An investigation of the activation process of high temperature shift catalyst

The aim of this work is to address the activation process of a high temperature shift (HTS) catalyst, composed of Fe2O3/Cr2O3/CuO, by analyzing it before activation (HTS-V) and after activation (HTS-A) using complementary characterization techniques. The textural and morphological characterizations were done by transmission electron rnicroscopy (TEM) and nitrogen physisorption at 77 K; crystallographic structure was confirmed by X-ray diffraction (XRD); electronic structure was analyzed by X-ray absorption spectroscopy (XAS) and the chemical composition of the catalyst`s surface was obtained by X-ray photoelectron spectroscopy (XPS). The investigation pointed out that the HTS-V catalyst presents good textural and morphological properties, which are not deeply affected by the activation process (sample HTS-A). The iron oxide phase in the HTS-V catalyst is hematite whereas in HTS-A catalyst is magnetite with Fe2+/Fe3+ ratio close to the expected value (0.5). For both samples, the Cr ions seem to be incorporated in the iron oxide lattice with higher concentration at particle surface. In the HTS-V catalyst, the Cu ions have oxidation number II and occupy in average distorted octahedral sites; after the activation, the Cu ions are partially reduced, suggesting that the reduction of the Cu species is complex. (C) 2007 Elsevier B.V. All rights reserved.

Time Evolution of the Activation Energy in a Batch Chemical Oscillator

The batch-operated bromate/phosphate/acetone/dual catalyst system was studied at four temperatures between 5 and 35 degrees C. The dynamics was simultaneously followed by potential measurements with platinum and bromide selective electrodes, and spectroscopically at two different wavelengths. By simultaneously recording these four time series it was possible to characterize the dynamics of the sequential oscillations that evolve in time. The existence of three sequential oscillatory patterns at each temperature allowed estimating the activation energies in each case. Along with the activation energy of the induction period, it was possible to trace the time evolution of the overall activation energy at four different stages as the reaction proceeds. The study was carried out for two different sets of initial concentrations and it was observed that the overall activation energy increases as reactants turn into products. This finding was propounded as a result of the decrease in the driving force, or the system`s affinity, of the catalytic oxidative bromination of acetone with acidic bromate, as the closed system evolves toward the thermodynamic equilibrium.

Activation Energies of the Electrooxidation of Formic Acid on Pt(100)

The electrooxidation of small organic molecules on platinum surfaces usually involves different structure-dependent steps that include adsorption and desorption of various species and multiple reaction pathways. Because temperature plays a decisive role on each individual step, understanding its global influence on the reaction mechanism is often a difficult task, especially when the system is studied under far from equilibrium conditions in the presence of kinetic instabilities. Aiming at contributing to unravel this problem, herein, we report an experimental study of the role played by temperature on the electrooxidation of formic acid on a Pt(100) electrode. The system was investigated under both close and far from equilibrium conditions, and apparent activation energies were estimated using different strategies. Overall, comparable activation energies were estimated under oscillatory and quasi-stationary conditions, at high potentials. At low potentials, the poisoning process associated with the formic acid dehydration step presented a negligible dependence with temperature and, therefore, zero activation energy. On the basis of our experimental findings, we suggest that formic acid dehydration is the main, but maybe not the unique, step that differentiates the temperature dependence of the oscillatory electrooxidation of formic acid on Pt(100) with that on polycrystalline platinum.

On the activation and physical degradation of boron-doped diamond surfaces brought on by cathodic pretreatments

The electrochemical activation and physical degradation of boron-doped diamond (BDD) electrodes with different boron doping levels after repeated cathodic pretreatments are reported. Galvanostatic cathodic pretreatment passing up to -14000 C cm(-2) in steps of -600 C cm(-2) using -1 A cm(-2) caused significant physical degradation of the BDD surface, with film detachment in some areas. Because of this degradation, a great increase in the electrochemically active area was observed in Tafel plots for the hydrogen evolution reaction (HER) in acid media. The minimum cathodic pretreatment needed for the electrochemical activation of the BDD electrodes without producing any observable physical degradation on the BDD surfaces was determined using electrochemical impedance spectroscopy (EIS) measurements and cyclic voltammetry: -9 C cm(-2), passed at -1 A cm(-2). This optimized cathodic pretreatment can be safely used when electrochemical experiments are carried out on BDD electrodes with doping levels in the range between 800 and 8000 ppm.

Thermal stability of extracellular hemoglobin of Glossoscolex paulistus: Determination of activation parameters by optical spectroscopic and differential scanning calorimetric studies

Glossoscolex paulistus hemoglobin (HbGp) was studied by dynamic light scattering (DLS), optical absorption spectroscopy (UV-VIS) and differential scanning calorimetry (DSC). At pH 7.0, cyanomet-HbGp is very stable, no oligomeric dissociation is observed, while denaturation occurs at 56 degrees C, 4 degrees C higher as compared to oxy-HbGp. The oligomeric dissociation of HbGp occurs simultaneously with some protein aggregation. Kinetic studies for oxy-HbGp using UV-VIS and DES allowed to obtain activation energy (E(a)) values of 278-262 kJ/mol (DES) and 333 kJ/mol (UV-VIS). Complimentary DSC studies indicate that the denaturation is irreversible, giving endotherms strongly dependent upon the heating scan rates, suggesting a kinetically controlled process. Dependence on protein concentration suggests that the two components in the endotherms are due to oligomeric dissociation effect upon denaturation. Activation energies are in the range 200-560 kJ/mol. The mid-point transition temperatures were in the range 50-65 degrees C. Cyanomet-HbGp shows higher mid-point temperatures as well as activation energies, consistent with its higher stability. DSC data are reported for the first time for an extracellular hemoglobin. (C) 2010 Elsevier B.V. All rights reserved.

Artificial fertilization of oocytes and sperm activation in pacu: effects of the spermatozoa:oocyte ratio, water volume, and in natura semen preservation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effects of the spermatozoa: oocyte ratio, water volume and water temperature on artificial fertilization and sperm activation of cascudo-preto

The objective of this study was to evaluate the effects of water volume and water temperature on the sperm motility duration and the number of spermatozoa, and the water volume on the fertilization rates of oocytes of Rhinelepis aspera. Experiments were carried out to evaluate the effect of semen dilutions (1.74×10-5, 1.74×10-4, 1.74×10-3, 1.74×10-2, 1.74×10-1 and 1.00 mL of sperm.mL-1 of water) and water temperature (5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 ºC) on spermatozoa motility duration. In addition, the effects of insemination dose (7×10³, 7×10(4), 7×10(5), 7×10(6) and 7×10(7) spermatozoa.oocyte-1) and water volume (1.0, 30.0, 60.0, 90.0 and 120.0 mL water.2.0 mL-1 oocytes) on the artificial fertilization rates of oocytes were evaluated. The longest sperm motility duration were observed for the semen dilution of 1.74×10-5 mL semen.mL-1 water and in water at 5 ºC. The highest fertilization rates were obtained for insemination doses between 7.00×10³ and 1.23×10(7) spermatozoa. oocyte-1 and water volume of 28.11 mL water.2.0 mL-1 oocytes.

Activation and early parthenogenesis of bovine oocytes treated with ethanol and strontium

Efficient artificial activation is indispensable for the success of cloning programs. Strontium has been shown to effectively activate mouse oocytes for nuclear transfer procedures, however, there is limited information on its use for bovine oocytes. The present study had as objectives: (1) to assess the ability of strontium to induce activation and parthenogenetic development in bovine oocytes of different maturational ages in comparison with ethanol; and (2) to verify whether the combination of both treatments improves activation and parthenogenetic development rates. Bovine oocytes were in vitro matured for 24, 26, 28, and 30 h, and treated with ethanol (E, 7% for 5 min) or strontium chloride (S, 10 mM SrCl2 for 5 h) alone or in combination: ethanol + strontium (ES) and strontium + ethanol (SE). Activated oocytes were cultured in vitro in synthetic oviductal fluid (SOF) medium and assessed for pronuclear formation (15-16 h), cleavage (46-48 h) and development to the blastocyst stage (M). Treatment with ethanol and strontium promoted similar results regarding pronuclear formation (E, 20-66.7%; S, 26.7-53.3%; P > 0.05) and cleavage (E, 12.8-40.6%; S, 16.1-41.9%; P > 0.05), regardless of oocyte age. The actions of both strontium and ethanol were influenced by oocyte age: ethanol induced greater activation rates after 28 and 30 h of maturation (48.4 and 66.7% versus 20.0 and 23.3% for 24 and 26 It, respectively; P < 0.05) and strontium after 30 It (53.3%) was superior to 24 and 26h (26.7% for both). Blastocyst development rates were minimal in all treatments (0.0-6.3%; P > 0.05), however, when the mean (+/-S.D.) cell number in blastocysts at the same maturational period was compared, strontium treatment was superior to ethanol for activation rates (82 +/- 5.7 and 89.5 +/- 7.8 versus 54 and 61, at 28 and 30 h, respectively). Improved results were obtained by combined treatments. The combination of ethanol and strontium resulted in similar pronuclear formation (ES, 36.7-83.9%; SE, 53.1-90.3%) and cleavage rates (ES, 31.3-81.3%; SE, 65.6-80.7%). Regarding embryo development, there was no difference (P > 0.05) between treatments, and blastocysts were only obtained in treatment SE at 24 and 26 h (6.5% for both). It is concluded that, SrCl2 induces activation and parthenogenetic development in bovine oocytes. (C) 2003 Elsevier B.V. All rights reserved.

Parthenogenetic activation of bovine oocytes using single and combined strontium, ionomycin and 6-dimethylaminopurine treatments

In vitro-matured (IVM) bovine oocytes were activated with single and combined treatments of strontium (S), ionomycin (1) and 6-DMAP (D). Using oocytes IVM for 26 h, we observed that activation altered cell cycle kinetics (faster progression, MIII arrest, or direct transition from MII to pronuclear stage) when compared to in vitro fertilization. The effect of oocyte age on early parthenogenesis was assessed in oocytes IVM for 22, 26 and 30 h. Better results in pronuclear development were obtained in treatments ISD (81.7%) at 22 h; D (66.7%), IS (63.3%), ID (73.3%) and ISD (76.7%) at 26 h; and D (86.7%), IS (85.0%) and ID (78.3%) at 30 h. Higher cleavage occurred on ISD (80.0%) at 22 h; ID (83.3%) and ISD (91.7%) at 26 h; and 1 (86.7%), IS (90.0%), ID (85.0%) and ISD (95.0%) at 30 h. More blastocysts were achieved in ID (25.0%) and ISD (18.3%) at 22h; and in ID at 26h (45.0%) and 30h (50.0%). We also observed that IS allowed higher haploid (77.4%) embryonic development, whilst ID was better for diploid (89.1%) development. It was concluded that association of S and D without I was not effective for blastocyst development; treatments using S were less influenced by oocyte age, but when S was associated with D there was a detrimental effect on aged oocytes; treatment ISD promoted higher activation and cleavage rates in young oocytes and ID protocol was the best for producing blastocysts.

Oocyte activation and preimplantation development of bovine embryos obtained by specific inhibition of cyclin-dependent kinases

Realizaram-se dois experimentos para avaliar a eficiência da bohemina e roscovitina associadas à ionomicina para ativação partenogenética e desenvolvimento embrionário inicial de bovinos. No primeiro, foram testadas diferentes concentrações (0, 50, 75 ou 100µM) e diferentes tempos de exposição (2, 4 ou 6 horas) à bohemina ou à roscovitina na ativação de oócitos bovinos maturados in vitro (MIV) pré-expostos à ionomicina. Os melhores tratamentos, bohemina 75µM e roscovitina 50µM, ambos por seis horas, foram utilizados no segundo experimento, no qual oócitos bovinos MIV foram expostos à ionomicina seguido ou não pelo tratamento com inibidores específicos das quinases dependentes de ciclina (CDKI), e avaliados quanto à configuração nuclear, taxa de ativação e desenvolvimento até blastocisto. Os tratamentos combinados (ionomicina+CDKI) apresentaram melhor taxa de ativação (77,3%) e desenvolvimento embrionário inicial (35,2%) do que a ionomicina sozinha (69,4% e 21,9%, respectivamente), e também promoveram ativação mais uniforme (aproximadamente 90% de formação de um pronúcleo). Estes resultados demonstram que os CDKIs potencializam o efeito da ionomicina na ativação e desenvolvimento embrionário inicial e podem auxiliar na obtenção de protocolos de ativação mais eficientes, aumentando a capacidade de desenvolvimento de embriões produzidos por meio de biotécnicas reprodutivas.

Activation of bovine oocytes by strontium combined or not with an electric pulse

O objetivo deste trabalho foi avaliar as taxas de ativação e de clivagem de oócitos bovinos tratados com estrôncio (10mm de SrCl2), após maturação in vitro por 27-28 horas. No experimento 1, os tratamentos foram: S4 - ativação pelo estrôncio por 4 horas; S12 - ativação pelo estrôncio por 12 horas; S30 - ativação pelo estrôncio por 30 horas; e P - ativação por pulso elétrico (3 pulsos de 1,0kv/cm). No experimento 2 os tratamentos foram: PS4 - ativação combinada pelo pulso elétrico e pelo estrôncio por 4 horas; S4P - ativação pelo estrôncio por 4 horas e pelo pulso elétrico; e PS30 - ativação pelo pulso elétrico e pelo estrôncio por 30 horas. No experimento 1, todos os tratamentos apresentaram taxas similares de ativação (83-90%; P>0,05). Para clivagem, P foi melhor (53%; P<0,05) do que todos os tratamentos com estrôncio (6 a 28%). No experimento 2, o tratamento S4P apresentou melhor taxa de ativação (88%; P<0,05) do que PS4 e PS30 (60 e 68%, respectivamente). Para clivagem, observou-se o mesmo padrão, S4P (65%; P<0,05) e PS4 e PS30 (37% e 44%, respectivamente). Conclui-se que o estrôncio é capaz de ativar oócitos bovinos e sua combinação com pulso elétrico não melhora a ativação. Este é o primeiro relato demonstrando que o estrôncio ativa oócitos bovinos.

Effect of acibenzolar-S-methyl and Saccharomyces cerevisiae on the activation of Eucalyptus defences against rust

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of the carbon dioxide chemical fixation-activation by guanidines

Fixation of CO2 is one of the most important priorities of the scientific community dedicated to reduce global warming. In this work, we propose new methods for the fixation of CO2 using the guanidine bases tetramethylguanidine (TMG) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD). In order to understand the reactions occurring during the CO2 fixation and release processes, we employed several experimental methods, including solution and solid-state NMR, FTIR, and coupled TGA-FTIR. Quantum mechanical NMR calculations were also carried out. Based on the results obtained, we concluded that CO2 fixation with both TMG and TBD guanidines is a kinetically reversible process, and the corresponding fixation products have proved to be useful as transcarboxylating compounds. Afterward, CO2 thermal releasing from this fixation product with TBD was found to be an interesting process for CO2 capture and isolation purposes. (C) 2008 Elsevier Ltd. All rights reserved.

Antimycobacterial activity of Indigofera suffruticosa with activation potential of the innate immune system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Susceptibility to Yersinia pseudotuberculosis Infection is Linked to the Pattern of Macrophage Activation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)