Resumo em português Construiu-se um biossensor para a determinação do pirimicarbo, pela co-imobilização de acetilcolinesterase (AChE) e colina oxidase (ChOx) numa membrana de poliétersulfona modificada. A membrana foi aplicada a um sistema base de eléctrodos da Universal Sensors e monitorizou-se o peróxido de hidrogénio formado quando da adição de acetilcolina (ACh) a um tampão apropriadamente escolhido onde se mergulhou o biossensor. O peróxido de hidrogénio é o produto da hid (mais) rólise da colina, catalisada pela colineoxidase. A colina formou-se pela acção da acetilcolinesterase na acetilcolina. O pirimicarbo inibe estas reacções e esse facto pode ser usado para determinar a sua concentração. Obteve-se um gráfico de calibração para o pirimicarbo. Resumo em inglês A biosensor for the determination of pirimicarb was constructed by the co-immobilization of acetylcholinesterase and choline oxidase on a derivatised polyethersulfone membrane. The membrane was applied to an Universal Sensors electrode base system and the hydrogen peroxide formation was monitored upon addition of acetylcholine to an appropriately chosen buffer where the biosensor was dipped. The hydrogen peroxide is the product of the hydrolysis of choline, catalysed by c (mais) holineoxidase. Choline was formed by the action of acetylcholinesterase on acetylcholine. Pirimicarb inhibits these reactions and that fact can be used to determine its concentration. A calibration plot for pirimicarb was obtained.
Resumo em inglês In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 c (mais) atalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.
Utilização de endoperóxidos de derivados de naftaleno como fontes químicas de oxigênio singlete em sistemas biológicos/ Naphthalene endoperoxides as chemical sources of singlet oxygen in biological systems
Resumo em inglês Molecular oxygen, in the first excited state (singlet oxygen, ¹O2), has a substantial reactivity towards electron-rich organic molecules, such as biological targets, including unsaturated fatty acids, proteins, RNA and DNA. Considering the complexity of biological systems and the great variety of reactive species generated by photochemistry, efforts have been devoted to develop suitable ¹O2 generators based on the thermolysis of water soluble naphthalene endoperoxides. (mais) These compounds are chemically inert and have been employed as versatile sources of ¹O2. The synthesis is based on structural modifications in position 1,4 of dimethylnaphtalene, grafting hydrophilic substituents. The correspondent endoperoxide can be generated using photochemical method, or molybdate-catalyzed disproportionation of hydrogen peroxide.
Resumo em português O frio acumulado em regiões de inverno ameno é insuficiente para superar a dormência de algumas cultivares de pessegueiro, como o Chiripá, sendo necessária a utilização de produtos químicos para melhorar a brotação, a floração e a produção. O objetivo deste trabalho foi avaliar o efeito de diferentes doses de cianamida hidrogenada (CH2N2) e óleo mineral (OM) na floração, brotação e produção do pessegueiro cv. Chiripá, cultivado no município de Pato (mais) Branco. O uso de 1% CH2N2 combinada com 1% de OM antecipa, aumenta e uniformiza a floração, a brotação e a colheita de pessegueiro cv. Chiripá, promovendo maior frutificação efetiva e produção por planta, viabilizando o plantio comercial dessa cultivar. Resumo em inglês The chilling accumulated in areas of mild winter climate is not enough to overcome the endodormancy of some cultivars, like 'Chiripá', being necessary the use of chemical products for a better budding, blooming and cropping. The objective of this work was to evaluate the effect of different doses of hydrogen Cyanamid (CH2N2) and mineral oil (MO) in the blooming, budding and production of peach tree, cv. Chiripá cultivated in Pato Branco, Paraná. The use of 1% CH2N2 com (mais) bined with 1% of MO, increase, anticipate and homogenize blooming, budding and cropping of peach tree cv. Chiripá, promoting larger fruit set and production per plant, making possible the commercial orchards of this cultivar.
Resumo em inglês Green coconut shells were treated with acid, base and hydrogen peroxide solutions for 3, 6, 12 and 24 h for removing toxic metals from synthetic wastewater. The removal of ions by the adsorbent treated with 0.1 mol L-1 NaOH/ 3h was 99.5% for Pb2+ and 97.9% for Cu2+. The removal of Cd2+, Ni2+, Zn2+, using adsorbent treated with 1.0 mol L-1 NaOH/3 h, was 98.5, 90.3 and 95.4%, respectively. Particle size, adsorbent concentration and adsorption kinetics were also studied. An (mais) adsorbent size of 60-99 mesh and a concentration of 30-40 g/L for 5 min exposure were satisfactory for maximum uptake of Pb2+, Ni2+, Cd2+, Zn2+ and Cu2+ and can be considered as promising parameters for treatment the aqueous effluents contaminated with toxic metals.
Resumo em inglês This article describes the current status of several analytical methodologies using vegetal tissue and crude extracts as enzymatic source. In this divulgation paper the obtention of vegetal crude extract and/or tissue and selected enzymatic procedures are presented emphasizing its characteristics and peculiarities. Examples of many biosensors and/or flow injection procedures using vegetal tissues or crude extracts for the determination of many analytes, such as amines, as (mais) corbic acid, ethanol, glutamate, hydrogen peroxide, oxalic acid, pectins, phenolic compounds and urea of biologic, environmental, food, pharmaceutical and industrial interests are also given and discussed.
Resumo em inglês The Balmer equation is obtained from the hydrogen spectrum in an empirical way, using a graphic method; from this equation the energy level terms are derived. Emphasis is given to concepts in order to make clear the meaning of quantum numbers, eigenvalues and eigenfunctions in the Schrödinger equation.
Resumo em inglês The present article is devoted to Chemistry or Physics undergraduate students, given their difficulty to understand fundamental concepts and technical language used in atomic spectroscopy and quantum mechanics. An easy approach is shown in the treatment of the emission spectrum of the sodium atom without any involved calculations. In a previous article, the hydrogen spectrum was considered and the energy degeneracy of the angular momentum quantum number was observed. For (mais) the sodium spectrum, due to the valence electron penetration into internal shells, a breakdown of this degeneracy occurs and a dependence of this penetration on the angular momentum quantum number is observed. The eigenvalues are determined introducing the quantum defect correction (Rydberg correction) in the denominator of the Balmer equation, and the energy diagram is obtained. The intensity ratio for the observed doublets is explained by introducing new wave functions, containing the magnetic quantum number of the total angular momentum.
Uma abordagem robusta de cálculo aplicada a um sistema potenciométrico de medida de concentrações hidrogeniônicas em soluções aquosas/ A robust calculation approach applied to the evaluation of hydrogen ion concentrations through potentiometric measurements in aqueous solutions
Resumo em inglês The data analyzed in this work were generated following the methodology developed by Molina et al.(J. Electroanal. Chem., 1979) for the calibration of a potentiometric system of measurement of hydrogen-ion concentrations resulting from neutralizations, at 25 ºC, of acidic or alkaline solutions at constant ionic strength (0.1 mol.l-1) held with NaClO4. The observed data present a serious deviation in relation to the mathematical model derived from the Nernst equation, for (mais) pH values ranging from 3 to 11, where pH=-log[H+]. We show that the minimization of the sum of the absolute values of the residuals gives estimates that are not influenced by outlying values.
Resumo em inglês An experiment is proposed to introduce some fundamentals of flow analysis, chemiluminescence and kinetic monitoring of enzymatic reactions in undergraduate courses. Chemiluminescence detection is performed with a simple spectrophotometer equipped with a lab-made spiral flow cell constructed from a polyethylene tube. The hydrogen peroxide produced by the glucose oxidation in the presence of glucose oxidase is continuously monitored by the reaction with luminol in alkaline (mais) media in a flow injection system. The exercise allows also the discussion of important analytical features and the comparison with different optical methods of analysis.
Um estudo teórico relativo à não-linearidade da ligação de hidrogênio em sistemas heterocíclicos C2H4O-C2H2 e C2H4S-C2H2/ A theoretical study about the non-linearity of the hydrogen bonding in the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic systems
Resumo em inglês B3LYP/6-31G(d,p) calculations were used to determine the optimized geometries of the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic hydrogen-bonded complexes. Results of structural, rotational, electronic and vibrational parameters indicate that the hydrogen bonding is non-linear due to the pi bond of the acetylene interacting with the hydrogen atoms of the methyl groups of the three-membered rings. Moreover, the theoretical investigation showed that the non-linearity is much mor (mais) e intriguing, since there is a structural disjunction on the acetylene within the heterocyclic system.
Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF/ A theoretical study of molecular properties of C2H4···2HF, C2H2···2HF AND C3H6···2HF trimolecular hydrogen-bonded complexes
Resumo em inglês We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p) calculations, the most important structural deformations are related to the C=C (C2H4), C≡C (C2H2), C-C (C3H6) and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid (mais) molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.
Resumo em inglês Hydrogen peroxide and chlorine are compared as possible disinfectants for water-cooling circuits. To this purpose, samples taken from the cooling system of a steel making plant were treated (at 25ºC and pH values of 5.5 and 8.5) with varying amounts of the two oxidizing agents (0.0 mg/L, 2.0 mg/L and 6.0 mg/L). The results were evaluated through bacterial counting and measurement of corrosion rates upon AISI1020 carbon steel coupons. Bacterial removal and corrosion effects proved to be similar and satisfactory for both reagents.
Resumo em inglês The fuel cell principle was discovered by Sir Grove 150 years ago. However material problems prohibited its commercialization for a long time. A change has been occurring during the last 30 years, so two types of fuel cell technologies can be distinguished: low and high temperature operation cells. Nowadays, only phosphoric acid cells are commercially offered as 200 kWel power plants. Membrane cells are more suitable for automobile electrotraction with a very low (or no) (mais) environmental impact. The fuel continues, however, to play a very particular role, since hydrogen is not easy to store and to transport. The more promising target is the utilization of liquid methanol. The Brazilian scenario concerning this kind of technology is discussed.
Sistema de injeção em fluxo espectrofotométrico para monitorar peróxido de hidrogênio em processo de fotodegradação por reação foto-Fenton/ Flow injection spectrophotometric system for hydrogen peroxide monitoring in photo-Fenton degradation processes
Resumo em inglês A flow injection spectrophotometric system was projected for monitoring hydrogen peroxide during photodegradation of organic contaminants in photo-Fenton processes (Fe2+/H2O2/UV). Sample is injected manually in a carrier stream and then receives by confluence a 0.1 mol L-1 NH4VO3 solution in 0.5 mol L-1 H2SO4 medium. The product formed shows absorption at 446 nm which is recorded as a peak with height proportional to H2O2 concentration. The performance of the proposed sys (mais) tem was evaluated by monitoring the consumption of H2O2 during the photodegradation of dichloroacetic acid solution by foto-Fenton reaction.
Resumo em português A filtração em múltiplas etapas (FiME) se apresenta como uma alternativa para realizar o tratamento de água de comunidades de pequeno porte, entretanto, a eficiência quanto à remoção de cor verdadeira associada ao carbono orgânico dissolvido (COD) ou às substâncias húmicas, tem sido questionada ou relatada como baixa. A presente pesquisa avaliou a remoção de substâncias húmicas na FiME com pré-oxidação, com ozônio e peróxido de hidrogênio, utilizando (mais) para essa avaliação parâmetros indiretos como cor verdadeira, absorvância UV (254 nm) e COD. Foram realizados cinco ensaios, utilizando quatro filtros lentos, sendo dois com camada de carvão ativado granular (CAG). Foram ensaiadas várias alternativas de pré-oxidação com ozônio e peróxido de hidrogênio. Foram obtidos bons resultados, tendo como principal conclusão que os filtros lentos com CAG, precedidos de oxidação com ozônio e depois peróxido de hidrogênio, apresentaram remoção média de cor verdadeira de 64%, mas que o peróxido de hidrogênio afeta o desenvolvimento da camada biológica, interferindo no desenvolvimento da perda de carga, na remoção de turbidez, na remoção de coliformes e na remoção de substâncias húmicas. Resumo em inglês The multistage filtration (FiME) is an alternative to accomplish water treatment for small communities, however, as for removal of true color associated to dissolved organic carbon (DOC) or humic substances, it have been questioned or reported as low efficiency. The present research evaluated the removal of humic substances in the FiME using ozone and hydrogen peroxide as a pre-oxidation, using for this indirect parameters how true color, UV absorbance (254nm) and DOC. Fi (mais) ve experiments were conducted using four slow filters, from this two were composed the intermediate layer of granulate activated carbon (GAC). The assays were conducted with pre-oxidation alternatives using ozone and hydrogen peroxide in several applications forms. It was obtained good result, as main conclusion were the slow filters with GAC, preceded of oxidation with ozone and hydrogen peroxide in appropriate dosage, presented medium removal of true color of 64%, but that the hydrogen peroxide interfering in the development of the biological layer, in the increase of the head loss, in the turbidity removal, in the coliforms removal and in the humic substances removal.
Resumo em inglês This paper summarizes the result of a degradation test of two azo-reactive dyes (Reactive Blue 214, Reactive Red 243) under UV irradiation in the presence of H2O2. Five different doses of hydrogen peroxide (0 mM, 5 mM, 10 mM, 20 mM and 30 mM) at constant initial concentration of the substrate (100 mg/L) were used. The radiation source were three 15 W-lamps. Complete destruction of the color of the solutions was attained in 40-50 min of irradiation. UV/H2O2 proved capable of complete discoloration and degradation of the above azo reactive dyes.
Relação entre transferência de carga e as interações intermoleculares em complexos de hidrogênio heterocíclicos/ Relationship between charge transfer and intermolecular interactions in heterocyclic hydrogen-bonded complexes
Resumo em inglês Hydrogen-bonded complexes formed by the interaction of the heterocyclic molecules C2H4O and C2H5N with HF, HCN, HNC and C2H2 have been studied using density functional theory. The hydrogen bond strength has been analyzed through electron density charge transfer from the proton acceptor to the proton donor. The density charge transfer has been estimated using different methods such as Mulliken population analysis, CHELPG, GAPT and AIM. It has been shown that AIM-estimated (mais) charge transfer correlates very well with the hydrogen bond energy and the infrared bathochromic effect of the proton donor stretching frequencies.
Resumo em inglês This work describes a process for metal recovery from spent NiMo and CoMo/Al2O3 commercial hydrorefining catalysts. The samples were treated by fusion with potassium hydrogen sulfate (5 h, 600 ºC) with a KHSO4/catalyst mass ratio of 10:1. After fusion the solid was solubilized in water (100 ºC), leaving silicon compounds as residue. Losses of nickel and cobalt may reach 16 wt% of the amount present in the sample, depending on the silicon content. Soluble metals were iso (mais) lated by selective precipitation techniques (nickel, cobalt, aluminum) or by solvent extraction with methyl-isobutyl ketone (molybdenum) in a hydrochloric acid medium. All metals were recovered in very good yields except for nickel and cobalt in the presence of considerable amounts of silicon. Soluble wastes consist of potassium/sodium sulfates/chlorides. Solid wastes correspond to about 4 wt% of the catalyst and can be discarded in industrial dumps.
Resumo em inglês The "active mass" (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 ºC) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the "active mass" was treated with potassium hydrogen sulfate (500 ºC) and dissolved in water. Cobalt was precipitated together with copp (mais) er after addition of sodium hydroxide. Lithium was partially recovered as lithium fluoride. Co-processing of other battery components (aluminum and copper foils) affected negatively the behavior of the recovery procedures. Previous segregation of battery components is essential for an efficient and economical processing of the "active mass".
Reciclagem do crômio de resíduos químicos provenientes da determinação de carbono oxidável em fertilizantes orgânicos/ Recycling of chromium in chemical waste from oxidizable carbon determination in organic fertilizer
Resumo em inglês This work proposes a separation, recovery and reuse procedure of chemical residues with chromium. This residue was generated by the determination of oxidizable carbon in organic fertilizers samples. The Cr(VI) of the residue was reduced with ethanol and precipitated with NaOH. The Cr(OH)3 precipitate was separated and oxidized to dichromate ions with hydrogen peroxide. This solution was used another time in organic carbon determination. The uses of recycled dichromate sol (mais) ution were appropriated in four successive recycling. The accuracy was proven using potassium hydrogen phthalate and ten organic fertilizer samples. The organic carbon results, determined with recycled solutions, were similar the conventional solution.
Resumo em inglês Isotopic and elemental analysis of N, C and S in liquid and solid samples has been simplified with the advent of automated systems. The simplest method of automation for this kind of analysis involves an elemental analyzer interfaced directly to the ion source of an IRMS (Isotope Ratio Mass Spectrometry). In the analyzer reduction system, an expressive amount of oxidized copper is generated as solid residue. This material is normally imported and the price is very high. A (mais) methodology was proposed for the recovery of metallic copper in order to recycle this reagent in the reduction system of a GC-IRMS, using the hydrogen gas in the vacuum line. Results show that it is possible to obtain a recycle of about 95 % of the initial metallic copper used in the reduction system.
Resumo em inglês Quantum chemistry describes the hydrogen atom as one of the few systems that permits an exact solution of the Schrödinger equation. Students tend to consider that little can be learned from the hydrogen atom and forget that it can be used as a standard to test numerical procedures used to calculate properties of multielectronic systems. In this paper, four different numerical procedures are described in order to solve the Schrödinger equation for the hydrogen atom. The (mais) basic motivation is to identify new insights and methods that can be obtained from the application of powerful numerical techniques in a well-known system.
Resumo em inglês Cu/Ni/gamma-Al2O3 catalysts were prepared by an impregnation method with 2.5 or 5% wt of copper and 5 or 15% wt of nickel and applied in ethanol steam reforming. The catalysts were characterized by atomic absorption spectrophotometry, X-ray diffraction, temperature programmed reduction with hydrogen and nitrogen adsorption. The samples showed low crystallinity, with the presence of CuO and NiO, both as crystallites and in dispersed phase, as well as of NiO-Al2O3. The cata (mais) lytic tests carried out at 400 ºC, with a 3:1 water/ethanol molar ratio, indicated the 5Cu/5Ni/Al2O3 catalyst as the most active for hydrogen production, with a hydrogen yield of 77% and ethanol conversion of 98%.
Resumo em inglês In an effort to minimize the impact on the environment, removal of pollutants, such as phenolic compounds, from the industrial wastewater has great importance nowadays because of the high toxicity and low biodegradability of these compounds. This work discusses the different methods to remove these compounds from industrial wastewater, showing their advantages and disadvantages. Advanced Oxidation Process (AOPs) are presented as a promising technology for the treatment of (mais) wastewater containing phenolic compounds. Among the AOPs, photolysis, photocatalysis and the processes based on hydrogen peroxide and on ozone are discussed with emphasis on the combined processes and the oxidation mechanisms.
Resumo em inglês This work presents two recycling processes for spent Li/MnO2 batteries. After removal of the solvent under vacuum the cathode + anode + electrolyte was submitted to one of the following procedures: (a) it was calcined (500 ºC, 5 h) and the calcined solid was submitted to solvent extraction with water in order to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Manganese was recovered as sulfate; (b) the solid was trea (mais) ted with potassium hydrogeno sulfate (500 ºC, 5 h). The solid was dissolved in water and the resulting solution was added dropwise to sodium hydroxide. Manganese was recovered as dioxide. The residual solution was treated with potassium fluoride in order to precipitate lithium fluoride.
Preparação de compostos lamelares: síntese do hidrogenofosfato de zircônio cristalino e sua intercalação com aminas. Um experimento para estudantes de graduação/ Preparation of lamellar compounds: synthesis of the crystalline zirconium hydrogenphosphate and its intercalation with amines. An experiment for undergraduate students
Resumo em inglês The present paper describes the synthesis of crystalline zirconium hydrogen phosphate by direct precipitation and its intercalation with pyridine and n-butylamine. The simple experiment was tested in the undergraduate inorganic chemistry laboratory course for chemistry students at IQ-UNICAMP using inexpensive reagents. The materials were characterized by powder X-ray diffraction and infrared analyses in order to obtain detailed information of the solid structure changes a (mais) s a result of the intercalation process. Pyridine and n-butylamine are focused in this work as clear and elucidative examples leading to acid-base interactive processes that result in the well-formed infinite sequence of inorganic lamellar structures.
Potencial hidrogeniônico de soluções de cloridrato de dobutamina expostas a condições ambientais de unidades de cuidados intensivos neonatais/ Hydrogen-ion potential of dobutamine hydrochloride solutions exposed to environmental conditions of neonatal intensive care units
Resumo em português OBJETIVO: Verificar o potencial hidrogeniônico (pH) de soluções de cloridrato de dobutamina sob condições ambientais que mimetizam unidades de cuidados intensivos neonatais. MÉTODOS: Analisou-se pH do fármaco em solução glicosada 5% ou NaCl 0,9% segundo temperatura (22 e 37 °C), luz (escuro, lâmpadas fluorescentes ambiente e equipamento de fototerapia) e equipos (incolor e âmbar) em intervalos de tempo (0, 1, 24, 48, 72 e 96 horas). RESULTADOS: Evidenciaram-se (mais) valores próximos de pH do fármaco na apresentação comercial e diluído. Obteve-se média de pH de 3,45±0,19 a 22 °C e de 3,55±0,20 a 37 °C. A média de pH das soluções mantidas no escuro foi de 3,62±0,09, na luz ambiente, de 3,63±0,07, e sob fototerapia, de 3,31±0,16. Soluções em equipos incolores tiveram média menor (3,41±0,24) do que em âmbares (3,52±0,15). Obtiveram-se menores valores de pH nas soluções sob fototerapia em equipos incolores (3,17±0,03) do que em âmbares (3,55±0,03). CONCLUSÃO: Sob a luz da fototerapia houve maior variação do pH das soluções, e o emprego de equipos âmbares minimizou tal efeito. Resumo em inglês OBJECTIVE: To verify the hydrogen-ion potential (pH) of dobutamine hydrochloride solutions under environmental conditions similar to those of neonatal intensive care units. METHODS: We analyzed the pH of the drug diluted in 5% dextrose in water or 0.9% NaCl under different conditions of temperature (22 and 37 °C) and light (dark, fluorescent light bulbs, and phototherapy equipment), using colorless and amber intravenous sets at time intervals of 0, 1, 24, 48, 72, and 96 (mais) hours. RESULTS: The pH values of the marketed form of the drug and the diluted drug were similar. The pH means were 3.45±0.19 at 22 °C and 3.55±0.20 at 37 °C. The average of the pH according to light conditions were as follows: in the dark = 3.62±0.09, under room light = 3.63±0.07, and exposed to phototherapy = 3.31±0.16. Solutions stored in colorless intravenous sets had a lower mean (3.41±0.24) than those kept in amber intravenous sets (3.52±0.15). We found lower pH values in the solutions exposed to phototherapy using colorless intravenous sets (3.17±0.03) than in those using amber intravenous sets (3.55±0.03). CONCLUSION: There was higher variation in the pH of the solutions exposed to phototherapy, and the use of amber intravenous sets reduced such effect.
Resumo em português O presente trabalho teve como objetivos avaliar os sinais clínicos, as concentrações do sulfeto de hidrogênio ruminal e as alterações anatomopatológicas associadas à intoxicação experimental por enxofre em bovinos. Foram utilizados dez bezerros mestiços leiteiros, sendo que quatro bovinos ingeriram ração sem sulfato de sódio (G1) e seis consumiram ração com sulfato de sódio (G2). Exames clínicos (temperatura retal, frequência cardíaca e respiratória e (mais) motricidade ruminal) e laboratoriais (hemograma, fibrinogênio, proteína plasmática, pH do fluido ruminal, concentração do sulfeto de hidrogênio ruminal, líquido cerebrospinal e histopatológico) foram realizados. A temperatura retal, frequência cardíaca, hemograma, fibrinogênio, proteína plasmática, pH do fluido ruminal e os valores do líquido cerebrospinal estavam dentro dos valores de referência para a espécie. Taquipnéia, hipomotricidade ruminal e elevados valores de sulfeto de hidrogênio ruminal foram observados nos bezerros do grupo G2. Um bezerro do grupo G2 apresentou sinais neurológicos e lesões histopatológicas de PEM. Dois animais de cada grupo foram eutanasiados. Lesões microscópicas foram observadas nos bezerros do G2. Histologicamente as alterações observadas foram necrose neuronal cortical e lesões hemorrágicas nos núcleos basais, tálamo, mesencéfalo, ponte e bulbo. O protocolo experimental constituído por uma dieta rica em carboidrato de alta fermentação, baixa quantidade de fibra efetiva e altos níveis de enxofre (0,52%) ocasionou alterações clinicas e histológicas e elevadas concentrações de sulfeto de hidrogênio ruminal compatíveis com quadro de intoxicação por enxofre. Resumo em inglês The aims of this study were to evaluate the clinical signs, the ruminal hydrogen sulfide concentration and the histological lesions induced by sulfur toxicosis in cattle. Ten crossbred calves were fed an experimental diet, four without sodium sulfate (G1) and six with (G2). The calves were submitted to clinical (rectal temperature, cardiac and respiratory rate and ruminal motricity) and laboratorial (hemogram, fibrinogen, total plasma protein, ruminal fluid pH, ruminal hy (mais) drogen sulfide concentration, cerebrospinal fluid and histopathological) evaluations. Rectal temperature, cardiac rate, hemogram, fibrinogen, total plasma protein, ruminal fluid pH and cerebrospinal fluid values were within normal reference ranges in animals from both groups. Ruminal hypomotricity and increased respiratory rate and ruminal hydrogen sulfide concentration occurred in G2 animals. One out of six calves in G2 developed neurological signs and lesions of PEM. Two calves of each Group were euthanized. Microscopic lesions of PEM were observed in G2 animals. Histologically there were cortical neuronal necrosis and hemorrhagic lesions in basal nuclei, thalamus, midbrain, pons and medulla oblongata. The experimental model consisting of a diet with high carbohydrate and low in long fiber content with high sulfur concentrations (0.52%) resulted in clinical and histological abnormalities and high ruminal hydrogen sulfide concentration consistent with sulpur toxicosis in cattle.
Resumo em inglês A brief discussion about the hydrogen peroxide importance and its determination is presented. It was emphasized some consideration of the H2O2 as reagent (separated or combined), uses and methods of analysis (techniques, detection limits, linear response intervals, sensor specifications). Moreover, it was presented several applications, such as in environmental, pharmaceutical, medicine and food samples.
Nióbia sintética modificada como catalisador na oxidação de corante orgânico: utilização de H2O2 e O2 atmosférico como oxidantes/ Modified synthetic niobia as catalyst in the oxidation of organic dye: utilization of H2O2 and atmospheric O2 as oxidants
Resumo em inglês In this work synthetic niobia was used to promote the oxidation of methylene blue dye in aqueous medium. The niobia was characterized by N2 adsorption/desorption, XRD and TG measurements. The presence of reactive species on the niobia surface strongly increased the oxidation rate of the methylene blue dye. The reaction mechanism was studied by ESI-MS suggesting that the oxidation of the organic dye involve oxidizing species generated mainly after previous treatment with H (mais) 2O2. It can be observed that the catalyst is a good material in the activation of gas (atmospheric oxygen) or liquid (hydrogen peroxide) oxidant agent with a total discoloration of the dye solution after only 1 h of reaction.
Resumo em inglês Zeolite catalysts have been extensively used in petroleum refining and the chemical industry although they are deactivated by coke deposition. In order to find the best condition to avoid deactivation, the coke formation on H-mordenite was studied in this work. The coke was produced during benzene transalkylation with C9+ aromatics, under several reaction conditions. It was found that hydrogenated coke was produced in all samples without affecting the selectivity of toluene and xylene formation. This is explained in terms of the mordenite structure and the presence of hydrogen.
Nanocompósitos de poliuretana termoplástica e nanotubos de carbono de paredes múltiplas para dissipação eletrostática/ Thermoplastic polyurethane and multi-walled carbon nanotubes nanocomposites for electrostatic dissipation
Resumo em inglês Polyurethane/multi-walled carbon nanotube (MWCNT) nanocomposites have been prepared with nanotube concentrations between 0.01 wt% and 1 wt%. MWCNT as-synthesized samples with ~74 nm diameter and ~7 μm length were introduced by solution processing in the polyurethane matrix. Scanning electron microscopy (SEM) images demonstrated good dispersion and adhesion of the CNTs to the polymeric matrix. The C=O stretching band showed evidence of perturbation of the hydrogen int (mais) eraction between urethanic moieties in the nanocomposites as compared to pure TPU. Differential scanning calorimetry and positron anihilation lifetime spectroscopy measurements allowed the detection of glass transition displacement with carbon nanotube addition. Furthermore, the electrical conductivity of the nanocomposites was significantly increased with the addition of CNT.
Métodos simples de formação de monocristal de substância orgânica para estudo estrutural por difração de raios X/ Simple methods of monocrystal formation of organic compounds for X-ray structural studies
Resumo em inglês This work presents three operationally simple laboratory protocols for monocrystal growth of small-molecule organic compounds, which have been applied with success in the last ten years for the formation of single crystals for X-ray structural studies. In addition, five structure hints were formulated as general guidelines for selecting a small-molecule organic compound as a candidate for monocrystal growth: molecular weight >200 D, melting point >100 ºC, two or more aro (mais) matic rings in the structure, at least two sites for intermolecular hydrogen bond formation, and a halogen or other heavy atom in the structure.
Resumo em inglês The broad variety of hydrogenation methods of polydienes is presented. Homogeneous and heterogeneous catalysis are reviewed emphasizing also hydrogen transfer from donor compounds.
Resumo em inglês This paper describes in detail a technique employed to grow quasi-spherical single crystals of noble metals for electrochemical applications, using platinum as an example. The metal beads were formed by melting the extremity of a wire in an oxygen / butane flame. X-ray techniques were used to check the crystallization and to determine the orientation of the crystals. Treatment with a pure hydrogen flame followed by a cooling procedure in a hydrogen / argon atmosphere were (mais) used for conditioning the well-defined platinum single crystal surfaces. Finally, electrochemical characterization of the Pt(111), Pt(110) and Pt(100) surfaces was done in diluted sulfuric acid solution in the hydrogen adsorption / desorption potential region.
Resumo em inglês We present a theoretical study of solvent effect on C2H5N···HF hydrogen-bonded complex through the application of the AGOA methodology. By using the TIP4P model to orientate the configuration of water molecules, the hydration clusters generated by AGOA were obtained through the analysis of the molecular electrostatic potential (MEP) of solute (C2H5N···HF). Thereby, it was calculated the hydration energies on positive and negative MEP fields, which are maxima (PEMmax (mais) ) and minima (PEMmin) when represent the -CH2- methylene groups and hydrofluoric acid, respectively. By taking into account the higher and lower hydration energy values of -370.6 kJ mol-1 and -74.3 kJ mol-1 for PEMmax and PEMmin of the C2H5N···HF, our analysis shows that these results corroborate the open ring reaction of aziridine, in which the preferential attack of water molecules occurs at the methylene groups of this heterocyclic.
Resumo em inglês A very short-strong hydrogen bond (20kcal/mol) is found in the monoanion of certain dicarboxylic acids derived from maleic and dialkylmalonic acids. Certain aromatic diamines that are known as proton sponge have exceptionally high basicity (pKa) and are only monoprotonated with strong acids like percloric acid. The closed proximity between the two basic centers provokes a strong steric interaction that is relieved upon protonation. Similar effects are found in dic (mais) arboxylic acids (hydrogen maleate and hydrogen dialkylmalonates) that present a very short distance between the two oxygens and a short-strong hydrogen bond.
Resumo em inglês Irving Langmuir received the Nobel Prize in Chemistry in 1932 "...for his outstanding discoveries and investigations within the field of surface chemistry", according to the Swedish Academy. However, few people know that his work comprises other very important contributions, and not only for chemistry, such as the discovery of plasma, the atomic hydrogen, the pure thermoionic phenomenon, the development of the cloud seeding technique for weather modification, among many o (mais) thers. This paper summarizes Langmuir's most important discoveries and theories, with an especial mention for his practical inventions and his work on the atomic theory.
Influência de M/C (M = Mo, Cu, Fe e W) incorporado à camada difusora do eletrodo de difusão de gás frente à reação de oxidação de hidrogênio na presença de CO/ The effect of M/C (M = Mo, Cu, Fe and W) in the diffusion layer of gas diffusion electrodes on the hydrogen oxidation reaction in the presence of carbon monoxide
Resumo em inglês The performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anodes is drastically lowered when CO-containing hydrogen is used to feed the system, because of the strong adsorption of CO on platinum. In the present work the effects of the presence of a conversion layer of CO to CO2 composed by several M/C materials (where M = Mo, Cu, Fe and W) in gas diffusion anodes formed by Pt catalysts were investigated. The diffusion layers formed by Mo/C e W/C show go (mais) od CO-tolerance, and this was attributed to the CO removal by parallel occurrence of the water-gas shift reaction and the so-called bifunctional mechanism.
Resumo em inglês High levels of substrate-based 1,5-stereoinduction are obtained in the boron-mediated aldol reactions of beta-oxygenated methyl ketones with achiral and chiral aldehydes. Remote induction from the boron enolates gives the 1,5-anti adducts, with the enolate pi-facial selectivity critically dependent upon the nature of the beta-alkoxy protecting group. This 1,5-anti aldol methodology has been strategically employed in the total synthesis of several natural products. At pres (mais) ent, the origin of the high level of 1,5-anti induction obtained with the boron enolates is unclear, although a model based on a hydrogen bonding between the alkoxy oxygen and the formyl hydrogen has been recently proposed.
Hidrogenação de compostos orgânicos utilizando método eletroquímico para geração de hidrogênio in situ: hidrogenação eletrocatalítica/ Hydrogenation of organic compounds by an electrochemical method for in situ hydrogen generation: electrocatalytic hydrogenation
Resumo em inglês Electrocatalytic hydrogenation (HEC) may be compared to catalytic hydrogenation (HC). The difference between these methods is the hydrogen source: HC needs a hydrogen gas supply; HEC needs a source of protons (solvent) to be reduced at a cathode surface. HEC has presented interesting advances in the last decades due to investigation of the influence of the supporting electrolyte, co-solvent, surfactant, presence of inert gas and the composition of the electrode on the rea (mais) ction. Several classes of organic compounds have been hydrogenated through HEC: olefins, ketones, aldehydes, aromatics, polyaromatics and nitro-compounds. This paper shows some details about the HEC which may be regarded as a promising technique for the hydrogenation of organic compounds both in industrial processes and in laboratories.
Fenologia, brotação de gemas e produção de frutos de macieira em resposta à aplicação de cianamida hidrogenada e óleo mineral/ Phenology, budbreak and apple fruit production by hydrogen cyanamide and mineral oil application
Resumo em português A aplicação de indutores de brotação é uma das principais estratégias de manejo utilizadas para minimizar os problemas da falta de frio em frutíferas de clima temperado. Em razão da influência dos indutores de brotação sobre a resposta produtiva das plantas, a mensuração de seus efeitos ao longo do ciclo produtivo torna-se importante. Assim, o presente trabalho foi desenvolvido no ciclo 2007/2008, em Caçador/SC, objetivando avaliar diferentes combinações d (mais) e cianamida hidrogenada e óleo mineral sobre a fenologia, brotação de gemas e produção de frutos em macieiras. O delineamento experimental foi em blocos casualizados, com seis repetições compostas de uma planta, seguindo arranjo fatorial (5x2), com cinco níveis de indutor de brotação (1. testemunha; 2. óleo mineral 3,2%; 3. óleo mineral 3,2% + cianamida hidrogenada 0,20%; 4. óleo mineral 3,2% + cianamida hidrogenada 0,39%; 5. óleo mineral 3,2% + cianamida hidrogenada 0,59%) e duas cultivares (Imperial Gala e Fuji Suprema). A aplicação dos indutores de brotação antecipou e reduziu o período de florescimento, aumentando a coincidência de florescimento das cultivares Imperial Gala e Fuji Suprema. Os indutores de brotação uniformizaram e aumentaram a brotação de gemas axilares e terminais, obtendo-se máxima brotação na cultivar Imperial Gala com 0,44% de cianamida hidrogenada e 3,2% de óleo mineral. O aumento da concentração de cianamida hidrogenada revelou a tendência de diminuir a frutificação efetiva. Observaram-se respostas diferenciadas entre tratamentos quanto à produção e à massa média dos frutos, podendo ser atribuídas ao predomínio da produção de frutos em distintas estruturas de frutificação. Resumo em inglês The budbreak promoters application is one of main management strategies used to decrease the problems of insufficient winter chilling on temperate fruit trees. Because the influence of budbreak promoters on productive behaviour of plants, detecting this effects along of productive season became important. Thus, this study was carried out during 2007/2008 season, in Caçador, Santa Catarina State, Brazil, aiming to evaluate different hydrogen cyanamide and mineral oil comb (mais) inations on phenology, budbreak and apple fruit production. The experimental design was a randomized block, with six replications, in factorial arrangement (5x2), with five budbreak promoter treatments (1. control; 2. mineral oil 3.2%; 3. mineral oil 3.2% + hydrogen cyanamide 0.20%; 4. mineral oil 3.2% + hydrogen cyanamide 0.39%; 5. mineral oil 3.2% + hydrogen cyanamide 0.59%) and two cultivars (Imperial Gala and Suprema's Fuji). The budbreak promoters application anticipated and reduced the blooming period, increasing the blooming overlap between Imperial Gala and Suprema's Fuji cultivars. The budbreak promoters equalized and increased the budbreak in axillary and terminal buds, with the major budbreak level observed in Imperial Gala cultivar with 0.44% of hydrogen cyanamide and 3.2% of mineral oil treatment. The increase of hydrogen cyanamide concentration showed the tendency to decrease the fruit set. It was observed different treatment responses on production and mean fruit weight, probably to be related to fruit production predominance in different frutification structures.
Resumo em inglês This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD (mais) on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.
Resumo em inglês The purpose of this work is to study theoretically stereoelectronic aspects of the interaction between heme and artemisinin in the transitional heme-artemisinin complex. Through semi-empirical calculations using the PM3 method, the potential energy barrier of artemisinin rotation relative to heme in the heme-artemisinin complex was studied in vacuum and in the partially solvated state. The minimum heat of formation obtained for the complex with and without water molecules (mais) is -702.39 and -100.86 kcal mol-1, respectively, which corresponds to the dihedral angle C-Fe-O1-O2 of 43.93º and 51.90º around the iron-oxygen O1 bond, respectively. The water molecules bind to heme via 13 hydrogen bonds and O-HO and 6 C-HO interactions, which accounts for -67.23 kcal mol-1. It is observed that the inclusion of water molecules does not affect significantly the stability of the heme-artemisinin complex.
Estudo por espectroscopia no infravermelho da interação metal-suporte em Pt/TiO2. A influência da adsorção de hidrogênio/ An infrared spectroscopy study of metal-support interaction on Pt/TiO2. The influence of hydrogen adsorption
Resumo em inglês The influence of the presence of hydrogen on Pt/TiO2 catalysts submitted to reduction treatment has been studied by FT-IR at room temperature. After submitting to LTR treatment, the hydrogen spillover has been detected and the presence of hydrogen at the bulk is shown to produce a strong absorption in the infrared spectral region. After HTR treatment, the hydrogen is strongly chemissorbed.
Estudo do efeito do tratamento superficial por moagem sobre as propriedades das partículas de uma liga de hidreto metálico/ Effect of a milling surface treatment on the properties of metal hydride alloy particles
Resumo em inglês This work reports results of studies on the electrochemical and structural properties of a Ti/Zr-based metal hydride alloy covered by Ni and LaNi4,7Sn0,3 powder additives by ball milling. The effect of this treatment is investigated for the activation time, hydrogen storage capacity and equilibrium pressure, cycling stability and the hydration/dehydration kinetics. Charge and discharge cycles show a significant decrease of the activation time due to an increase of the act (mais) ive area caused by the milling treatment, independent of the additive. However, other results have evidenced little effect of the milling surface treatment on the charge storage capacity, hydrogen equilibrium pressure, and hydration/dehydration kinetics, for both the Ni and LaNi4,7Sn0,3 covered materials.
Estudo do efeito de tratamentos térmicos em catalisadores de PtRu/C frente à reação de oxidação de hidrogênio na presença de CO/ Study of the effect of thermal treatments of PtRu/C catalysts on the hydrogen oxidation reaction in the presence of CO
Resumo em inglês In this work the effects of time and temperature of thermal treatments under reducing atmosphere (H2) on PtRu/C catalysts for the hydrogen oxidation reaction (HOR) in the presence of CO on a proton exchange membrane fuel cell (PEMFC) single cells have been studied. It can be seen that the increase of the treatment temperature leads to an increasing sintering of the catalyst particles with reduction of the active area, although the catalyst treated at 550 ºC presents more CO tolerance for the HOR.
Estudo do comportamento eletroquímico da enzima peroxidase na presença de peróxido de hidrogênio e ácido 5-aminossalicílico/ Investigation on electrochemical behavior of peroxidase enzyme in the presence of hydrogen peroxide and 5-aminosalicylic acid
Resumo em português O comportamento eletroquímico da enzima peroxidase (HRP) foi estudado utilizando o peróxido de hidrogênio como substrato enzimático e o ácido 5-aminossalicílico (5-ASA) como mediador de elétrons sobre eletrodo de grafite. Diversos parâmetros foram otimizados, tais como, o potencial aplicado à técnica amperométrica fixado em -0,125V, a solução tampão fosfato-citrato 0,1 mol L-1 pH 5,0 como eletrólito suporte e a proporção entre o 5-ASA e H2O2 em 1:7, entre (mais) outros. Foi observada a catálise da reação de oxidação do peróxido de hidrogênio na presença da enzima HRP e do mediador 5-ASA. O produto dessa oxidação foi reduzido na superfície do eletrodo, evidenciando um significativo aumento na intensidade da corrente catódica. Resumo em inglês The electrochemical behavior of the enzyme peroxidase (HRP) was investigated using the hydrogen peroxide as enzymatic substrate and the 5-aminosalicylic acid (5-ASA) as mediator of electrons on graphite electrodes. Several parameters were optimized, namely, the applied potential to the amperometric technique fixed in -0.125V, the 0.1 mol L-1 phosphate-citrate buffer at pH 5.0 as supporting electrolyte and the proportion between the 5-ASA and H2O2 in 1:7, among others. It (mais) was observed the catalysis of the oxidation reaction of the H2O2 in the presence of the enzyme HRP and 5-ASA. The oxidation product was reduced in the electrode surface, evidencing a significant increase in the intensity of the cathodic current.
Resumo em inglês Cu catalysts supported on CeO2, TiO2 and CeO2/TiO2 were prepared by precipitation method and used for preferential oxidation of carbon monoxide contained in a hydrogen flow generated by methane steam reforming. The samples were characterized by XRD, BET and TPR techniques. The catalytic properties were studied in the 50-330ºC range by using a quartz micro-reactor vertically positioned on an electrical furnace. The results showed that the small copper particles generated (mais) with the lower metal content are the most easily reducible and give the best catalytic performance. In respect of support effect, the strong metal-support interaction and the redox characteristics of the CuOx-CeO2 series resulted in the best catalytic results, especially with the sample with 1% copper content.
Estudo da reatividade do estado excitado triplete de 1,4-diaza-9-fluorenonas frente a doadores de hidrogênio e de elétron/ The reactivity of the triplet excited state of 1,4-diaza-9-fluorenones towards hydrogen and electron donors
Resumo em inglês The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. (mais) Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.
Resumo em inglês A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is impl (mais) emented. The magnitude of the free energy obtained from this simulation did not permit us to conclude that urea is non-planar in water.
Resumo em inglês The structure and hydration of the HNP-3 have been derived from molecular dynamics data using root mean square deviation, radial and energy distributions. Three antiparallel beta sheets were found to be preserved. 15 intramolecular hydrogen bonds were identified together with 36 hydrogen bonds on the backbone and 35 on the side chain atoms. From the point of view of the hydration dynamics, the analysis shows a high solvent accessibility of the monomer and attractive interactions with water molecules.
Esquema geral para elucidação de substâncias orgânicas usando métodos espectroscópico e espectrométrico/ General scheme for elucidating the structure of organig compounds using spectroscopic and spectrometric methods
Resumo em inglês This work describes a systematic method to be applied in undergraduate courses of organic chemistry, correlating infrared spectra, hydrogen and carbon-13 nuclear magnetic resonance, and mass spectra. To this end, a scheme and a table were developed to conduct the elucidation of the structure of organic compounds initially using infrared spectra. Interpretation of hydrogen and carbon-13 nuclear magnetic resonance spectra and of mass spectra is used to confirm the proposed structure.
Resumo em português A biossíntese dos hormônios da tireóide depende do funcionamento normal de uma série de proteínas que são necessárias tanto para a captação de iodeto através da membrana basolateral dos tireócitos como para sua incorporação à proteína aceptora, a tireoglobulina (Tg), o que ocorre na superfície apical da célula folicular. O co-transportador sódio-iodeto (NIS) é responsável pela captação tireoideana de iodeto, a primeira etapa da biossíntese hormonal (mais) tireoideana. No pólo apical dos tireócitos, o iodeto é transportado através da membrana celular pela pendrina (PDS) e subseqüentemente incorporado à Tg, uma proteína de alto peso molecular secretada no lúmen folicular. A oxidação do iodeto e sua organificação parecem ocorrer principalmente na superfície apical da célula folicular, e estas reações são catalisadas pela tireoperoxidase (TPO) na presença de peróxido de hidrogênio. Assim, a organificação tireoideana do iodo depende da atividade TPO, a qual é modulada pelas concentrações de substrato (tireoglobulina e iodeto) e cofator (peróxido de hidrogênio). A enzima responsável pela geração de peróxido de hidrogênio associada à hormonogênese tireoideana é a NADPH oxidase (ThOx), que encontra-se no pólo apical dos tireócitos, é estimulada pela tireotrofina e inibida pelo iodo. Aparentemente, a geração de peróxido de hidrogênio é o passo limitante da biossíntese dos hormônios da tireóide em condições de suficiência de iodo. Resumo em inglês Thyroid hormone biosynthesis depends on iodide uptake and its incorporation into the acceptor protein thyroglobulin (Tg), a high molecular weight protein secreted into the follicular lumen. The sodium-iodide symporter (NIS) is responsible for thyroid iodide uptake, the first step in thyroid hormonogenesis. Iodide is subsequently transported through the cellular membrane by pendrin (PDS) and then incorporated into Tg. Iodide oxidation and organification occur mainly in the (mais) thyrocyte apical surface and these reactions are catalyzed by thyroperoxidase (TPO) in the presence of hydrogen peroxide. Thus, thyroid iodide organification depends on TPO activity, which is modulated by the concentration of substrates (thyroglobulin and iodide) and cofactor (hydrogen peroxide). Hydrogen peroxide generation is catalyzed by the thyroid NADPH oxidase (ThOx), which is present in the apical pole of thyrocytes, is stimulated by thyrotropin and is inhibited by iodide. Hydrogen peroxide generation is the limiting step in thyroid hormone biosynthesis under iodine sufficiency conditions.
Resumo em inglês In this paper a general view about the modern molecular structure theory is developed discussing the ionized hydrogen molecule. We introduce some necessary approximation methods for the electronic and nuclear spectra study adopting a systematic approach. In addition though, we have performed calculations in order to illustrate these methods.
Enraizamento de estacas lenhosas de cultivares de ameixeira com aplicação de ácido indolbutírico e cianamida hidrogenada/ Hardwood cuttings rooting of plum tree cultivars with application of indolbutyric acid and hydrogen cyanamide
Resumo em português O objetivo deste trabalho foi verificar o efeito do ácido indolbutírico (AIB) e cianamida hidrogenada, no enraizamento de estacas lenhosas de três cultivares de ameixeira (Pluma 7, Rosa Mineira e Amarelinha), tratadas com concentrações de 0 e 4.000 mg L-1 de AIB e 0, 0,5 e 1% de cianamida hidrogenada. O experimento foi conduzido no período de junho a setembro de 2004, em casa de vegetação, em delineamento inteiramente casualizado, com quatro repetições e 12 esta (mais) cas por parcela, num esquema fatorial 3x3x2 (cultivares x concentrações de cianamida hidrogenada x concentrações de AIB). O uso de AIB não teve influência na formação de raízes das cultivares Pluma 7, Rosa Mineira e Amarelinha, e a aplicação de 0,5% de cianamida hidrogenada afetou o enraizamento da cultivar Amarelinha. Resumo em inglês The objective of this work was to verify the effect of indolbutyric acid (IBA) and hydrogen cyanamide on the rooting of hardwood cuttings of three cultivars of plum tree (Pluma 7, Rosa Mineira and Amarelinha), treated with IBA (0 and 4,000 mg L-1) and hydrogen cyanamide (0, 0.5 and 1%). The experiment was carried out from June to September 2004, in greenhouse, in a completely randomized design, with four replicates and 12 cuttings per plot in factorial 3x3x2 (cultivars x (mais) hydrogen cyanamide concentrations x IBA concentrations). Root formation was not influenced by IBA aplication, in Pluma 7, Rosa Mineira and Amarelinha cultivars, and the application of hydrogen cyanamide 0.5% affected rooting of the Amarelinha cultivar.
Enraizamento de estacas apicais lenhosas de figueira 'Roxo de Valinhos'com aplicação de AIB e cianamida hidrogenada/ Rooting of apical hardwood cuttings of fig tree 'Roxo de Valinhos' with application of IBA and hydrogen cyanamide
Resumo em português O objetivo do presente trabalho foi avaliar a ação do AIB e cianamida hidrogenada no enraizamento de estacas apicais lenhosas de figueira 'Roxo de Valinhos'. Estacas caulinares lenhosas da porção apical dos ramos, coletadas no final da primeira quinzena de julho, foram padronizadas com 20 cm de comprimento e diâmetro próximo a sete mm. As estacas foram tratada ou não com AIB a 2.000 mg L-1 por 10 seg. e, em seguida, foram enterradas em leito de areia umedecido sob (mais) telado constituído de sombrite com 50% de luminosidade. Imediatamente após o plantio, cinco cm do ápice das estacas foram pincelados, com diferentes concentrações de cianamida hidrogenada: 0; 5; 10; 15; 20 e 25 mL L-1. Passados 60 dias da estaquia, foram mensurados a porcentagem de estacas vivas, enraizadas, brotadas, o número médio das brotações e raízes, além do comprimento médio das brotações. Uma amostragem de cada tratamento foi transplantada para sacolas plásticas com capacidade de 3 L (30 x 18 cm), preenchidas com substrato à base de casca de pínus e foram desbrotadas, preservando apenas uma única brotação por estaca. Aos 30; 60 e 90 dias após o transplantio, mensurou-se o comprimento médio da brotação. Para a melhoria do enraizamento adventícios, emissão e crescimento das brotações em estacas lenhosas apicais de figueira, devem-se aplicar 2.000 mg L-1 de AIB associados com 10 mL L-1 de cianamida hidrogenada. Resumo em inglês The objective of the present work was to verify the action of IBA and hydrogen cyanamide in the rooting of fig tree apical cuttings 'Roxo de Valinhos'. Woody cutting of apical portion was collected in the end of first fifteen days of July, standardized with 20 cm of length and seven millimeters of diameter. The cutting was treated or not with 2000 mg L-1 of IBA for 10 seconds. Soon after, the cuttings were buried in bed of sand humidified in nursery conditions with 50% of (mais) brightness. Immediately after the plantation, five cm of the apex of the cutting was painted with a brush, with different hydrogen cyanamide concentrations: 0, 5, 10, 15, 20 and 25 mL L-1. After 60 days, the percentage of alive, rooted, sprouted, the medium number of the sprouting and roots, besides the medium length of the sprouting were evaluated. A sampling of each treatment was transplanted for plastic sacks with capacity of 3 L (30 x 18 cm), filled with substrate the base of pinus peel, preserving a unique sprouting for cutting. The 30, 60 and 90 days after the transplantation, the medium length of the sprouting was evaluated. It was concluded that the cutting apical fig tree 'Roxo de Valinhos' should be treated with 2000 mg L-1 of IBA and 10 mL L-1 of hydrogen cyanamide.
Resumo em inglês The hydrated sodium salt of EDTA, Na2H2Y·2H2O, cannot be used as a primary standard for titrations due to uncertainties in the water content. An alkalimetric titration of the homogenized solid in the presence of a small excess of BaCl2·2H2O allows one to titrate quantitatively the released two hydrogen cations with end-point indication by phenolphthalein or potentiometry. This leads one to calculate the average molar mass of the reagent and its water content (mais) , allowing to use it to prepare EDTA standard solutions. One titrated sample led to the formula Na2H2Y·1.876 H2O, and 370.01 g.mol-1 for the average molar mass.
Resumo em inglês The results of an exercise on electrochemistry for General Chemistry students are presented. The difficulty encountered by students in predicting the shift in the potential of the hydrogen electrode under non-standard conditions prompted a search in textbooks on how the subject is developed. Besides several instances of inconsistencies in defining the standard state, such as including the temperature in the definition, a number of incorrect depictions of the hydrogen elec (mais) trode were discovered. Of the 28 General Chemistry books, 16 Physical Chemistry books and 24 Internet pages, 30, 20 and 46%, respectively, showed devices that would not work in practice.
Resumo em inglês This work considers mainly the problem of environmental pollution due to the production of energy by burning fossil fuels, particularly in urban vehicles. Electrochemical energy conversion is proposed as a partial solution to this problem, through the use of hydrogen in fuel cells. In both the production of hydrogen by electrolysis and in the electrochemical processes in fuel cells, the key factor is electrocatalysis. The concept of electrocatalysis, the production of catalysts and supported catalysts and their use in practical systems for the conversion of energy is discussed.
Resumo em inglês This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and co (mais) ntinuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.
Resumo em inglês The effect of substituents on the energies and geometries of 3-hydroxypropenal was studied using the B3LYP/6-311++G(d,p) model. The hydrogen bond energies indicate that the strongest donors and the weakest acceptors present the highest and the weakest hydrogen bonds, respectively, indicating the validity of the Madsen RAHB model. Geometric parameters indicate that the intensity of the hydrogen bond is proportional to the resonance, as suggested by the RHAB model. The effe (mais) ct of substituents diverges from the model proposed by Gilli et al. Sometimes the results indicate that the donor or acceptor effect is more important than the point of substitution.
Efeitos da beta-polinitração na eficiência catalítica de rutenioporfirinas em reações de oxidação de cicloexano/ Effects of beta-polynitration on the catalytic efficiency of rutheniumporphyrins in cyclohexane oxidation
Resumo em inglês Rutheniumporphyrins, especially with several nitro groups in b-positions, were used in the cyclohexane oxidation in the presence of iodosylbenzene, hydrogen peroxide and sodium hypochlorite as oxygen donors, under mild conditions. The beta-polynitrated complexes were able to promote the catalytic cyclohexane oxidation. They show an exceptionally high catalytic efficiency and resistance to attack by strong oxidizing agents. The cyclohexane oxidation was monitored by gas ch (mais) romatography and the results showed that the beta-polynitrated rutheniumporphyrins are better catalysts when compared to other complexes not beta-polynitrated. In all cases, the 2-phenylsubstituted complexes were more efficient than 4-phenylsubstituted complexes. The importance of the ortho effect to oxidation was shown.
Efeito dos dióxidos de enxofre e de nitrogênio no desempenho de uma célula a combustível de membrana de intercâmbio de prótons/ Effect of sulfur and nitrogen dioxides on the performance of a proton exchange membrane fuel cell
Resumo em inglês There is presently much interest in the clean and efficient generation of energy by proton exchange membrane fuel cells (PEMFC), using hydrogen as fuel. The generation of hydrogen by the reforming of other fuels, anaerobic fermentation of residual waters and other methods, often produce contaminants that affect the performance of the cell. In this work, the effect of gaseous SO2 and NO2 on the performance of a H2/O2 single PEMFC is studied. The results show that SO2 decre (mais) ases irreversibly the performance of the cell under operating conditions, while NO2 has a milder effect that allows the recovery of the system.
Resumo em inglês The development of cobalt catalysts to produce hydrogen from ethanol is the goal of this investigation. Co/Al2O3 catalysts were prepared by impregnation and characterized by atomic absorption, nitrogen adsorption, X-ray diffraction, Raman spectroscopy, temperature programmed reduction and carbon analysis. The catalysts contained Co3O4 oxide and Co3+ and Co2+ species interacting with alumina. The cobalt load affects the crystal size and the crystalline structure and higher (mais) Co loads influence the reaction mechanism, changing the selectivity of the catalysts, decreasing the amount of CO produced and avoiding the formation of products catalyzed by the support. The ethanol conversion was 50-70% with 10-
Resumo em inglês New chemical systems have been recently designed for the study of complex phenomena such as oscillatory dynamics in the temporal domain and spatiotemporal pattern formation. Systems derived from oscillators based on the chemistry of bromate are the most extensively studied, with the celebrated Belousov-Zhabotinsky (BZ) reaction being the most popular example. Problems such as the formation of bubbles (CO2) and solid precipitate in the course of the reaction and the occurr (mais) ence of simply short-lived oscillations under batch conditions are very common and, in some cases, compromise the use of some of these systems. It is investigated in this paper the dynamic behavior of the bromate/hypophosphite/acetone/dual catalyst system, which has been sugested as an interesting alternative to circumvent those inconvenients. In this work, manganese and ferroin are employed as catalysts and the complete system (BrO3-/H2PO2-/acetone/Mn(II)-ferroin) is studied under batch conditions. Temporal symmetry breaking was studied in a reactor under agitation by means of simultaneous records of the potential changes of platinum and Ag/AgBr electrodes, both measured versus a reversible hydrogen electrode. Additionally, spatio-temporal formation of target patterns and spiral waves were obtained when the oscillating mixture was placed in a quasi two-dimensional reactor.
Resumo em inglês This paper describes a simple and rapid spectrophotometric method for quantitative determination of sildenafil citrate based on its reaction with p-chloranil accelerated by hydrogen peroxide, producing a stable purple compound (λmax= 535 nm). In the absence of peroxide this reaction is very slow. The experimental conditions were optimized by using response surface methodologies. Beer's law is obeyed in a concentration range of 8.52 x 10-5 - 1.70 x 10-3 mol L-1 (r = 0 (mais) .999). The detection limit was 1.96 x 10-5 mol L-1. The method was successfully applied for the determination of sildenafil citrate in medicines with good accuracy and precision.
Determinação de paracetamol em produtos farmacêuticos usando um biossensor de pasta de carbono modificado com extrato bruto de abobrinha (Cucurbita pepo)/ Determination of paracetamol in pharmaceutical products using a carbon paste biosensor modified with crude extract of zucchini (Cucurbita pepo)
Resumo em inglês Crude extracts of several vegetables such as peach (Prunus persica), yam (Alocasia macrorhiza), manioc (Manihot utilissima), artichoke (Cynara scolymus L), sweet potato (Ipomoea batatas (L.) Lam.), turnip (Brassica campestre ssp. rapifera), horseradish (Armoracia rusticana) and zucchini (Cucurbita pepo) were investigated as the source of peroxidase (POD: EC 18.104.22.168). Among those, zucchini (Cucurbita pepo) crude extract was found to be the best one. This enzyme in the pre (mais) sence of hydrogen peroxide catalyses the oxidation of paracetamol to N-acetyl-p-benzoquinoneimine which the electrochemical reduction back to paracetamol was obtained at a peak potential of ¾0.10V. A cyclic voltammetric study was performed by scanning the potential from + 0.5 to ¾ 0.5 V. The recovery of paracetamol from two samples ranged from 97.3 to 106% and a rectilinear calibration curve for paracetamol concentration from 1.2x10-4 to 2.5x10-3 mol L-1 (r=0.9965) were obtained. The detection limit was 6.9x10-5 mol L-1 and the relative standard deviation was less than 1.1% for a solution containing 2.5x10-3 mol L-1 paracetamol and 2.0x10-3 mol L-1 hydrogen peroxide (n=12). The results obtained for paracetamol in pharmaceutical products using the proposed biosensor and Pharmacopoeial procedures are in agreement at the 95% confidence level.
Determinação de arsênio em amostras da cadeia produtiva de frangos de corte por espectrometria de absorção atômica com forno de grafite/ Determination of arsenic in chicken and chicken production-related samples using graphite furnace atomic absorption spectrometry
Resumo em inglês Chicken meat is largely consumed in human nutrition and it is produced in extremely large scale in some countries, including Brazil. In this work graphite furnace atomic absorption spectrometry was used for determination of arsenic in chicken and chicken production-related samples. These samples were digested employing a microwave-assisted procedure in closed vessels using a 7 mol L-1 nitric acid solution plus concentrated hydrogen peroxide. The concentration range of tot (mais) al As determined in chicken production-related samples varied from 1.30 to 29.8 mg kg-1 of As. The detection and quantification limits reached were 0.055 and 0.182 mg kg-1, respectively (n = 15).
Determinação da origem biossintética de ácido acético através da técnica "Site Specific Natural Isotopic Fractionation Studied by Nuclear Magnetic Resonance (SNIF-NMR)"/ Biosynthetic origin of acetic acid using SNIF-NMR
Resumo em inglês The main purpose of this work is to describe the use of the technique Site-Specific Natural Isotopic Fractionation of hydrogen (SNIF-NMR), using ²H and ¹H NMR spectroscopy, to investigate the biosynthetic origin of acetic acid in commercial samples of Brazilian vinegar. This method is based on the deuterium to hydrogen ratio at a specific position (methyl group) of acetic acid obtained by fermentation, through different biosynthetic mechanisms, which result in different (mais) isotopic ratios. We measured the isotopic ratio of vinegars obtained through C3, C4, and CAM biosynthetic mechanisms, blends of C3 and C4 (agrins) and synthetic acetic acid.
Determinação da espessura da camada polimérica de fases estacionárias imobilizadas para cromatografia líquida de alta eficiência por termogravimetria/ Determination of polymeric layer thickness on immobilized stationary phases for high-performance liquid chromatography using thermogravimetric analyses
Resumo em inglês This paper presents a simple and practical thermogravimetric method for determining the layer thickness of immobilized polymer stationary phases used in reversed-phase high-performance liquid chromatography. In this method, the weight loss of different polysiloxanes immobilized onto chromatographic supports, determined over the temperature range 150-650 ºC, demonstrated excellent agreement with the sum of carbon and hydrogen content obtained by elemental analysis. The re (mais) sults presented here suggest that the thermogravimetric procedure is an accurate and precise method to determine the polymeric material content on polymer-coated stationary phases.
Desenvolvimento, caracterização e aplicação eletroanalítica de um compósito fluido de adesivo epóxi, grafite e ciclo-hexanona/ Development, characterization and electroanalytical application of a fluid composite made of epoxy adhesive, graphite, and ciclohexanone
Resumo em inglês A fluid conducting composite material prepared from graphite powder, commercial epoxy resin Araldite®, and cyclohexanone has been developed. The composition was optimized considering the mechanical properties as conductivity and adhesiveness using response surface methodology. This work employed cyclic voltammetry and amperometry to investigate the characteristics of such composite electrodes without and with the insertion of Prussian blue in the electrode body (bulk mod (mais) ified electrode). The composite electrodes were also successfully used for the amperometric detection of hydrogen peroxide at 0.0V vs Ag/AgCl.
Desenvolvimento de um spot test para o monitoramento da atividade da peroxidase em um procedimento de purificação/ Development of a spot test for peroxidase activity monitoring during a purification procedure
Resumo em inglês In this work we describe both a chromatographic purification procedure and a spot test for the enzyme peroxidase (POD: EC 22.214.171.124). The enzyme was obtained from crude extracts of sweet potatoes and the chromatographic enzyme purification procedure resulted in several fractions. Therefore a simple, fast and economic spot test for monitoring peroxidase during the purification procedure was developed. The spot test is based on the reaction of hydrogen peroxide and guaiacol, which is catalyzed by the presence of peroxidase yielding the colored tetraguaiacol.
Resumo em inglês A simple and low cost device (ca. US$ 150) that comprises two photodiodes fixed in lab-made Perspex flow cell is proposed for chemiluminescence measurements. The characteristics of the device (large observation window and reduced thickness) allow maximizing the amount of the emitted radiation detected. A sensitivity improvement of ca. 50 % was observed by employing two photodiodes for signal measurements. The performance of the device was assessed by the oxidation of lumi (mais) nol by hydrogen peroxide, yielding a linear response within the range of 2.50 to 500 µmol L-1 H2O2. The detection limit was estimated as 0.8 µmol L-1 hydrogen peroxide which is comparable with those obtained by using equipments based on photomultipliers.
Desenvolvimento de processo de produção de conjuntos eletrodo-membrana-eletrodo para células a combustível baseadas no uso de membrana polimérica condutora de prótons (PEMFC) por impressão a tela/ Development of a sieve printing process for the production of membrane electrode assembly for proton exchange membrane fuel cell
Resumo em inglês Proton exchange membrane fuel cell (PEMFC) requires membrane electrode assemblies (MEA) to generate electrical energy from hydrogen and oxygen. In this study a MEA production process by sieve printing and an ink composition were developed to produce catalyst layers of MEAs. The deposition of the exact catalyst content was possible on cathodes and anodes with only one print step. The optimal ink developed shown viscosity of 2.75 Pa s, density 1.27 g cm-3, total solid conte (mais) nt of 33.76 % and tack of 92 U.T. The electrodes prepared in only one printing step showed higher performance than those prepared in several steps.
Resumo em inglês In this work the degradation of aqueous solutions of reactive azo-dyes is reported using a combined reductive/advanced oxidative process based in the H2O2/zero-valent iron system. At optimized experimental conditions (pH 7, H2O2 100 mg L-1, iron 7 g L-1) and using a continuous system containing commercial iron wool, the process afforded almost total discolorization of aqueous solutions of three reactive azo-dyes (reactive orange 16, reactive black 5 and brilliant yellow 3 (mais) G-P) at a hydraulic retention time of 2.5 min. At these conditions the hydrogen peroxide is almost totally consumed while the released total soluble iron reaches a concentration compatible with the current Brazilian legislation (15 mg L-1).
Resumo em português Neste artigo calculamos a taxa de ionização para o átomo de hidrogênio na presença de um campo elétrico uniforme. A probabilidade de penetração da barreira é calculada usando a aproximação WKB. Para a realização desse cálculo utilizamos dois modelos de potenciais unidimensionais: no primeiro modelo o potencial coulombiano é considerado apenas na região próxima ao núcleo atômico, o que permite uma solução exata da integral a ser resolvida. No segundo m (mais) odelo o potencial coulombiano é levado em conta em todo o espaço, o que leva a uma integral cuja solução deixa de ser trivial. Contudo, é possível resolvê-la em termos de integrais elípticas. Os resultados obtidos são comparados com o resultado aceito como o correto [4F -1 exp (-2/3F )] devido a Landau e Lifshitz. Resumo em inglês In this paper we calculated the model dependence of the field ionization rate of hydrogen atom in a uniform electric field. In order to calculate the probability of barrier penetration we use semiclassical (WKB) approximation, which is calculated for two model potentials. In the model 1 the Coulomb potential is used only near the nucleus. In model 2 the Coulomb potential is used in all regions. These results are compared with the accepted result of 4F -1 exp (-2/3F ).
Resumo em português A corrosão de estruturas metálicas enterradas representa custos significativos para diversos setores industriais. A necessidade de avaliação da agressividade de solos tem levado ao estudo de medidas indiretas que correlacionam as propriedades do solo com sua corrosividade absoluta. Neste trabalho foram realizadas medidas físico-químicas e eletroquímicas para determinação de resistividade, pH, potencial de corrosão e sobretensão de hidrogênio em diferentes tipo (mais) s de solos. Tais medidas, em conjunto com ensaios de perda de massa, visaram definir um critério original para caracterizar a corrosividade de solos. Este critério é baseado na redução do hidrogênio e se aplica a solos onde tal reação é predominante. Em solos com baixos valores de resistividade, onde a reação catódica de redução do oxigênio pode estar facilitada, esse critério deve ser cuidadosamente analisado. Resumo em inglês The corrosion of buried metallic structures demands significant costs from many industrial sectors. The necessity of proper evaluation of the soil aggressiveness, for instance, requires indirect measurements that correlate the soil properties with its absolute corrosivity. In this work, physical-chemical and electrochemical parameters have been obtained for several soil samples, such as resistivity, pH, corrosion potential and hydrogen overpotential. Such measurements, in (mais) cluding weight loss results, define an original criterion to characterize the soil corrosivity. This criterion is based on the hydrogen reduction cathodic reaction. In soils with low resistivity values, oxygen reduction can be present and, in this case, the study should be carefully analyzed.
Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111), Pt(100) e Pt(110)/ The correlation between the atomic surface structure and the reversible adsorption-desorption of hydrogen on single crystal Pt (111), Pt (100) and Pt (110) electrodes
Resumo em inglês Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic (mais) properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100), Pt(110) and Pt(111), in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.
Construção e aplicação de biossensores usando diferentes procedimentos de imobilização da peroxidase de vegetal em matriz de quitosana/ Construction and analytical applications of biosensors using different immobilization procedures of vegetable peroxidase on chitosan matrix
Resumo em inglês Biosensors were developed by immobilization of gilo (Solanum gilo) enzymatic extract on chitosan biopolymers using three different procedures: glutaraldehyde, carbodiimide/glutaraldehyde and epichlorohydrin/glutaraldehyde. The best biosensor performance was obtained after the immobilization of peroxidase on chitosan with epichlorohydrin/glutaraldehyde. Linear analytical curves for hydroquinone concentrations from 2.5x10-4 to 4.5x10-3 mol L-1 with a detection limit of 2.0x (mais) 10-6 mol L-1 and recovery of hydroquinone ranging from 95.1 to 105% were obtained. The relative standard deviation was
Resumo em inglês This paper presents some results that may be used as previous considerations to a hydrogen peroxide electrogeneration process design. A kinetic study of oxygen dissolution in aqueous solution is carried out and rate constants for oxygen dissolution are calculated. Voltammetric experiments on vitreous carbon cathode shown that the low saturation concentration drives the oxygen reduction process to a mass transfer controlled process which exhibits low values of limiting cur (mais) rents. Results have shown that the hydrogen peroxide formation and its decomposition to water are separated by 400 mV on the vitreous carbon surface. Diffusion coefficients for oxygen and hydrogen peroxide are calculated using data taken from Levich and Tafel plots. In a series of bulk electrolysis experiments hydrogen peroxide was electrogenerated at several potential values, and concentration profiles as a function of the electrical charged passed were obtained. Data shown that, since limiting current plateaus are poorly defined onto reticulated vitreous carbon, cathodic efficiency may be a good criterion for choosing the potential value in which hydrogen peroxide electrogeneration should be carried out.
Resumo em inglês In a tropical coastal area. During 6 months the composition of rain samples collected simultaneously over 24h with an open collector and with an automatic opened collector (KFA - J¸lich Type) at 500m of the Atlantic coastline of Salvador were compared. All average concentrations were higher for the "total" samples than for the "wet only" samples, except for hydrogen ions, nitrate and ammonium.
Resumo em inglês The reduction kinetics of a CuO/ZnO/Al2O3 catalyst by hydrogen was investigated isothermally and by temperature programmed reduction (TPR). Two reducible Cu2+ species were detected; the first one was identified as CuO bulk and the other as Cu2+ strongly interacting with alumina, possibly in the form of copper aluminate. The activation energies for the reduction of these two species were 60 and 90 kJ mol-1, respectively, and the reaction order with respect to hydrogen was (mais) one. The isothermal reduction data showed that the isotropic growth model is the most appropriate to describe the reaction rate data for both Cu2+ species.
Resumo em português A celulose do bagaço de cana-de-açúcar foi usada para sintetizar acetato de celulose com diferentes graus de substituição, os quais foram caracterizados por ¹H-RMN através da relação entre as áreas dos picos dos átomos de hidrogênio presentes nos grupos acetato (-(C=O)OCH3) e os picos dos hidrogênios ligados aos átomos de carbono dos anéis glicosídicos. A supressão de alguns sinais foi feita para remover sinais de ressonância da água residual nos materi (mais) ais e também para remover sinais de impurezas no triacetato de celulose. Um método de deconvolução para o cálculo computacional do grau de substituição foi proposto. Os graus de substituição das amostras de acetato de celulose foram 2,94 e 2,60, o que está de acordo com os resultados por determinação química através de uma titulação ácido base. Resumo em inglês Cellulose from sugarcane bagasse was used for synthesizing cellulose acetate with different degrees of substitution, which were characterized by ¹H-NMR through the relationship between the peak areas of the hydrogen atoms of the acetate groups (-(C=O)OCH3) and the peaks of the hydrogen bonded to the carbon atoms of the glucosidic rings. Suppression of some signals was carried out in order to remove the residual water resonance in the materials and those related to impuri (mais) ties in cellulose triacetate as well. A deconvolution method for the computation of the degree of substitution of acetylation is proposed. The degrees of substitution for the cellulose samples were 2.94 and 2.60, in good agreement with those obtained by chemical determination through an acid-base titration.
Brotação e produção das videiras 'Cabernet Sauvignon' e 'Pinot Noir' submetidas a diferentes concentrações de cianamida hidrogenada/ Shoot growth and production of Cabernet Sauvignon and Pinot Noir grapevines sprayed with different concentrations of hydrogen cyanamide
Resumo em português A ausência de frio invernal na videira produz efeitos adversos, como o atraso e desuniformidade de brotação das gemas, dificuldades de manejo fitossanitário, produção escalonada e de baixa qualidade. O trabalho foi realizado no município de Garibaldi, na região da Encosta Superior do Nordeste do Estado do Rio Grande do Sul, com 640 metros de altitude, com objetivo de testar concentrações de cianamida hidrogenada de 0; 0,5; 1,0; 1,5; 2,0 e 2,5% nas cultivares vin (mais) íferas Cabernet Sauvignon e Pinot Noir. Os melhores resultados para brotação de gemas de vara foram de 1,75 e 2,0 % em 'Cabernet Sauvignon' e 'Pinot Noir', respectivamente. Concentrações superiores a 1,5 % ocasionaram uniformidade de brotação, independentemente do ano. A maior produtividade foi obtida com cianamida.hidrogenada 2,0% nas duas cultivares, com elevação média de cinco ton/ha. Houve maior fertilidade nas gemas de vara do que em esporão. Os aspectos qualitativos das uvas não foram afetados pela cianamida hidrogenada, com exceção do peso médio dos cachos na 'Pinot Noir', na safra de 2004. Resumo em inglês The lack of chilling for grapevines produces adverse effects such as the delay and unevenness of budburst; difficulties for phytosanitary procedures, extension of the harvesting period and low fruit quality. The work was carried out close to Garibaldi, at an altitude of 640 meters in the region of "Encosta Superior" Northern of the State of Rio Grande do Sul. The objective of this work was to test concentrations of hydrogen Cyanamid varying from 0; 0,5; 1,0; 1,5 ; 2,0 and (mais) 2.5% sprayed onto Cabernet Sauvignon and Pinot Noir cultivars. The best shoot growth results were obtained from sprays of 1.75% and 2.0% in Cabernet Sauvignon and Pinot Noir, respectively. Concentrations beyond to 1.5% promoted shoot growth uniformity, independent of the year. The highest productivity was obtained with 2.0% hydrogen Cyanamid in both cultivars, with an average increase of 5 ton/ha. There was a larger fertility in the cane buds than in the spurs. The qualitative aspects of the grapes were not affected by the hydrogen Cyanamid sprays except for the average weight of the Pinot Noir clusters in the 2004 harvest.
Resumo em inglês Optimum conditions to run the P Mo stage for bleaching eucalyptus kraft pulp were 90 ºC, pH 3.5, 2 h, 0.1 kg/t Mo and 5 kg/t H2O2. The P Mo stage efficiency increased with decreasing pH (1.5-5.5) and increasing temperature (75-90 ºC), time (2-4 h), and hydrogen peroxide (3-10 kg/t) and molybdenum concentration (0.1-0.4 kg/t). The implementation of the P Mo stage, as replacement for the A stage, decreased total active chlorine demand of the OAZDP sequence by 6 kg/t to re (mais) ach 90% ISO, both in laboratory and mill scale. Such practice resulted in decreased bleaching chemical costs to produce fully bleached pulp of 90% ISO.
Resumo em inglês Nickel metal hydride (Ni-MH) batteries have emerged as an alternative for replacement of nickel-cadmium batteries, because of their more environmental compatibility and high energy capacity. In this article, we described the properties and applications for Ni-MH batteries, giving some emphasis on the metal-hydride electrode, including the description of composition, the charge storage capacity and the discharge profile. The key component of the nickel-metal hydride electr (mais) ode is a hydrogen storage alloy whose composition is formulated to obtain a high stable material over a large number of charge-discharge cycles.
Resumo em português O potencial hidrogeniônico (pH) do solo é um parâmetro que indica o nível de acidez ou alcalinidade do mesmo. Sabe-se que as plantas respondem de diferentes maneiras às mudanças no pH dos solos. Poucos artigos relacionam o crescimento e produtividade de plantas medicinais à variação do pH dos solos. O objetivo deste experimento foi avaliar o efeito de diferentes potenciais hidrogeniônicos, em solo Latossolo Vermelho Distroférrico, no crescimento e produção de (mais) sálvia. Com o auxílio de curva de neutralização da acidez do solo foram aplicadas diferentes doses de CaCO3 para atingir pH de 4,5; 5,0; 5,5; 6,0 e 6,5. O experimento foi conduzido em casa de vegetação durante 18 meses, perfazendo as fases de semeadura, transplantio e três cortes. Os parâmetros avaliados foram altura de plantas, massa seca de folhas, raízes e da parte aérea (soma das massas secas das folhas, ramos e caule), área foliar e volume das raízes. O crescimento e produção das plantas de sálvia foram diretamente afetados com a variação do pH do solo. A manutenção de pH > 5,0 foi suficiente para aumentar significativamente a área foliar, a massa seca das folhas e da parte área das plantas de sálvia em 52,2%, 60,5% e 42,4%, respectivamente, e não afetou o desenvolvimento das raízes de sálvia cultivadas em solos com diferentes pHs. Resumo em inglês The soil potential of hydrogen (pH) is a parameter that indicates the acidity or alkalinity level. Plants are known to react differently to changes in the soil pH. Few studies have related growth and productivity of medicinal plants to the soil pH variation. The aim of this experiment was to evaluate the effect of different potentials of hydrogen in Oxisol on sage growth and productivity. With the aid of a soil acidity neutralization curve, different CaCO3 levels were app (mais) lied to reach pH values of 4.5, 5.0, 5.5, 6.0 and 6.5. The experiment was carried out in a greenhouse during 18 months, covering sowing, transplanting and three-pruning phases. Plant height, leaf, root and shoot dry matter (sum of leaf, branch and stem dry matter), leaf area and root volume were evaluated. Sage growth and productivity were directly affected by the soil pH variation. The maintenance of pH > 5.0 was enough to significantly increase leaf area, and leaf and shoot dry matter of sage plants at 52.2%, 60.5% and 42.4%, respectively, and did not affect root development of sage plants grown in soils presenting different pH levels.
Avaliação da susceptibilidade à fragilização induzida por hidrogênio na soldagem de um aço microligado para blindagens por meio de um ensaio de implante com geometria modificada/ Evaluation of susceptibility of hydrogen induced cracking in microalloyed armor steel welds using a geometry modified implant test
Resumo em português A susceptibilidade à fragilização induzida pelo Hidrogênio (FIH) foi avaliada em soldas de aço para blindagem temperado e revenido (T&R) de 4,5mm de espessura. As soldas foram desenvolvidas utilizando o processo SMAW com um baixo aporte de calor e consumível AWS E11018M de 2,4 mm. A susceptibilidade a FIH foi avaliada por médio de um ensaio de implante com geometria modificada em juntas soldadas com e sem aplicação de preaquecimento, utilizando consumíveis em co (mais) ndições de estocagem ideais e expostos à atmosfera. Encontrou-se que a condição de estocagem do consumível foi mais relevante que o preaquecimento na susceptibilidade ao FIH. Resumo em inglês The Hydrogen Induced Cracking (HIC) susceptibility of 4,5mm thickness quenched and tempered (Q&T) armor plate steel welding joints was evaluated. The joints were obtained using low heat input and SMAW process with 2,4 mm AWS E11018M electrode. The HIC susceptibility was evaluated using a geometry modified implant test for thin plates. The joints studied were produced with and without preheating and using welding electrodes with and without exposure to atmospheric conditio (mais) ns. The HIC resistance was severely impaired by improperly storage while preheating conditions did not preclude HIC.
Resumo em inglês A general overview about the more useful activating agents of the hydrogen peroxide in the epoxidation of unfunctionalized alkenes, focusing mechanistic proposals. Moreover, reactivity and stereochemistry, including the stereogenic effect of the hydroxyl group is presented.
Resumo em inglês Increased production of biomass is currently the only immediately accessible alternative for large-scale carbon sequestration and it can produce large amounts of food, fuel and raw materials for the chemical industry that can in turn growingly replace oil as a source of organic building blocks and also of hydrogen and sulfur. Development of processes for biomass and abundant minerals transformation into chemical raw materials should now benefit from large inputs from nano (mais) technologies, biotechnologies, information and micro-reactor technologies. Success in R&D&Innovation along this line can yield new products and processes needed to perform desirable functions within a sustainable development paradigm.
Análise estrutural de ciclodextrinas: um estudo comparativo entre métodos teóricos clássicos e quânticos/ Structural analysis of cyclodextrins: a comparative study of classical and quantum mechanical methods
Resumo em inglês In the present work, we analyzed the accuracy of distinct theoretical methods to reproduce the solid state structures of cyclodextrins. The a, b and g-cyclodextrins (CD) were considered and also their hydrates with included water molecules: a-CD.2H2O, b-CD.10H2O and g-CD.12H2O. The geometries were fully optimized using Molecular Mechanics (MM2), semiempirical (AM1 and PM3) and ab initio (HF/3-21G) methods and quantitatively compared with experimental data from X ray diffr (mais) action. The results obtained from the classical MM2 method were in best agreement with the experiment. The semiempirical and ab initio structures were also in satisfactory accordance with the experimental data. In general, the PM3 method was found to be more suitable than the AM1 to describe the CD geometries, mainly when the intramolecular hydrogen bonds are considered.
Resumo em português OBJETIVO: Este estudo objetivou quantificar o teor de ácido cianídrico em folhas de mandioca, que receberam tratamento prévio antes da secagem, e a concentração de ácido fítico na multimistura submetida à cocção úmida. MÉTODOS: Utilizou-se a multimistura produzida pela Pastoral da Criança da cidade de Pelotas (RS), constituída por: farelos de trigo (30%) e arroz (30%): farinhas de milho (15%) e trigo (10%); pós de casca de ovo (5%), de folha de mandioca (5% (mais) ) e de sementes (5%, abóbora ou girassol). Foi realizada orientação ao fornecedor da folha de mandioca sobre a forma recomendada de preparo antes da secagem. RESULTADOS: O conteúdo de ácidos cianídrico e fitatos no suplemento alimentar foram respectivamente de 85mg.kg-1 e 35.90mg.100-1. CONCLUSÃO: Verificou-se que a mudança na forma de secagem das folhas de mandioca foi eficiente para a redução de glicosídeos cianogênicos, e que o processo de torrefação dos ingredientes foi suficiente para produzir a redução de ácido fítico da multimistura aos níveis preconizados pela legislação, não sendo observadas diferenças estatisticamente significantes quando comparadas as amostras que também foram tratadas com calor úmido. Resumo em inglês OBJECTIVE: The objective of this study was to quantify the amount of hydrogen cyanide in cassava leaves that were treated before drying and the concentration of phytic acid in a multimixture submitted to wet cooking. METHODS: The multimixture produced by the Pastoral da Criança of the city of Pelotas (RS) consisting of wheat flour (30%), rice flour (30%), corn flour (15%), wheat (10%), egg shell powder (5%), cassava leaves (5%) and pumpkin or sunflower seeds (5%) was use (mais) d. The supplier was advised on how to process the cassava leaves before drying them. RESULTS: The hydrogen cyanide and phytic acid contents of the feeding supplement are 85mg.kg-1 and 35.90mg.100-1 respectively. CONCLUSION: Changing the way the cassava leaves were dried was efficient to reduce the amount of cyanogenic glucosides. The cooking process of the ingredients was enough to reduce the phytic acid content in the multimixture to the levels recommended by the legislation. Significant statistical differences were not observed between these samples and those treated with moist heat.
Adsorção e propriedades de volume de misturas binárias água álcool: um experimento didático com base em medidas de tensão superficial/ An undergraduate experiment in physical chemistry: adsorption and bulk properties of alcohol-water mixtures based on surface tension measurements
Resumo em inglês An undergraduate physical chemistry experiment based on the drop counting method for surface tension measurements is proposed to demonstrate adsorption isotherms of binary aqueous solutions of ethanol, n-propanol, and n-butanol. Excess surface is obtained by the derivative of surface tension taken with respect to alcohol activity, after this activity calculation using van Laar equation. Laboratory class contents are surface tension, excess surface, percolation of hydrogen bonds, micelle, activity, and ideal solution.
A topologia molecular QTAIM e a descrição mecânico-quântica de ligações de hidrogênio e ligações de di-hidrogênio/ The QTAIM molecular topology and the quantum-mechanical description of hydrogen bonds and dihydrogen bonds
Resumo em inglês Hydrogen bonds formed through the interaction between a high electronic density center (lone electron pairs, π or pseudo-π bonds) and proton donors cause important electronic and vibrational phenomena in many systems. However, it was demonstrated that proton donors interact with hydrides, such as alkali and alkaline earth metals (BeH2, MgH2, LiH and NaH), what yields a new type of interaction so-called dihydrogen bonds. The characterization of these interactions (mais) has been performed at light of the Quantum Theory of Atoms in Molecules (QTAIM), by which the electronic densities ρ are quantified and the intermolecular regions are characterized as closed-shell interactions through the analysis of the Laplacian field ∇2ρ.
Resumo em inglês Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-i (mais) ndandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.
Resumo em português Neste trabalho evidenciamos a importância da radiação de ponto-zero para a estabilidade do átomo de hidrogênio do ponto de vista clássico. Nossos resultados estão baseados em trabalhos anteriores de T. H. Boyer e trata-se de uma revisão do trabalho por um dos autores , que usa eletromagnetismo clássico com a introdução de elementos estocásticos. Resumo em inglês We discuss the importance of the zero-point radiation to the stability of the hydrogen atom from a classical perspective. Our review is based in previous work of Boyer on stochastic electrodynamics and in works of one of us  on the subject.