Annual Report 2004-2005
Support to frontier areas of research in chemical
sciences continued during this year. Several projects in contemporary
areas such as nanomaterials, protein folding, ionic liquids,
new organometallic reagents etc. received funding. The sub-area
wise projects funded are given below:
- Study of novel multicomponent reactions involving nucleophilic
carbenes and related chemistry.
- This work may result in novel heterocyclic compounds showing
- A novel atom economical route has been proposed for organic
stereoselective processes using Baylis-Hillman reaction.
This study would be directed towards synthesis of important
biologically active molecules via the Baylis-Hillman methodology.
- Design and synthesis of dual PPAR ã /á agonists
having novel carbazole moieties with antidiabetic and hypolipidemic
activity. The compounds obtained would be screened for antihyperglycemic
and anti hyperlipidemic activities.
- Design, synthesis and biological studies of neoglycoconjugates.
Different functionalized molecules, both cyclic and linear
would be synthesized using carbohydrates as scaffold and
their biological activities would be studied.
- Catalytic asymmetric 1,3-dipolar cycloaddition reaction
of azomethineylides: Application towards the asymmetric
total synthesis of (+)- and (-)-spirotryprostatins. Novel
synthetic methodologies for synthesizing chiral pyrrolidine
will be developed and this methodology will be applied towards
synthesis of potent antimitotic agents, spirotryprostatins.
- Enzyme-mediated resolutions and deracemizations in ionic
liquids. Application of enzymes such as proteases, lipases
and substilisin in ionic liquids would be explored for the
preparation of commercially important agrochemicals and
- Novel bile acid derived dendritic structures: Design,
synthesis, properties and potential applications. Synthesis
of novel bile acid derived dendritic structures would be
undertaken and their application as drug conjugates, light
harvesting system and as drug catalysts will be investigated.
- New organometallic reagents for green chemistry: An attempt
would be made to develop organobismuth reagents as potential
organometallic alternative reagent for organic synthesis.
- Synthesis of chiral hydrocyanins as intermediates for
industrially important bio-active compounds through chiral
catalytic route. This involved design and synthesis of chiral
inorganic metal complexes and their application as catalyst
in the preparation of commercially useful chiral cyanohydrins.
The research highlights of the projects
are as follows:
- A Patent has been filed for improved enzymatic process
for the preparation of amino acyl esters of mono and disaccharides;
- A new route to C-aryl glycosides was achieved which may
open up the possibility of entry into C-nucleosides;
- A Patent has been filed for a chemoenzymatic process for
the stereoselective preparation of ®-ã-amino-â-hydroxy
butyric acid (R-GABOB) and ® -carnitine;
- Studies of glycoside cluster effect in carbohydrate-protein
interaction have led to better understanding of complex
carbohydrate mediated biological processes;
- Short and efficient methods have been developed for the
synthesis of scyllo-inositol and its thoformate derivatives;
- Several newer ionic liquids based on imidazolium salts
were synthesized and their inherent acidity has been used
as reaction media/promoters to environment friendly processes
with minimal or no waste;
- A new T-tecton keto phenol 8 was developed to build host-guest
ladder networks; and
- New fluorescent and chiral GPI and PI probes have been
prepared to address important questions regarding membrane
organization and biology.
The projects received in the five identified
areas (aqueous organometallic chemistry; molecular precursors
for advanced inorganic materials; metalloenzymes and their
mimics; green chemistry; and f-block elements) were considered
and four were funded (two in the area of metalloenzymes
and their mimics; one each in the area of molecular
precursors for advanced inorganic materials and f-block
elements). Among the two projects in the area of metalloenzymes
and their mimics one deals with mimicking of structural
and functional aspects of iron and manganese containing metalloproteins
using extradiol cleaving enzymes, while the other deals with
the synthesis of selenocysteine derivatives and use them for
biomimetic studies. This study is expected to throw some light
on the role of selenium in biological systems. A project on
molecular precursor for advanced inorganic materials
deals with the synthesis of molecular container of different
size and shape through self-assembly of chiral transition
metal complexes; while the project in the area of fblock
elements deals with the synthesis of new 4f and 5f inorganic
compounds using hydrothermal/solvo thermal methods and study
their luminescence properties for possible use as fluorescence
markers for DNA.
In addition, projects in other areas are
- Design, synthesis and cation recognition study of fluorescent
molecular sensors. This study is expected to help in development
of fluorescent probe for alkali, alkaline earth and toxic
- Mapping the reaction coordinate for the oxidative addition
of molecular hydrogen to a metal center. This study would
help in designing systems that may show improved efficiency
and better catalytic activity.
- Green chemistry with water-tolerant reactions and reagents.
The development of organic reactions in water will contribute
significantly to the progress of green chemistry.
- Design and development of peroxo-metal mediated environmentally
benign reagents and reactions. A greener (environment friendly)
synthesis of chloro compounds is proposed.
- Development of new procedure for the synthesis of optical
active organocobaloximes and study their Co-C bond reactivity
in molecular oxygen insertion reactions and in hydrogenation
reactions. This study is a first attempt to exploit the
role of organocobaloximes for this purpose.
- Synthesis of new class of polynuclear ruthenium and osmium
complexes in different valence states and study their photophysical
and electrochemical properties. This study might possibly
lead to new materials having high degree of nonlinear optical
- Synthesis of novel late transition metal complexes with
N-heterocyclic carbene based legands with the aim of designing
new catalysts for olefin polymerization and co-polymerization.
These complexes are expected to be air and moisture stable
and would thus be an improvement over the existing polymerization
- Synthesis of a range of redox active copper and other
transition metal complexes having ligand system containing
photo synthesizing abilities and study photoinduced DNA
cleaving activity. The study has implications in the photodynamic
therapy and cancer treatment. The research highlights of
projects are given below:
- New first generation metallodendritic supramolecular assemblies
have been developed.
- It has been shown for the first time that the hydrolysis
of commercially available air and moisture stable early
transition metal compounds, Cp2MCl2 (M=Ti, V, or Zr), can
be advantageously used for generating active catalysts for
aqueous emulsion polymerization.
- Some new chiral cyclophosphazenes have been synthesized
and they were structurally characterized.
- Novel Ru-pac complexes were synthesized and few of them
showed anti-tumour activity.
- Efficient routes have been developed for synthesis of
polynuclear complexes of platinium metals.
- Efficient processes for recovery of uranium and palladium
from low grade minerals and seawater have been developed.
- High Performance Liquid Chromotography system has been
sanctioned at IISc, Bangalore (Figure 2.3). This system
will be used for separation and purification of selenium
containg aminoacids, peptides and proteins.
High precision crystal structure studies on
some ferroic crystals to obtain precise charge density maps
as a function of temperature across their phase transitions.
Investigation of the formation of C-H H-B
dihydrogen bond clusters between various substituted benzenes
and boranetrimethylamine in gas phase using electronic and
vibration spectroscopy methods. Dehydrogenation reaction via
dry hydrogen bonded intermediates as a possible method to
active C-H bonds will be investigated. It is an interesting
study from the point of view of understanding weak inter molecular
reactions in chemistry of di-hydrogen bond systems as it has
not been well understood
- Studies of electron and proton transfer processes in ionic
liquids have been funded. New class of ionic liquids based
on pyrrolidinum salts, which are expected to have better
expected transparancy in the near UV region, would be prepared
and their photophysical properties would be investigated.
- Synthesis of mono and bimetallic nano particles in controlled
conditions, study of dsorption of biomolecules on the surface
of nanoparticles and the interaction of nano particles with
biomolecules in organized media. This study is expected
to yield nanomaterials with different size and shape distribution
which is extremely important in nano science.
- Investigation of the dynamics of water surrounding a
protein and the effect of water during the folding of proteins.
The free energy landscapes of small proteins through minimalistic
models, kinetics of association of proteins and to develop
a theory of protein folding are attempted. This study has
implications in drug discovery
- Development of soft-computing methods for bound state
electronic structure calculations.
Green Chemistry Programme
The Green Chemistry programme took concrete
shape during the year. A separate Task Force was constituted
to promote this area. A Seminar-cum-Workshop was organized
at IICT, Hyderabad in September, 2004. Around 100 researchers
from academic institutions and industry participated in the
event. Lectures were delivered by eminent people practicing
Green Chemistry in the workshop. Another Workshop in the eastern
region is planned in February, 2005 at IIT, Guwahati.
Proposals were invited in the area of Green
Chemistry under two categories: (i) Open-ended and (ii) industry
collaborative projects. Under the industry collaborative projects
projects have been recommended for funding. One project related
to conversion of waste material into useful products. This
proposal is for conversion of bulk circuit waste coming from
Jhamarkotra plant, Rajasthan into calcium magnesium phosphate
fertilizer. Rajasthan State Mines and Minerals Limited is
contributing 30% of the recurring cost to this project. Another
project is on development of novel ecofriendly bromine-less
bromination protocols, brominating agents and development
of newer catalysts for a variety of oxidations. This project
will be partly funded by Ranbaxy Limited.