Annual Report 2006-2007
Support to frontier areas of research continued during this
year. It covers many contemporary areas such as chiral catalysis,
rational design and synthesis of biologically active molecules,
molecular materials, green chemistry etc. Special initiative
was launched in the area of bioinorganic chemistry. Eighteen
researchers were awarded Raja Rammana Fellowship for outstanding
performance in their respective ongoing projects.
The following are some of the projects funded in this year.
- design and develop diversity oriented green synthesis
of industrially and pharmaceutically important heterocyclic
scaffolds using carbohydrates as biorenewable feedstocks.
- development of new methodology for the synthesis of cyclic
ethers. The methodology developed will be applied to synthesize
molecules of biological interest.
- synthesis of novel dendrimers and explore their catalytic
- synthesis of modified oligonucleotides to mimic biological
- synthesis of d-glucose based nonionic Gemini surfactants
as micellar and reverse micellar mimics and explore their
use in chiral recognition.
- develop methodology for the construction of enantiopure
bi-, tri and spirocyclic building blocks from a-pinene and
use of some of these building blocks in total synthesis
of biologically important natural products.
- synthesize new chiral liquid crystalline materials containing
at least one cholesteryl moiety and study their mesogenic
property towards practical application.
- study the utility of olefin metathesis reaction for the
synthesis of furanomycin, a-amino acids of nonnatural origin
and several heterocyclic systems.
- synthesize and characterize various oligomers based on
thiophene for possible application as NLO or LED devices.
- undertake diversity oriented synthesis of bicyclic enediyenes
by using intramolecular Kinugasa and [3+2] cycloaddition
reactions and study structure-activity relationship. This
study may lead to new molecular entities with biological
Few interaction meetings with potential project investigators
from less endowed institutions were organized. The investigators
were requested to make a presentation of the proposed work
and suggestions were made with a view to help them prepare
a "fundable" project.
Some of the salient achievements in the ongoing projects
- A series of bifunctional acridine conjugates were synthesized
with potential application as DNA binding and cleaving agents.
- A patent has been filed both in India and abroad for developing
a supramolecular fluorescent marker for the detection and
quantification for GTP and ATP in buffer and biological
- Dendrimer type systems capable of sequential electron
transfer has been synthesized, which may have applications
in photovoltaic system, sensors, xerography etc.
- Significant knowledge has been generated in synthesizing
polyoxazole based natural products and in particular towards
the structures related to the important natural product,
telomestatin. Two macrocyclic structures related to this
important anti-cancer natural product have been synthesized
which may find application as telomerase inhibitor.
- A new approach has been adopted for synthesis of pyridine
ring of camptothecins and related alkaloids by using RCM
methodology. This study has opened up new vistas for the
synthesis of alkaloids and other natural and non-natural
products of industrial importance.
- In a project on crystal engineering, strategies have been
developed towards the synthesis of organic/ inorganic hybrid
framework materials with the required properties. Specifically,
the compounds racemic 2,2'-binol and 4,4'- bipyridine were
shown to form two types of host frameworks via O-H
hydrogen bonds which have affinity to include variety of
aromatic guest molecules such as biphenyl, toluene and xylene.
Both the architectures does not contain inversion centre
and maintains the chirality, but the packing architectures
generates the inversion centre. The author was able to replicate
the above observed 1D-host framework with chiral 2,2'- binol
and bipyridine with guest molecules such as toluene and
- In a project on polymer chemistry, it has been shown that
the incorporation of 3,4-ethylenedioxythoiphene (EDOT) moieties
in the main chain high performance polyesters and polyureas
improves the processability without compromising thermal
properties. Furthermore, the exocyclic bond angle of EDOT
unit is found to be compatible with the formation of liquid
crystalline phases as the main chain polyesters based on
EDOT were found to exhibit mesophasic behaviour. This opens
up various avenues wherein new high performance materials
can be designed by replacing benzene units with EDOT units
wherein the processability can be improved without compromising
thermal stability of resulting polymers.
Launching of new initiative in bioinorganic chemistry was
highlight of the year. Ten research proposals in different
aspects of bioinorganic chemistry were funded. A major program
on "Metal based drugs" is being evolved. Seven research
fellowships (6 pre-doctoral and 1 post-doctoral) were also
awarded to undertake research in this area. In addition, support
to research in other frontier areas of inorganic chemistry
The following projects were funded as part of the bioinorganic
- study of functional analogues of molybdenum and tungsten
containing oxido-reductase enzymes, generate hybrid enzymes,
isolate and purify native proteins of this class. This is
an internationally competitive research which aims at understanding
the molecular role of molybdenum and tungsten enzymes which
have prominent roles in the carbon, nitrogen and sulphur
cycles of nature.
- prepare and investigate a series of novel iron, manganese
and ruthenium complexes being able to act as structural
and functional models for non-heme monooxygenase iron enzymes.
This study helps to understand structure-function relationship
in monooxygenase systems.
- preparation of new polymer based ligands (nucleobase
polymers, organic-inorganic hybrid polymers) and their metal
complexes, test their efficacy as catalysts for phosphate
ester hydrolysis and peptide bond modifications. The phospho-diester
bonds of DNA are resistant to hydrolysis, and with the introduction
of metal ions as cofactors, nucleases are able to accelerate
the rate enormously. The challenge is in the design of metallopolymers
with specific catalytic activities.
- development of gadolinium complexes as contract enhancing
agents for magnetic resonance imaging.
- synthesis of novel metal complexes and study their interaction
with DNA and cleavage activities.
- synthesis of glycol-conjugates and their metal complexes
and study their interaction with biomolecules like lectin
and plasmid DNA.
Some of the salient achievements in the ongoing projects
- In a projct on exploring the catalytic activity of platinum
metal complexes containing a variety of phosphorus based
functionalized or hemilabile ligands, the author has developed
novel ligand systems, prepared their transition metal complexes
and studied their catalytic applications with excellent
results. Several phosphorus and nitrogen based ligands have
been identified for C-C coupling reactions with remarkable
efficiency and turnover numbers. Bis (2-diphenylphosphinoxynaphthalen-1-yl)
methane and other related ligands were found to show excellent
catalytic activity in homogeneous catalysis (hydrogenation,
Suzuki Cross-coupling reactions, Heck reactions, cycloproponation
reactions, arylation of ketones, halogen exchange and halogenation
reactions). Cyclodiphosphazanes containing hemilabile ponytails
were synthesized which exhibit versatile coordination properties.
The exclusive formation of either cis or trans Pd(II) complexes
was achieved using appropriate metal reagents. The cyclodiphosphazane
having ether functionality was found to preferably form
the tetranuclear rhodium(I) metallacycle, whereas cyclodiphosphazanes
containing thioether and amine functionality gives the bichelated
dinuclear rhodium(I) complexes. The latter complexes are
the first examples of cyclodiphosphazanes performing as
eight-electron donor tetradentate ligands.
- In a project on synthesis and study of magnetic properties
of 3d-4f and 4f-nitroxide systems, two compartmental Schiff
base ligands have been synthesized and characterized. These
ligands have been used to derive two new discrete dinuclear
CuIIGdIII compounds, [CuII(H2O)LIGdIII(NO3)3] and [CuIIL2GdIII(NO3)3].
The structures of both the compounds have been determined.
Variable temperature magnetic susceptibility as well as
variable-field magnetization studies reveal that the metal
centers in these two compounds are coupled by strong ferromagnetic
interaction. The compound [CuII (H2O)L1GdIII(NO3)3] exhibits
strongest ferromagnetic interaction among the related compounds
reported so far.
- A number of glycol-conjugates based on galactose and
ribose have been synthesized and characterized. The PI has
been able to introduce naphthyl moiety at C1-position of
carbohydrate and keep all other position free so that the
molecules are suitable not only for fluorescence measurements
but also for studying their interactions with lectins and
glycosidases. A number of transition metal ion complexes
were synthesized using the derivatives based on galactosyl
and ribosyl moieties. Absorption and fluorescence study
of the selective recognition of Cu(II) ions by 1-(â-D-galactopyranosyl-1'-deoxy-1'-
iminomethyl)-2-hydroxynaphthalene in HEPES buffer has been
Some of the projects funded are as follows:
- synthesis of a new class of materials based on delafossite
structure using a new synthetic strategy. These materials
are potentially important as p-type transparent conductors.
- development of new photocatalytic materials with absorption
in visible light for removing organic pollutants. The photocatalytic
materials proposed are BiVO4, CeVO4 and AgNbO3.
- further exploration of the recently developed "Fer"
expansion in NMR. This expansion has novel features such
as better convergence under certain conditions and may lead
to design of novel pulse sequences for solid-state NMR leading
to improved line-width and ultimately improve applications
of NMR for the study of bio-molecules.
- synthesis of aluminophosphates and investigating their
photo catalytic properties towards degradation of organic
- study photolesion of microhydrated DNA building block
in vacuum. This research has a promise of solving important
fundamental issues regardless of its potential application.
- studies relating to heteropolyacids supported on titania
and mesoporous materials as catalysts for acid and redox
organic transformations. This work attempts to discover
eco-friendly solid acid catalysts for preparation of fine
- synthesis of nano-composites and their characterization
in order to study their usability as barrier membranes for
separating volatile organic compounds from water.
Some interesting results obtained from ongoing projects are
- Studies on ionic liquids were carried out with a view
to understand their role as green solvents. Several combinations
of ionic liquids were synthesized. Properties such as density,
speed of sound, compressibility and viscosity for a variety
of ionic liquids were measured at four different temperatures.
Investigations were done to find out how these properties
play an important role in carrying out organic reactions.
For this purpose, some Diels-Alder reactions in ionic liquids
and in water were carried out. The author demonstrated that
room temperature ionic liquids are not as effective as water
in promoting Diels-Alder reactions.
- Solid state metathesis route has been developed for synthesizing
perovskite oxides of current interest, such as LaCoO3, LaMnO3,
AMnO3 and ATiO3 (A = Ca, Sr, Ba) from rock salt metal oxides.
This route has been used for the synthesis of double perovskite
oxides, Sr2MWO6 (M = Mg, Mn, Fe, Ni) that enabled to obtain
cation-ordered phases at a considerably lower temperature
(~750oC) than what was employed in conventional synthesis
of these materials. Investigation of the interaction of
hydrogen with alkaline earth manganites (IV) AMnO3 (A =
Ca, Sr, Ba), dispersed with 1 at % Pt. revealed an unprecedented
uptake of hydrogen by BaMnO3/Pt to the extent of ~1.25 mass%
at moderate temperatures (190-260oC) and ambient pressure.
The work suggests the possibility of developing new hydrogen
storage materials based on electropositive metal-transition
- Detailed molecular dynamics and Monte Carlo calculations
have been made to obtain a more fundamental understanding
of diffusion of real molecular systems within porous solids
such as zeolites. A method has been proposed that can yield
separation with separation factors that are orders of magnitude
higher than existing methods. The usual separation factors
obtainable with the existing methods of separation are 103.
In contrast, the proposed method can provide a separation
factor of the order of 109 with columns of nanometer dimensions
(as compared to several metres in normal separations). Another
important result is a new and general explanation of the
conductivity maximum for ions in polar solvents. Although
many theories are available in literature, none of them
have been able to explain all the observed conductivity
data. For example, they have not been able to explain the
conductivity variation with pressure. The author has proposed
that Levitation Effect (LE) is the right theory and provides
the underlying reason for the observed maximum. The predictions
of the Levitation Effect such as the lower activation energy
for the ion with maximum conductivity, etc. have received
support and the existing experimental data seem to support
LE as the underlying cause.
- In a project on investigating biodegradable polymeric
hydrogels and exploring them for drug delivery, a simple
and new method has been developed to crosslink chitosan
using polyethylene glycol (PEG) with different molecular
weights. PEG-crosslinked chitosan (PEG-Ch) showed a pH-independent
swelling behavior: swelled in both the stimulated stomach
(pH 1.1) and intestinal (pH 7.4) solutions. Thus, the prepared
PEG-Ch could be a better biomaterial than chitosan in the
development of orally sustained drug-delivery devices.
A workshop was organized at MS University of Baroda, Vadodara.
An interaction meeting was held at Ankleswar with industry
representatives to create awareness about the practice of
Green Chemistry principles in industrial processes. Several
problems have been identified which could be solved using
green chemistry approach. Further discussion is in progress.
The following projects were funded:
- How to make ionic liquids more effective for promoting
organic reactions. The proposal attempts to investigate
the limitations of using ionic liquids for various organic
reactions and come up with solution for tailoring the properties
of ionic liquids for facile synthesis.
- Non-hazardous bromination with bromide/bromate couple
obtained as intermediate of bromine recovery plants. In
this project, the use of alkaline bromine intermediate as
an inexpensive and eco-friendly brominating agent would
be explored in place of liquid bromine.