Caracterização ácido-base da superfície de espécies mistas da alga Spirulina através de titulação potenciométrica e modelo de distribuição de sítios discretos

Acid base properties of mixed species of the microalgae Spirulina were studied by potentiometric titration in medium of 0.01 and 0.10 mols L-1 NaNO3 at 25.0±0.10 C using modified Gran functions or nonlinear regression techniques for data fitting. The discrete site distribution model was used, permitting the characterization of five classes of ionizable sites in both ionic media. This fact suggests that the chemical heterogeneity of the ionizable sites on the cell surface plays a major role on the acid-base properties of the suspension in comparison to electrostatic effects due to charge-charge interactions. The total of ionizable sites were 1.75±0.10 and 1.86±0.20 mmolsg-1 in ionic media of 0.01 and 0.10 mols L-1 NaNO3, respectively. A major contribution of carboxylic groups was observed with an average 34 and 22% of ionizable sites being titrated with conditional pcKa of 4.0 and 5.4, respectively. The remaining 44% of ionizable sites were divided in three classes with averaged conditional pcKa of 6.9, 8.7 and 10.12, which may be assigned respectively to imidazolic, aminic, and phenolic functionalities.

Extracellular disulfide exchange and the regulation of cellular function

An emerging concept is that disulfide bonds can act as a dynamic scaffold to present mature proteins in different conformational and functional states on the cell surface. Two examples are the conversion of the receptor, integrin a alpha(IIb)beta(3), from a low affinity to a high affinity state, and the interaction of CD4 receptor with the HIV-1 envelope glycoprotein gp120 to promote virus-cell fusion. In both of these cases there is a remodeling of the protein disulfide bonding pattern. The formation and rearrangement of disulfide bonds is modulated by a family of enzymes known as the thiol isomerases, which include protein disulfide isomerase (PDI), ERp5, ERp57, and ERp72. While these enzymes were reported originally to be restricted in location to the endoplasmic reticulum, in some cells thiol isomerases are found on the cell surface. This may indicate a wider role for these enzymes in cell function. In platelets it has been shown that reagents that react with cell surface sulfhydryl groups are capable of blocking a number of functional responses, including integrin-mediated aggregation, adhesion, and granule secretion. Furthermore, the use of function blocking antibodies to either PDI or ERp5 causes inhibition of these functional responses. This review summarizes current knowledge of the extracellular regulation of disulfide exchange and the implications of this in the regulation of cell function.

Heterogenisation of Os species on MCM-41 structure for epoxidation of trans-stilbene

Metal organic chemical vapour deposition technique (MOCVD) has been used to immobilise Os species onto the internal porous structure of MCM-41. Evidence suggests that volatile Os-3(CO)(12) cluster reacts with surface silanol groups of the MCM-41 via an oxidative addition reaction to yield a trinuclear HOs3(CO)(10)(OSi-) surface species. After heat treatment in air or at their very low surface coverage, these triangular sites break up to partially oxidised mononuclear surface species. In the presence of tert-butyl hydroperoxide (TBHP) as an oxidant, we demonstrate that the mononuclear species form extremely active species that catalyse the oxidation of trans-stilbene selectively to the corresponding epoxide. By carefully controlling the parameters of the MOCVD method (loading and calcination temperature), we report a new class of optimised MCM-41 porous heterogeneous catalysts carrying isolated but active Os sites for the selective oxidation of trans-stilbene in liquid phase. The reaction selectivity of the solid supported Os is apparently higher than the soluble homogeneous Os-3(CO)(12) cluster. It is envisaged that our solid supported catalysts not only facilitate separation from products but also offer an excellent utilisation of Os for catalysis. (C) 2003 Elsevier Science B.V. All rights reserved.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Molecular dynamics simulation insight into the mechanism of phenol adsorption at low coverages from aqueous solutions on microporous carbons

MD simulation studies showing the influence of porosity and carbon surface oxidation on phenol adsorption from aqueous solutions on carbons are reported. Based on a realistic model of activated carbon, three carbon structures with gradually changed microporosity were created. Next, a different number of surface oxygen groups was introduced. The pores with diameters around 0.6 nm are optimal for phenol adsorption and after the introduction of surface oxygen functionalities, adsorption of phenol decreases (in accordance with experimental data) for all studied models. This decrease is caused by a pore blocking effect due to the saturation of surface oxygen groups by highly hydrogen-bounded water molecules.

Magnetic coupled electrochemistry: Exploring the use of superparamagnetic nanoparticles for capturing, transporting and concentrating trace amounts of analytes

We propose the use of functionalized superparamagnetic nanoparticles for capturing, and transporting analytes, in association with an external miniature magnet to deposit such nanocarrier species at the electrode surface. This approach can be employed for the electroanalytical determination of chemical species capable of interacting with the nanoparticles, or in the opposite case, to block their response at the electrode surface. The concept was successfully demonstrated by using aminofunctionalized nanoparticles to block the discharge of hexacyanoferrate(II) ions, and to enhance the signals of aquapentacyanoferrate(II) ions via coordination to the surface amino groups. Selective analysis was also performed for silver ions, surpassing the stripping methods in terms of versatility and usefulness. (C) 2010 Elsevier B.V. All rights reserved.

Estudo da molhabilidade de tecidos 100% poliéster tratados em plasma N2/O2 em função do seu envelhecimento natural

This work reports the influence of the poly (ethylene terephthalate) textile surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min. Other parameters, such as working gas composition and treatment time, were modified as the following: to the O2 plasma modified samples only the treatment time was changed (10, 20, 30, 40, 50 and 60 minutes). To the plasma with O2 and N2 only the chemical concentrations were changed. Through Capillary tests (vertical) an increase in textile wettability was observed as well as its influence on aging time and its consequence on wettability. The surface functional groups created after plasma treatments were investigated using X-ray Photoelectron Spectroscopy (XPS). The surface topography was examined by scanning electron microscope (SEM)

Efeito da localização do nó de sutura na recuperação morfofuncional do tendão flexor digital profundo do membro torácico do cão após tenorrafia experimental

Este estudo teve por escopo comparar a influência do nó de sutura em três diferentes localizações na recuperação morfofuncional do tendão flexor digital profundo (TFDP) do cão. Foram utilizados 20 cães divididos em três grupos de oito, sete e cinco animais. Os TFDP do segundo e quinto dedos do membro torácico esquerdo foram seccionados e suturados pela técnica de Kessler modificada, alterando-se a localização do nó e o tipo de sutura no epitendíneo. No grupo um, o nó da sutura ficou localizado na região ventral do tendão e no grupo dois na face dorsal. em ambos os grupos, o epitendão foi suturado com pontos simples separados. No grupo três, o nó da sutura ficou interno ao endotendíneo e o epitendíneo foi suturado com ponto simples contínuo. Após a cirurgia, foi realizada diariamente a movimentação passiva controlada do membro do primeiro ao 15º dia. No 7º e no 15º dia os animais foram sacrificados por anestesia profunda e os tendões foram colhidos para avaliação macroscópica do processo de reparo tendíneo. O critério de comparação utilizou como parâmetros para avaliar a recuperação morfofuncional a ruptura do tendão, o afastamento dos cotos e a coaptação completa dos cotos tendíneos. O grupo que apresentou melhor resultado com relação aos parâmetros avaliados foi o terceiro, com ausência de ruptura e índice de afastamento de apenas 2,5% dos cotos tendíneos. Os resultados encontrados permitem concluir que a localização do nó de sutura na tenorrafia do TFDP interfere na resposta reparadora e biomecânica.

Effect of oral hygiene education and motivation on removable partial denture wearers: longitudinal study

The purpose of this study was to determine the effect of two different preventive oral hygiene education and motivation programmes on the plaque and gingival index, as well as denture hygiene of patients provided with removable partial denture (RPD) during a 12-month follow-up.A total of 53 partially edentulous patients were recruited for this study. The presence or absence of plaque and gingival bleeding by gentle probing was scored on all tooth surfaces at the preliminary visit. The plaque and gingival indexes were measured using the Loe index. Following treatment, the patients were randomly divided into three groups. In Control Group I, subjects were instructed to continue their personal oral hygiene routine. In Group II, participants were given verbal instructions and a self-educational manual on oral hygiene without illustrations. In Group III, oral hygiene guidance was delivered using a combination of verbal instructions and a self-teaching manual. To evaluate the effect of the different modes of instruction, the presence or absence of plaque and gingival bleeding was scored on all tooth surfaces (day zero examination) and re-examined 7, 15 and 30 days, 3, 6 and 12 months following RPD placement. The state of denture hygiene was evaluated 7, 15 and 30 days and 3, 6 and 12 months following rehabilitation. Parametric statistics was applied to dental plaque and gingival indexes. For accumulation of plaque and calculus on the RPD, non-parametric statistic was applied.The frequency of plaque found during the preliminary visit was higher than that found in the other periods. With regard to gingival index, significant difference was found between the preliminary visit examination and other periods. There was a significant difference in the plaque accumulation on the denture surface between groups I and III.The different methods of oral hygiene instruction used in this study indicate that the type of education was not of significant importance.

Effect of conditioning methods on the microtensile bond strength of phosphate monomer-based cement on zirconia ceramic in dry and aged conditions

The objective of this study was to evaluate the durability of bond strength between a resin cement and aluminous ceramic submitted to various surface conditioning methods. Twenty-four blocks (5 X 5 X 4 mm 3) of a glass-in filtrated zirconia-alumina ceramic (inCeram Zirconia Classic) were randomly divided into three surface treatment groups: ST1-Air-abrasion with 110-mu m Al2O3 particles + silanization; ST2-Laboratory tribochemical silica coating method (110-mu m Al2O3, ilO-PM Silica) (Rocatec) + silanization; ST3-Chairside tribochemical silica coating method (30-mu m SiOx) (CoJet) + silanization. Each treated ceramic block was placed in its silicone mold with the treated surface exposed. The resin cement (Panavia F) was prepared and injected into the mold over the treated surface. Specimens were sectioned to achieve nontrimmed bar specimens (14 sp/block) that were randomly divided into two conditions: (a) Dry-microtensile test after sectioning; (b) Thermocycling (TC)-(6,000X, 5-55 degrees C) and water storage (150 days). Thus, six experimental groups were obtained (11 = 50): Gr1-ST1 + dry; Gr2-ST1 + TC. Gr3-ST2 + dry; Gr4-ST2 + TC; Gr5-ST3 + dry; Gr6ST3 + TC. After microtensile testing, the failure types were noted. ST2 (25.1 +/- 11) and ST3 (24.1 +/- 7.4) presented statistically higher bond strength (MPa) than that of STI (17.5 +/- 8) regardless of aging conditions (p < 0.0001). While Gr2 revealed the lowest results (13.3 +/- 6.4), the other groups (21.7 +/- 7.4-25. 9 +/- 9.1) showed statistically no significant differences (two-way ANOVA and Tukey's test, a 0.05). The majority of the failures were mixed (82%) followed by adhesive failures (18%). Gr2 presented significantly higher incidence of ADHESIVE failures (54%) than those of other groups (p = 0.0001). Both laboratory and chairside silica coating plus silanization showed durable bond strength. After aging, airabrasion with 110-mu m Al2O3 + silanization showed the largest decrease indicating that aging is fundamental for bond strength testing for acid-resistant Arconia ceramics in order to estimate their long-term performance in the mouth. (c) 2007 Wiley Periodicals, Inc.

2-DIMENSIONAL QUANTUM GAS

Identical impenetrable particles in a 2-dimensional configuration space obey braid statistics, intermediate between bosons and fermions. This statistics, based on braid groups, is introduced as a generalization of the usual statistics founded on the symmetric groups. The main properties of an ideal gas of such particles are presented. They do interpolate the properties of bosons and fermions but include classical particles as a special case. Restriction to 2 dimensions precludes lambda points but originates a peculiar symmetry, responsible in particular for the identity of boson and fermion specific heats.

Hydrophilization of PVC surfaces by argon plasma immersion ion implantation

Commercial polyvinylchloride (PVC) sheets were treated by plasma immersion ion implantation, PIII. Samples were immersed in argon glow discharges and biased with 25 kV negative pulses. Exposure time to the bombardment plasma changed from 900 to 10,800 s. Through contact angle measurements, the effect of the exposure time on the PVC wettability was investigated. Independent of t, all samples presented contact angles, theta, equal to zero after the treatment. However, in some cases, surface hydrophilization was not stable, as revealed by the temporal evolution of theta. Samples bombarded for shorter periods recovered partially or totally the hydrophobic character while the one exposed for the longest time stayed highly hydrophilic. These modifications are ascribed to the Cl loss and O incorporation as shown by XPS measurements. Furthermore, the mobility of surface polar groups and the variation in the cross-linking degree can also affect the PVC wettability.

Avaliação in vitro da resistência de união do cerômero ao sistema de cimentação adesiva, através do teste de micro-tração. Efeito de diferentes tratamentos de superfície

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

Obtenção e caracterização de carvão ativado de caroço de buriti (Mauritia flexuosa L. f.) para avaliar o processo de adsorção de uma solução de Cu (II)

Produziu-se carvão de caroço de buriti (CCB) a partir do rejeito da produção artesanal do fruto, destinado à extração de óleo, à temperatura de 400ºC. O CCB então foi ativado a temperaturas de 800ºC e 900ºC. Ensaios de adsorção foram executados para se avaliar o desempenho dessas temperaturas de ativação na adsorção de uma solução de cobre (II) de concentração inicial conhecida de 50 mg/L. Após a análise dos resultados, decidiu-se pela ativação do carvão a 900ºC. Caracterizou-se o carvão ativado do caroço de buriti (CACB) a 900ºC de acordo com as propriedades comerciais, tais como: área específica, porosimetria, densidades aparente e real, porosidade de um leito fixo, microscopia eletrônica de varredura, conteúdo de cinzas, pH, umidade, carbono fixo e grupos funcionais de superfície ácida presentes no CACB. Realizaram-se ensaios de equilíbrio de adsorção para se determinar a influência do diâmetro das partículas de CACB (D < 0,595 mm; 0,595 < D < 1,19 mm e D > 1,19 mm); a influência do tempo de contato adsorvente/adsorvato (15, 30, 60, 120, 180, 240 e 300 minutos); a influência do pH (3,00; 4,01; 5,18 e 6,00) e a influência da concentração inicial da solução de cobre (II) (5, 10, 30, 50, 80, 100 e 200 mg/L) para se avaliar a eficiência de remoção. Os resultados mostraram uma maior eficiência de remoção de cobre (II) para o diâmetro D < 0,595 mm; para o tempo de contato de 300 minutos; para o pH de 4,01 e para as concentrações iniciais de cobre (II) de 50 e 80 mg/L. Os modelos matemáticos de Langmuir e Freundlich foram aplicados para os dados de equilíbrio de adsorção. O modelo matemático de Langmuir foi o que melhor se ajustou aos dados de equilíbrio. De acordo com os dados da cinética de equilíbrio, observa-se que a partir do tempo de contato de 15 minutos todas as concentrações de equilíbrio ficaram abaixo do máximo permitido de 1,0 mg/L previsto pela legislação CONAMA nº 357/2005 para lançamento de efluentes em corpos receptores. Os resultados experimentais encontrados são indicativos de que é possível a remoção de cobre (II) de efluentes industriais utilizando CACB ativado fisicamente a 900ºC por um período de 60 minutos.

Adsorção de cromo (VI) por carvão ativado granular de soluções diluídas utilizando um sistema batelada sob pH controlado

Na Amazônia o cromo é empregado principalmente na indústria de couro e de madeira, sendo responsável por vários problemas de saúde porque é tóxico para os seres vivos. A remoção de cromo de efluentes industriais é feita por meio de diversos processos como a adsorção. Este trabalho mostra os resultados da adsorção de Cr(VI) por carvão ativado granular comercial (CAG) como adsorvente de soluções diluídas empregando um sistema de adsorção batelada com controle de pH. Os grupos funcionais da superfície do CAG foram determinados pelo método de Boehm. Além disso, o efeito do pH na adsorção de Cr(VI), o equilíbrio e a cinética de adsorção foram estudados nas condições experimentais (pH = 6, MA = 6g, tempo de adsorção 90min.). Na superfície do CAG, os grupos carboxílicos foram determinados em maior concentração (MAS=0,43 mmol/gCAG), estes, presentes em concentrações elevadas aumentam a adsorção do metal, principalmente em valores de pH ácidos. A capacidade de adsorção é dependente do pH da solução, devido a sua influência nas propriedades de superfície do CAG e nas diferentes formas iônicas das soluções de Cr(VI). Os dados de equilíbrio da adsorção foram ajustados satisfatoriamente pela isoterma de Langmuir (R²=0,988), tipo favorável. A partir da cinética de adsorção a 5mg/L e 20mg/L, os resultados obtidos foram compatíveis com o valor limite preconizado na legislação nacional (Res. nº 357/05). Portanto, para o sistema experimental utilizando CAG foi eficiente na remoção de Cr(VI) a partir de correntes líquidas contendo baixas concentrações do metal.