UGC Start Up Grant-Sanctioned-10Lakhs

Protonated amino groups are ubiquitous in nature and important in the fields of chemistry and biology. Efficient polyamine analogues, have been developed with DFT calculations on the interactions of some simple cyclic and constrained protonated diamines with the DNA base pairs from our group showing stronger interactions of the cyclic ones than the known linear ones. 

Our next target is to 

i) develop full polyamine drugs with DFT and MD simulations with DNA duplex to fight with cancerous diseases.   

ii) Develop new inhibitors to check the production of natural polyamines in a malignant manner.

Photo catalysis is the acceleration of a photoreaction in the presence of a catalyst. In photogenerated catalysis, the photocatalytic activity (PCA) depends on the capability of the catalyst to create electron–hole pairs which generates free radicals that are able to undergo reactions. Applications of photocatalysts may be in various fields such as (i) conversion of water to hydrogen gas by photocatalytic water splitting; (ii) oxidation of organic matter from the free radicals generated by TiO2; (iii) oxidation of organic contaminants using magnetic particles that are coated with titanium dioxide nanoparticles and disturbed using a magnetic field while being exposed to UV light. Several work have been done to increase the efficiency of a n-type semiconductor like TiO2 along with some of my publications. 

Photocatalytic splitting of water is of tremendous importance in the present day as it has a grand future prospect for solving the crisis of energy.8 However, very little is known about the the interplay of light absorption, directional electron transfer and catalytic processes. The current understanding based on experimental methods is limited to the first electron transfer, while hydrogen evolution requires two electrons and water oxidation four. In other words the total mechanism of the overall catalytic process still needs to be clarified in detail.

Our aim of the study is intimately related to the field of energy conversion and renewable energies which are of uttermost importance for our society. The renewable source of energy causing less pollution in our project view is the hydrogen fuel cell. The main aim of the project is intimately related to the field of renewable source of energy from sunlight through Artificial Photosynthesis. P-type semiconductors are already known to split water to produce Hydrogen gas which can be directly used as renewable fuels or can be major component for future fuels but the major setback is the efficiency of such DSSC devices and the effective cost. My research will be dedicated to (a) develop effective dye sensitizer (organic and metal organic); (b) Promising alternative support materials in place of NiO shall be proposed and their properties as support materials theoretically assessed; (c) understanding the transfer of electrons from the dye to the catalyst through the molecular bridging ligand and also understanding the mechanism of the catalytic effect.

We have addressed one of the fundamental questions in the literature towards the solvation of alkali halides esp. potassium chloride at molecular and crystal level. Our findings showed that the formation of prismatic structure of Potassium Chloride with 4 water molecules is sufficient to separate the cation and the anion. This result revealed the smallest water cluster used to dissociate an alkali halide. I have further addressed the solvation phenomena of potassium chloride crystals in bulk water with quantum chemical and molecular dynamics studies. The quantum chemical calculations with (KCl)6 microcluster and 1-15 water molecules showed that four water molecules initiated the dissociation of the cluster by pulling out the edge Cl- ion. Six water molecules enhance the situation. It has been observed that one or two ions move out from cluster with upto 15 water molecules but a complete salvation is not attended. Molecular dynamics simulation with larger clusters and bulk water molecules in a PBC condition was performed to see the dissolution phenomenon of the KCl crystal. The simulation studies show that {100} surface of the KCl is more stable than {110} or {111} and the dissolution process of the {100} surface occurs from the top layer while other layers remain intact. While for the other surfaces {110} and {111} dissolution occurs from all the sides. Further Calculations can be performed for other important alkiali halides.

We have addressed, the role of solvent on the conformational behavior of stereoelectronic organic systems specifically on piperazine systems. Further studies are being done on other hetero molecules to understand their stability and interactions to other small molecules. 

 We have also addressed the stereo selection of sterically unbiased olefins with electrophiles and also the solvent effect on these electrophilic additions with quantum chemical calculations and molecular dynamic simulations. Our calculations showed that the well known Cieplak effect is not always true for predicting the facial selectivities. We introduced a new theoretical approach to predict the selectivity for such sterically unbiased systems. We also showed that in some cases solvent plays a very important role to predict the selectivity.