The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

Primidone oxidation catalyzed by metalloporphyrins and Jacobsen catalyst

Primidone (PRM) oxidation by various oxidants such as iodosylbenzene (PhIO), tert-butyl hydroperoxide 70wt.% (t-BOOH), 3-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide 30wt.%, mediated by either a salen complex or metalloporphyrins, was investigated. The catalytic systems led to phenylethyl-malondiamide (PEMA) and phenobarbital (FEND), the same metabolites obtained in vivo with P450 enzymes, although three other products were also detected. Product formation was highly dependent on the oxidant, co-catalyst (imidazole), pH and dioxygen. These biomimetic chemical models have potential application in the synthesis of drug metabolites. which should provide samples for pharmacological tests. They can also be employed in studies that pursue the elucidation of in vivo drug metabolism. (C) 2008 Elsevier B.V. All rights reserved.

Jacobsen catalyst immobilized on chitosan membrane as interface catalyst in organic/aqueous system for alkene oxidation

The Jacobsen catalyst, Mn(salen), was immobilized in chitosan membrane. The obtained Mn(salen)-Chit was characterized by thermogravimetric analysis (TC), differential thermal analysis (DTA), differential scanning calorimetry (DSC), infrared spectroscopy (FT-IR), degree of N-acetylation by (1)H NMR, and UV-vis spectroscopy. The UV-vis absorption spectrum of the encapsulated catalyst displayed the typical bands of the Jacobsen catalyst, and the FT-IR presented an absorption band characteristic of the imines present in the Jacobsen catalyst. The chitosan membranes were available, in a biphasic system, as a catalytic barrier between two different phases: an organic substrate phase (cyclooctene or styrene) and an aqueous solution of either m-CPBA, t-BuOOH or H(2)O(2), and dismissing the need for phase transfer agents and leading to better product yields compared with the catalyst in homogeneous medium. This new catalyst did not leach from the support and was reused many times, leading to high turnover frequencies. (C) 2009 Elsevier B.V. All rights reserved.

Amphiphilic cerium(III) beta-diketonate as a catalyst for reducing diesel/biodiesel soot emissions

This work reports on the synthesis, characterization and applications of the new cerium(III) beta-diketonate Ce(hdacac)(3)(Hhdacac)(3)center dot 2H(2)O (where hdacac and Hhdacac denote, respectively, the hexadecylpentane-2,4-dionate and hexadecylpentane-2,4-dione ligands) as catalyst for the reduction of automotive emissions. Due to its amphiphilic character, this complex can be solubilized in non-polar fuels, thus generating cerium(IV) oxide particles, which efficiently catalyze the oxidation of diesel/biodiesel soot. The synthesized complex was characterized by microanalysis (C, H), thermal analysis, and infrared spectroscopy. Scanning electron microscopy, X-ray diffractometry, and specific surface area measurements attested that the complex can act as a soluble precursor of homogeneous CeO(2) spherical nanoparticles. The efficiency of this compound as catalyst for the reduction of soot emission was evaluated through static studies (comprising carbon black oxidation), which confirmed that increasing concentrations of the complex result in lower carbon black oxidation temperatures and lower activation Gibbs free energies. Dynamic studies, which embraced the combustion of diesel/biodiesel blends containing different amounts of the solubilized complex in a stationary motor, allowed a comparative evaluation of the soot emission through diffuse reflectance spectroscopy. These analyses provided very emphatic evidences of the efficiency of this new cerium complex for the control of soot emission in diesel/biodiesel motors. (c) 2009 Published by Elsevier B.V.

Lead Poisoning by Intradiscal Firearm Bullet A Case Report

Study Design. The report of a rare case of lead poisoning by an intradiscal firearm bullet is presented. Objective. To describe and discuss the clinical and radiologic features (by computed tomography and magnetic resonance imaging) of a gunshot wound in the L2-L3 space which caused lead poisoning 5 years afterwards. Summary of Background Data. Lead poisoning from firearm bullets is rare, but the possibility should be investigated in the case of bullets lodged in the joints. Methods. A 30-year-old man presented to the emergency room with an intense lumbar pain complaint, colic, intestinal constipation, insomnia, and progressive headache for 20 days. He had a history of a gunshot wound 5 years previously, and the bullet was left in situ, in the intravertebral disc between L2 and L3, as confirmed by radiographs, computed tomography, and magnetic resonance imaging. The hypothesis of lead poisoning was confirmed by the laboratory results. Chelation treatment with calcium versenate (disodium ethylenediaminetetraacetate, or CaNa (2) EDTA) was indicated. The patient was admitted and treated once again, before surgical removal of the bullet. Results. After removal of the bullet, the patient had an episode of recurrence, and a new chelation cycle was performed, with complete resolution. Conclusion. Lead poisoning can result in severe clinical disorders that require rapid treatment. In this case, both clinical and surgical treatments led to complete resolution of the symptoms.

EFFECTS OF A POTENT PEROXYNITRITE DECOMPOSITION CATALYST IN MURINE MODELS OF ENDOTOXEMIA AND SEPSIS

Excessive free-radical production due to various bacterial components released during bacterial infection has been linked to cell death and tissue injury. Peroxynitrite is a highly reactive oxidant produced by the combination of nitric oxide (NO) and superoxide anion, which has been implicated in cell death and tissue injury in various forms of critical illness. Pharmacological decomposition of peroxynitrite may represent a potential therapeutic approach in diseases associated with the overproduction of NO and superoxide. In the present study, we tested the effect of a potent peroxynitrite decomposition catalyst in murine models of endotoxemia and sepsis. Mice were injected i.p. with LPS 40 mg/kg with or without FP15 [Fe(III) tetrakis-2-(N-triethylene glycol monomethyl ether) pyridyl porphyrin] (0.1, 0.3, 1, 3, or 10 mg/kg per hour). Mice were killed 12 h later, followed by the harvesting of samples from the lung, liver, and gut for malondialdehyde and myeloperoxidase measurements. In other subsets of animals, blood samples were obtained by cardiac puncture at 1.5, 4, and 8 h after LPS administration for cytokine (TNF-alpha, IL-1 beta, and IL-10), nitrite/nitrate, alanine aminotransferase, and blood urea nitrogen measurements. Endotoxemic animals showed an increase in survival from 25% to 80% at the FP15 doses of 0.3 and 1 mg/kg per hour. The same dose of FP15 had no effect on plasma levels of nitrite/nitrate. There was a reduction in liver and lung malondialdehyde in the endotoxemic animals pretreated with FP15, as well as in hepatic myeloperoxidase and biochemical markers of liver and kidney damage (alanine aminotransferase and blood urea nitrogen). In a bacterial model of sepsis induced by cecal ligation and puncture, FP15 treatment (0.3 mg/kg per day) significantly protected against mortality. The current data support the view that peroxynitrite is a critical factor mediating liver, gut, and lung injury in endotoxemia and septic shock: its pharmacological neutralization may be of therapeutic benefit.

Clinical observations of cattle and buffalos with experimentally induced chronic copper poisoning

The susceptibility of cattle and buffalos to chronic copper poisoning (CCP) was compared by using cattle (n = 10) and buffalo (n = 10) steers distributed into two copper supplemented (n = 6) and two control (n = 4) groups. Supplemented animals received 2 mg copper (Cu)/kg body weight daily for one week, with an additional 2 mg weekly until the end of the experiment (day 105). Three liver biopsies (day 0, 45, and 105) were obtained for mineral analyses; clinical examinations and blood samples were obtained every 15 days. Three supplemented cattle and two buffalos with typical manifestations of CCP died. There were no differences in the frequency of mortality between cattle and buffalos; hepatic copper concentration was higher in cattle than buffalos. These findings suggest that buffalos and cattle might be equally susceptible to CCP. However, buffalos accumulate less liver copper than cattle and have a lower threshold of hepatic Cu accumulation, which leads to clinical manifestation of CCP. (c) 2009 Elsevier Ltd. All rights reserved.

Accumulative copper poisoning in buffaloes

The main objective of this study was to evaluate the clinical and hematological alterations, and the hepatic concentration of Cu in buffaloes with chronic copper poisoning (CCP). Ten buffalo yearling steers were randomly distributed into two groups: one copper supplemented (BUFCu; n = 6) and another control group (BUF; n = 4). The group BUFCu received, by ruminal fistula, 2 mg Cu/kgBW (as CuSO4.5H2O) daily during one week; after which 2 mg Cu/kgBW was added during each additional week, until the end or the experiment (105(th) day). Three liver biopsies were realized during the experiment (day zero, 45(th), and 105(th) day) to determine the degree of copper accumulation. Alterations in body weight, clinical examination, and hematological values were monitored every 15 days. Two buffaloes supplemented with copper demonstrated clinical manifestations consistent with CCP, and died. Two distinct clinical manifestations were observed, one classical (n = 1) and another atypical (n = 1), characterized by remarkable high levels of liver copper, progressive hyporexia followed by anorexia, dehydration, severe apathy, decreased rumen movements, oliguria, and death. Some animals were resistant to CCP although high copper intake. In buffalos with clinical picture similar to the one described as atypical, CCP should be considered as a possible diagnostic even without presence of macroscopic hemoglobinuria.

A single-step procedure for the preparation of palladium nanoparticles and a phosphine-functionalized support as catalyst for Suzuki cross-coupling reactions

We here report the preparation of supported palladium nanoparticles (NPs) stabilized by pendant phosphine groups by reacting a palladium complex containing the ligand 2-(diphenylphosphino)benzaldehyde with an amino-functionalized silica surface The Pd nanocatalyst is active for Suzuki cross-coupling reaction avoiding any addition of other sources of phosphine ligands The Pd intermediates and Pd NPs were characterized by solid-state nuclear magnetic resonance and transmission electron microscopy techniques The synthetic method was also applied to prepare magnetically recoverable Pd NPs leading to a catalyst that could be reused for up to 10 recycles In summary we gathered the advantages of heterogeneous catalysis magnetic separation and enhanced catalytic activity of palladium promoted by phosphine ligands to synthesize a new catalyst for Suzuki cross-coupling reactions The Pd NP catalyst prepared on the phosphine-functionalized support was more active and selective than a similar Pd NP catalyst prepared on an amino-functionalized support (C) 2010 Elsevier Inc All rights reserved

Catalytic hydrodechlorination of chlorobenzene over supported palladium catalyst in buffered medium

The catalytic hydrodechlorination (HDC) reaction, which is an attractive abatement process for chlorinated organic wastes, was studied over a magnetically recoverable supported Pd(0) catalyst. We investigated the most favorable reaction conditions under which to obtain the highest substrate conversion rates while preserving the catalyst properties and morphology. Sodium hydroxide, triethylamine and buffered solutions were used as proton scavengers in the HDC of chlorobenzene under mild conditions. It was observed that sodium hydroxide caused corrosion of the silica support, triethylamine in 2-propanol preserved the morphology of the catalyst which could be recycled for up to five successive H DC reactions, and aqueous buffer solutions preserved the catalyst morphology and the catalytic activity for up to four successive HDC reactions. The use of buffer solutions to neutralize the HCl formed during the HDC reaction is an interesting, less aggressive, alternative approach to HDC reactions. (C) 2010 Elsevier B.V. All rights reserved.

On the catalytic hydrogenation of polycyclic aromatic hydrocarbons into less toxic compounds by a facile recoverable catalyst

Here we present the catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) to less toxic mixtures of saturated and partial unsaturated polycyclic hydrocarbons under mild reaction conditions using a magnetically recoverable rhodium catalyst and molecular hydrogen as the exclusive H source. The catalyst is easily recovered after each reaction by placing a permanent magnet on the reactor wall and it can be reused in successive runs without any significant loss of catalytic activity. As an example, anthracene was totally converted into the saturated polycyclic hydrocarbon form (ca. 60%) and the partially hydrogenated form, 1,2,3,4,5,6,7,8-octahydroanthracene (ca. 40%). The catalyst operates in a broad range of temperature and H(2) pressure in both organic and aqueous/organic solutions of anthracene and it also exhibits significant activity at low substrate concentrations (20 ppm). This can be an efficient recycling process for hydrogenation of PAHs present in contaminated fluid waste streams. (C) 2009 Elsevier B.V. All rights reserved.

Ruthenium nanoparticles prepared from ruthenium dioxide precursor: Highly active catalyst for hydrogenation of arenes under mild conditions

The hydrogenation of benzene and benzene derivatives was studied using Ru(0) nanoparticles prepared by a very simple method based on the in situ reduction of the commercially available precursor ruthenium dioxide under mild conditions (75 degrees C and hydrogen pressure 4atm) in imidazolium ionic liquids. Total turnovers (TTO) of 2700 mol/mol Ru were obtained for the conversion of benzene to cyclohexane under solventless conditions and TTO of 1200 mol/mol Ru were observed under ionic liquid biphasic conditions. When corrected for exposed ruthenium atoms, TTO values of 7940 (solventless) and 3530 (biphasic) were calculated for benzene hydrogenation. These reaction rates are higher than those observed for Ru nanoparticles prepared from decomposition of an organometallic precursor in similar conditions. The presence of the partially hydrogenated product cyclohexene was also detected at low conversion rates. (C) 2008 Elsevier B.V. All rights reserved.

Detection of Paraquat in Oral Fluid, Plasma, and Urine by Capillary Electrophoresis for Diagnosis of Acute Poisoning

FAPESP

Selective Allylic oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst

In this work, we prepared a new magnetically recoverable CoO catalyst through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles to facilitate the solid separation from liquid media. The catalyst was fully characterized and presented interesting properties in the oxidation of cyclohexene, as for example, selectivity to the allylic oxidation product. It was also observed that CoO is the most active species when compared to Co(2+), Co(3)O(4) and Fe(3)O(4) in the catalytic conditions studied.