Kinetics and Mechanism of the Ligand Substitution Reaction of the Di-<Emphasis Type="Italic">μ</Emphasis>-hydroxobis(bipyridyl)dipalladium(II) Ion with some Bio-relevant Ligands

The interaction of di-μ-hydroxobis(bipyridyl)dipalladium(II) with the selected bio-relevant ligands: thioglycolic acid (HL¹), glutathione(HL²) and DL-penicillamine(HL³) has been studied spectrophotometrically in aqueous medium as a function of complex and ligand concentrations, pH, and temperature at constant ionic strength. Two consecutive reaction steps are observed: the first step is dependent on the incoming ligand concentration and the second step which is independent, is assigned to ring closure. The activation parameters, conductivity data and IR data obtained also support the proposed mechanism.     

Invariant Solutions of Inhomogeneous Universe with Electromagnetic Field in Lyra Geometry

The present study deals with the cylindrically symmetric inhomogeneous cosmological models for perfect fluid distribution with electro-magnetic field in Lyra geometry. Lie group analysis has been used to identify the generators (symmetries) that leave the given system of partial differential equations (field equations) invariant. With the help of canonical variables associated with these generators, the assigned system of partial differential equations is reduced to an ordinary differential equations whose simple solutions provide nontrivial solutions of the original system. They obtained a new class of invariant (similarity) solutions by considering the potentials of metric and displacement field are functions of coordinates t and x. The physical behavior of the derived models are also discussed.     

Discrepancy between subcritical and fast rupture roughness: a cumulant analysis

Rough crack fronts in a sheet of paper, obtained during a creep experiment, do not follow true scaling laws. Local roughness exponents are estimated using the first order cumulant, a quantity recently introduced in the turbulence literature [J. Delour, J. F. Muzy, and A. Arneodo, Eur. Phys. J. B 23, 243 (2001)10.1007/s100510170074]. Using a large data set (102 fronts), we find a significant difference in local roughness between the slow (subcritical) and the fast growth regime.     

Selectivity in Garratt-Braverman cyclization: an experimental and computational study

Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity.     

Structure and gas sorption behavior of a new three dimensional porous magnesium formate

A new three-dimensional magnesium formate polymorph, namely, γ-[Mg(3)(O(2)CH)(6)] has been synthesized via in situ formate anion generation method. γ-Mg-formate crystallizes in space group Pbcn, and structural determination by X-ray single crystal diffraction reveals a three-dimensional network of Mg(2+) linked by formate anions. All formate anions possess similar binding mode to the metal center with one oxygen of a particular formate anion binds to one metal center (μ(1) oxygen) and other oxygen binds to two metal centers (μ(2) oxygen). N(2) adsorption studies indicate that the framework displays permanent porosity. The specific surface area of γ-Mg-formate (BET, 120 m(2) gm(-1)) is lower than the α- polymorph (BET, 150 m(2) gm(-1)). However, the initial hydrogen uptake of γ-Mg-formate reached almost 1.0 wt % when the adsorbate pressure approached 760 Torr at 77 K. This is higher than the hydrogen uptake of α-Mg-formate (0.6 wt %). γ-Mg-formate, shows a moderate affinity and capacity for CO(2) (3.4 ? kinetic diameter) at 298 K. The CO(2) uptake at 760 Torr is 2.01 mmol gm(-1) (47.0 cc gm(-1)). Although this CO(2) uptake is somewhat modest, it compares well with the CO(2) uptake of several Mg-MOFs and ZIFs reported in the literature.     

Ultrafast Raman loss spectroscopy (URLS): instrumentation and principle

In this paper, we report on the concept and the design principle of ultrafast Raman loss spectroscopy (URLS) as a structure‐elucidating tool. URLS is an analogue of stimulated Raman scattering (SRS) but more sensitive than SRS with better signal‐to‐noise ratio. It involves the interaction of two laser sources, namely, a picosecond (ps) Raman pump pulse and a white‐light (WL) continuum, with a sample, leading to the generation of loss signals on the higher energy (blue) side with respect to the wavelength of the Raman pump unlike the gain signal observed on the lower energy (red) side in SRS. These loss signals are at least 1.5 times more intense than the SRS signals. An experimental study providing an insight into the origin of this extra intensity in URLS as compared to SRS is reported. Furthermore, the very requirement of the experimental protocol for the signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which appears on the red side. Unlike CARS, URLS signals are not precluded by the non‐resonant background and, being a self‐phase‐matched process, URLS is experimentally easier. Copyright © 2011 John Wiley & Sons, Ltd.     

A newly developed highly selective ratiometric fluoride ion sensor: spectroscopic, NMR and density functional studies

A new easy-to-synthesize chemosensor, 3,3'-bis(indolyl)-4-chlorophenylmethane (hereafter S), was designed, synthesized and employed as a selective optical chemosensor for fluoride ions.(1)H NMR and density functional studies on the system have been carried out to determine the nature of the interaction between S and X(-) (X = inorganic anions) responsible for the significant fluoride-induced changes in the absorption properties of S. The experimental results reveal that abstraction of an acidic proton of S by the fluoride ion, leading to the formation of anionic species, is responsible for the spectral changes. These changes allow signaling for the fluoride ion to detect and estimate the concentration of fluoride ion present even at the submicromolar level, accurate up to 2 μM. Calculations of the transition energies of S, S(-), and S···F(-) (hydrogen bonded complex) show that only S(-) is responsible for the long-wavelength absorption band in the presence of F(-).     

A fin design employing an inverse approach using simplex search method

This paper is aimed at estimating unknown parameters in a rectangular fin satisfying a predefined temperature. The differential transformation along with simplex method is used. The study has been done for different initial guess, random errors and measurement points. It is observed that, there is unique value of the convection-conduction parameter, but different conductivity and radiative parameters exist which will be useful in adjusting the parameters amongst various alternatives.     

Microstructural analysis of neutron-irradiation induced changes in polyester fibre studied using EPMA

Electron microscopy is an important characterization technique for the study of textile fibre as it gives more information on fabric wear, nature of fibre fracture, chemical degradation, abrasion, fatigue and many others. Electron Probe Micro Analyzer (EPMA) micrographs of virgin and some neutron-irradiated samples (graphite coated) are discussed. The filament diameter, D, of virgin PET fibre obtained from EPMA study was 12.5 μn. The surface topography of single filament distinctly reveals the core and sheath parts of the filament. The core diameter of the virgin fibre was estimated to be 1.43 μm. The fibre irradiated at fluence 1 × 10¹² n/cm² shows radiation induced sphere like polymer balls or spherulites of diameter 2.27 μm in the expanded core region. Due to irradiation, the sheath area crosslinks with expanded core region, which may be responsible for increase of strength and hardness of the polymer materials. Moreover, the micrograph at 3000 X magnifications clearly shows that there is no preferred orientation of the polymer in any direction confirming the isotropic nature of the sample.