistry, 1996, 67, 207-343. (d) Rajappa, S., Tetrahedron 1981, 37, 1453-1480, Tetrahedron Report Number 107.
2. Review: (a) Junjappa, H.; Ila, H.; Asokan, C. V. Tetrahedron 1990, 46, 5423-5506, Tetrahedron Report No. 278. (b) Dieter,
R. K. Tetrahedron 1986, 42, 3029-3096, Tetrahedron Report No. 202.
333

P 232 NATIONAL SYMPOSIUM IN CHEMISTRY
A Short, Enantioselective Synthesis Of 2-Hydroxy Piperidine Dderivatives
From ddddd-Hydroxy Lactones
Lourdusamy Emmanuvel, Arumugam Sudalai*
Chemical Engineering & Process Development Division, National Chemical Laboratory,
Dr. Homi Bhabha Road, Pune-411008, Maharastra.
Substituted piperdine is often encountered in the biologically active alkaloids and possess diverse biological
activities. The plant enzymes readily synthesize piperidine from amino acids. However, the construction of six-
membered heterocycle of piperidine nucleus in the laboratory with fixed stereochemistry is challenging to chemists.
Here, we present the synthesis of 2-hydroxypiperidine derivatives i.e (+)-L-733, 060 and epiquinamide. (+) L-733,
060 is a synthetic NK1 receptor antagonist to show clinical utility in a variety of disorders including migraine,
rheumatoid arthritis and pains. Epiquinamide has been found to be highly selective for b2 nicotinic acetylcholine
receptors (nAChRs), as such representing a new structural class of nicotinic agonists and could be considered a lead
compound for the development of nAChR therapeutic agents. The synthesis of (+) L-733, 060 involves the Shi’
epoxidation of g,d-alkenoate to get the d-hydroxy lactone with trans selectivity while the latter make use of asymmetric
dihydroxylation to obtain the syn selectivity. Both the synthesis involve similar reaction sequences such as Johnson-
Claisen rearrangement, formation of hydroxy lactone, inversion of hydroxyl group with azide, reductive cyclization
of azidolactone to give the hydroxy piperidine. This route is practical and high yielding to construct the piperidine
rings.
334

NATIONAL SYMPOSIUM IN CHEMISTRY P 233
Synthesis Of Homoallylic Alcohols Using Cui As Catalyst
Arun Jyoti Borah, Hima Rani Kalita, Biswapran Kashyap, Pabitra kumar kalita and Prodeep
Phukan*
Department of Chemistry, Gauhati University, Guwahati -781014, Assam
The addition of allyl metal reagents to aldehydes is an important method for carbon –carbon bond formation.
In recent years, several Lewis acids, especially metal Lewis acids or transition metal complexes have been utilized
extensively to catalyze this transformation. Most of these methodologies are fraught with limitations such as excess
use of catalyst (or co-catalyst), moisture sensitive conditions, stoichiometric amount of promoter and poor substrate
selectivity. There has been increasing interest in the development of new catalysts, which are cheap, air-stable and
easily available commercially. Recently CuI has emerged as a very effective catalyst for various organic
transformations. We have developed a simple methodology for the synthesis of homoallylic alcohols using allyl
tributyl stannane as allylating agent in presence of CuI as catalyst (Scheme -1) [1].
Scheme-1
The reaction was carried out by stirring a mixture of an aldehyde (1 mmol), allyl tributylstannane (1.05 mmol)
CuI (0.15 mmol) in DMF (2 ml) at room temperature. Both aromatic and aliphatic aldehydes underwent homoallylation
efficiently to produce homoallylic alcohols in good yield (69-86%).
References
1. Kalita, H. R., Borah, A. J.; Phukan, Tetrahedron Lett., 2007, 48, 5047-5049.
335

P 234 NATIONAL SYMPOSIUM IN CHEMISTRY
Deoximation By Phase Transfer Oxidants Under Microwave Irradiation In
Solvent Less System
A.Dewan and D. K. Kakati*
Department of Chemistry, Gauhati Universuty, Guwahati-781014, Assam
The protection of certain functional groups and the deprotection of the protected derivatives constitute important
processes in the multistep synthesis of polyfunctional molecules. Regeneration of ketone and aldehyde from their
oximes is an important reaction in synthetic organic chemistry as the oxime serves as an efficient protecting group
for carbonyl compounds
[1, 2]
. Further, as the oxime can also be prepared from non-carbonyl compounds, the formation
of carbonyl compounds from oximes represents a potential route for the synthesis of aldehyde and ketone
[3]
.
Thus
there has been continuing interest in the development of new reagents and methodologies for the regeneration of
carbonyl compounds from their oximes and several deoximation reagents have so far been developed.
Solvent less reactions under microwave irradiation is gaining ground in organic synthesis, because of the
increased emphasis on eliminating and if not possible minimizing the use of organic solvents. Further the use of
microwave irradiation results in manifold reduction of reaction time. We have been investigating the use of cerium
based phase transfer oxidants in the oxidation of alcohol as well as the oxidative deoximation of oximes to their
parent carbonyl compounds both in homogeneous and heterogeneous systems. It has been observed that reactions
under microwave irradiation take much less time, but give good yields. The reaction also involves easy work up
procedures for the recovery of the products. Here in we report the use of two phase transfer oxidants cetyl dimethyl
benzyl ammonium cerium nitrate and cetyl trimethyl ammonium cerium nitrate in the regeneration of carbonyl
compounds from their oximes.
The carbonyl compounds were characterized by their spectroscopic analysis and the comparison of the data
with authentic samples. Of the two reagents, cetyl trimethyl ammonium cerium nitrate was found to be a better and
more effective deoximation reagent. Further, the nature of the other functional groups present in the neighbourhood
was found to influence the efficiency of the deoximation reagents.
References
1. Sander S.R, Karow, Organic Functional Group Preparation, 2
nd
ed., A.P, London, 1989, 413.
2. Green T.W, Wuts P.G.M, Protective group in Organic Synthesis, Wiley N.Y, 1919, 2
nd
ed., 214.
3. Barton D.H.R, Beaton J.M, Geller, J. Am. Ch. Soc., 1961, 83, 4076.
336

NATIONAL SYMPOSIUM IN CHEMISTRY P 235
Isolation Of Bioinsecticides From The Striped Tiger Butterfly, Danaus
Genutia (Lepidoptera: Nymphalidae)
Arunava Das,
a,b
Chandan Mithra
b
, R.Revanna,
b
A.R.V. Kumar,
b
K. Chandrashekara*
b
a
CMR Institute of Management Studies, Kalyannagar, Bangalore- 43.
b
Department of Entomology, College of Agriculture (South Block), University of Agriculture
Sciences, Gandhi Krishi Vigyana Kendra, Hebbal, Bangalore-65.
Most of the attempts have centered on the idea of isolating and charecterizing the cardenolides derived from
these insects or plants, however this is the first such attempt to study and analyze the effect of cardenolide containing
extract as a source of potential bio-insecticides. We wish to analyse the possible effects of toxic alkaloids isolated
from these butterflies as bio-insecticides.
All works reported here have been carried out under strict laboratory conditions at the Department of
Entomology, College of Agriculture, UAS, GKVK with permission from respective departments. We took extracts
from wholebody Striped Tiger butterflies, with 95% pre chilled ethanol, filtered and concentrated by HPLC and
then spraying the extract on pre-trimmed mustard leaf (each concentration having a set of three petriplates with one
leaf each having 10 Diamond Black Moth larvae released) with corresponding concentrations of the concentrated
and diluted extracts. Then, we checked the mortality rate for each concentration every 24 hours for seven continuous
days and reported the same.
At the end of 168 hours, i.e., after 7 days, 2% Extract showed a maximum of 68.99% of Corrected Mortality
and a minimum of 41.11% of Corrected Mortality. 0.25% Extract showed a maximum of 42.91% of Corrected
Mortality and a minimum of 14.44% of Corrected Mortality. This clearly shows that 2% Extract has given the best
results followed by 0.25% Extract.
Thus, we showed that the Butterfly Extract contains toxic alkaloids & cardenolides that have the capacity to
kill the larvae of the DBM, the pest of spinach. As expected results were interpreted and calculated and it was seen
that the 2% concentration of extract showed the best results i.e., 68.99% mortality followed by 0.25% concentration
of extract which showed 42.91% mortality. The data obtained from the graph shows the best results in 2% Extract,
but the 3% extract has shown a diminished mortality rate because the larvae did not feed on such a higher concentration
of extract sprayed leaf. Our next step is to procure more of 2% and 0.25% Extracts on a large scale basis and subject
them to purification procedures of Dialysis and HPLC for separation at a highly concentrated manner, concentrating
and characterization of the toxic alkaloids such that we can proceed to Field Trials on a broader axis.
337

P 236 NATIONAL SYMPOSIUM IN CHEMISTRY
A First One-Pot Synthesis, Isomerization And Synthetic Utility Of Mono
And Bis Morita-Baylis-Hillman Adducts Of 1,1’-Ferrocenedialdehyde
Suchithra Madhavan, Kodirajan Selvakumar, Vadivel Vaithiyanathan, Baby Viswambharan,
and Ponnusamy Shanmugam
*
Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science
and Technology (NIIST), Thiruvananthapuram-695 019, Kerala
The chemistry of ferrocene is still an important research area due to its applications in the area of novel
materials development,

asymmetric catalysts, nonlinear optics, biological properties and electrochemistry [1]. Amongst
various C-C bond forming reactions, the Baylis-Hillman reaction is an important reaction giving rise to densely
functionalized molecules and is considered to be atom economic. Functionalisation of ferrocene under mild conditions
is difficult task as it requires multi-step rigorous reaction condition. To address the problem and in continuation of
our research in the area of novel synthetic applications of Baylis-Hillman adducts [2], particularly with ferrocene
derivative, we have recently examined the reaction of Baylis-Hillman adduct of ferrocenealdehyde 2 with various
oxygen and carbon nucleophiles in presence of montmorillonite K10 clay catalyst. The reaction was found to afford
highly functionalised excellent yield of E- and Z-trisubstituted alkene derivatives of ferrocenealdehyde. This poster
aims to explain on our recent findings of a novel and first one-pot synthesis of mono- and bis- adduct of Morita-
Baylis-Hillman adduct of 1,1’-ferrocenedialdehyde. These adducts undergone a facile stereoselective isomerization
reaction with a number of saturated, unsaturated, aromatic alcohols to yield highly functionalised trisubstituted
alkene derivatives in excellent yield. Synthetic utility of mono and bis- propargyl derivative of 1.1-ferrocenedialdeyde
has been demonstrated in the synthesis of novel macrocycles. The study is shown in Scheme 1. The results will be
discussed in detail.
References
1. Gan, K.S-.; Hor, T.S.A. in Ferrocenes Homogeneous Catalysis, Organic Synthesis, Materials Science (Eds.: A.Togani, T.
Hayashi), VCH, Weinheim, 1995, pp.3-104;
2. Shanmugam, P.; Vaithiyanathan, V.; Baby, V. Tetrahedron 2006, 62, 4342-4347;
338

NATIONAL SYMPOSIUM IN CHEMISTRY P 237
Synthesis Of Aminoethyl-aaaaa,bbbbb-Diaminopropionyl (Aedap) PNA - Strategic
Modification To Reduce Hydrophobicity
Roopa Mitra
1
and K. N. Ganesh
2*
1
Division of Organic Chemistry, National Chemical Laboratory, Pune ;
2
Indian Institute of
Science Education and Research (IISER), Pune
The astonishing discovery of Peptide nucleic acids (PNAs) by Nielsen et. al. [1] that bind with higher affinity
to complementary nucleic acids than their natural counterparts, and obey the Watson-Crick base pairing rules resulted
in the rapid establishment of a new branch of research focused on the diagnostic and therapeutic applications of this
highly interesting class of compounds. PNA is a neutral DNA mimic derived by replacement of sugar-phosphate
backbone with N-(1-aminoethyl)glycine units carrying natural nucleobases A, T, G and C with a carbonyl linker
having a great potential to act as antisense agents.
Despite advantages offered by the achiral PNA, it has
been of interest to replace the glycine moiety of the
backbone with chiral amino acids as mentioned by Corradini
et. al.[2]. The side chains of the amino acids were envisaged
to be valuable for controlling binding affinity, specificity,
hydrophobicity and attachment of ligands to PNA. PNA
oligomers incorporating chiral monomers retained the
hybridization properties with tolerance for small and
medium substituents at the glycine-
a position. The lysine-
modified oligomers (I) as reported by Haaima et al [3], are
known to be more readily soluble in aqueous systems.
We aimed to synthesize PNA monomers having b-aminoalanine moiety in the backbone to get a modified
PNA, aminoethyl a,b-diaminopropionyl ) PNA (II), with a chiral backbone. This is expected to be stable due to the
presence of intramolecular hydrogen bonding. In addition, due to the presence of hanging amine functionality, the
low solubility and cellular penetration problems found in classical PNAs might be overcome.
The strategy towards the synthesis of target monomer used asparagine as the starting material. The a,b-
diaminopropionic acid was synthesized from it, which after reductive alkylation gave the backbone of desired PNA.
Later on, attachment of nucleobase (Thymine) via a methylene carbonyl linker to the backbone gave the desired
monomer (II). All the intermediates and the final molecule have been characterized using
1
H,
13
C-NMR and MS
analyses. The syntheses of oligomers were performed following Merrifield Solid Phase Oligomer Synthesis using
Boc-strategy and MBHA resin. Sequential combination of the aeg-T monomer with our desired monomer were
done at different positions of the oligomers e.g. N-terminal, C-terminal, middle modification etc. This was followed
by their cleavage from the resin, purification and characterization using rp-HPLC and MALDI-TOF MS techniques
respectively. The comparative biophysical studies with DNA/RNA that includes study of duplex and triplex stability
by UV-T
m
experiments are in the future plans.
References
1. Nielsen, P. E.; Egholm, M.; Berg, R. H.; Buchardt, O. Science. 1991, 254, 1497
2. Corradini, R.; Sforza, S.; Tedeschi, T.; Totsingan, F.; Marchelli, R.; Curr. Top. Med. Chem., 2007, 7, 681
3. Haaima, G.; Lohse, A.; Buchardt, O.; Nielson, P. E.; Angew.Chem. Int. Ed. Engl., 1996, 35, 1939
339

P 238 NATIONAL SYMPOSIUM IN CHEMISTRY
Un-symmetrical polyaza [N
12
] macrocycle as a potential encapsulating
agent: Spectroscopic and Electro–chemical characterization of homo–
bimetallic complexes
S. Kumar and Zafar Ahmad Siddiqi*
Inorganic Chemistry Division, Chemistry Department
Aligarh Muslin University, Aligarh 202002, U.P.
Email: [email protected]
Coordination chemistry of polyaza macrocyclic ligands has been a fascinating area of investigations to
coordination and bio-inorganic chemists. Macrocyclic ligands capable to bind two or more metal ions giving discrete
homo or hetero–bimetallic / polymetallic complexes have received much attentions. However, un–symmetrical
polyaza macrocycles which contain non – equivalent coordination sites to bind metal ions have attracted chemists
only recently [1]. The polymetallic complexes of such macrocycles can be used as suitable models to elaborate the
asymmetrical binding of various metal ions in the metallo–biosites. The individual metal ions exhibits different role
in the functioning of the polnuclear metallo – enzyme. Recently, we have reported [2–3] that use of protected two
armed reactive substrate, N,N’–bis(N-ethylaniline)propane,1,3-diimine generated from condensation of 1,3-
diamionopropane with N-acetylaniline (1:2 mole ratio) induces (in–situ) cyclo–addition reactions with a mixture of
amine and HCHO (1:3 mole ratio). This in turn results in stable dihydroperchlorate salt of big size 20–membered
[N
8
] or 32–membered [N
12
] un-symmetrical dinucleating macrocycles as stable solid product. An analogous reactive
substrate N,N’–bis(N-ethylaniline)–hydrazine-1,3-diimine obtained from reaction of N-acetylaniline and hydrazine
(2:1 mole ration) also undergoes an in–situ cyclization process with mixture of 1,3-diaminopropane and HCHO (1:3
mole ratio) which in the presence of HClO
4
produces stable solid product identified as dihydroperchlorate salt of
26–membered un–symmetrical [N
12
] macrocycle, 8,14,24,30 tetramethyl-
7,15,23,31tetraphenyl[1,5,7,9,13,15,17,21,23,25,29,31] dodecaazacyclodotri aconta-8,14,24,30-
tetraene.dihydroperchlorate. Here-in we report reactions of this macrocyclic ligand towards metal salts and their
derivative complexes which afford affording stable solid metal encapsulated products. The products have been
characterized using elemental analyses, FTIR, UV–visible (ligand field), FAB–mass spectral and magnetic moment
measurements. The cyclic voltametric studies indicate formation of quasi–reversible redox couples M
III/II
and M
II/I
compatible with the flexible nature of the macrocyclic cavity.
References:
1. S. Brooker, T.J. Simpson, J. Chem. Soc., Dalton Trans., 1151 (1998); S. Brooker, J.S. Danwar, J.B. Johnson, Polyhedron.
18, 679 (1999).
2. Z.A. Siddiqi, M.M. Khan, Syn. React. Inorg. – Org. Chem., 34, 894 (2004).
3. Z.A. Siddiqi, M.M. Khan, M. Khaid and S. Kumar, Tran. Metal Chem., 32, 913 (2007).
340

NATIONAL SYMPOSIUM IN CHEMISTRY P 239
Time Resolved Resonance Raman Spectroscopy: A Journey from
Nanosecond to Femtosecond Time Domain
S. K. Sahoo, B. Mallick, Adithya L. Y., R. Pandey, S. Umapathy
*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore-560012
Time resolved resonance Raman (TR3) spectroscopy, a pump-probe technique in fast and ultrafast time
domain, provides information directly about vibrational structure, reactivity and dynamics in the excited state [1].
The pump beam excites the molecule to the higher excited state and the probe beam detects the transient species thus
formed after a certain delay time, governed either electronically or optically.
In presence of suitable hydrogen donor, aromatic ketones undergo hydrogen abstraction reaction in their
excited triplet state. The triplet state thus formed, via intersystem crossing from singlet state, interacts with the
ground state hydrogen donor to form a ketyl radical, which may undergo further photoreaction. The triplet state
structure and reactivity of isomeric benzoylpyridines, heterocyclic analogues of benzophenone were studied using
nanosecond TR3 spectroscopy. The shortening of triplet state lifetime and decrease in intersystem crossing yield is
explained on the basis of position of the heteroatom that affects the charge density of carbonyl group and determines
the characteristics of the excited state and its efficiency for the hydrogen abstraction reaction.
It is well known that solvent polarity brings out changes in the structure and dynamics of excited triplet
state. Xanthone is structurally similar to benzophenone and well known for its solvatochromic behavior [2]. In the
present study, effect of solvent polarity on structure in both ground and excited triplet state of xanthone will be
discussed.
TR3 spectroscopy has its own limitations of interference from fluorescence background and due to transform
limit it can’t further be extended to subpicosecond time domain. Femtosecond stimulated Raman spectroscopy
(FSRS) [3] can overcome all the above obstacles. FSRS produces good quality vibrational spectra, free from strong
background fluorescence and provides quality information in femtosecond time domain. This technique uses two
NIR-pulses, one picosecond narrow-bandwidth (5-20 cm
-1
) Raman pump pulse centered at 787 nm and a broadband
continuum Raman probe pulse (800-1050 nm). When the two fields overlap spatially and temporally on the sample,
one observes gain features on top of the Probe beam. The ratio of the probe spectrum for Raman pump ON and
Raman pump OFF, gives the gain spectrum. Recently FSRS set up is designed and developed in our research group.
The preliminary SRS spectrum obtained from various solvents like benzene, CCl
4
and cyclohexane will be presented.
Also the SRS spectra of b-carotene in two different solvents are reproduced to validate the setup.
References
1. Phillips, D. L.; Kwok, W. M.; Ma, C. in Reviews of Reactive Intermediate Chemistry; Platz, M. S.,
Moss, R. A. Jones, M., Jr., Eds.; John Wiley and Sons, 2007; pp 123.
2. Heinz, B.; Schmidt, B.; Root C.; Satzger H.; Milota F.; Fierz B.; Kiefhaber T.; Zinth W.; Gilch P. Phys. Chem. Chem.
Phys. 2006, 8, 3432.
3. McCamant, David W.; Kukura, Phillip; Mathies, Richard. A. J. Phys. Chem. A 2003, 107, 8208.
341

P 240 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis Of Biscoumarins From 4-Hydroxycoumarin And Aaromatic
Aldehydes–A Comparative Assessment Of Percent Yield Under Thermal
And Microwave-Assisted Conditions
Saima Qadir, Khaliquz Zaman Khan*, Aijaz Ahmad Dar.
Department of Chemistry, University of Kashmir, Hazratbal, 190006, Srinagar, Kashmir
Coumarins form an important group of organic compounds possessing enormous pharmacological, industrial
and biological value. 4-Hydroxycoumarin and its derivatives are known for their anticoagulant,

spasmolytic,
antibacterial and antifungal

activity [1]. In addition to this, certain derivatives have also been reported as antitumor
and anti-HIV agents [2]. Besides, coumarins find diverse applications as food additives, cosmetics, laser media,
non-linear optical chromophores,

agrochemicals

as well as analytical reagents [3].
In this backdrop, efforts are being made to synthesize as many derivatives of 4-hydroxycoumarin and dicoumarols
as possible using microwave eco-friendly methods. Herein, we report convenient syntheses of various biscoumarins
by condensing a series of aldehydes with 4-hydroxycoumarin under microwave irradiation for the first time along
with a comparative account of their syntheses under conventional conditions. Under microwave, the reaction time
has been reduced considerably with improvement in yields in comparison to thermal conditions. Reactions have
been carried out both under solvent as well as in solvent-free environment and the adopted procedure provides an
energy and time-saving protocol.
References 1. Chohan, Z.H.; Shaikh, A.U.; Rauf,A.; Supuran, C.T. J. Enzym. Inhibition. Med. Chem. 2006, 21, 6, 744-748 and references
cited therein.
2. Jung, J.C.; Lee, J.H.; Oh, S., Lee J.G.; Park, O.S. Bioorg. Med. Chem. Lett. 2004, 14, 22, 5527-5531 and references cited
therein.
3. Chen,R.F.; Anal. Lett. 1968, 1, 423-428.
342

NATIONAL SYMPOSIUM IN CHEMISTRY P 241
Triphase Catalytic Activity Of A New Insoluble Multi-Site Phase Transfer
Catalyst In Etherification Of Methyl Salicylate
P.Gopinath and E.Murugan*
Department of Physical Chemistry, School of Chemical Sciences,
University of Madras, Guindy Campus, Chennai 600 025, Tamil Nadu.
Phase transfer catalysis emerged as an indispensable organic technique to carry out the reactions between two
immiscible reagents. It is an environmentally friendly and economically profitable method to synthesize wide range
of organic chemicals [1,2]. However, the removal and recovery of catalyst was found to be expensive and difficult
process in the case of soluble PTCs. This problem can be overcome by immobilizing the PTC on a solid polymeric
support i.e. insoluble polymer-supported PTC (PS-PTC) as introduced by Regen [3] and hence it can be easily
separated by filtration and recycled. So far, numerous studies have been reported on the use of soluble and insoluble
single-site PTCs for various organic reactions, but their activity was very poor due to the presence of single active-
site. The important considerations in the selection of the catalyst are economy of scale and efficiency of the phase
transfer catalysts specifically on the industrial-scale preparation of organic compounds. In order to fulfill these
requirements, multi-site PTCs (MPTCs) containing more than one active-site were developed by Idoux et al. Further,
there are only few reports available on the synthesis of polymer-supported MPTCs. In the present study, a new
polymer-supported MPTC containing three active-sites has been synthesized, characterized and its catalytic activity
was determined through etherification of methyl salicylate.
Initially, the polystyrene bound polymer beads were prepared by suspension copolymerization of styrene
(73%), divinylbenzene (2%), and vinylbenzylchloride (25%) using AIBN as a free radical initiator. The resulting
co-polymer beads containing pendant chloromethyl groups was condensed with triethyl methanetricarboxylate
followed by reduction with LiAlH
4
. The obtained condensed product was chlorinated using thionylchloride and then
quaternized with triethylamine to form a new insoluble tri-site PS-MPTC. The new PS-MPTC was characterized by
FT-IR technique, [chloride ion], and SEM analyses. The catalytic efficiency was ascertained through etherification
of methyl salicylate using epichlorohydrin under pseudo-first order reaction conditions and compared the same with
single-site PS-PTC. The rate constants were calculated by following the disappearance of substrate (methyl slaicylate)
through Gas Chromatography. It was found that the tri-site PS-MPTC was » three-fold more active than single-site
PS-PTC in terms of rate constant. The kinetic study was performed by varying the experimental parameters, viz.,
stirring speed, [substrate], [NaOH], [catalyst], and temperature. The observed results reveal that all the kinetic
parameters are dependency of the rate of reaction. The activation energy and thermodynamic parameters viz. enthalpy,
entropy and free energy change were also calculated. Based on the observed kinetic and thermodynamic results, an
interfacial mechanism was proposed for the etherification reaction.
References
1. C. M. Starks, J. Am. Chem. Soc., 93, 195 (1971).
2. E.V.Dehmlow, Angew. Chem., Int. Ed. Eng., 16, 493 (1977).
3. S.L.Regen, J. Am. Chem. Soc., 97, 5956 (1975).
343

P 242 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Antibacterial Activity of Chalcone Dendritic Architectures
Sebastian Raja and Perumal Rajakumar*
Department of Organic Chemistry, University of Madras, Chennai- 600 025
Dendrimers are a new class of spherical polymeric materials. They are highly branched, monodisperse
macromolecules. Dendrimers occupies prominent role in macromolecules because of its various applications in the
field of biology and material sciences.[1,2] In the recent years, biological applications of dendrimers have been of
growing interest.[3] In view of this, chalcone nucleus an important precursor for many potentially bioactive compounds
abundantly present in plants. Chalcone derivatives find application as antioxidant, antibiotic and antibacterial agents.
However the synthesis of biological active chalcone based dendritic architecture are yet to be investigated. We
describe herein the synthesis and antibacterial activity of chalcone based dendritic architectures 1a, 1b and 2a, 2b.
References
1. Stiriba,S.E.; Frey,H.; Haag,R. Angew.Chem., Int.Ed. 2002, 41, 1329.
2. Gillies, E.R.; Jonsson, T.B.; Fréchet, J.M.J.J.Am.Chem.Soc.2004, 126,11936.
3. Cloninger, M.J. Curr. Opin. Chem. Biol. 2002, 6, 742.
344

NATIONAL SYMPOSIUM IN CHEMISTRY P 243
New Ursane-Type Antiplasmodial Triterpenes from Tarenna Zeylanica
Leaf
Venkata Siva Satyanarayana Kantamreddi* and Colin W. Wright
The School of Pharmacy, University of Bradford, Bradford, United Kingdom – BD7
Malaria, a leading cause of death continues to challenge the world [1]. Resistance of Plasmodium falciparum
to chloroquine and some other antimalarial drugs continues to increase. In the present study, the phytochemical
investigation was carried out on an active leaf extract of Tarenna zeylanica collected from forest in the locality of
Bhubaneswar, Orissa, aimed at identifying the active antiplasmodials for further research.
Antiplasmodial activities were assessed using the parasite lactate dehydrogenase assay [2] and chloroquine
and artemether were used as positive controls. Flash chromatography was performed using TLC grade silica gel
(60G, 45ì) and for TLC studies, analytical silica gel 60F254 plates (Merck) were used. Spectra were acquired using
NMR (Jeol ECA 600MHz), IR Spectroscopy (Digilab UMA 400) and EI-MS (Finnigan MAT 90 spectrometer) &
Micromass Quattro Ultima HPLC- MSMS.
The leaf methanolic extract of T. zeylanica possessed antiplasmodial activity with low IC
50
values, 14.2 and
31.4 µg/ml against chloroquine sensitive (3D7) and resistant (K1) strains of P. falciparum respectively. A Literature
search revealed that no phytochemical studies have been reported on T. zeylanica. In the present study, seven
constituents were isolated viz. ZAL1, ZAL3A, ZAL3B, ZAL7, ZAL15 and ZAL16. The activity of ZAL3A, ZAL3B
and ZAL7 against strain K1 (IC
50
= 6.12, 0.72 and 0.67 µg/ml respectively) confirms the activity of T. zeylanica seen
in this study. The structural identification of these active compounds ZAL3A, ZAL3B and ZAL7 were established
by IR, UV, EI & ES-MS and advanced NMR (1H, 13C, Dept, DQF Cosy, HMQC & HMBC) techniques. Compound
ZAL 3A was identified as ursa-11, 13(18)-dien-3b, 28-diol and is reported for the first time. The identification of
ZAL3B and ZAL7 is in progress and preliminary spectral analysis suggests that these compounds also ursane type
of triterpenes.
References
[1] WHO (2003) World Health Organisation Fact Sheet No. 94: WHO information.
[2] Makler, M.T. et al (1993) Am J Trop Med Hyg 48: 205-210.
345

P 244 NATIONAL SYMPOSIUM IN CHEMISTRY
Click Chemistry On Sugar-Derived Alkynes And Azido-Alkynes
Palanichamy Kalanidhi and Krishna P. Kaliappan
*
Department of Chemistry, IIT Bombay, Mumbai-400 076
Click reaction is a reaction that is modular, wide in scope, gives very high yields, generates only inoffensive
byproducts that can be removed by nonchromatographic methods, and be stereospecific. Its salient features are
simple reaction conditions, the use of readily available starting materials and reagents, and water such solvent, and
simple product isolation as well.[1,2] The word “click” was coined to describe the guiding principle. Among the
various classes of click chemistry, Huisgen dipolar cycloaddition of azides and alkynes [3] to afford 1,4-triazoles in
a regioselective manner, is extensively explored because of its pharmaceutical applications.
Single click chemistry: While click chemistry of sugar-derived azides is well known, that of sugar-derived
alkynes is not much explored. We have studied Huisgen 1,3-dipolar cycloaddition of various sugar-derived alkynes
with several alkyl and aryl azides using CuI, DIPEA and acetonitrile as the co-solvent to synthesize a number of 1,4-
triazoles in excellent yields.
Double click in one pot: By a sequential addition of sugar-derived azido-alkynes and an azide in a proper time
lag to a copper metalated alkyne, using CuI, DIPEA and acetonitrile, we have accomplished a double click in one
pot to synthesize a number of bis-triazoles.
Our future plan, triple click in one pot, and the details of our single and double click work will elaborately be
discussed in the poster.
References
1. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 2004-2021.
2. Rostovstev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed. 2002, 41, 2596-2599.
3. Huisgen, R. Pure Appl. Chem. 1989, 61, 613-628.
346

NATIONAL SYMPOSIUM IN CHEMISTRY P 245
Metal Nanoparticles: A New Generation Catalyst For Organic Synthesis
Vikas Bansal, Neeraj Kumar Mishra, Mazaahir Kidwai*
Green Chemistry Research Laboratory, Department of Chemistry,
University of Delhi, Delhi-110007
Nanoscience is a combination of “nano”, from the Greek “nano” or Latin “nanus” meaning dwarf and the word
“science”. The word nano means 10
-9
, so nanometer is one billionth of a meter. Two principal factors causes the
properties of nanomaterials to differ from other materials are increased relative surface area and quantum effects.
Nanoparticles are core base materials for implementing nanotechnology and have attracted researchers not only in
field of chemistry but also in other fields such as physics, medicine, biology and material science, due to their
current and promosing applications in organic synthesis, magnetic storage media, cell and DNA separation, drug
delivery. In the growing field of metal nanoparticles they can also be used for the preparation of porous metallic
ensembles and as filters for polymers. Metal nanoparticles provide an immense potential in organic synthesis and
various organic transformations due to their characteristic, high surface to volume ratio and a higher concentration
of partially co-coordinated surface sites than the corresponding bulk materials. The metal nanoparticles are supposed
to environmentally benign as they can be readily recovered and reused, and thus economically acceptable.
Our research group has carried out several organic transformations [1] and synthesis of biological active
moieties using various metal nanoparticles [2]. One of the recent work include A
3
coupling of aldehyde, amines and
alkynes using Au(0) of 10-15 nm. nanoparticles to give propargylamines. We had also carried out Ulmann coupling
to form diaryl ether from phenol and aryl halide using Cu(0) metal nanoparticles. Ni- metal Nanoparticle has immense
potential for reduction and can perform reduction chemoselectively.
Reference
[1] (a) M. Kidwai, V. Bansal, N. K. Mishra, A. Kumar, and S. Mozumdar, SYNLETT, 2007, 1581–1584., (b) M. Kidwai,
V. Bansal, A. Saxena, S. Aerry and S. Mozumdar, Tetrahedron Lett., 2006, 47, 8049–8053.
[2] M. Kidwai, V. Bansal, A. Kumar, and S. Mozumdar, Green Chem., 2007, 9, 742–745.
347

P 246 NATIONAL SYMPOSIUM IN CHEMISTRY
Design, Synthesis and Evaluation of New Bis Pyridinium Oxime:
Reactivators for Human Acetylcholinesterase Inhibited by Nerve Agent
Sarin
Jyotiranjan Acharya, Arvind Kumar Gupta and Devendra Kumar Dubey
Process Technology Development Division, Defence Research & Development Establishment,
Jhansi Road, Gwalior, 474002.
The extensive use of neurotoxic organophosphorus (OP) compounds as pesticides in the agriculture, as well
as their potential use as mass destruction agents in chemical warfare (nerve agents) during military conflicts and
terrorism, has attracted attention to the development of effective medical counter measures for such type of poisoning.
The acute toxic effects of nerve agents such as sarin, soman, tabun, cyclosarin and VX are due to inhibition of
activity of acetylcholinesterase (AChE), an enzyme that plays an important role in the nervous system by hydrolyzing
acetylcholine, a neurotransmitter. This leads to a variety of cholinergic effects such as myosis, salivation, hypotension,
bradycardia, muscle tremors, convulsions, and respiratory depression culminating in death due to respiratory failure.
Current medical protection against the toxicity of OP poisoning consists of a regimen of anti-cholinergic
drugs, such as atropine, to counteract the accumulations of acetylcholine and oximes viz. 2-PAM, TMB-4, HI-6 and
Obidoxime to reactivate OP-inhibited AChE. However the currently used reactivators are associated with limitations
like poor lipid solubility and unstable in solution as well. Further an effective therapy by a single oxime for all the
known nerve agents is still lacking. In view of the above a search is being continued to find out a universal reactivator
which would be active against a broad spectrum of nerve agents.
In this regard we have synthesized a novel series of bis-pyridinium oximes connected by xylene linker and
their in-vitro reactivation efficacy was evaluated for sarin inhibited human AChE. Reactivation efficacy of synthesized
compounds was compared with 2-PAM and obidoxime. Among the synthesized compounds, the bis-pyridinium
oxime N,N’-p-xylene-bis[(2,2-hydroxyiminomethyl)-pyridinium] dibromide (2P-pX) exhibited 45% reactivation
of human AChE inhibited by sarin as against 34% and 24% reactivation exhibited respectively by 2-PAM and
obidoxime at a concentration of 10
-4
M within 10 minutes. The time dependent reactivation profile of the new
oximes indicated that the oxime 2P-pX was able to reactivate 56% of the sarin inhibited human AChE after 30
minutes.
348

NATIONAL SYMPOSIUM IN CHEMISTRY P 247
Aqueous-Ionic Liquid Mixtures As Effective Reaction Media
Nageshwar Khupse
a
, Shraeddha Tiwari, Sumit Turkar, Shabana Kurolikar, Anil Kumar
b
*
Physical Chemistry Division, National Chemical Laboratory, Pune – 411008.
The use of ionic liquids (ILs) as “green” alternatives to the conventional organic solvents has been increasing
over the last few years. With the ever increasing interest in the use of ILs as reaction media, there is a growing
awareness about their shortcomings. The high viscosity of ionic liquids is believed to be one of the important
detrimental factors affecting chemical transformations [1].
Water is known to reduce the viscosity of ILs to a great extent [2, 3]. The addition of water to ILs also affects
other characteristic properties of ILs like the polarity parameters. In this work we have analyzed the various
physicochemical properties (e.g. polarity, viscosity etc.) for a range of aqueous mixtures of ILs at several temperatures.
We have then examined the effect of addition of water as a co-solvent on the progress of different C-C bond-forming
organic reactions, including the Diels-Alder reaction. The correlation of the reactivities with the properties of binary
mixtures leads to an in depth understanding of the solute-solvent interactions at the molecular level. The analysis
indicates that use of water as a “viscosity-reducer” in ILs leads to highly-enhanced rates of reactions, but the other
effects of change in polarity cannot be excluded. The binary mixture when used for organic reactions gives higher
rates (as compared to ILs) and should be considered as a viable option in the scale-up stage of ILs.
References
1. S. Tiwari, A. Kumar Angew. Chem. Int. Ed. (2006) 45, 4824
2. M. J. Earle, K. R. Seddon, Pure Appl. Chem. (2000) 72, 1391
3. E. Gomez, B. Gonzalez, A. Dominguez, E. Tojo, J. Tojo. J. Chem. Eng. Data (2006) 51, 696
349

NATIONAL SYMPOSIUM IN CHEMISTRY P 91
Nanoparticle Catalyzed Clock Reaction
Tarasankar Pal* and Surojit Pande
Department of Chemistry, Indian Institute of Technology, Kharagpur – 721302, India
Bulk Cu
2
O or cuprite is the only stable copper (I) compound present in plentiful amount in earth crust. It is a
challenging job to take bulk Cu
2
O to a nanoregime and to stabilize them in solution. No wonder that Cu
2
O in its
nanoregime would act as a photo catalyst. We report a synthetic protocol for the first time to obtain monodispersed,
stable, exclusively cubic Cu
2
O nanoparticles in surfactant free condition and its catalytic action for methylene blue
(MB)–hydrazine reaction in aqueous medium. The blue color of the dye, MB faded away upon the addition of
hydrazine producing colorless leuco methylene blue (LMB) indicating the progress of the redox reaction. The rate
of this redox reaction has been found to be enhanced in the presence of the Nan catalyst, Cu
2
O. The success of the
reaction demonstrates a simple ‘clock reaction’. An oscillation between a blue MB color and colorless solution due
to formation of LMB is observed on periodic shaking. This oscillation continues for over fifteen cycles. Studies on
the effect of bulk Cu
2
O, nanoparticles of CuO and Cu(0) have not been successful for demonstration of the ‘clock
reaction’. Thus the importance of Cu
2
O nanoparticles in the clock reaction is established beyond doubt. The Cu
2
O
nanoparticles were characterized by different physical methods. TEM studies authenticate the cube shaped
monodispersed particles. The electrochemical studies indicate that nano-Cu
2
O shows a couple of redox peaks which
correspond to the redox Cu(II)/Cu(I) system. Kinetic studies authenticate first-order reaction mechanism. Further
quantum chemical calculations reveal that the nanoparticles reduce the activation energy by ~17 kcal/mol thereby
make the reaction 2.4
´10
7
times faster compared to the gas-phase.
Scheme to show the catalytic activity of Cu
2
O nanocubes for the ‘clock reaction’.
References
[1] Landolt, H. Ber. Dtsch. Chem. Ges. 1886, 19, 1317.
[2] Mambo, E.; Simoyi, R. H. J. Phys. Chem. 1993, 97, 13662.
[3] Lente, G.; Fa´bian, I. Inorg. Chem. 2004, 43, 4019.
193

P 92 NATIONAL SYMPOSIUM IN CHEMISTRY
Surface Enhanced Raman Scattering with Core-Shell Nanoparticles
G.V. Pavan Kumar, Nashiour Rohman, Chandrabhas Narayana
*
Light Scattering Lab, Chemistry and Physics of Materials Unit,
Jawaharlal Nehru Center for Advanced Scientific Research, Jakkur, Bangalore – 560064
In recent years, surface enhanced Raman scattering (SERS) has emerged as one of the most potent tools in
ultra-trace molecular analysis. It blends single molecule sensitivity with chemical fingerprint capabilities, which
make it a unique tool for biomolecular detection. Metallic nanoparticle substrates are one of the important requirements
of SERS experiments, on which, molecules adsorb to exhibit enhanced Raman signatures. Conventionally, Ag and
Au nanoparticles have been extensively used for SERS studies. Of late, core-shell nanoparticles have derived enormous
attention in the field of SERS because of their unique optical properties like tunable surface plasmon.
In this paper, we present two novel techniques used to harness the core-shell properties of nanoparticles for
biomolecular detection purpose:
1) We show the creation of electromagnetic hot spots in Ag core-Au shell nanoparticles, which provide enhanced
optical fields for SERS. Further, we use them to detect biomolecules like p300 (a human transcriptional coactivator
enzyme) at physiological concentrations.
2) We show the possibilities of using magnetic core-metallic shell nanoparticles for SERS applications. We
synthesize, and use Fe
2
O
3
core–Ag shell and Fe
2
O
3
core–Au shell nanoparticles for SERS studies of bio-related
molecules. Also, by performing SERS microscopy in the temperature range of 77 K to 473 K, we show that the
metal-coated magnetic nanoparticles are robust with respect to variation in temperature.
194

NATIONAL SYMPOSIUM IN CHEMISTRY P 93
Pd Nanoparticls as Efficient Catalyst for Carbon-Carbon Bond Formation
Kalicharan Chattopadhyay, Laksmikanta Adak, Amit Saha, Sukalyan Bhadra, Debasree Saha,
Raju Dey and Brindaban C. Ranu*
Department of Organic Chemistry, Indian Association of the Cultivation of Science, Jadavpur,
Kolkata 70032, India
An efficient procedure for the stereo selective synthesis of (E)- and (Z)-2-alkene-4-ynoates and –nitriles by a
simple reaction of vis-diido-(E)-alkenes with acrylic esters and nitrile catalyzed by in situ prepared Pd(0) nanoparticles
in water has been developed.
Palladium (0) nanoparticles have also been used as efficient catalyst for the bis-allylation of active methylene
compounds by allyl acetate in one step in THF solvent without requirement of any ligand. Interestingly, the reaction
in water provides monoallylated product with high selectivity.
The formation of Pd nanoparticles was detected from analysis of the reaction mixture by transmission electron
microscopy (TEM) and Energy Dispersive X-ray spectroscopy (EDS). The TEM image and EDS showed the
palladium nanoparticles with a size of 2-6 nm. The palladium nanoparticles were recycled for two runs with out any
loss of efficiency.
195

P 94 NATIONAL SYMPOSIUM IN CHEMISTRY
Mesopores in Organic Cresol Formaldehyde MATRICES
Mahasweta Nandi, Asim Bhaumik*
Department of Materials Science and Center for Advanced Materials,
Indian Association for the Cultivation of Science,
2A & B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Cresol-formaldehyde resins are versatile polymer having numerous applications in ion exchange, catalysis,
supercapacitors, photo resistant materials etc. Purely organic mesoporous materials are the area of major research
interest in recent times [1-3], especially in the context of developing the low-k dielectric materials. Mesostructured
cresol formaldehyde composites synthesized by template assisted route have not been explored much. Here we
present a very simple procedure for the preparation of a nanostructured cresol-formaldehyde material through
hydrothermal condensation of m-cresol and formaldehyde at 363 K under mild alkaline condition in the presence of
supramolecular assembly of cationic surfactant, cetyltrimethyl ammonium bromide as structure directing agent or
template. The resulting material was characterized by powder X-Ray diffraction, TEM, TG-DTA, UV-Vis and
fluorescence spectroscopy. Removal of template from the as-synthesized material gave the template free mesoporous
material. TEM image analysis revealed nanorod morphology with diameter of the rods of 30-40 nm. These nanorods
have disordered wormhole-like nanostructure with pores of dimensions of ca. 2.5 nm. These composite materials
exhibit photoluminescence property at room temperature, distinctly different from the material having non-porous
resol matrix.
References
[1] Simon, F. -X.; Khelfallah, N. S.; Schmutz, M.; Diaz, N.; Mesini, P. J. J. Am. Chem. Soc. 2007, 129, 3788.
[2.] Chandra, D.; Jena, B. K.; Raj, C. R.; Bhaumik, A. Chem. Mater. 2007 (in press).
[3] Nandi, M.; Gangopadhyay, R.; Bhaumik, A. Microporous Mesoporous Mater. 2007 (in press).
196

P 86 NATIONAL SYMPOSIUM IN CHEMISTRY
Nanocrystalline Assisted Photoreduction of Co
III
(pn)
2
LCl
2+
in Water/1,4-
Dioxane Mixtures
L. Devaraj Stephen and K. Anbalagan*
Department of Chemistry, Pondicherry University, Puducherry 605 014, India
Nanocrystalline titanium dioxide assisted reduction of Co
III
(pn)
2
LCl
2+
(L = RC
6
H
4
NH
2
; R = m-OCH
3
, p-F, H, m-
CH
3
, p-CH
3
, p-OC
2
H
5
and p-OCH
3
) in a series of water/1,4-dioxane (Diox) mixtures (water/Diox = 100/0, 95/5, 90/
10, 85/15, 80/20, 75/25, and 70/30) was monitored spectrally. Irradiation of nm-TiO
2
particles with l
max
= 254 nm
flux leads to generation of Co
I
species. In neat water the photo reduction yield (F
Co(II)
) is low, however, addition of
1,4 - dioxane causes a measurable rise in F
Co(II)
. That is, in nm-TiO
2
+ Co
II
+ hn ® Co
I
, (F
Co(II)
is low, when x
2
=
0.0109 but it is high when x
2
= 0.0831, where x
2
is mole fraction of Diox). SEM images illustrate the growth of
particle size upon irradiation and the changes in photo efficiency yields are interpreted in terms of correlation model
expressions containing solvent empirical parameters. The particle size increases and the porosity get decreases.
EDAX illustrate the amount of Co(III) present on the surface of the TiO
2
before and after irradiation. The binding
property of Co(III) with TiO
2
surface was characterized using TEM.
188

NATIONAL SYMPOSIUM IN CHEMISTRY P 87
Statistical Theory for Combinatorial Protein Design by Energy
Landscaping
Arnab Bhattacherjee and Parbati Biswas*
Department of Chemistry, University of Delhi, Delhi-110007
Developing a predictive understanding of protein folding requires quantitative measures of sequence-structure
compatibility. A foldability criterion accounts for this compatibility and is used in both structure prediction and
protein design. A self-consistent theory is presented here which is used to estimate the number and composition of
sequences consistent with a generalized foldability criterion. This generalized foldability criterion characterizes the
properties of sequences by quantifying the energetic separation of the target state from the ensemble of unfolded
states and the fluctuations of the energies in the unfolded ensemble The theory yields site-specific pair correlated
monomer probabilities which is useful in exploring correlated mutations. The results of a simple lattice model are
compared with the results of exact enumeration. The theory may provide a quantitative framework for design and
interpretation of combinatorial experiments involving proteins, where a library of amino acid sequences is searched
for sequences that fold to a desired structure.
References
[1] Biswas, P: Zou, J. ; Saven, J.G. J. Chem. Phys. 2005, 123, 154908.
[2] Zou, J. ; Saven, J.G. J. Mol. Biol. 2000, 296, 281.
[3] Klimov, D.K.; Thirumalai, D. J. Chem. Phys. 1998, 109, 4119.
189

P 88 NATIONAL SYMPOSIUM IN CHEMISTRY
Potentiometric Sensor for Arsenate
Abhinaba Banerjee
1
, Abhishek Chatterjee
1
, Priyabrata Pal
2
, Priyabrata Sarkar
2*
1. Department of Chemical Engineering, Jadavpur University,
188, Raja S.C. Mallick Road, Kolkata-700 032
2. Department of Polymer Science and Technology, University of Calcutta
92 A.P.C. Road, Kolkata- 700009
Arsenic is known as ‘silent killer’. Consumption of arsenic contaminated water can cause skin melanosis, liver
and kidney problems, gangrene, cancer etc. Because of the negative health effects of arsenic, World Health
Organization (WHO) has established a maximum contamination level of 10 parts per billion (ppb) in drinking water.
Nowadays a variety of techniques are available to detect arsenic in ppb level, but these methods require expensive
instrumentation, highly skilled personnel and cannot be employed for on-site analysis. More over most of these
methods are not suitable for detection below 10 ppb. We have developed potentiometric sensor for arsenic that
utilizes a complexation reaction (Figure 1) between three molecules of Catechol and one molecule of Arsenate (Pal
et.al. [1]). The change in concentration of arsenate due to this complexation reaction, was monitored potentiometrically.
The sensor could estimate arsenic as low as a few ppb (Figure 2).
References:
(1) Pal, A.; Jana, N.R.; Bandopadhyay, T.K.; Pal, M.; T.S. Anal.Commun. 1996, 33, 315
Complexation of Arsenate with Catechol Fig 2.
Calibration curve for Arsenate
190

NATIONAL SYMPOSIUM IN CHEMISTRY P 89
V
2
O
5
as a new promising catalytic activator for Al-Zn sacrificial anodes
K.K. Binoj, M. Ajeesh, S.M.A.Shibli*
Department of chemistry, University of Kerala,
Kariavattom Campus, Thiruvananthapuram, Kerala-695 581, India.
Aluminum alloy sacrificial anodes are preferentially selected for cathodic protection of steel objects due to
their high current capacity, low specific weight, high thermal and electrical conductivity and nominal cost.
Conventionally a small amount of zinc (~5 %) is added to aluminum to prevent the formation of passive Al
2
O
3
film
on the anode surface. The major draw back of Al-Zn alloy sacrificial anodes is the noncolumbic corrosion loss and
low galvanic efficiency. Incorporation of metal oxides in the interior of the alloy may refine the grains and suppressing
the grain boundary corrosion that results in improvement of the anode performance. In the present study vanadium
pentoxide (V
2
O
5
), one of the efficient catalysts in many electro chemical reactions was explode as an effective
activator for Al-Zn alloy sacrificial anodes. The metallurgical suture of the anode was characterized by optimizing
the casting parameters. The catalytic effect of V
2
O
5
in the interior layer of the anode was characterized by different
electrochemical techniques. The anode incorporated with optimum quantity of

V
2
O
5
(0.5 %) exhibited excellent
galvanic performance under different experimental conditions in 3 %

NaCl solution when they were indented to
protect steel. There was a significant reduction in pitting, high and steady negative potential, very low polarization
and high galvanic efficiency. The promising anodes were cost effective also.
191

P 90 NATIONAL SYMPOSIUM IN CHEMISTRY
Damping of Electronic Excited States Near Nanoscopic Systems
R. S. Swathi and K. L. Sebastian*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore, 560 012.
Fluorescence Resonance Energy Transfer (FRET) is an interesting photo-physical process [1] that involves
transfer of excitation energy from donor to acceptor in a non-radiative fashion. It has been extensively used in
biology as a spectroscopic ruler to understand the conformational dynamics of biopolymers in the 10-100Å range.
The rate of non-radiative damping of dye molecules near quenchers like other dye molecules is found to vary as
R
-6
where R is the distance between the donor and the acceptor. Recently, there has been tremendous interest towards
using nanoscopic materials like nanoparticles, nanotubes etc. as energy acceptors. There have been reports of
nanoparticle surface energy transfer (NSET) [2] between fluorescein and 1.4 nm diameter gold nanoparticle, both of
which are connected by a DNA as a bridge. They observe an R
-4
dependence of the rate on the distance, which is
quite useful because it more than doubles the range of distances that could be measured using conventional FRET.
There have also been attempts to explain the R
-4
dependence for the case of nanoparticle [3]. We have done a
detailed calculation of the rate of energy transfer from fluorescein to a 1.4 nm gold nanoparticle taking the electron-
hole pair excitations as well as the plasmonic excitations explicitly into account.
Nanotubes have also been found to be efficient quenchers for the electronic excited states of molecules like
pyrene . Interestingly, to the best of our knowledge, there are no reports of distance dependence of the rates of such
processes, either experimentally or theoretically. A nanotube can be imagined to be a rolled up sheet of a single layer
of graphite, graphene. The starting point for any theoretical investigation of the nanotubes is graphene. In view of
this fact and the recent experimental advances in graphene, we have studied the distance dependence of the rate of
damping of molecular electronic excited states near graphene. This would provide a starting point for the theoretical
study of such states near nanotubes and motivation for the experimentalists to probe such processes.
References:
[1]. L. Stryer, R. P. Haugland, Proc. Natl. Acad. Sci. U.S.A. 1967, 58, 719.
[2]. C. S. Yun et. al., J. Am. Chem. Soc. 2005, 127, 9, 3115.
[3]. Somnath Bhowmick et. al. J. Chem. Phys. 2006, 125, 181102.
192

NATIONAL SYMPOSIUM IN CHEMISTRY P 81
Intersystem Crossing Effects in the O + Ethylene Reaction Dynamics
Biswajit Maiti
Department of Chemistry, Faculty of Science,
Banaras Hindu University, Varanasi, 221005, India
Spin-orbit coupling (SOC) induced intersystem crossing (ISC) has long been believed to play a crucial
role in determining the product distributions in the O(
3
P) + C
2
H
4
reaction. In this paper we will be presenting the
first nonadiabatic dynamics study of the title reaction at two center-of-mass collision energies: 0.56 Ev, which is
barely above the H-atom abstraction barrier on the triplet surface, and 3.0 Ev which is in the hyperthermal regime.
The calculations were performed using a quasiclassical trajectory surface hopping (TSH) method with the potential
energy surface generated on the fly at the unrestricted B3LYP/6-31G(d, p) level of theory. To simplify our calculations,
nonadiabatic transitions were only considered when the singlet surface intersects the triplet surface. At the crossing
points, Landau-Zener transition probabilities were computed assuming a fixed spin-orbit coupling parameter which
was taken to be 70 cm
-1
in most calculations. Comparison with a recent crossed molecular beam experiment at 0.56
Ev collision energy shows qualitative agreement as to the primary product branching ratios, with the CH
3
+ CHO
and H + CH
2
CHO channels accounting for over 70% of total product formation. However, our direct dynamics TSH
calculations overestimate ISC so that the total triplet/singlet ratio is 25:75, compared to the observed 43:57. Smaller
values of SOC reduce ISC resulting in better agreement with the experimental product relative yields; we demonstrate
that these smaller SOC values are close to being consistent with estimates based on CASSCF calculations. As the
collision energy increases, ISC becomes much less important and at 3.0 Ev, the triplet to singlet branching ratio is
71:29. As a result, the triplet products CH
2
+ CH
2
O, H + CH
2
CHO and OH + C
2
H
3
dominate over the singlet
products CH
3
+ CHO, H
2
+ CH
2
CO, etc.
183

P 82 NATIONAL SYMPOSIUM IN CHEMISTRY
The possibility of Using Locally Available Garware Polyester Film (GPF)
as UV dosimeter
Chhavi Agarwal, P.C.Kalsi*
Radiochemistry Division,
Bhabha Atomic Research Centre,
Trombay-400085.
Polymers are becoming very popular in the field of radiation dose measurements [1] because of their
low cost. The possibility of using CR-39 polymer as a UV dosimeter has been recently studied by Shweikani et
al [2]. The lower LET (Linear Energy Transfer) radiations such as UV, X-rays, electrons and gamma on interacting
with polymers produce the bulk changes in the form of many broken molecular chains, leading to change in
bulk-etch rate and optical density. These changes can be used for the evaluation of radiation doses. In the
present investigation, the effects of ultraviolet radiation produced by a lamp at 254 nm on locally available
Garware Polyester Film (GPF) were studied. This was done by using two techniques: Bulk -etch technique and
UV-Visible spectrophotometry. GPF sheets were exposed to UV light (
» 254 nm) for different times (0.5, 1, 2,
4 and 8 hrs) at a fixed distance. The UV exposed detectors were then subjected to chemical etching using 6N
NaOH as the etchant at 60
o
C for ~5 hrs for bulk-etch rate (V
B
) measurements. Bulk-etch rate was found to
increase with increase in UV exposure time. A linear relation was seen between the V
B
and UV exposure time upto
4 hrs (Figure 1). In the case of UV-Visible spectrometry also, a linear relation was seen between the change in
absorbance due to UV and the UV exposure time upto 4 hrs at a characteristic wavelength of 316 nm (Figure 2).
From these studies, it can be concluded that locally available GPF can be used as a UV dosimeter. To see the
changes induced by UV irradiation on GPF film, the bulk-etch rates were also determined at three different
temperatures and the activation energy values for bulk etching were calculated by using Arrhenius equation. The
activation energy values for bulk-etching were found to decrease with increase in UV irradiation time. The value of
activation energy for 8 hrs UV irradiated sample was found to be 31.3 kJ/mole as compared to 49.9 kJ/mole for the
unirradiated sample. This indicates that scission of the detector is taking place with UV irradiation.
References
[1] Gopalini, D. ; Jodha, A.S.; Sarawanan, S.; Kumar, D.; Kumar, S. in : Proc. 12
th
National Symposium on Solid State
Nuclear Track Detectors, Swan Printing Press, Jalandhar (2001) p 151.
[2] Shweikani, R. ; Raja, G. ; Sawaf, A.A. Radiation Measurements 2002, 35, 281.
184

NATIONAL SYMPOSIUM IN CHEMISTRY P 83
Spider Web as Environmental Assessment Indicator of Carbon Nanotubes
in Airborne Suspended Black Particulate Matter
Sumit Kumar Sonkar, Sabyasachi Sarkar*
Department of Chemistry,
Indian Institute of Technology Kanpur, Kanpur, India.
Since the discovery of carbon nanotubes in 1991 several facets of its utility have been predicted and a few are
already showing result. The other part like the environmental problems caused by the nanoparticles have not been
addressed. Recently the issue of global warming has been implicated mainly due to the green house effect. However
the second contribution to the global warming is black carbon particulate present in the aerosols. In this work we
want to demonstrate that the black particles which is popularly called black carbon associated with aerosols
predominantly contains carbon nanotubes (CNT). Inside a room we generate these black particulates by day to day
activities and outside the house excessive fossil fuel burning contributes to this at the maximum level. Using spider
web (Fig.1a-b) as particulate matter indicator we have accessed these webs and found that the airborne particles do
contain carbon nanotubes (Fig.1 c-f), and it is speculated that exposure to combustion-generated CNT in fine
Particulates play a significant role in global warming and also in air pollution-related cardiopulmonary diseases.
Therefore, CNTs from combustion sources in the environment could have adverse effects on human health along
with its contribution to respirable diseases when inhaled inside the body.
Fig 1. (a) Indian domestic spider (b) Spider with its web
(c) SEM (d) TEM (e) AFM images of CNT (f) RAMAN Spectrum.
(a) (b) (c)
(d) (e) (f)
185

P 84 NATIONAL SYMPOSIUM IN CHEMISTRY
Topological and Thermodynamical studies of ternary mixtures: Molar
excess volumes and Excess isentropic compressibilities
J.S. Yadav, Dimple , K.C. Singh, V.K. Sharma *
Department of Chemistry, Maharshi Dayanand University, Rohtak – 124001, INDIA
Molar excess Volumes, V
E
ijk
and speeds of sound , U
ijk
of o- toluidine (i) + benzene (j) + toluene (j) or o- or p-
xylene (k) ternary mixture have been measured as a function of composition at 308.15 K. The observed speeds of
sound data have been utilized to determine excess isentropic compressiblities,
of ternary (i + j + k) mixtures.
Moelwyn- Huggins concept [M.L.Huggins, Polymer 12, 389 (1971)] between the surfaces of the constituents of
binary mixtures has been extended for ternary mixtures (using the concept of connectivity parameter of third degree
of a molecule, which in turn depends on its topology) to obtain an expression that describes well the observed
V
E
ijk
and
data. The observed data have also analyzed in terms of Flory theory.
186

NATIONAL SYMPOSIUM IN CHEMISTRY P 85
Modification of Photochemical Behavior of trans-Strylpyridines Inside
Cyclodextrin Cavities
Palaniswamy Suresh, Ismail Abulkalam Azath and Kasi Pitchumani*
School of Chemistry, Madurai Kamaraj University, Madurai-625021
Cyclodextrins (CDs) are cyclic oligomers consisting of six, seven or eight D-(+)-glucose units (a-, b- and g-
CDs respectively) with a hydrophobic inner cavity and a hydrophilic outside and are known to form inclusion
complexes with a variety of organic guests. The inclusion phenomenon in CDs enables guest molecules to exhibit
different and some times new properties from those of free molecules. In particular, the photochemical properties of
a number of substrates are sensitive to the CD microenvironment. In this context, the modified polarity inside the
cavities and the imposed steric constraints are among the main factors governing the photo reactivity of CD inclusion
complexes[1].
Isomerisation and cyclization are the major photochemical reaction of styrylpyridines in isotropic media[2].
Photo physical behavior of various styrylpyridines has also been studied in isotropic media[3]. Baring a recent
reports photochemical behavior of styrylpyridine inside cyclodextrin cavity has scarily been reported In the present
study, photochemical behavior of various styrylpyridines and its methoxy substituted derivatives are studied inside
cyclodextrin cavities. Modifications in photochemical behavior of styrylpyridines are observed inside cyclodextrin
cavities. The change in the photochemical behaviors inside the cyclodextrin cavities are rationalized by mode of
inclusion and proposing a suitable mechanism.
References
1. V. Ramamurthy, Photochemistry in Organized and Constrained Media V,ed. V. Ramamurthy,
VCH Publishers, Cambridge, UK, 1991.
2. G. Galiazzo, P. Bortolus and G. Cauzo, Tetrahedron Lett., 1966, 31, 3717.
3. G. Bartocci, U. Mazzucato and F. Masetti, J. Phys. Chem., 1980,84, 847
187

P 76 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis And Characterization of Heterogenised Chiral Schiff Base
ligands with SBA-15, MCM-41, KIT-6 and its Application on the
Enantioselective Reduction Prochiral Ketones
N. Ananthi ,U. Bala Krishnan, Dr. S. Velmathi*
Department of Chemistry, National Institute of Technology, Tiruchirappalli-620 015
The novel chiral Ligands from Schiff bases of various amino acids such as L valine and L-proline amino acids
with aldehydes, and heterogenised using various mesoporous materials like SBA-15, MCM-41, and KIT-6. These
chiral Ligands were synthesized by the reported procedure[1] and confirmed its structures using FT IR,
1
H NMR,
and
13
C

NMR spectroscopic methods. These catalysts were then anchored with various mesoporous materials
mentioned above using 3-chloropropyltriethoxysilane as a reactive surface modifier [2,3]. The immobilization of
these chiral Ligands was confirmed by SEM, XRD, EDAX and Nitrogen adsorption-desorbtion methods[4]. These
newly synthesized Ligands used as a catalyst for the reduction of various prochiral ketones, and the enantioselectivity
was determined using chiral HPLC and Digital polarimeter. The ee(75-80%) determined shows that the catalyst
immobilized in silica with larger pore diameters was found to be more active compare to homogeneous catalyst [5].
The catalysts were reusable with neither significant drop in enantioselectivity nor loss of mesostructures and recycled
several times by simple filtration.
References:
1. S.Velmathi, S.Narasimhan. Tetrahedron Lett. 2001, 42,719-721.
2. Qihua Yang, Guiru Zhu, Hong Wang, Journal of Catalysis, Volume 239, Issue 1, 1 April 2006, Pages 65-73
3. R.I.Kureshy, N.H.Khan, Journal of molecular catalysis,
178

NATIONAL SYMPOSIUM IN CHEMISTRY P 77
Artemisinin and Synthetic Derivatives: a DFT Based Comparison
Kalyan Kr. Hazarika
1
, Ramesh Ch. Deka
2
, Nabin Ch. Barua
*

1
Department of Molecular Biology & Biotechnology,
2
Department of Chemical Sciences, Tezpur University, Napaam-784028, Assam
*
Natural Products Chemistry Division, Regional Research Laboratory (CSIR)
Jorhat-785006, Assam
Malaria is one of the most worrying infectious diseases currently affecting the human race. Forty percent of the
world’s population is at risk of malaria infection causing around 300 to 500 million illnesses and up to 3 million
deaths each year [1]. The worldwide malaria situation is serious since malarial parasites have developed resistance
to the most common drugs. However, artemisinin, a sesquiterpene endoperoxide, isolated from a Chinese medicinal
herb is found to be a potent antimalarial drug against the resistant strains of Plasmodium falciparum. But, still there
is a need for better one and so numerous derivatives of this promising molecule are being synthesised to reach the
goal [2]. Theoretical prediction prior to synthesis may be of great help in minimizing the cost and time factors while
developing a better antimalarial drug.
Figure: Artemisinin and derivatives
A theoretical comparison of artemisinin with few of its synthetic derivatives viz. dihydroartemisinin, artemether,
arteether, artesunate and artelinate is reported. Geometries of the molecules are optimized by DMol3 software at an
SGI-Altix 350 machine with various combinations of basis set and functional using Mulliken and Hirshfeld population
analyses. Density functional theory (DFT) [3] based reactivity descriptors such as global softness (S), philicity (w),
Fukui function (f
+
& f
-
) and relative nucloephilicity/ electrophilicity, calculated at the optimized geometries are used
for searching and comparing the functionally important part of the molecules. The results obtained are in excellent
agreement with the experimental reports.
References:
[1]. World Health Organization. The World Health Report 1999.
179

P 78 NATIONAL SYMPOSIUM IN CHEMISTRY
Structure and Electronic Properties of DNA Base-pairs and
Modified DNA
Sairam S. Mallajosyula, Swapan K. Pati*
Theoretical Sciences Unit, Jawaharlal Nehru Center for Advanced Scientific Research
Jakkur, Bangalore - 560064
We have investigated the effect of metal electrodes and metal clusters on electronic properties of DNA bases
and base-pairs. We find that Nucleobases trapped within two gold metals on either side undergo expansion. This
primarily arises due to the concomitant increase in all the bond lengths in molecules. Such expansion of the molecules
can be qualitatively understood on the basis of classical harmonic potentials in the bonds and loss of aromaticity in
the rings, resulting in charge redistribution in the system. As a very important consequence of this, the nature of H-
bonds potential change substantially within these electrodes. These hydrogen bonds have a single-well potential
energy profile (of the type N…H…O and N…H…N) instead of double-well potentials (like N-H…O or N-H…N/
N…H-N types) [1]. With such an understanding, we tried to capture the potential use the DNA bases for reversible
H-bonding under ambient conditions. Protonation of DNA basepairs is a reversible phenomenon that can be controlled
by tuning the pH of the system. We find that, under mild acidic pH conditions, the A:T basepair shows excellent
nano-switch rectification behavior that is, however, absent in the G:C basepair. We also consider the noncanonical
A:A basepair and find that it can be used as efficient pH dependent molecular switch. The switching action in the
A:A basepair can be understood in the light of ð- ð interactions, which lead to efficient delocalization over the entire
basepair [2].
We have also studied the alignment of magnetic ions, Cu
2+
and Mn
2+
, along a modified B-DNA helix. We find
that doping with magnetic ions induces conducting states in the gap region of natural DNA. These magnetic ions are
found to interact ferromagnetically along the DNA helix. Calculations of optical conductivity about the helical axis
suggest that the origin of magnetic characteristics depend crucially on the metal ions; the Cu(Mn)-DNA favors in-
plane(out-of-plane)
s (?)-like delocalization over the base pairs. Such an alignment of magnetic ions offers promising
perspectives for creating low-dimensional polarized spin channel within the DNA helix [3]. Similar alignment
within stacking backbone (with V atoms) can also be used for creating half-metallic modified one-dimensional
single-strand DNA motif for advanced Spintronics applications
References:
[1] Mohan P. J., Ayan Datta, Sairam S.M. and Swapan K. Pati, J. Phys. Chem. B 110, 18661 (2006).
[2] Sairam S. Mallajosyula and Swapan K. Pati, J. Phys. Chem. B (Letters) 111 (40), 11614 (2007).
[3] Sairam S. Mallajosyula, Swapan K. Pati, Phys. Rev. Lett. 98, 136601 (2007).
180

NATIONAL SYMPOSIUM IN CHEMISTRY P 79
Universal Variation of Dielectric Behaviour Induced by Nanoscale Dopants
in Dielectric Oxides: Evidence of Fractal Geometry
Vishnu Shanker
a
, Pankaj Rastogi
a
, Rama Kant
b
and Ashok K. Ganguli
a
*
a
Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas,
New Delhi, 110016, India.
b
Department of Chemistry, University of Delhi, Delhi, 110007, India.
Apart from the bulk (micron-sized) materials or nanomaterials, composites having matrix and filler with
physically or chemically different properties have become the most challenging areas of current scientific and
technological research. In order to tune the dielectric properties we decided to vary the range of interfaces on
addition of nanoscale particles to micron-sized particles of the same composition “nµ-composites”, to vary the
interfacial density. Since the microstructure is influenced by the nature and extent of sinteribility we have looked at
the microscopic features carefully along with detailed thermal studies and surface area analysis [1]. Our studies
show that addition of nanoparticles to micron-sized particles leads to fractal geometry formation [2], which result in
optimal dielectric properties at certain compositions. We have observed enhancement (decrease) of the dielectric
constant (dielectric loss) by nearly 3 times of the bulk value at an optimum concentration of micron and nano sized
particles [3]. This interesting variation of the dielectric constant with increase in the amount of nanoparticles in the
nµ-composites is observed in many classes of titanates, zirconates, niobates and tantalates.
References:
[1] V. Shanker Ph.D thesis, IIT Delhi (2007).
[2] V. Shanker, Rama Kant and A. K. Ganguli (manuscript under preparation).
[3] Shanker, V. ; Ahmad, T.; H. Ip and A. K. Ganguli, J. Mater. Res. 2006, 21, 816.
181

P 80 NATIONAL SYMPOSIUM IN CHEMISTRY
Influence of Surface Properties on Controlled Drug Relesae from
Mesoporous Oxide Drug Delivery Systems
Shyamal Kumar Das and Aninda J. Bhattacharyya*
Solid State and Structural Chemistry Unit,
Indian Institute of Science, Bangalore 560012
While considerable efforts are being made in the discovery of new drugs for treatment of several complex
human ailments, controlled delivery of such drugs has also received almost similar attention. Out of several
drug delivery systems (DDS) proposed in literature, systems based on mesoporous oxide (M. Vallet Regi et al
[1]) materials (such as SiO
2
, Al
2
O
3
, TiO
2
) appear to be very promising for the sustained release of drugs at specific
targets. Mesoporous materials several attractive features, such as large surface area (300-1000 m
2
g
-1
), tunable pore
sizes (2-50 nm) and volumes (~ 1 cm
3
g
-1
), easier manipulation of surface properties and higher stability and
biocompatibility. Among the various parameters of a mesoporous oxide material which influences drug release,
surface acidity/basicity of the functional groups play a critical role. In this contribution we report a systematic study
(S.K. Das et al [2]) of the dependence of drug loading and its rate of release on the surface functional groups of
mesoporous alumina (abbreviated as MPA). MPA (BET surface area ~ 155 m
2
g
-1
; pore size ~ 5.8 nm) with varying
degree of acidity and basicity were chosen as the DDS for the study. Contrary to the oft-employed methods proposed
in literature, an alternative procedure was employed to impregnate MPA with drug ibuprofen (IBU), a non steroidal
anti-inflammatory drug (NSAID). Our method of drug incorporation in MPA showed a significantly higher loading
compared to proposed procedures in literature. The oxide-drug composites were characterized by using Fourier
transform infrared (FTIR) spectroscopy, x-ray diffraction (XRD), thermogravimetric analysis (TGA) and N
2
adsorption/desorption. It was observed that the amount of drug loading is highest in case of acidic-MPA (26% of
MPA-IBU w/w) in comparison to basic-MPA (22% of MPA-IBU w/w). Further, in vitro drug release was carried out
in simulated body fluid (SBF) at room temperature with oxides varying in surface properties. Interestingly, basic-
MPA exhibited faster IBU release compared to acidic-MPA. In case of basic-MPA 100% IBU release took place in
45 hours whereas in the time period, only 50% was released from acidic-MPA. Rate of IBU release from composites
having a requisite mixture of basic and acidic MPA lay between the slower acidic MPA and faster basic MPA release
rates. This information would suitably aid in tailoring controlled drug delivery systems. Release kinetics was also
studied as a function of SBF Ph. The release kinetics for IBU from an acidic to a basic medium changed dramatically
resembling a switching mechanism. Implications of this observation would benefit in the design of responsive DDS
for specific purposes.
References
[1] Vallet Regi , M. ; Ramila, A.; Del Real, R. P.; Perez-Pariente, J. Chem. Mater. 2001, 13, 308.
[2] Shyamal K. Das and Aninda J. Bhattacharyya, manuscript under preparation.
182

NATIONAL SYMPOSIUM IN CHEMISTRY P 71
Large Scale Self Organization of Gold Nanorods Leading to One, Two and
Three Dimensional Superstructures Induced by Monolayers
T. S. Sreeprasad, A. K. Samal and T. Pradeep*
DST Unit on Nanoscience, Department of Chemistry and Sophisticated Analytical Instrument
Facility, Indian Institute of Technology Madras, Chennai - 600 036, India
Gold nanorods are versatile material for diverse applications..[1] A method is described for assembling gold
nanorods into one, two and three dimensional superstructures. The addition of dimercaptosuccinic acid (DMSA)
into the nanorod solution was found to induce self assembly of nanorods into one-dimensional ‘tape-like’, two-
dimensional ‘sheet-like’ and three-dimensional ‘superlattice-like’ structures depending on the DMSA concentrations.
Assembly was found to be following smectic structure, where the nanorod long axes are parallel to each other. The
rods are spaced 8.5
±0.3 nm apart in the resulting structures, which extends over micrometer in length. We formed
organization perpendicular to the grid also. The nanorod tapes were found to bend and form globular assemblies as
well. The assembly and morphology of the nanorod structures were characterized by transmission electron microscopy
(TEM) and UV-vis spectroscopy. The effect of DMSA concentration as well as the pH of the medium was also
studied. Based on several control experiments utilizing several similar, charge neutralization of the nanorods by the
carboxylic group of the DMSA was found to be the principal reason for such an assembly, while the mercapto
groups render additional stability. A mechanistic model of the assembly is proposed [2]. This type of assemblies
would plausibly function as plasmonic waveguides [3]) in potential nanodevices.
References
1) Juste, J. P.; Santos, I. P.; Liz-Marz’an, L. M.; Mulvaney, P. Coord. Chem. Rev. 2005, 249, 1870.
2) Sreeprasad, T. S.; Samal, A. K.; Pradeep, T. Unpublished.
3) Ozbay, E. Science 2006, 13, 189.
173

P 72 NATIONAL SYMPOSIUM IN CHEMISTRY
A Computational Study Towards The Rotational Barriers of
Thioamides
Manoj Kumar Kesharwani and Bishwajit Ganguly*
Analytical Science Discipline, Central Salt and Marine Chemicals Research Institute,
Bhavnagar: 364002, Gujarat, India
Rotational barrier heights for several thioamides (X
2
NC(=S), H=Y, X) have been investigated in the gas phase
by applying density functional theory. The calculated results suggest that the electrostatic and electronic effects can
tune the planar form of amides to pyramidal forms. The variations of rotational barriers around the formally single
C-N bond in all compounds are studied in comparative context with thioformamide. These results will be useful for
the studies in immunosuppressant agent like FK506.
174

NATIONAL SYMPOSIUM IN CHEMISTRY P 73
Rapid Measurement of
3
J(H
N
-Ha) and
3
J(N-Hb) Coupling Constants
In Polypeptides
Ravi Pratap Barnwal,
1
Ashok K. Rout,
1
H.S. Atreya
2*
and Kandala V.R. Chary
1*
1
Department of Chemical Sciences, Tata Institute of Fundamental Research, Mumbai 400 005
India
2
NMR Research Centre, Indian Institute of Science, Bangalore-560012, India
We have developed two NMR experiments, (3,2)D H
NHA and (3,2)D HNHB, for rapid and accurate measurement
of
3
J(H
N
-H
a
) and
3
J(N-H
b
) coupling constants in polypeptides based on the principle of G-matrix Fourier transform
NMR spectroscopy
1
and quantitative J-correlation. These experiments, which facilitate fast acquisition of three-
dimensional data with high spectral/digital resolution and chemical shift dispersion, will provide renewed opportunities
to utilize them for sequence specific resonance assignments, estimation/characterization of secondary structure
with/without prior knowledge of resonance assignments, stereospecific assignment of prochiral groups and 3D
structure determination, refinement and validation. Taken together, these experiments have a wide range of applications
from structural genomics projects to studying structure and folding in polypeptides
2
.
Reference
1. Atreya, H. S.; Szyperski ,T. Methods Enzymol. 2005, 394, 78.
2. Barnwal, R. P.; Rout, A. K.; Chary, K. V. R.; Atreya, H. S. J. Biol. NMR. 2007 (in press).
175

P 74 NATIONAL SYMPOSIUM IN CHEMISTRY
Intra and Intermolecular Hydrogen Bonding in Formohydroxamic acid
Ruchi Kohli, Damanjit Kaur*
Chemistry Department, Guru Nanak Dev University, Amritsar 143005
The hydrogen bonding of water with biomolecules like DNA, polypeptides and other molecules etc. significantly
affect the structure and reactivity of these basic molecules of life. Hydroxamic acids are molecules of biological
importance due to their applications as tumor inhibitors, antimicrobial agents, antituberculosis agents etc. The present
theoretical studies suggest, inspite of the presence of multiple potential sites for hydrogen bonding in formohydroxamic
acids(FHA), only one of the isomer 1Z shows H-bond interactions, though the distances between H-bond donor and
acceptor are less than sum of their van der Waal radii, the X…H-A bond angle does not allow the H-bond stabilization.
The aggregation of four lowest energy isomeric forms 1Z, 1E, 2Z and 2E with single water at MP2/Aug-cc-pVDZ
level leads to stabilization energies in the range 3.5-10.9 kcal/mol, which indicate that the intermolecular H-bond is
stronger than intramolecular H-bond. The dimerization of various isomeric forms at MP2/6-31+G* resulted in
stabilization energies of the order 2.6-16.1 kcal/mol. 1Z-1Z(1) homodimer is most stable dimer and the optimized
structure is having two symmetrical strong H-bond interactions between carbonyl oxygen of one FHA unit with the
hydroxyl hydrogen of the second unit. Carbonyl oxygen is the strongest H-bond acceptor site in FHA as suggested
by the dimerization and FHA-H
2
O adduct studies. Cooperativity and synergic enhancement of intramolecular H-
bonding is suggested in addition to the charge transfer and electrostatic interaction stabilization [1].
References: Kaur, D. ; Kohli, R. Int. J. Quant. Chem., 2008, 108, 119.
176

NATIONAL SYMPOSIUM IN CHEMISTRY P 75
Anthracene-9,10-dione – A versatile Platform for Both Cation and Anion
Chemosensors
Kuljit Kaur, Navneet Kaur, Vijay Luxami, Nidhi and Subodh Kumar
*
Department of Chemistry, Guru Nanak Dev University, Amritsar-143005
The development of new molecular systems for colorimetric detection of cations, anions and neutral molecules
have attained prime significance due to their biological and environmental applications. Anthracene-9,10-diones
due to their diverse chemical features depending on the substitution pattern have shown wide spread potential for
the development of dye stuff materials, DNA intercalators, redox active and optical sensors. The possibility of color
tuning and in-sights into the mechanisms responsible for these color changes can lead to further refinements in
procedures.
The augmentation of electron-withdrawing or electron-donating groups on anthracene-9,10-dione moiety tunes
the interactions of resulting receptors towards analytes bearing either negative or positive charge. Further the variation
in electron density polarization tunes their selective or differential binding towards various heavy metal ions. The
use of this meticulous control of varied binding sites in developing wide range of anthracene-9,10-dione based
sensors for Cu
2+
, Ni
2+
, Co
2+
, Hg
2+
, Ag
+
and F
-
will be presented
1,2
.
References:
1. Navneet Kaur and Subodh Kumar, Chem. Commun., 2007, 3069-3070.
2. Navneet Kaur and Subodh Kumar, Dalton Trans., 2006, 3766-3771.
177

P 66 NATIONAL SYMPOSIUM IN CHEMISTRY
Ruthenium(II) Complexes of Bipyridine - Glycoluril and their Interactions
with DNA
Megha S. Deshpande, Anupa A. Kumbhar and Avinash S. Kumbhar*
Department of Chemistry, University of Pune, Pune–411 007, India.
The synthesis, structural and photophysical characterization, DNA binding and cleavage by Ru(II)
polypyridyl complexes of the type [Ru(N-N)
2
(BPG)]Cl
2
1-4, [Ru(BPG)
3
]Cl
2
5

and [Ru(N-N)(BPG)
2
]Cl
2
6-9 where
N-N is 2,2‘-bipyridine (bpy), 1,10-phenanthroline (phen), dipyrido[3,2-d:2‘,3‘-f]quinoxaline (dpq), dipyrido[3,2-
a:2‘,3‘-c]phenazine (dppz) which incorporates the bipyridine glycoluril ligand have been studied to investigate the
influence of the ancillary ligand. The X-ray structure of urea fused bipyridine ligand BPG reveal inherent H-bond
donor (N-H) and acceptor groups (C=O) which exhibit a potential to generate supramolecular motifs as well as offer
H-bonding groups for DNA binding. Single crystal X-ray analysis of 1, 5 and 7 indicate a butterfly like structure for
the cationic secondary building units evidencing this H-bonding capacity which results in a supramolecular self-
assembled metal-organic frameworks (MOF) forming channels in 1 and 5 encapsulating tetradecameric water cluster,
mixed water-dimethylsulfoxide cluster and a network of water molecules and chlorine anions surrounding secondary
building units in 7. The binding ability of these complexes to DNA is dependent on the planarity of the intercalative
polypyridyl ligand, which is further influenced by the ancillary bipyridine-glycoluril ligand. Interaction of complexes
1-9 with plasmid pBR322 DNA reveals that all complexes cleave DNA efficiently at micro molar concentrations
under dark and anaerobic conditions probably by a hydrolytic mechanism. Molecular mechanics calculations of
these systems confirm two different binding modes for the complexes.
References: 2) Deshpande, M. S.; Kumbhar, A. S.; Puranik, V. G.; Selvaraj, K. Cryst. Growth Des. 2006, 6, 743.
3) Deshpande, M. S.; Kumbhar, A. A.; Kumbhar, A. S. Inorg. Chem. 2007, 46, 5450.
168

NATIONAL SYMPOSIUM IN CHEMISTRY P 67
Performance Evaluation of Waste Activated Carbon from ‘Aquaguard’ as
an Adsorbent for the Removal of Phenol from Aquatic Environment
Bijoli Mondal and Anjali Pal*
Department of Civil Engineering, Indian Institute of Technology, Kharagpur-721302, India
Water pollution is a persistent problem. Phenolic compounds widely exist in the effluents coming from industries
such as oil refineries, coal tar, plastics, leather, textile, paint, varnishes, steel, phenol producing industries, explosive
manufacturing industries, fertilizer and pesticide industries, pharmaceutical industries, coke oven plants, dye
manufacturing industries, etc., and are acutely toxic. Also, during chlorination of phenol bearing wastewater,
chlorophenols are produced. These chlorophenols are toxic and they are considered as persistent organic pollutants
(POP). Among several processes available for the removal of phenolic compounds from wastewater, adsorption has
been found to be an efficient and economically beneficial process. However, commercially available activated
carbon remains to be a rather expensive material. In the present study the waste activated carbon from ‘Aquaguard’
water purifier after it is disposed of, was used for phenol removal. Removal of phenol by waste ‘Aquaguard’ carbon
(WAC) was studied separately in batch and continuous mode. WAC was found to be very efficient, and it is almost
a ‘no-cost’ material. Under optimized conditions ~98 % efficiency could be achieved for the removal of phenol
when present even at a high concentration (20 mg/l). The kinetic studies showed that 4 hours shaking time was
sufficient to achieve the equilibrium for phenol. The removal of phenol followed the pseudo-second order reaction
kinetics. Study was conducted to see the effects of adsorbent dose on the removal of phenol using WAC. The pH was
kept at 6.5±0.1. The optimum adsorbent dose was found to be 2 g/l. The effects of different parameters like pH,
presence of different ions, temperature, agitation speed etc. were studied. The removal of phenol increased with
increase in pH up to 6.0 and then decreased. There was no effect of agitation speed. The effect of different ions for
the removal of phenol was within
±5 %. No effect of humic acid, 2, 4-D, atrazine and endosulfan was noticed. The
removal of phenol decreased with increase in temperature. The adsorption isotherm was well described by the
Freundlich isotherm model. The maximum adsorption capacity of WAC was found to be 25.57 mg/g for phenol
having concentration 20 mg/l at 27±2°C. Evaluation of thermodynamic parameters revealed that the adsorption
process was spontaneous and exothermic in nature. Fixed bed column studies were conducted for the removal of
phenol from aqueous environment. The column with 2 cm diameter having bed depths of 5, 10 and 15 cm could treat
5.92, 12.11 and 16.65 liter of phenol bearing wastewater (phenol concentration 20 mg/l). The bed was almost 95 %
saturated at the time of breakthrough. The adsorption rate constant (K) and adsorption capacity were found to be
0.013105 l/mg-h and 13.886 kg/m
3
. Effect of flow rate and initial concentration was studied.
169

P 68 NATIONAL SYMPOSIUM IN CHEMISTRY
Estimation of Thermodynamic Properties of Cyclic Paraphenylacetylenes
(CPPA) by Isodesmic and Homodesmic Reaction Methods
Mohamad Akbar Ali and Mangala Sunder Krishnan*
Department of Chemistry, IIT Madras, Chennai 600036
Polycyclic hydrocarbons containing phenyl rings connected to each other at the para positions by acetylenic
bonds form a novel group of hydrocarbon molecules with potential applications in carbon nanotubes, molecular
devices and molecular electronics.
1
The polymeric structures of polycyclic phenylacetylenes (n = 2 – 7) are given
below:
The strain energy becomes less as n increases leading to substantially different chemical stabilities for these
compounds. Due to the strain many of these compounds are not yet synthesized in the laboratory, and accurate ab
initio studies will hopefully provide for estimations of chemical properties. Isodesmic and homodesmic reactions
2
have been very useful tools in the past few years for performing theoretical calculations of thermodynamic properties.
In this paper details of various schemes and the results of calculations performed with the help of Gaussian-03
3-4
will
be described along with theoretical analyses for the variation of properties with n.
References:
1. T. Kawase et al., Cyclic [6] and [8] paraphenylacetylenes, Angew. Chem.Int. ed., 35 2664 (1996)
2. Pople, J. A et al.., Ab initio molecular orbital theory (Wiley Interscience, 1985)
3. Frisch A., et al, Gaussian’ 03 User’s Reference” (Gaussian Inc., 2003)
170

NATIONAL SYMPOSIUM IN CHEMISTRY P 69
In situ Cryo-Crystallisation of Chloro and Bromo Substituted Anilines and
its Intermolecular Interactions.
Susanta K. Nayak, S. J. Prathapa and T. N. Guru Row*
Solid State and Structural Chemistry Unit, Indian Institute of Science,Bangalore-560012.
In situ cryo-crystallization of a liquid, the subsequent structure determination and its study of intermolecular
interactions has emerged as an area of contemporary interest. In -situ cryo-crystallization of fluoro- substituted
anilines and the evaluation of the variability in halogenated trifluoroacetophenones (Chopra et al.[1, 2] ) clearly
bring out the importance of interactions generated by fluorine in crystalline lattices and establishes that indeed
fluorine has a directing influence in molecular assembly. In order to evaluate the propensity of interactions in
halogens in general, o - chloro and o -bromo anilines were crystallized from their respective liquids via in situ cryo
crystallization method. The crystal structures are isostructural belonging to a trigonal system, space group P 3
1
. The
crystal packing is due to intramolecular N-H…Cl / Br and intermolecular N-H….N hydrogen bonds. However, in
the case of o-bromo aniline short Br…Br contacts (3.64 Å ) are observed suggesting that this interaction is a
consequence of the size of the Br atom.
References 1. Chopra, D.; Thiruvenkatum, V.; Guru Row, T. N. Cryst. Growth Des. 2006, 6, 843.
2. Chopra, D.; Thiruvenkatum, V.; Manjunath S. G.; Guru Row, T. N. Cryst. Growth Des. 2007, 7, 868.
171

P 70 NATIONAL SYMPOSIUM IN CHEMISTRY
Electronic Properties of Transverse Substituted and Unsubstituted t-PA: a
Comparative DMRG Study
Manoranjan Kumar and S. Ramasesha
Solid State and Structural Chemistry Unit, Indian Institute of Science,
Bangalore 560012, India.
The optical properties of conjugated polymers have been a frontier area of research because of their potential
applications in the non-linear optoelectronic devices. Strong photoluminesence (PL) is one of the most important
requirements for making optoelectronic devices [1-3]. Designing of strong PL material requires complete
understanding of mechanism involved in the optical phenomenon. According to Kasha’s Rule, E(2A
g
)>E(1B
u
) is the
essential condition for strong PL. Trans-polyacetylene (t-PA) is an excellent example of non-emissive material. But
replacement of H of t-PA chain by phenyl groups, or its derivatives leads to strong . This behavior can be understood
by considering coulomb interaction of the p electrons in these conjugated systems. Mazumdar et. al have considered
electronic correlation in substituted t-PA and used Pariser Parr and Pople (PPP) model to study the
Polydiphenylacetylene (PDPA) in the Single Configuration Interaction (SCI) picture In this work, we have used
finite symmetrized Density Matrix Renormalization Group (SDMRG) method for Polydiethylacetylene (PDEA)
and t-PA systems. To obtain E(2A
g
) and E(1B
u
) states, spatial symmetry C
2,
spin parity and electron hole symmetry
are used. We find that there is no level crossing of E(2A
g
) and E(1B
u
) states as function of bond alternation, d up to
0.1. Singlet-Triplet gap does not go to zero in PDEA, but it vanishes for t-PA as ä goes to zero. We also compare the
non-linear optical properties of these two systems.
References:
[1] J. L. Bredas and R. Silbey, Conjugated Polymers: the Novel Science and Technology of Highly Conducting and Nonlinear
Optically Active Materials (Kluwer Academic, Dordrecht, 1991).
[2] Blatch J. W. Blatchford and A. J. Epstein, Am. J. Phys. 64, 120 (1996).
[3] D. de Leeuw, Phys. World 12, 31 (1999).
172

NATIONAL SYMPOSIUM IN CHEMISTRY P 61
Task Specific Ionic Liquid Bronsted Acid-clay Hybrid Nanocomposite
Catalyzed Transesterification Reaction
Vasundhara Singh*, R.Ratti, M.Vaultier
a
* Department of Applied Sciences, Punjab Engineering College, Deemed University,
Chandigarh
a
Institute de Chimie, University of Rennes 1, Rennes, France
Transesterification is one of the important organic transformations that have relished numerous laboratory and
industrial uses. The ester to ester transformation is particularly significant when the parent carboxylic acids are
labile and difficult to isolate. b- ketoesters are muticomponent coupling reagents having electrophilic carbonyl and
nucleophilic carbon which make them important synthons for the total synthesis of number of natural products.
Since transesterification, used for the synthesis of new b- ketoesters, is an equilibrium process, it is accelerated by
the simultaneous removal of low boiling coproduct alcohol during the process by distillation. This reaction is catalyzed
by a number of chemical species like organic and inorganic acids, bases, anion exchange resins, DMAP, molecular
sieves, Lewis acids, titanium tetra oxide, zeolites, clay, Mo-ZrO
2
, Envirocat EPZG to list a few. But all these
procedures are flawed with one drawback or another like volatility and toxicity of acid catalysts, long reaction times,
hostility of catalysts to environmental issues and their non-recoverability.
Due to rigorous environmental statutes, the scientific community is under great stress to develop ecocompatible
synthetic methodologies. So present day chemistry is more inclined to re-scrutinize the existing synthetic procedures
thereby making them more congenial. More than 60% of products and more than 90% of processes worldwide rely
on the rapidly expanding field of catalysis. The use of ionic liquids as either solvents or catalysts is emerging as
subject of considerable recent attention in accordance with prospects of ‘Green Catalysis’. Keeping in view these
concerns we have synthesized a TSIL- bronsted acid and its clay hybrid which is successfully used as catalyst for the
transesterification of b- ketoesters with various alcohols. The results of the same will be presented.
163

P 62 NATIONAL SYMPOSIUM IN CHEMISTRY
Novel Cyclic Trimeric Thermotropic Liquid Crystals: Synthesis and
Characterisation
A. Shanavasà, A. Sultan Nasarà & T. Narasimhaswamy*
à

Department of Polymer Science, University of Madras, Guindy Campus,
Chennai 600025
Polymer Lab, Central Leather Research Institute, Adyar, Chennai 600020
Thermotropic liquid crystals are recognized as an important class of organic electronics due to their sensitivity
to external stimuli. From molecular structural point of view, they are primarily classified into calamitics and discotics.
Usually, the mesogen consists of core made up of substituted phenyl rings connected through linking groups and
flexible terminal units. In recent years, molecular topology of mesogen has been identified as one of the crucial
factor in the formation of mesophase. The calamitic mesogens generally have linear like structures while discotics
possessed disk-like cores. The cyclic trimers, on the other hand, show different topology leading to the formation of
calamitic and columnar phases depending up on the terminal and linking units. Moreover, these oligomers (e.g.
trimers) are considered as model compounds for
polymeric liquid crystals. In the present work novel
cyclic trimeric liquid crystals are synthesized using
1,3,5-tricarboxylic acid as precursor (Scheme 1).
All the intermediates and target mesogens are
characterized using FT-IR and
1
H and
13
C NMR
spectroscopy (representative spectra are shown).
The terminal alkoxy chains are varied from 2-16
(even series) and the mesophase characteristics like
melting, clearing temperatures and phase stability
is determined by optical polarizing microscope and
DSC. The transition enthalpy values further
confirm the mesophase identified by the
microscope. Despite lower phase stability, the
appearance of smectic polymorphism is an
interesting feature of the series. The structure-
property relationship with respect to core and
terminal group chain length are discussed.
164

NATIONAL SYMPOSIUM IN CHEMISTRY P 63
Mimicking Simultaneous and Selective Decoupling of Different
Heteronuclei and Determination of Relative Signs of Dipolar Couplings
Using Multiple Quantum Spin State Selection
Sankeerth Hebbar
#
and N Suryaprakash
*
#
Solid State and Structural Chemistry Unit and *NMR Research Centre,
Indian Institute of Science, Bangalore 560012.
The non-selective excitation of a homonuclear multiple quantum in a heteronuclear spin system does not
disturb the spin states of the heteronuclei resulting in the detection of single quantum transitions based on the spin
states of the heteronuclei. The cross section taken along the single quantum dimension thus mimics the decoupling
of heteronucleus. In addition, the spin state selected transitions are significantly lower in number compared to
normal one dimensional spectrum, but suffice for the precise determination of homonuclear couplings. When more
than two heteronuclei are involved, the technique can be extended for mimicking simultaneous decoupling of all the
heteronuclei. Furthermore, the detection of any heteronuclear multiple quantum results in the selective decoupling
of the passive heteronuclei. The methodology can thus be exploited for the analysis of the complex spectrum and
for the determination of the relative signs of the dipolar couplings. The results of the work on different isotopomers
of acetonitrile,
13
CH
3
13
CN,
13
CH
3
C
15
N, CH
3
13
C
15
N and
13
CH
3
13
C
15
N aligned in thermotropic liquid crystals, including
the theoretical description of the behaviour of the spins using polarization operators will be discussed.
165

P 64 NATIONAL SYMPOSIUM IN CHEMISTRY
Effect Of Various Additives On The Gel-To-Liquid- Crystalline Phase
Transition Temperature Of Dimethyldioctadecylammonium-Bromide
Vesicles
Moazzam Ali and Swapan. K. Saha*
Department of Chemistry, University of North Bengal, Siliguri 734 013
The effect of alkyltrimethylammonium bromides (Tetradecyltrimethyl-ammoniumbromide (TTAB),
Hexadecyltrimethylammoniumbromide CTAB and Octadecyltrimethylammonium-bromide OTAB) and
alkylpyridiniumhalides (Cetylpyridiniumbromide CPB and Cetylpyridiniumchloride CPC ) on the gel-to liquid
crystalline phase transition temperature (T
m
) of spontaneously formed vesicle dispersions of
dimethyldioctadecylammoniumbromide (DDOAB) have been examined using differential scanning calorimetry
(DSC). The alkyltrimethylammonium bromides, affected the T
m
in a complex manner, depending on the hydrocarbon
chain length. OTAB elevated the T
m
whereas TTAB and CTAB depressed the Tm of DDOAB vesicles. However, the
planar pyridinium heads of CPC and CPB, having similar tail length as that of CTAB, affected the T
m
only weakly,
although the decreasing tendency of T
m
is observable. In addition the shape of the main peak i.e. the gel-to-liquid
crystalline phase transition peak shows very little sign of peak broadening. It seems that the lateral attraction between
the DDOAB molecules of the bilayer is not reduced significantly by the penetration of the pyridinium moiety. The
perturbing effect of aromatic hydroxyl compounds viz.; 1-Naphthol, 2-Naphthol, 2,3-Dihydroxynaphthalene and
2,7- Dihydroxynaphthalene on the gel-to-liquid-crystalline phase transition temperature of the vesicle membrane
have also been studied using the same technique. A significant decrease in T
m
was observed with the addition of
these hydroxy compounds. However, for 2,7-dihydroxynaphthalene the Tm first decreases upto a certain concentration
and then increases. The present study reveals some aspects of the interaction of various additives with spontaneously
formed vesicles of DDOAB.
Gel to liquid crystalline transition
166

NATIONAL SYMPOSIUM IN CHEMISTRY P 65
Photo Catalytic Activity of Lanthanide (Ce, Pr AND Nd) Molybdates
Sudarshan Mahapatra
a
, Giridhar Madras*
b
and T.N. Guru Row
a
a
Solid State and Structural Chemistry Unit and
b
Department of Chemical Engineering,
Indian Institute of Science, Bangalore 560 012
Lanthanide (Ce, Pr, and Nd) molybdovanadates were synthesized by the solid-state method. These compounds
crystallize in the tetragonal space group I41/amd with a = b = 7.3750 (4) and c= 6.4867 (4) Å and Z = 4. The
crystal structure has been analyzed by FTIR, UV-visible spectroscopy, and powder X-ray diffraction. Particle sizes
are in the range of 300-400 nm as observed by scanning electron microscopy. Energy-dispersive X-ray analysis
suggests the formation of Ln
0.95
Mo
0.15
V
0.85
O
4
(Ln = Ce, Pr, and Nd) and the Rietveld refinements of the powder X-ray
data substantiate this observation. Thermal analysis of these solids shows stability of the phase up to 800° C. These
materials were investigated for photocatalytic activity by degrading different dyes such as methylene blue(MB),
orange G (OG), Rhodamine B (RB), Rhodamine Blue (RBL), Alizarine Red S (ARS) and Remazol brilliant blue
(RBBR) under solar and UV irradiation since they exhibited lower band gaps. The degradation rates for all the dyes
show enhancement as compared to the commercial titania catalyst, Degussa P-25, both in UV and sunlight. These
compounds degrade chlorinated phenols much faster than titania, which indicates selectivity toward chloro substitution.
Variation of the degradation rate of MB with initial concentration under solar radiation for Cerium molybdovanadate
and Degussa P-25 titania.
References:
1. Fuess, H.; Kallel, A. J. Solid State Chem. 1972, 5, 11.
2. Rice, C. E.; Robinson, W. R. Acta Crystallogr., Sect. B 1976, 32, 2232.
3. Chakoumakos, B. C.; Abraham, M. M.; Boatner, L. A. J. SolidState Chem. 1994, 109, 197.
167

P 56 NATIONAL SYMPOSIUM IN CHEMISTRY
Determination of Chloride in Liquid Detergent Using Ion-selective
Electrode with a Method of Standard Addition
Sangita D. Kumar, Ayushi, Niyoti Shenoy, and P.V.Ravindran
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085
.
Liquid detergent finds wide applications in cleaning of different instruments such as healthcare instruments,
electronic components and various reactor components etc. Cleaning surfaces may involve large variety of construction
materials viz. glass, metal, ceramic, plastic, cement and fiberglass. It is commonly used for leak detection on any
system where there is a pressure differential. It is for this type of application in reactors i.e. leak test of certain
facility that the presence of chloride in the liquid detergent becomes very crucial. The presence of chloride as
impurity affects the physical properties of the metal and accelerates the rate of corrosion in the system [1-3]. Hence,
the determination of chloride in the liquid detergent is very important.
The liquid detergent comprises of alkyl benzene sulfonate surfactant. It contains about 0.1 to 3 % of magnesium
salt. The magnesium salt helps in improved cleaning performance and better skinning properties. Magnesium chloride,
either anhydrous or hydrated (e.g., hexahydrate), is especially preferred in the formulation. The method contained in
ISO 457:1983 standard for the determination of chloride is based on the titrimetry method. The method is applicable
to detergents having chloride content equal to or greater than 0.1%. For the quantitative determination of chloride at
trace level a new accurate method has been developed using chloride ion-selective electrode. The method of standard
addition is frequently employed for samples of variable matrix; hence this was applied for the determination of
chloride in liquid detergent.
In the method of standard addition to sample, the following equation was applied
C
0
= C
s
/ 10
DE1/S
( 1+V
0
/ V
1
) – V
0
/V
1
(1)
Where S is the electrode calibration slope, V
0
and V
1
are the volumes; C
0
and C
s
are the concentrations of the
sample and the standard respectively. DE
1
= E
1
– E
0
where E
1
and E
0
are the potentials measured for the sample with
and without standard addition. For this method, the slope of the electrode response curve must be known and should
be linear, interfering species must be absent and, finally, the liquid junction potential between the reference electrode
and the solution must not change.
Samples of liquid detergent were obtained from local market (Bright liquid detergent). The sample solution (1
mL) was taken in a polyethylene beaker. To this, 5 mL of 0.1 M KNO
3
was added and final volume was made up to
10 mL with deionised water. The KNO
3
solution is added to adjust total ionic strength of different samples. The
potential of this solution was measured with an ion meter (Metrohm, Switzerland) using chloride selective electrode
(Orion) and Ag/AgCl reference electrode. For standard addition appropriate volume of chloride standard solution
(1 mg L
-1
) was added in steps in the range 0.1 – 1 mL. The potential was measured after each standard addition. The
concentration of the chloride ion was calculated by using the equation (1). The results obtained for two liquid
detergents samples are presented in Table 1. The limit of detection for the determination of chloride is 10 mg mL
-1
and the relative standard deviation was 5 % for the overall method.
Attempt was made to validate the method by measuring the chloride concentration in the samples by turbidimetry
and ion chromatography (IC) method. Both these measurements were not successful because of serious interference
from the matrix elements in turbidimetry and column contamination in IC methods. Hence the method has been
validated by standard addition recovery studies.
A simple, rapid and accurate method has been developed for the determination of chloride in liquid detergent
solutions. It makes use of readily available chemicals and equipment.
References:
1. H.H. Unlig, Corrosion and corrosion control, John Wiley and Sons, New York, 1971.
2. Process industries corrosion,. NACE, Texas, 1975.
3. NACE Basic Corrosion Course, NACE, Texas, 1975.
158

NATIONAL SYMPOSIUM IN CHEMISTRY P 57
Tunable optical and electronic property of Oligo(phenyleneethynylenes)
Reji Thomas and G.U. Kulkarni
Chemistry and Physics of Materials Unit and DST Unit on Nanoscience, Jawaharlal Nehru
Center for Advanced Scientific Research, Jakkur (P.O.) Bangalore- 560064
Oligo(phenyleneethynylenes) (OPE) are a class of molecules, which are well known for their interesting electronic
and photophysical properties.
1
The greater interest in these molecules is attributed to their tunable property by introducing
various functional groups and inducing geometric changes. Among various functionalized OPEs and related polymers
the alkoxy substituted phenylethynylenes are well studied for their interesting photo physical properties such as optical
absorption and emission.
1b
Recent literature reports various studies on change in the fluorescence behavior of these
molecules on suitable substitution of the phenyleneethyneylene backbone.
3
There are similar studies on the electronic
properties of these molecules, and these studies confirm that the rearrangement of electronic states of conjugated p-
backbone on substitution and conformational changes.
4
In order to understand the effect non-conjugated side chain in the
transport characteristics of these molecules, we have carried out combined X-ray crystallographic and photophysical
studies alkoxy substituted phenylene ethynylene molecules with varying alkoxy chain length. These molecules show
high emission properties both in solution and solid state with large blue shift in the film. Interestingly, on varying the
alkoxy side chain length of the alkoxy substitution, the molecules exhibit variation in planarity and in turn a systematic
variation in molecular transmission.
Reference
1. Reed, M. A.; Zhou, C.; Muller, C. J.; Burgin, T. P.; Tour, J. M. Science 1997, 278, 252 – 254. (b) Kim, J.; Swager, T. M.,
Nature, 2001, 411, 1030-1034.
2. Chen, J.; Wang, W.; Reed, M. A.; Rawlett, A. M.; Price, D. W.; Tour J. M., Appl. Phys. Lett. 2000, 77, 1224-1226.
3. Kim, J., Pure Appl. Chem., 2002, 74, 2031–2044.
159

P 58 NATIONAL SYMPOSIUM IN CHEMISTRY
Adsorption kinetics of alkanethiols on Au nanocrystals in a 2D lattice
using optical absorption spectroscopy
Ved Varun Agrawal, G. U. Kulkarni and C. N. R. Rao
Chemistry and Physics of Materials Unit and DST Unit on Nanoscience, Jawaharlal Nehru
Center for Advanced Scientific Research, Jakkur (P.O.) Bangalore- 560064
We have investigated how the optical absorption property of a 2D lattice of metal nanocrystals can be
tuned with alkane thiols of different chain lengths. This 2D lattice is a tightly packed assembly of gold
nanocrystals obtained via a self assembly process at the liquid-liquid interface[1, 2]. The absorption band is
situated at 700 nm for the pristine lattice which gets blue shifted upon adsorption of alkane thiols, the
magnitude of the shift being proportional to the chain length. The disordered nanocrystals thus created (
l
max,
530 m) are in equilibrium with the ordered nanocrystals in the lattice (l
max,
700 m) as indicated by an isosbestic point
around 600 nm. The rate of interaction of thiols with the Au nanocrystal lattice decreases with decreasing chain
length. The long chain thiols disintegrate or disorder the lattice more effectively, as evidenced by the increased
population of the thiol-capped Au nanocrystals in the solution. The effect of an alkanethiol is specific and the effects
with long and short chains are reversible. The changes in the Au plasmon band due interparticle separation has been
satisfactorily modeled on the basis of the Maxwell-Garnett formalism [3].
References
[1] V.V. Agrawal, G.U. Kulkarni, C.N.R. Rao, J. Phys. Chem. B 109 (2005) 7300.
[2] C.N.R. Rao, G.U. Kulkarni, V.V. Agrawal, U.K. Gautam, M. Ghosh, U. Tumkurkar, J. Colloid Interface Sci. 289 (2005)
305.
[3] J.C.M. Garnett, Philosophical transaction of the royal society of london, series A 203 (1904) 385.
160

NATIONAL SYMPOSIUM IN CHEMISTRY P 59
Exfoliated Graphite Oxide - Based Assemblies
for Amperometric Sensing
G. K. Ramesha and S. Sampath*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore 560 012
Exfoliated Graphite Oxide (EGO) is a layered material, lighter than graphite, both in colour and in
density. It consists of oxidised graphite sheets with hydroxyl and epoxy functional groups in the basal plane
and carboxyl and carbonyl functional groups at the edges. The functional groups make EGO hydrophilic and
water molecules can readily intercalate into the interlayer galleries. Hence, EGO is regarded as graphite-type
intercalation compound with covalently bound oxygen and non-covalently bound water between the carbon
layers. The presence of a large amount of functional groups leads to the stabilization of negatively charged
EGO as a colloid in a wide pH range of 2-11.
In the present studies, EGO is prepared by chemical oxidation of exfoliated graphite (prepared by thermal
exfoliation of bisulphate ion intercalated graphite) and characterized using spectroscopic and electrochemical
techniques. Thin film of EGO on glassy carbon electrode (GC) was formed by evaporation technique using
colloidal EGO deposited on the GC surface. The EGO film is subsequently used to detect Pb(II) in aqueous
medium. The detection limit is found to be picomolar and two linear calibration ranges are obtained in 1pM
to 0.1 µM and 10 µM to 10 mM.
In the second part of the studies, electrostatic layer-by-layer assembly of EGO and redox protein
(haemoglobin) is formed on a gold surface and their electrochemical properties are studied. An amperometric
sensor is developed and the system is further applied to the electrocatalytic reduction of hydrogen peroxide.
Reference:
G.K. Ramesha and S. Sampath, Electroanalysis, 2007, 19(23), 2472.
161

P 60 NATIONAL SYMPOSIUM IN CHEMISTRY
162
Application of Majority Rule in the Self-assembly of Aminoacid
Functionalized Oligo(p-phenylenevinylene)s
S. Santhosh Babu, Vakayil K. Praveen and Ayyappanpillai Ajayaghosh*
Photosciences & Photonics Group, Chemical Sciences & Technology Division
National Institute for Interdisciplinary Science and Technology (NIIST)
Trivandrum, India-695019.
Manifestation of molecular chirality into supramolecular helicity in synthetic molecules, leading to a
preferred handedness is a challenging task[1].

The “majority rule” approach reported by Green et al. have been
used for chirality amplification in supramolecular assemblies, using a slight exess of one enantiomer that leads to a
strong bias toward the helicity preferred by the enantiomer that is present in majority[2]. Oligo(p-phenylenevinylene)s
(OPVs) are known to form helical assemblies and gels in nonpolar hydrocarbon solvents[3]. Herein we explore the
possibilities of amino acid moieties as chiral motifs for the creation of helical assemblies of OPVs leading to the
formation of gels even in moderately polar solvents such as chloroform and toluene. Addition of a very small
concentration of the chiral molecule to the racemes mixture resulted in induction and amplification of chirality’s in
the gel state. The enantiomeric excess and co-operating units will therefore act together to favour the helical
sense preferred by the configuration of the majority and thereby making the expression of the chirality of a particular
enantiomer from a racemic mixture. SEM and TEM studies gave further insight into the morphological features of
these chiral OPV self assemblies. The details of these studies will be presented.
References
1. Palmans, A. R. A, Meijer, E. W. Angew. Chem., Int. Ed. 2007, 46,
2. Green, M. M.; Park, J.-W.; Sato, T.; Teramoto, A.; Lifson, S.; Selinger, R. L. B.; Selinger, J. V. Angew. Chem., Int.
Ed. 1999, 38, 3138.
3. Ajayaghosh, A.; Varghese, R.; George, S. J.; Vijayakumar, C. Angew. Chem., Int. Ed. 2006, 45, 1141.
DL
DL

P 76 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis And Characterization of Heterogenised Chiral Schiff Base
ligands with SBA-15, MCM-41, KIT-6 and its Application on the
Enantioselective Reduction Prochiral Ketones
N. Ananthi ,U. Bala Krishnan, Dr. S. Velmathi*
Department of Chemistry, National Institute of Technology, Tiruchirappalli-620 015
The novel chiral Ligands from Schiff bases of various amino acids such as L valine and L-proline amino acids
with aldehydes, and heterogenised using various mesoporous materials like SBA-15, MCM-41, and KIT-6. These
chiral Ligands were synthesized by the reported procedure[1] and confirmed its structures using FT IR,
1
H NMR,
and
13
C

NMR spectroscopic methods. These catalysts were then anchored with various mesoporous materials
mentioned above using 3-chloropropyltriethoxysilane as a reactive surface modifier [2,3]. The immobilization of
these chiral Ligands was confirmed by SEM, XRD, EDAX and Nitrogen adsorption-desorbtion methods[4]. These
newly synthesized Ligands used as a catalyst for the reduction of various prochiral ketones, and the enantioselectivity
was determined using chiral HPLC and Digital polarimeter. The ee(75-80%) determined shows that the catalyst
immobilized in silica with larger pore diameters was found to be more active compare to homogeneous catalyst [5].
The catalysts were reusable with neither significant drop in enantioselectivity nor loss of mesostructures and recycled
several times by simple filtration.
References:
1. S.Velmathi, S.Narasimhan. Tetrahedron Lett. 2001, 42,719-721.
2. Qihua Yang, Guiru Zhu, Hong Wang, Journal of Catalysis, Volume 239, Issue 1, 1 April 2006, Pages 65-73
3. R.I.Kureshy, N.H.Khan, Journal of molecular catalysis,
178

NATIONAL SYMPOSIUM IN CHEMISTRY P 77
Artemisinin and Synthetic Derivatives: a DFT Based Comparison
Kalyan Kr. Hazarika
1
, Ramesh Ch. Deka
2
, Nabin Ch. Barua
*

1
Department of Molecular Biology & Biotechnology,
2
Department of Chemical Sciences, Tezpur University, Napaam-784028, Assam
*
Natural Products Chemistry Division, Regional Research Laboratory (CSIR)
Jorhat-785006, Assam
Malaria is one of the most worrying infectious diseases currently affecting the human race. Forty percent of the
world’s population is at risk of malaria infection causing around 300 to 500 million illnesses and up to 3 million
deaths each year [1]. The worldwide malaria situation is serious since malarial parasites have developed resistance
to the most common drugs. However, artemisinin, a sesquiterpene endoperoxide, isolated from a Chinese medicinal
herb is found to be a potent antimalarial drug against the resistant strains of Plasmodium falciparum. But, still there
is a need for better one and so numerous derivatives of this promising molecule are being synthesised to reach the
goal [2]. Theoretical prediction prior to synthesis may be of great help in minimizing the cost and time factors while
developing a better antimalarial drug.
Figure: Artemisinin and derivatives
A theoretical comparison of artemisinin with few of its synthetic derivatives viz. dihydroartemisinin, artemether,
arteether, artesunate and artelinate is reported. Geometries of the molecules are optimized by DMol3 software at an
SGI-Altix 350 machine with various combinations of basis set and functional using Mulliken and Hirshfeld population
analyses. Density functional theory (DFT) [3] based reactivity descriptors such as global softness (S), philicity (w),
Fukui function (f
+
& f
-
) and relative nucloephilicity/ electrophilicity, calculated at the optimized geometries are used
for searching and comparing the functionally important part of the molecules. The results obtained are in excellent
agreement with the experimental reports.
References:
[1]. World Health Organization. The World Health Report 1999.
179

P 78 NATIONAL SYMPOSIUM IN CHEMISTRY
Structure and Electronic Properties of DNA Base-pairs and
Modified DNA
Sairam S. Mallajosyula, Swapan K. Pati*
Theoretical Sciences Unit, Jawaharlal Nehru Center for Advanced Scientific Research
Jakkur, Bangalore - 560064
We have investigated the effect of metal electrodes and metal clusters on electronic properties of DNA bases
and base-pairs. We find that Nucleobases trapped within two gold metals on either side undergo expansion. This
primarily arises due to the concomitant increase in all the bond lengths in molecules. Such expansion of the molecules
can be qualitatively understood on the basis of classical harmonic potentials in the bonds and loss of aromaticity in
the rings, resulting in charge redistribution in the system. As a very important consequence of this, the nature of H-
bonds potential change substantially within these electrodes. These hydrogen bonds have a single-well potential
energy profile (of the type N…H…O and N…H…N) instead of double-well potentials (like N-H…O or N-H…N/
N…H-N types) [1]. With such an understanding, we tried to capture the potential use the DNA bases for reversible
H-bonding under ambient conditions. Protonation of DNA basepairs is a reversible phenomenon that can be controlled
by tuning the pH of the system. We find that, under mild acidic pH conditions, the A:T basepair shows excellent
nano-switch rectification behavior that is, however, absent in the G:C basepair. We also consider the noncanonical
A:A basepair and find that it can be used as efficient pH dependent molecular switch. The switching action in the
A:A basepair can be understood in the light of ð- ð interactions, which lead to efficient delocalization over the entire
basepair [2].
We have also studied the alignment of magnetic ions, Cu
2+
and Mn
2+
, along a modified B-DNA helix. We find
that doping with magnetic ions induces conducting states in the gap region of natural DNA. These magnetic ions are
found to interact ferromagnetically along the DNA helix. Calculations of optical conductivity about the helical axis
suggest that the origin of magnetic characteristics depend crucially on the metal ions; the Cu(Mn)-DNA favors in-
plane(out-of-plane)
s (?)-like delocalization over the base pairs. Such an alignment of magnetic ions offers promising
perspectives for creating low-dimensional polarized spin channel within the DNA helix [3]. Similar alignment
within stacking backbone (with V atoms) can also be used for creating half-metallic modified one-dimensional
single-strand DNA motif for advanced Spintronics applications
References:
[1] Mohan P. J., Ayan Datta, Sairam S.M. and Swapan K. Pati, J. Phys. Chem. B 110, 18661 (2006).
[2] Sairam S. Mallajosyula and Swapan K. Pati, J. Phys. Chem. B (Letters) 111 (40), 11614 (2007).
[3] Sairam S. Mallajosyula, Swapan K. Pati, Phys. Rev. Lett. 98, 136601 (2007).
180

NATIONAL SYMPOSIUM IN CHEMISTRY P 79
Universal Variation of Dielectric Behaviour Induced by Nanoscale Dopants
in Dielectric Oxides: Evidence of Fractal Geometry
Vishnu Shanker
a
, Pankaj Rastogi
a
, Rama Kant
b
and Ashok K. Ganguli
a
*
a
Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas,
New Delhi, 110016, India.
b
Department of Chemistry, University of Delhi, Delhi, 110007, India.
Apart from the bulk (micron-sized) materials or nanomaterials, composites having matrix and filler with
physically or chemically different properties have become the most challenging areas of current scientific and
technological research. In order to tune the dielectric properties we decided to vary the range of interfaces on
addition of nanoscale particles to micron-sized particles of the same composition “nµ-composites”, to vary the
interfacial density. Since the microstructure is influenced by the nature and extent of sinteribility we have looked at
the microscopic features carefully along with detailed thermal studies and surface area analysis [1]. Our studies
show that addition of nanoparticles to micron-sized particles leads to fractal geometry formation [2], which result in
optimal dielectric properties at certain compositions. We have observed enhancement (decrease) of the dielectric
constant (dielectric loss) by nearly 3 times of the bulk value at an optimum concentration of micron and nano sized
particles [3]. This interesting variation of the dielectric constant with increase in the amount of nanoparticles in the
nµ-composites is observed in many classes of titanates, zirconates, niobates and tantalates.
References:
[1] V. Shanker Ph.D thesis, IIT Delhi (2007).
[2] V. Shanker, Rama Kant and A. K. Ganguli (manuscript under preparation).
[3] Shanker, V. ; Ahmad, T.; H. Ip and A. K. Ganguli, J. Mater. Res. 2006, 21, 816.
181

P 80 NATIONAL SYMPOSIUM IN CHEMISTRY
Influence of Surface Properties on Controlled Drug Relesae from
Mesoporous Oxide Drug Delivery Systems
Shyamal Kumar Das and Aninda J. Bhattacharyya*
Solid State and Structural Chemistry Unit,
Indian Institute of Science, Bangalore 560012
While considerable efforts are being made in the discovery of new drugs for treatment of several complex
human ailments, controlled delivery of such drugs has also received almost similar attention. Out of several
drug delivery systems (DDS) proposed in literature, systems based on mesoporous oxide (M. Vallet Regi et al
[1]) materials (such as SiO
2
, Al
2
O
3
, TiO
2
) appear to be very promising for the sustained release of drugs at specific
targets. Mesoporous materials several attractive features, such as large surface area (300-1000 m
2
g
-1
), tunable pore
sizes (2-50 nm) and volumes (~ 1 cm
3
g
-1
), easier manipulation of surface properties and higher stability and
biocompatibility. Among the various parameters of a mesoporous oxide material which influences drug release,
surface acidity/basicity of the functional groups play a critical role. In this contribution we report a systematic study
(S.K. Das et al [2]) of the dependence of drug loading and its rate of release on the surface functional groups of
mesoporous alumina (abbreviated as MPA). MPA (BET surface area ~ 155 m
2
g
-1
; pore size ~ 5.8 nm) with varying
degree of acidity and basicity were chosen as the DDS for the study. Contrary to the oft-employed methods proposed
in literature, an alternative procedure was employed to impregnate MPA with drug ibuprofen (IBU), a non steroidal
anti-inflammatory drug (NSAID). Our method of drug incorporation in MPA showed a significantly higher loading
compared to proposed procedures in literature. The oxide-drug composites were characterized by using Fourier
transform infrared (FTIR) spectroscopy, x-ray diffraction (XRD), thermogravimetric analysis (TGA) and N
2
adsorption/desorption. It was observed that the amount of drug loading is highest in case of acidic-MPA (26% of
MPA-IBU w/w) in comparison to basic-MPA (22% of MPA-IBU w/w). Further, in vitro drug release was carried out
in simulated body fluid (SBF) at room temperature with oxides varying in surface properties. Interestingly, basic-
MPA exhibited faster IBU release compared to acidic-MPA. In case of basic-MPA 100% IBU release took place in
45 hours whereas in the time period, only 50% was released from acidic-MPA. Rate of IBU release from composites
having a requisite mixture of basic and acidic MPA lay between the slower acidic MPA and faster basic MPA release
rates. This information would suitably aid in tailoring controlled drug delivery systems. Release kinetics was also
studied as a function of SBF Ph. The release kinetics for IBU from an acidic to a basic medium changed dramatically
resembling a switching mechanism. Implications of this observation would benefit in the design of responsive DDS
for specific purposes.
References
[1] Vallet Regi , M. ; Ramila, A.; Del Real, R. P.; Perez-Pariente, J. Chem. Mater. 2001, 13, 308.
[2] Shyamal K. Das and Aninda J. Bhattacharyya, manuscript under preparation.
182

NATIONAL SYMPOSIUM IN CHEMISTRY P 81
Intersystem Crossing Effects in the O + Ethylene Reaction Dynamics
Biswajit Maiti
Department of Chemistry, Faculty of Science,
Banaras Hindu University, Varanasi, 221005, India
Spin-orbit coupling (SOC) induced intersystem crossing (ISC) has long been believed to play a crucial
role in determining the product distributions in the O(
3
P) + C
2
H
4
reaction. In this paper we will be presenting the
first nonadiabatic dynamics study of the title reaction at two center-of-mass collision energies: 0.56 Ev, which is
barely above the H-atom abstraction barrier on the triplet surface, and 3.0 Ev which is in the hyperthermal regime.
The calculations were performed using a quasiclassical trajectory surface hopping (TSH) method with the potential
energy surface generated on the fly at the unrestricted B3LYP/6-31G(d, p) level of theory. To simplify our calculations,
nonadiabatic transitions were only considered when the singlet surface intersects the triplet surface. At the crossing
points, Landau-Zener transition probabilities were computed assuming a fixed spin-orbit coupling parameter which
was taken to be 70 cm
-1
in most calculations. Comparison with a recent crossed molecular beam experiment at 0.56
Ev collision energy shows qualitative agreement as to the primary product branching ratios, with the CH
3
+ CHO
and H + CH
2
CHO channels accounting for over 70% of total product formation. However, our direct dynamics TSH
calculations overestimate ISC so that the total triplet/singlet ratio is 25:75, compared to the observed 43:57. Smaller
values of SOC reduce ISC resulting in better agreement with the experimental product relative yields; we demonstrate
that these smaller SOC values are close to being consistent with estimates based on CASSCF calculations. As the
collision energy increases, ISC becomes much less important and at 3.0 Ev, the triplet to singlet branching ratio is
71:29. As a result, the triplet products CH
2
+ CH
2
O, H + CH
2
CHO and OH + C
2
H
3
dominate over the singlet
products CH
3
+ CHO, H
2
+ CH
2
CO, etc.
183

P 82 NATIONAL SYMPOSIUM IN CHEMISTRY
The possibility of Using Locally Available Garware Polyester Film (GPF)
as UV dosimeter
Chhavi Agarwal, P.C.Kalsi*
Radiochemistry Division,
Bhabha Atomic Research Centre,
Trombay-400085.
Polymers are becoming very popular in the field of radiation dose measurements [1] because of their
low cost. The possibility of using CR-39 polymer as a UV dosimeter has been recently studied by Shweikani et
al [2]. The lower LET (Linear Energy Transfer) radiations such as UV, X-rays, electrons and gamma on interacting
with polymers produce the bulk changes in the form of many broken molecular chains, leading to change in
bulk-etch rate and optical density. These changes can be used for the evaluation of radiation doses. In the
present investigation, the effects of ultraviolet radiation produced by a lamp at 254 nm on locally available
Garware Polyester Film (GPF) were studied. This was done by using two techniques: Bulk -etch technique and
UV-Visible spectrophotometry. GPF sheets were exposed to UV light (
» 254 nm) for different times (0.5, 1, 2,
4 and 8 hrs) at a fixed distance. The UV exposed detectors were then subjected to chemical etching using 6N
NaOH as the etchant at 60
o
C for ~5 hrs for bulk-etch rate (V
B
) measurements. Bulk-etch rate was found to
increase with increase in UV exposure time. A linear relation was seen between the V
B
and UV exposure time upto
4 hrs (Figure 1). In the case of UV-Visible spectrometry also, a linear relation was seen between the change in
absorbance due to UV and the UV exposure time upto 4 hrs at a characteristic wavelength of 316 nm (Figure 2).
From these studies, it can be concluded that locally available GPF can be used as a UV dosimeter. To see the
changes induced by UV irradiation on GPF film, the bulk-etch rates were also determined at three different
temperatures and the activation energy values for bulk etching were calculated by using Arrhenius equation. The
activation energy values for bulk-etching were found to decrease with increase in UV irradiation time. The value of
activation energy for 8 hrs UV irradiated sample was found to be 31.3 kJ/mole as compared to 49.9 kJ/mole for the
unirradiated sample. This indicates that scission of the detector is taking place with UV irradiation.
References
[1] Gopalini, D. ; Jodha, A.S.; Sarawanan, S.; Kumar, D.; Kumar, S. in : Proc. 12
th
National Symposium on Solid State
Nuclear Track Detectors, Swan Printing Press, Jalandhar (2001) p 151.
[2] Shweikani, R. ; Raja, G. ; Sawaf, A.A. Radiation Measurements 2002, 35, 281.
184

NATIONAL SYMPOSIUM IN CHEMISTRY P 83
Spider Web as Environmental Assessment Indicator of Carbon Nanotubes
in Airborne Suspended Black Particulate Matter
Sumit Kumar Sonkar, Sabyasachi Sarkar*
Department of Chemistry,
Indian Institute of Technology Kanpur, Kanpur, India.
Since the discovery of carbon nanotubes in 1991 several facets of its utility have been predicted and a few are
already showing result. The other part like the environmental problems caused by the nanoparticles have not been
addressed. Recently the issue of global warming has been implicated mainly due to the green house effect. However
the second contribution to the global warming is black carbon particulate present in the aerosols. In this work we
want to demonstrate that the black particles which is popularly called black carbon associated with aerosols
predominantly contains carbon nanotubes (CNT). Inside a room we generate these black particulates by day to day
activities and outside the house excessive fossil fuel burning contributes to this at the maximum level. Using spider
web (Fig.1a-b) as particulate matter indicator we have accessed these webs and found that the airborne particles do
contain carbon nanotubes (Fig.1 c-f), and it is speculated that exposure to combustion-generated CNT in fine
Particulates play a significant role in global warming and also in air pollution-related cardiopulmonary diseases.
Therefore, CNTs from combustion sources in the environment could have adverse effects on human health along
with its contribution to respirable diseases when inhaled inside the body.
Fig 1. (a) Indian domestic spider (b) Spider with its web
(c) SEM (d) TEM (e) AFM images of CNT (f) RAMAN Spectrum.
(a) (b) (c)
(d) (e) (f)
185

P 84 NATIONAL SYMPOSIUM IN CHEMISTRY
Topological and Thermodynamical studies of ternary mixtures: Molar
excess volumes and Excess isentropic compressibilities
J.S. Yadav, Dimple , K.C. Singh, V.K. Sharma *
Department of Chemistry, Maharshi Dayanand University, Rohtak – 124001, INDIA
Molar excess Volumes, V
E
ijk
and speeds of sound , U
ijk
of o- toluidine (i) + benzene (j) + toluene (j) or o- or p-
xylene (k) ternary mixture have been measured as a function of composition at 308.15 K. The observed speeds of
sound data have been utilized to determine excess isentropic compressiblities,
of ternary (i + j + k) mixtures.
Moelwyn- Huggins concept [M.L.Huggins, Polymer 12, 389 (1971)] between the surfaces of the constituents of
binary mixtures has been extended for ternary mixtures (using the concept of connectivity parameter of third degree
of a molecule, which in turn depends on its topology) to obtain an expression that describes well the observed
V
E
ijk
and
data. The observed data have also analyzed in terms of Flory theory.
186

NATIONAL SYMPOSIUM IN CHEMISTRY P 85
Modification of Photochemical Behavior of trans-Strylpyridines Inside
Cyclodextrin Cavities
Palaniswamy Suresh, Ismail Abulkalam Azath and Kasi Pitchumani*
School of Chemistry, Madurai Kamaraj University, Madurai-625021
Cyclodextrins (CDs) are cyclic oligomers consisting of six, seven or eight D-(+)-glucose units (a-, b- and g-
CDs respectively) with a hydrophobic inner cavity and a hydrophilic outside and are known to form inclusion
complexes with a variety of organic guests. The inclusion phenomenon in CDs enables guest molecules to exhibit
different and some times new properties from those of free molecules. In particular, the photochemical properties of
a number of substrates are sensitive to the CD microenvironment. In this context, the modified polarity inside the
cavities and the imposed steric constraints are among the main factors governing the photo reactivity of CD inclusion
complexes[1].
Isomerisation and cyclization are the major photochemical reaction of styrylpyridines in isotropic media[2].
Photo physical behavior of various styrylpyridines has also been studied in isotropic media[3]. Baring a recent
reports photochemical behavior of styrylpyridine inside cyclodextrin cavity has scarily been reported In the present
study, photochemical behavior of various styrylpyridines and its methoxy substituted derivatives are studied inside
cyclodextrin cavities. Modifications in photochemical behavior of styrylpyridines are observed inside cyclodextrin
cavities. The change in the photochemical behaviors inside the cyclodextrin cavities are rationalized by mode of
inclusion and proposing a suitable mechanism.
References
1. V. Ramamurthy, Photochemistry in Organized and Constrained Media V,ed. V. Ramamurthy,
VCH Publishers, Cambridge, UK, 1991.
2. G. Galiazzo, P. Bortolus and G. Cauzo, Tetrahedron Lett., 1966, 31, 3717.
3. G. Bartocci, U. Mazzucato and F. Masetti, J. Phys. Chem., 1980,84, 847
187

P 86 NATIONAL SYMPOSIUM IN CHEMISTRY
Nanocrystalline Assisted Photoreduction of Co
III
(pn)
2
LCl
2+
in Water/1,4-
Dioxane Mixtures
L. Devaraj Stephen and K. Anbalagan*
Department of Chemistry, Pondicherry University, Puducherry 605 014, India
Nanocrystalline titanium dioxide assisted reduction of Co
III
(pn)
2
LCl
2+
(L = RC
6
H
4
NH
2
; R = m-OCH
3
, p-F, H, m-
CH
3
, p-CH
3
, p-OC
2
H
5
and p-OCH
3
) in a series of water/1,4-dioxane (Diox) mixtures (water/Diox = 100/0, 95/5, 90/
10, 85/15, 80/20, 75/25, and 70/30) was monitored spectrally. Irradiation of nm-TiO
2
particles with l
max
= 254 nm
flux leads to generation of Co
I
species. In neat water the photo reduction yield (F
Co(II)
) is low, however, addition of
1,4 - dioxane causes a measurable rise in F
Co(II)
. That is, in nm-TiO
2
+ Co
II
+ hn ® Co
I
, (F
Co(II)
is low, when x
2
=
0.0109 but it is high when x
2
= 0.0831, where x
2
is mole fraction of Diox). SEM images illustrate the growth of
particle size upon irradiation and the changes in photo efficiency yields are interpreted in terms of correlation model
expressions containing solvent empirical parameters. The particle size increases and the porosity get decreases.
EDAX illustrate the amount of Co(III) present on the surface of the TiO
2
before and after irradiation. The binding
property of Co(III) with TiO
2
surface was characterized using TEM.
188

NATIONAL SYMPOSIUM IN CHEMISTRY P 87
Statistical Theory for Combinatorial Protein Design by Energy
Landscaping
Arnab Bhattacherjee and Parbati Biswas*
Department of Chemistry, University of Delhi, Delhi-110007
Developing a predictive understanding of protein folding requires quantitative measures of sequence-structure
compatibility. A foldability criterion accounts for this compatibility and is used in both structure prediction and
protein design. A self-consistent theory is presented here which is used to estimate the number and composition of
sequences consistent with a generalized foldability criterion. This generalized foldability criterion characterizes the
properties of sequences by quantifying the energetic separation of the target state from the ensemble of unfolded
states and the fluctuations of the energies in the unfolded ensemble The theory yields site-specific pair correlated
monomer probabilities which is useful in exploring correlated mutations. The results of a simple lattice model are
compared with the results of exact enumeration. The theory may provide a quantitative framework for design and
interpretation of combinatorial experiments involving proteins, where a library of amino acid sequences is searched
for sequences that fold to a desired structure.
References
[1] Biswas, P: Zou, J. ; Saven, J.G. J. Chem. Phys. 2005, 123, 154908.
[2] Zou, J. ; Saven, J.G. J. Mol. Biol. 2000, 296, 281.
[3] Klimov, D.K.; Thirumalai, D. J. Chem. Phys. 1998, 109, 4119.
189

P 88 NATIONAL SYMPOSIUM IN CHEMISTRY
Potentiometric Sensor for Arsenate
Abhinaba Banerjee
1
, Abhishek Chatterjee
1
, Priyabrata Pal
2
, Priyabrata Sarkar
2*
1. Department of Chemical Engineering, Jadavpur University,
188, Raja S.C. Mallick Road, Kolkata-700 032
2. Department of Polymer Science and Technology, University of Calcutta
92 A.P.C. Road, Kolkata- 700009
Arsenic is known as ‘silent killer’. Consumption of arsenic contaminated water can cause skin melanosis, liver
and kidney problems, gangrene, cancer etc. Because of the negative health effects of arsenic, World Health
Organization (WHO) has established a maximum contamination level of 10 parts per billion (ppb) in drinking water.
Nowadays a variety of techniques are available to detect arsenic in ppb level, but these methods require expensive
instrumentation, highly skilled personnel and cannot be employed for on-site analysis. More over most of these
methods are not suitable for detection below 10 ppb. We have developed potentiometric sensor for arsenic that
utilizes a complexation reaction (Figure 1) between three molecules of Catechol and one molecule of Arsenate (Pal
et.al. [1]). The change in concentration of arsenate due to this complexation reaction, was monitored potentiometrically.
The sensor could estimate arsenic as low as a few ppb (Figure 2).
References:
(1) Pal, A.; Jana, N.R.; Bandopadhyay, T.K.; Pal, M.; T.S. Anal.Commun. 1996, 33, 315
Complexation of Arsenate with Catechol Fig 2.
Calibration curve for Arsenate
190

NATIONAL SYMPOSIUM IN CHEMISTRY P 89
V
2
O
5
as a new promising catalytic activator for Al-Zn sacrificial anodes
K.K. Binoj, M. Ajeesh, S.M.A.Shibli*
Department of chemistry, University of Kerala,
Kariavattom Campus, Thiruvananthapuram, Kerala-695 581, India.
Aluminum alloy sacrificial anodes are preferentially selected for cathodic protection of steel objects due to
their high current capacity, low specific weight, high thermal and electrical conductivity and nominal cost.
Conventionally a small amount of zinc (~5 %) is added to aluminum to prevent the formation of passive Al
2
O
3
film
on the anode surface. The major draw back of Al-Zn alloy sacrificial anodes is the noncolumbic corrosion loss and
low galvanic efficiency. Incorporation of metal oxides in the interior of the alloy may refine the grains and suppressing
the grain boundary corrosion that results in improvement of the anode performance. In the present study vanadium
pentoxide (V
2
O
5
), one of the efficient catalysts in many electro chemical reactions was explode as an effective
activator for Al-Zn alloy sacrificial anodes. The metallurgical suture of the anode was characterized by optimizing
the casting parameters. The catalytic effect of V
2
O
5
in the interior layer of the anode was characterized by different
electrochemical techniques. The anode incorporated with optimum quantity of

V
2
O
5
(0.5 %) exhibited excellent
galvanic performance under different experimental conditions in 3 %

NaCl solution when they were indented to
protect steel. There was a significant reduction in pitting, high and steady negative potential, very low polarization
and high galvanic efficiency. The promising anodes were cost effective also.
191

P 90 NATIONAL SYMPOSIUM IN CHEMISTRY
Damping of Electronic Excited States Near Nanoscopic Systems
R. S. Swathi and K. L. Sebastian*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore, 560 012.
Fluorescence Resonance Energy Transfer (FRET) is an interesting photo-physical process [1] that involves
transfer of excitation energy from donor to acceptor in a non-radiative fashion. It has been extensively used in
biology as a spectroscopic ruler to understand the conformational dynamics of biopolymers in the 10-100Å range.
The rate of non-radiative damping of dye molecules near quenchers like other dye molecules is found to vary as
R
-6
where R is the distance between the donor and the acceptor. Recently, there has been tremendous interest towards
using nanoscopic materials like nanoparticles, nanotubes etc. as energy acceptors. There have been reports of
nanoparticle surface energy transfer (NSET) [2] between fluorescein and 1.4 nm diameter gold nanoparticle, both of
which are connected by a DNA as a bridge. They observe an R
-4
dependence of the rate on the distance, which is
quite useful because it more than doubles the range of distances that could be measured using conventional FRET.
There have also been attempts to explain the R
-4
dependence for the case of nanoparticle [3]. We have done a
detailed calculation of the rate of energy transfer from fluorescein to a 1.4 nm gold nanoparticle taking the electron-
hole pair excitations as well as the plasmonic excitations explicitly into account.
Nanotubes have also been found to be efficient quenchers for the electronic excited states of molecules like
pyrene . Interestingly, to the best of our knowledge, there are no reports of distance dependence of the rates of such
processes, either experimentally or theoretically. A nanotube can be imagined to be a rolled up sheet of a single layer
of graphite, graphene. The starting point for any theoretical investigation of the nanotubes is graphene. In view of
this fact and the recent experimental advances in graphene, we have studied the distance dependence of the rate of
damping of molecular electronic excited states near graphene. This would provide a starting point for the theoretical
study of such states near nanotubes and motivation for the experimentalists to probe such processes.
References:
[1]. L. Stryer, R. P. Haugland, Proc. Natl. Acad. Sci. U.S.A. 1967, 58, 719.
[2]. C. S. Yun et. al., J. Am. Chem. Soc. 2005, 127, 9, 3115.
[3]. Somnath Bhowmick et. al. J. Chem. Phys. 2006, 125, 181102.
192

NATIONAL SYMPOSIUM IN CHEMISTRY P 91
Nanoparticle Catalyzed Clock Reaction
Tarasankar Pal* and Surojit Pande
Department of Chemistry, Indian Institute of Technology, Kharagpur – 721302, India
Bulk Cu
2
O or cuprite is the only stable copper (I) compound present in plentiful amount in earth crust. It is a
challenging job to take bulk Cu
2
O to a nanoregime and to stabilize them in solution. No wonder that Cu
2
O in its
nanoregime would act as a photo catalyst. We report a synthetic protocol for the first time to obtain monodispersed,
stable, exclusively cubic Cu
2
O nanoparticles in surfactant free condition and its catalytic action for methylene blue
(MB)–hydrazine reaction in aqueous medium. The blue color of the dye, MB faded away upon the addition of
hydrazine producing colorless leuco methylene blue (LMB) indicating the progress of the redox reaction. The rate
of this redox reaction has been found to be enhanced in the presence of the Nan catalyst, Cu
2
O. The success of the
reaction demonstrates a simple ‘clock reaction’. An oscillation between a blue MB color and colorless solution due
to formation of LMB is observed on periodic shaking. This oscillation continues for over fifteen cycles. Studies on
the effect of bulk Cu
2
O, nanoparticles of CuO and Cu(0) have not been successful for demonstration of the ‘clock
reaction’. Thus the importance of Cu
2
O nanoparticles in the clock reaction is established beyond doubt. The Cu
2
O
nanoparticles were characterized by different physical methods. TEM studies authenticate the cube shaped
monodispersed particles. The electrochemical studies indicate that nano-Cu
2
O shows a couple of redox peaks which
correspond to the redox Cu(II)/Cu(I) system. Kinetic studies authenticate first-order reaction mechanism. Further
quantum chemical calculations reveal that the nanoparticles reduce the activation energy by ~17 kcal/mol thereby
make the reaction 2.4
´10
7
times faster compared to the gas-phase.
Scheme to show the catalytic activity of Cu
2
O nanocubes for the ‘clock reaction’.
References
[1] Landolt, H. Ber. Dtsch. Chem. Ges. 1886, 19, 1317.
[2] Mambo, E.; Simoyi, R. H. J. Phys. Chem. 1993, 97, 13662.
[3] Lente, G.; Fa´bian, I. Inorg. Chem. 2004, 43, 4019.
193

P 92 NATIONAL SYMPOSIUM IN CHEMISTRY
Surface Enhanced Raman Scattering with Core-Shell Nanoparticles
G.V. Pavan Kumar, Nashiour Rohman, Chandrabhas Narayana
*
Light Scattering Lab, Chemistry and Physics of Materials Unit,
Jawaharlal Nehru Center for Advanced Scientific Research, Jakkur, Bangalore – 560064
In recent years, surface enhanced Raman scattering (SERS) has emerged as one of the most potent tools in
ultra-trace molecular analysis. It blends single molecule sensitivity with chemical fingerprint capabilities, which
make it a unique tool for biomolecular detection. Metallic nanoparticle substrates are one of the important requirements
of SERS experiments, on which, molecules adsorb to exhibit enhanced Raman signatures. Conventionally, Ag and
Au nanoparticles have been extensively used for SERS studies. Of late, core-shell nanoparticles have derived enormous
attention in the field of SERS because of their unique optical properties like tunable surface plasmon.
In this paper, we present two novel techniques used to harness the core-shell properties of nanoparticles for
biomolecular detection purpose:
1) We show the creation of electromagnetic hot spots in Ag core-Au shell nanoparticles, which provide enhanced
optical fields for SERS. Further, we use them to detect biomolecules like p300 (a human transcriptional coactivator
enzyme) at physiological concentrations.
2) We show the possibilities of using magnetic core-metallic shell nanoparticles for SERS applications. We
synthesize, and use Fe
2
O
3
core–Ag shell and Fe
2
O
3
core–Au shell nanoparticles for SERS studies of bio-related
molecules. Also, by performing SERS microscopy in the temperature range of 77 K to 473 K, we show that the
metal-coated magnetic nanoparticles are robust with respect to variation in temperature.
194

NATIONAL SYMPOSIUM IN CHEMISTRY P 93
Pd Nanoparticls as Efficient Catalyst for Carbon-Carbon Bond Formation
Kalicharan Chattopadhyay, Laksmikanta Adak, Amit Saha, Sukalyan Bhadra, Debasree Saha,
Raju Dey and Brindaban C. Ranu*
Department of Organic Chemistry, Indian Association of the Cultivation of Science, Jadavpur,
Kolkata 70032, India
An efficient procedure for the stereo selective synthesis of (E)- and (Z)-2-alkene-4-ynoates and –nitriles by a
simple reaction of vis-diido-(E)-alkenes with acrylic esters and nitrile catalyzed by in situ prepared Pd(0) nanoparticles
in water has been developed.
Palladium (0) nanoparticles have also been used as efficient catalyst for the bis-allylation of active methylene
compounds by allyl acetate in one step in THF solvent without requirement of any ligand. Interestingly, the reaction
in water provides monoallylated product with high selectivity.
The formation of Pd nanoparticles was detected from analysis of the reaction mixture by transmission electron
microscopy (TEM) and Energy Dispersive X-ray spectroscopy (EDS). The TEM image and EDS showed the
palladium nanoparticles with a size of 2-6 nm. The palladium nanoparticles were recycled for two runs with out any
loss of efficiency.
195

P 94 NATIONAL SYMPOSIUM IN CHEMISTRY
Mesopores in Organic Cresol Formaldehyde MATRICES
Mahasweta Nandi, Asim Bhaumik*
Department of Materials Science and Center for Advanced Materials,
Indian Association for the Cultivation of Science,
2A & B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Cresol-formaldehyde resins are versatile polymer having numerous applications in ion exchange, catalysis,
supercapacitors, photo resistant materials etc. Purely organic mesoporous materials are the area of major research
interest in recent times [1-3], especially in the context of developing the low-k dielectric materials. Mesostructured
cresol formaldehyde composites synthesized by template assisted route have not been explored much. Here we
present a very simple procedure for the preparation of a nanostructured cresol-formaldehyde material through
hydrothermal condensation of m-cresol and formaldehyde at 363 K under mild alkaline condition in the presence of
supramolecular assembly of cationic surfactant, cetyltrimethyl ammonium bromide as structure directing agent or
template. The resulting material was characterized by powder X-Ray diffraction, TEM, TG-DTA, UV-Vis and
fluorescence spectroscopy. Removal of template from the as-synthesized material gave the template free mesoporous
material. TEM image analysis revealed nanorod morphology with diameter of the rods of 30-40 nm. These nanorods
have disordered wormhole-like nanostructure with pores of dimensions of ca. 2.5 nm. These composite materials
exhibit photoluminescence property at room temperature, distinctly different from the material having non-porous
resol matrix.
References
[1] Simon, F. -X.; Khelfallah, N. S.; Schmutz, M.; Diaz, N.; Mesini, P. J. J. Am. Chem. Soc. 2007, 129, 3788.
[2.] Chandra, D.; Jena, B. K.; Raj, C. R.; Bhaumik, A. Chem. Mater. 2007 (in press).
[3] Nandi, M.; Gangopadhyay, R.; Bhaumik, A. Microporous Mesoporous Mater. 2007 (in press).
196

NATIONAL SYMPOSIUM IN CHEMISTRY P 51
ZnO/Immobilised Resin Based Photo Catalyst Using for Transformation of
Organic Molecule (Congo red)
Ram Babu Pachwarya, Vijay Kumar and R.C.Meena*
Department of Chemistry, Jai Narayan Vyas University, Jodhpur, Rajasthan – 342001
The Photo catalytic transformation of organic molecule (Congo red) has been investigated in ZnO /immobilized
Resin aqueous suspension. It was attempted to determine the feasibility of such transformation by varying different
parameters. In addition to prompt removal of the color, ZnO/immobilized resin based photo catalyst was
simultaneously able to complete transformation of the organic molecules, with a complete mineralization of Carbon
into CO
2
, Sulphur a heteroatom into SO
4
-2
. The mineralization of Nitrogen was more complex, Nitrogen atom in –
3 oxidation state, such as in amino group, remain at this reduction degree and produces NH
4
+
cations, subsequently
and strongly change into NO
3
-
ions.
These results revels that ZnO/immobilized resin photo catalysis may be employed in methods for treatment of
colored wastewater, not only for de-colorization, but also for de-toxification, in particular in textile industries in
semi-arid countries.
References:
1. T.Robinson. T, G.McMullan. G, R.Marchant. R,P.Nigam. P, Bioresource Technol. 2001, 77, 247.
2. P.P Zamora, A.Kunz, S.G. Moraes, R. Pelegrini, P.C. Moleiro, J. Reyes, N. Duran, Chemosphere 1999, 38, 835.
3. S.Ledakowicz, M. Solecka, R. Zylla, J. Biotechnol. 2001, 89, 175.
153

P 52 NATIONAL SYMPOSIUM IN CHEMISTRY
Photo-redox chemistry of cobalt (III) ammine complexes coordinated to
unsaturated carboxylic acids: Product analysis and quantum yields
determination
K. Jothivenkatachalam and P.Natarajan*
Department of Chemistry, Anna University, Trichy – 24, Tamil Nadu.
National Centre for Ultrafast Processes, University of Madras, Taramani Campus, Chennai
600 113, India.
Cobalt(III) pentaammine complexes with unsaturated carboxylic acids coordinated to the metal lead to
photoredox processes from the charge-transfer-to-metal (CTTM) excited states [Horvath et al (1)]. We have
investigated the photoredox chemistry of the complexes of the type Co(NH
3
)
5
X
2+
where X is crotonic acid,
cinnamic acid or sorbic acid and examined in detail the nature of the decomposition products from the carboxylate
free radical. The complxes on excitation in the CTTM band lead to the reaction
The photooxidised ligand fragments were isolated and characterized by NMR, IR, UV-Vis and mass spectral analysis. The quantum yields were determined for the photoredox reaction. The formation of the organic molecules from the photooxidised carboxylic acids shows interesting reaction pathways, which will be presented.
References 1. O. Horvath, K. L. Stevenson, Charge Transfer Photochemistry of Coordination Compounds, VCH, New York, 1993.
154

NATIONAL SYMPOSIUM IN CHEMISTRY P 53
Probing Geometry of Complexes in Solution by Depolarized Hyper-
Rayleigh Scattering
Sampa Ghosh, Puspendu K. Das*
Department of Inorganic and Physical Chemistry, Indian Institute of Science
Bangalore-560012, India
Noncovalent interactions are important in a number of chemical and biological processes. It plays an
important role in dictating structures of liquids, structure of DNA and the geometry of protein-ligand binding.
These interactions may be as weak as van der Waals force or as strong as hydrogen bonding and charge
transfer interactions. The smallest unit where we find the manifestation of these intermolecular interactions
are 1:1 aromatic donor-acceptor complexes. Relative orientation of the component molecules in such complexes
is determined by the nature of interaction and the two extreme geometries known are the parallel stacked and
the T shaped geometries. In experiments, the main attention, so far, has been given to determine the geometries
of such complexes in the solid state and in the gas phase. Though many groups have attempted to probe the
structures of such complexes in solution by NMR spectroscopy, they were unable to provide the details of
relative orientation in terms of the tilt and twist angles between the component molecules. In this work, we
use depolarized hyper-Rayleigh scattering technique to probe the geometry of noncovalently bound 1:1
molecular donor-acceptor complexes in solution. It provides the characterization of structure of such complexes
in solution in terms of the first hyperpolarizability tensor (b
ijk
). The origin of second order optical nonlinearity is
purely electronic in nature and thus the electronic structure of such complexes can be described in terms of its
hyperpolarizality tensor elements in the molecular frame. The molecular anisotropy is defined as u =
(where123
is the molecular frame, 1 being the direction of the principal axis of symmetry). We measure the depolarization ratio
(D) in the laboratory fixed frame (XYZ, X being the direction of polarization and Z the direction of propagation of
the incident light), where D = (b
XXX
, b
XXZ
are the first hyperpolarizability tensor elements in the same frame)
and correlate to u through co-ordinate transformation. How the symmetry of the molecules and that of light can be
combined to find geometrical information will be illustrated in this poster with examples such as 1,2,4,5-
tetracyanobenzene(TCNB)-1,2,4,5-tetramethylbenzene(durene), 2,3,5,6-tetrachloro-1,4-benzoquinone(Chloranil)-
durene, and benzene-naphthalene pairs.
155

P 54 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Sequestration of Au Nanoparticles by Alpha Amylase

Jashmini Deka
1
, Anumita Paul
1
, Aiyagari Ramesh
2
and Arun Chattopadhyay
1,3
*
Department of Chemistry
1
, Department of Biotechnology
2
and Centre for Nanotechnology
3
Indian Institute of Technology Guwahati, Guwahati 781 039
We shall present our recent results on the use of alpha amylase enzyme for the synthesis of Au nanoparticle
(NP) as well as their sequestration. The sequestration could be the result of attachment of enzyme to the NPs after
synthesis or it could be due to uptake from Au NP-starch composite following digestion.
We have for the first time synthesized Au NPs from AuCl
4
-
by using a pure enzyme such as a-amylase as the
reducing agent [1]. We find that in the composite, the activity of the enzyme is retained, as revealed by the kinetics
of starch digestion, which is similar to that of pure enzyme. The presence of free and exposed S-H groups is essential
in the reduction of AuCl
4
-
to Au NPs as well as their stabilization.
Further, we have carried out systematic study of the kinetics as well as the mechanism of digestion of starch-
Au NP composite by a-amylase [2]. This is relevant to starch-based polymers being used for pulsatile release of
drugs, peptides and other bioactive agents and starch-encapsulated magnetic particles for superior magnetic resonance
contrast agents. We observed that not only the digestion kinetics of the composite was similar to that of pure starch,
but the enzyme also sequestered the NPs following digestion. Finally, it was established that the surface plasmon
resonance of the Au NPs could be a direct probe for the study of digestion of starch (in the composite) by the
enzyme. A qualitative model for the digestion of the composite by a-amylase has also been proposed, which is
important for nanoscale drug delivery systems.
Reference
[1] Retention of Enzymatic Activity of a-Amylase in the Reductive Synthesis of Gold Nanoparticles. Abhijit Rangnekar, Tridib
Kumar Sarma, Atul Kumar Singh, Jashmini Deka, Aiyagari Ramesh, and Arun Chattopadhyay.Langmuir 2007, 23, 5700-5706
[2] Probing Au Nanoparticle Uptake by Enzyme Following Digestion of Starch-Au-Nanoparticle Composite. Jashmini Deka,
Anumita Paul, A. Ramesh, and Arun Chattopadhyay . Communicated.
156

NATIONAL SYMPOSIUM IN CHEMISTRY P 55
The Model Study of Proton Transfer Phenomena in Various Forms of GC
Base Pair
Rajib Lochan Sarma, Bipul Bezbaruah , C Medhi
Department of Chemistry, Gauhati University
Guwahati-781014, India
The structural changes and destabilization of base pair are some of the important consequences of radical
formation within DNA. The most energetic radicals can distort the flexible nucleic acid structure drastically [1]. The
schematic representation of proton transfer within hydrogen bonding region of normal GC base pair has been compared
with the proton transfer reactions through GC radical, GC cation and cationated GC radical to demonstrate the most
favorable proton transfer pathway. There are significant differences in the energy levels of proton transfer in these
systems and generation of cation and radical species at the equilibration region of proton transfer are distinctly
indicated. The two local minima detected in the cationic radical types of proton transfer are (GH
+
)C and G(H
+
C),
herein the minimum corresponding to G(H
+
C) occurs at lower energy level than the one for (GH
+
)C [2]. Hence the
proton is more stable at the cytosine nucleobase rather than guanine. The formation of G
+
is found in cationated GC.
Similarly two local minima are found at different energy levels in GC radical and cationated GC radical. Here we
have studied only the energies for the single proton transfer mechanism within hydrogen bonding region, where the
formation of cationated GC radical is found to be stable than the Watson Crick GC base pair. On the other hand the
formation of CG
+
may drastically disturb the rate of proton transfer within normal DNA due to the stabilization of
cationated species.
References:
[1] M. D. Sevilla, D. Becker; Electron Paramagnetic Resonance (RSC), 2004, 19, 243-278
[2] J. Bertran, A. Oliva, L. Rodriguez – Santiago, M. Sodupe; J Am Chem Soc, 1998,120, 8159-8167
157

P 46 NATIONAL SYMPOSIUM IN CHEMISTRY
1,1’-Ferrocenedicarboxylate-bridged Redox-active Organotin and -
tellurium-containing 16-membered Macrocycles. Synthesis, Structure and
Electrochemistry
Vadapalli Chandrasekhar,* and Ramalingam Thirumoorthi
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur – 208016, India.
Recently there has been considerable interest in the application of inorganic rings and cages as scaffolds
for the preparation of multiredox compounds [1]. Organostannoxane-supported multiferrocene assemblies
are readily prepared in a reaction involving an organotin precursor and ferrocenecarboxylic acid [2]. Reactions
of 1,1’-ferrocenedicarboxylic acid, LH
2
, with (nBu)
2
SnO under solvothermal conditions at 180 ºC afforded a
completely dealkylated octanuclear cage [Sn
8
O
4
L
6
] [3]. This compound was not electrochemically stable and
decomposed under cyclic voltammetric conditions. We reacted LH
2
with diorganotin halides R
2
SnCl
2
(R = n-Bu
and Bn) and Ar
2
TeCl
2
(Ar = 4-OMe-C
6
H
4
) in normal reflux conditions [4] and obtained molecular compounds. The
molecular structures of these compounds have been confirmed by single crystal X-ray analysis. This reveals that the
two main-group metal atoms within each macrocycle are bridged to each other by two ferrocenecarboxylate ligands.
In the case of the organotin derivatives the ferrocenedicarboxylate ligand acts in an anisobidentate chelating manner
leading to a hexacoordinate tin present in a skewed trapezoidal bipyramid geometry. In contrast, in the tellurium
analogue the ferrocenecarboxylate ligand is monodentate leading to a tetra-coordinate tellurium in a see-saw geometry.
ESI-MS studies on these macrocylic complexes reveal that they retain their structural integrity in solution.
Electrochemcial studies reveal that [n-Bu
2
SnL]
2
and [Ar
2
TeL]
2
show two quasi-reversible oxidation processes. These
compounds have low comproportionation constants (K
c
) and can be described as being intermediate between no-
coupling and weakly-coupled systems. [Bn
2
SnL]
2
also shows two oxidation processes. However, in this instance,
the second event is irreversible.
References:
1. a) Chandrasekhar, V.; Gopal, K.; Thilagar, P. Acc. Chem. Res. 2007, 40, 420. b) Chandrasekhar, V.; Nagendran, S.;
Baskar, V. Coord. Chem. Rev. 2002, 235, 1.
2. Chandrasekhar, V.; Nagendran, S.; Bansal, S.; Kozee, M. A.; Powell, D. R. Angew. Chem. Int. Ed. 2000, 39, 1833.
3. Zheng, G.-L.; Ma, J.-F.; Su, Z.-M.; Yan, L.-K.; Yang, J.; Li, Y.-Y.; Liu, J.-F. Angew. Chem. Int. Ed. 2004, 43, 2409.
148

NATIONAL SYMPOSIUM IN CHEMISTRY P 47
Rhodium Catalyzed Regiospecific Multiple Carbenoid Insertion Approach
to Indolophanes
T. Rajasekaran, C. Gunanathan and S. Muthusamy*
School of Chemistry, Bharathidasan University, Tiruchirappalli-620 024, Tamilnadu
Cyclophanes have received much attention due to the structural versatility and opportunities for synthetic
modifications, host-guest complexation, molecular self assembly and specific receptor activity [1,2]. However,
aromatic groups contained in the cyclophanes are mainly carbocyclic rings such as benzene and naphthalene
derivatives. Not many cyclophanes are reported with heteroaromatic ring systems. Herein, we report the
Rh
2
(OAc)
4
catalysed regiospecific intermolecular double carbenoid insertion reactions of cyclic diazoamides affording
indolophanes via two carbon-carbon bonds formation in a single synthetic step.
Employing 3-diazo-1,3-dihydro-2H-indol-2-one as the carbene source, we recently described the first
regioselective intermolecular carbenoid insertion reactions of cyclic rhodium(II) carbenoids to afford quantitative
yields of intermolecular insertion products [3,4]. Our enticement in developing the new synthetic strategies

using
tandem reactions of diazocarbonyl compounds encouraged us to investigate the application of this methodology for
the synthesis of cyclophanes. The Rh
2
(OAc)
4
catalysed intermolecular double carbenoid insertion strategy has been
successfully implemented for the synthesis of indolophanes as mixture of diastereomers. The notable details of our
investigations will be presented.
X, Y = Aliphatic or aromatic Spacers
References:
[1] J. Breitenbach. J, Boosfeld. J, Vögtle. F, In Comprehensive Supramolecular Chemistry, Ed. F. Vögtle, Pergamon, New
York, 1996, Vol. 2, pp. 29-67.
[2] Streed. W. W, Atwood. J. L, In Supramolecular Chemistry, Wiely, New York, 2000.
[3] Muthusamy. S, Gunanathan. C, Babu. S. A, Suresh. E, Dastidar. P, Chem. Commun. 2002, 824.
149

P 48 NATIONAL SYMPOSIUM IN CHEMISTRY
Computational Studies on the Structures of B
8
H
8
2-
Vibha Kumar and P.P.Thankachan
*
Department of Chemistry, Indian Institute of Technology-Roorkee, Roorkee-247667,
Several structures of B
8
H
8
2-
species have been characterized at the Hartree-Fock and density functional (B3LYP)
levels of calculation, using several basis sets in each case. Some of the previously suggested structures [1] (O
h
, D
3h
and D
3d
symmetries) are seen not to correspond to true energy minima on the potential energy surface and some
previously unreported stable structures are identified.
References:
1. Daniel A. Kleier and William N. Lipscomb, Inorg. Chem, 18(5), 1312-18 (1979).
150

NATIONAL SYMPOSIUM IN CHEMISTRY P 49
Anion-Directed Synthesis of Metal-Organic Frameworks Based on
2-Picolinate Cu(II) Complexes: A Ferromagnetic Alternating Chain and
Two Unprecedented Ferromagnetic Fish Backbone Chains
Pampa Mukherjee,
†
Chaitali Biswas,
†
Michael G. B. Drew,
‡
Carlos J. Gomez-Garcýa,,
§
and
Ashutosh Ghosh*,
†
†
Department of Chemistry, University College of Science, University of Calcutta, 92, A.P.C.
Road, Kolkata-700 009, India,
‡
School of Chemistry, The University of Reading, P.O. Box 224,Whiteknights, Reading RG6
6AD, United Kingdom,
§
Institute of Molecular Science (ICMol), University of Valencia, Pol. La Coma s/n, 46980
Paterna, Valencia, Spain
2-picolinic acid on reaction with Cu(II) salts produces discrete, mononuclear ‘inner metallic complex’ [Cu(pic)
2
]
which can potentially be used as a “metalloligand” building block to construct high-nuclearity copper complexes. In
our study, three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu
2
(pic)
3
(H
2
O)]ClO
4
}n (1),
{[Cu
2
(pic)
3
(H
2
O)]BF
4
}n (2), and [Cu
2
(pic)
3
(H
2
O)
2
(NO
3
)]n (3), have been synthesized by the reaction of
“metalloligand” [Cu(pic)
2
] with the corresponding copper(II) salts. Crystal structure analyses show that compounds
1 and 2 are isomorphous and are constructed by “fish backbone” chains but 3 possess a very different polymeric
network. Therefore, these compounds provide very interesting examples of the anion-directed template synthesis of
metal-organic frameworks by using the versatile coordination mode of 2-picolinic acid. The present work shows
how a slight change in coordination ability of the anion along with the difference in the H-bonding network can play
a crucial role in determining the overall structure of the coordination network. Variable-temperature (2-300 K)
magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes
that have been fitted with a fish back bone model developed for 1 and 2 (J = 1.74 and 0.99 cm
-1
; J’ = 0.19 and 0.25
cm
-1
, respectively) and an alternating chain model for 3 (J = 1.19 cm
-1
and J’ = 1.19 cm
-1
).
151

P 50 NATIONAL SYMPOSIUM IN CHEMISTRY
Anaerobic DNA Cleavage in Red-light by a Dicopper(II) Complex on
Disulfide Bond Activation
Debojyoti Lahiri, Biswarup Pathak, Ashis K. Patra, Eluvathingal D. Jemmis
Munirathinam Nethaji, and Akhil R Chakravarty
*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore-560 012
Anaerobic DNA damage is of immense biological importance. Cancer cells generally have hypoxic conditions
within it. Therefore, compounds that are capable of cleaving DNA anaerobically are of potential use in the chemistry
of new generation anticancer drugs. We have prepared a copper-based disulfide complex that shows efficient DNA
strand scission on photolysis at red light under anaerobic conditions (argon atmosphere). The results are of importance
in the chemistry of photodynamic therapy (PDT) of cancer [1]. The currently used PDT drug is Photofrin®. It is a
porphyrin-based compound that cleaves DNA in red light aerobically involving singlet oxygen as the reactive species.
Our dicopper(II) complex(1), in contrast, on photolysis in red light under argon leads to the formation of disulfide
anion radicals as DNA cleaving species by accepting an electron from the electron donor solvent. The chemistry of
photoactive compounds showing anaerobic DNA cleavage in red light is virtually limited. The organic dyes require
aerobic conditions for their activity. It is thus of importance to develop the chemistry of metal-based compounds as
anaerobic photocleaver of DNA for PDT applications.
In this work we report the synthesis, structure, DNA binding and cleavage properties of a ternary copper(II)
complex [Cu
2
(3,3’-dtdp)
2
(phen)
2
] (1). The complex displays efficient photonuclease activity on irradiation with
monochromatic UV-A radiation of 365 nm or visible light of 647 and 745 nm wavelengths. The mechanistic pathway
involves formation of disulfide anion radical as a reactive species.
References:
[1] Detty, M. R.; Gibson, S. L.; Wagner, S. J. J. Med. Chem. 2004, 47, 3897-3915. Boerner, L. J. K.; Zaleski, J. M.
Curr. Opin. Chem. Biol. 2005, 9, 135-144.
152

NATIONAL SYMPOSIUM IN CHEMISTRY P 41
DNA Binding And Nuclease Activity of Binuclear Copper(II) Complexes of
Cuminaldehyde Thiosemicarbazones
P. Murali Krishna
a
, K. Hussain Reddy
a
, J. P. Pandey
b
, S. Dayananda
b
a
Department of Chemistry, Sri Krishnadevara University, Anantapur-515 003 (A.P),India.
b
School of Life sciences, University of Hyderabad, Hyderabad-500 046 (A. P, India.
Binuclear copper(II) complexes of CTH, CMTH, CETH and CPTH (where CTH = cuminaldehyde
thiosemicarbazone, CMTH = cuminaldehyde-4-methyl-3-thiosemicarbazone,CETH=cuminaldehyde-4-ethyl-3-
thiosemicarbazone, CPTH = cuminaldehyde-4-phenyl-3-thiosemicarbazone) have been synthesized and characterized
on the basis of elemental analysis, conductivity measurements, magnetic susceptibility data, electronic, IR and ESR
spectroscopy. Electrochemical behaviour of these complexes has been investigated by cyclic voltammetry. All
complexes undergo quasi-reversible one electron electrochemical reduction (Cu
II
/Cu
I
) in the potential range 0.505 –
0.545 V against Ag/AgCl reference electrode. The formula weight of the complexes is determined using LC-MS.
The DNA binding of copper complexes with CT-DNA has been investigated using absorption spectrophotometry.
The apparent binding constants for complexes are in the order of 10
7
to 10
8
M
-1
. Based on the data obtained in the
DNA binding studies is suggested that the complexes binds to DNA very effectively. DNA cleavage activity is
carried on plasmid pUC18 DNA. All complexes show hydrolytic cleavage activity. The efficiency of cleavage
activity is in the order [Cu
2
(CMT)
2
Cl
2
] > [Cu
2
(CET)
2
Cl
2
] > [Cu
2
(CPT)
2
Cl
2
].
143

P 42 NATIONAL SYMPOSIUM IN CHEMISTRY
Acylmethyl(aryl)tellurium(IV, II) derivatives: Restricted Rotation About
Te-C(mesityl) Bond
Ashok K. S. Chauhan,
a1
Puspendra Singh,
a
Ramesh C. Srivastava,
a
and Andrew Duthie
b
a
Department of Chemistry, University of Lucknow, Lucknow 226007, India,
b
School of Life and Environmental Sciences, Deakin University, Geelong 3217, Australia.
Electrophilic substitution of methyl ketones, RCOCH
3
(R = i-Pr,1; Et,2; Me,3) with aryltellurium trichlorides,
ArTeCl
3
(Ar = 1-C
10
H
7
, Np, A; 2,4,6-Me
3
C
6
H
2
, Mes, B; 4-MeOC
6
H
4,
Anisyl, C) at room temperature affords the
corresponding acylmethyl(aryl)tellurium dichlorides. Reduction of the dichlorides, gives tellurides, (RCOCH
2
)ArTe,
1A-3C, which give the corresponding dihalides, (RCOCH
2
)ArTeX
2
(X = Cl, 1Aa-3Ca; Br, 1Ab-3Cb; I, 1Ac-3Cc )
when reacted in situ with SO
2
Cl
2
, Br
2
and I
2
. The unsymmetric tellurides are labile towards disproportionation and
attempts to obtain them lead to the isolation of Ar
2
Te
2
and Ar
2
Te except in the case of i-PrMesTe (2B), which
represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellrium(IV)
derivatives show separate
1
H and
13
C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands.
The telluride, 2B with free rotation about Te-C(mesityl) bond show, like the unsymmetric diorganotellurium(IV)
dihalides, only one
125
Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV)
compounds is inferred from the X-ray diffraction data for 1Ac, 1Ba, 1Bb, 1Ca,and 1Cc which are indicative of the
presence of intramolecular Te···O secondary bonding interactions (SBIs) at least in the solid state. Intermolecular C-
H···O H-bonding interactions present in the crystal packings of 1Ba and 1Bb that are devoid of Te involved SBIs,
appear to be retained in solution as well and result in the loss of rotational symmetry of the ortho methyl substituents
of the mesityl ligands.
144

NATIONAL SYMPOSIUM IN CHEMISTRY P 43
Synthesis, crystal, molecular structure and properties of some new
phenylmercury(II) dithio complexes
Abhinav Kumar,
†
Kieran C. Molloy,
‡
and Mary F. Mahon
‡
, Nanhai Singh,*
†
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005,
India. School of Chemistry, University of Bath, Bath BA2 7AY, UK.
A series of new phenylmercury(II) dithio complexes [(PhHg)
2
cdc] (1; cdc
2-
yanodithioimidocarbonate), [PhHg
Bu
2
n
dtc] (2; Bu
2
n
dtc
-
= di-n-butyldithiocarbamate), [PhHg morphdtc] (3; morphdtc
-
= morpholinedithiocarbamate),
[(PhHg)
2
NED] (4; NED
2-
= 1- nitroethylene – 2, 2 - dithiolate), [PhHg methoxethxant] (5; methoxethxant
-
= 2 –
methoxyethyl xanthate) and [PhHg Bz
2
dtc] (6; Bz
2
dtc = dibenzyldithiocarbamate) have been prepared and
characterized by elemental analysis, UV – Vis., IR,
1
H and
13
C NMR spectra and mass spectrometry. The crystal
structures of 2, 3 and 6 showed almost linear Hg(II) core at the centre of the molecule. The weak intra- and inter-
molecular Hg···S interactions provide stacked antiparallel molecular framework. Interestingly, the reaction of
PhHgOOCCH
3
with Bu
2
n
dtc gave the known dimeric complex [Hg(Bu
2
n
dtc)
2
]
2
while the Ni(O
2
CCH
3
)
2
mediated
reaction gave 2 instead of expected heterobimetallic complex [PhHgNi(Bu
2
n
CS
2
)
2
]OOCCH
3
. Upon excitation at
358 nm 6 exhibited a medium strong photoluminescence emission at 420 nm. All of the complexes are weakly
conducting (ó
rt
~ 10
-12
S cm
-1
). However 1 and 3 exhibited semiconductivity with band gaps 0.39 and 0.94 eV
respectively. Density functional theory has been used to investigate the molecular structures of 1, 4 and 5.
145

P 44 NATIONAL SYMPOSIUM IN CHEMISTRY
Oxidation of Styrene Catalyzed by Cu(SALEN) Intercalated a-Zirconium
Phosphate
S. Khare
*
and R. Chokhare
School of Chemical Sciences, Takshashila Campus, Khandwa Road, Devi Ahilya University,
Indore -452017 (M. P.) India
The heterogenization of tranistion metal complexes is an area of growing interest, particularly on zeolites,
mesoporous silicate materials, polymers and activated carbon [1-3]. We have synthesized Cu(Salen) intercalated
a-
Zirconium phosphate [
a-ZrP.Cu(Salen)] in situ by the flexible ligand method and characterized by XRD, SEM and
IR spectroscopic techniques. Its catalytic behaviour for the epoxidation of styrene using tert-butylhydroperoxide
and H
2
O
2
as an oxidant was studied. Various parameters of the catalytic reaction along with kinetics will be presented.
References:
[1] Canali. L, Sherrington. D. C, Chem. Soc. Rev. 1999, 28, 85.
[2] Song. C. E, Lee. S. G, Chem. Rev. 2002, 102, 3495.
[3] Li. C, Catal. Rev. Sci. Eng. 2004, 46, 419.
146

NATIONAL SYMPOSIUM IN CHEMISTRY P 45
Synthesis, Derivatization, Transition Metal Chemistry and Catalytic
Investigations of a Novel Tetraphosphorus Ligand
C. Ganesamoorthy, M. S. Balakrishna*
Department of Chemistry, IIT Bombay, Mumbai-400 076
Metal complexes of phosphorus-based ligands play central role in various metal-catalyzed organic transformation
reactions. In recent days, the progress on ligand chemistry and substantial development of high efficient catalytic
systems become a major goal in the community of organic and inorganic chemists. In view of this, we present herein
the synthesis, coordination chemistry and catalytic investigations of a new family of aminotetra(phosphines) derived
from [C
6
H
4
(NP
2
Cl
4
)
2
-p] (1).[1] Molecular structure of 1 shows an unprecedented intermolecular P…P interactions
leading to the formation of a 2-D sheet. The aminotetra(phosphonites), p-C
6
H
4
[N{P(OC
6
H
4
OMe-o)
2
}
2
]
2
(2) and p-
C
6
H
4
[N{P(OMe)
2
}
2
]
2
(3) have been prepared by reacting 1 with appropriate amount of 2-(methoxy)phenol or methanol
in presence of triethylamine. The oxidation reactions of 2 and 3 with H
2
O
2
, elemental sulfur or selenium afforded the
tetrachalcogenides, p-C
6
H
4
[N{P(O)(OC
6
H
4
OMe-o)
2
}
2
]
2
(4), p-C
6
H
4
[N{P(S)(OMe)
2
}
2
]
2
(5) and
p-C
6
H
4
[N{P(Se)(OMe)
2
}
2
]
2
(6) in good yield. The ligand 2 has been extensively used for the synthesis of several
di-, tetra- and polynuclear late transition metal complexes. The use of these complexes towards various organic
transformations such as Suzuki-Miyaura cross-coupling and transfer hydrogenation reactions will be presented.
References:
[1] a) C. Ganesamoorthy, M. S. Balakrishna, P. P. George, J. T. Mague, Inorg. Chem. 2007, 46, 848-858.
[2] b) C. Ganesamoorthy, J. T. Mague, M. S. Balakrishna, J. Organomet. Chem. 2007, 692, 3400-3408.
[3] c) B. Punji, C. Ganesamoorthy, M. S. Balakrishna, J. Mol. Catal. A: Chem. 2006, 259, 78-83.
147

P 36 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Characterization of La (III) Incorporated Carboxylated
Chitosan Beads for Fluoride Removal
Natrayasamy Viswanathana, C. Sairam Sundaramb, S. Meenakshia*
a
Department of Chemistry, Gandhigram Rural University, Gandhigram- 624 302,
Tamil Nadu, India
b
Department of Science and Humanities, Karaikal Polytechnic College,
Karaikal- 609 609, Puducherry, India
Chitosan beads (CB) as such have very low defluoridation capacity [DC] of 51mg F
-
/kg has been modified by
carboxylation and chelation with La
3+
ion (La-CCB), in order to effectively utilize both hydroxyl and amine groups
for defluoridation. The modified beads showed an enhanced DC to a very significant level of 4787 mg F
-
/kg. The
fluoride removal process is governed by both adsorption and complexation mechanism simultaneously (cf. Scheme
1). The sorbent was characterized using FTIR and SEM with EDAX. The sorption process follows both Freundlich
and Langmuir isotherms. The experimental data have been fitted with kinetic models. Thermodynamic parameters
such as
DG
o
, DH
o
and DS
o
were calculated to predict the nature of sorption is spontaneous and endothermic. A field
trial was carried out with fluoride water collected from a nearby fluoride-endemic village to test the suitability of
sorbent at field conditions. Suitable eluent was also identified for the continuous use of the sorbent.
Scheme 1. Mechanism of fluoride removal by La-CCB.
138

NATIONAL SYMPOSIUM IN CHEMISTRY P 37
New Diorganotin(IV) Derivatives of Tyrosinylphenylalanine: Synthesis
and Structural Characterization, Crystal Structure of Me
2
Sn (TYR-PHE)
Mala Nath
1*
, Hitendra Singh
1
, George Eng
2
, Xueqing Song
2
1
Department of Chemistry, Indian Institute of Technology-Roorkee, Roorkee 247667,
2
Department of Chemistry and Physics, University of the District of Columbia, 4200
Connecticut Avenue, NW Washington, DC 20008, USA
1*
Correspondence to: Mala Nath, Department of Chemistry, Indian Institute of Technology-
Roorkee, Roorkee 247667, India.
New diorganotin(IV) derivatives of tyrosinylphenylalanine (H
2
Tyr-Phe) with general formulae R
2
Sn(Tyr-Phe)
where R = Me, n-Bu, Ph and n-Oct have been synthesized. The bonding and coordination behaviour in these derivatives
are discussed on the basis of FT-IR, multinuclear
1
H,
13
C and
119
Sn NMR and
119
Sn Mössbauer spectroscopic studies.
These investigations suggest that the dipeptide in R
2
Sn(Tyr-Phe) acts as dianionic tridentate coordinating through
COÕ, NH
2
and N
peptide
groups and the polyhedron around tin in R
2
Sn(Tyr-Phe) is a trigonal-bipyramidal. It is further
confirmed by the single crystal X-ray structure of Me
2
Sn(Tyr-Phe) which shows two methyl groups and peptide
nitrogen (N
peptide
) are in the equatorial positions, while the two axial positions are occupied by the carboxylic
oxygen(COÕ) and the amino nitrogen (NH
2
) atom from the same ligand molecule and the tin atom is at centrally
located position.
139

P 38 NATIONAL SYMPOSIUM IN CHEMISTRY
Cyclotriphosphazene appended with six porphyrins
M. Rajeswara Rao, M. Ravikanth*
Indian Institute of Technology Bombay, Mumbai-400 076
The design and construction of novel porphyrin architectures, in particular well-defined porphyrin arrays,
is an area of increasing current interest. These porphyrin assemblies are of fundamental importance not only
as models for the study of the energy and electron-transfer functions of the light-harvesting antenna and the
photosynthetic reaction centers but also as building blocks for the construction of functional molecular devices,
i.e., molecular scale wires, switches and photovoltaic devices, etc.[1] In the case of the natural antenna
systems, the function and properties of the chromophoric arrays are controlled by the spatial arrangement
and orientation of the molecules, which themselves are held in a specific architecture through predominantly
noncovalent interactions within a protein and carotenoid scaffold. The resulting assemblies, which can consist
of up to several hundred porphyrins, are able to transfer energy over large distances with a very high efficiency.
The first step toward mimicking the properties of such systems is the development of techniques which
enable the construction of well-defined multichromophore arrays. Our group has been involved in the synthesis
of appropriate porphyrin building blocks with different porphyrin cores such as N
4
, N
3
S, N
3
O, N
2
S
2
etc and used
them for the construction of porphyrin dyads, triads, tetrads including photonic wire[2]. In this poster, we present
our recent results on new type of hexameric multiporphyrin arrays in which all porphyrin chromophores are anchored
to cyclotriphosphazene. The synthesis and studies of such novel systems will be presented.
References: (1) Wagner, R. W.; Johnson, T. E.; Lindsey, S. J. J. Am. Chem .Soc. 1994, 116, 9759.
(2) Wagner, R. W.; Lindsey, S. J. J. Am. Chem. Soc. 1996, 118, 11167.
(3) Gupta, I.; Ravikanth, M. J. Org. Chem. 2004, 69, 6801.
140

NATIONAL SYMPOSIUM IN CHEMISTRY P 39
Kinetics of Electron Transfer From Lactic Acid to Tris –
(Dimethylgloximato) Nickelate (IV) in Aqueous Medium
B. Kirthika Rani and T.K. Ganesan
Department of Chemistry, The American College, Madurai- 625 002, Tamil Nadu.
The kinetics of electron transfer from Lactic acid [S] to tris-(dimethylglyoximato) nickelate(IV), [Ni(dmg)
3
]
2-
(dmg
2-
= dimethylglyoximate anion), have been studied in aqueous medium at pH 11. The kinetics exhibit a pseudo-
first order disappearance of [Ni(dmg)
3
]
2-
when excess lactic acid is present. The pseudo-first-order rate constants
k
obs
are linearly dependent on [S]
o
for varying concentration of the reactant. The pH rate profiles with low [S]
o
show
a monotonic decrease in rates with increasing pH. The results are interpreted in terms of a probable mechanism
involving a rate-determining outer-sphere one-electron transfer from the reductant to the unprotonated and one
protonated species of the Ni
IV
complex present in the solution, followed by a subsequent and kinetically
indistinguishable rapid reaction of the Ni
III
intermediate (eq.1). The major product of the oxidation of Lactic acid by
the Ni(IV) complex is pyruvic acid (eq.2).
141

P 40 NATIONAL SYMPOSIUM IN CHEMISTRY
Multinuclear Copper(II) Complexes: Effective Catalysts for Peroxidative
Oxidation of Cyclohexane, Toluene and Benzene
Partha Roy
a,b
, Pradyot Banerjee
a,
*
a
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata-700 032
b
Vidyasagar College For Women, 39 Sankar Ghosh Lane, Kolkata 700 006
Large attention on multinuclear copper(II) complexes owes their origin to the effective role for catalytic
enzymatic reactions.
1
Model enzymatic reactions for the oxidation of hydrocarbons in nature have been mimicked
with copper complexes in the presence of several oxidants.
2
The study of the oxidation of cyclohexane assumes a
special attention owing to the fact that its oxidized products are of immense industrial importance.
3
Benzene and
substituted aromatic hydrocarbon (e.g. toluene) occupy a prominent position with regard to their role in commercial
purpose as well as their hazardous impact on the environment.
4
We report here the syntheses and characterization of
three copper(II) complexes with N
2
O donor system, [Cu
2
(L
1
)(m
2
-pz)(CH
3
COO)
2
] (1), [Cu
4
(L
1
)
2
(m
4
-O)(m
2
-
CH
3
COO)
2
(m
1,1
-N
3
)(N
3
)] (2) and [Cu
2
(L
2
)(m
1,1
-N
3
) )(m
1,3
-N
3
)
2
]

¥ (3) (where pz = pyrazolato, HL
1
= 2,6-
bis(morpholinomethyl)-4-tert-butylphenol and HL
2
= 2,6-bis(morpholinomethyl)-4-methylphenol) X-ray
crystallographic studies confirm the formation of di-, tetra- and polynuclear copper(II) complexes. These compounds
show very effective catalytic property for the peroxidative oxidation of cyclohexane and toluene under mild conditions
using H
2
O
2
as the oxidant. The products are cyclohexanol and cyclohexanone in the case of cyclohexane oxidation;
the corresponding products are benzyl alcohol and benzaldehyde for toluene. The oxidation of benzene to phenol
has been carried out at 50 ºC using the same oxidant.
References:
1. S. Itoh, In Comprehensive Coordination Chemistry, 2nd ed.; McCleverty, J. A.; Meyer, T. J.; Que, L.; Tolman, W.
B. Eds.; Elsevier: Dordrecht, 2003; Vol. 8, Chapt. 8.15, pp 369-393.
2. J. T. Groves; S. Krishnan; G. E. Avaria; T. Nemo, J. Adv. Chem. Ser. 1980, 191, 277.
3. R. Whyman, Applied Organometallic Chemistry and Catalysis, Oxford University Press, Oxford, 2001.
142

NATIONAL SYMPOSIUM IN CHEMISTRY P 31
Specific Calcium Ion Fluorescence Sensor: Signaling by Conformatonal
Switching Induced Pet Suppression in a Bichromophoric Acridinedione
Foldamer
P. Ashokkumar and P. Ramamurthy*
National Centre for Ultrafast Processes, University of Madras,
Taramani Campus, Chennai-600 113, India
The design of chemosensors which are specific for the detection of biologically relevant cations, such as Na
+
,
K
+
, Mg
2+
, Ca
2+
, is a topic of considerable interest [1]. Selective detection of Ca
2+
in the presence of Na
+
, K
+
& Mg
2+
is important because many of the physiological processes are triggered, regulated or influenced by Calcium ion [2].
Even though a variety of crown-ether and related macrocyclic based chemosensors are known, the corresponding
acyclic poly-ether (podand) based sensors are relatively rare [3]. Herein, we report the synthesis & selective binding
studies of a novel acridinedione based bichromophore linked to an oxyethylene chain (podand) as the flexible
recognition moiety. This bichromophore shows weak fluorescence due to the Photoinduced electron transfer (PET)
from the electron rich –OMe group to the relatively electron deficient excited state of the fluorophore. The binding
of Ca
2+
ion induces conformational folding, in which Ca
2+
binds with both the –OMe group. This binding suppresses
the PET process and results in the fluorescence enhancement. This binding event was confirmed by
1
HNMR titration
studies & time resolved fluorescence technique. Na
+
, K
+
& Mg
2+
ions

do not show any significant variation, which
clearly shows the unique ability of 1 to detect Ca
2+
ions specifically. The binding of cations in noncyclic polyethers
will mainly depend on the charge density & coordination number of the cation, which may be the reason for the
specific binding of Ca
2+
over other cations.
References: 1. G.W. Gokel, Crown Ethers and Cryptands, CRC Press LLC, Boca Raton, 1991, pp.99-128 2. Stryer, L. Biochemistry, 3
rd
ed.; W.H. Freeman and co.: New York,1988.
3. Y.Suzuki, T. Morozumi, H. Nakamura, M. Shimomura, T. Hayashita, R.A. Bartsh, J. Phys. Chem. B 1998.
133

P 32 NATIONAL SYMPOSIUM IN CHEMISTRY
Palladium Complexes of Some Semicarbazones Efficient Building Blocks
for Heterodinuclear Complexes
Sayanti Datta and Samaresh Bhattacharya*
Department of Chemistry, Inorganic Chemistry Section, Jadavpur University,
Kolkata – 700 032
There has been considerable interest in the chemistry of transition metal complexes of the semicarbazone
ligands, primarily because of their bioinorganic relevance and particularly because of their potentially beneficial
biological (viz. antibacterial, antimalarial, antiviral, and antitumor) activities. However, we have been studying
chemistry of the platinum metal complexes of the semicarbazone ligands with special reference to the variable
coordination modes displayed by these ligands. In the present work, salicylaldehyde semicarbazone (1), and
two related ligands (viz. 2-hydroxyacetophenone semicarbazone, and 2-hydroxynaphthaldehyde semicarbazone)
have been chosen as the main ligands,
and palladium has been selected as the metal. As the source of palladium the [Pd(PPh
3
)
2
Cl
2
] complex has been
utilized. Reaction of [Pd(PPh
3
)
2
Cl
2
] with the selected semicarbazone ligands in the presence of a base has afforded
a family of complexes (2), where the semicarbazones are coordinated to palladium as dianionic tridentate O,N,N-
donors. Utilizing these palladium complexes (2) as the building block, interesting heterodinuclear complexes (3),
containing ruthenium as the second metal) have been prepared. The chemistry of all these complexes is described in
this presentation, with special reference to their formation and characterization.
134

NATIONAL SYMPOSIUM IN CHEMISTRY P 33
Chlorocarbonyl Ruthenium(II) Complexes of Tripodal Triphos
{MeC(CH
2
PPh
2
)
3
}: Isolation and Structural Investigation
Bhaskar Jyoti Sarmah, Biswajit Deb and Dipak Kumar Dutta*
Material Science Division, North-East Institute of Science & Technology (CSIR), Jorhat,
Assam, India, 785 006
Tridentate tertiary phosphines are recognized as one of the most important classes of ligands in homogeneous
catalysis by transition metals. Recently, several ruthenium(II) carbonyl complexes containing polyphosphine ligands
have shown interesting chemistry and catalytic activity which prompted us to synthesize ruthenium carbonyl complexes
of tripodal tridentate phosphine ligand {MeC(CH
2
PPh
2
)
3
} (tdpme) and to study their structural characteristics.
[Ru(CO)
2
Cl
2
]
n
reacts with the tripodal triphos ligand {MeC-(CH
2
PPh
2
)
3
},(tdpme), to form the di carbonyl complex
[Ru(CO)
2
{MeC(CH
2
PPh
2
)
3
}-Cl
2
](1), which exhibits two equally intense í(CO) bands at 2054 and 1988 cm
-1

indicating
cis disposition of carbonyl groups. The complex 1 underwent decarbonylation in dichloromethane to afford the
monocarbonyl complex [Ru(CO){MeC(CH
2
PPh
2
)
3
}Cl
2
] (2) exhibiting a single terminal í(CO) band at 1959 cm
-1
.
The molecular structure of the complex 2 has been determined by Single Crystal X-ray diffraction (Figure 1). The
complex [Ru(CO){MeC(CH
2
PPh
2
)
3
}Cl
2
] is monoclinic, Cc, with a = 21.8609(4) Å, b = 10.3959(2) Å, c = 18.5067(4)
Å and a = 90°, b = 117.467(2)° and g = 90°. The ruthenium atom occupies the centre of a slightly distorted octahedral
geometry. The complexes were characterized by elemental analyses, IR,
1
H NMR,
31
P NMR spectroscopy.
Fig 1. Single Crystal X-ray structure of [Ru(CO){MeC(CH
2
PPh
2
)
3
}Cl
2
].
135

P 34 NATIONAL SYMPOSIUM IN CHEMISTRY
Tripodalorganoselenoethers as Potential Ag(I) Extractant
Abhishek Kumar
1
, Shabana Khan
1
, Maya Kumari
1
, Jai Deo Singh
1
,* and Bishan Lal
Khandelwal
2
1
Department of Chemistry, Indian Institute of Technology Delhi (IITD), Hauz Khas,
New Delhi-110012
2
Disha Institute of Management and Technology (DIMT) Satya Vihar, Vidhan Sabha-
Chandrakhuri Marg, Mandir Masaud, Raipur 492101
In continuation of our studies on the polychalcogen bearing species, we have synthesized a series of
tripodalorganochalcogenoethers of the type N (CH
2
CH
2
ER)
3
[E= Se, Te].The tripodalorganoselenoethers exhibit a
remarkable selectivity towards silver ions over a variety of other metal ions including alkali (Na
+
, K
+
), alkaline-
earth(Mg
2+
,Ca
2+
,Ba
2+
), transition and heavy metal ions(Co
2+
,Ni
2+
,Cu
2+
,Zn
2+
,Cd
2+
and Pb
2+
).Studies carried out on
these tripodal ligands clearly indicated that the tripodalorganoselenoethers are able to extract out the Ag (I) ions
highly efficiently in an extremely short span of time.
136

NATIONAL SYMPOSIUM IN CHEMISTRY P 35
Metallaboranes of Earlier Transition Metals:
Synthesis and Spectroscopic Characterization of Tantalaborane
{hhhhh
5
-C
5
Me
5
Ta}
2
B
5
H
10
(C
6
H
4
CH
3
)
Shubhankar Kumar Bose, Geetha Rani, Babu Varghese and Sundargopal Ghosh*
Department of Chemistry, Indian Institute of Technology, Madras, Chennai 600 036, India.
Reaction of 6 equiv of LiBH
4
with Cp*TaCl
4
(Cp* = h
5
-C
5
Me
5
) followed by thermolysis with BH
3
·THF in
toluene at 95°C leads to the formation of electronically unsaturated tantalaborane, {Cp*Ta}
2
B
5
H
10
(C
6
H
4
CH
3
)
.
The
spectroscopic characterization and solid state X-ray structure shows that it is isostructural with Mo, Cr and W
analogues and is best described as bicapped closo trigonal bipyramidal geometry.
Reference:
1. Aldrige, S.; Hashimoto, H.; Kawamura, K.; Shang, M.; Fehlner, T. P. Inorg. Chem. 1998, 37, 928.
2. Aldridge, S.; Hashimoto, H.; Shang, M.; Fehlner, T. P. Chem. Commun. 1998, 207.
3. Ting, C.; Messerle, L. J. Am. Chem. Soc. 1989, 111, 3449.
137

NATIONAL SYMPOSIUM IN CHEMISTRY P 51
ZnO/Immobilised Resin Based Photo Catalyst Using for Transformation of
Organic Molecule (Congo red)
Ram Babu Pachwarya, Vijay Kumar and R.C.Meena*
Department of Chemistry, Jai Narayan Vyas University, Jodhpur, Rajasthan – 342001
The Photo catalytic transformation of organic molecule (Congo red) has been investigated in ZnO /immobilized
Resin aqueous suspension. It was attempted to determine the feasibility of such transformation by varying different
parameters. In addition to prompt removal of the color, ZnO/immobilized resin based photo catalyst was
simultaneously able to complete transformation of the organic molecules, with a complete mineralization of Carbon
into CO
2
, Sulphur a heteroatom into SO
4
-2
. The mineralization of Nitrogen was more complex, Nitrogen atom in –
3 oxidation state, such as in amino group, remain at this reduction degree and produces NH
4
+
cations, subsequently
and strongly change into NO
3
-
ions.
These results revels that ZnO/immobilized resin photo catalysis may be employed in methods for treatment of
colored wastewater, not only for de-colorization, but also for de-toxification, in particular in textile industries in
semi-arid countries.
References:
1. T.Robinson. T, G.McMullan. G, R.Marchant. R,P.Nigam. P, Bioresource Technol. 2001, 77, 247.
2. P.P Zamora, A.Kunz, S.G. Moraes, R. Pelegrini, P.C. Moleiro, J. Reyes, N. Duran, Chemosphere 1999, 38, 835.
3. S.Ledakowicz, M. Solecka, R. Zylla, J. Biotechnol. 2001, 89, 175.
153

P 52 NATIONAL SYMPOSIUM IN CHEMISTRY
Photo-redox chemistry of cobalt (III) ammine complexes coordinated to
unsaturated carboxylic acids: Product analysis and quantum yields
determination
K. Jothivenkatachalam and P.Natarajan*
Department of Chemistry, Anna University, Trichy – 24, Tamil Nadu.
National Centre for Ultrafast Processes, University of Madras, Taramani Campus, Chennai
600 113, India.
Cobalt(III) pentaammine complexes with unsaturated carboxylic acids coordinated to the metal lead to
photoredox processes from the charge-transfer-to-metal (CTTM) excited states [Horvath et al (1)]. We have
investigated the photoredox chemistry of the complexes of the type Co(NH
3
)
5
X
2+
where X is crotonic acid,
cinnamic acid or sorbic acid and examined in detail the nature of the decomposition products from the carboxylate
free radical. The complxes on excitation in the CTTM band lead to the reaction
The photooxidised ligand fragments were isolated and characterized by NMR, IR, UV-Vis and mass spectral analysis. The quantum yields were determined for the photoredox reaction. The formation of the organic molecules from the photooxidised carboxylic acids shows interesting reaction pathways, which will be presented.
References 1. O. Horvath, K. L. Stevenson, Charge Transfer Photochemistry of Coordination Compounds, VCH, New York, 1993.
154

NATIONAL SYMPOSIUM IN CHEMISTRY P 53
Probing Geometry of Complexes in Solution by Depolarized Hyper-
Rayleigh Scattering
Sampa Ghosh, Puspendu K. Das*
Department of Inorganic and Physical Chemistry, Indian Institute of Science
Bangalore-560012, India
Noncovalent interactions are important in a number of chemical and biological processes. It plays an
important role in dictating structures of liquids, structure of DNA and the geometry of protein-ligand binding.
These interactions may be as weak as van der Waals force or as strong as hydrogen bonding and charge
transfer interactions. The smallest unit where we find the manifestation of these intermolecular interactions
are 1:1 aromatic donor-acceptor complexes. Relative orientation of the component molecules in such complexes
is determined by the nature of interaction and the two extreme geometries known are the parallel stacked and
the T shaped geometries. In experiments, the main attention, so far, has been given to determine the geometries
of such complexes in the solid state and in the gas phase. Though many groups have attempted to probe the
structures of such complexes in solution by NMR spectroscopy, they were unable to provide the details of
relative orientation in terms of the tilt and twist angles between the component molecules. In this work, we
use depolarized hyper-Rayleigh scattering technique to probe the geometry of noncovalently bound 1:1
molecular donor-acceptor complexes in solution. It provides the characterization of structure of such complexes
in solution in terms of the first hyperpolarizability tensor (b
ijk
). The origin of second order optical nonlinearity is
purely electronic in nature and thus the electronic structure of such complexes can be described in terms of its
hyperpolarizality tensor elements in the molecular frame. The molecular anisotropy is defined as u =
(where123
is the molecular frame, 1 being the direction of the principal axis of symmetry). We measure the depolarization ratio
(D) in the laboratory fixed frame (XYZ, X being the direction of polarization and Z the direction of propagation of
the incident light), where D = (b
XXX
, b
XXZ
are the first hyperpolarizability tensor elements in the same frame)
and correlate to u through co-ordinate transformation. How the symmetry of the molecules and that of light can be
combined to find geometrical information will be illustrated in this poster with examples such as 1,2,4,5-
tetracyanobenzene(TCNB)-1,2,4,5-tetramethylbenzene(durene), 2,3,5,6-tetrachloro-1,4-benzoquinone(Chloranil)-
durene, and benzene-naphthalene pairs.
155

P 54 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Sequestration of Au Nanoparticles by Alpha Amylase

Jashmini Deka
1
, Anumita Paul
1
, Aiyagari Ramesh
2
and Arun Chattopadhyay
1,3
*
Department of Chemistry
1
, Department of Biotechnology
2
and Centre for Nanotechnology
3
Indian Institute of Technology Guwahati, Guwahati 781 039
We shall present our recent results on the use of alpha amylase enzyme for the synthesis of Au nanoparticle
(NP) as well as their sequestration. The sequestration could be the result of attachment of enzyme to the NPs after
synthesis or it could be due to uptake from Au NP-starch composite following digestion.
We have for the first time synthesized Au NPs from AuCl
4
-
by using a pure enzyme such as a-amylase as the
reducing agent [1]. We find that in the composite, the activity of the enzyme is retained, as revealed by the kinetics
of starch digestion, which is similar to that of pure enzyme. The presence of free and exposed S-H groups is essential
in the reduction of AuCl
4
-
to Au NPs as well as their stabilization.
Further, we have carried out systematic study of the kinetics as well as the mechanism of digestion of starch-
Au NP composite by a-amylase [2]. This is relevant to starch-based polymers being used for pulsatile release of
drugs, peptides and other bioactive agents and starch-encapsulated magnetic particles for superior magnetic resonance
contrast agents. We observed that not only the digestion kinetics of the composite was similar to that of pure starch,
but the enzyme also sequestered the NPs following digestion. Finally, it was established that the surface plasmon
resonance of the Au NPs could be a direct probe for the study of digestion of starch (in the composite) by the
enzyme. A qualitative model for the digestion of the composite by a-amylase has also been proposed, which is
important for nanoscale drug delivery systems.
Reference
[1] Retention of Enzymatic Activity of a-Amylase in the Reductive Synthesis of Gold Nanoparticles. Abhijit Rangnekar, Tridib
Kumar Sarma, Atul Kumar Singh, Jashmini Deka, Aiyagari Ramesh, and Arun Chattopadhyay.Langmuir 2007, 23, 5700-5706
[2] Probing Au Nanoparticle Uptake by Enzyme Following Digestion of Starch-Au-Nanoparticle Composite. Jashmini Deka,
Anumita Paul, A. Ramesh, and Arun Chattopadhyay . Communicated.
156

NATIONAL SYMPOSIUM IN CHEMISTRY P 55
The Model Study of Proton Transfer Phenomena in Various Forms of GC
Base Pair
Rajib Lochan Sarma, Bipul Bezbaruah , C Medhi
Department of Chemistry, Gauhati University
Guwahati-781014, India
The structural changes and destabilization of base pair are some of the important consequences of radical
formation within DNA. The most energetic radicals can distort the flexible nucleic acid structure drastically [1]. The
schematic representation of proton transfer within hydrogen bonding region of normal GC base pair has been compared
with the proton transfer reactions through GC radical, GC cation and cationated GC radical to demonstrate the most
favorable proton transfer pathway. There are significant differences in the energy levels of proton transfer in these
systems and generation of cation and radical species at the equilibration region of proton transfer are distinctly
indicated. The two local minima detected in the cationic radical types of proton transfer are (GH
+
)C and G(H
+
C),
herein the minimum corresponding to G(H
+
C) occurs at lower energy level than the one for (GH
+
)C [2]. Hence the
proton is more stable at the cytosine nucleobase rather than guanine. The formation of G
+
is found in cationated GC.
Similarly two local minima are found at different energy levels in GC radical and cationated GC radical. Here we
have studied only the energies for the single proton transfer mechanism within hydrogen bonding region, where the
formation of cationated GC radical is found to be stable than the Watson Crick GC base pair. On the other hand the
formation of CG
+
may drastically disturb the rate of proton transfer within normal DNA due to the stabilization of
cationated species.
References:
[1] M. D. Sevilla, D. Becker; Electron Paramagnetic Resonance (RSC), 2004, 19, 243-278
[2] J. Bertran, A. Oliva, L. Rodriguez – Santiago, M. Sodupe; J Am Chem Soc, 1998,120, 8159-8167
157

P 56 NATIONAL SYMPOSIUM IN CHEMISTRY
Determination of Chloride in Liquid Detergent Using Ion-selective
Electrode with a Method of Standard Addition
Sangita D. Kumar, Ayushi, Niyoti Shenoy, and P.V.Ravindran
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085
.
Liquid detergent finds wide applications in cleaning of different instruments such as healthcare instruments,
electronic components and various reactor components etc. Cleaning surfaces may involve large variety of construction
materials viz. glass, metal, ceramic, plastic, cement and fiberglass. It is commonly used for leak detection on any
system where there is a pressure differential. It is for this type of application in reactors i.e. leak test of certain
facility that the presence of chloride in the liquid detergent becomes very crucial. The presence of chloride as
impurity affects the physical properties of the metal and accelerates the rate of corrosion in the system [1-3]. Hence,
the determination of chloride in the liquid detergent is very important.
The liquid detergent comprises of alkyl benzene sulfonate surfactant. It contains about 0.1 to 3 % of magnesium
salt. The magnesium salt helps in improved cleaning performance and better skinning properties. Magnesium chloride,
either anhydrous or hydrated (e.g., hexahydrate), is especially preferred in the formulation. The method contained in
ISO 457:1983 standard for the determination of chloride is based on the titrimetry method. The method is applicable
to detergents having chloride content equal to or greater than 0.1%. For the quantitative determination of chloride at
trace level a new accurate method has been developed using chloride ion-selective electrode. The method of standard
addition is frequently employed for samples of variable matrix; hence this was applied for the determination of
chloride in liquid detergent.
In the method of standard addition to sample, the following equation was applied
C
0
= C
s
/ 10
DE1/S
( 1+V
0
/ V
1
) – V
0
/V
1
(1)
Where S is the electrode calibration slope, V
0
and V
1
are the volumes; C
0
and C
s
are the concentrations of the
sample and the standard respectively. DE
1
= E
1
– E
0
where E
1
and E
0
are the potentials measured for the sample with
and without standard addition. For this method, the slope of the electrode response curve must be known and should
be linear, interfering species must be absent and, finally, the liquid junction potential between the reference electrode
and the solution must not change.
Samples of liquid detergent were obtained from local market (Bright liquid detergent). The sample solution (1
mL) was taken in a polyethylene beaker. To this, 5 mL of 0.1 M KNO
3
was added and final volume was made up to
10 mL with deionised water. The KNO
3
solution is added to adjust total ionic strength of different samples. The
potential of this solution was measured with an ion meter (Metrohm, Switzerland) using chloride selective electrode
(Orion) and Ag/AgCl reference electrode. For standard addition appropriate volume of chloride standard solution
(1 mg L
-1
) was added in steps in the range 0.1 – 1 mL. The potential was measured after each standard addition. The
concentration of the chloride ion was calculated by using the equation (1). The results obtained for two liquid
detergents samples are presented in Table 1. The limit of detection for the determination of chloride is 10 mg mL
-1
and the relative standard deviation was 5 % for the overall method.
Attempt was made to validate the method by measuring the chloride concentration in the samples by turbidimetry
and ion chromatography (IC) method. Both these measurements were not successful because of serious interference
from the matrix elements in turbidimetry and column contamination in IC methods. Hence the method has been
validated by standard addition recovery studies.
A simple, rapid and accurate method has been developed for the determination of chloride in liquid detergent
solutions. It makes use of readily available chemicals and equipment.
References:
1. H.H. Unlig, Corrosion and corrosion control, John Wiley and Sons, New York, 1971.
2. Process industries corrosion,. NACE, Texas, 1975.
3. NACE Basic Corrosion Course, NACE, Texas, 1975.
158

NATIONAL SYMPOSIUM IN CHEMISTRY P 57
Tunable optical and electronic property of Oligo(phenyleneethynylenes)
Reji Thomas and G.U. Kulkarni
Chemistry and Physics of Materials Unit and DST Unit on Nanoscience, Jawaharlal Nehru
Center for Advanced Scientific Research, Jakkur (P.O.) Bangalore- 560064
Oligo(phenyleneethynylenes) (OPE) are a class of molecules, which are well known for their interesting electronic
and photophysical properties.
1
The greater interest in these molecules is attributed to their tunable property by introducing
various functional groups and inducing geometric changes. Among various functionalized OPEs and related polymers
the alkoxy substituted phenylethynylenes are well studied for their interesting photo physical properties such as optical
absorption and emission.
1b
Recent literature reports various studies on change in the fluorescence behavior of these
molecules on suitable substitution of the phenyleneethyneylene backbone.
3
There are similar studies on the electronic
properties of these molecules, and these studies confirm that the rearrangement of electronic states of conjugated p-
backbone on substitution and conformational changes.
4
In order to understand the effect non-conjugated side chain in the
transport characteristics of these molecules, we have carried out combined X-ray crystallographic and photophysical
studies alkoxy substituted phenylene ethynylene molecules with varying alkoxy chain length. These molecules show
high emission properties both in solution and solid state with large blue shift in the film. Interestingly, on varying the
alkoxy side chain length of the alkoxy substitution, the molecules exhibit variation in planarity and in turn a systematic
variation in molecular transmission.
Reference
1. Reed, M. A.; Zhou, C.; Muller, C. J.; Burgin, T. P.; Tour, J. M. Science 1997, 278, 252 – 254. (b) Kim, J.; Swager, T. M.,
Nature, 2001, 411, 1030-1034.
2. Chen, J.; Wang, W.; Reed, M. A.; Rawlett, A. M.; Price, D. W.; Tour J. M., Appl. Phys. Lett. 2000, 77, 1224-1226.
3. Kim, J., Pure Appl. Chem., 2002, 74, 2031–2044.
159

P 58 NATIONAL SYMPOSIUM IN CHEMISTRY
Adsorption kinetics of alkanethiols on Au nanocrystals in a 2D lattice
using optical absorption spectroscopy
Ved Varun Agrawal, G. U. Kulkarni and C. N. R. Rao
Chemistry and Physics of Materials Unit and DST Unit on Nanoscience, Jawaharlal Nehru
Center for Advanced Scientific Research, Jakkur (P.O.) Bangalore- 560064
We have investigated how the optical absorption property of a 2D lattice of metal nanocrystals can be
tuned with alkane thiols of different chain lengths. This 2D lattice is a tightly packed assembly of gold
nanocrystals obtained via a self assembly process at the liquid-liquid interface[1, 2]. The absorption band is
situated at 700 nm for the pristine lattice which gets blue shifted upon adsorption of alkane thiols, the
magnitude of the shift being proportional to the chain length. The disordered nanocrystals thus created (
l
max,
530 m) are in equilibrium with the ordered nanocrystals in the lattice (l
max,
700 m) as indicated by an isosbestic point
around 600 nm. The rate of interaction of thiols with the Au nanocrystal lattice decreases with decreasing chain
length. The long chain thiols disintegrate or disorder the lattice more effectively, as evidenced by the increased
population of the thiol-capped Au nanocrystals in the solution. The effect of an alkanethiol is specific and the effects
with long and short chains are reversible. The changes in the Au plasmon band due interparticle separation has been
satisfactorily modeled on the basis of the Maxwell-Garnett formalism [3].
References
[1] V.V. Agrawal, G.U. Kulkarni, C.N.R. Rao, J. Phys. Chem. B 109 (2005) 7300.
[2] C.N.R. Rao, G.U. Kulkarni, V.V. Agrawal, U.K. Gautam, M. Ghosh, U. Tumkurkar, J. Colloid Interface Sci. 289 (2005)
305.
[3] J.C.M. Garnett, Philosophical transaction of the royal society of london, series A 203 (1904) 385.
160

NATIONAL SYMPOSIUM IN CHEMISTRY P 59
Exfoliated Graphite Oxide - Based Assemblies
for Amperometric Sensing
G. K. Ramesha and S. Sampath*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore 560 012
Exfoliated Graphite Oxide (EGO) is a layered material, lighter than graphite, both in colour and in
density. It consists of oxidised graphite sheets with hydroxyl and epoxy functional groups in the basal plane
and carboxyl and carbonyl functional groups at the edges. The functional groups make EGO hydrophilic and
water molecules can readily intercalate into the interlayer galleries. Hence, EGO is regarded as graphite-type
intercalation compound with covalently bound oxygen and non-covalently bound water between the carbon
layers. The presence of a large amount of functional groups leads to the stabilization of negatively charged
EGO as a colloid in a wide pH range of 2-11.
In the present studies, EGO is prepared by chemical oxidation of exfoliated graphite (prepared by thermal
exfoliation of bisulphate ion intercalated graphite) and characterized using spectroscopic and electrochemical
techniques. Thin film of EGO on glassy carbon electrode (GC) was formed by evaporation technique using
colloidal EGO deposited on the GC surface. The EGO film is subsequently used to detect Pb(II) in aqueous
medium. The detection limit is found to be picomolar and two linear calibration ranges are obtained in 1pM
to 0.1 µM and 10 µM to 10 mM.
In the second part of the studies, electrostatic layer-by-layer assembly of EGO and redox protein
(haemoglobin) is formed on a gold surface and their electrochemical properties are studied. An amperometric
sensor is developed and the system is further applied to the electrocatalytic reduction of hydrogen peroxide.
Reference:
G.K. Ramesha and S. Sampath, Electroanalysis, 2007, 19(23), 2472.
161

P 60 NATIONAL SYMPOSIUM IN CHEMISTRY
162
Application of Majority Rule in the Self-assembly of Aminoacid
Functionalized Oligo(p-phenylenevinylene)s
S. Santhosh Babu, Vakayil K. Praveen and Ayyappanpillai Ajayaghosh*
Photosciences & Photonics Group, Chemical Sciences & Technology Division
National Institute for Interdisciplinary Science and Technology (NIIST)
Trivandrum, India-695019.
Manifestation of molecular chirality into supramolecular helicity in synthetic molecules, leading to a
preferred handedness is a challenging task[1].

The “majority rule” approach reported by Green et al. have been
used for chirality amplification in supramolecular assemblies, using a slight exess of one enantiomer that leads to a
strong bias toward the helicity preferred by the enantiomer that is present in majority[2]. Oligo(p-phenylenevinylene)s
(OPVs) are known to form helical assemblies and gels in nonpolar hydrocarbon solvents[3]. Herein we explore the
possibilities of amino acid moieties as chiral motifs for the creation of helical assemblies of OPVs leading to the
formation of gels even in moderately polar solvents such as chloroform and toluene. Addition of a very small
concentration of the chiral molecule to the racemes mixture resulted in induction and amplification of chirality’s in
the gel state. The enantiomeric excess and co-operating units will therefore act together to favour the helical
sense preferred by the configuration of the majority and thereby making the expression of the chirality of a particular
enantiomer from a racemic mixture. SEM and TEM studies gave further insight into the morphological features of
these chiral OPV self assemblies. The details of these studies will be presented.
References
1. Palmans, A. R. A, Meijer, E. W. Angew. Chem., Int. Ed. 2007, 46,
2. Green, M. M.; Park, J.-W.; Sato, T.; Teramoto, A.; Lifson, S.; Selinger, R. L. B.; Selinger, J. V. Angew. Chem., Int.
Ed. 1999, 38, 3138.
3. Ajayaghosh, A.; Varghese, R.; George, S. J.; Vijayakumar, C. Angew. Chem., Int. Ed. 2006, 45, 1141.
DL
DL

NATIONAL SYMPOSIUM IN CHEMISTRY P 61
Task Specific Ionic Liquid Bronsted Acid-clay Hybrid Nanocomposite
Catalyzed Transesterification Reaction
Vasundhara Singh*, R.Ratti, M.Vaultier
a
* Department of Applied Sciences, Punjab Engineering College, Deemed University,
Chandigarh
a
Institute de Chimie, University of Rennes 1, Rennes, France
Transesterification is one of the important organic transformations that have relished numerous laboratory and
industrial uses. The ester to ester transformation is particularly significant when the parent carboxylic acids are
labile and difficult to isolate. b- ketoesters are muticomponent coupling reagents having electrophilic carbonyl and
nucleophilic carbon which make them important synthons for the total synthesis of number of natural products.
Since transesterification, used for the synthesis of new b- ketoesters, is an equilibrium process, it is accelerated by
the simultaneous removal of low boiling coproduct alcohol during the process by distillation. This reaction is catalyzed
by a number of chemical species like organic and inorganic acids, bases, anion exchange resins, DMAP, molecular
sieves, Lewis acids, titanium tetra oxide, zeolites, clay, Mo-ZrO
2
, Envirocat EPZG to list a few. But all these
procedures are flawed with one drawback or another like volatility and toxicity of acid catalysts, long reaction times,
hostility of catalysts to environmental issues and their non-recoverability.
Due to rigorous environmental statutes, the scientific community is under great stress to develop ecocompatible
synthetic methodologies. So present day chemistry is more inclined to re-scrutinize the existing synthetic procedures
thereby making them more congenial. More than 60% of products and more than 90% of processes worldwide rely
on the rapidly expanding field of catalysis. The use of ionic liquids as either solvents or catalysts is emerging as
subject of considerable recent attention in accordance with prospects of ‘Green Catalysis’. Keeping in view these
concerns we have synthesized a TSIL- bronsted acid and its clay hybrid which is successfully used as catalyst for the
transesterification of b- ketoesters with various alcohols. The results of the same will be presented.
163

P 62 NATIONAL SYMPOSIUM IN CHEMISTRY
Novel Cyclic Trimeric Thermotropic Liquid Crystals: Synthesis and
Characterisation
A. Shanavasà, A. Sultan Nasarà & T. Narasimhaswamy*
à

Department of Polymer Science, University of Madras, Guindy Campus,
Chennai 600025
Polymer Lab, Central Leather Research Institute, Adyar, Chennai 600020
Thermotropic liquid crystals are recognized as an important class of organic electronics due to their sensitivity
to external stimuli. From molecular structural point of view, they are primarily classified into calamitics and discotics.
Usually, the mesogen consists of core made up of substituted phenyl rings connected through linking groups and
flexible terminal units. In recent years, molecular topology of mesogen has been identified as one of the crucial
factor in the formation of mesophase. The calamitic mesogens generally have linear like structures while discotics
possessed disk-like cores. The cyclic trimers, on the other hand, show different topology leading to the formation of
calamitic and columnar phases depending up on the terminal and linking units. Moreover, these oligomers (e.g.
trimers) are considered as model compounds for
polymeric liquid crystals. In the present work novel
cyclic trimeric liquid crystals are synthesized using
1,3,5-tricarboxylic acid as precursor (Scheme 1).
All the intermediates and target mesogens are
characterized using FT-IR and
1
H and
13
C NMR
spectroscopy (representative spectra are shown).
The terminal alkoxy chains are varied from 2-16
(even series) and the mesophase characteristics like
melting, clearing temperatures and phase stability
is determined by optical polarizing microscope and
DSC. The transition enthalpy values further
confirm the mesophase identified by the
microscope. Despite lower phase stability, the
appearance of smectic polymorphism is an
interesting feature of the series. The structure-
property relationship with respect to core and
terminal group chain length are discussed.
164

NATIONAL SYMPOSIUM IN CHEMISTRY P 63
Mimicking Simultaneous and Selective Decoupling of Different
Heteronuclei and Determination of Relative Signs of Dipolar Couplings
Using Multiple Quantum Spin State Selection
Sankeerth Hebbar
#
and N Suryaprakash
*
#
Solid State and Structural Chemistry Unit and *NMR Research Centre,
Indian Institute of Science, Bangalore 560012.
The non-selective excitation of a homonuclear multiple quantum in a heteronuclear spin system does not
disturb the spin states of the heteronuclei resulting in the detection of single quantum transitions based on the spin
states of the heteronuclei. The cross section taken along the single quantum dimension thus mimics the decoupling
of heteronucleus. In addition, the spin state selected transitions are significantly lower in number compared to
normal one dimensional spectrum, but suffice for the precise determination of homonuclear couplings. When more
than two heteronuclei are involved, the technique can be extended for mimicking simultaneous decoupling of all the
heteronuclei. Furthermore, the detection of any heteronuclear multiple quantum results in the selective decoupling
of the passive heteronuclei. The methodology can thus be exploited for the analysis of the complex spectrum and
for the determination of the relative signs of the dipolar couplings. The results of the work on different isotopomers
of acetonitrile,
13
CH
3
13
CN,
13
CH
3
C
15
N, CH
3
13
C
15
N and
13
CH
3
13
C
15
N aligned in thermotropic liquid crystals, including
the theoretical description of the behaviour of the spins using polarization operators will be discussed.
165

P 64 NATIONAL SYMPOSIUM IN CHEMISTRY
Effect Of Various Additives On The Gel-To-Liquid- Crystalline Phase
Transition Temperature Of Dimethyldioctadecylammonium-Bromide
Vesicles
Moazzam Ali and Swapan. K. Saha*
Department of Chemistry, University of North Bengal, Siliguri 734 013
The effect of alkyltrimethylammonium bromides (Tetradecyltrimethyl-ammoniumbromide (TTAB),
Hexadecyltrimethylammoniumbromide CTAB and Octadecyltrimethylammonium-bromide OTAB) and
alkylpyridiniumhalides (Cetylpyridiniumbromide CPB and Cetylpyridiniumchloride CPC ) on the gel-to liquid
crystalline phase transition temperature (T
m
) of spontaneously formed vesicle dispersions of
dimethyldioctadecylammoniumbromide (DDOAB) have been examined using differential scanning calorimetry
(DSC). The alkyltrimethylammonium bromides, affected the T
m
in a complex manner, depending on the hydrocarbon
chain length. OTAB elevated the T
m
whereas TTAB and CTAB depressed the Tm of DDOAB vesicles. However, the
planar pyridinium heads of CPC and CPB, having similar tail length as that of CTAB, affected the T
m
only weakly,
although the decreasing tendency of T
m
is observable. In addition the shape of the main peak i.e. the gel-to-liquid
crystalline phase transition peak shows very little sign of peak broadening. It seems that the lateral attraction between
the DDOAB molecules of the bilayer is not reduced significantly by the penetration of the pyridinium moiety. The
perturbing effect of aromatic hydroxyl compounds viz.; 1-Naphthol, 2-Naphthol, 2,3-Dihydroxynaphthalene and
2,7- Dihydroxynaphthalene on the gel-to-liquid-crystalline phase transition temperature of the vesicle membrane
have also been studied using the same technique. A significant decrease in T
m
was observed with the addition of
these hydroxy compounds. However, for 2,7-dihydroxynaphthalene the Tm first decreases upto a certain concentration
and then increases. The present study reveals some aspects of the interaction of various additives with spontaneously
formed vesicles of DDOAB.
Gel to liquid crystalline transition
166

NATIONAL SYMPOSIUM IN CHEMISTRY P 65
Photo Catalytic Activity of Lanthanide (Ce, Pr AND Nd) Molybdates
Sudarshan Mahapatra
a
, Giridhar Madras*
b
and T.N. Guru Row
a
a
Solid State and Structural Chemistry Unit and
b
Department of Chemical Engineering,
Indian Institute of Science, Bangalore 560 012
Lanthanide (Ce, Pr, and Nd) molybdovanadates were synthesized by the solid-state method. These compounds
crystallize in the tetragonal space group I41/amd with a = b = 7.3750 (4) and c= 6.4867 (4) Å and Z = 4. The
crystal structure has been analyzed by FTIR, UV-visible spectroscopy, and powder X-ray diffraction. Particle sizes
are in the range of 300-400 nm as observed by scanning electron microscopy. Energy-dispersive X-ray analysis
suggests the formation of Ln
0.95
Mo
0.15
V
0.85
O
4
(Ln = Ce, Pr, and Nd) and the Rietveld refinements of the powder X-ray
data substantiate this observation. Thermal analysis of these solids shows stability of the phase up to 800° C. These
materials were investigated for photocatalytic activity by degrading different dyes such as methylene blue(MB),
orange G (OG), Rhodamine B (RB), Rhodamine Blue (RBL), Alizarine Red S (ARS) and Remazol brilliant blue
(RBBR) under solar and UV irradiation since they exhibited lower band gaps. The degradation rates for all the dyes
show enhancement as compared to the commercial titania catalyst, Degussa P-25, both in UV and sunlight. These
compounds degrade chlorinated phenols much faster than titania, which indicates selectivity toward chloro substitution.
Variation of the degradation rate of MB with initial concentration under solar radiation for Cerium molybdovanadate
and Degussa P-25 titania.
References:
1. Fuess, H.; Kallel, A. J. Solid State Chem. 1972, 5, 11.
2. Rice, C. E.; Robinson, W. R. Acta Crystallogr., Sect. B 1976, 32, 2232.
3. Chakoumakos, B. C.; Abraham, M. M.; Boatner, L. A. J. SolidState Chem. 1994, 109, 197.
167

P 66 NATIONAL SYMPOSIUM IN CHEMISTRY
Ruthenium(II) Complexes of Bipyridine - Glycoluril and their Interactions
with DNA
Megha S. Deshpande, Anupa A. Kumbhar and Avinash S. Kumbhar*
Department of Chemistry, University of Pune, Pune–411 007, India.
The synthesis, structural and photophysical characterization, DNA binding and cleavage by Ru(II)
polypyridyl complexes of the type [Ru(N-N)
2
(BPG)]Cl
2
1-4, [Ru(BPG)
3
]Cl
2
5

and [Ru(N-N)(BPG)
2
]Cl
2
6-9 where
N-N is 2,2‘-bipyridine (bpy), 1,10-phenanthroline (phen), dipyrido[3,2-d:2‘,3‘-f]quinoxaline (dpq), dipyrido[3,2-
a:2‘,3‘-c]phenazine (dppz) which incorporates the bipyridine glycoluril ligand have been studied to investigate the
influence of the ancillary ligand. The X-ray structure of urea fused bipyridine ligand BPG reveal inherent H-bond
donor (N-H) and acceptor groups (C=O) which exhibit a potential to generate supramolecular motifs as well as offer
H-bonding groups for DNA binding. Single crystal X-ray analysis of 1, 5 and 7 indicate a butterfly like structure for
the cationic secondary building units evidencing this H-bonding capacity which results in a supramolecular self-
assembled metal-organic frameworks (MOF) forming channels in 1 and 5 encapsulating tetradecameric water cluster,
mixed water-dimethylsulfoxide cluster and a network of water molecules and chlorine anions surrounding secondary
building units in 7. The binding ability of these complexes to DNA is dependent on the planarity of the intercalative
polypyridyl ligand, which is further influenced by the ancillary bipyridine-glycoluril ligand. Interaction of complexes
1-9 with plasmid pBR322 DNA reveals that all complexes cleave DNA efficiently at micro molar concentrations
under dark and anaerobic conditions probably by a hydrolytic mechanism. Molecular mechanics calculations of
these systems confirm two different binding modes for the complexes.
References: 2) Deshpande, M. S.; Kumbhar, A. S.; Puranik, V. G.; Selvaraj, K. Cryst. Growth Des. 2006, 6, 743.
3) Deshpande, M. S.; Kumbhar, A. A.; Kumbhar, A. S. Inorg. Chem. 2007, 46, 5450.
168

NATIONAL SYMPOSIUM IN CHEMISTRY P 67
Performance Evaluation of Waste Activated Carbon from ‘Aquaguard’ as
an Adsorbent for the Removal of Phenol from Aquatic Environment
Bijoli Mondal and Anjali Pal*
Department of Civil Engineering, Indian Institute of Technology, Kharagpur-721302, India
Water pollution is a persistent problem. Phenolic compounds widely exist in the effluents coming from industries
such as oil refineries, coal tar, plastics, leather, textile, paint, varnishes, steel, phenol producing industries, explosive
manufacturing industries, fertilizer and pesticide industries, pharmaceutical industries, coke oven plants, dye
manufacturing industries, etc., and are acutely toxic. Also, during chlorination of phenol bearing wastewater,
chlorophenols are produced. These chlorophenols are toxic and they are considered as persistent organic pollutants
(POP). Among several processes available for the removal of phenolic compounds from wastewater, adsorption has
been found to be an efficient and economically beneficial process. However, commercially available activated
carbon remains to be a rather expensive material. In the present study the waste activated carbon from ‘Aquaguard’
water purifier after it is disposed of, was used for phenol removal. Removal of phenol by waste ‘Aquaguard’ carbon
(WAC) was studied separately in batch and continuous mode. WAC was found to be very efficient, and it is almost
a ‘no-cost’ material. Under optimized conditions ~98 % efficiency could be achieved for the removal of phenol
when present even at a high concentration (20 mg/l). The kinetic studies showed that 4 hours shaking time was
sufficient to achieve the equilibrium for phenol. The removal of phenol followed the pseudo-second order reaction
kinetics. Study was conducted to see the effects of adsorbent dose on the removal of phenol using WAC. The pH was
kept at 6.5±0.1. The optimum adsorbent dose was found to be 2 g/l. The effects of different parameters like pH,
presence of different ions, temperature, agitation speed etc. were studied. The removal of phenol increased with
increase in pH up to 6.0 and then decreased. There was no effect of agitation speed. The effect of different ions for
the removal of phenol was within
±5 %. No effect of humic acid, 2, 4-D, atrazine and endosulfan was noticed. The
removal of phenol decreased with increase in temperature. The adsorption isotherm was well described by the
Freundlich isotherm model. The maximum adsorption capacity of WAC was found to be 25.57 mg/g for phenol
having concentration 20 mg/l at 27±2°C. Evaluation of thermodynamic parameters revealed that the adsorption
process was spontaneous and exothermic in nature. Fixed bed column studies were conducted for the removal of
phenol from aqueous environment. The column with 2 cm diameter having bed depths of 5, 10 and 15 cm could treat
5.92, 12.11 and 16.65 liter of phenol bearing wastewater (phenol concentration 20 mg/l). The bed was almost 95 %
saturated at the time of breakthrough. The adsorption rate constant (K) and adsorption capacity were found to be
0.013105 l/mg-h and 13.886 kg/m
3
. Effect of flow rate and initial concentration was studied.
169

P 68 NATIONAL SYMPOSIUM IN CHEMISTRY
Estimation of Thermodynamic Properties of Cyclic Paraphenylacetylenes
(CPPA) by Isodesmic and Homodesmic Reaction Methods
Mohamad Akbar Ali and Mangala Sunder Krishnan*
Department of Chemistry, IIT Madras, Chennai 600036
Polycyclic hydrocarbons containing phenyl rings connected to each other at the para positions by acetylenic
bonds form a novel group of hydrocarbon molecules with potential applications in carbon nanotubes, molecular
devices and molecular electronics.
1
The polymeric structures of polycyclic phenylacetylenes (n = 2 – 7) are given
below:
The strain energy becomes less as n increases leading to substantially different chemical stabilities for these
compounds. Due to the strain many of these compounds are not yet synthesized in the laboratory, and accurate ab
initio studies will hopefully provide for estimations of chemical properties. Isodesmic and homodesmic reactions
2
have been very useful tools in the past few years for performing theoretical calculations of thermodynamic properties.
In this paper details of various schemes and the results of calculations performed with the help of Gaussian-03
3-4
will
be described along with theoretical analyses for the variation of properties with n.
References:
1. T. Kawase et al., Cyclic [6] and [8] paraphenylacetylenes, Angew. Chem.Int. ed., 35 2664 (1996)
2. Pople, J. A et al.., Ab initio molecular orbital theory (Wiley Interscience, 1985)
3. Frisch A., et al, Gaussian’ 03 User’s Reference” (Gaussian Inc., 2003)
170

NATIONAL SYMPOSIUM IN CHEMISTRY P 69
In situ Cryo-Crystallisation of Chloro and Bromo Substituted Anilines and
its Intermolecular Interactions.
Susanta K. Nayak, S. J. Prathapa and T. N. Guru Row*
Solid State and Structural Chemistry Unit, Indian Institute of Science,Bangalore-560012.
In situ cryo-crystallization of a liquid, the subsequent structure determination and its study of intermolecular
interactions has emerged as an area of contemporary interest. In -situ cryo-crystallization of fluoro- substituted
anilines and the evaluation of the variability in halogenated trifluoroacetophenones (Chopra et al.[1, 2] ) clearly
bring out the importance of interactions generated by fluorine in crystalline lattices and establishes that indeed
fluorine has a directing influence in molecular assembly. In order to evaluate the propensity of interactions in
halogens in general, o - chloro and o -bromo anilines were crystallized from their respective liquids via in situ cryo
crystallization method. The crystal structures are isostructural belonging to a trigonal system, space group P 3
1
. The
crystal packing is due to intramolecular N-H…Cl / Br and intermolecular N-H….N hydrogen bonds. However, in
the case of o-bromo aniline short Br…Br contacts (3.64 Å ) are observed suggesting that this interaction is a
consequence of the size of the Br atom.
References 1. Chopra, D.; Thiruvenkatum, V.; Guru Row, T. N. Cryst. Growth Des. 2006, 6, 843.
2. Chopra, D.; Thiruvenkatum, V.; Manjunath S. G.; Guru Row, T. N. Cryst. Growth Des. 2007, 7, 868.
171

P 70 NATIONAL SYMPOSIUM IN CHEMISTRY
Electronic Properties of Transverse Substituted and Unsubstituted t-PA: a
Comparative DMRG Study
Manoranjan Kumar and S. Ramasesha
Solid State and Structural Chemistry Unit, Indian Institute of Science,
Bangalore 560012, India.
The optical properties of conjugated polymers have been a frontier area of research because of their potential
applications in the non-linear optoelectronic devices. Strong photoluminesence (PL) is one of the most important
requirements for making optoelectronic devices [1-3]. Designing of strong PL material requires complete
understanding of mechanism involved in the optical phenomenon. According to Kasha’s Rule, E(2A
g
)>E(1B
u
) is the
essential condition for strong PL. Trans-polyacetylene (t-PA) is an excellent example of non-emissive material. But
replacement of H of t-PA chain by phenyl groups, or its derivatives leads to strong . This behavior can be understood
by considering coulomb interaction of the p electrons in these conjugated systems. Mazumdar et. al have considered
electronic correlation in substituted t-PA and used Pariser Parr and Pople (PPP) model to study the
Polydiphenylacetylene (PDPA) in the Single Configuration Interaction (SCI) picture In this work, we have used
finite symmetrized Density Matrix Renormalization Group (SDMRG) method for Polydiethylacetylene (PDEA)
and t-PA systems. To obtain E(2A
g
) and E(1B
u
) states, spatial symmetry C
2,
spin parity and electron hole symmetry
are used. We find that there is no level crossing of E(2A
g
) and E(1B
u
) states as function of bond alternation, d up to
0.1. Singlet-Triplet gap does not go to zero in PDEA, but it vanishes for t-PA as ä goes to zero. We also compare the
non-linear optical properties of these two systems.
References:
[1] J. L. Bredas and R. Silbey, Conjugated Polymers: the Novel Science and Technology of Highly Conducting and Nonlinear
Optically Active Materials (Kluwer Academic, Dordrecht, 1991).
[2] Blatch J. W. Blatchford and A. J. Epstein, Am. J. Phys. 64, 120 (1996).
[3] D. de Leeuw, Phys. World 12, 31 (1999).
172

NATIONAL SYMPOSIUM IN CHEMISTRY P 71
Large Scale Self Organization of Gold Nanorods Leading to One, Two and
Three Dimensional Superstructures Induced by Monolayers
T. S. Sreeprasad, A. K. Samal and T. Pradeep*
DST Unit on Nanoscience, Department of Chemistry and Sophisticated Analytical Instrument
Facility, Indian Institute of Technology Madras, Chennai - 600 036, India
Gold nanorods are versatile material for diverse applications..[1] A method is described for assembling gold
nanorods into one, two and three dimensional superstructures. The addition of dimercaptosuccinic acid (DMSA)
into the nanorod solution was found to induce self assembly of nanorods into one-dimensional ‘tape-like’, two-
dimensional ‘sheet-like’ and three-dimensional ‘superlattice-like’ structures depending on the DMSA concentrations.
Assembly was found to be following smectic structure, where the nanorod long axes are parallel to each other. The
rods are spaced 8.5
±0.3 nm apart in the resulting structures, which extends over micrometer in length. We formed
organization perpendicular to the grid also. The nanorod tapes were found to bend and form globular assemblies as
well. The assembly and morphology of the nanorod structures were characterized by transmission electron microscopy
(TEM) and UV-vis spectroscopy. The effect of DMSA concentration as well as the pH of the medium was also
studied. Based on several control experiments utilizing several similar, charge neutralization of the nanorods by the
carboxylic group of the DMSA was found to be the principal reason for such an assembly, while the mercapto
groups render additional stability. A mechanistic model of the assembly is proposed [2]. This type of assemblies
would plausibly function as plasmonic waveguides [3]) in potential nanodevices.
References
1) Juste, J. P.; Santos, I. P.; Liz-Marz’an, L. M.; Mulvaney, P. Coord. Chem. Rev. 2005, 249, 1870.
2) Sreeprasad, T. S.; Samal, A. K.; Pradeep, T. Unpublished.
3) Ozbay, E. Science 2006, 13, 189.
173

P 72 NATIONAL SYMPOSIUM IN CHEMISTRY
A Computational Study Towards The Rotational Barriers of
Thioamides
Manoj Kumar Kesharwani and Bishwajit Ganguly*
Analytical Science Discipline, Central Salt and Marine Chemicals Research Institute,
Bhavnagar: 364002, Gujarat, India
Rotational barrier heights for several thioamides (X
2
NC(=S), H=Y, X) have been investigated in the gas phase
by applying density functional theory. The calculated results suggest that the electrostatic and electronic effects can
tune the planar form of amides to pyramidal forms. The variations of rotational barriers around the formally single
C-N bond in all compounds are studied in comparative context with thioformamide. These results will be useful for
the studies in immunosuppressant agent like FK506.
174

NATIONAL SYMPOSIUM IN CHEMISTRY P 73
Rapid Measurement of
3
J(H
N
-Ha) and
3
J(N-Hb) Coupling Constants
In Polypeptides
Ravi Pratap Barnwal,
1
Ashok K. Rout,
1
H.S. Atreya
2*
and Kandala V.R. Chary
1*
1
Department of Chemical Sciences, Tata Institute of Fundamental Research, Mumbai 400 005
India
2
NMR Research Centre, Indian Institute of Science, Bangalore-560012, India
We have developed two NMR experiments, (3,2)D H
NHA and (3,2)D HNHB, for rapid and accurate measurement
of
3
J(H
N
-H
a
) and
3
J(N-H
b
) coupling constants in polypeptides based on the principle of G-matrix Fourier transform
NMR spectroscopy
1
and quantitative J-correlation. These experiments, which facilitate fast acquisition of three-
dimensional data with high spectral/digital resolution and chemical shift dispersion, will provide renewed opportunities
to utilize them for sequence specific resonance assignments, estimation/characterization of secondary structure
with/without prior knowledge of resonance assignments, stereospecific assignment of prochiral groups and 3D
structure determination, refinement and validation. Taken together, these experiments have a wide range of applications
from structural genomics projects to studying structure and folding in polypeptides
2
.
Reference
1. Atreya, H. S.; Szyperski ,T. Methods Enzymol. 2005, 394, 78.
2. Barnwal, R. P.; Rout, A. K.; Chary, K. V. R.; Atreya, H. S. J. Biol. NMR. 2007 (in press).
175

P 74 NATIONAL SYMPOSIUM IN CHEMISTRY
Intra and Intermolecular Hydrogen Bonding in Formohydroxamic acid
Ruchi Kohli, Damanjit Kaur*
Chemistry Department, Guru Nanak Dev University, Amritsar 143005
The hydrogen bonding of water with biomolecules like DNA, polypeptides and other molecules etc. significantly
affect the structure and reactivity of these basic molecules of life. Hydroxamic acids are molecules of biological
importance due to their applications as tumor inhibitors, antimicrobial agents, antituberculosis agents etc. The present
theoretical studies suggest, inspite of the presence of multiple potential sites for hydrogen bonding in formohydroxamic
acids(FHA), only one of the isomer 1Z shows H-bond interactions, though the distances between H-bond donor and
acceptor are less than sum of their van der Waal radii, the X…H-A bond angle does not allow the H-bond stabilization.
The aggregation of four lowest energy isomeric forms 1Z, 1E, 2Z and 2E with single water at MP2/Aug-cc-pVDZ
level leads to stabilization energies in the range 3.5-10.9 kcal/mol, which indicate that the intermolecular H-bond is
stronger than intramolecular H-bond. The dimerization of various isomeric forms at MP2/6-31+G* resulted in
stabilization energies of the order 2.6-16.1 kcal/mol. 1Z-1Z(1) homodimer is most stable dimer and the optimized
structure is having two symmetrical strong H-bond interactions between carbonyl oxygen of one FHA unit with the
hydroxyl hydrogen of the second unit. Carbonyl oxygen is the strongest H-bond acceptor site in FHA as suggested
by the dimerization and FHA-H
2
O adduct studies. Cooperativity and synergic enhancement of intramolecular H-
bonding is suggested in addition to the charge transfer and electrostatic interaction stabilization [1].
References: Kaur, D. ; Kohli, R. Int. J. Quant. Chem., 2008, 108, 119.
176

NATIONAL SYMPOSIUM IN CHEMISTRY P 75
Anthracene-9,10-dione – A versatile Platform for Both Cation and Anion
Chemosensors
Kuljit Kaur, Navneet Kaur, Vijay Luxami, Nidhi and Subodh Kumar
*
Department of Chemistry, Guru Nanak Dev University, Amritsar-143005
The development of new molecular systems for colorimetric detection of cations, anions and neutral molecules
have attained prime significance due to their biological and environmental applications. Anthracene-9,10-diones
due to their diverse chemical features depending on the substitution pattern have shown wide spread potential for
the development of dye stuff materials, DNA intercalators, redox active and optical sensors. The possibility of color
tuning and in-sights into the mechanisms responsible for these color changes can lead to further refinements in
procedures.
The augmentation of electron-withdrawing or electron-donating groups on anthracene-9,10-dione moiety tunes
the interactions of resulting receptors towards analytes bearing either negative or positive charge. Further the variation
in electron density polarization tunes their selective or differential binding towards various heavy metal ions. The
use of this meticulous control of varied binding sites in developing wide range of anthracene-9,10-dione based
sensors for Cu
2+
, Ni
2+
, Co
2+
, Hg
2+
, Ag
+
and F
-
will be presented
1,2
.
References:
1. Navneet Kaur and Subodh Kumar, Chem. Commun., 2007, 3069-3070.
2. Navneet Kaur and Subodh Kumar, Dalton Trans., 2006, 3766-3771.
177

P 26 NATIONAL SYMPOSIUM IN CHEMISTRY
Cobalt(III) Catalysed Oxidation of Ethylbenzene Under Enviromentally
Friendly Conditions
Rajesh Chakrabarty,
§
Birinchi K Das*
Department of Chemistry, Gauhati University, Guwahati 781014
§
Present address: Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore 560 012.
Although cobalt(II) catalysts are well known for aerobic oxidation of alkylaromatics, cobalt(III)-based catalysts
also have been shown to be effective for the oxidation of alkylaromatic hydrocarbon feedstock [1]. Olive green oxo-
bridged Co(II) cubane complexes Co
4
(?
3
-O)
4
(?-O
2
CMe)
4
(py)
4
(1) and Co
4
(?
3
-O)
4
(?-O
2
CPh)
4
(4-CNpy)
4
(2) – py,
pyridine and 4-CNpy, 4-cyanopyridine – have been prepared by H
2
O
2
oxidation of a mixture of Co
2+
, RCO
2
- and
py/4-CNpy in methanol at an elevated temperature and tested as catalysts for ethylbenzene oxidation [2].
Using complexes 1 and 2 as homogeneous catalysts air oxidation of neat ethylbenzene has been investigated
under atmospheric pressure at 120ºC. While the reaction catalyzed by 1 has resulted in 68.6% yield of acetophenone
at 99% selectivity, compound 2 catalyzes the reaction giving acetophenone in 60% yield and 94% selectivity at the
end of 22h at 120
°C.
The above combination of yield and selectivity shows that cobalt(III) complexes having a cubane-like [(Co
III
)
4
(?-
O)
4
]
4+
core are highly active in the aerobic oxidation of ethylbenzene under solvent free, hence environmentally
attractive conditions.
References
[1]. (a) B. K. Das; J. H. Clark Chem. Commun. 2000, 605-606; (b) J.-Y. Qi ; H.-X. Ma ; X.-J. Li ; Z.-Y. Zhou ; M. C. K. Choi ;
A. S. C. Chan ; O.-Y. Yang Chem. Commun. 2003, 1294-95.
[2] R. Chakrabarty; S.J. Bora; B. K. Das Inorg. Chem. 2007, 46, 9450-9462.
128

NATIONAL SYMPOSIUM IN CHEMISTRY P 27
Synthesis, Adsorption Studies and Analytical Applications of N-Cetyl-N, N-
Trimethyl Ammonium Bromide Based Cerium(IV) Phosphate: A Novel
Surfactana Based Hybrid Fibrous Ion Exchanger
Amita Somya, M. Z. A. Rafiquee and K. G. Varshney
Department of Applied Chemistry, Z.H. College of Engineering and Technology,
Aligarh Muslim University, Aligarh 202002, India
A recent interest has been developed in the synthesis of hybrid fibrous ion-exchangers [1] due to their outstanding
chemical, mechanical and thermal stability, in addition to metal ion selectivity. It has been observed that the introduction
of organic species into an inorganic material enhances its reproducibility in ion-exchange behavior and its chemical
stability to some extent. A large number of hybrid fibrous ion-exchange materials [2-6] have been synthesized in
these laboratories by incorporating organic monomers/polymers with inorganic ion-exchange materials, showing
the promising ion-exchange characteristics. Surfactants or surface-active agents have shown the enhancement in
adsorption of metal ions on the surface of ion exchangers [7-9] by reducing the interfacial tensions between the
material (solid) and aqueous phase (liquid). Efforts have, therefore, been made in these laboratories to synthesize
some surfactant based hybrid fibrous ion-exchange materials. Surfactant, when present in the matrix of inorganic
ion-exchanger not only, enhances the ion-exchange capacity of the material but also the adsorption of metal ions.
The present work deals with the synthesis of N-cetyl-N, N, N-trimethyl ammonium bromide based cerium (IV)
phosphate (CTAB-CeP) as a new surfactant based hybrid fibrous ion-exchanger.
CTAB-CeP was synthesized by mixing the solutions of ceric sulphate, phosphoric acid and N-cetyl-N, N, N-
trimethyl ammonium bromide of optimum concentrations to obtain a material having good ion-exchange capacity
(2.95 meq/dry g).
Adsorption studies have been performed for alkaline earths and heavy metal ion in different concentrations of HCl, HNO
3
and HClO
4
media. On the basis of the adsorption studies, the material has been found highly selective for Cd (II) ions, one of the
most toxic heavy metals. Hence, its analytical utility has been established by achieving some binary separations of Cd (II) from
other ions on its column, as:
Hg(II)-Cd(II), Mg(II)- Cd(II), Sr(II)- Cd(II) and Ni(II)- Cd(II).
The synthesized material (CTAB-CeP) has been found to have higher ion-exchange capacity than the other hybrid ion-
exchangers [2-7], prepared earlier. Further, it has been found Cd (II)-selective, exploring its potential role in environmental and
pollution chemistry where the separation of this ion is needed/required.
References:
[1] S.C. Mojumdar, K. G. Varshney and A. Agrawal, Res. J. Chem. & Environ, 10 (2006) 89.
[2] K. G. Varshney, N.Tayal and U. Gupta, Coll. Surf A: Physiochem. Eng. Asp, 145 (1998) 71
[3] K. G. Varshney, P. Gupta and N. Tayal, Ind. J. Chem., 42A (2003) 89
129

P 28 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis, Structural And Complexation Studies of Pentaerythritoxy-
Bridged and Lariat Ether Type Cyclocarbaphosphazenes
Nabakrushna Behera, Senthil Kumar M. and Anil J Elias*
Department of Chemistry, IIT Delhi, Hauz Khas, New Delhi-110016.
Reactions of dilithiated diols [HO(CH
2
)
3
OH, and HO(CH
2
CH
2
O)
n
H, n = 2, 3 and 4] with 3, 5- bis (N,
N-dimethylamino)-1,1-dichlorodicarbaphosphazene (1) in THF in 1:1 molar ratio have been carried out to afford
the first examples of lariat ether type spirocyclic dicarbaphosphazene derivatives. The tetrasodium
salt of pentaerythritol also reacts with 1 in 1:2 molar ratio to give a pentaerythritoxy-bridged spiro-spiro
product. All the new compounds were stable to hydrolysis and have been characterized by spectroscopic
and analytical methods and a few also by X-ray diffraction method. Complexation studies of spirocyclic compounds
with Na
I
, K
I
, Ag
I
and Cu
II
ions were carried out by conductance measurements. The studies
indicate mostly 1:1 complex formation between the metal ions and the lariat ether type
cyclocarbaphosphazene derivatives. The reaction of dicarbaphosphazenes with aza-18-crown-6 and aza-
15-crown-5 ethers resulted in the formation of azacrown derived carbaphosphazenes. The characterization
and complexation studies of these compounds will also be presented.
130

NATIONAL SYMPOSIUM IN CHEMISTRY P 29
Design and Synthesis of Redox Switched Ionophores and Their Use in
Transport of Main Group Metal Ions Through Supported Liquid
Membrane
Anubhuti Awasthy

and Uma Sharma*
School of studies in Chemistry, Vikram University, Ujjain-456010, M.P., India.
Carrier mediated transport through supported liquid membranes is one of the important applications of
supramolecular chemistry. In the late 1960s Pedersen, Lehn, Cram Vogtle et al published [1-3] the synthesis of
macrocyclic molecules (crown ether, cryptand, spherands, podands) that are able to selectively bind ions or small
organic molecules via noncovalent interaction. Lariat ethers are combination of anthraquinone moiety with different
podands; these were developed by G.W. Gokel [4]. Lariat ethers are macrocycic polyether compounds having one
or more donor group bearing side arms. In the systems prepared to date, side arms are attached to carbon (carbon
pivot lariat ethers).
A novel series of redox switched anthraquinone derived single armed [5], bridged and double armed lariat
ethers (A
1
) 1-(1-anthraquinonyloxy) 3, 6, 9-trioxanonane-9-methane (A
2
), 1-(1- anthraquinonyloxy), 3, 6 -
dioxahexane-6-methane, (A
3
) 1, 11-(dianthraquinonyloxy) 3, 6, 9 trioxaundecane, (A
4
) 1, 8-(dianthraquinonyloxy)
3, 6 dioxaoctane, (A
5
) 1, 5 bis (2-(2-(2-(2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) anthracene-9-10 dione, (A
6
) 1, 5
bis (2-(2-(2-hydroxyethoxy) ethoxy) ethoxy) anthracene-9-10 dione , (A
7
)1, 5 bis (2-(2-hydroxyethoxy) ethoxy)
anthracene-9-10 dione (A
8
)1, 5 bis (2-(2-(2-butoxy) ethoxy) ethoxy) anthracene-9-10 dione scheme1 have been
synthesized by reacting anthraquinone moiety with different podands and characterized by m.p., TLC and spectral
analysis. These redox switched lariat ethers were used in carrier-facilitated transport of main group metal ions
across supported liquid membrane (SLM). These membranes were impregnated with ionophore (10
-3
M) dipped at
overnight and used as membrane support.
The results of SLM studies with ionophores (A
1
-A
8
) are listed in Table1 & 2. Ionophore A
1
having triethylene
glycol side arm, shows strong binding affinity with small size of cation, so it forms stable complexes with Li
+
and
Na
+
. Therefore it shows less transport for K
+
, Na
+
ion and no transport for Ca
2+
, Mg
2+
. Ionophore A
2
having diethylene
glycol chain shows tremendous increased carrier ability as compared to A
1
and the trend for cation transport as
Li
+
>Na
+
.
Using cellulose nitrate membrane as support, ionophore A
3
-A
6
shows carrier ability for all the cations. Ionophore
A
3
& A
5
showing best result for K
+
ion due to long glycol chain moiety attached to the anthraquinone end group. Li
+
,
Na
+
& K
+
have ability to be transported by all the ionophores (A
1
-A
8
). Ca
2+
and Mg
2+
are not at all transported by
ionophore A
7
& A
8
, due to shorter glycol side arm. On the basis of selectivity ratio ionophore A
3
and A
6
shows
higher transport for K
+
and Ca
2+
. In SLM, ionophores do not move freely, they are fixed on the membrane and due
to this their flexibility and mobility is checked. Hence sequence is different as observed in BLM [6] system. Electron
microscope studies are in under process. Cellulose nitrate membrane is a better support as compared to onion
membrane. This selectivity can be used in fabrication of sensors and redox switchable devices.
Scheme 1
131

P 30 NATIONAL SYMPOSIUM IN CHEMISTRY
Cationic Homo/Hetero Bi- And Tri-Nuclear Ruthenium Complexes
Ashish Kumar Singh, Sanjeev Sharma, Sanjay Kumar Singh, and Daya Shankar Pandey
*
Department of Chemistry, Banaras Hindu University,
Varanasi -221 005 (U.P.) India
Considerable recent attention has been paid towards the synthesis and characterization of homo/hetero bi- or
multinuclear complexes bridged by poly-pyridyl and azo aromatic ligands because of their potential use in various
fields.

In such complexes specific role of the bridging ligands is largely influenced by acceptor and donor properties
of coordination sites, the length and rigidity of spacers, presence or absence of conjugated bonds, orientation of the
substituents and scope of manipulating ligand charge. Although, poly-pyridyl ligands have extensively been used in
this regard, closely related pyridyl azine ligands viz., pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picolino)-
aldimine (pbp), p-biphenylene-bis(picoline)-aldimine (bbp) have relatively been less studied. To examine the
applicability of such complexes in the synthesis of homo/hetero bi or tri-nuclear complexes, the representative
complex [(
h
5
-C
5
H
5
)Ru(PPh
3
)(k
2
-paa)]PF
6
and [(h
5
-C
5
H
5
)Ru(k
1
-dppm)(k
2
-paa)]BF
4
reported previously by our group
have been used as potential metallo-ligand to produce a range of Ru/Ru, Ru/Rh, Ru/Pt homo/hetero dyads and Ru/
Ru/Ru and Ru/Ru/Rh triads. [1]
Reference
[1] S. K. Singh; M. Chandra; D. S. Pandey; M. C. Puerta; P. Valerga J. Organomet. Chem., 2004,
689, 3612-3620.
132

NATIONAL SYMPOSIUM IN CHEMISTRY P 21
DNA-Binding And Photocleavage Activities of Metallointercalators
Containing Immidazo-phenanthroline Ligand: [Ru(en)
2
(aip)]
2+
and
[Co(en)
2
(aip)]
3+
Penumaka Nagababu and S. Satyanarayana
Department of Chemistry, Osmania University, Hyderabad, Andhra Pradesh, India.
Two novel Ruthenium(II) complexes (1) [Ru(en)
2
(aip)]
2+
,
and (2) [Ru(en)
2
(pyip)]
2+
,
have been synthesized and
characterized. The interaction of these complexes with calf thymus DNA was investigated by absorption (UV/vis),
emission spectroscopy, viscosity measurements, DNA melting and DNA photo cleavage, the results suggest that the
two complexes bind to DNA via intercalative mode and complex 2 binds more strongly to CT DNA than complex
1. Moreover, these two complexes have been found to promote the photocleavage of plasmid DNA pBR322 under
irradiation.
123

P 22 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Characterization of ORGANOSILANOLS Bearing
Pendant Carbosilyl Groups
Meenal Batra,
Chemistry Department, Baaesthali University, P.O Banasthali Vidyapith
Rajasthan
The organosilanols, the silicon analogues of alcohols are the compounds containing two or more Si-OH
bonds. The synthesis and characterization of organosilandiols with general formula R
3
SiCH
2
CH
2
Si(OH)
2
have
been carried out. The primary interest in these studies is focused to understand the role of bulky R
3
Si substutents (R
3
= PhMe, Ph) linked to CH
2
CH
2
groups on the stabilty of organosilanediols.The following organosilanediols (1-4)
have been prepared by controlled hydrolysis of their corresponding diorganodichlorosilanes derivatives in the ether
mixture in presence of Et
3
N which acts as scavenger.
1.CH
2
=CHSi( p OCH
3
C
6
H
6
) (OH)
2
_
2. Ph
2
MeSiCH
2
CH
2
Si(p OCH
3
C
6
H
4
)(OH)
2
3.Ph
3
SiCH
2
CH
2
SiPh(OH)
2
4.Ph
2
MeSiCH
2
CH
2
HexSi(OH)
2
The organosilanediols thus obtained are viscous liquids, soluble in organic solvents and are characterize by IR and
proton NMR spectroscopy.
To study the Hydrogen bonding interactions in amine adduct of these organosilanediols (1-4) have been prepared
and characterized by IR and 1HNMR spectroscopy.
A no of organic amines such as 4, 4’ bipyridyl, 2, 2’ bipyridyl, pyrazine, 3, 5 dimethoxyaniline and N, N-dimethyaniline
have been investigated.
A strong evidence in favor of HYDROGEN bonding (O-H….N) in these adducts have been obtained from IR
spectra. Due to strong intermolecular hydrogen bonding interactions of Si-OH groups with amines, the IR stretching
frequencies ÖO-H vibrations is shifted to lower frequency compared to that of free organosilanediols.
124

NATIONAL SYMPOSIUM IN CHEMISTRY P 23
m-Oxo-Bridged Dinuclear Iron(III) Complexes of Tripodal 4NLigands as
Functional Models for methane Monoxygenase Enzymes
Mani Balamurugan,
a
Ramasamy Mayilmurugan,
a
Eringathodi Suresh
b
and Mallayan
Palaniandavar*
a
a
School of Chemistry, Bharathidasan University, Tiruchirappalli - 620 024, India
b
Analytical Science Discipline, Central Salt and Marine Chemicals Research Institute,
Bhavnagar-364 002, India
The soluble methane monoxygenase (sMMO) isolated from methanotropic organism catalyzes the
transformation of methane to methanol. Several intermediates in the catalytic cycle of sMMO have been characterized
but the mechanism of catalytic hydroxylation of unactivated C-H bonds is not fully understood. Modeling of sMMO
has been receiving much attention due to development of bio-inspired iron based catalysts for the efficient and
selective hydrocarbon oxidation. Three new iron(II) complexes [Fe
2
(m-O)(L1)
2
Cl
2
]Cl
2
1 and [Fe
2
(m-O)(L2)
2
Cl
2
]Cl
2
2, where L1 = N,N-dimethyl-N’,N’-bis(pyrid-2-yl- methyl)ethylenediamine and L2 = N,N-diethyl-N’,N’-bis(pyrid-
2-ylmethyl)- ethylenediamine, have been isolated as functional models for sMMO and successfully employed as
catalysts for C-H activation of alkanes. All the complexes have been characterized using absorption spectral and
electrochemical techniques. The molecular structure of [Fe
2
(m-O)(L1)
2
Cl
2
]Cl
2
1 has been determined by single crystal
X-ray diffraction. The complex 1 possesses an Fe-O-Fe core and the coordination geometry around each iron(III)
center is distorted octahedral. The tetradentate ligand L1 occupies four coordination sites, (
m-oxo) bridging O atom
lies at the fifth position and the labile Cl
-
ion occupies the sixth coordination position of iron(III) center. The -NMe
2
group in 1 forces the Fe-O-Fe core to be linear as revealed from the Fe-O-Fe bond angle of 180°. In the presence of
m-CPBA cyclohexane is selectively (A/K: 1, 6.9; 2, 6.1) oxidized to cyclohexanol and small amounts of cyclohexanone
(CyO) and 1-chlorocyclo- hexane are also observed as oxidative ligand transfer (OLT) reaction product. Interestingly,
the oxidation of adamantane by 1 and 2 affords 1-adamantanol exclusively (40%), 2-adamantanol (6.0%) and small
amount of adamantanone (2.1%) with enhanced yield within 30 mins. The diiron(III) complexes 1-2 have the potential
to be developed into selective and efficient catalysts for epoxidation and alkane fictionalization.
References
[1] Costas, M. ; Chen, K. ; Que, L. Coord. Chem.Rev. 2000, 200-202, 512
[2] Fontecave, M. ; Menage, S. ; Duboc-Toia, C. Coord. Chem.Rev. 1998, 178-180, 1555
125

P 24 NATIONAL SYMPOSIUM IN CHEMISTRY
Lanthanide complexes of tetradentate macrocyclic ligand: Synthesis and
Spectroscopic investigation
Sulekh Chandra
a*
, Smriti Raizada
b
, Soni Rani
a
a
Department of Chemistry, Zakir Husain College (University of Delhi), J.L. Nehru Marg, New
Delhi-110002, India.
b
Department of Chemistry, M. M. H. College, Ghaziabad-201001.
In the present paper, the lanthanide complexes derived from 1,5,8,12-tetraaza-2,4,9,11-tetramethyl cyclotetraaza-
1,4,8,11-tetraene were synthesized. The general composition of the complexes is [Ln(L)X
2.
H
2
O]X, where M = La,
Ce, Nd, Sm and Eu and X = NO
3
-
and Cl
-
. The ligand was characterized on the basis of elemental analyses, IR,
Mass, and
1
H NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance
measurements, magnetic susceptibility measurements, IR and electronic spectral techniques. The ligand acts as a
tetradentate chelate and coordinates through four nitrogen atoms of azomethine groups. The lanthanum complexes
are diamagnetic while the other Ln(III) complexes are paramagnetic due to the presence of 4f
n
unpaired electrons.
The spectral parameters i.e. nephelauxetic effect (
b), covalency factor (b
1/2
), Sinha parameter (d%) and covalency
angular overlap parameter (
h) have been calculated from absorption spectra of Nd(III) and Sm(II) complexes.
These parameters suggest the metal-ligand covalent bonding. In the present study, the complexes show the coordination
number seven.
References:
1) Evans, W. J. J. Organomet. Chem. 2002, 642, 2.
2) Kaltsoyannis, N.; Scott, P. The f-Elements. Oxford University Press, Oxford U.K. 1999.
3) Aspinall, H. C. Chemistry of the f-Elements. Taylor & Francis, London, 2001.
126

NATIONAL SYMPOSIUM IN CHEMISTRY P 25
{Ru
II
-NO}
6
and {Ru
II
-NO
·
}
7
: Formation, Reactivity and Photorelease of
Metal Bound Nitrosyl to the Biological Target
Somnath Maji and Goutam Kumar Lahiri*
Department of Chemistry, Indian Institute of Technology-Bombay, Powai,
Mumbai – 400076
The relevance of nitric oxide (NO) in a wide range of biological processes have introduced a renewed interest
in developing alternative molecular devices capable of functioning as efficient “NO” donors under biological
conditions. In that context the present report demonstrates nitrosyl complexes with {Ru-NO}
6
and {Ru-NO}
7
configurations in the framework of [1]
3+
and [1]
2+
, respectively. [1]
3+
exhibits NO
+
® NO· and NO·® NO-
reductions at +0.49 and –0.26 V versus SCE. A sizeable shift (300 cm-
1
) in n(NO) frequency takes place on
moving from {Ru
-NO
+
} to [{Ru
II
-NO·}. The simulation of the EPR spectrum of {Ru
II
-NO·} suggests partial
metal contribution (1/3) to the SOMO. The {Ru
-NO
+
} is transformed to the corresponding {Ru-NO2- } in the
presence of OH
- with k = 2.02 ´10-
4
s-
1
at 303 K. In the presence of a steady flow of dioxygen gas {Ru
II
-NO·}
state oxidizes to {Ru
-NO
+
} through an associatively activated pathway with k/s-
1
of 5.33 ´10-
3
. On irradiation
with light {Ru
II
-NO·} undergoes facile photo release of NO (k
NO
= 2.0 x 10-
1
min-
1
and t
1/2
» 3.5 min) with the
concomitant formation of the solvate species [Ru(trpy)(L)(CH
3
CN)]
2+
. The photoreleased NO can be scavenged by
myoglobin as Mb
-NO adduct.
References:
(1) Maji, S.; Sarkar,B.; Patra,M.; Das,A.K.; Mobin,S.M.; Kaim,W.; Lahiri, G. K. Inorg.
Chem. 2007, In press.
(2) Maji, S.; Chatterjee, C.; Mobin, S. M.; Lahiri, G. K. Eur. J. Inorg. Chem. 2007, 3425.
(3) Videla, M.; Roncaroli, F.; Slep, L. D.; Olabe, J. A. J. Am. Chem. Soc. 2007, 129, 278. 127

P 16 NATIONAL SYMPOSIUM IN CHEMISTRY
Bis-calix[4]pyrrole: Potential Host for Cooperative Anion Binding
Sanjeev Pran Mahanta, Pradeepta K. Panda*
School of Chemistry, University of Hyderabad, Hyderabad-500046
Over the last two decades, considerable effort has been devoted towards the synthesis of neutral host molecules
that can bind guest molecules in a cooperative manner[1]. However systems that can effect cooperative binding,
remain rare[2]. While powerful anion binding agents, albeit monomeric hosts are difficult to prepare. By contrast,
the calix[4]pyrroles, an alternative class of pyrrole-based anion receptors, are easy to synthesize and functionalize
too[3].
While calix[4]pyrrole itself binds to a variety of anions[3] and it’s strapped derivatives show a great selective
towards anions, but none of them show any cooperative effect toward anions. Sessler et. al. tried to make calix[4]pyrrole
dimmers bearing rigid spacers to observe limited success. The present investigation deals with a very simple strategy
to synthesize biscalix[4]pyrrole,1 in about 10 % yield, in two steps starting from 2,3-butanedione and it’s preliminary
anion binding study.
References
[1] Comprehensive Supramolecular Chemistry; Atwood, J. L.; Davies, J. E. D.; MacNicol, D. D.; Vogtle, F., Eds.;Elsevier:
Exeter, 1996.
[2] (a) Rebek Jr., J. Acc. Chem. Res. 1990, 23, 399. (b) Haino, T.; Yanase, M.; Fukazawa, Y. Angew. Chem. Int. Ed. Engl. 1998,
37, 997. (c) Kral, V.; Andrievsky, A.; Sessler, J. L. Chem. Commun. 1995, 2349.
[3] Gale, P. A.; Sessler, J. L.; Kral, V.; Lynch, V. J. Am. Chem. Soc. 1996, 118, 5140.
118

NATIONAL SYMPOSIUM IN CHEMISTRY P 17
Iron(IV)corrole-catalysed oxidations by m-chloroperbenzoic acid: Search
for reactive intermediates
Achintesh Narayan Biswas, Purak Das, Abhisek Saha, Uday Sankar Agarwalla and Pinaki
Bandyopadhyay*
Department of Chemistry, University of North Bengal, Siliguri-734 013, Darjeeling, India.
Since the breakthrough discovery of facile synthetic methodology [1] for the preparation of corroles, a
tremendous amount of interest has been generated in the chemistry of this contracted macrocycles [2]. However, the
mechanistic study of metallocorroles catalyzed oxidation reactions is still in its infancy [3]. In this present study we
have explored simple methods that can enable us to predict the reaction pathway and to identify the intermediates
involved. The reaction of m-chloroperbenzoic acid (m-CPBA) with meso-tris(pentafluoro-phenyl)corrolatoiron(IV)
chloride [(F
15
TPC)FeCl] has been studied in acetonitrile medium. The reactive intermediates formed have been
quantitatively trapped by 2,4,6-tri-t-butylphenol (TTBP). Kinetic analysis of the (F
15
TPC)FeCl-catalysed oxidation
of TTBP has been found to be consistent with rapid reaction of organic substrate with an intermediate formed in the
first and rate-determining step. The intermediate has been identified as an Iron(IV)-oxo corrole radical cation based
on electronic and EPR spectral data.
References:
1) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Ed. 1999, 38, 1427-1429.
2) Aviv, I.; Gross, Z. Chem. Commun. 2007, 1987-1999.
3) (a) Wasbotten, I.; Ghosh, A. Inorg. Chem. 2006, 45, 4910-4913. (b) Harischandra, D. N.; Zhang, R.; Newcomb, M. J. Am.
Chem. Soc. 2005, 127, 13776-13777.
119

P 18 NATIONAL SYMPOSIUM IN CHEMISTRY
Synthesis and Characterisation of Penta and Hexa Coordinated Silicon
compounds with Schiffs Bases containing NCS functionality
Raghubir Singh, Gurjaspreet Singh, Komal Matharu and Jugal Kishore Puri*
Department of Chemistry, Panjab University, Chandigarh –160014, India.
All the compounds were prepared in a one pot reaction between diethoxydiisothiocyanato silane and the
corresponding ligands in 1:1 molar ratio under mild conditions according to the proposed scheme as below.
All these compounds are hygroscopic in nature and are found to be soluble in solvents like dimethylsulfoxide
and dimethylformamide. The compounds have been characterized by elemental analysis, Infrared and multinuclear
(
1
H,
13
C and
29
Si) NMR studies.
120

NATIONAL SYMPOSIUM IN CHEMISTRY P 19
Mapping the Reaction Coordinate for the Oxidative Addition of Molecular
Hydrogen to a Metal Center
Saikat Dutta and Balaji R. Jagirdar*
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012
The binding of molecular hydrogen to a metal center leads to the elongation of the H-H bond and subsequently
to its cleavage along the reaction coordinate for the oxidative addition of H
2
. There has been considerable interest in
the study of the activation of dihydrogen and map out the reaction coordinate for the homolysis of H
2
on a metal
center. A large number of H
2
complexes reported to date possess H-H distances ranging from 0.8 to 1.0 Å. A
relatively fewer examples of elongated dihydrogen complexes wherein the H-H distances fall in the range of 1.0 to
1.5 Å, are known. Study of the elongated dihydrogen complexes is of great significance because of its relevance in
important catalytic processes such as hydrogenation, hydrogenolysis, and hydroformylation. One of the current
goals is to study the smooth gradation of the H-H distances along the continuum for the oxidative addition of H
2
to
a metal center. In order to accomplish this, the electron donor abilities of the phosphorus coligands was systematically
varied in the metal complexes such that the back-donation from the M(d
p) to the H
2
(s*) is increased in small
increments. We synthesized a series of new ruthenium dihydrogen complexes bearing the 1,2-
bis(diarylphosphino)ethane ligands wherein the aryl group is a benzyl moiety with a substituent (p-fluoro, H, m-
methyl, p-methyl, p-isopropyl); in this series of complexes, a small increment in the electron donor ability of the
chelating phosphine ligand results in an elongation of the H-H bond in a systematic manner.
1
We also synthesized a
series of 16-electron dicationic dihydrogen complexes bearing elongated dihydrogen ligand.
2
In addition, we prepared
a series of dihydrogen complexes of the type [Cp/Cp*Ru(PP)(
h
2
-H
2
)]
+
(PP = chelating phosphine) containing
elongated H
2
ligand (d
HH
= 1.0 to 1.17 Å) which shows smooth increment of the H-H distances along the reaction
coordinate for the oxidative addition of H
2
.
3
The H-H bond lengths vary in small increments, correlating with the donor properties of the substituents
(Hammett substituent constants) on the benzyl moiety of the chelating phosphine ligand. We have thus constructed
H
2
complexes along the reaction coordinate for the oxidative addition of H
2
to a metal center. The results of these
studies will be presented.
References
[1] Dutta, S.; Jagirdar, B. R.; Nethaji, M. Inorg. Chem. 2007 (in press).
[2] Dutta, S.; Jagirdar, B. R. Inorg. Chem. 2006, 45, 7047-7049.
[3] Dutta, S.; Jagirdar, B. R. (Manuscript under preparation)
121

P 20 NATIONAL SYMPOSIUM IN CHEMISTRY
Ruthenium(II) Complexes of Bipyridine - Glycoluril and their Interactions
with DNA
Megha S. Deshpande, Anupa A. Kumbhar and Avinash S. Kumbhar*
Department of Chemistry, University of Pune, Pune–411 007, India.
The synthesis, structural and photophysical characterization, DNA binding and cleavage by Ru(II) polypyridyl
complexes of the type [Ru(N-N)
2
(BPG)]Cl
2
1-4, [Ru(BPG)
3
]Cl
2
5

and [Ru(N-N)(BPG)
2
]Cl
2
6-9 where N-N is 2,2‘-
bipyridine (bpy), 1,10-phenanthroline (phen), dipyrido[3,2-d:2‘,3‘-f]quinoxaline (dpq), dipyrido[3,2-a:2‘,3‘-
c]phenazine (dppz) which incorporates the bipyridine glycoluril ligand have been studied to investigate the influence
of the ancillary ligand. The X-ray structure of urea fused bipyridine ligand BPG reveal inherent H-bond donor (N-
H) and acceptor groups (C=O) which exhibit a potential to generate supramolecular motifs as well as offer H-
bonding groups for DNA binding. Single crystal X-ray analysis of 1, 5 and 7 indicate a butterfly like structure for the
cationic secondary building units evidencing this H-bonding capacity which results in a supramolecular self-assembled
metal-organic frameworks (MOF) forming channels in 1 and 5 encapsulating tetradecameric water cluster, mixed
water-dimethylsulfoxide cluster and a network of water molecules and chlorine anions surrounding secondary
building units in 7. The binding ability of these complexes to DNA is dependent on the planarity of the intercalative
polypyridyl ligand, which is further influenced by the ancillary bipyridine-glycoluril ligand. Interaction of complexes
1-9 with plasmid pBR322 DNA reveals that all complexes cleave DNA efficiently at micro molar concentrations
under dark and anaerobic conditions probably by a hydrolytic mechanism. Molecular mechanics calculations of
these systems confirm two different binding modes for the complexes.
References:
1) Deshpande, M. S.; Kumbhar, A. S.; Puranik, V. G.; Selvaraj, K. Cryst. Growth Des. 2006, 6, 743.
2) Deshpande, M. S.; Kumbhar, A. A.; Kumbhar, A. S. Inorg. Chem. 2007, 46, 5450.
122

NATIONAL SYMPOSIUM IN CHEMISTRY P 11
Interaction of Vanadium (IV) Complexes with DNA
Sujata Kashyap, Udai P. Singh*
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee - 247 667, India
The application of the macrocyclic transition metal complexes is of great interest as they are used as artificial
restriction enzyme for cleaving nucleic acid (DNA, RNA). The intrinsic specificity for the hybridization between
the two complementary DNA chains has been used as a bio recognition event in the design of DNA biosensor [1].
The vanadium compounds exhibit antitumor activity by inhibiting growth of numerous malignant cell lines including
L1210 leukemia, Hela cells and human ovary carcinoma, by induction of cell cycle arrest and / or cytotoxic effects
and is widely implicated in many biological systems as insulin mimetic and antitumor agents. Reaction of VCl
3
with
one equivalent of ligand [L: N,N’ Bis(salicylidene)-1,2-phenylenediamine; N,N’Bis(salicylidene)-3, 4-
diaminotoluene; N,N’Bis(salicylidene)-3, 4-diaminobenzoic acid; N,N’Bis(salicylidene)-1, 2-ethylenediamine;
N,N’Bis(orthohydroxyacetophenone)-1, 2-ethylenediamine] in air resulted the formation of [V
IV
OL] complexes.
The structure of [V
IV
OL] (L: N,N’ Bis(salicylidene)-1,2-phenylenediamine) has been shown in Fig. 1. These complexes
were further used for the interaction study with DNA, through absorption and emission spectroscopy, melting
temperature and viscosity experiment and cleavage study with gel electrophoresis (Fig. 2).
Fig.1 Fig.2 Cleavage study with gel electrophoresis
Reference
[1] M. R-Parra; T. Garcia; E. Lorenzo; F. Pariente Biosensors and Bioelectronics, 2007, 22, 2675.
113

P 12 NATIONAL SYMPOSIUM IN CHEMISTRY
Studies on the DNA Binding Properties of Half Sandwich Complexes of
Ruthenium(II)
Sangeeta Das, Shrabani Dinda and A.G.Samuelson*
Department of Inorganic and Physical chemistry, Indian Institute of Science,
Bangalore-12
Ruthenium is the one of the most promising metals after platinum in the treatment of cancer. In
comparison with platinum based drugs, ruthenium based anticancer drugs are expected to exhibit low general
toxicity and greater specificity. Some prominent examples of ruthenium drugs under investigation are the
ruthenium (III) complexes [imidH][trans-RuCl
4
(DMSO)(imid)] NAMI-A and [indH][trans-RuCl
4
(ind)
2
] KP1019
[1]. More recently, increasing attention has been focused on organometallic compounds, specifically on ruthenium
(II) arene complexes. A series of complexes with the general formula [(
h
6
-arene)RuCl(en)][PF
6
] [2] have been
studied for their in vitro anticancer activity. The mechanism by which these complexes show anticancer activity is
assumed to be similar to that of cisplatin.
On the basis of our earlier studies on copper(I) complexes with P(III) ligands [3], we wished to investigate the
effect of replacing en with P(III) ligands. We present the synthesis of some neutral and cationic piano stool complexes
containing different P(III) ligands. The reaction of these complexes with DNA was investigated in biologically
relevant media by spectroscopic methods and viscosity measurements. The thermodynamic aspects of the aquation
reaction in different half sandwich complexes were investigated using the Jaguar program available in the Schrodinger
suite. Subsequently their interaction with DNA was probed using the ONIOM method available in the Gaussian
suite of programs. A protocol for carrying out a computational study on the drug-DNA adduct will be described. An
attempt is made to understand the activity of these complexes on the basis of drug-DNA interactions.
References
[1] Hartinger, C. G.; Zorbas-Seifried, S.; Jakupee, M. A.; Kynast, B. Zorbas, H.; Keppler,B.K.; J.Inorg.Biochem. 2006, 100,
891-904
[2] Morris, R. E.; Aird, R. E.; Murdoch, P. S.; Chen, H.; Cummings, J.; Hughes, N. D.; Parsons, S.; Parkin, A.; Boyd, G.;
Jodrell, D. I.; Sadler, P. J. J.Med.Chem. 2001, 44, 3616-3621.
[3] Sanghamitra, N. J.; Phatak, P.; Das, S.; Samuelson, A. G.; Somasundaram, K. J.Med.Chem 2005, 48, 977-985.
114

NATIONAL SYMPOSIUM IN CHEMISTRY P 13
Kinetics and Mechanism of Reaction between 4-Nitrophenol and
Carbonates of Nickel, Zinc, and Cadmium in Solid State
H. Askari
Department of Chemistry, North-Eastern Hill University, Shillong-793022, India
4-Nitrophenol [4-NP] has always been in analytical uses [1] and its biological, biochemical and medicinal
studies have been the topic of interest [2, 3]. The formation of coordination complexes in solution is well understood.
However, general solid state coordination chemistry has not yet picked up. Despite the increased attention that has
been paid to solid state reactions in recent years, it remains confined to mostly inorganic-inorganic or organic-
organic processes; references to inorganic-organic systems are few. 4-NP appears to have strong coordinating action
in solid state as well. In continuation of our work [4, 5], the present work reports the kinetics and mechanism of the
solid state interaction of 4-NP with metal carbonates (MCO
3
; M = Ni, Zn and Cd). The data for the lateral diffusion
for each reaction fitted the rate equation X
n
= k t, where X is the thickness of the product layer at time t, and n and k
are constants. When kinetics was studied gravimetrically, the data followed the equation
DW = k' t, where D W is the
change in the product’s weight at any time t, and k' is the rate constant. The activation energies calculated from the
progress of the reaction studied by either technique are different for the low and high temperature ranges. At lower
temperatures, the rate of the processes is reaction controlled, whereas at higher temperatures, it is diffusion controlled.
In lower temperature range, the diffusion is faster than the chemical reaction and as the temperature is raised, a
situation is reached where the chemical reaction becomes faster and consequently n decreases gradually with increasing
temperature turning the rate equation parabolic in case of lateral diffusion studies. 4-NP diffuses into metal carbonate
grains; penetration to the grains occurs via vapor phase and the possibility of surface migration is negated as the
reaction propagated at the same rate with different lengths of the air-gap between the reactants. In gravimetric
method, a deviation was observed in the case of [ZnCO
3
-(4-NP)] reaction where rate constant deviated from the
normal straight line of Arrhenius plot at 90
o
C and above. At and above 90
o
C, the decomposition of ZnCO
3
becomes
appreciable and thus the expected increase in weight due to reaction is marred by the decrease in weight resulting
from its decomposition. The reactions were followed by chemical analysis, IR spectral studies, X-ray diffraction,
and thermal and conductivity measurements. A single addition product [(MCO
3
-(4-NP)] was obtained in all cases.
References
1. Kolthoff, M. I.; Elving, P. J. (eds) Treatise on Analytical Chemistry, part II, Vol.7, p 306, Interscience Publishers, John
Wiley & Sons, New York, London 1961.
2. Joergensen, L.; Johansend, T. Acta Pharmacol. Toxicol. 1983, 53, 70.
3. Kit chin, K. T.; Ebron, M. T. Toxicology 1983, 26, 243.
115

P 14 NATIONAL SYMPOSIUM IN CHEMISTRY
Removal of Dyes Using Solid Wastes from Tanneries: Dual Advantage
Technology
N Nishad Fathima, R Aravindhan, J Raghava Rao*
Chemical Lab, Central Leather Research Institute, Adyar,Chennai-20, India.
Solid waste emanating from tanneries poses a serious challenge to environmentalists. Raw trimmings of hides/
skins from a tannery constitute a huge percentage of this solid waste from tanneries. In this study, raw trimmings,
after a pretreatment with glutaraldehyde, have been used as adsorbent material for removal of dyes from wastewaters.
Various parameters like adsorbent dosage, dye concentration and pH have been optimized. The effect of neutral
salts on the dye adsorption capacity of trimmings has been studied. The adsorption of dye by aldehyde treated
trimmings follows Langmuir isotherm. Above 95% dye removal efficiency has been achieved. Commercial trials
prove the potential use of trimmings as adsorbent for dye containing waste waters. Also, the dye loaded trimmings
have been employed in the manufacture of a tanning salt, which can be used in leather industry, thus giving a holistic
solution to the challenging solid waste disposal problem.
116

NATIONAL SYMPOSIUM IN CHEMISTRY P 15
Stannoxane Capping Derived from Chiral Tridentate NNO Donor Ligand
for Nickel and Copper Macrocycles: Comparative Binding Studies of
Stannoxane Moiety and its Modulated Copper Complex with CTDNA
Mala Chauhan and Farukh Arjmand*
Department of Chemistry, Aligarh Muslim University, Aligarh-202002, India.
Novel stannoxane type dinuclear tin complex C
16
H
13
N
4
O
2
Sn
2
Cl
7
1 and its modulated macrocyclic complexes
[C
24
H
36
N
10
O
3
Sn
2
CuCl
7
] ClO
4
2 and [C
24
H
34
N
10
O
2
Sn
2
NiCl
7
] ClO
4
3 were synthesized and characterized by elemental
analysis and various spectroscopic techniques (IR,
1
H,
13
C,
119
Sn NMR, ESI-MS, EPR and Uv-Visible).
119
Sn NMR
shows the presence of two tin metal centers in different environment. The proposed pseudo octahedral geometry of
copper in complex 2 and square pyramidal geometry of nickel in complex 3 were established by the analysis of
spectroscopic data. Absorption and fluorescence spectral studies and viscosity measurements have been carried out
to assess the comparative binding of dinuclear stannoxane complex 1 and its modulated copper complex 2 with calf
thymus DNA. The intrinsic binding constants K
b
of the complex 1 and 2 were determined as 4.4 x 10
4
M
-1
and 7.5 x
10
4
M
-1
, respectively. Cyclic voltammetric studies have also been employed to ascertain the binding of complex 2
with CTDNA. The results suggest that the complex 2 binds to CTDNA twice in the order of magnitude compared
to complex 1 [1]. Interaction studies of complex 2 with guanosine 5’-monophosphate further confirm the binding
via N
7
position of guanine and phosphate moiety [2].
References
[1] S. Ghosh, A.C. Barve, A.A. Kumbhar, A.S. Kumbhar, V.G. Puranik, P.A. Dater, U.B. Sonawane, R.R. Joshi, J. Inorg.
Biochem. 2006, 100, 331.
[2] T. Ito, S. Thyagarajan, K. D. Karlin, S. E. Rokita, Chem. Comm. 2005, 4812.
117

Lecture
Index

Special Lectures
LECTURE INDEXCRSI-Medal Lectures
Page No.
Mark Ratner CNR Rao Award lecture .... 33
Keiji Morokuma Mizhushima-Raman lecture ... 52
Edward I. Solomon A. Chakravarty Endowment lecture .... 54
C.N.R. Rao 10th Anniversary Special Lecture ... 42
Richard N. Zare CRSI-SL1 ... 56
Chi-Huey Wong CRSI-SL1 ... 58
K. Weighart CRSI-SL3 ... 82
D.K.Chattoraj CRSI-ML_G1 ... 78
S.K. Rangrajan CRSI-ML_G1 ... 80
Deevi Basavaiah CRSI-ML-S1 .... 34
N. Chandrakumar CRSI-ML-S2 .... 36
T. K. Chandrashekar CRSI-ML-S3 .... 44
Ganesh Pandey CRSI-ML-S4 .... 68
S. Ramasesha CRSI-ML-S5 .... 84
E. Arunan CRSI-ML-B12 ... 38
Maravanji S. Balakrishna CRSI-ML-B1 .... 40
Sundarababu Baskaran CRSI-ML-B2 .... 46
Prasad V. Bharatam CRSI-ML-B3 .... 48
N. Jayaraman CRSI-ML-B4 ... 50
Faiz Ahmed Khan CRSI-ML-B5 .... 70
Samudranil Pal CRSI-ML-B6 .... 72
Parimal Paul CRSI-ML-B7 .... 74
H. Surya Prakash Rao CRSI-ML-B8 .... 76
Debashis Ray CRSI-ML-B9 .... 86
Subhas C. Roy CRSI-ML-B10 .... 88
V. Subramanian CRSI-ML-B11 .... 90
CRSI-Special Symposium Lectures
Pavel Hobza CRSI-SSL1 .... 60
Ashwini Nangia CRSI-SSL2 .... 62
Shridhar R. Gadre CRSI-SSL3 .... 64
Sanjay Wategaonkar CRSI-SSL4 .... 66
T.N. Guru Row CRSI-SSL5 ... 92
Pinak Chakrabarti CRSI-SSL6 .... 94
G.U. Kulkarni CRSI-SSL7 ... 96
P.Venugopalan CRSI-SSL8 .... 98
i

Poster
Index

Poster Author Index
A
Abaji, G. G. P267
Abdul, R. A. S. P102
Abhimanew, D. P132
Abhinaba, B. P88
Abhinav, K. P43
Abhisek, S. P17
Abhishek, C. P88
Abhishek, K. P34
Abraham, S. P186
Abraham, J. S. P6
Achintesh, N. B. P17
Adinarayana R. S. P175
Aditya, L. Y. R. P. P239
Agarwalla, U. S. P17
Aijaz, A. D. P240
Aiswarya, L. P. P203
Aiyagari, R. P54
Ajayaghosh, A. P60
Ajayakumar, G. P158
Ajaykumar, S. K. P102
Ajeesh, M. P89
Ajit Kumar P144
Ajnesh, S. P10
Akanksha P149
Alamsetti, S. K. P260
Alok, K. R. P204
Amit, J. P115
Amit, K. S. P109
Amit, S. P228
Amit, S. S. B. P93
Amita, S. P27
Amitabha Sarkar P217
Amit Kumar P108
Amol, R. D. P268
Ananda Kumar, C. S. P141
Ananthi, N. P76
Anbalagan, K. P86
Anbarasu, K. P261
Anil Kumar P247
Anil, J. E. P28
Animesh, S. P114
Aninda, J. B. P80
Anirudhan, T. S. P5
Anish Kumar P200
Anita, C. P150
Anjali, P. P67
Anjali, S. P109
Anju Das, M. P257
Ankita, S. P225
Ankita Rao P170
Ankur, B. P202
Anubhuti, A. P29
Anumita, P. P54
Anunidhi, S. P98
Anup Paul, P178
Anupa, A. K. P20
Anupa, A. K. P66
Aravindhan, R. P14
Archana, G. P109
Archana, M. P178
Archana, S. P273
Arindam, B. P183
Arlin, J. A. A. P96
Arnab, B. P87
Arora, M. P155
Arumugam, S. P232
Arun Jyoti, B. P233
Arun, C. P54
Arun, K. S. P138
Arun, K. T. P169
Aruna, D. P229
Arunan, E. P203
Arunava Das, P235
Arvind, K. G. P246
Arvind, M. P143
Asaithambi, M. P112
Ashim, J. T. P130
Ashis, K. P. P107
Ashis, K. P. P50
Ashish, K. S. P30
Ashish, V. P195
Ashish Kumar, T. P121
B
Bablee, M. P262
Babu, V. P35
Bajaj, H. C. P7
Balakrishna, M. S. P45
Balakrishnan, U. P76
Balamurugan, M. P23
Balaram, P. P156
Balasubramanian, S. P192
Ballav, M. B. P259
Bardhan, M. P193POSTER INDEX
ii

Basu Baul, T. S. P178
Basudeb, B. P262
Benaka Prasad, S. B. P141
Bhabesh, C. G. P125
Bhakiaraj, D. P. P113
Bhargava, B. L. P192
Bharti, B. P109
Bhaskar, J. S. P33
Bhattacharya, S. P153
Bhattacharya, S. P193
Bhattacharyya, K. P220
Bhuwan, B. M. P273
Bijoli, M. P67
Bijoy, K. P251
Bilgaiyan, P. P257
Biman B. P181
Binoj, K.K. P89
Bipin, P. P115
Bipul, B. P55
Birinchi, K. D. P26
Bisaria, C. S. P161
Bishan, L. K. P34
Bishwajit, G. P72
Biswajit, D. P33
Biswajit, M. P81
Biswapran, K. P233
Biswarup, P. P50
Biswas, A. N. P17
Bizzotto, D. P215
Bony, S. P274
Brahmachari, G. P255
Brijesh Kumar, S. P115
Brindaban, C. R. P93
Bulumoni, K. P201
Butcher, R. J. P221
Butoliya, S. S. P264
C
Campbell, S. A. P215
Carlo, G. P188
Carlos, J. G. G. P49
Chaitali, B. P49
Chakraborti, A. K. P230
Chakraborti, A. K. P225
Chakravarty, A. R. P50
Chakravarty, M. P163
Chandan M. P235
Chandan, S. P145
Chandra, A. S. P182
Chandrabhas, N. P92
Chandrasekaran, S. P224
Chandrasekhar, V. P46
Chandrashekara, K. P235
Chankeshwara, S. V. P230
Chary, K. V. R. P73
Chawla, H. M. P172
Chawla, S. K. P155
Chetana, P. R. P107
Chhama, A. P133
Chhavi, A. P82
Chincholkar, P. M. P102
Chokhare, R. P44
Churala, P. P120
D
Damanjit, K. P74
Damodara Reddy P131
Darshna, M. P135
Daya, S. P. P30
Dayananda, S. P41
Debabrata, B. P146
Debasree, S. P93
Debendra, K. M. P146
Deb Kumar, N. P120
Debojyoti, L. P50
Deepak, K. P257
Deshmukh P102
Deshpande, R. M. P249
Deshmukh, M. M. P188
Devaraj Stephen, L. P86
Devdutt, C. P140
Devendra, K. D. P246
Dewan, A. P234
Dhara D. P. P167
Dhaval, P. P274
Dhenadhayalan, N P196
Dhillon, R. S. P253
Dhiman, K. S P9
Dhrubo, J. S. P274
Dibakar Chandra, D. P136
Dilip, G. R. P268
Dimple P84
Dinesh, B. P150
Dinesh, S. B. P250
Dipak, K. D. P33
Dipankar, M. P214
Dipankar, S. P217
Dipika P. D. P167
Divya, A. P228
Divya Jyothi P126
POSTER INDEX
iii

Dubey, S. P. P159
E
Eknath, V. B. P250
Emmanuvel, L. P232
F
Farukh, A. P15
Fateh, V. S. P108
Fathima, N. N. P14
G
Ganesamoorthy, C. P45
Ganesamoorthy, S. P157
Ganesan, T.K. P39
Ganesh, K. N. P237
Gangopadhyay, A. P255
Ganguly, T P193
Gautam, P. P 185
Gautam, P. P134
Geetha, R. P35
Genwa, K. R. P212
George, E. P37
Giridhar, M. P65
Gopal Das P259
Gopal, K. P159
Gopidas, K. R. P158
Gopinath, C. S. P211
Gopinath, P. P241
Gorelsky, S. I. P214
Goswami, D. P197
Goswami, S. P111
Goutam, K. L. P25
Govindaraju, M. P112
Gumaste, V. K. P102
Gunanathan, C. P47
Gunasundari, T. P224
Gurjaspreet, S. P18
Gurnule, W. B. P264
Guru Row, T. N. P69
Guru Row, T.N. P65
H
Halligudi, S. B. P202
Hanumant, B. B. P267
Hardev, S. P117
Hariharan, M. P169
Hari Prasad, S. P126
Hementha, H. P. P266
Hima Rani, K. P233
Himanshu A. P3
Himanshu, M. P135
Hitendra, K. P103
Hitendra, S. P37
Hussain Reddy, K. P41
I
Ismail, A. A. P85
J
Jagadeesh, M. P150
Jagtap, S. V. P249
Jagirdar, B. R. P19
Jai, D. S. P34
Janardhan Reddy, K. P175
Jashmini, D. P54
Jasra, R. V. P7
Jatinder, K. P116
Jaya Pal, M. R. P194
Jaya Kumar, R. P198
Jayaraman, N. P147
Jayashree, N. P148
Jayendra, Z. P. P115
Jemmis, E. D. P160
Jemmis, E. D. P50
Jisha, V. S. P169
Jitendra Singh P179
Jitendra, K. B. P176
Jitendra, S. P179
Joshi, S P257
Jothivenkatachalam, K. P52
Joychandra Singh, S. P231
Joykrishna, D. P207
Jubaraj, B. B. P171
Jugal, K. P. P18
Jyoti, S. P166
Jyoti,P. S. P269
Jyotiranjan, A. P246
Jyotsna, C. P153
K
Kadia, M. V. P167
Kakati, D. K. P234
Kalanidhi, P. P244
Kalicharan, C. P93
Kalidhasan, S. P110
Kalsi, P. C. P82
Kalyan, J. B. P106
Kasthuri, J. P97
Kaushik, M. P. P103
Kawaljit, S. P228
Khaliquz, Z. K. P240
Khan, M. I. P100
Khare, S. P44
Khushbu, K. P109
POSTER INDEX
iv

Kieran, C. M. P43
Kiran, B. M. P147
Kiran, B. U. P127
Kiran, M. P272
Kiran, S. P274
Kirandeep, K. P104
Kirthika Rani, B. P39
Kishor, R. H. P105
Koena, G. P124
Komal, M. P18
Krishna, P. P274
Krishna, P. B. P137
Krishna, P. K. P244
Krishnacharya, G. A. P250
Krishnan, K. S. P156
Kuljit, K. P75
Kulkarni, G. U. P58
Kulkarni, G. U. P57
Kumar, A. R. V. P235
Kumar, R. S. P248
Kumar, S. P238
Kumaraguru, N. P1
Kumari, S. P136
Kushwaha, A. P189
L
Lakshmanan, M. P229
Lakshminarayanan, P. S. P2
Laksmikanta, A. P93
Laxmipathi, R. P95
Lloret, F. P3
M
Madan Gopal, B. P123
Mahasweta, N. P94
Maity, S. K. P119
Mala, C. P15
Mala, N. P37
Malathi, M. P154
Malhotra, N. P152
Mallick, B. P239
Mamata, S. P221
Manas, K. G. P124
Mandal, K. D. P204
Mandal, L. C. P255
Mangala, S. K. P68
Manikannan, R. P256
Manikrao, M. S. P268
Manisha, S. P103
Manoj, K. K. P72
Manoj Kumar P132
Manoj Kumar, S. P118
Manorama P210
Manoranjan, K. P70
Manu, V. P7
Marek, K. P120
Marek, Z. P120
Mary, F.M. P43
Mashhood Ali, S. P208
Mathesan, J. P254
Maulik, P. P274
Maya, K. P34
Maya, S. S. P269
Mayilmurugan, R. P23
Mazaahir, K. P245
Medhi, C. P55
Meena, R.C. P51
Meenakshia, S. P36
Meenal, B. P22
Meenal, G. P135
Meera, P. P100
Megha, M. P166
Megha, S. D. P20
Megha, S. D. P66
Mehta, B. K. P135
Menon, S. K. P200
Michael, G. B. D. P49
Mihir, K. C. P148
Minal, B. P101
Mishra, L. P174
Mitchell, K. A. R. P215
Moazzam, A. P64
Mody, H. M. P7
Mohamad, A. A. P68
Mohammad, H. P145
Mohammad, S. P143
Mohammed, S. P100
Mohan Das, T. P252
Mohan, P. S. P154
Mohan, R. P177
Mohan Rao, K. P168
Mridula, P. P106
Mugesh, G. P137
Mukesh, K. P. P109
Mukherjee, P.S. P151
Mukherjee, R. N. P3
Mukul, R. J. P115
Mukund, K. G. P146
Mulla, I. S. P100
Murali Krishna, P. P41
POSTER INDEX
v

Murugan, E. P241
Muthusamy, S. P47
Muthusubramanian, S. P256
N
Nabakrushna, B. P28
Nabanita, S. P176
Nabin, Ch. B. P77
Nagarajan, S. P211
Nagarajan, R. P227
Nageshwar, K. P247
Nageswara Reddy, C. P194
Namboothiri, I. N. N. P226
Namrata D. P174
Nanhai, S. P43
Narasimha Murthy, B. P147
Narasimhaswamy, T. P62
Narendra, N. P266
Naresh P. G. P203
Nasar, A. S. P62
Nashiour, R. P92
Natarajan, P. P52
Natarajan, P. P95
Natrayasamy, V. P36
Navneet, K. P75
Nayak, M. S. P194
Neeraj, K. M. P245
Neeta, S. P98
Neetu, S. P153
Nethaji, M. P153
Nethaji, M. P50
Nidhi G. P165
Nidhi, P75
Nidhi, J. L. P109
Nidhi, K. P274
Nidhi, R. G. P8
Nisha, S. P115
Nitin, B. D. P268
Niyati, S. P205
Nusrat, J. P109
P
Pabitra, K. K. P233
Padma malar, E. J. P198
Pallavi, S. P269
Paloth, V. P10
Palwinder, S. P116
Pampa, M. P49
Panda, D. P177
Panda, M. P111
Pande, U. C. P265
Pandey, J. P. P41
Pankaj, C. P101
Pankaj, K. P109
Pankaj, R. P79
Pankaj, R. P. P115
Paramjit, K. P213
Parasuraman, J. P120
Parbati, B. P87
Parikshit, C. M. P9
Parsons, P. R. P215
Partha Sarathi, S. P209
Partha, R. P40
Parveen, S. P182
Patel, D. S. P225
Pavan Kumar, G.V. P92
Penumaka, N. P21
Peerzada, G. M. P184
Periakaruppan, A. P95
Perumal, S. P248
Pethe, A.M. P101
Phani, P. M. P163
Pinak, M. P102
Pinaki, B.Y P17
Pitchai, P. P154
Pitre, K. S. P205
Prabal, D. P223
Prabhakaran, E. N. P131
Prabir Pal P218
Pradeep, K. P170
Pradeep, T. P71
Pradeep Kumar, P139
Pradeepta, K. P. P16
Pradhan, T. P222
Pradyot, B. P40
Pradyut, G. P2
Pramod, P. P191
Pramod, S. P226
Prasad V. B. P225
Prasad, K. L. P189
Prasanna S. G. P206
Prasanta Kumar, D. P128
Prasenjit, G. P177
Prasenjit, M. P115
Prathapa, S. J. P69
Pratibha, D. P143
Pratibha, S. P179
Pratik Sen P220
Praveen, V. K. P60
POSTER INDEX
vi

Preeti, R. P115
Priyabrata, P. P88
Priyabrata, S. P88
Prodeep P. P233
Purak, D. P17
Puranik, V. G. P102
Puspendra, S. P42
Puspendu, K. D. P53
Puspesh, K. U. P139
R
Rafiquee, M. Z. A. P27
Raghubir, S. P18
Raghunathan, R. P254
Rahul, S. P172
Rahul, D. S. P101
Rahul, J. P104
Rahul, P. P274
Rai, A. P133
Rai, V. K. P133
Raj, P.S. P10
Rajabhushan Reddy, S. P118
Raja Kumar, P. P242
Rajasekaran, T. P47
Rajeev, S. P109
Rajeev, G. P166
Rajendiran, N. P97
Rajesh, C. P26
Rajesh, Ch. P230
Rajesh, N. P110
Rajesh Kumar, P132
Rajeswara Rao. M. P38
Rajib, L. S. P55
Rajiv, K. V. P269
Rajkannan, R. P198
Raj Kumar, R. P114
Raju, D. P93
Raju, R. K. P273
Rakesh, K. M. P144
Rakesh, T. P269
Rakshit, S. P187
Ram, B. P. P51
Rama Kant P199
Rama, K. P79
Ramachandraiah, C. P175
Ramaiah, D. P169
Ramakrishnan, S. P114
Ramakrishna Rao P107
Rama Kumar, K. L. P170
Ramamurthy, P. P31
Raman, N. P216
Ramana Rao, R. V. P266
Ramaraj, R. P190
Ramarao, G. P103
Ramasesha, S. P70
Ramesh, A. P259
Ramesh, C. D. P201
Ramesh, C. S. P42
Ramesh, Ch. D. P77
Ramesha, G. K. P59
Rangappa, K. S. P141
Ranjan, P. P4
Ranjit, B. P222
Rao, C. N. R. P58
Rao, J. R. P14
Rao, K. N. P204
Rashid, M. P258
Ratti, R. P61
Ravi, P. B. P73
Ravikanth, M. P38
Ravi Kumar, I. P2
Ravindran, P.V. P56
Reena, P. K. P127
Reji, T. P57
Revanna, R. P235
Rew, D. P42
Rina, G. P119
Rina, S. P115
Ripal, C. P274
Rishikesh P. P174
Rita, M. P195
Ritu, M. P109
Rohini, O. P135
Rohit, K. R. P96
Romesh Chandra, B. P123
Roopa, M. P237
Roychoudhuary, P.K. P144
Ruchi, J. P270
Ruchi, K. P74
Ruli, B. P106
Rumila, M. P125
Rupam, S. P171
S
Sabyasachi, S. P83
Sachin, K. P150
Sachin, V. B. P268
Sahoo, S. K. P239
Saikat, D. P19
POSTER INDEX
vii

Saima, Q. P240
Sairam, S. C. P36
Sairam, S. M. P78
Sajal, D. P262
Sajal, K. P119
Sajal Kumar, D. P134
Sakthivel, A. P216
Samal, A. K. P71
Samantaray, M. K. P177
Samar, K. D. P164
Samaresh, B. P32
Samir, P. P274
Samit G. P183
Sampa, G. P53
Sampath, S. P59
Samuelson, A.G. P12
Sandeep, K. P213
Sangeeta, D. P12
Sangita S. P167
Sangita, D. K. P56
Sangita, M. P262
Sangita, R. P128
Sangmeshwer, P. S. P267
Sanjay, B. P271
Sanjay, K. S. P30
Sanjeev, P. M. P16
Sanjeev, S. P30
Sankar, P.R. P4
Sankeerth, H. P63
Santha Kumar, K. P1
Santhosh, B. S. P60
Santosh, J. G. P118
Santosh, K. U. P208
Sappanimuthu, T. P113
Saravanan, T. P113
Sarika M. B. P181
Sarkar, S. P255
Satveer K. P253
Satyanarayan, S. P172
Satyanarayana, S. P21
Saurabh, p. P265
Saurabh, S. P207
Saurin, R. P115
Savita, S. P166
Sawant, D. P251
Saxena, A. K. P161
Saxena, K. P161
Sayanti, D. P32
Sebastian, K. L. P90
Sebastian, R. P242
Seema, R. P98
Sekar, G. P260
Sekar, K.G. P261
Sekhar, K. P262
Selva Kumar, K. P236
Selvaraju, P196
Senthil, K. M. P28
Shabana, K. P34
Shabana, K. P247
Shailendra K. J. P199
Shalini, U. P144
Shameema, O. P160
Shanavas, A. P62
Shanbhag, P. P226
Shanmugam, P. P236
Shanmuga, S. K. P157
Sharma, P. P219
Sharma, V.K. P84
Shibi, I. G. P5
Shibli, S.M.A. P89
Shilpi, K. P109
Shinto, V. P186
Shiva Kumar, C. P162
Shraeddha, T. P247
Shridhar R. G. P188
Shrikant, P. N. P127
Shubhangi, B. P150
Shubhankar, K. B. P35
Shweta, S. P122
Shyamal Kumar C. P214
Shyamal, K. D. P80
Shyamal, K. J. P255
Siddhartha, De. P150
Siddhartha, P. S. P156
Siddiqi, Z. A. P238
Sinan, M. P111
Singh, A. K. P165
Singh, A. K. P259
Singh, J. K. P177
Singh, K.C. P84
Singh, N. K. P221
Singh, O. M. P231
Singh, U. P. P165
Siva, S. P. P109
Sivanesan, A. P6
Smriti, R. P24
Sneha E. A. P181
POSTER INDEX
viii

Sode, A. P215
Somnath, M. P25
Somnath, N. P271
Soni, A. S. P127
Soni, R. P24
Sonika P152
Sreedevi, M. P260
Sreedhar, N. Y. P194
Sreeprasad, T. S. P71
Srinivasa Raju, G. P192
Srinivasa Rao, A. P164
Srinivasan, K. V. P142
Srinivasan, N. P99
Srinivasa Reddy, B. P150
Sriparna, R. P177
Sripriya, S. P131
Srivastava, V. P122
Subash, P. C. P105
Subba Reddy, B.V. P270
Subhadip, G. P220
Subhash, C. J. P109
Subhendu, N. P214
Subodh, K. P75
Subodh, K. P8
Subrata, D. P130
Subrata, G. P272
Suchithra, M. P236
Sudarshan, M. P65
Sudeshna, S. P217
Sudip, K.G. P4
Suhail S. P258
Suheel, K. P. P118
Sujata, K. P11
Sujata, V. B. P127
Sujatha, D. P194
Sujit, K. S. P156
Sukhdeep, S. P228
Sukunath, N. P113
Sulekh, C. P24
Suleman, R. M. P267
Suman, S. P202
Sumit, D. P120
Sumit, K. S. P83
Sumit, T. P247
Sumita, H. P214
Sundargopal, G. P35
Sunil, K. P. P145
Sunita, B. P109
Suresh Das P186
Suresh, E. P23
Suresh, P. P85
Suresh, S. P. P142
Sureshbabu, V. V. P266
Surojit, P. P91
Suryaprakash, N. P63
Susac, D. P215
Susanta, K. N. P69
Susheel, K. M. P8
Sushobhan, G. P151
Sushuma, N. P231
Susmita, P. P262
Swapan, K. P. P78
Swapan, K. S. P64
Swarnalatha, K. P173
Swarupananda, M. P119
Swathi, R. S. P90
T
Talapatra, G. B. P218
Tarasankar, P. P91
Tejal, V. N. P129
Teo, M. P215
Thangavel, S. P190
Thankachan, P.P. P48
Thimmegowda, N. R. P141
Thirumala, K. P. P168
Thirumoorthi, R. P46
Thirunavukkarasu, K. P 211
Thomas, D. P142
Thomas, K. G. P191
Tiwari, I. P210
U
Udai, P. S. P11
Uday, S. A. P17
Uday Maitra P263
Uma, S. P29
Umapathy, S. P239
Upadhyay, K. K. P144
Uttam, R. K. P105
V
Vaithiyanathan, V. P236
Valarmathy, D. P112
Vandana, B. P117
Varada Reddy, A. P175
Varshney, K. G. P27
Vasudevan, S. P187
Vasundhara, S. P61
Vaultier, M. P61
Ved, V. A. P58
POSTER INDEX
ix

Vedprakash, S. P121
Veeraraghava, S. P113
Velmathi, S. P76
Velu, M. P185
Venkata, P. P. P150
Venkatachalam, S. G. P120
Venkatesan, K. P142
Venkatesan, R. P256
Venkateswaran, V. P112
Vibha, K. P48
Vijay, K. P51
Vijayamohanan, K. P100
Vijayaraghavan, R. K. P186
Vijayasree, V. P118
Vijay Luxami P75
Vikas P180
Vikas, B. P245
Vikas, N. T. P129
Vikas Kumar, P138
Vikram, G. P227
Vimal, P. P274
Vinita S. P179
Vinod K. K. S. P185
Vinod, K. T. P273
Vinoth Kumar P204
Vishnu, S. P79
Viswambharan, B. P236
Vitor, F. P10
W
Wong, K. C. P215
Wong, P. C. P215
Wright, C. W. P243
X
Xueqing, S. P37
Y
Yadav, J. S. P270
Yadav, J. S. P84
Yadav, L. D. S. P133
Yogesh, W. P150
Z
Zade, A. B. P264
Zhu, L. P215
Luwang M.N. P275
Srivastava S.K. P275
POSTER INDEX
x

The conference has been supported by generous
contributions from the following companies.
ADVINUS THERAPEUTICS PVT LTD.,
BRUKER INDIA SCIENTIFIC PVT LTD,
FMC INDIA R&D CENTER,
GE INDIA TECHNOLOGY CENTER,
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SYNGENTA,
Pune
Bangalore
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Chennai
UK

Printed at : Uma Prints, B’lore. 9448046893

P 6 NATIONAL SYMPOSIUM IN CHEMISTRY
Electrochemical Sensing of L-Cysteine Using Flat Oriented Phthalocyanine
Modified Electrodes
A. Sivanesan and S. Abraham John*
Department of Chemistry, Gandhigram Rural University, Gandhigram-624 302, Tamil Nadu
L-cystine/L-cysteine redox couple is generally used as a model for the role of the disulfide bond and thiol
group in proteins [1]. Moreover, it is an important amino acid owing to its crucial roles in many biological
systems. For example, it could be used as a prospective radiation protector and cancer indicator. Therefore,
it is very important to study its redox behavior and detection with high selectivity and sensitivity. Usually at
naked metal electrodes no electrochemical response was observed for L-cysteine at physiological pH. Hence,
in the present study we investigated the electrochemical determination of L-cysteine using self-assembled
monomolecular films of 1,8,15,22-Tetraaminophthalocyanatocobalt(II) (4a-Co
II
TAPc) and 2,9,16,23-
Tetraaminophthalo- cyanatocobalt(II) (4b-Co
II
TAPc) (Chart 1) on Au surfaces. Electrochemical and Raman studies
confirm that 4a-Co
II
TAPc adopts parallel orientation whereas 4b-Co
II
TAPc adopts perpendicular orientation on Au
surface [2]. Among the two electrodes, flat oriented 4a-Co
II
TAPc electrode shows well defined oxidation peak for
L-cysteine whereas perpendicularly oriented 4b-Co
II
TAPc shows no pronounced response (Fig.1). Thus 4a-Co
II
TAPc
modified electrode was used for the determination of L-cysteine. Interference studies, detection limit and
pharmaceutical analysis of L-cysteine will be presented in the poster.
References:
[1] Zhou, M. Ding, J. Guo, L.-p.; Shang, Q.-k. Anal. Chem. 2007, 79, 5328-5335.
[2] Sivanesan, A.; John, S. A. Langmuir (in press)
Chart 1. Structure of phthalocyaninesFig.1. LSVs of L-cysteine at (a) bare Au, (b) Au/4a-Co
II
TAPc
and (c) Au/4b-Co
II
TAPc electrodes in PB solution.
108

NATIONAL SYMPOSIUM IN CHEMISTRY P 7
Adsorption of Cu
2+
from Aqueous Solution of Copper Sulphate On
Functionalized Silica Gel with Different Loading of
Aminopropyltrimethoxysilane
Manu Vasudevan, H. M. Mody, H. C. Bajaj and R. V. Jasra
*
Discipline of Inorganic Materials and Catalysis Central Salt and Marine Chemicals Research
Institute G.B. Marg, Bhavnagar 364 002, Gujarat, INDIA
Silica Gel (G) and amino functionalized silica gel (GN) with different loading of aminopropyl groups (GN1:
0.49, GN2: 1.01 and GN3: 1.45 mM/g,) were synthesized and used for the adsorption of Cu
2+
from aqueous solution.
The amino group was anchored on the surface of silica gel (GN) by refluxing gel in toluene solution containing
appropriate amount of 3-aminopropyltrimethoxysilane for 24h. The GN adsorbent was filtered and washed with
toluene. Elemental analysis (CHN) using Perkin-Elmer CHNS/O Series II, 2400, was carried out to quantify the
number of organic moieties grafted on the silica gel [1]. The changes in the surface area and pore structure caused
by the grafting of organic moieties were determined by nitrogen physisorption at 77.4K using surface area analyzer
ASAP2010 Micromeritics USA. The surface area of silica gel decreases with the increases in the loading of
aminopropyl groups [574 to337 (m
2
/g)]. Adsorption study of Cu
2+
on functionalized silica was investigated. The
batch adsorption experiment was conducted at room temperature (303K+ 1). CuSO
4
.5H
2
O was used to prepare the
Cu
2+
solutions. The adsorption isotherm of copper (II) was measured using 0.1 g of adsorbent containing metal ions.
The initial and final concentrations of the metal in the solution were analyzed by inductively coupled plasma, atomic
emission spectrometry (ICP-AES, Perkin-Elmer optical emission spectrometer optima 2000DV). The adsorptions
isotherms of Cu
2+
were fitted with different models such as Langmuir, Frundlich, Sip and Redllich-Peterson. Sips
modal was found to give the best fit [2]. It has been observed that when loading of NH
2
group (number of NH
2
groups) is increased from 0.49 to 1.01 mM/g, mono layer adsorption capacity of Cu
2+
remain unchanged. The
loading of NH
2
group in GN1 and GN2 was 0.49 and 1.01 mM/g, (NH
2
/Cu ratio is 0.96 and 1.84 M/M respectively)
and in the case of GN3, the loading of amino group was 1.47 mM/g (NH
2
/Cu ratio 1.38 M/M). This study indicates
that the number NH
2
per unit area (population density) determines NH
2
/Cu ratio at saturation of Cu
2+
on the
functionalized silica gel. Diffuse reflectance spectroscopy (DRS) data indicate the complex formation of copper.
References:
[1] Jal, P.K.; Patel, S.; Mishra, B. K. Talanta, 2004, 62, 1005-1028.
[2] Jacques, R.A.; Airoldi, C.; Lima, E. C., Separation Science and Technology, 2007, 42, 591-609.
109

P 8 NATIONAL SYMPOSIUM IN CHEMISTRY
Nickel Selective Electrode Based on Liquid Membrane Containing N
4
Macrocycle As Ionophore
Nidhi Rani Gupta
a
, S.K. Ashok Kumar
a
, Subodh Kumar
b
, Susheel K Mittal
a*
a
School of Chemistry & Biochemistry, Thapar University, Patiala 147004, India;
b
Department
of Chemistry, Guru Nanak Dev University, Amritsar 143005, India.
Determination of nickel assumes importance due to its toxic nature, widespread use in catalytic processes and
its presence in various effluents. The toxicity of nickel can cause dermatitis, asthma and disorder of central nervous
system [1]. The first nickel-selective electrode was reported by Pungor and co-workers using a nickel-
dimethylglyoxime complex[2]. We have constructed a new PVC membrane nickel ion-selective electrode using N
4
compound as a neutral ionophore. Effect of various plasticizers, viz. o-nitrophenyloctyl ether (o-NPOE),
dibutylphthalate (DBP), bis 2-ethyl sebacate (BES) was studied and improved membrane performance was observed
[3]. The electrode was prepared with 4% ionophore, 63% o-NPOE (as plasticizer) and 33% PVC. The electrode
gave Nernstian slope 29 mV/decade over the concentration range of 1.5x10
-5
to 1.0x10
-1
M of Ni
2+
ions in the pH
range of 3.5–8.5. The limit of detection was 3.1x10
-6
M. It has a response time of <20 s and can be used for at least
three months without any considerable divergence in potentials. The proposed electrode shows good discrimination
of Ni
2+
ion from several cations. The effect of organic solvents on electrode response was examined. The results
show that this electrode can be used non-aqueous media up to 20% (v/v) concentration without interference. The
electrode was used as an indicator electrode in the potentiometric titrations. It was also successfully applied to the
determination of Ni
2+
ions in chocolate samples.
References:
[1] Greenwood, N.N.; Earnshaw, A.; Chemistry of the Elements, Pergamon Press Oxford, New York, 1984.
[2] Pungor, E. Toth, K.; Havas, J. Acta. Chim. Acad. Sci. Hung., 1966, 48, 1
[3] Bakker, E.; Buhlmann, P.; Pretsch, E.; Chem. Rev., 97(1997)3083.
110

NATIONAL SYMPOSIUM IN CHEMISTRY P 9
Synthesis, Spectroscopy and Cyclic Voltammetry of New iron(III)
Complexes with Bio-relevant Pyrazolyl Thiosemicarbazone.
Dhiman Kumar Sau
a*
and Parikshit Chandra Mandal
b
a
Department of Chemistry, Sarat Centenary College, P.O.- Dhaniakhali; Hooghly-712 302;
West Bengal;
b
Chemical Sciences Division, Saha Institute of Nuclear Physics,
Kolkata 700 064
The remarkable therapeutic success [1] of several heterocyclic thiosemicarbazones for removing excess iron
from iron-loaded mice through chelation therapy has accelerated further research in this specific area. In continuation
of our earlier work [2], We report here the synthesis and physico-chemical characterization of a new iron(III)
complexes with 5-methyl-3-formylpyrazole N(4)-cyclohexylthiosemicarbazone (HMPz4Cy). The complexes have
the general composition [Fe(MPz4Cy)
2
]X·nH
2
O (X = Cl, NO
3
, ClO
4
; n = 2-3 ). I.R. data for the free ligand and its
complexes indicate that the ligand acts as an uninegative NNS tridentate (MPz4Cy) through the pyrazolyl nitrogen
(tertiary), azomethine nitrogen and thiolato sulphur. Electronic spectral data (solid and MeOH) are suggestive of a
distorted octahedral environment for the hexacoordinated iron(II) species. X-ray crystallographic identifications of
iron(II) complexes with similar ligands support the proposed geometry of the complexes. E.p.r. data (r.t. and l.n.t.)
show the presence of a low-spin iron(III) cation with d
xz
2
d
yz
2
d
xy
1
configuration. Cyclic voltammograms of iron(III)
complexes indicate a quasireversible Fe
+3
/Fe
+2
couple. X-ray crystallographic identification of the species,
[Co(MPz4Cy)
2
]Cl·2.75H
2
O supports that the same ligand, HMPz4Cy exhibits almost identical coordination behaviour
with cobalt(III) chloride salt in like solvent. Cyclic voltammograms of cobalt(III) complexes also show a
quasireversible Co
+3
/Co
+2
couple [3].
References:
[1] Liberta, A. E.; West, D. X. Biometals, 1992, 5, 121.
[2]. Saha, N.; Sau, D. K.; Chaudhuri, S.; Mandal, P. C. Transition Met. Chem. 2005, 30, 532.
[3] Sau, D. K.; Saha, N.; Butcher, Ray J.; Chaudhuri, S. Transition Met. Chem., 2003, 28, 229.
111

P 10 NATIONAL SYMPOSIUM IN CHEMISTRY
Second Sphere Coordination In anion Binding: Synthesis, Characterization
And Single Crystal X-ray Structure of Tris(1, 10-Phenanthroline)
Cobalt(III) Periodate Dehydrate, [Co(phen)
3
](IO
4
)
3
.2H
2
O
Ajnesh Singh
a
, Vitor Felix
b
, Paloth Venugopalan
a
,
Raj Pal Sharma*
a
a
Department of Chemistry, Panjab University, Chandigarh-160014, India.
b
Departmento de Quimica, Universidade de Avieiro ,3810-193, Aveiro, Portugal
In continuation of our interest in cationic cobalt(II) complexes[1-3] as anion receptors, we synthesized single
crystals of [Co(phen)
3
](IO
4
)
3,
by slowly mixing the separately dissolved tris(1,10-phenanthroline)cobalt(II)chloride
with sodium metaperiodate in aqueous medium in 1:3 molar ratio. Elemental analyses, spectroscopic studies (IR,
UV/Visible,
1
H and
13
C NMR) and solubility product measurements were performed to characterize the complex
salt. The compound crystallizes in the monoclinic space group P2
1
/n with a = 11.6865(3), b = 19.9546(4), c =
16.6808(3) Å, b = 98.473(1)
o
,

V = 3847.5(6) Å
3
, Z = 4. X-ray structure determination revealed an ionic structure
consisting of one [Co(phen)
3
]
3+
,
three [IO
4
]
-
ions and two water molecules. The six nitrogen atoms, originating from
three 1, 10-phenanthroline ligands (each bidentate) show distorted octahedral geometry around the central Co(III)
metal ion. Supramolecular hydrogen bonding networks between ionic groups [Co-phenCH
d+…
O
d-
anion
] by second
sphere coordination besides electrostatic forces of attraction have been observed that stabilize the crystal lattice
.
The structural studies suggest that [Co(phen)
3
]
3+
is a potential anion receptor for the periodate ion, (IO
4
)
-
in aqueous
medium.
References:
1. Sharma. R, Sharma. R. P, Bala. R, Kariuki. B. M, J. Mol. Struct., 2007, 826, 177-184.
2. Sharma. R. P, Bala. R, Sharma. R, Burrows. A. D, Cassar. K and Mahon. M. F, J. Mol. Struct., 2007, 832, 156-163.
Bala. R, Sharma. R. P, and Bond. A. D, J. Mol. Struct., 2007 , 830 ,198-203.
112