Estudos eletroquímicos de permeação de hidrogênio e determinação de concentrações críticas de hidrogênio em um aço de alta dureza

Estudou-se, através do método eletroquímico de permeação, a difusão de hidrogênio no ferro puro e no aço DIN 90MnV8. Observou-se nestes materiais, que o coeficiente aparente de difusão de hidrogênio diminui no decorrer dos transientes de permeação, tendo-se interpretado este comportamento como causado pela presença de armadilhas reversíveis. Deduziu-se, para transientes de permeação obtidos entre dois estados estacionários de difusão, que a variação da concentração de hidrogênio preso a armadilhas reversiveis é dada por: Delta Ca = Na. In [(1+alfa)1/2 dividido por (1+beta)1/2], alfa = K.Co/p beta=K.Cl/p sendo Na a densidade de armadilhas; k e p, os parâmetros de captura e de liberação de uma armadilha e Co e Cl, a concentrasão inicial e final de H. Mediu-se, no ferro recozido, um coeficiente médio de difusão de hidrogênio de 6,4.10-5 cm²/s. A deformação com 50% de trabalho a frio no ferro reduz este valor em aproximadamente uma ordem de grandeza. Verificou-se no aço DIN 90MnV8 que o coeficiente de difusão de hidrogênio aumenta com o aumento dn temperatura de revenimento após a têmpera, atingindo o valor máximo de 7,0.10-6 cm²/s no aço esferoidizado. A dependência térmica do coeficiente de difusão no aço DIN 90MnV8 esferoidizado pode ser expressa por: D = 1,95 (+0,49) exp (-30,43kJ/mol.R.T.) (cm²/s) e neste mesmo aço temperado e revenido com 55RC de dureza por : D=0,29 (+- 0,05 ) exp (-28,47kJ/mol.R.T.) ( cm²/s). Uma nova metodolagia fractomecânica foi introduzida, a qual permite a determinação da cnncentração crítica de hidrogênio necessária para provocar o avanço de uma trinca estacionária. Observou-se no aço DIN 9OMnV8, que a concentração crítica de hidrogênio diminui com o aumento da dureza do aço e é menor quando um valor maior de KI é aplicado. O modo de fratura apresentado Por este aço revelou ser independente da concentração de hidrogênio e do valor de KI, sendo função unicamente de sua dureza.

A influência de modificações superficiais no aço 1045 formadoras de compostos de Fe-Sn quanto à permeação de hidrogênio

O objetivo deste trabalho foi estudar e desenvolver uma técnica que diminuísse a concentração de hidrogênio absorvido pelo aço SAE 1045. A técnica consistiu na modificação superficial de amostras de aço SAE 1045 através de eletrodeposição de Sn na superfície com posterior tratamento térmico para promover a difusão do Sn para o interior do aço. Por meio da técnica de RBS, foram caracterizados os perfis de concentração do Sn no aço com a profundidade. Por outro lado, com o uso da técnica de permeação eletroquímica, aplicada tanto em meio alcalino como neutro, foi avaliada a eficiência das modificações superficiais em inibir a absorção do hidrogênio pelo aço. Foram constatadas significativas reduções da absorção de H em amostras modificadas com a adição de 100nm de Sn eletrodepositado com posterior difusão. Utilizou-se também medidas de impedância eletroquímica e ensaios de voltametria potenciostática e potenciodinâmica para descrever as influências das modificações superficiais no processo de absorção.

O teste do hidrogênio expirado no diagnóstico da má absorção de doses fisiológicas de lactose em alunos de escolas públicas de Porto Alegre

Objetivo: Determinar a prevalência de má absorção de lactose e sua associação com a cor da pele e a idade em crianças e adolescentes de escolas públicas do município de Porto Alegre. Material e Métodos: Foi realizado um estudo transversal que incluiu 225 indivíduos de 8 a 18 anos, freqüentadores de escolas públicas do município de Porto Alegre. Os participantes foram classificados segundo a cor e a faixa etária. A má absorção de lactose foi diagnosticada através do teste do hidrogênio expirado após ingestão de 250 ml de leite. O teste teve duração de 3 horas e foi considerado como critério de positividade o aumento ≥ 20 partes por milhão na concentração de hidrogênio em relação ao nível basal. Resultados: Foram estudados 225 alunos, com uma média e desvio padrão de idade de 12,2 ± 2,0 anos. Cento e cinqüenta e quatro alunos eram de cor branca (68,4%) e os restantes, de cor não-branca (preta ou parda). A má absorção de lactose foi evidenciada em 19/225 casos (8,4%). Foram diagnosticados 8/154 casos (5,2%) nos alunos de cor branca e 11/71 casos (15,5%) nos alunos de cor não-branca (p = 0,02). Em relação à faixa etária, ocorreram 15/143 casos (10,5%) nos alunos entre 8 e 12 anos e 4/82 casos (4,9%) entre 13 e 18 anos (p = 0,227). Conclusões: A prevalência de má absorção de lactose encontrada em alunos de escolas pú-blicas de Porto Alegre é alta, especialmente se considerarmos que foram utilizadas doses fi-siológicas (250 ml de leite) para o diagnóstico. As taxas de má absorção foram maiores entre as crianças de cor não-branca em relação às crianças de cor branca, confirmando a influência racial na hipolactasia primária do tipo adulto.

Átomo de Hidrogênio (H)

Ilustração componente do jogo “Quimolécula (http://www.loa.sead.ufscar.br/quimolecula.html)” desenvolvido pela equipe do Laboratório de Objetos de Aprendizagem da Universidade Federal de São Carlos (LOA/UFSCar).

Coordenação entre as respostas da catalase e da ascorbato peroxidade em folhas de feijão caupi submetidas a diferentes fontes de peróxido de hidrogênio

The plants are often exposed to variations in environmental conditions that may trigger metabolic disturbances leading to a consequent loss in productivity of crops. These stressful conditions usually induce an accumulation of reactive oxygen species (ROS) in the cell, a condition known how oxidative stress. Among these species, hydrogen peroxide (H2O2) is an important molecule involved in numerous signaling mechanisms. The present study aimed to understand the relationship between the different enzymatic mechanisms of elimination of H2O2 by catalase (CAT) and ascorbate peroxidase (APX) in leaf tissues of seedlings of the species Vigna unguiculata L. Walp, under conditions of oxidative stress induced by application of CAT inhibitor, 3-amino-1,2,4-triazole (3-AT), and H2O2 itself on the roots. Three experiments were conducted. The first experiment was performed applying the compound 3-AT (5 mM) during the time (hours). In the second experiment, seedlings were exposed to different concentrations of H2O2 (2.5, 5.0, 7.5, 10 mM) for 48 h. The third strategy included the pre-treatment with H2O2 (2.5 mM) for 24 h, followed by subsequent treatment with the inhibitor 3-AT and recovery control condition. Treatment with 3-AT causes a strong inhibition of CAT activity in leaf tissues accompanied by an increase of activity of APX. However a decrease in oxidative damage to lipids is not observed as indicated by TBARS. It was observed that activity of APX is directly linked to the content of peroxide. Inductions in the activities of CAT and APX were observed mainly in the seedlings treated with 2.5 mM H2O2. This can be associated with a decrease in oxidative damage to lipids. In contrast, one same tendency was not observed in treatments with higher concentrations of this ROS. These results suggest that the concentration of 2.5 mM H2O2 can induce responses antioxidants later in seedling cowpea. This concentration when applied as pre-treatment for 24 h promoted an induction systems removers CAT and APX, both in activity and in terms of gene expression. However this increment was not observed in the recovered plants and the plants subsequently subjected to 3-AT. Additionally, the pretreatment was not sufficient to attenuate the inhibition of CAT activity and oxidative damage to lipids caused by the subsequent application of this inhibitor. The results showed that the application of 3-AT and H2O2 in the root systems of seedlings of cowpea promote changes in the parameters analyzed in leaf tissues that indicate a direct response to the presence of these factors or systemic signaling mecanisms. H2O2 appears to activate the responses of two antioxidant systems in this study thar does not promote greater protection in case of additional treatment with 3-AT. This demonstrates the importance of the CAT system. In this work, complete results indicate that there is a difference between the signaling and the effects caused by exposure to H2O2 and by treatment with 3-AT

Proteômica diferencial da Chromobacterium violaceum em resposta ao estresse oxidativo induzido por peróxido de hidrogênio

The β-proteobacterium Chromobacterium violaceum is a Gram-negative, free-living, saprophytic and opportunistic pathogen that inhabits tropical and subtropical ecosystems among them, in soil and water of the Amazon. It has great biotechnological potential, and because of this potential, its genome was completely sequenced in 2003. Genome analysis showed that this bacterium has several genes with functions related to the ability to survive under different kinds of environmental stresses. In order to understand the physiological response of C. violaceum under oxidative stress, we applied the tool of shotgun proteomics. Thus, colonies of C. violaceum ATCC 12472 were grown in the presence and absence of 8 mM H2O2 for two hours, total proteins were extracted from bacteria, subjected to SDS-PAGE, stained and hydrolysed. The tryptic peptides generated were subjected to a linear-liquid chromatography (LC) followed by mass spectrometer (LTQ-XL-Orbitrap) to obtain quantitative and qualitative data. A shotgun proteomics allows to compare directly in complex samples, differential expression of proteins and found that in C. Violaceum, 131 proteins are expressed exclusively in the control condition, 177 proteins began to be expressed under oxidative stress and 1175 proteins have expression in both conditions. The results showed that, under the condition of oxidative stress, this bacterium changes its metabolism by increasing the expression of proteins capable of combating oxidative stress and decreasing the expression of proteins related processes bacterial growth and catabolism (transcription, translation, carbon metabolism and fatty acids). A tool with of proteomics as an approach of integrative biology provided an overview of the metabolic pathways involved in the response of C. violaceum to oxidative stress, as well as significantly amplified understanding physiological response to environmental stress. Biochemical and "in silico" assays with the hypothetical ORF CV_0868 found that this is part of an operon. Phylogenetic analysis of superoxide dismutase, protein belonging to the operon also showed that the gene is duplicated in genome of C. violaceum and the second copy was acquired through a horizontal transfer event. Possibly, not only the SOD gene but also all genes comprising this operon were obtained in the same manner. It was concluded that C. violaceum has complex, efficient and versatile mechanisms in oxidative stress response

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Avaliação de parâmetros de estresse oxidativo em plantas de cana-de-açúcar tratadas com peróxico de hidrogênio

The genus Saccharum belongs to Poaceae family. Sugarcane has become important monocultures in Brazil due to their products: ethanol and sugar. The production may change between different regions from Brazil. This difference is related to soil, climatic conditions and temperature that promotes oxidative stress that may induce an early flowering. The aim of this work was to identify the effects of oxidative stress. In order to analyse this, sugarcane plants were submitted to oxidative stress using hydrogen peroxide. After this treatment, the oxidative stress were analyzed Then, the plant responses were analyzed under different approaches, using morphophysiological, biochemical and molecular tools. Thus, sugarcane plants were grown under controlled conditions and until two months they were subjected first to a hydroponics condition for 24 hours in order to acclimation. After this period, these plants were submitted to oxidative stresse using 0 mM, 10 mM, 20 mM and 30 mM hydrogen peroxide during 8 hours. The histomorphometric analysis allowed us to verify that both root and leaf tissues had a structural changes as it was observed by the increased in cell volume, lignin accumulation in cell walls. Besides, this observation suggested that there was a change in redox balance. Also, it was analyzed the activity of the SOD, CAT and APX enzymes. It was observed an increase in the SOD activity in roots and it was also observed a lipid peroxidation in leaves and roots. Then, in order to identify proteins that were differently expressed in this conditions it was used the proteomic tool either by bidimensional gel or by direct sequencing using the Q-TOF EZI. The results obtained with this approach identified more than 3.000 proteins with the score ranging from 100-5000 ions. Some of the proteins identified were: light Harvesting; oxygenevolving; Thioredoxin; Ftsh-like protein Pftf precusor; Luminal-binding protein; 2 cys peroxiredoxin e Lipoxygenase. All these proteins are involved in oxidative stress response, photsynthetic pathways, and some were classified hypothetical proteins and/or unknown (30% of total). Thus, our data allows us to propose that this treatment induced an oxidative stress and the plant in response changed its physiological process, it made changes in tissue, changed the redox response in order to survival to this new condition

Avaliação da remoção de sulfeto de hidrogênio do gás natural em uma coluna de absorção

Natural gas, although basically composed by light hydrocarbons, also presents in its composition gaseous contaminants such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). Hydrogen sulfide, which commonly occurs in oil and gas exploration and production activities, besides being among the gases that are responsible by the acid rain and greenhouse effect, can also cause serious harm to health, leading even to death, and damages to oil and natural gas pipelines. Therefore, the removal of hydrogen sulfide will significantly reduce operational costs and will result in oil with best quality to be sent to refinery, thereby resulting in economical, environmental, and social benefits. These factors highlight the need for the development and improvement of hydrogen sulfide sequestrating agents to be used in the oil industry. Nowadays there are several procedures for hydrogen sulfide removal from natural gas used by the petroleum industry. However, they produce derivatives of amines that are harmful to the distillation towers, form insoluble precipitates that cause pipe clogging and produce wastes of high environmental impact. Therefore, the obtaining of a stable system, in inorganic or organic reaction media, that is able to remove hydrogen sulfide without forming by-products that affect the quality and costs of natural gas processing, transport and distribution is of great importance. In this context, the evaluation of the kinetics of H2S removal is a valuable procedure for the treatment of natural gas and disposal of the byproducts generated by the process. This evaluation was made in an absorption column packed with Raschig ring, where natural gas with H2S passes through a stagnant solution, being the contaminant absorbed by it. The content of H2S in natural gas in column output was monitored by an H2S analyzer. The comparison between the obtained curves and the study of the involved reactions have not only allowed to determine the efficiency and mass transfer controlling step of the involved processes but also make possible to effect a more detailed kinetic study and evaluate the commercial potential of each reagent

Estudo da adsorção de hidrogênio e sulfeto na superfície de paládio: aspectos experimentais (eletroquímica) e teóricos (ab initio e Teoria do Funcional da Densidade)

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

Aplicação de argila branca comercial pura e modificada para adsorção de sulfeto de hidrogênio

In this work were synthesized matrix-based commercial white clay in its composition having large amounts of kaolinite and quartz, with a certain percentage of iron oxide for use as an adsorbent for hydrogen sulfide (H2S). To characterize the effect of initial matrix techniques were used to characterize XRD, FTIR, XRF and TG. The initial clay mineral matrix was placed in contact with 0.1 molar solutions of the salts of Co2+, Ni2+, Cr3+ and a solution 0.1 g / 100ml rhodamine B. During the synthesis process, the solutions were placed in contact with the initial matrix for a period of 48 hours in order to have ion exchange with the clay mineral. To check the amount of exchanged metals, we used the technique of X-ray Fluorescence (XRF). After synthesis was initiated the process of adsorption of H2S, where the arrays were placed in the reactor, then by passing a stream of hydrogen sulfide. The matrix along with the reactor was weighed before and after to measure the amount of gas adsorbed. Based on the gravimetric data the matrix which had the highest performance of the adsorption matrix was exchanged with Ni2+ ions, obtaining a result of 11.13 mg H2S / g matrix, then the matrix coated with rhodamine B which was reached 10.13 mg H2S / g matrix