Improved exchange-correlation potential for polarizability and dissociation in density functional theory

The authors propose a novel approach to the problem of polarizabilities and dissociation in electric fields from the static limit of the Vignale-Kohn (VK) functional. The response to the purely scalar part of the VK response potential is considered. This potential has ground-state properties that notably improve over the full VK response density and over usual (semi-)local functionals. The correct qualitative behavior of our potentials means that it is expected to work well for polarizabilities in cases such as the H(2) chain, and it will also correctly dissociate open-shell fragments in a field.     

Long-range excitations in time-dependent density functional theory

Adiabatic time-dependent density functional theory fails for excitations of a heteroatomic molecule composed of two open-shell fragments at large separation. Strong frequency dependence of the exchange-correlation kernel is necessary for both local and charge-transfer excitations. The root of this is the static correlation created by the step in the exact Kohn-Sham ground-state potential between the two fragments. An approximate nonempirical kernel is derived for excited molecular dissociation curves at large separation. Our result is also relevant when the usual local and semilocal approximations are used for the ground-state potential, as static correlation there arises from the coalescence of the highest occupied and lowest unoccupied orbital energies as the molecule dissociates.     

Activity and Conformation of Yeast Alcohol Dehydrogenase (YADH) Entrapped in Reverse Micelles

Yeast alcohol dehydrogenase (YADH) solubilized in reverse micelles of aerosol OT (i.e., AOT or sodium bis (2-ethyl hexyl) sulfosuccinate) in isooctane has been shown to be catalytically more active than that in aqueous buffer under optimum conditions of pH, temperature, and water content in reverse micelles. Studies of the secondary structure conformational changes of the enzyme in reverse micelles have been made from circular dichroism spectroscopy. It has been seen that the conformation of YADH in reverse micelles is extremely sensitive to pH, temperature, and water content. A comparison has been made between the catalytic activity of the enzyme and the α-helix content in the conformation and it has been observed that the enzyme is most active at the maximum α-helix content. While the β-sheet content in the conformation of the entrapped enzyme was found to be dependent on the enzyme–micelle interface interaction, the α-helix and random coil conformations are governed by the degree of entrapment and the extent of rigidity provided by the micelle core to the enzyme structure.     

Cross-linked polyvinylpyrrolidone nanoparticles: a potential carrier for hydrophilic drugs

Injectable hydrogel polymeric nanoparticles of polyvinylpyrrolidone cross-linked with N,N'-methylene bis-acrylamide and encapsulating water-soluble macromolecules such as FITC-dextran (FITC-Dx) have been prepared in the aqueous cores of reverse micellar droplets. These particles are 100 nm and below in diameter with a narrow size distribution. When dispersed in aqueous buffer these particles appear to be transparent and give an optically clear solution. Lyophilized powder of these nanoparticles is redispersable in aqueous buffer without any change in the size and morphology of the particles. The efficiency of FITC-Dx entrapment by these nanoparticles is high (>70%) and depends on the amount of cross-linking agent present in the polymeric material. The release of the entrapped molecules from these nanoparticles depends on the degree of cross-linking of the polymer, particle size, pH of the medium, and extent of loading, as well as temperature.     

5-enolpyruvylshikimate 3-phosphate synthase: chemical synthesis of the tetrahedral intermediate and assignment of the stereochemical course of the enzymatic reaction

A chemical synthesis of both diastereomers of the tetrahedral intermediate involved in 5-enolpyruvylshikimate 3-phosphate synthase (EPSPS) catalysis has been accomplished. Combination of methyl dibromopyruvate with a protected shikimic acid derivative, phosphorylation, and lactonization afforded the intermediates (S)-15 and (R)-15, whose configurations were assigned by NMR. After introduction of the 3-phosphate group and deprotection, photoinitiated radical debromination of the dibromo analogues (S)-5 and (R)-5 was accomplished with tributyltin hydride in mixed aqueous solvents in the presence of surfactant to give the pyruvate ketal phosphates (R)-TI and (S)-TI, respectively. These compounds are stable at high pH, but decompose at pH 7 with a half-life of ca. 10 min. (R)-TI proved to be inert to EPSPS, while (S)-TI was converted by the enzyme to a mixture of 5-enolpyruvylshikimate 3-phosphate, shikimate 3-phosphate, and phosphoenolpyruvate. The demonstration that the enzymatic intermediate possesses the S-configuration at the ketal center confirms the mechanism as an anti addition followed by a syn elimination. Furthermore, it appears that the syn stereochemistry of the second step requires the phosphate leaving group to serve as the base in catalyzing its own elimination.     

Location of solubilizate in water-AOT-isooctane systems using positron lifetime spectroscopy

In the present work, positrons have been used as a probe to locate the interaction site of the additive molecules in a membrane mimetic system similar to reverse micelles. The systems investigated are water-AOT Aerosol OT [Sodium bis(2-ethylhexyl) sulfosuccinate)-isooctane solutions. Positron lifetime measurements have been performed in water-AOT-isooctane solutions containing chloroform and dichloromethane, respectively, as additives. The choice of these additives is based on their physiological importance. A comparison of the behavior of positron annihilation parameters in surfactant solutions containing the additives with that in systems without them has been made. It has provided some information about the location of the interaction site of the additive molecules in these solutions. In chloroform, the additive molecules tend to migrate from the bulk solvent to the aggregates and are adsorbed either at the interface or close to it. The dichloromethane molecules, on the other hand, tend to get distributed near the hydrocarbon tail of the AOT molecules closer to the bulk solvent.     

A Synergistic Approach towards Optimization of Coupled Cluster Amplitudes by Exploiting Dynamical Hierarchy

The coupled cluster iteration scheme for determining the cluster amplitudes involves a set of nonlinearly coupled difference equations. In the space spanned by the amplitudes, the set of equations are analyzed as a multivariate time-discrete map where the concept of time appears in an implicit manner. With the observation that the cluster amplitudes have difference in their relaxation timescales with respect to the distributions of their magnitudes, the coupled cluster iteration dynamics are considered as a synergistic motion of coexisting slow and fast relaxing modes, manifesting a dynamical hierarchical structure. With the identification of the highly damped auxiliary amplitudes, their time variation can be neglected compared to the principal amplitudes which take much longer time to reach the fixed points. We analytically establish the adiabatic approximation where each of these auxiliary amplitudes are expressed as unique parametric functions of the collective principal amplitudes, allowing us to study the optimization with the latter taken as the independent degrees of freedom. Such decoupling of the amplitudes significantly reduces the computational scaling without sacrificing the accuracy in the ground state energy as demonstrated by a number of challenging molecular applications. A road-map to treat higher order post-adiabatic effects is also discussed.     

Kinetics study of geopolymerization of fly ash using isothermal conduction calorimetry

Isothermal conduction calorimetry has been used to study the reaction kinetics of early geopolymerization of fly ash. Fly ash particles were subjected to react with NaOH solution in 2:1 ratio at isothermal temperatures of 34, 39, 45, 52, and 60 °C. The reaction kinetic parameters such as activation energy, rate of reaction, and pre-exponential function were calculated using the rate of heat evolution data. It is observed that the geopolymerization reaction followed a nucleation and growth mechanism. The activation energy obtained from an Arrhenius plot was around ~100 kJ mol^?1.