Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.

Substrate specificity of the Chamaerops excelsa palm tree peroxidase. A steady-state kinetic study

The steady state kinetic mechanism of the H(2)O(2)-supported oxidation of different organic substrates by peroxidase from leaves of Chamaerops excelsa palm trees (CEP) has been investigated. An analysis of the initial rates vs. H(2)O(2) and reducing substrate concentrations is consistent with a substrate-inhibited Ping-Pong Bi Bi reaction mechanism. The phenomenological approach expresses the peroxidase Ping-Pong mechanism in the form of the Michaelis-Menten equation and leads to an interpretation of the effects in terms of the kinetic parameters K(m)(H2O2)center dot K(m)(AH2)center dot k(cat)center dot K(SI)(AH2) and of the microscopic rate constants k(1) and k(3) of the shared three-step catalytic cycle of peroxidases. (C) 2011 Elsevier B.V. All rights reserved.

Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Crystallization and preliminary X-ray diffraction of malate dehydrogenase from Plasmodium falciparum

The expression, purification, crystallization and preliminary X-ray diffraction characterization of malate dehydrogenase (MDH) from the malarial parasite Plasmodium falciparum (PfMDH) are reported. In order to gain a deeper understanding of the function and role of PfMDH, the protein was purified to homogeneity. The purified protein crystallized in space group P1, with unit-cell parameters a = 72, b = 157, c = 159 angstrom, a = 105, beta = 101, ? = 95 degrees. The resulting crystals diffracted to a maximal resolution of 2.24 angstrom and the structure has been solved by molecular replacement, with 16 monomers in the asymmetric unit. The 16 monomers are arranged into four independent tetramers, in agreement with previous reports demonstrating the tetrameric solution state of PfMDH. The X-ray structure of PfMDH is expected to clarify the differences in catalysis by PfMDH compared with other MDH family members and to provide a basis for the structure-based design of specific PfMDH inhibitors as well as general MDH inhibitors.

The bactericidal effect of human secreted group IID phospholipase A(2) results from both hydrolytic and non-hydrolytic activities

The Human Secreted Group IID Phospholipase A(2) (hsPLA2GIID) may be involved in the human acute immune response. Here we have demonstrated that the hsPLA2GIID presents bactericidal and Ca2+-independent liposome membrane-damaging activities and we have compared these effects with the catalytic activity of active-site mutants of the protein. All mutants showed reduced hydrolytic activity against DOPC:DOPG liposome membranes, however bactericidal effects against Escherichia coli and Micrococcus luteus were less affected, with the D49K mutant retaining 30% killing of the Gram-negative bacteria at a concentration of 10 mu g/mL despite the absence of catalytic activity. The H48Q mutant maintained Ca2+-independent membrane-damaging activity whereas the G30S and D49K mutants were approximately 50% of the wild-type protein, demonstrating that phospholipid bilayer permeabilization by the hsPLA2GIID is independent of catalytic activity. We suggest that this Ca2+-independent damaging activity may play a role in the bactericidal function of the protein. (C) 2012 Elsevier Masson SAS. All rights reserved.

Crystallization and preliminary X-ray diffraction analysis of three myotoxic phospholipases A2 from Bothrops brazili venom

Two myotoxic and noncatalytic Lys49-phospholipases A2 (braziliantoxin-II and MT-II) and a myotoxic and catalytic phospholipase A2 (braziliantoxin-III) from the venom of the Amazonian snake Bothrops brazili were crystallized. The crystals diffracted to resolutions in the range 2.562.05 angstrom and belonged to space groups P3121 (braziliantoxin-II), P6522 (braziliantoxin-III) and P21 (MT-II). The structures were solved by molecular-replacement techniques. Both of the Lys49-phospholipases A2 (braziliantoxin-II and MT-II) contained a dimer in the asymmetric unit, while the Asp49-phospholipase A2 braziliantoxin-III contained a monomer in its asymmetric unit. Analysis of the quaternary assemblies of the braziliantoxin-II and MT-II structures using the PISA program indicated that both models have a dimeric conformation in solution. The same analysis of the braziliantoxin-III structure indicated that this protein does not dimerize in solution and probably acts as a monomer in vivo, similar to other snake-venom Asp49-phospholipases A2.

Recent advances in the development of magnetically recoverable metal nanoparticle catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale-up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

'Synthetic lipase' production from a newly isolated Sporidiobolus pararoseus strain by submerged fermentation

The lipase produced by a newly isolate Sporidiobolus pararoseus strain has potential catalysis ability for esterification reactions. In order to improve its synthetic activity, this work aimed at optimizing 'synthetic lipase' production by submerged fermentation of a conventional media based on peptone, yeast extract, NaCl and olive oil using experimental design technique. According to the results obtained in the first experimental design (2(4-1)), yeast extract and NaCl concentrations were tested to further optimization by response surface methodology. The maximum 'synthetic lipase' activity obtained was 26.9 U/mL in the optimized media (5.0, 6.8, 7.0 and 1.0% (wt/v) of peptone, yeast extract, NaCl and olive oil, respectively), representing a 6.36-fold increase compared to the initial medium. The time course of 'synthetic lipase' production in the optimized condition was evaluated in terms of synthetic activity, protease activity, biomass and total carbon and the maximum synthetic activity was observed during the stationary phase of growth.

Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy

Although electrochemical oxidation of simple organic molecules on metal catalysts is the basic ingredient of fuel cells, which have great technological potential as a renewable source of electrical energy, the detailed reaction mechanisms are in most cases not completely understood. Here, we investigate the ethanol-platinum interface in acidic aqueous solution using infrared-visible sum frequency generation (SFG) spectroscopy and theoretical calculations of vibrational spectra in order to identify the intermediates present during the electro-oxidation of ethanol. The complex vibrational spectrum in the fingerprint region imply on the coexistence of several adsorbates. Based on spectra in ultra-high-vacuum (UHV) and electrochemical environment from the literature and our density functional theory (DFT) calculations of vibrational spectra, new adsorbed intermediates, never before observed with conventional infrared (IR) spectroscopy, are proposed here: g2-acetaldehyde, g2-acetyl, ethylidyne, monodentate acetate, methoxy, tertiary methanol derivative, COH residue, g2-formaldehyde, mono and bidentate formate, CH3 and CH2 residues. In addition, we present new evidences for an ethoxy intermediate, a secondary ethanol derivative and an acetyl species, and we confirm the presence of previously observed adsorbates: a tertiary ethanol derivative, bidentate acetate, and COad. These results indicate that the platinum surface is much more reactive, and the reaction mechanism for ethanol electro-oxidation is considerably more complex than previously considered. This might be also true for many other molecule-catalyst systems.