Increased Dispersion of Supported Gold during Methanol Carbonylation Conditions

The active site in supported gold catalysts for the carbonylation of methanol has been identified as dimers/trimers of gold which are formed from large gold particles >10 nm in diameter. Methyl iodide was found to be critical for this dispersion process and to maintain the catalyst in the active form. This study also shows that it may be possible to redisperse gold catalysts, in general, after reaction.

The Co-Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol-gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co-entrapped with the ionic liquid [Bmim]NTf(2) inside a silica matrix by a sot-gel method. These catalytic ionogels have been compared to simple catalyst-doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh-doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X-ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.

Adding value to renewables: a one pot process combining microbial cells and hydrogen transfer catalysis to utilise waste glycerol from biodiesel production

Waste glycerol was converted to secondary amines in a one pot reaction, using Clostridium butyricum and catalytic hydrogen transfer-mediated amination.

A simple chemical free arsenic removal method for community water supply - A case study from West Bengal, India

This report describes a novel technology for arsenic removal from groundwater. The work was carried out in India in collaboratio with three Indian and three European partners. European partners include Leiden University of the Netherlands and Stuttgart University of Germany. The work was funded by The World Bank.

Ligand differentiated complementary Rh-catalyst systems for the enantioselective desymmetrization of meso-cyclic anhydrides

Two distinct systems for the rhodium-catalyzed enantioselective desymmetrization of meso-cyclic anhydrides have been developed. Each system has been optimized and are compatible with the use of in situ prepared organozinc reagents. Rhodium/PHOX species efficiently catalyze the addition of alkyl nucleophiles to glutaric anhydrides, while a rhodium/phosphoramidite system is effective in the enantioselective arylation of succinic and glutaric anhydrides.

Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon

The adsorption behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous solution onto activated carbon was investigated under various experimental conditions. The adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH 7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and Smith classification. The experimental adsorption data showed good correlation with the Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45, 0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes, respectively. Experimental data indicated that the adsorption capacity of activated carbon for the dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of dye increased with increase in the ionic strength of solution, this was attributed to aggregation of reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes onto activated carbon was an endothermic process. The adsorption enthalpy (?H) for C.I. Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol, respectively. The negative values of free energy (?G) determined for these systems indicated that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298-328 K). © 2007 Elsevier Ltd. All rights reserved.

COD removal from textile industry effluent: pilot plant studies

This work involved the treatment of industrial waste water from a nylon carpet printing plant. As dyeing of nylon is particularly difficult, acid dyes, fixing agents, thickeners, finishing agents, are required for successful colouration and cause major problems with the plant's effluent disposal in terms of chemical oxygen demand (COD). Granular activated carbon (GAC) Filtrasorb 400 was used to treat a simulated process plant effluent containing all the pollutants. Equilibrium isotherm experiments were established and experimental data obtained showed good empirical correlation with Langmuir isotherm theory. Column experimental data, in terms of COD were correlated using the bed depth service time (BDST) model. Solid phase loading in the columns were found to approach that in equilibrium studies indicating an efficient use of adsorbent. The results from the BDST model were then used to design a pilot adsorption rig at the plant. The performance of the pilot plant column were accurately predicted by scale-up from the bench scale columns. (C) 2001 Elsevier Science BN. All rights reserved.

The Y-procedure: How to extract the chemical transformation rate from reaction-diffusion data with no assumption on the kinetic model

The paper presents a new method to extract the chemical transformation rate from reaction–diffusion data with no assumption on the kinetic model (“kinetic model-free procedure”). It is a new non-steady-state kinetic characterization procedure for heterogeneous catalysts. The mathematical foundation of the Y-procedure is a Laplace-domain analysis of the two inert zones in a TZTR followed by transposition to the Fourier domain. When combined with time discretization and filtering the Y-procedure leads to an efficient practical method for reconstructing the concentration and reaction rate in the active zone. Using the Y-procedure the concentration and reaction rate of a non-steady state catalytic process can be determined without any pre-assumption regarding the type of kinetic dependence. The Y-procedure is the basis for advanced software for non-steady state kinetic data interpretation. The Y-procedure can be used to relate changes in the catalytic reaction rate and kinetic parameters to changes in the surface composition (storage) of a catalyst.

The Role of Process Parameters in Determining Wall Thickness Distribution in Plug-Assisted Thermoforming

This article describes the results of a comprehensive investigation to determine the link between process parameters and observed wall thickness output for the plug-assisted thermoforming process. The overall objective of the work was to systematically investigate the process parameters that may be adjusted during production to control the wall thickness distribution of parts manufactured by plug-assisted thermoforming. The parameters investigated were the sheet temperature, plug temperature, plug speed, plug displacement, plug shape, and air pressure. As well as quantifying the effects of each parameter on the wall thickness distribution, a further aim of the work was to improve the understanding of the physical mechanisms of deformation of the sheet during the different stages of the process. The process parameters shown to have the greatest effect on experimentally determined wall thickness distribution were the plug displacement, sheet temperature, plug temperature, and plug shape. It is proposed that during the plug-assisted thermoforming of polystyrene the temperature dependent friction between the plug and sheet surface was the most important factor in determining product wall thickness distribution, whereas heat transfer was shown to play a less important role. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers

The absence of creativity in Feist and the computational process

The decision of the U.S. Supreme Court in 1991 in Feist Publications, Inc. v. Rural Tel. Service Co. affirmed originality as a constitutional requirement for copyright. Originality has a specific sense and is constituted by a minimal degree of creativity and independent creation. The not original is the more developed concept within the decision. It includes the absence of a minimal degree of creativity as a major constituent. Different levels of absence of creativity also are distinguished, from the extreme absence of creativity to insufficient creativity. There is a gestalt effect of analogy between the delineation of the not original and the concept of computability. More specific correlations can be found within the extreme absence of creativity. "[S]o mechanical" in the decision can be correlated with an automatic mechanical procedure and clauses with a historical resonance with understandings of computability as what would naturally be regarded as computable. The routine within the extreme absence of creativity can be regarded as the product of a computational process. The concern of this article is with rigorously establishing an understanding of the extreme absence of creativity, primarily through the correlations with aspects of computability. The understanding established is consistent with the other elements of the not original. It also revealed as testable under real-world conditions. The possibilities for understanding insufficient creativity, a minimal degree of creativity, and originality, from the understanding developed of the extreme absence of creativity, are indicated. 

Claw removal and feeding ability in the edible crab, Cancer pagurus: Implications for fishery practice

Feeding ability and motivation were assessed in the edible crab, Cancer pagurus, to investigate how the fishery practice of de-clawing may affect live crabs returned to the sea. Crabs were either induced to autotomise one claw, or were only handled, before they were offered food. Initially, autotomised and handled crabs were offered mussels, Mytilis edulis, a large part of their natural diet. After 3 days, both autotomised and handled crabs were then offered fish, a more readily handled food source. Autotomy induced crabs consumed significantly fewer mussels and less mussel mass, but ate significantly more mass of fish. This indicates that the effect of autotomy was a reduction of ability to feed on mussels rather than a general reduction of feeding motivation. The discontinuation of claw removal needs to be considered, both for the sustainability of the fishery and animal welfare concerns. (C) 2008 Elsevier B.V. All rights reserved.

Proton pumping by complex I (NADH : ubiquinone oxidoreductase) from Yarrowia lipolytica reconstituted into proteoliposomes

The mechanism of energy converting NADH:ubiquinone oxidoreductase (complex 1) is Still unknown. A current controversy centers around the question whether electron transport of complex I is always linked to vectorial proton translocation or whether in some organisms the enzyme pumps sodium ions instead. To develop better experimental tools to elucidate its mechanism, we have reconstituted the affinity purified enzyme into proteoliposomes and monitored the generation of Delta pH and Delta psi. We tested several detergents to solubilize the asolectin used for liposome formation. Tightly coupled proteoliposomes containing highly active complex I were obtained by detergent removal with BioBeads after total solubilization or the phospholipids with n-octyl-beta-D-glucopyranoside. We have used dyes to monitor the formation of the two components of the proton motive force, Delta pH and Delta psi, across the liposomal membrane, and analyzed the effects of inhibitors, uncouplers and ionophores on this process. We show that electron transfer of complex I of the lower eukaryote Y. lipolytica is clearly linked to proton translocation. While this study was not specifically designed to demonstrate possible additional sodium translocating properties of complex 1, we did not find indications for primary or secondary Na+ translocation by Y lipolytica complex I. (c) 2005 Elsevier B.V. All rights reserved.

Adsorption of Ni(SO4) on Malaysian rubber-wood ash

The possible use of wood ash as an adsorbent of nickel sulphate from dilute solutions and the effect of operating parameters were investigated in this study. The rate constants of adsorption were determined at different concentrations and temperatures. The applicability of the first-order reversible equation and an empirical kinetic model were tested to understand the kinetics of nickel sulphate removal at different concentrations. Pore diffusion was found as the rate-controlling step. The Langmuir and Freundlich isotherms were applied to find out the adsorption parameters. The activation energy of adsorption was -11.54 kJ mol-1. The value of the enthalpy change was ?H=-10.35 kcal mol-1.

Remote chiral induction in the organocatalytic hydrosilylation of aromatic ketones and ketimines

Lewis basic, metal-free pyridyloxazolines catalyze the redn. of prochiral arom. ketones and ketimines with Cl3SiH in good enantioselectivity (? 94% ee). Arene-arene interactions between the substrate and the catalyst are likely to play a role in the enantiodifferentiation process.