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Monomers of L-alanine (ALA) were isolated in cryogenic nitrogen matrices at 14 K. Two conformers were identified for the compound trapped from the gas-phase into the solid nitrogen environment. The potential energy surface (PES) of ALA was theoretically calculated at the MP2 and QCISD levels. Twelve minima were located on this PES. Seven low-energy conformers fall within the 0-10 kJ mol(-1) range and should be appreciably populated in the equilibrium gas phase prior to deposition. Observation of only two forms in the matrices is explained in terms of calculated barriers to conformational rearrangements. All conformers with the O=C-O-H moiety in the cis orientation are separated by low barriers and collapse to the most stable form I during deposition of the matrix onto the low-temperature substrate. The second observed form II has the O=C-O-H group in the trans orientation. The remaining trans forms have very high relative energies (between 24 and 30 kJ mol(-1)) and are not populated. The high-energy trans form VI, that differs from I only by rotation of the OH group, was found to be separated from other conformers by barriers that are high enough to open a perspective for its stabilization in a matrix. The form VI was photoproduced in situ by narrow-band near-infrared irradiation of the samples at 6935-6910 cm(-1), where the first overtone of the OH stretching vibration in form I appears. The photogenerated form VI decays in N2 matrices back to conformer I with a characteristic decay time of ∼15 min. The mechanism of the VI → I relaxation is rationalized in terms of the proton tunneling.

This paper evaluates the effects of different light sources on the monomer conversion (DC%) and Vickers microhardness number (VHN) of a nanocomposite resin. Three different depths were measured in this study (1, 2 and 3 mm), and photoactivation methods including a halogen lamp, a LED and an argon ion laser were used. In contrast to other studies, the conditions for each photoactivation source such as the exposure time and the same power density were considered and kept the same. It was also shown that increasing the depth lowered the VHN. At each of the depths, it was observed that the three light sources behaved similarly. The correlation between the VHN and DC% is shown. However, only a weak correlation was observed, which implies that a higher DC% value does not necessarily indicate a higher VHN.

Este estudo avaliou o efeito da concentração de solvente na resistência coesiva de um adesivo experimental contendo um derivado do difeniliodônio. Uma blenda monomérica baseada em Bis-GMA, TEGDMA e HEMA foi utilizada como resina adesiva modelo. Foram avaliados dois sistemas de fotoiniciação: um sistema bináriocanforquinona (CQ) e etil 4-dimetilamino benzoato (EDAB)] e um sistema ternário [CQ, EDAB e hexafluorfosfato de difeniliodônio (DPI)]. Nestas resinas foram adicionadas diferentes concentrações de etanol, 0, 5, 10, 20, 30, 40% e teste de resistência coesiva foi utilizado para investigar o efeito deste solvente sobre as propriedades do material. A presença de solvente reduziu a resistência coesiva do polímero, independentemente do sistema de fotoiniciação utilizado. Além disso, o uso do sal de iodônio no sistema de fotoiniciação aumentou a resistência coesiva quando comparado com o sistema binário, e independentemente da concentração de solvente, a resistência coesiva dos polímeros contendo difeniliodônio foi superior à do sistema binário de fotoiniciação. This study evaluated the effect of organic solvent concentration on the tensile strength for an experimental adhesive resin containing a ternary photoinitiator system. A monomer blend based on the Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin. Two photoinitiation systems were used: a binary system camphorquinone (CQ) and ethyl 4-dimethylamine benzoate (EDAB)] and a ternary system CQ, EDAB and diphenyliodonium hexafluorphosphate (DPIHFP)]. Varied ethanol concentrations were added to the resins, viz. 0, 5, 10, 20, 30, 40 wt%. The ultimate tensile strength test was used to investigate the influence of the solvent amount on the resistance of resins. Furthermore, the use of iodonium salt in photoinitiation system increased the cohesive strength when compared with the binary system. Regardless of solvent concentration, the cohesive strength of polymers containing diphenyliodonium was higher than for the binary photoinitiator system.

The new generation of catalytic systems for Controlled/“Living” Radical Polymerization (CLRP) of vinyl monomers should be non-toxic, inexpensive and provide fast polymerizations in environmentally friendly media. Herein, we report the successful ambient temperature ATRP of several vinyl monomers (MA, n-BA, MMA and DMAEMA) catalyzed by inorganic sulfites (Na2S2O4 and Na2S2O5) and small amounts of a Cu(II)Br2/Me6TREN system in alcohol–water mixtures. The controlled character of ATRP of acrylates and methacrylates was confirmed by the linear increase of molecular weights with monomer conversion, narrow molecular weight distributions (Mw/Mn ∼ 1.05) and by reinitiation experiments (copolymerization and chain extension). 1H NMR and MALDI-TOF analyses confirmed the molecular structure and chain-end functionality of the obtained polymers. ATRP of MA using this novel catalytic system in alcohol–water mixtures with multifunctional Br-based initiators provides 4 and 6 arm star polyacrylates in a controlled manner without any observable gel formation. The data presented open up the possibility of using fast ATRP catalyzed by inorganic sulfites (approved by FDA as food and beverage additives) in solvents that are inexpensive, eco-friendly and widely used in chemical industrial processes.

HYDROGEN BOND STUDY BY AB INITIO CALCULATIONS FOR DIMERS FORMED FROM H2O, NH3, HF, HCl AND HBr MONOMERS. Hydrogen bond energies of fifteen dimers were calculated using the large basis set 6-311++G(3df,3pd), at HartreeFock (HF) level including Moller-Plesset (MP2) calculations. The procedure for obtaining such energies were based on the dimer’s energy rise provoked by increasing in intermolecular distance of the system component units. Deviations from a strictly linear hydrogen bond were investigated and rotational barriers were also computed allowing the calculation of the second order attractive interactions. In order to provide a more objective definition of hydrogen bond, a lower energy limit was proposed in place of the merely empirical parameters employed in the classical definition.

Made available in DSpace on 2014-08-20T14:30:17Z (GMT). No. of bitstreams: 1 Dissertacao_Eliana_do_Nascimento_Torre.pdf: 1908566 bytes, checksum: 7f4e5292cab07c5cd5840870b92b0df1 (MD5) Previous issue date: 2011-07-19 Adhesive fillings are satisfactory on short-term evaluation. However, when the evaluation period of longevity of these fillings is longer, problems with the stability of the polymer formed by the adhesive system and the degradation of collagen forming the hybrid layer provoke a large decrease in the durability of this type of filling. The extracellular matrix metalloproteinases (MMPs) are enzymes, which have been associated with the degradation of collagen present at the hybrid layer. Therefore, the possibility of inhibiting the activity of these enzymes has been considered an important strategy to maintain and increase the longevity of adhesive fillings. Hence, the aim of this work is to evaluate the inhibitory potential of MMPs through the addiction of the monomers with promising characteristics reported in previous studies. These monomers have molecules known as ―kidnappers‖ of bivalent cations. This characteristic is important because the catalytic place of MMPs has zinc and calcium in its constitution. Therefore, the coordination of molecules with the catalytic place of the enzyme would be able to inhibit the activity of the MMPs. Dentine from teeth recently pulled will be used to obtain and purify the MMPs of dentine.. The analysis of MMPs inhibition will be carried out through a zymography. In case of positive results for the inhibition of MMPs, cytotoxicity and genotoxicity tests will be carried out in cellular lineages of human pulp fibroblasts apart from an immortalized lineage of fibroblasts of 3T3/NIH mice. The MTT (bromide 3-(4.5-dimethylthiazol-2-ilo)-2.5-diphenyltetrazolium) colorimetric test will be used to measure the cytotoxicity of the products tested and the test of micronucleus will be used to measure genotoxicity. In all groups the 10mM concentration induced 100% cell death. There was no difference in sensitivity in both strains. Statistically, in relation to the control group/untreated, the monomers were more cytotoxic in HPFs of groups 4 and 5. Similar results were found for the 3T3 lineage, except for group 2, which also showed statistical significance for all concentrations. There was a higher number of micronucleated cells in the groups where the two monomers of intermediate chains longer (PEG200 and PEG400 DMA) were used when compared to control. The results suggest that these two monomers are more cytotoxic and genotoxic. Most of the methacrylate monomers showed considerable but not total inhibition of MMP-2 by zymography. The exception was the PEG200 DMA, which only the concentration of 5 mM inhibited the activity of this gelatinolitic MMP Restaurações adesivas apresentam desempenho satisfatório em avaliações de curto prazo, porém quando o período de avaliação da longevidade dessas restaurações é maior, problemas com a estabilidade do polímero formado pelo sistema adesivo e com a degradação do colágeno formador da camada híbrida, provocam uma queda expressiva na durabilidade desse tipo de restauração. As metaloproteinases da matriz extracelular (MMPs) são enzimas que têm sido associadas com a degradação do colágeno formador da camada híbrida e, por isso, a possibilidade de inibir a atividade dessas enzimas tem sido considerada uma estratégia importante para a manutenção e aumento da longevidade das restaurações adesivas. O objetivo do presente estudo foi avaliar o potencial inibitório da MMP-2 por monômeros com características promissoras relatadas na literatura relacionadas ao seu potencial inibidor de MMPs, sendo estes, EGDMA (1), TEGDMA (2), T4GDMA (3), PEG200 DMA (4) e PEG400 DMA (5). Dentina humana derivada de dentes recentemente extraídos foi utilizada para a obtenção e purificação das MMPs. O ensaio de inibição da MMP-2 foi realizado por zimografia. Testes de citotoxicidade e genotoxicidade foram realizados com uma linhagem primária de fibroblastos pulpares humanos (FPH), além de uma linhagem imortalizada de fibroblastos de camundongos 3T3/NIH. O teste colorimétrico MTT (brometo de 3-(4,5-dimetiltiazol-2-ilo)-2,5-difeniltetrazólio) foi usado para medir a citotoxicidade dos produtos testados, enquanto que o teste de formação de micronúcleos foi usado para avaliar a genotoxicidade. Em todos os grupos a concentração de 10mM induziu a 100% de morte celular. Não houve diferença de sensibilidade nas duas linhagens estudadas. Estatisticamente, em relação ao grupo controle/não tratado, os monômeros foram mais citotóxicos nos FPHs nos grupos 4 e 5. Resultados semelhantes foram encontrados na linhagem 3T3, à exceção do grupo 2, que apresentou diferença estatística em todas as suas concentrações, nesta célula. Houve maior número de células micronucleadas nos grupos onde foram utilizados os dois monômeros de cadeias intermediárias mais longas (PEG200 DMA e PEG400 DMA) quando comparados ao controle, sugerindo os resultados, que estes monômeros são mais citotóxicos e genotóxicos. A maioria dos monômeros metacrilatos apresentou considerável, mas não total inibição da MMP-2 em todas as concentrações através dos ensaios de zimografia. A exceção foi o PEG200DMA, o qual somente a concentração de 5mM inibiu a atividade gelatinolítica da referida MMP

Made available in DSpace on 2014-08-20T14:30:13Z (GMT). No. of bitstreams: 1 Dissertacao_Marilia_Oliveira_Barbosa.pdf: 1068284 bytes, checksum: 523346df7ee3bd1a1ce4c3ee23aff3e8 (MD5) Previous issue date: 2011-03-31 HEMA is a monomer widely used in the adhesive systems, although the biologic performance has been found as negative it has been tried to solve this problem by testing new monomers with lower citotoxic potential. We analyzed the biocompatibility of five experimental dimethacrylate monomers: Bis-EMA 10, Bis- EMA 30, PEG 400, PEG 400 UDMA, PEG 1000. First, it was made an in vitro test using 3T3 mouse fibroblast cell culture. So, the cytotoxic test was made using primers at 20% and 2%. The dilutions were maintained in contact with the cells for a period of 24h and after the survival these cells was verified photometrically using MTT assay. After it was performed cytotoxic test with the resin bonds as follows: hese monomers were polymerized and leaving in immersion in DMEM for 24h and later the eluate obtained was inserted on the 3T3 cell for 24h. The statistical analysis was performed by Kruskal wallis method, followed by a multiple-comparison Dunn´s test (p

As cerâmicas celulares têm sido produzidas por diferentes métodos, resultando em uma ampla faixa de estruturas e propriedades. Este trabalho descreve uma nova rota para a produção de cerâmicas celulares, a qual se baseia na gelificação de emulsões constituídas de suspensões cerâmicas aquosas contendo monômeros orgânicos solúveis em água e uma fase líquida apolar emulsificada (querosene). Os efeitos do teor de sólidos e da fração de querosene nas propriedades reológicas das emulsões foram avaliados. A estrutura celular foi analisada por microscopia eletrônica de varredura e revelou poros isolados nas amostras de baixa porosidade, os quais mudaram para uma rede interconectada de poros com o aumento da porosidade. Compressão diametral foi usada para avaliar a resistência mecânica das amostras sinterizadas, a qual variou entre 2,0 e 48 MPa, dependendo da porosidade. Cellular ceramics have been produced by several methods, resulting in a wide range of structures and properties. This work describes a novel route to produce cellular ceramics based on the gel casting of emulsions consisting of an aqueous ceramic suspension containing water-soluble organic monomers and an emulsified insoluble liquid phase (kerosene). The effects of solids loading and kerosene content on the rheological properties of emulsions were evaluated. SEM of the cellular structure revealed isolated pores for samples with low porosity, which changed to an interconnected network of pores as the porosity increased. Diametrical compression was used to evaluate the strength of sintered samples, which varied in the range of 2.0 and 48 MPa, depending on the porosity.

Na fritura, os óleos e gorduras sofrem degradação formando os compostos polares, como os triacilgliceróis polimerizados e os monômeros de triacilgliceróis oxidados, estes últimos têm sido relacionados a patologias e se constituem de grupos como os monoepoxiácidos, monocetoácidos e monohidroxiácidos. Foram determinados os teores destes três grupos de substâncias, através da análise cromatográfica a gás dos ésteres metílicos de ácidos graxos após derivação a frio das amostras e concentração posterior das substâncias de interesse mediante extração em fase sólida, e os teores dos ácidos graxos polares polimerizados, utilizando a combinação das técnicas cromatográficas de adsorção em coluna e por exclusão, em gordura de soja parcialmente hidrogenada e óleos de soja e de palma, aquecidos a 180 °C por 25 horas, provenientes de experimentos de fritura. Foram encontrados teores de 3,30 a 8,24; 1,51 a 4,32 e 3,42 a 8,71 mg.g-1 de monoepoxiácidos, monocetoácidos e monohidroxiácidos, respectivamente, nas amostras com níveis de compostos polares de 20,8 a 44,1% (m/m), e predominância de formação de polímeros. Os resultados sugeriram que óleos e gorduras monoinsaturados apresentam maior tendência à formação de monômeros oxidados e menor tendência à formação de polímeros, ao contrário dos óleos poliinsaturados. During frying, fats and oils undergo degradation with the formation of polar compounds. Among these are polymeric triglycerides, as well as oxidized monomeric triglycerides. The last group has been related to several diseases and contains groups including epoxy, keto and hydroxy groups of importance from a quantitative point of view. In this study, monoepoxyacids, monoketoacids and monohydroxyacids were quantified in partially hydrogenated soybean oil, soybean oil and palm oil, after heating for 25 hours, at 180 °C, in frying experiments. The determination was carried out by gas chromatography after fat derivatization to fatty acid methyl esters at room temperature and concentration of the compounds of interest by solid phase extraction on silica cartridges. Quantitative analyses of polar fatty acids were also obtained by combination of adsorption and size exclusion chromatography. The major content corresponded to polymeric compounds. Amounts ranging from 3.30 to 8.24; from 1.51 to 4.32 and from 3.42 to 8.71 mg.g-1 were found for monoepoxyacids, monoketoacids and monohydroxyacids, respectively, for samples containing polar compounds between 20.8 and 44.1%. The results suggested that monounsaturated oils have a higher tendency to the formation of oxidized monomers while polyunsaturated oils have a higher tendency to the formation of polymers.

OBJETIVO: duas marcas comerciais de resinas acrílicas ativadas quimicamente (RAAQ), uma de uso ortodôntico (Orto Cril®) e outra de uso protético (Jet®), polimerizadas em presença e ausência de pressão, foram analisadas em relação ao conteúdo de monômero (MMA) residual liberado em solução, em diferentes intervalos de tempo (0,083; 0,25; 1; 1,25; 2,17; 5; 9; 14 e 21 dias). METODOLOGIA: a espectroscopia de absorção no ultravioleta foi utilizada na análise de soluções aquosas de MMA, com concentrações conhecidas, visando a determinação de uma curva de calibração. Soluções aquosas contendo corpos-de-prova, confeccionados com as citadas RAAQ, foram também submetidas à análise por espectroscopia de absorção no ultravioleta. RESULTADOS E CONCLUSÕES: os resultados foram comparados aos dados da curva de calibração, visando estabelecer a concentração de MMA residual das amostras. Eles permitiram concluir que o nível de MMA residual liberado em solução foi mais elevado durante as primeiras 24 horas, havendo uma tendência à estabilização a partir desse período e que a resina acrílica de uso ortodôntico apresentou níveis mais elevados de MMA em solução do que a de uso protético, em ambas as condições de polimerização empregadas, com presença e ausência de pressão. Além disso, a presença de pressão, durante a polimerização das duas resinas, elevou a concentração de MMA em solução, não havendo, entretanto, efeito da interação entre as marcas das resinas e a presença e ausência de pressão na concentração de MMA em solução, medida ao longo do tempo. Porém, todas as três variáveis (tempo, resina e pressão) foram significantes.

Neste trabalho foi investigada a influência da concentração de uma mistura dos emulsificantes nonilfenol etoxilado e sulfato sódico de nonilfenol etoxilado (não iônico e iônico, respectivamente) e concentração de protetor coloidal, poli (álcool vinílico) na estabilidade coloidal de látices do copolímero acetato de vinila (AV)/acrilato de butila (AB) com alto teor de sólidos. Foram determinados o teor de sólidos e o tamanho médio das partículas ao longo da reação e foram obtidas as viscosidades das emulsões finais. Os ensaios foram realizados de acordo com um projeto fatorial com 3 níveis de concentração de emulsificantes e de protetor coloidal. Foi verificado que são necessárias maiores quantidades relativas de emulsificantes e de protetor coloidal pela massa total de monômeros para se obter látices estáveis com teores de sólidos de 70 e 73% (m/m). Os tamanhos médios das partículas no final de cada ensaio foram relativamente elevados (800 a 1000 nm) e as viscosidades a 20°C relativamente baixas (500 mPa.s) para teor de sólidos de 67% (m/m); para teor de sólidos de 70% (m/m) as viscosidades variaram de 5.000 a 10.000 mPa.s e para teor de sólidos de 73% (m/m) a viscosidade foi de 365.000 mPa.s. In this work the influence of the concentration of ionic (alkyl phenol polyglycol ether sodium sulfate), and non-ionic (alkyl phenol polyglycol ether), surfactants mixture and of protective colloid (polyvinyl alcohol) on the colloidal stability of high solid contents butyl acrylate/vinyl acetate copolymers latexes was investigated. Solid contents and particle diameter were determined along the reaction and, at the end of each run, also the emulsion viscosity. The experiments were carried out according to a factorial design with three levels of surfactant and protective colloid concentrations. Higher amounts of surfactant and protective colloid per total monomers were required for the colloidal stability of emulsions with total solid contents of 70 and 73 wt. (%). The particle diameters at the end of the experiment were rather large (800 to 1000 nm) and the viscosities at 20 °C rather small (500 mPa.s) for solid contents of 67 wt. (%); for higher values of solid contents (70 and 73 wt. (%)) the viscosities were as high as 5000 to 10000 and 365000 mPa.s, respectively.

UV-Vis and fluorescence spectroscopic studies of the native and reconstituted d monomers of Glossoscolex paulistus were performed in acid medium. The coexistence of distinct species shows the complexity of the equilibria. Besides the hexacoordinate low spin hemichrome, with bands at 535 and 565 nm, a pentacoordinate high spin hemichrome is identified by the blue-shifted low intensity Soret band (371 nm) and the LMCT band (643 nm). The pentacoordinate hemichrome must be related to the partial unfolding of the polypeptide.

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.

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:49:13Z No. of bitstreams: 1 S0100-46702004000100007.pdf: 167566 bytes, checksum: acca2c2165e63156999f56984f76ccf8 (MD5) Made available in DSpace on 2013-08-22T18:49:13Z (GMT). No. of bitstreams: 1 S0100-46702004000100007.pdf: 167566 bytes, checksum: acca2c2165e63156999f56984f76ccf8 (MD5) Previous issue date: 2004-01-01 Made available in DSpace on 2013-09-30T19:10:26Z (GMT). No. of bitstreams: 2 S0100-46702004000100007.pdf: 167566 bytes, checksum: acca2c2165e63156999f56984f76ccf8 (MD5) S0100-46702004000100007.pdf.txt: 13791 bytes, checksum: 6e75559db8398c108598ab1db0c4c9a9 (MD5) Previous issue date: 2004-01-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T14:20:35Z No. of bitstreams: 2 S0100-46702004000100007.pdf: 167566 bytes, checksum: acca2c2165e63156999f56984f76ccf8 (MD5) S0100-46702004000100007.pdf.txt: 13791 bytes, checksum: 6e75559db8398c108598ab1db0c4c9a9 (MD5) Made available in DSpace on 2014-05-20T14:20:35Z (GMT). No. of bitstreams: 2 S0100-46702004000100007.pdf: 167566 bytes, checksum: acca2c2165e63156999f56984f76ccf8 (MD5) S0100-46702004000100007.pdf.txt: 13791 bytes, checksum: 6e75559db8398c108598ab1db0c4c9a9 (MD5) Previous issue date: 2004-01-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Ciclopaladados diméricos do tipo [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) reagem com tiouréia (tu), à temperatura ambiente, resultando espécies mononucleares do tipo [Pd(dmba)(X)(tu)]. Todos os compostos foram caracterizados por análise elementar, espectroscopias no IV e de RMN de ¹H e com base nessas técnicas as estruturas, desses compostos, foram propostas. Os espectros de absorção no infravermelho mostraram que a coordenação da tiouréia, ao paládio, ocorre através do átomo de enxofre. O anel ciclometalado foi confirmado através da espectroscopia de RMN de ¹H. Reactions of [Pd(dmba)(m-X)]2 (dmba = N,N-dimethylbenzylamine; X = Cl, N3, NCO) with thiourea (tu), were performed at room temperature, giving compounds of the type [Pd(dmba)(X)(tu)]. All compounds were characterized by elemental analyses, I. R. and ¹H NMR spectroscopies. The infrared spectra showed that the coordination of thiourea to palladium occured through the sulphur atom. The cyclometallated ring was confirmed by ¹H NMR spectroscopy. Taking into account these techniques the structures of these compounds were proposed as being monomers with a square-planar coordination geometry around the palladium atom. Universidade Estadual Paulista Instituto de Química Departamento de Química Geral e Inorgânica Universidade Estadual Paulista Instituto de Química Departamento de Química Geral e Inorgânica

Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-27T11:20:25Z No. of bitstreams: 0Bitstream added on 2014-05-27T14:45:02Z : No. of bitstreams: 1 2-s2.0-0036519768.pdf: 449177 bytes, checksum: 3de6fa7e337698b4ce898c89a15644bb (MD5) Made available in DSpace on 2014-05-27T11:20:25Z (GMT). No. of bitstreams: 0 Previous issue date: 2002-03-01 This work describes a modified sol-gel method for the preparation of V 2O 5/TiO 2 catalysts. The samples have been characterized by N 2 adsorption at 77K, x-ray diffractometry (XRD) and Fourier Transform Infrared (FT-IR). The surface area increases with the vanadia loading from 24 m 2 g -1, for pure TiO 2, to 87 m 2 g -1 for 9wt.% of V 2O 5. The rutile form is predominant for pure TiO 2 but became enriched with anatase phase when vanadia loading is increased. No crystalline V 2O 5 phase was observed in the catalysts diffractograms. Two species of surface vanadium observed by FT-IR spectroscopy a monomeric vanadyl and polymeric vanadates, the vanadyl/vanadate ratio remains practically constant. Instituto de Física de São Carlos Universidade de São Paulo, CP 369, 13560-970 São Carlos - SP Departamento de Química Faculdade de Ciências Universidade Estadual Paulista Júlio de Mesquita Filho, CP 473, 17001-970 Bauru - SP Departamento de Química e Bioquímica Instituto de Bioquímica Universidade Estadual Paulista Júlio de Mesquita Filho, CP 510, 18618-000 Botucatu - SP Departamento de Química Faculdade de Ciências Universidade Estadual Paulista Júlio de Mesquita Filho, CP 473, 17001-970 Bauru - SP Departamento de Química e Bioquímica Instituto de Bioquímica Universidade Estadual Paulista Júlio de Mesquita Filho, CP 510, 18618-000 Botucatu - SP

Suportes poliméricos à base de estireno (Sty) e divinilbenzeno (DVB) foram preparados por polimerização em suspensão aquosa em presença de diluente (mistura de tolueno e n-heptano em composição variada) em um grau de diluição de 100 % e com quatro teores diferentes de DVB (10, 20, 40 e 60 %). Os suportes foram caracterizados nos estados seco e inchado. No estado seco foram analisados quanto à densidade aparente, área específica, volume de poros e morfologia, e no estado inchado foi observado o comportamento em dois diferentes tipos de solventes, um bom e um mau solvente para o copolímero de estireno-divinilbenzeno. As propriedades dos suportes poliméricos, nos estados seco e inchado, foram relacionadas com os parâmetros de síntese. Os suportes poliméricos foram sulfonados em presença de solvente capaz de inchar a rede polimérica (1,2-dicloroetano). Os catalisadores sulfônicos obtidos foram caracterizados no estado seco e inchado e a atividade catalítica foi avaliada em reações de esterificação de ácido acético com n-butanol. Também foi avaliado o efeito da reciclagem dos catalisadores na sua atividade catalítica. Polymer supports based on styrene and divinylbenzene were prepared by aqueous suspension polymerization in presence of diluents (mixtures of toluene and heptane in varied compositions) at 100% v/v of dilution degree (relative to the monomers volume) at four DVB proportions (10, 20, 40 and 60%). The supports were characterized in the dry and swollen states. In the dry state, the apparent density, surface area, pore volume and morphology were determined. In the swollen state, the behavior in two different solvents, one good and one bad for the styrene-divinylbenzene copolymer, was observed. The polymer support properties in the dry and swollen states were related with the respective synthesis parameters. The polymer supports were sulfonated in the presence of a solvent able to swell the polymer network (1,2-dichloroethane). The obtained supported catalysts were also analyzed in the dry and swollen states. The catalysts activities were evaluated in the acetic acid esterification with n-butanol, and the recycling effect of two different catalysts on its activities was also evaluated.

Adsorption of cationic dyes on clays can be used as a model for the interactions between organic compounds and these minerals. Cationic dyes like methylene blue are used to study these interactions because of the spectroscopic changes observed when their molecules are adsorbed on clay surfaces. Depending on the structure and layer charge of the clay particles several processes may occur, like adsorption of dye monomers and aggregates on the external and internal surfaces of the clay tactoids, migration towards internal surfaces, protonation, etc. Under certain conditions the deaggregation-aggregation of the clay particles are accelerated trapping dye species during these processes. A general scheme is proposed for the processes occurring between clays and dyes in aqueous suspensions, which can be used to explain the behaviour of specific systems.

Polyaddition of commercial monomers is easily performed on a domestic microwave oven. The rate of polymerization depends on the structure of the monomer, power and time of irradiation. This methodology can easily be used to demonstrate the acceleration of organic reactions promoted by microwaves.

Hidroxiapatita porosa foi produzida por meio de uma nova técnica de processamento, visando aplicações na área de implantes ósseos. A produção do material poroso é feita através da produção de espumas pela agitação de suspensões cerâmicas aquosas contendo tensoativos adequados. A solidificação que segue é obtida pela adição de reagentes iniciadores da polimerização in situ de monômeros orgânicos, inicialmente incluídos nas composições, formando um gel. Este método permite a produção de corpos com formatos de alta complexidade e elevada resistência mecânica com níveis de porosidade próximos de 90%vol, que suportam corte e torneamento no estado a verde. Os aditivos orgânicos são eliminados a 300 °C e sinterização a 1350 °C é efetuada para consolidação da matriz. A otimização da resistência mecânica decorre da combinação entre uma matriz cerâmica de alta densidade a uma estrutura de poros esféricos com diâmetros que variam de 20-1000 mm possuindo inter-conecções de aproximadamente 10-100 mm, dependendo da densidade. O material sinterizado foi avaliado quanto a sua citoxicidade, utilizando-se o método quantitativo de formação de colônias que calcula o índice de citotoxicidade IC50(%) após contato do extrato do material com células de mamíferos. Os resultados mostraram que o processo de fabricação e os reagentes utilizados não afetaram os baixos níveis de toxicidade do pó de hidroxiapatita que era originalmente de pureza biomédica. A novel technique has been applied to manufacture porous hydroxyapatite for implant applications. The process involved generation of foam from an aqueous suspension of the powder followed by in situ polymerisation of organic monomers, which had been previously added to the compositions. This method produces strong gelled and complex-shaped bodies with up to 90% porosity that can withstand machining in the green state. The organic additives are eliminated at temperatures above 300 °C and sintering is carried out for consolidation of the ceramic matrix. An optimized mechanical strength results from a highly densified matrix combined with spherical inter-connected cells of diameter ranging from 20 to 1000 mm and channels of 10-100 mm, depending on the specimen density. Cytotoxicity test was conducted with sintered HA extracts in contact with mammalian cells, based on a quantitative method of colonies formation suppression. The in vitro test revealed that the original purity of the biomedical-grade hydroxyapatite powder was neither affected through processing nor by the employed reagents.

Neste trabalho, os géis termossensíveis poli(N-isopropilacrilamida) - IPAA - foram caracterizados através de Espectroscopia de Vida Média de Pósitrons (EVMP) e Análise Térmica como função das concentrações do monômero principal N-isopropilacrilamida e do agente reticulante N,N'-Metilenobisacrilamida. A EVMP foi usada para determinar o raio médio dos volumes livres dos géis. Os géis IPAA foram sintetizados em solução aquosa via radicais livres. Após a síntese, os géis foram cortados em cubos, lavados e secos em estufa. Depois de secos foram moídos e caracterizados através de Análise Termogravimétrica (TGA) e Calorimetria Exploratória Diferencial (DSC). Os géis com composição de monômero principal e agente reticulante variando de 10x1 a 10x6, 10x1 a 16x1 e 10x1 a 16x6 mostraram um raio médio em torno de 2,8Å. O volume livre estimado para os géis não variaram com a variação da composição de monômero principal e agente reticulante. Os resultados foram interpretados em termos da estrutura desses géis. In this work, poly (N-isopropylacrylamide) gels were characterized through Positron Annihilation Lifetime Spectroscopy (PALS) and thermal analysis as function of the N-isopropylacrylamide monomer and N,N-methylenebisacrylamide crosslinker concentrations. PALS was used to determine the average free volume radii of gels. The gels with monomer and crosslinker composition varying from 10x1 to 10x6, 10x1 to 16x1 and 10x1 to 16x6 showed a radius near of 2.8Å. The free volume estimated for the gels no change with the variation of the monomer and crosslinker composition. The results are discussed in terms of the changes in the gels' structure due to polymer-polymer interactions.

The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:58:26Z No. of bitstreams: 0 Made available in DSpace on 2013-08-22T18:58:26Z (GMT). No. of bitstreams: 0 Previous issue date: 1997-04-01 Made available in DSpace on 2013-09-30T19:54:08Z (GMT). No. of bitstreams: 0 Previous issue date: 1997-04-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T13:43:29Z No. of bitstreams: 0 Made available in DSpace on 2014-05-20T13:43:29Z (GMT). No. of bitstreams: 0 Previous issue date: 1997-04-01 Foi avaliada a resistência de união entre dentes e base de dentadura, ambos de resina acrílica. Os dentes foram incluídos em blocos cilíndricos de resina e, posteriormente, torneados, para se obterem cilindros de 5mm de diâmetro. Sobre a extremidade do dente, era adaptado um padrão de cera de mesmo diâmetro, que, após inclusão na mufla, era substituído por resina acrílica termicamente ativada pelo método de processamento convencional de base de dentadura. Como variáveis, usaram-se duas marcas de dentes, duas fases de inclusão (plástica e borrachóide) e aplicação ou não de detergente e monômero sobre os dentes. Os corpos-de-prova, antes dos ensaios de ruptura por tração, foram armazenados em água destilada, a 37ºC, por 2 semanas. Os resultados mostraram que: marca de dente e fase de condensação não influíram nos resultados; somente o uso de detergente ou de monômero aumenta a retentividade e o seu uso conjunto apresenta efeito acumulativo. An investigation was carried out to evaluate the bonding strength between acrylic teeth and heat-cured denture acrylic resin. The teeth were fixed in resin blocks and lathe milled to a cylinder shape of 5 mm of diameter. A wax pattern with the same diameter was adapted on the top of the cylinder and then invested in a flask. Following the conventional denture base resin procedures, the wax pattern was eliminated and heat-cured resin was packed. The variables were: two acrylic teeth brands; two resin phases (full dough and rubber); cleaning or not of the flask with detergent; application or not of monomer over the teeth before resin packing. After polymerization specimens were stored in water at 37ºC, for 2 weeks. Tests were performed by tensile loads. The results showed that teeth brands and resin phases did not influence data; the use of monomer or detergent increased strengths, and when used together the effects were cumulative. UNESP Universidade de São Paulo UNESP