Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Cyclometallated compounds of intramolecular coordination.

This article supplies a review on the chemistry of cyclometallated compounds. Emphasis is given to those formed by cyclometallation reactions. In this class of complexes, called organometallic intramolecular-coordination compounds, a special attention is given to the reactivity of cyclometallated of palladium(II) due to their use in important chemical processes. Metal-carbon bonds in these palladium(II) complexes can undergo a large variety of insertion reactions and they offer a potentially important sequence in organic synthetic methodology,homogeneous catalysis and liquid crystals manufacturing.

In vitro evaluation of the microhardness of bovine enamel exposed to acid solutions after bleaching

Acid erosion is a superficial loss of enamel caused by chemical processes that do not involve bacteria. Intrinsic and extrinsic factors, such as the presence of acid substances in the oral cavity, may cause a pH reduction, thus potentially increasing acid erosion. The aim of this study was to evaluate the microhardness of bleached and unbleached bovine enamel after immersion in a soda beverage, artificial powder juice and hydrochloric acid. The results obtained for the variables of exposure time, acid solution and substrate condition (bleached or unbleached enamel) were statistically analyzed by the ANOVA and Tukey tests. It was concluded that a decrease in microhardness renders dental structures more susceptible to erosion and mineral loss, and that teeth left unbleached show higher values of microhardness compared to bleached teeth.

Mecanismos de ação e controle da digestão de proteínas e peptídios em humanos

This review aims to report the major control mechanisms of protein and peptides digestion of special interest in human patients. Regarding protein assimilation its digestive process begins at the stomach with some not so indispensable actions comparatively to those of duodenal/jejunal lumen. However even the intestine processes are partially under gastric secretion control. Proteolytic enzyme activities are related to protein structure and amino acid constituents, tertiary and quartenary structures need HCl - denaturation prior to enzymatic hydrolysis. Thereafter the exopeptidases are guided by either NH 2 (aminopeptidases) or COOH (carboxypeptidases) terminals of the molecule while endopeptidases are oriented by the specific amino acids constituents of the peptide. Both dietary and luminal secreted proteins and polypeptides undergo to either limited or complete proteolysis resulting basic or neutral free-amino acids (40%) or dioctapeptides. The brush border peptidases continue to degrade oligopeptide to di-tripeptides and neutral free-amino acids. Some peptides are uptaked by the enterocytes whose cytosolic peptidases complete the hydrolysis. Hence the digestive products flowing in the portal vein are mainly free-amino acids from either luminal or cytosolic hydrolysis and some di-tripeptides intactly absorbed. Both mechanical and chemical processes of digestion are under neural (vagal), neuroendocrinal(acetilcholine),endocrinal(gastrin, secretin and cholecystokinin) or paracrinal (histamine) controls. The gastric phase (hydrochloric acid and pepsinogen secretions) is activated by gastrin, histamine and acetilcholine which respond to both dietary-amino acids (tryptophan and phenylalanine) and mechanic distention of stomach. The pancreatic secretion is stimulated by either cephalic or gastric phases and has influence on the intestinal phase of digestion. The intestinal types of cells S and I release secretin and cholecystokinin respectively in response of acid quimo (cells S) or amino acids and peptides (cells I) in the lumen. Secretin stimulates the releasing of water, bicarbonate and enteropeptidases whereas cholecystokinin acts on pancreatic enzymes.

Cutting performance of diamond coated Si3N4 tool during turning

Silicon nitride cutting tools have been used successfully for machining hard materials, like: cast irons, nickel based alloys, etc. However these cutting tools with diamond coating present little information on dry turning operations of gray cast iron. In the present work, Si3N4 square inserts was developed, characterized and subsequently coated with diamond for dry machining operations on gray cast iron. All experiments were conducted with replica. It was used a 1500, 3000, 4500 m cutting length, feed rate of 0.33 mm/rev and keeping the depth of cut constant and equal to 1 mm. The results show that wear in the tool tips of the Si3N4 inserts, in all cutting conditions, was caused by both mechanical and chemical processes. To understand the tool wear mechanisms, a morphological analysis of the inserts, after experiments, has been performed by SEM and optical microscopy. Diamond coated PVD inserts showed to be capable to reach large cutting lengths when machining gray cast iron. © (2010) Trans Tech Publications.

Formação de compostos de alumínio por associação radioativa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização estrutural e propriedades óticas e mecânicas do diglime polimerizado a plasma

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação dos atributos do solo sob diferentes ocupações na microbacia hidrográfica do córrego da Fazenda Glória Em Taquaritinga (SP)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação in vitro da microdureza superficial do esmalte bovino exposto a soluções ácidas, após receber ou não, clareamento com peróxido de hidrogênio a 35%

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Simulação numérica da gaseificação de biomassa em leito fixo

O objetivo deste trabalho foi avaliar a potencialidade das sementes de açaí rejeitadas após beneficiamento em Belém – Pará, a fim de ser usada como fonte de biomassa para a produção de energia por gaseificação. Resultados da análise elementar obtidas no LABCAT – UNB em base seca foram obtidas com percentuais de Carbono, 46,06 %, Hidrogênio 6,01 % Oxigênio 43,37 %, Nitrogênio 4,33 % e Enxofre 0,08%. Tais valores entre outros parâmetros obtidos em estudo experimental realizados por Santos 2011 e Cruz, 2010, foram utilizados para realizar uma simulação numérica do processo de gaseificação por meio de um código FORTRAN zero dimensional desenvolvido especificamente para esta finalidade. Variações da influência da razão de equivalência e teor de umidade nas concentrações de CO, H2 e CH4 foram comparados a resultados experimentais. Um modelo transiente unidimensional também foi analisado. Utilizando a aplicação de um mecanismo de pirólise de dois passos onde o alcatrão primário (ou oxigenados) são inicialmente formados e então craqueados em alcatrão secundário (ou hidrocarbonetos) e outros gases combustíveis. Assim se revela a complexidade dos processos físicos e químicos que ocorrem no reator pelo uso do balanço de energia e massa e com informações das taxas de reação das reções químicas e os processos de transporte físicos. O modelo computacional é capaz de prever o perfil da composição de gases, temperatura, alcatrão primário e secundário ao longo do eixo longitudinal do gaseificador. Foram obtidos resultados para simulações realizadas nos dois modelos e posteriormente analisado tal comportamento em comparação ao resultado experimental obtidos por Santos (2011).

Estudo experimental de chamas difusivas livres turbulentas de gás natural submetidas a oscilações acústicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da distribuição e do potencial de metilação do mercúrio em solos e sedimentos de áreas a serem inundadas para aproveitamento hidrelétrico: Vinicius Marques Gomes. -

Pós-graduação em Química - IQ

Relações entre produção de biogás em aterro sanitário e variações no potencial elétrico natural

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo para a implementação de um sistema de desbaste de cobre para manufatura de placas de circuito impresso

This paper presents a study on the development of a manufacturing system of printed circuit boards through copper milling. An advantage of this system is the replacement of chemical processes by physical process presenting a sustainable solution. The paper uses programs that will generate G-code needed to establish the coordinates where the milling forms the tracks. After obtaining the code, it will be transformed into steps that will be sent through the serial port to the microcontroller and the serial communication control will be in software. After obtaining information the microcontroller will execute the movement of the stepper motors through their drivers, H-bridge, the microcontroller also drives the spindle motor responsible for rotating the grinding tool, using a driver with a optocoupler and TRIAC