Surface modification of semiconductor photoelectrodes for better photoelectrochemical performance

The present paper describes the modification and solar hydrogen production studies employing a new semiconductor-septum (SC-SEP) photoelectrode ns-TiO₂/In₂O₃ based photoelectrochemical solar cell. The current-voltage characteristics of the above SC-SEP cell revealed that an enhancement in short-circuit current (I_SC) up to three times (5 ～ 14.6 mA cm^?2). The optimum hydrogen production rate was found to be 11.8 lh^?1 m^?2 for 5M H₂SO₄ and with a further increase in H₂SO₄ concentration, the hydrogen production rate was found to be invariant. In yet another part of our study instead of using new SC-SEP solar cell design, we used another new oxide material form such as ns-TiO₂/WO₃. The ns-TiO₂/WO₃ exhibited a high photocurrent and photo-voltage of 15.6 mA cm^?2, 960 mV, respectively. The ns-TiO₂/WO₃ electrode exhibited a higher hydrogen gas evolution rate of 13.8 lh^?1 m^?2. Evidences and arguments are put forward to show that, whereas for the bare ns-TiO₂ electrode, the improvement in the performance of this photo-electrode compared with its original form was due to the higher quantum yield. In the case of ns-TiO₂/In₂O₃ and ns-TiO₂/WO₃ photo-electrodes, the improvement is due to the improved spectral response resulting from decrease of energy band gap.     

Sensitive and selective methods for determination of antipsychotic drug olanzapine in pharmaceuticals

Two simple and sensitive spectrophotometric methods have been developed for analysis of the antipsychotic drug olanzapine in pharmaceuticals. Method A is based on liberation of iodine by reaction between the drug and potassium iodate, followed by reaction with leuco crystal violet (LCV), the color of oxidized LCV being measured at 598 nm. Method B is based on oxidation of olanzapine with chloramine-T (CAT) in acidic medium, the unconsumed CAT being determined with rhodamine B, measuring the absorbance at 550 nm. Calibration graphs were linear over the ranges of 0.05–2.0 and 0.1–1.6 μg mL^?1 olanzapine for method A and B, respectively. The molar absorptivity, Sandell’s sensitivity, detection limit, and quantitation limit were found to be 1.59 × 10⁵, 0.00132, 0.038, and 0.117, respectively, for method A and 0.953 × 10⁵, 0.00221, 0.064, and 0.192, respectively, for method B. The optimum conditions and other analytical parameters were evaluated. The proposed methods have been applied successfully for analysis of olanzapine in pure form and its dosage forms, and no interference was observed from common excipients present in pharmaceutical formulations.     

Spectrophotometric analysis of trichloroethylene in various environmental and biological samples

A simple sensitive extractive spectrophotometric method for determination of trichloroethylene is proposed. Trichloroethylene is treated with pyridine to form glutaconic aldehyde by heterolytic cleavage of the pyridine ring. Glutaconic aldehyde is further coupled with 4-aminoacetanilide to form an orange–red dye which is extractable in 3-methyl-1-butanol. The extracted dye shows absorption maximum at 520 nm. The system obeys Beer’s law in the range of 0.05–0.8 μg mL^?1. Important analytical parameters such as time, temperature, reagent concentration, acidity etc. have been optimized for complete colour reaction. Sandell’s sensitivity and molar absorptivity for the system were found to be 0.001 μg cm^?2 and 1.2 × 10⁵ L mol^?1 cm^?1, respectively. The proposed method is satisfactorily applied to micro-level determination of trichloroethylene in various environmental and biological samples.     

Comparative Antioxidant Study of Stem and Stem Induced Callus of Phyllanthus fraternus Webster—An Important Antiviral and Hepatoprotective Plant

Phyllanthus fraternus is widely used in the cure of various liver diseases and possess antiviral properties especially against hepatitis virus. In the present study, evaluation of the antioxidant activity of stem and calli induced from stem has been done by different assays. Extraction was done by standard method in water and ethanol. Total antioxidant capacity was measured by 1, 1-diphenyl-2-picrylhydrazyl free radical scavenging method. Lipid peroxidation was measured in terms of thiobarbituric acid-reactive substances (TBARS) by using egg yolk homogenates as lipid-rich media, and superoxide radical scavenging activity was measured using riboflavin–light–nitro blue tetrazolium assay. Reducing power was determined on the basis of Fe³⁺–Fe²⁺ transformation in the presence of the extract. In addition to the antioxidant activity, polyphenolic compounds like total phenolics and flavonoids were also measured by spectroscopic method. Results showed that the ethanolic extract of stem is more potent in antioxidant activity than its aqueous extract and ethanolic extract of calli. A significant correlation between antioxidant capacity and polyphenolic content and reducing potential was observed, indicating that phenolic compounds and reducers present in extract are major contributors to the antioxidant potential. Thus, this plant extract could be used as a potent natural antioxidant.     

Enantioselective synthesis of (R)-phenylephrine hydrochloride

An efficient method for the synthesis of enantiomerically pure (R)-phenylephrine hydrochloride 1 is described using a Sharpless asymmetric dihydroxylation as the key step.     

Kinetics and mechanism of the ruthenium(III)-catalyzed oxidation of hydroxy-acids byN-bromosuccinimide

Summary The kinetics of the Ru^III-catalyzed oxidation of the hydroxy acids; lactic, tartaric, malic and citric acids byN-bromosuccinimide in HClO₄ and in the presence of Hg(OAc)₂ have been studied. The reactions exhibit a first order rate dependence with respect to the oxidant and zeroth order rate dependence with respect to substrate. The rate is retarded by [H⁺], accelerated at law Ru^III concentrations but independent of [Ru^III] at higher Ru^III concentrations. A mechanism consistent with the observed kinetic data is proposed.     

Electrochemical approach for synthesis of 3-substituted indole derivatives

An efficient and economical method was developed for synthesis of 3-substituted indole by using electrochemically induced condensation of various aldehyde, indole and malononitrile.     

Palladium(II) inhibition during cerium(IV) oxidation of aldoses: a kinetic study

Summary The kinetics of oxidation of aldoses, namely xylose, arabinose, galactose and glucose, by Ce^IV have been studied in HClO₄ + H₂SO₄ medium and in the presence of Pd^II. The reactions exhibit a first order rate dependence with respect to oxidant. The rate is inversely dependent on the [HSO _inf4 ^sup– ][H⁺] ratio. The order of reaction with respect to aldose decreases at higher [aldose]. Due to the formation of a complex between Ce^IV and Pd^II, a retarding effect of [Pd^II] on the rate of disappearance of [Ce^IV] has been observed. A mechanism consistent with the observed kinetic data is proposed.     

An ab initio study of water clusters in gas phase and bulk aqueous media: (H2O)n,n=1–12

Geometries of several clusters of water molecules including single minimum energy structures of n‐mers (n=1–5), several hexamers and two structures of each of heptamer to decamer derived from hexamer cage and hexamer prism were optimized. One structural form of each of 11‐mer and 12‐mer were also studied. The geometry optimization calculations were performed at the RHF/6‐311G* level for all the cases and at the MP2/6‐311++G** level for some selected cases. The optimized cluster geometries were used to calculate total energies of the clusters in gas phase employing the B3LYP density functional method and the 6‐311G* basis set. Frequency analysis was carried out in all the cases to ensure that the optimized geometries corresponded to total energy minima. Zero‐point and thermal free energy corrections were applied for comparison of energies of certain hexamers. The optimized cluster geometries were used to solvate the clusters in bulk water using the polarized continuum model (PCM) of the self‐consistent reaction field (SCRF) theory, the 6‐311G* basis set, and the B3LYP density functional method. For the cases for which MP2/6‐311++G** geometry optimization was performed, solvation calculations in water were also carried out using the B3LYP density functional method, the 6‐311++G** basis set, and the PCM model of SCRF theory, besides the corresponding gas‐phase calculations. It is found that the cage form of water hexamer cluster is most stable in gas phase among the different hexamers, which is in agreement with the earlier theoretical and experimental results. Further, use of a newly defined relative population index (RPI) in terms of successive total energy differences per water molecule for different cluster sizes suggests that stabilities of trimers, hexamers, and nonamers in gas phase and those of hexamers and nonamers in bulk water would be favored while those of pentamer and decamer in both the phases would be relatively disfavored. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 81: 90–104, 2001     

Growth of Cyanobacteria: Optimization for Increased Carbohydrate Content

Growths of Lyngbya limnetica and Oscillatoria obscura were investigated at varying pH, light intensity, temperature, and trace element concentration with a view to optimize these parameters for obtaining the maximum carbohydrate content. The maximum growth for both strains was obtained at pH 9.0 and temperature 20 ± 3 °C using a light intensity of 68.0 μmol m^?2 s^?1 with continuous shaking. Growth under the nitrogen starvation condition affected the carbohydrate content more compared to the phosphorus starvation, and maximum concentrations were found as 0.660 and 0.621 g/g of dry biomass for L. limnetica and O. obscura, respectively. Under the optimized nitrogen-rich conditions, the specific growth rates for the two strains were found to be 0.187 and 0.215 day^?1, respectively. The two-stage growth studies under nitrogen-rich (stage I) followed by nitrogen starvation (stage II) conditions were performed, and maximum biomass and carbohydrate productivity were found as 0.088 and 0.423 g L^?1 day^?1 for L. limnetica. This is the first ever attempt to evaluate and optimize various parameters affecting the growth of cyanobacterial biomass of L. limnetica and O. obscura as well as their carbohydrate contents.