Oxidation of Ru(III)‐Bound Thiocyanate with Peroxomonosulfate: Kinetic and Mechanistic Studies

The reaction of [Ru^III(edta)(SCN)]^2? (edta^4? = ethylenediaminetetraacetate; SCN^? = thiocyanate ion) with the peroxomonosulfate ion (HSO₅^?) has been studied by using stopped‐flow and rapid scan spectrophotometry as a function of [Ru^III(edta)], [HSO₅^?], and temperature (15–30ºC) at constant pH 6.2 (phosphate buffer). Spectral analyses and kinetic data are suggestive of a pathway in which HSO₅^? effects the oxidation of the coordinated SCN^? by its direct attack at the S‐atom (of SCN^?) coordinated to the Ru^III(edta). The high negative value of entropy of activation (ΔS^≠ = ?90 ± 6 J mol^?1 deg^?1) is consistent with the values reported for the oxygen atom transfer process involving heterolytic cleavage of the O‐O bond in HSO₅^?. Formation of SO₄^2?, SO₃^2?, and OCN^? was identified as oxidation products in ESI‐MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.     

Synthesis and photophysical study of silver nanoparticles stabilized by unsaturated dicarboxylates

Solution-phase synthesis of nanometer-sized silver particles is reported by sodium borohydride reduction of AgNO_3. Two isomeric dicarboxylates (sodium maleate and sodium fumarate) have been used as stabilizing agents. The dicarboxylate-stabilized silver nanoparticles are characterized by UV-vis spectroscopy, high-resolution transmission electron microscopy (HR-TEM) and fourier transform infrared (FT-IR) spectroscopy. A qualitative comparison is made between the UV-vis spectral characteristic of the SPR band and the simulated curve obtained from modified Mie's theory. Silver nanoparticles prepared using these two isomeric dicarboxylates show intense fluorescence in the visible region. DFT with hybrid functional (B3LYP)-based frequency (IR) calculation of both the dicarboxylates and the respective nanoparticles are in good agreement with the experimental IR frequency. On the basis of this calculation a model has been proposed for the stabilization of silver nanoparticles by these two isomeric dicarboxylate anions.     

New phenylethanoid glycosides from Bacopa monniera

Three new phenylethanoid glycosides, viz. monnierasides I-III (1-3) along with the known analogue plantainoside B were isolated from the glycosidic fraction of Bacopa monniera. Their structures were elucidated mainly on the basis of two dimensional (2D) NMR spectral analyses.     

Triple minima in the free energy of semiflexible polymers

We study the free energy of the worm-like-chain model, in the constant-extension ensemble, as a function of the stiffness lambda for finite chains of length L. We find that the polymer properties obtained in this ensemble are qualitatively different from those obtained using constant-force ensembles. In particular, we find that as we change the stiffness parameter, t=L/lambda, the polymer makes a transition from the flexible to the rigid phase and there is an intermediate regime of parameter values where the free energy has three minima and both phases are stable. This leads to interesting features in the force-extension curves.     

Effect of time delay in an autotroph-herbivore system with nutrient cycling

In the present study we consider a mathematical model of a non-interactive type autotroph-herbivore system in which the amount of autotroph biomass consumed by the herbivore is assumed to follow a Holling type II functional response. We have also incorporated discrete time delays in the numerical response term to represent a delay due to gestation, and in the recycling term which represents the time required for bacterial decomposition. We have derived conditions for global asymptotic stability of the model in the absence of delays. Conditions for delay-induced asymptotic stability of the steady state are also derived. The length of the delay preserving stability has been estimated and interpreted ecologically.     

Effect of adsorption of vapours on the electrical conductivity of lycopene crystals: Evidence of a three-stage adsorption process

Upon adsorption of various vapours, the electrical conductivity of lycopene semiconductor changes appreciably This phenomenon had been used as a probe to study the adsorption and desorption processes in these polyene crystals The adsorption and desorption kinetics have been found to follow a modified Roginsky-Zeldovich relation A three-stage adsorption process has been identified The first stage gives a Lennard-Jones potential energy curve, followed by a transition over a potential barrier to the second stage of adsorption in a potential well In the third stage a deep potential energy surface is reached by activation over a second potential barrier and strongly bound complexes between the vapour molecules and the surface molecules of the crystals are finally formed.