Kinetics and mechanism of esterification of epoxy resin in presence of triphenylphosphine

The kinetics of esterification of bisphenol‐A based epoxy resin with acrylic acid in presence of triphenylphosphine has been studied. The reaction exhibits a first‐order rate dependence with respect to [Epoxy] and [Catalyst]. A first‐order dependence of rate with respect to [Acid] has been observed during a particular kinetic run. However, a retarding effect of [Acid] on the rate has been observed by increasing the initial concentration of acid. A suitable mechanism consistent with the kinetic data is proposed and discussed. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 280–285, 2004     

On Shock Reflection–Diffraction in a van der Waals Gas

The problem of a weak shock, reflected and diffracted by a wedge, is studied for the two‐dimensional compressible Euler system. Some recent developments are overviewed and a perspective is presented within the context of a real gas, modeled by the van der Waals equation of state. The regular reflection configuration and the detachment criterion are studied in the light of real gas effects. Some basic features of the phenomenon and the nature of the self‐similar flow pattern are explored using asymptotic expansions. The analysis presented here predicts several inviscid flow properties of the real gases undergoing shock reflection–diffraction phenomenon.     

Change of Boron Substitution Improves the Lasing Performance of Bodipy Dyes: A Mechanistic Rationalisation

Bodipy laser dyes are highly efficient but degrade rapidly in solution by reacting with in situ generated singlet oxygen (¹O₂). To increase the lasing lifetimes of these dyes, we have designed and synthesised two different congeners of the widely studied Pyrromethene 567 (PM567) by substitution at the boron centre and/or at both the boron centre and the meso position. The two new dyes showed high lasing efficiencies with increased photostability. The results of theoretical and pulse radiolysis studies revealed that the substitution at the boron centre reduced the ¹O₂ generation capacity of these dyes as well as their rate of reaction with ¹O₂, thereby enhancing their lifetimes even under lasing conditions.     

High-conducting,economical, and flexible polymer-in-salt electrolytes (PISEs) suitable for energy devices: a reality due to glutaraldehyde crosslinked starch as host

Journal of Solid State Electrochemistry - In the 1990s, polymer-in-salt electrolytes (PISEs) came into the picture with the hope to overcome the problem of slow ion motion and low cation...     

Electrical transport study of potato starch-based electrolyte system

A biopolymer electrolyte system having conductivity ∼1.3 × 10⁻⁴ S cm⁻¹ has been prepared using potato starch, NaI, glutaraldehyde and poly(ethylene glycol) (PEG; molecular weight = 300). High ionic transference numbers (∼0.99) of the material confirmed its electrolytic behaviour. Conductivity and dielectric behaviour as a function of frequency has been studied. Conductivity follows ‘universal power law’ (σ = σ ₀ + Aω ⁿ ) with exponent ‘n’ varying from 0.94 to 1.18. Cross-linking and plasticization increases long pathways motion of charge carriers, comparable to sample dimension. Humidity-independent behaviour (up to 80% relative humidity), of impedance and water intake by the system, indicates the system’s potentiality as a promising candidate for humidity immune device fabrication. The addition of PEG has a twofold effect on the material’s conductivity. It not only increases conductivity but also improves the material’s immunity towards humid atmosphere.     

Effect of 100 keV N+ ion irradiation on the organic single crystal of hippuric acid for nonlinear optical applications

The potential organic nonlinear optical material of hippuric acid (HA) single crystal has been grown by the slow evaporation solution growth technique using N, N-dimethylformamide as the solvent. Single crystals of pure HA were irradiated at room temperature with 100 keV Nitrogen (N⁺) ions at fluence 1×10¹⁶ and 5×10¹⁶ ions/cm². The pure and irradiated HA single crystals were characterized by different characterization technique. The photoluminescence and UV–visible absorption were performed at room temperature. The crystalline perfection of the pure and irradiated single crystals has been examined by high-resolution X-ray diffraction. Vickers microhardness technique was used to study the effect on the mechanical strength of the crystal at different ion fluences. The structural changes were analyzed by powder X-ray diffraction analysis. The functional groups of the synthesized compound have been identified by Fourier transform infrared spectroscopy. The dielectric constant and dielectric loss as a function of frequency were analyzed at room temperature.     

Kinetics and mechanism of interaction of dipeptide (glycyl–glycine) with ninhydrin in aqueous micellar media

The rates of reaction between ninhydrin and dipeptide glycyl–glycine (Gly–Gly) have been determined by studying the reaction spectrophotometrically at 70°C and pH 5.0 in aqueous and in aqueous cationic micelles of cetyltrimethylammonium bromide (CTAB). The reaction follows first‐ and fractional‐order kinetics, respectively, in [Gly–Gly] and [ninhydrin]. The observed rate constant is affected by [CTAB] changes and the maximum rate enhancement is ca. three‐fold. As the k_ψ ? [CTAB] profile shape is characteristic of bimolecular reactions catalyzed by micelles, the catalysis is explained in terms of the pseudo‐phase model of the micelles (proposed by Menger and Portnoy and developed by Bunton and Romsted). The presence of inorganic salts (NaCl, NaBr, Na₂SO₄) does not reveal any regular effect but the data with organic salts (NaBenz, NaSal) show an increase in the rate followed by a decrease. The kinetic data have been used to calculate the micellar binding constants K_S for Gly–Gly and K_N for ninhydrin and the respective values are 317 and 69 mol^?1 dm³. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 643–650, 2006     

Electrothermal atomic absorption spectrometric determination of lithium,sodium, potassium and copper in uranium without preliminary chemical separation

Graphite furnace atomization is used for the direct determination of Li (0.25–4 ppm), Na (8–70 ppm), K (20–300 ppm) and Cu (0.5–25 ppm) in uranium dissolved in nitric acid, with relative standard deviations of 4–9%. Only iron seriously depresses the signals from the alkali metals.     

Complexation of fluoroquinolone antibiotics with human serum albumin: A fluorescence quenching study

Mechanism of interaction and detailed physico-chemical characterization of the binding of four fluoroquinolones: levofloxacin, sparfloxacin, ciprofloxacin HCl and enrofloxacin with human serum albumin has been studied at physiological pH (7.4) using fluorescence spectroscopic technique. The stoichiometry of interaction was found to be 1:1 for all the drugs used. The association constants for the interaction were of the order of 10⁴ in most cases. At low drug:protein ratios, a significant fraction of the added drug was bound. The predominant interactions involved are hydrogen bonding and Van der Waal’s interactions in the case of levofloxacin, hydrophobic interactions in the case of ciprofloxacin hydrochloride and enrofloxacin and hydrogen bonding, hydrophobic and electrostatic interactions in the case of sparfloxacin.The drug binding region did not coincide with that of the hydrophobic probe, 1-anilinonaphthalene-8-sulfonate (ANS). From the displacement of site-specific probes and site-marker drugs, it was concluded that ciprofloxacin hydrochloride is site II-specific while enrofloxacin is a site I-specific drug. Levofloxacin binds at both site I and site II with equal affinity. Sparfloxacin had higher affinity for site II than site I. It is also possible that sparfloxacin binds at the interface between site I and site II. Stern-Volmer analysis of the data showed that the quenching mechanism is predominantly collisional for the binding of ciprofloxacin HCl and enrofloxacin while both static and collisional quenching mechanisms are operative in the case of levofloxacin and sparfloxacin. High magnitude of the rate constant for quenching showed that the process is not entirely diffusion controlled. Circular dichroism (CD) spectroscopic studies showed that the presence of drugs did not cause any major changes in the secondary structure of HSA.