Filmes de óxidos anódicos de nióbio: efeito eletrocrômico e cinética da reação de eletro-intercalação

The aim of this work is to study the electrochromism and the reaction kinetics of lithium electrointercalation in anodic niobium oxide films. The oxide grown in an acid environment by application of an alternating potential shows interference colour (iridescence) and when reduced in lithium perclorate/PC solution, the intercalation of Li+ ions and electrons causes a reversible colour change (electrochromism), characterized here by electrochemical and optical measurements. A model where the reaction kinetics is dominated by diffusion of ionic pairs (Li+, e-) in the oxide film permitted the reproduction of current and absorbance temporal dependence, confirming the relationship between the electrochromic and electrochemical reactions. From the results obtained, a relation was established where the colour change is associated to the reduction of Nb+5 to Nb+4 ions with simultaneous cations injection.

Ozonólise das ligninas organossolve e kraft eucalipto. Parte II: cinética nos meios ácido e básico

Organosolv and kraft lignins were treated with ozone both in basic and acid media and the reaction was studied kinetically. In contrast to reported studies, ozone was more efective in basic medium. Kraft lignin was degraded faster than organosolv lignin in both media but in the basic medium the rate of reaction was very much faster than in the acid one: for kraft lignin, the observed degradation was 93% for 2 min of reaction in the basic medium and 56% for 10 min of reaction in the acid medium; for organosolv lignin, 47% and 25%, respectively, in the same times. Higher phenolic hydroxyl groups contents increase the reaction rate.

Estudio de laboratorio del efecto de las concentraciones de calcio y caseína, el pH y la temperatura sobre la incorporación de proteínas lácteas al coágulo obtenido por acción enzimática

The effect of casein concentration, Ca2+ concentration, temperature and pH on the amount and size of protein aggregates (fines) in the whey produced by enzimic coagulation of nonfat milk was studied in laboratory conditions. Casein concentrations about 0.3 g/L showed a minimal amount of caseins in the whey, with presence of small aggregates of casein micellles. Ca2+ concentrations higher than 5 mM were neccesary to reduce the whey protein to a minimum constituted by protein particles smaller than casein micelles. The coagulation temperature, in the 35 - 45oC range, produced almost no variations in the whey proteins. The obtention of a minimum amount of whey proteins was possible only in a narrow pH range around 6.4. These results pointed to casein concentration and pH as important variables to be controlled in connection with the process yield.

Cinética e mecanismo da reação de auto-oxidação de S(IV) catalisada por íons metálicos de transição

The oxidation process of sulfur (IV) species (SO2, HSO3- e SO32-) by oxygen, catalysed by trace metal ion and complexes, can play an important role in atmospheric, analytical and bioinorganic chemistry. An overview of the most important reactions in these fields is presented. A fascinating redox cycling of the metal ions and complexes during such autoxidation process was revealed by the combination of kinetics and coordination chemistry studies.

O emprego de lipases como agentes de resolução cinética de enantiômeros em síntese orgânica: aspectos gerais sobre a influência do solvente

In organic synthesis, lipases are the most frequently used biocatalysts. They are efficient stereoselective catalysts in the kinetic resolution of a wide variety of chiral compounds. The discovery that enzymes possess catalytic activity in organic solvents has made it possible to address the question of reaction medium influence on enzymatic specificity. Perhaps the most exciting and significant development in this emerging area is the discovery that enzyme specificity, in particular enantioselectivity, can be affected by changing from one organic solvent to another. This article discusses the scope and possible mechanistic models of this phenomenon in hydrolases, specially lipases, as well as directions of future research in the area.

Estudo da influência do diluente reativo PGE na cinética de cura de resina epóxi utilizada em compósitos estruturais

Phenil glycidyl ether (PGE), a monofunctional diluent, has been used in epoxy resins formulations in order to increase the toughness of the epoxy molded composite. In a systematic study concerning its influence in the cure kinetics of the epoxy resin, it was used in concentrations of 2,5; 5,0; 10 and 20% in relation to a diglycidyl ether bisphenol-A (DGEBA)/diamino diphenil-sulfone (DDS) base matrix. Dynamic and isothermal scanning analysis were carried out using a differential scanning calorimety (DSC) equipment. For all the concentrations of PGE, a n order kinetics was observed, with n varing between 0,35 -- 0,91 as a function of the increase in the PGE concentration.

Uso analítico de tecidos e de extratos brutos vegetais como fonte enzimática

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, ascorbic 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.

Determinação enzimática de dopamina em formulações farmacêuticas utilizando sistema de análise por injeção em fluxo com extrato bruto de abacate (Persea americana)

In this work, a spectrophotometric flow injection analysis system using a crude extract of avocado (Persea americana) as a source of polyphenol oxidase to dopamine determination was developed. The substrates and enzyme concentrations from 2.4x10-7 to 5.3x10-4 mol L-1 and 28 to 332 units mL-1 were evaluated, respectively. In addition, the FIA parameters such as sample loop (50 to 500 µL), flow rate (1.4 to 4.3 mL min-1) and reactor length (100 to 500 cm) were also evaluated in a 0.1 mol L-1 phosphate buffer solution (pH 7.0). Dopamine solution concentrations were determined using 277 units mL-1 enzyme solution, 400 mL enzyme loop, 375 µL sample loop, 2.2 mL min-1 flow rate and a reactor of 350 cm. The analytical curve showed a linearity from 5.3x10-5 to 5.3x10-4 mol L-1 dopamine with a detection limit of 1.3x10-5 mol L-1. The analytical frequency was 46 h-1 and the RSD lower than 0.5% for 5.3x10-4 mol L-1 dopamine solution (n=10). A paired t-test showed that all results obtained for dopamine in commercial formulations using the proposed flow injection procedure and a spectrophotometric procedure agree at the 95% confidence level.

Sínteses química e enzimática de peptídeos: princípios básicos e aplicações

This review begins with a brief discussion of the biological importance and chemical features of peptides. A description of the existing synthetic methods follows with emphasis on the basic aspects of the chemical and enzymatic syntheses. Techniques used to purify and characterize the synthesized peptides are also discussed. Finally, a few applications of the final products in chemistry, biochemistry, immunology and medicine are presented, such as identification and quantification of naturally occurring peptides, inspection of structure-activity relationships, therapeutics, development and/or improvement of analytical techniques and search for new vaccines.

Aplicação da calorimetria exploratória diferencial no estudo da cinética de transição alfa -> delta HMX

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) or octogen is a white crystalline substance which occurs in four polymorphous forms. It is used in a wide variety of military and industrial formulations owing to its suitable properties. Researchers have demonstrated the usefulness of this energetic material in explosive components. In the present work we apply differential scanning calorimetry (DSC) to measure the a ® d solid-solid phase transition energy of HMX. The results obtained by Kissinger's and Ozawa's methods were 487 and 495 kJ/mol, respectively.

Estudo da influência do solvente, carboidrato e ácido graxo na síntese enzimática de ésteres de açúcares

The aim of this work was to gain knowledge of enzymatic processes for the synthesis fatty acid esters of sugar, with the objective to develop an enzymatic process for the preparation of non-toxic biodegradable surface-active agents derived entirely from renewable resources. A wide range of data were collected for reaction conditions involving different sugars (glucose, fructose and sucrose), fatty acids (oleic, palmitic, lauric), solvents (hexane, heptane and t-butanol) and different sources of lipases in both free and immobilized forms. As a solvent t-butanol provided the best conditions to create a catalytic liquid phase in which the reaction occurs. Sugars were preferentially esterified in the following order: fructose > glucose > sucrose, depending on the enzyme preparation. For fructose no influence was found concerning de acyl donor and similar rates were achieved for all tested fatty acids. Ester synthesis was maximized for substrates containing fructose, lauric or oleic acids, t-butanol and lipase from porcine pancreas immobilized on polysiloxane-polyvinyl alcohol particles. Under such conditions molar conversions were higher than 50%.

Cinética e caracterização físico-química do fermentado do pseudofruto do caju (Anacardium occidentale L.)

The production of cashew apple wine has the purpose of minimizing the wastage in the Brazilian cashew production. Knowing that the cashew apple fermentation produces a good cashew wine, a study of alcoholic fermentation kinetics of the cashew apple and the physico-chemical characterization of the product were made. The cashew wine was produced in an stirred batch reactor. The results of the physico-chemical analysis of volatiles, residual sugars, total acidity and pH of cashew wine showed that their concentrations were within the standard limits established by the Brazilian legislation for fruit wines.

Estudo do equilíbrio e cinética da biossorção do pb2+ por saccharomyces cerevisiae

The biosorption, based on the use of biomass for removal of ions is distinguished as an innovative and promising technology when compared with the traditional methods. In this context, the aim of the present work is to use Saccharomyces cerevisiae as biosorbent for the retention of Pb2+ metal ions. Factorial design was used for evaluation of the process. The observed equilibrium data were well described by Langmuir and Freundlich adsorption isotherms. The maximum adsorption capacity was 1486.88 mg/g. The results indicated that Saccharomyces cerevisiae is suitable for biosorption of Pb2+ metal ions.

Cinética de redução do catalisador CuO/ZnO/Al2O3

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 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.

Uma perspectiva computacional sobre catálise enzimática

Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.