The effect of ultra-low proton concentration on the electrocatalytic reduction of nitrate over platinum

The electrocatalytic reduction of NO3- (aq) over platinum has been investigated in sulfuric acid solutions with proton concentrations between 1 mM and 50 mM. Cyclic voltammetry indicates that for [H+] < 10 mM, NO3- (aq) is reduced in two distinct regions of potential: one reduction peak occurs at approximately 0.1 V vs. RHE and one occurs at -0.13 V vs. RHE. This second reduction peak has never before been observed, and is not present for proton concentrations >10 mM, where hydrogen electroreduction prevails below 0.0 V vs. RHE. Chronoamperometry shows that the kinetics of the two reduction peaks are distinct, suggesting that the two reduction peaks may correspond to the evolution of different products. Results are discussed in the context of tuning the product selectivity of the electrocatalytic reduction of NO3- (aq). (C) 2007 Elsevier B.V. All rights reserved.

Reduction of NO by CO on Cu/ZrO(2)/Al(2)O(3) catalysts: Characterization and catalytic activities

ZrO(2), gamma-Al(2)O(3) and ZrO(2)/gamma-Al(2)O(3)-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H(2), Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO(2)/gamma-Al(2)O(3) matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO(2). Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO(2). (C) 2009 Published by Elsevier Ltd.

Optical Characterization and Optimization of Display Components : Some Applications to Liquid-Crystal-Based and Electrochromics-Based Devices

This dissertation is focused on theoretical and experimental studies of optical properties of materials and multilayer structures composing liquid crystal displays (LCDs) and electrochromic (EC) devices. By applying spectroscopic ellipsometry, we have determined the optical constants of thin films of electrochromic tungsten oxide (WOx) and nickel oxide (NiOy), the films’ thickness and roughness. These films, which were obtained at spattering conditions possess high transmittance that is important for achieving good visibility and high contrast in an EC device. Another application of the general spectroscopic ellipsometry relates to the study of a photo-alignment layer of a mixture of azo-dyes SD-1 and SDA-2. We have found the optical constants of this mixture before and after illuminating it by polarized UV light. The results obtained confirm the diffusion model to explain the formation of the photo-induced order in azo-dye films. We have developed new techniques for fast characterization of twisted nematic LC cells in transmissive and reflective modes. Our techniques are based on the characteristics functions that we have introduced for determination of parameters of non-uniform birefringent media. These characteristic functions are found by simple procedures and can be utilised for simultaneous determination of retardation, its wavelength dispersion, and twist angle, as well as for solving associated optimization problems. Cholesteric LCD that possesses some unique properties, such as bistability and good selective scattering, however, has a disadvantage – relatively high driving voltage (tens of volts). The way we propose to reduce the driving voltage consists of applying a stack of thin (~1µm) LC layers. We have studied the ability of a layer of a surface stabilized ferroelectric liquid crystal coupled with several retardation plates for birefringent color generation. We have demonstrated that in order to accomplish good color characteristics and high brightness of the display, one or two retardation plates are sufficient.

Genetic heterogeneity of residual variance : estimation of variance components using double hierarchical generalized linear models

Background: The sensitivity to microenvironmental changes varies among animals and may be under genetic control. It is essential to take this element into account when aiming at breeding robust farm animals. Here, linear mixed models with genetic effects in the residual variance part of the model can be used. Such models have previously been fitted using EM and MCMC algorithms. Results: We propose the use of double hierarchical generalized linear models (DHGLM), where the squared residuals are assumed to be gamma distributed and the residual variance is fitted using a generalized linear model. The algorithm iterates between two sets of mixed model equations, one on the level of observations and one on the level of variances. The method was validated using simulations and also by re-analyzing a data set on pig litter size that was previously analyzed using a Bayesian approach. The pig litter size data contained 10,060 records from 4,149 sows. The DHGLM was implemented using the ASReml software and the algorithm converged within three minutes on a Linux server. The estimates were similar to those previously obtained using Bayesian methodology, especially the variance components in the residual variance part of the model. Conclusions: We have shown that variance components in the residual variance part of a linear mixed model can be estimated using a DHGLM approach. The method enables analyses of animal models with large numbers of observations. An important future development of the DHGLM methodology is to include the genetic correlation between the random effects in the mean and residual variance parts of the model as a parameter of the DHGLM.

Early and post transition metal complexes as a single of combined components in the ethylene and isoprene polynerization

In this work is reported, in a first step, the effect of different experimental parameters and their relation with polymer properties using the homogeneous binary catalyst system composed by Ni(α-diimine)Cl2 (α-diimine = 1,4-bis(2,6-diisopropylphenyl)- acenaphthenediimine) and {TpMs*}V(Ntbu)Cl2 (TpMs* = hydridobis(3-mesitylpyrazol-1- yl)(5-mesitylpyrazol-1-yl)) activated with MAO. This complexes combination produces, in a single reactor, polyethylene blends with different and controlled properties dependent on the polymerization temperature, solvent and Nickel molar fraction (xNi). In second, the control of linear low density polyethylene (LLDPE) production was possible, using a combination of catalyst precursors {TpMs}NiCl (TpMs = hydridotris(3- mesitylpyrazol-1-yl)) and Cp2ZrCl2, activated with MAO/TMA, as Tandem catalytic system. The catalytic activities as well as the polymer properties are dependent on xNi. Polyethylene with different Mw and controlled branches is produced only with ethylene monomer. Last, the application group 3 metals catalysts based, M(allyl)2Cl(MgCl2)2.4THF (M = Nd, La and Y), in isoprene polymerization with different cocatalysts systems and experimental parameters is reported. High yields and polyisoprene with good and controlled properties were produced. The metal center, cocatalysts and the experimental parameters are determinant for the polymers properties and their control. High conversions in cis-1,4- or trans-1,4-polyisoprene were obtained and the polymer microstructure depending of cocatalyst and metal type. Combinations of Y and La precursors were effective systems for the cis/transpolyisoprene blends production, and the control of cis-trans-1,4-microstructures by Yttrium molar fraction (xY) variation was possible.

Critical periods of weed control in naturally green colored cotton BRS Verde

Cotton with naturally colored fiber is increasing as a commercial crop due specially to its textile processing with reduced environmental impact, as dying is not necessary. The critical period of weed control and the weed community were studied in a field with the naturally green colored fiber cv. BRS Verde cultivated in Missao Velha, Brazil. Without weed control during all the cycle, a reduction of 82.9% in yield was observed. The critical period of weed control was between 31 and 74 days after emergence for a reduction of 5% in yield. The weed community was composed of 21 species, with higher relative importance and dominance of monocotyledonous species. The beginning of the critical period was found to be more influential on yield than the ending. Thus, defining the right moment to start weed control can be more important to yield than determining the moment to cease it. (C) 2011 Elsevier B.V. All rights reserved.

Estimation models of variance components for farrowing interval in swine

Este trabalho teve como objetivo principal avaliar a importância da inclusão dos efeitos genético materno, comum de leitegada e de ambiente permanente no modelo de estimação de componentes de variância para a característica intervalo de parto em fêmeas suínas. Foram utilizados dados que consistiam de 1.013 observações de fêmeas Dalland (C-40), registradas em dois rebanhos. As estimativas dos componentes de variância foram realizadas pelo método da máxima verossimilhança restrita livre de derivadas. Foram testados oito modelos, que continham os efeitos fixos (grupos de contemporâneo e covariáveis) e os efeitos genético aditivo direto e residual, mas variavam quanto à inclusão dos efeitos aleatórios genético materno, ambiental comum de leitegada e ambiental permanente. O teste da razão de verossimilhança (LR) indicou a não necessidade da inclusão desses efeitos no modelo. No entanto observou-se que o efeito ambiental permanente causou mudança nas estimativas de herdabilidade, que variaram de 0,00 a 0,03. Conclui-se que os valores de herdabilidade obtidos indicam que esta característica não apresentaria ganho genético como resposta à seleção. O efeito ambiental comum de leitegada e o genético materno não apresentaram influência sobre esta característica. Já o ambiental permanente, mesmo sem ter sido significativo o seu efeito pelo LR, deve ser considerado nos modelos genéticos para essa característica, pois sua presença causou mudança nas estimativas da variância genética aditiva.

Reduction of enantioselectivity in the kinetic disposition and metabolism of verapamil in rats exposed to toluene

Toluene and verapamil are subject to extensive oxidative metabolism mediated by CYP enzymes, and their interaction can be stereoselective. In the present study we investigated the influence of toluene inhalation on the enantioselective kinetic disposition of verapamil and its metabolite, norverapamil, in rats. Male Wistar rats (n = 6 per group) received a single dose of racemic verapamil (10 mg/kg) orally at the fifth day of nose-only toluene or air (control group) inhalation for 6 h/day (25, 50, and 100 ppm). Serial blood samples were collected from the tail up to 6 h after verapamil administration. The plasma concentrations of verapamil and norverapamil enantiomers were analyzed by LC-MS/MS by using a Chiralpak AD column. Toluene inhalation did not influence the kinetic disposition of verapamil or norverapamil enantiomers (p > 0.05, Kruskal-Wallis test) in rats. The pharmacokinetics of verapamil was enantioselective in the control group, with a higher plasma proportion of the S-verapamil (AUC 250.8 versus 120.4 ng.h.mL(-1); p <= 0.05, Wilcoxon test) and S-norverapamil (AUC 72.3 versus 52.3 ng.h.mL(-1); p <= 0.05, Wilcoxon test). Nose-only exposure to toluene at 25, 50, or 100 ppm resulted in a lack of enantioselectivity for both verapamil and norverapamil. The study demonstrates the importance of the application of enantioselective methods in studies on the interaction between solvents and chiral drugs.

Electrochemical evidence of sulfinic acid derivative as an intermediate in the reduction of aromatic sulfonyl chloride in an aprotic medium

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

Absence of gluonic components in axial and tensor mesons

A quarkonium-gluonium mixing scheme previously developed to describe the characteristic of the pseudoscalar mesons is applied to axial and tensor mesons. The parameters of the model are determined by fitting the eigenvalues of a mass matrix. The corresponding eigenvectors give the proportion of light quarks, strange quarks and glueball in each meson. However, the predictions of the model for the branching ratios and electromagnetic decays are incompatible with the experimental results. These results suggest the absence of gluonic components in the states of axial and tensor isosinglet mesons analyzed here.

Waveshapes of continuing currents and properties of M-components in natural positive cloud-to-ground lightning

This work analyses the waveshapes of continuing currents and parameters of M-components in positive cloud-to-ground (CG) flashes through high-speed GPS synchronized videos. The dataset is composed of only long continuing currents (with duration longer than 40 ms) and was selected from more than 800 flashes recorded in Sao Jose dos Campos (45.864 degrees W, 23.215 degrees S) and Uruguaiana (29.806 degrees W, 57.005 degrees S) in Southeast and South of Brazil, respectively, during 2003 to 2007 summers. The videos are compared with data obtained by the Brazilian Lightning Location System (BrasilDAT) in order to determine the polarity of each flash and select only positive cases. There are only two studies of waveshapes of continuing currents in the literature. One is based on direct current measurements of triggered lightning, in which four different types of waveshapes were observed; and the other is based on measurements of luminosity variations in high-speed videos of CG negative lightning, in which besides the four types above mentioned two additional types were observed. The present work is an extension of the latter, using the same method but now applied to obtain the waveshapes of positive CG lightning. As far as the authors know, this is the first report on M-components in positive continuing currents. We also have used the luminosity-versus-time graphs to observe their occurrence and measure some parameters (duration, elapsed time and time between two successive M-components), whose statistics are presented and compared in detail to the data for negative flashes. We have plotted a histogram of the M-components elapsed time over the total duration of the continuing current for positive flashes, which presented an exponential decay (correlation coefficient: 0.83), similar to what has been observed for negative flashes. (C) 2008 Elsevier B.V. All rights reserved.

Reduction of podocytes number in late diabetic alloxan nephropathy: prevention by glycemic control

OBJETIVO: Avaliar o número de podócitos e espessamento da membrana basal glomerular (MBG) em ratos diabéticos com e sem controle glicêmico com 6 e 12 meses da indução. MÉTODOS: 100 ratos Wistar com 200-300g compuseram 6 grupos: Normal (N6, N12 - 25 animais) Diabético (D6,D12 - 25 animais) e diabético tratado com insulina 1,8 a 3,0 U/Kg e acarbose misturada a ração (50g para cada 100g de ração) (DT6 e DT12 - 25 animais). Aloxana foi ministrada via endovenosa na dose de 42mg/Kg. Peso, ingestão hídrica e diurese de 24 horas e glicemia e glicosúria foram determinados antes da inoculação, 7 e 14 dias após e mensalmente. No 14ª dia foi iniciado o tratamento. Três grupos de animais (N6, D6 e DT6) foram sacrificados no 6° mês e três grupos (N12, D12 e DT12), no 12ª mês sendo o tecido renal processado para estudo à microscopia eletrônica. RESULTADOS: A glicemia dos animais DT6 e DT12 diferiram significativamente, dos ratos D6 e D12, e não diferiram dos grupos N6 e N12. O número de podócitos do grupo DT6 não diferiu de N6 e D6 (mediana=11); o número de podócitos de DT12 (mediana=11) diferiu de D12 (mediana=8) e não diferiu de N12 (mediana=11). O espessamento da MBG de D6 (0,18 micrômetros) foi menor que D12 (0,29 micrômetros); de DT6 (0,16 micrômetros) foi menor que D6 (0,18 micrômetros) e de DT12 (0,26 micrômetros) foi menor que D12 (0,29 micrômetros). CONCLUSÃO: O controle da hiperglicemia preveniu o espessamento da MBG na nefropatia diabética aloxânica precoce (6 meses) e tardia (12 meses), e a diminuição do número de podócitos.

Reduction of humeroulnar congenital elbow luxation in 8 dogs by using the transarticular pin

The purpose of this study was to evaluate the clinical and radiographic outcome in 8 dogs of surgical reduction of congenital humeroulnar luxation by using the transarticular pin. Five cases were bilateral and 3 were unilateral, for a total of 13 elbows. The treatment was performed in animals between 45 and 150 days of age. Articular stabilization was achieved by using a transarticular pin driven from the caudal aspect of the olecranon into the body of the humerus or into the distal condyle and distal metaphysis of the humerus. The follow-up period was between 1 and 19 months. There were 5 postsurgical reluxations, 3 related to the insertion of the pin into the humeral condyle and 3 related to the insertion into the humeral body. These animals needed further surgery. Six animals showed near normal return to limb function and 2 had lameness. We conclude that the use of the transarticular pin is an effective and simple method for the treatment of humeroulnar congenital elbow luxation.

Effect of Er : YAG and diode lasers on the adhesion of blood components and on the morphology of irradiated root surfaces

Objectives: the aim of this study was to evaluate in vitro, by scanning electron microscopy (SEM), the adhesion of blood components on root surfaces irradiated with Er:YAG (2.94 mu m) and GaAlAs Diode (808 nm) lasers and the effects on the morphology of irradiated root surfaces.Methods: One hundred samples of human teeth were obtained. They were previously planed and scaled with manual instruments and divided into five groups of 20 samples each: G1 (control group) - absence of treatment; G2 - Er:YAG laser (7.6 J/cm(2)); G3 - Er:YAG laser (12.9 J/cm(2)); G4 - Diode laser (90 J/cm(2)) and G5 - Diode laser (108 J/cm(2)). After these treatments, 10 samples of each group received a blood tissue but the remaining 10 did not. After laboratory treatments, the samples were obtained by SEM, the photomicrographs were analysed by the score of adhesion of blood components and the results were statistically analysed (Kruskall-Wallis and Mann-Whitney test).Results: In relation to the adhesion of blood components, the study showed no significant differences between the control group and the groups treated with Er:YAG laser (p = 0.9633 and 0.6229). Diode laser radiation was less effective than control group and Er:YAG laser radiation (p < 0.01).Conclusion: None of the proposed treatments increased the adhesion of blood components in a significant way when compared to the control group. Although the Er:YAG laser did not interfere in the adhesion of blood components, it caused more changes on the root surface, whereas the Diode laser inhibited the adhesion.