Monte Carlo simulation and experimental validation of plant microtubules cathode in biodegradable battery.

For the first time, electrochemical methods are utilized to study the response of tubulin monomers (extracted from plant source such as Green Peas: Arachis Hypogea) towards charge perturbations in the form of conductivity, conformational changes via self-assembly and adsorption on Au surface. The obtained dimerization and surface adsorption energetics of the tubulins from Cyclic Voltammetry agree well with the literature value of 6.9 and 14.9 kCal/mol for lateral and longitudinal bond formation energy respectively. In addition to the effects of charge perturbations on change in structure, ionic and electronic conductivity of tubulin with increasing load are investigated and found to be 1.25 Sm-1 and 2.89 mSm-1 respectively. The electronic conductivity is 1.93 times higher than the literature value of 1.5 mSm-1, demonstrating the fact that the microtubules (dimer of tubulins, MTs) from plant source can be used as a semiconductor electrode material in energy conversion and storage applications. Thus, motivated by the Monte Carlo simulation and electrochemical results the MTs extracted from plant source are used as cathode material for energy storage device such as Bio-battery and the Galvanostatic Charge/Discharge studies are carried out in coin cell configuration. The configuration of the bio-battery cell is as follows: Al/CB//PP-1M KCl//MTs/SS; where SS and Al are used as current collectors for cathode and anode respectively, Polypropylene (PP) membrane soaked in 1M KCl as electrolyte and Carbon Black (CB) is the anode material. Another configuration of the cell would be replacement of CB by biopolymer such as ethyl cellulose anode (Al/EC/PP-1M KCl/MTs/SS).

Computational mechanistic insights on Ag2O as a host for Li in lithium-ion batteries.

The lithiation mechanism of Ag2O with one and two Li atoms per unit cell carried out using density functional theory (DFT) studies indicate the adsorption of one Li atom at the tetrahedral interstitial site (TIS) as the most stable one with the formation of the Li-Ag2O compound. PDOS plots depict the hybridization of Li 2s with O 2p and Ag 5s states, resulting in the formation of both Li-O and Li-Ag bonds. Also, the Bader charge analysis validates the bonding of Li at TIS with both Ag and O atoms. The band structure plots showcase a surge in electronic conductivity, accounting for the metallic transition of Ag2O with the addition of Li. The difference in the charge distribution between the pairs of surface and subsurface silver atoms in charge density difference plots (CDDP) reveal the incorporation of Li, invoking charge inequivalence in addition to the symmetry inequivalence in the optimized structure. In the case of two Li atoms, Li placed on the top of oxygen (Otop) and at the subsurface of silver (Agss) was found to be the most stable structure with the formation of two strong Li-O bonds, indicating the feasibility of the conversion mechanism. The increase in the Bader charge of O (-1.28e) as well as CDDP establish the formation of Li2O by the conversion mechanism. Thus, the increase in the Li+ ion concentration becomes the deciding factor for the transition of the lithiation mechanism from Li-Ag2O compound formation to the conversion mechanism. The molecular dynamics (MD) simulations feature Li as an "antisite defect producing guest", leading to the formation of Li-O bonds with a concomitant reduction in the number of Ag-O bonds as a function of time. This confirms a shift in the reaction kinetics from the formation of Li-Ag2O to the conversion mechanism.

Investigation of Adsorption Behavior of Anticancer Drug on Zinc Oxide Nanoparticles: A Solid State NMR and Cyclic Voltammetry (CV) Analysis.

The present study aims to comprehend the adsorption behavior of a set of anticancer drugs namely 5-fluorouracil (5-FU), doxorubicin and daunorubicin on ZnO nanoparticles (ZnO NPs) proposed as drug delivery systems employing solid state (ss) NMR, FTIR and Cyclic Voltammetry (CV) analysis. FTIR and 1H MAS ssNMR data recorded for bare ZnO nanoparticle confirmed the presence of adsorbed -OH groups on the surface. 13C CP-MAS NMR spectra recorded for free and ZnO surface adsorbed drug samples exhibited considerable line broadening and chemical shift changes that complemented our earlier report on UV-DRS and XRD data of surface adsorption in case of 5-FU. Moreover, a remarkable enhancement of 13C signal intensity in case of loaded 5-FU was observed. This clearly indicated rigid nature of the drug on the surface allowing efficient transfer of 1H polarization from the hetero nitrogen of 5-FU to ZnO to form surface hydroxyl (-OH) groups and the same has been observed in the quantum chemical calculations. To further analyze the motional dynamics of the surface adsorbed 5-FU, longitudinal relaxation times (T1) were quantified employing Torchia method that revealed significant enhancement of 13C relaxation rate of adsorbed 5-FU. The enhanced rate suggested an effective role of quadrupolar contribution from 67Zn to the 13C relaxation mechanism of ZnO_5-FU. The heterogeneous rate constant (khet), average free energy of activation (∆G≠) and point of zero charge (PZC) measured for free and drug loaded ZnO NPs samples using CV further support the SS-NMR results.

Ag(I) and Au(III) Mercaptobenzothiazole complexes induced apoptotic cell death.

2-Mercaptobenzothiazole (MBT) complexes of Ag(I) and Au(III) were synthesized by wet chemical method. The structural, optical, 1HNMR, ICP - MS and electrochemical studies of the complexes were carried out. The TUNEL assay studies of Ag(I)MBT and Au(III)MBT complexes on A549 cell line indicated induced apoptosis in the cells. TUNEL assay showed 60% cell viability for Ag(I)MBT whereas 80% for Au(III)MBT. Thus Ag(I)MBT can induce cell apoptosis in cells at a higher rate than Au(III)MBT. Therefore these complexes studied here can be a viable option as anti - proliferating agent.

Environmentally available biowastes as substrate in microbial fuel cell for efficient chromium reduction.

Dual chambered microbial fuel cells with Potassium dichromate (22 g/L, MFC-1) and tannery effluent waste water containing 26 mg/L (MFC-2), 5 mg/L (MFC-3) of Cr(VI) as catholyte, sweet lime waste inoculated by cowdung as anolyte and graphite electrodes were used to reduce toxic Cr(VI) to Cr(III) with simultaneous power generation. Cr (VI) in the cathode chamber reduced to Cr2O3 within 24 h. Complete reduction of Cr(VI) from tannery effluents by microbial fuel cell is noticed within 10 days. The 16 s rRNA sequencing studies demonstrated presence of Geobacter Metallireducens in mixed culture bacteria in anaerobic anode. The power density of the device is 396.7 mW/m2on day1which is 7.2 times higher than literature data of 55.5 mW/m2. The processes involved on the biofilm/electrolyte interface and graphite/electrolyte interface is studied by Electrochemical Impedance Spectroscopy. Electrochemical studies demonstrated the active growth of biofilm on anode which reduces charge transfer resistance from day 1 to day 25. The concentration of Cr(VI) reduced in the present studies are approximately 1000 times higher than those reported in the literature.

l-Alanine capping of ZnO nanorods: increased carrier concentration in ZnO/CuI heterojunction diode.

ZnO nanorods were capped with a simple amino acid, viz., l-alanine to increase the carrier concentration and improve the performance of ZnO/CuI heterojunction diodes. The effect of l-alanine capping on the morphology, structural, optical, electrochemical and electrical properties of ZnO nanorods had been studied in detail. The stable structure with two equally strong Zn-O coordinate bonds predicted by density functional theory was in agreement with the experimental results of FTIR spectroscopy. Due to the presence of electron-releasing (+I effect) moieties in l-Alanine, the carrier concentration of capped ZnO nanorods was two orders of magnitude higher and the ZnO/CuI heterojunction device showed more than a two-fold increase in the photovoltaic power conversion efficiency.

Grand Canonical Monte Carlo coupled multiscale simulation for electrochemical and solvent parameters of silver halide systems in water.

Grand Canonical Monte Carlo methods in conjunction with continuum Multiscale simulation to estimate the hydration energies and surface potentials of silver halides as demonstrated elsewhere is employed by incorporating random distribution of molecules, nearest neighbor distances and hydration numbers. The extent of dehydration during each step and the corresponding variation in the hydration numbers are evaluated, assuming the validity of hard spheres. These estimates are then employed to deduce the redox potential of the reaction viz. 2AgX(solution)⇔2Ag(solid)+X2(gas). The dependence of these values on the nature of the halides and solvation characteristics is indicated.

Monte Carlo simulation of electrodeposition of copper: a multistep free energy calculation.

Electrodeposition of copper (Cu) involves length scales of a micrometer or even less. Several theoretical techniques such as continuum Monte Carlo, kinetic Monte Carlo (KMC), and molecular dynamics have been used for simulating this problem. However the multiphenomena characteristics of the problem pose a challenge for an efficient simulation algorithm. Traditional KMC methods are slow, especially when modeling surface diffusion with large number of particles and frequent particle jumps. Parameter estimation involving thousands of KMC runs is very time-consuming. Thus a less time-consuming and novel multistep continuum Monte Carlo simulation is carried out to evaluate the step wise free energy change in the process of electrochemical copper deposition. The procedure involves separate Monte Carlo codes employing different random number criterion (using hydrated radii, bare radii, hydration number of the species, redox potentials, etc.) to obtain the number of species (CuCl(2) or CuSO(4) or Cu as the case may be) and in turn the free energy. The effect of concentration of electrolyte, influence of electric field and presence of chloride ions on the free energy change for the processes is studied. The rate determining step for the process of electrodeposition of copper from CuCl(2) and CuSO(4) is also determined.

Analysis of electron transfer processes across liquid/liquid interfaces: estimation of free energy of activation using diffuse boundary model.

The evaluation of the free energy of activation pertaining to the electron-transfer reactions occurring at liquid/liquid interfaces is carried out employing a diffuse boundary model. The interfacial solvation numbers are estimated using a lattice gas model under the quasichemical approximation. The standard reduction potentials of the redox couples, appropriate inner potential differences, dielectric permittivities, as well as the width of the interface are included in the analysis. The methodology is applied to the reaction between [Fe(CN)6](3-/4-) and [Lu(biphthalocyanine)](3+/4+) at water/1,2-dichloroethane interface. The rate-determining step is inferred from the estimated free energy of activation for the constituent processes. The results indicate that the solvent shielding effect and the desolvation of the reactants at the interface play a central role in dictating the free energy of activation. The heterogeneous electron-transfer rate constant is evaluated from the molar reaction volume and the frequency factor.

A simple simulation methodology for estimation of dehydration energies and surface potentials of concentrated NaCl solutions.

A novel simulation procedure for estimating the dehydration energies of NaCl solutions spanning a wide range of concentrations, which incorporates ionic and molecular sizes, ion-pair formation, etc., is proposed on geometric and phenomenological considerations. The extent of dehydration during each movement of the hydrated molecule is evaluated using the expected and actual displacement of the species and mean nearest-neighbor distances. The interdependence between the size of the simulation box, number of molecules, and electrolyte concentration is pointed out.

Estimation of exchange current density for ferric/ferrous reaction at electrode surfaces--influence of ionic desolvation and dipolar adsorption.

The dependence of the exchange current density of the ferric/ferrous reaction on electrode surfaces has been investigated using the work functions of metals, surface potentials of the reactants, adsorption characteristics of water dipoles, hydration numbers, etc. The extent of dehydration of the reactant species at the reaction zone, as well as the influence of desorption of water dipoles from the electrode surface on the magnitude of exchange current density, is demonstrated.

Condensation of nucleobases at mercury/aqueous solution interface--a structural perspective using hydrogen bonding considerations.

The two-dimensional condensation behavior exhibited by nucleobases at a mercury/aqueous solution interface is analyzed on the basis of their hydrogen-bonded quadruplex structures, and the experimentally observed critical temperatures are rationalized incorporating different types of hydrogen bonding, surface coordination effects, and stacking considerations. The proposed methodology provides a structural basis for the interpretation of critical temperatures and enables the calculation of the same pertaining to different modified nucleobases. The applicability of the procedure to order-disorder transitions of water dipoles at Hg electrodes is also indicated.