932 resultados para heterogeneous polymerization
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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An investigation was made on the adsorption and kinetics of photodegradation of potassium hydrogenphthalate in an aqueous suspension of TiO2. Two models, Langmuir and Freundlich, were used to describe the adsorption process and the model proposed by Langmuir-Hinshelwood (L-H) was employed to describe the kinetics of the photodecomposition reactions of hydrogenphthalate. The results of the adsorptions were fitted to the models proposed by Langmuir and Freundlich. Adsorption was found to be a function of the temperature, with adsorption capacity increasing from 2.4 to 4.5 mg/g when the temperature rose from 20 to 30 degrees C. The kinetic model indicates that the rate constant, k, of the first order reaction, is high in the 10.0 to 100 mg/l interval, which is coherent with the low value of the adsorption constant, K. The results fitted to the L-H model led to an equation that, within the range of concentrations studied here, theoretically allows one to evaluate the photodegradation rate. (c) 2005 Elsevier Ltd. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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psi-Condensation of DNA fragments of about 4 kbp was induced by poly(ethylene glycol) (PEG), with degrees of polymerization ranging from 45 to 182, and univalent salt (NaCl). Using circular dichroism spectroscopy, we were able to accurately determine the critical amount of PEG needed to induce condensation, as a function of the NaCl concentration. A significant dependence on the PEG degree of polymerization was found. Phase boundaries determined for the multimolecular condensation were very similar to those observed previously for the monomolecular collapse, with two asymptotic regimes at low and high salt concentrations. We analyze our data using a theoretical model that properly takes into account both the polyelectrolyte nature of the DNA and the liquid crystallinity of the condensed phase. The model assumes that all PEG is excluded from the condensates and shows reentrant decondensation only at low salt. We also systematically study reentrant decondensation and find a very strong dependence on PEG molecular weight. At low PEG molecular weight, decondensation occurs at relatively low concentrations of PEG, and over a wide range of salt concentrations. This suggests that in the reentrant decondensation the flexible polymers used are not completely excluded from the condensed phase.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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In this work, the effect of cerium (IV) ammonium nitrate (CAN) addition on the polymerization of bis-[triethoxysilyl]ethane (BTSE) film applied on carbon steel was studied. The electrochemical characterization of the films was carried out in 0.1 mol L(-1) NaCl solution by open-circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance spectroscopy (EIS). Morphological and chemical characterization were performed by atomic force microscopy (AFM), contact angle measurements, infrared-spectroscopy, nuclear magnetic resonance and thermogravimetric analysis. The results have clearly shown the improvement on the protective properties of the Ce(4+) modified film as a consequence of the formation of a more uniform and densely reticulated silane film. A mechanism is proposed to explain the accelerating role of Ce(4+) ions on the cross-linking of the silane layer. (C) 2008 Elsevier Ltd. All rights reserved.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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No presente trabalho, testou-se o efeito de fatores químicos liberados por coespecíficos sobre o crescimento e sua variabilidade no grupo (crescimento heterogêneo, CHet), numa espécie gregária, o curimbatá, Prochilodus lineatus. O CHet foi avaliado pelo coeficiente de variação do peso dos animais, em dois períodos consecutivos de 21 dias. Os peixes foram agrupados em aquários (4 peixes cada) que receberam água corrente, com vazão constante, de tanques contendo (C) ou não (N) coespecíficos. Quatro condições foram delineadas de acordo com a água que abastecia os aquários: a) água com contato prévio com coespecíficos durante todo o experimento (CC); b) água sem contato prévio com coespecíficos durante todo o experimento (NN); c) água com contato prévio com coespecíficos apenas no primeiro período, 0 a 21 dias (CN); e d) apenas no período de 21 a 42 dias (NC). Ao término dos experimentos, verificou-se que ocorre modulação química sobre a variabilidade de crescimento em P. lineatus: os peixes que receberam água com contato prévio com coespecífico (C) apresentaram exacerbação do CHet. Fato que corrobora a idéia de que o mecanismo predominante da determinação da variação intra-específica do crescimento, em espécies gregárias, está associado à ação de fatores químicos liberados por coespecíficos.
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The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe-imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated (FeP)-P-III and high-spin mono-coordinated (FeP)-P-III species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated (FeP)-P-III. These FePIPG catalysts also contain (FeP)-P-II species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe-O ligation and they are present as high-spin (FeP)-P-III species. The cationic FePs supported on SiSO3- are also high-spin (FeP)-P-III species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3- groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices,both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3- shows that this FeP maintains its activity in a second reaction. (C) 1999 Elsevier B.V. B.V. All rights reserved.
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Due to their excellent aesthetics, photopolymers have been extensively used in several dentistry applications. However, several problems are reported, e.g. low mechanical and abrasion resistance, shrinkage during polymerization, etc. Properties of the final restorations are intrinsically related to the polymerization stage, which can be conveniently studied by photocalorimetry. In the present work the polymerization reaction and the filler content of different photocurable commercial dental methacrylate-based composites were studied by means of photocalorimetry and thermogravimetry, respectively. The results show that the values of curing rate, the heat of polymerization and the filler content vary significantly from one composite to another.
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The two-dimensional hybrid organic-inorganic materials Zn-2-Cr and Zn-2-Al-LDHs (Layered Double Hydroxides) containing 4-(1H-pyrrol-1yl)benzoate anions as the interlayer anions were synthesized by the co-precipitation method at constant pH followed by subsequent hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, ESR, TGA, and TEM. The basal spacing found by the X-ray diffraction technique is coincident with the formation of bilayers of the intercalated anions. Solid-state C-13 NMR and ESR data strongly suggest the partial in situ polymerization of the 4-(1H-pyrrol-1yl)benzoate anions during coprecipitation. (c) 2006 Elsevier Ltd. All rights reserved.