Oneand twodimensional single quantumand multiplequantumNMR methodologies: tools for chiral analyses

It is well known that enantiomers cannot be distinguished by NMR spectroscopy unless diastereomorphic interactions are imposed. Several chiral aligning media have therefore been reported for their visualization, although extensive studies are carried out using the liquid crystal made of polypeptide poly-γ-benzyl-L-glutamate (PBLG) in organic solvent. In PBLG medium the spin systems are weakly coupled and the first order analyses of the spectra are generally possible. But due to large number of pair wise interactions of nuclear spins resulting in many degenerate transitions the 1H NMR spectra are not only complex but also broad and featureless, in addition to an indistinguishable overlap of the spectra of enantiomers. This enormous loss of resolution severely hinders the analyses of proton spectra, even for spin systems with 5–6 interacting protons, thereby restricting itsroutine application. In this review we discuss our recently developed several one and multidimensional NMR experiments to circumvent these difficulties taking specific examples of the molecules containing a single chiral centre.

Ion Transport in Liquid Salt Solutions with Oxide Dispersions:``Soggy Sand'' Electrolytes

``Soggy sand'' electrolyte, which essentially consists of oxide dispersions in nonaqueous liquid salt solutions, comprises an important class of soft matter electrolytes. The ion transport mechanism of soggy sand electrolyte is complex. The configuration of particles in the liquid solution has been observed to depend in a nontrivial manner on various parameters related to the oxide (concentration, size, surface chemistry) and solvent (dielectric constant, viscosity) as well as time. The state of the particles in solution not only affects ionic conductivity but also effectively the mechanical and electrochemical properties of the solid liquid composite. Apart from comprehensive understanding of the underlying phenomena that govern ion transport, which will benefit design of better electrolytes, the problem has far-reaching implications in diverse fields such as catalysis, colloid chemistry, and biotechnology.

``On-the-fly'' kinetics of enzymatic racemization using deuterium NMR in DNA-based chiral oriented media

We report the in situ and real-time monitoring of the interconversion of L- and D-alanine-d(3) by alanine racemase from Bacillus stearothermophilus directly observed by H-2 NMR spectroscopy in anisotropic phase. The enantiomers are distinguished by the difference of their H-2 quadrupolar splittings in a chiral liquid crystal containing short DNA fragments. The proof-of-principle, the reliability, and the robustness of this new method is demonstrated by the determination of the turnover rates of the enzyme using the Michaelis Menten model.

Effect of analyte concentration on the laser-induced plasma temperature and electron density in liquid matrix

In the present work, we report spectroscopic studies of laser-induced plasmas produced by focusing the second harmonic (532nm) of a Nd:YAG laser onto the laminar flow of a liquid containing chromium. The plasma temperature is determined from the coupled Saha-Boltzmann plot and the electron density is evaluated from the Stark broadening of an ionic line of chromium Cr(II)] at 267.7nm. Our results reveal a decrease in plasma temperature with an increase in Cr concentration up to a certain concentration level; after that, it becomes approximately constant, while the electron density increases with an increase in analyte (Cr) concentration in liquid matrix.

Glass, Gel, and Liquid Crystals: Arrested States of Graphene Oxide Aqueous Dispersions

Colloidal systems with competing interactions are known to exhibit a range of dynamically arrested states because of the systems' inability to reach its underlying equilibrium state due to intrinsic frustration. Graphene oxide (GO) aqueous dispersions constitute a class of 2D-anisotropic colloids with competing interactions long-range electrostatic repulsion, originating from ionized groups located on the rim of the sheets, and weak dispersive attractive interactions originating from the unoxidized graphitic domains. We show here that aqueous dispersions of GO exhibit a range of arrested states, encompassing fluid, glass, and gels that coexist with liquid-crystalline order with increasing volume fraction. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces. This can be realized by changing the ionic strength of the medium. We observe at low salt concentrations, where long-range electrostatic repulsion dominates, the formation of a repulsive Wigner glass, while at high salt concentrations, when attractive forces dominate, the formation of gels exhibits a nematic to columnar liquid-crystalline transition. The present work highlights how the chemical structure of GO hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet gives rise to a rich and complex array of arrested states.

Simple three parameter equations for correlating liquid phase compositions in subcritical and supercritical systems

Two Chrastil type expressions have been developed to model the solubility of supercritical fluids/gases in liquids. The three parameter expressions proposed correlates the solubility as a function of temperature, pressure and density. The equation can also be used to check the self-consistency of the experimental data of liquid phase compositions for supercritical fluid-liquid equilibria. Fifty three different binary systems (carbon-dioxide + liquid) with around 2700 data points encompassing a wide range of compounds like esters, alcohols, carboxylic acids and ionic liquids were successfully modeled for a wide range of temperatures and pressures. Besides the test for self-consistency, based on the data at one temperature, the model can be used to predict the solubility of supercritical fluids in liquids at different temperatures. (C) 2014 Elsevier B.V. All rights reserved.