A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex

Liquid-phase homogeneous catalytic oxidation of styrene with Wilkinson complex by molecular oxygen in toluene medium gave selectively benzaldehyde and formaldehyde as the primary products. Higher temperatures and styrene conversions eventually led to acid formation due to co-oxidation of aldehyde.A reaction induction period and an initiation period, typical of free-radical reactions, characterized the oxidation process. The effects of temperature and catalyst and styrene concentrations on the conversion of styrene to benzaldehyde and acid formation have been studied. The optimum reaction parameters have been determined as a styrene-to-solvent mole ratio of 0.5, a catalyst-to-styrene mole ratio of 5.0 X lo4, and a reaction temperature of 75 "C. A reaction scheme based upon free-radical mechanism yielded a pseudo-first-order model which agreed well with the observed kinetic data in the absence of co-oxidation of aldehyde. A second-order model was found to fit the experimental data better in the case of aldehyde conversion to acid.

Studies on removal of metal ions and sulphate reduction using rice husk and Desulfotomaculum nigrificans with reference to remediation of acid mine drainage

The utility of rice husk as an adsorbent for metal ions such as iron, zinc and copper from acid mine water was assessed. The adsorption isotherms exhibited Langmuirian behavior and were endothermic in nature. The free energy values for adsorption of the chosen metal ions onto rice husk were found to be highly negative attesting to favorable interaction. Over 99% Fe3+, 98% of Fe2+ and Zn2+ and 95% Cu2+ uptake was achieved from acid mine water, with a concomitant increase in the pH value by two units using rice husk. The remediation studies carried out on acid mine water and simulated acid mine water pretreated with rice husk indicated successful growth of Desulfotomaculum nigrificans (D. nigrificans). The amount of sulphate bioreduction in acid mine water at an initial pH of 5.3 was enhanced by D. nigrificans from 21% to 40% in the presence of rice husk filtrate supplemented with carbon and nitrogen. In simulated acid mine water with fortified husk filtrate, the sulphate reduction was even more extensive, with an enhancement to 73%. Concurrently, almost 90% Fe2+, 89% Zn2+ and 75% Cu2+ bioremoval was attained from simulated acid mine water. Metal adsorption by rice husk was confirmed in desorption experiments in which almost complete removal of metal ions from the rice husk was achieved after two elutions using 1 M HCl. The possible mechanisms of metal ion adsorption onto rice husk and sulphate reduction using D. nigrificans are discussed.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

Synthesis of both enantiomers of 1-phenylethane-1,2-diol via chirality transfer from bile acid derivatives

Both enantiomers of 1-phenylethane-1,2-diol were synthesized with good to excellent enantioselectivities via selective reduction of the phenylglyoxalates derived from bile acids, followed by reductive cleavage. (C) 2000 Elsevier Science Ltd. All rights reserved.

Enantiodiscrimination and extraction of short and long range homo- and hetero-nuclear residual dipolar couplings by a spin selective correlation experiment

A two dimensional correlation experiment for the measurement of short and long range homo- and hetero- nuclear residual dipolar couplings (RDCs) from the broad and featureless proton NMR spectra including C-13 satellites is proposed. The method employs a single natural abundant C-13 spin as a spy nucleus to probe all the coupled protons and permits the determination of RDCs of negligible strengths. The technique has been demonstrated for the study of organic chiral molecules aligned in chiral liquid crystal, where additional challenge is to unravel the overlapped spectrum of enantiomers. The significant advantage of the method is demonstrated in better chiral discrimination using homonuclear RDCs as additional parameters. (C) 2010 Elsevier B.V. All rights reserved.

An assessment of the reduction potential of hydrogen plasma

Hydrogen plasma can be used for deoxidation of functional materials containing reactive metals in both bulk and thin film forms. Since the different species in the plasma are not in thermodynamic equilibrium, application of classical thermodynamics to the analysis of such a system is associated with some difficulties. While global equilibrium approaches have been tried, with and without additional approximations or constraints, there is some ambiguity in the results obtained. Presented in this article is the application of a local equilibrium concept to assess the thermodynamic limit of the reaction of each species present in the gas with oxides or oxygen dissolved in metals. Each reaction results in a different pal tial pressure of H2O. Because of the higher reactivity of the dissociated and ionized species and the larger thermodynamic driving force for reactions involving these species, they act as powerful reducing agents. It is necessary to remove the products of reaction from the plasma to prevent back reaction and gradual approach to global equilibrium. A quantitative description using the framework of the Ellingham-Richardson-Jeffes diagrams is presented.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2.

Generation of a Manganese Specific Restriction Endonuclease with Nicking Activity

A typical feature of type II restriction endonucleases (REases) is their obligate sequence specificity and requirement for Mg2+ during catalysis. R.KpnI is an exception. Unlike most other type II REases, the active site of this enzyme can accommodate Mg2+, Mn2+, Ca2+, or Zn2+ and cleave DNA. The enzyme belongs to the HNH superfamily of nucleases and is characterized by the presence of a beta beta alpha-Me finger motif. Residues D148, H149, and Q175 together form the HNH active site and are essential for Mg2+ binding and catalysis. The unique ability of the enzyme to cleave DNA in the presence of different metal ions is exploited to generate mutants that are specific to one particular metal ion. We describe the generation of a Mn2+-dependent sequence specific endonuclease, defective in DNA cleavage with Mg2+ and other divalent metal ions. In the engineered mutant, only Mn2+ is selectively bound at the active site, imparting Mn2+-mediated cleavage. The mutant is impaired in concerted double-stranded DNA cleavage, leading to accumulation of nicked intermediates. The nicking activity of the mutant enzyme is further enhanced by altered reaction conditions. The active site fluidity of R Eases allowing flexible accommodation of catalytic cofactors thus forms a basis for engineering selective metal ion-dependent REase additionally possessing nicking activity.

Electrochemical reduction of Cu(II)-CyDTA complex at dropping mercury electrode. An impedance approach

The electrochemical reduction of Cu(II)-CyDTA (CyDTA — trans 1,2-cyclohexanediamine N, N, N′, N′ tetraacetic acid) by impedance method reveals the unusual behaviour of complex plane polarograms owing to potential dependence of double layer capacitance. The impedance plane plots by frequency variation method indicates the quasi-reversible nature of the system. From these plots the chargetransfer resistance at various potentials was evaluated. The standard rate constant was evaluated which complements the prediction of impedance plots for the quasireversible behaviour of the system.

Directing role of functional groups in selective generation of C-H center dot center dot center dot pi interactions: In situ cryo-crystallographic studies on benzyl derivatives

The in situ cryo-crystallization study of benzyl derivatives reveals that the molecular packing in these compounds is either through methylene (sp(3)) C-H center dot center dot center dot pi or aromatic (sp(2)) C-H center dot center dot center dot pi interactions depending on the level of acidity of the benzyl proton. These studies of low melting compounds bring out the subtle features of such weak interactions and point to the directional preferences depending on the nature (electron withdrawing, polarizability) of the neighbouring functional group.

Electrochemical reduction of Cu(II)-EDTA complex at dropping mercury electrode. An impedance approach

The study of electrochemical reduction of Cu(II)-EDTA system by phase sensitive a.c. impedance method at dropping mercury electrode reveals several interesting features. The complex plane polarograms exhibit loop like shape in contrast to the classical zinc ion reduction where crest like shape is found. Again, the relative placement of peaks of in-phase and quadrature components, and the relative placement of portions before and after the peaks of complex plane polarograms are different from that of zinc ion reduction. The complex plane plots suggest that electrochemical reduction of Cu-EDTA is charge transfer controlled.