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Gel formation in aqueous suspension nitroxide-mediated radical co-polymerization of styrene/divinylbenzene

Gonçalves, Miguel; Pinto, Virgínia; Dias, Rolando; Costa, Mário; Aguiar, Leandro; Giudici, Reinaldo
Fonte: WILEY-VCH Publicador: WILEY-VCH
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
47.512485%
Results from an experimental study concerning gel formation with nitroxide-mediated radical polymerization (NMRP) of styrene (S) and divinylbenzene (DVB) in aqueous suspension are reported. Influence of certain polymerization parameters on the dynamics of network formation was measured, namely the polymerization temperature and initial composition. Soluble polymer formed at different polymerization times was analyzed by size exclusion chromatography (SEC) with refractive index (RI) and multi angle laser light scattering (MALLS) detection. Concentration of pendant double bonds (PDB) was quantified by means of ICl titration and the morphology of the S/DVB particles was inspected by SEM. Incidence of cyclizations was assessed and the improvement of network homogeneity when using NMRP/FRP is discussed.

Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

MEDEIROS, Simone F.; BARBOZA, Jayne C. S.; RE, Maria I.; GIUDICI, Reinaldo; SANTOS, Amilton M.
Fonte: JOHN WILEY & SONS INC Publicador: JOHN WILEY & SONS INC
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
47.79595%
The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010; CAPES; CNPq; FAPESP

Investigation of Cationic Polymerization of beta-Pinene Using Calorimetric Measurements

POCO, Joao Guilherme Rocha; DANESE, Modesto; GIUDICI, Reinaldo
Fonte: WILEY-V C H VERLAG GMBH Publicador: WILEY-V C H VERLAG GMBH
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
47.66083%
An experimental investigation of the kinetics of cationic polymerization of beta-pinene was performed using two different initiator systems under two different operating conditions (shot additions of initiator, and continuous feeding of monomer). The experiments were done using calorimetric measurements under isoperibolic conditions. The heat of polymerization of beta-pinene was found to be -30.6 kcal . mol(-1). A simple kinetic model was tentatively proposed, and the model fit reasonably well to the different experimental runs. Different values of the fitting parameters were obtained for runs carried out under different conditions, which can probably be ascribed to the presence of adventitious impurities in the commercial-grade monomer used.; Petroquimica Uniao S.A.; IPT; FAPESP; CNPq

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Ely, Caroline; Schneider, Luis Felipe J.; Ogliari, Fabricio A.; Schmitt, Carla C.; Correa, Ivo C.; Lima, Giana da S.; Samuel, Susana M. W.; Piva, Evandro
Fonte: ELSEVIER SCI LTD; OXFORD Publicador: ELSEVIER SCI LTD; OXFORD
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
57.739287%
Objectives. The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. Methods. A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R-p(max)) profile of the model resin. Results. In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region...

Avaliação do grau de conversão monomérica, parâmetros de cinética de polimerização e determinação de monômeros residuais em resinas experimentais; Evaluation of degree of monomer conversion, the polymerization kinetic parameters and determination of residual monomers in experimental resins

Amaral, Aline Bassi Denis Bordini do
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 06/07/2012 PT
Relevância na Pesquisa
47.79595%
Este estudo teve como objetivo investigar múltiplos aspectos relacionados a polimerização da resina composta como: o grau de conversão monomérica (GC), parâmetros da cinética de polimerização e a determinação de monômeros residuais TEGDMA e BisGMA, além de avaliar o desempenho de aparelhos fotoativadores. As resinas compostas experimentais foram manipuladas variando-se os fotoiniciadores R1-) canforoquinona/amina, R2-) PPD/amina, R3-) PPD + canforoquinona/amina) e foram utilizados dois aparelhos para a fotoativação (I-) lâmpada halógena (Demetron LC/ SDS Kerr-USA) e II-) LED (Poly 600/Kavo-Brasil) ambos com 600 mW cm-2, por 40 s. O GC após 300 s e os parâmetros de cinética como taxa máxima de conversão (Rpmáx), tempo em que ocorreu a taxa máxima de polimerização (tmáx) e a conversão quando ocorreu a Rpmáx, foram determinados por meio de espectroscopia de absorção no infravermelho em tempo real (RT-FTIR), Os espectros foram coletados dos espécimes (n=5) no modo cinética, durante 305 s, entre 1680 e 1550 cm-1. As 5 primeiras varreduras coletadas serviram para fornecer o espectro de absorção da resina não polimerizada (utilizado no cálculo do GC). Na 6º varredura, o fotoativador foi ligado (por 40 segundos) enquanto o espectro continuava a ser coletado até 300 s após a ativação da luz. A presença de monômeros residuais (TEGDMA e BisGMA) foi avaliada por meio da cromatografia líquida de alta eficiência (HPLC)...

Compósitos a base de dimetacrilatos ou silorano: caracterização da cinética e tensão de polimerização, com respectivos parâmetros determinantes; avaliação da rede polimérica formada por análise dinâmico-mecânica e estudo de extratos lixiv; Composites based on dimethacrylate or silorane: characterization of kinetics and polymerization stress, with their respective determining parameters; polymer network formed evaluation by dynamic mechanical analysis and leachable extracts study

Yamasaki, Lilyan Cardoso
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 28/09/2012 PT
Relevância na Pesquisa
58.397114%
OBJETIVO: caracterizar a interação entre tensão e cinética de polimerização e seus parâmetros determinantes, e avaliar a qualidade da rede polimérica e propriedades mecânicas de compósitos comerciais para dentes posteriores a base de dimetacrilato ou de silorano. A cinética de polimerização foi avaliada sob influência da intensidade da fonte de luz, da temperatura e da umidade. Por fim, o grau de conversão (GC) do compósito a base de silorano foi avaliado por espectroscopia e titulação. MÉTODOS: foram utilizados três compósitos de baixa contração: Kalore (KAL - GC America) e N´Durance (NDUR Septodont), a base de dimetacrilatos; e Filtek P90 (P90 - 3MESPE), a base de silorano. O EsthetX HD (EHD - Dentsply) foi utilizado como controle. A tensão de polimerização (TP) dos espécimes (n = 5; Ø = 5 mm; h = 1 mm, 10 min) foi obtida em máquina universal de ensaios mecânicos. A contração volumétrica (CVol) foi determinada em linômetro (n = 3; Ø = 6 mm; h = 1,5 mm; 10 min). O módulo de elasticidade em flexão (MeFlex) e a resistência à flexão (RFlex) (n = 10; 10 x 2 x 1 mm) foram obtidos através do teste de dobramento em três pontos (8 mm entre apoios; 0.5 mm/min). O GC e a taxa de polimerização (Rp) dos espécimes (n = 3; Ø = 6...

Efeito do modo de ativação de cimentos resinosos duais sobre a cinetica de conversão, prolpriedades mecanicas, resistencia de união e geração de tensões; Effec of activation mode of dual-cured resin cements on polymerization kinetics, mechanical properties, bond strength and stress generation

Andre Luis Faria e Silva
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 15/07/2008 PT
Relevância na Pesquisa
47.872324%
Durante os procedimentos de cimentação de restaurações indiretas e pinos intra-radiculares usando cimentos resinosos, a polimerização apropriada do cimento é essencial para o sucesso clínico da restauração. Entretanto, o potencial de polimerização dos componentes de ativação química e por luz de cimentos resinosos duais demonstra ser muito variável. Em adição, o rápido aumento da viscosidade causado pela fotoativação pode inibir a polimerização ativada quimicamente e reduzir o grau de conversão (GC) final. Assim, os objetivos deste estudo foram avaliar o efeito da fotoativação (ausência, imediata ou tardia) de três cimentos resinosos duais (Enforce, RelyX ARC e Panavia F) sobre: 1 - cinética de taxa de polimerização (Tp); 2 - resistência à tração diametral (RTD) e rigidez relativa (RR); 3 - tensão de contração de polimerização (TC); 4 - resistência máxima à tração (RMT) e 5 - resistência de união ao cisalhamento (RU). Para este último, o tempo do teste (10 minutos ou 24 horas) também foi avaliado. A fotoativação aumentou o GC para todos os cimentos resinosos. A ativação tardia melhorou o GC para o Enforce, reduziu para o RelyX ARC e para o Panavia F. Entretanto, este modo de ativação reduziu a Tp para todos os cimentos. O Panavia F apresentou a mais lenta reação de polimerização e os menores GC quando usado na ausência de fotoativação. O uso do ED Primer com este cimento aumentou o GC para todos os modos de ativação. A ausência de fotoativação reduziu a RTD apenas para o Panavia F. Para a fotoativação tardia...

Effects of Prepolymerized Particle Size and Polymerization Kinetics on Volumetric Shrinkage of Dental Modeling Resins

Kwon, Tae-Yub; Ha, Jung-Yun; Chun, Ju-Na; Son, Jun Sik; Kim, Kyo-Han
Fonte: Hindawi Publishing Corporation Publicador: Hindawi Publishing Corporation
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
47.944434%
Dental modeling resins have been developed for use in areas where highly precise resin structures are needed. The manufacturers claim that these polymethyl methacrylate/methyl methacrylate (PMMA/MMA) resins show little or no shrinkage after polymerization. This study examined the polymerization shrinkage of five dental modeling resins as well as one temporary PMMA/MMA resin (control). The morphology and the particle size of the prepolymerized PMMA powders were investigated by scanning electron microscopy and laser diffraction particle size analysis, respectively. Linear polymerization shrinkage strains of the resins were monitored for 20 minutes using a custom-made linometer, and the final values (at 20 minutes) were converted into volumetric shrinkages. The final volumetric shrinkage values for the modeling resins were statistically similar (P > 0.05) or significantly larger (P < 0.05) than that of the control resin and were related to the polymerization kinetics (P < 0.05) rather than the PMMA bead size (P = 0.335). Therefore, the optimal control of the polymerization kinetics seems to be more important for producing high-precision resin structures rather than the use of dental modeling resins.

Time-dependent effect of refrigeration on viscosity and conversion kinetics of dental adhesive resins

Faria e Silva, Andr?? Luis; Piva, Evandro; Moraes, Rafael Ratto de
Fonte: Medknow Publications Publicador: Medknow Publications
Tipo: Artigo de Revista Científica
EN_US
Relevância na Pesquisa
57.979146%
Objectives: This study evaluated the effect of refrigeration at 4oC and post-refrigeration times (immediate, 5, 10, 15, or 20 min) on the viscosity and conversion kinetics of adhesive bonding resins. Methods: Scotchbond Dual-Cure (3M ESPE) and Clearfil SE Bond (Kuraray) were tested. Control samples were kept at 25oC for 24 h. At each post-refrigeration time, the temperature was checked with a K-type thermocouple. Viscosity measurements as a function of temperature were performed using a cone-plate viscometer. Real-time polymerization was monitored by infrared spectroscopy. Degree of conversion (DC) was calculated for each second during polymerization, and the rate of polymerization analyzed. Data were separately submitted to two-way ANOVA and Tukey???s test (P<.05). Results: Clearfil presented faster increase in temperature after exposure to room temperature than Scotchbond. A continuous decrease in viscosity (Pa.s) was observed for both Scotchbond (0.49, 0.34, 0.30, 0.26, 0.23, 0.23) and Clearfil (0.38, 0.37, 0.34, 0.25, 0.24, 0.22). For Scotchbond, higher final DC was detected for the control (62.7%) compared with the immediate (53.3%) and 5 min (54.7%) groups. For Clearfil, the control sample (81.4%) showed higher DC than all refrigerated groups (68.8??? 69.5%). Clearfil always showed significantly higher DC than Scotchbond. Conclusions: Refrigeration presented a significant time- and material-dependent effect on the viscosity and polymerization kinetics of the bonding resins. Under clinical conditions...

Uso do hexafluorfosfato de difeniliod??nio na polimeriza????o radicalar fotoiniciada de metacrilatos; Diphenyliodonium hexafluorphosphate effect on the radical polymerization of methacrylates

OGLIARI, Fabr??cio Aulo
Fonte: Universidade Federal de Pelotas; Odontologia; Programa de P??s-Gradua????o em Odontologia; UFPel; BR Publicador: Universidade Federal de Pelotas; Odontologia; Programa de P??s-Gradua????o em Odontologia; UFPel; BR
Tipo: Tese de Doutorado Formato: application/pdf
POR
Relevância na Pesquisa
47.89928%
The present investigation evaluated the effect of the diphenyliodonium hexafluorphosphate (DPIHFP) on the radical polymerization of methacrylates. Rate of polymerization from binary and ternary photoinitiation systems, performance of such systems in the presence of solvent and its effects on the bonding strength to bovine dentin were investigated. As a model adhesive resin, a blend of Bis-GMA, TEGDMA and HEMA (50/25/25 %wt) was prepared. Real-time degree of conversion was performed in a Fourier transform infrared spectrometer. To assess the photoinitiator system efficiency in a dental adhesive composition, the adhesion between the model resin and bovine dentin was investigated using microtensile bond strength(μTBS). When CQ was used as photo-initiator, a slow polymerization reaction was observed. The addition of a second component (onium salt or amine) increases the polymerization rate and conversion independent on the co-initiator concentration. Ternary photo-initiator system showed an improvement on the polymerization rate of the dental adhesive model resin leading to high conversion in short photo-activation time.The addition of a solvent to the monomer blends decreased the polymerization kinetics, directly affecting the rate of polymerization...

Kinetics, Synthesis and Characterization of copolymers containing the bio-renewable monomer g-methyl-a-methylene-g-butyrolactone (MeMBL)

Cockburn, Robert A
Fonte: Quens University Publicador: Quens University
Tipo: Tese de Doutorado
EN; EN
Relevância na Pesquisa
48.03581%
The bio-renewable monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL) has been thoroughly investigated in this thesis. MeMBL is a relatively unstudied monomer that had received little attention since the early 1980’s but has become a subject of renewed interest since a process to produce it from biomass derivatives was developed in 2004. The principle interest with this monomer aside from the “green” potential associated with bio-renewables results from its structure being cyclically analogous to methyl methacrylate (MMA) as well as improved solvent resistance and a high (215oC+) glass transition temperature (Tg) compared to most petroleum sourced acrylics. There are three major areas of focus in this work, examining polymerization kinetics, synthesis and polymer characterization. The polymerization kinetics of MeMBL were investigated with a variety of petroleum sourced monomers. MeMBL is in all cases preferentially incorporated into copolymers, presenting challenges for composition control. Preliminary investigations of aqueous phase polymerizations of MeMBL were problematic and led to investigations of organic phase polymerizations. The dispersion polymerization method was used to produce copolymers of MeMBL and MMA; during the study we obtained new insight into the mechanisms of particle nucleation and growth. With the acquired knowledge of MeMBL polymerization kinetics...

Stable Free Radical Polymerization Conducted In Emulsion Polymerization Systems

Maehata, Hideo
Fonte: Quens University Publicador: Quens University
Tipo: Tese de Doutorado
EN; EN
Relevância na Pesquisa
47.980854%
Free radical polymerization is the most common polymerization technique that is used for the manufacturing of polymers, due to the ease of the polymerization initiation, wide latitude of the material design for a large variety of monomers, and the excellent process robustness for commercial production. In the 1990’s, research activities for the precise control of radical polymerization process resulted in the discovery of ‘Living Radical Polymerization’. The discoveries opened the door for the next generation of radical polymerizations. Extensive research has been conducted to understand the mechanisms and kinetics for numerous practical applications, particularly for polymerization in bulk and solution systems. However, despite the interest of industry, the mechanistic understanding in aqueous dispersed systems such as emulsion and miniemulsion polymerization is far behind the aforementioned two systems. There are still major challenges from the production viewpoint. One reason for the poor understanding is the complexity of the heterogeneous system, which includes multiple reaction phases that are accompanied by the segregation and transfer of the reaction species among different phases. The purpose of this research was to investigate living radical polymerization or “Stable Free Radical Polymerization” (SFRP) in aqueous dispersed systems to obtain better mechanistic understanding of how the heterogeneous nature of the system interacts with the novel living radical chemistry. The theoretical and experimental feasibility of the SFRP emulsion process were studied in this research...

"Avaliação in vitro e in vivo da resina composta pré-aquecida em relação à cinética de polimerização ; In vitro and in vivo appraisal of pre-heated resin composite with relation to polymerization kinetics

Daronch, Márcia
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 04/07/2005 PT
Relevância na Pesquisa
67.809316%
O objetivo do trabalho foi investigar múltiplos aspectos relacionados ao pré-aquecimento da resina composta anterior à fotoativação: o grau de conversão e a cinética da polimerização em função da temperatura de polimerização, tempo de fotoativação e profundidade; o desempenho da fonte aquecedora (temperatura máxima, estabilidade térmica do aparelho e variações de temperatura ao pré-aquecer compules) e aspectos clínicos (o efeito de ciclos de pré-aquecimento repetidos e prolongados sobre o grau de conversão, a variação da temperatura intrapulpar in vitro e a variação da temperatura in vivo ao usar resina composta pré-aquecida ou a temperatura ambiente. A conversão de monômeros e os parâmetros de cinética foram determinados através de FTIR-ATR. Os espécimes foram fotoativados por 5, 10, 20 ou 40s entre 3 o e 60 o C. Foram calculados o grau de conversão em tempo real, a taxa máxima de conversão, o tempo em que ocorreu a taxa máxima, e a conversão na taxa máxima. Os dados foram tratados por análise de variância, teste-t e análise de regressão (p ≤0,05). O desempenho do dispositivo aquecedor foi medido monitorando-se a mudança de temperatura em tempo real com o auxílio de um termopar tipo-k conectado a um conversor analógico-digital. Os termopares foram colocados no aquecedor e dentro de compules de compósito. Os dados foram analisados com teste t (p ≤0...

Actin polymerization kinetics, cap structure, and fluctuations

Vavylonis, Dimitrios; Yang, Qingbo; O'Shaughnessy, Ben
Fonte: National Academy of Sciences Publicador: National Academy of Sciences
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
47.809316%
Polymerization of actin proteins into dynamic structures is essential to eukaryotic cell life, motivating many in vitro experiments measuring polymerization kinetics of individual filaments. Here, we model these kinetics, accounting for all relevant steps revealed by experiment: polymerization, depolymerization, random ATP hydrolysis, and release of phosphate (Pi). We relate filament growth rates to the dynamics of ATP–actin and ADP–Pi–actin caps that develop at filament ends. At the critical concentration of the barbed end, ccrit, we find a short ATP cap and a long fluctuation-stabilized ADP–Pi cap. We show that growth rates and the critical concentration at the barbed end are intimately related to cap structure and dynamics. Fluctuations in filament lengths are described by the length diffusion coefficient, D. Recently Fujiwara et al. [Fujiwara, I., Takahashi, S., Takaduma, H., Funatsu, T. & Ishiwata, S. (2002) Nat. Cell Biol. 4, 666–673] and Kuhn and Pollard [Kuhn, J. & Pollard, T. D. (2005) Biophys. J. 88, 1387–1402] observed large length fluctuations slightly above ccrit, provoking speculation that growth may proceed by oligomeric rather than monomeric on–off events. For the single-monomer growth process, we find that D exhibits a pronounced peak below ccrit...

Polymerization Kinetics of Methacrylic Groups in Organic-Inorganic hybrid Polymeric Thin Films

Zha, Congji; Luo, Xinshi; Luther-Davies, Barry
Fonte: Materials Research Society Publicador: Materials Research Society
Tipo: Conference paper
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In this paper, the polymerization kinetics of unsaturated double bonds (C=C) in TiO2- and ZrO2-doped hybrid polymeric thin films during UV irradiation and thermal curing is studied by monitoring the variation of C=C absorption band at 1630 cm-1 using FT-I

Free Radical Polymerization studies of vinyl ester monomers using Pulsed-Lased Polymerization with Size Exclusion Chromatography (PLP-SEC)

Monyatsi, Otlaatla
Fonte: Quens University Publicador: Quens University
Tipo: Tese de Doutorado
EN; EN
Relevância na Pesquisa
48.0699%
Polyvinyl acetate and other polyvinyl esters, and their copolymers are used in coatings, adhesives and plastics, and hence fundamental understanding of the mechanisms and polymerization kinetics is vital for process development, and production of existing and new polymer grades in an effective and safe manner. The propagation kinetics of radical homopolymerization (bulk) of vinyl acetate (VAc), vinyl pivalate (VPi) and vinyl benzoate (VBz) was studied using Pulsed-Laser Polymerization coupled with Size Exclusion Chromatography (PLP-SEC) at laser pulse repetition rate (prr) between 2 and 500 Hz, and the temperature range of 25 - 90 °C. The propagation rate coefficient, kp, determined for VAc and VPi increases significantly with prr (20 % between 200 and 500 Hz prr), with the kp value for VPi ~50 % higher than that of VAc. This significant increase in kp with prr has been explained by the head-to-head addition defects that occur during vinyl ester polymerizations. For VBz, no kp value was reported due to lack of PLP-structure, likely due to resonance stabilization of the radical. Solution polymerization of VAc and VPi was also studied by PLP-SEC using ethyl acetate (EAc) and heptane (50 % by volume) at 50 °C, with the kp values having no substantial solvent effect. The polymerization kinetics of these vinyl ester monomers were also investigated using small-scale batch polymerization at 60 °C both in bulk and in solution (using EAc). The monomer conversion profiles obtained showed the same pattern in both bulk and solution...

Actin Polymerization Kinetics, Cap Structure and Fluctuations

Vavylonis, Dimitrios; Yang, Qingbo; O'Shaughnessy, Ben
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Relevância na Pesquisa
47.809316%
Polymerization of actin proteins into dynamic structures is essential to eukaryotic cell life. This has motivated a large body of in vitro experiments measuring polymerization kinetics of individual filaments. Here we model these kinetics, accounting for all relevant steps revealed by experiment: polymerization, depolymerization, random ATP hydrolysis and release of phosphate (Pi). We relate filament growth rates to the dynamics of ATP-actin and ADP-Pi-actin caps which develop at filament ends. At the critical concentration of the barbed end, c_crit, we find a short ATP cap and a long fluctuation-stabilized ADP-Pi cap. We show that growth rates and the critical concentration at the barbed end are intimately related to cap structure and dynamics. Fluctuations in filament lengths are described by the length diffusion coefficient, D. Recently Fujiwara et al. [Nature Cell Biol. (2002) 4, 666] and Kuhn and Pollard [Biohys. J. (2005) 88, 1387] observed large length fluctuations slightly above c_crit, provoking speculation that growth may proceed by oligomeric rather than monomeric on-off events. For the single monomer growth process we find that $D$ exhibits a pronounced peak below c_crit}, due to filaments alternating between capped and uncapped states...

Mechanism and Kinetics of Dithiobenzoate-Mediated RAFT Polymerization. 1. The Current Situation

Barner-Kowollik, Christopher; Buback, Michael; Charleux, Bernadette; Coote, Michelle; Drache, Marco; Fukuda, Takeshi; Goto, Atsushi; Klumperman, Bert; Lowe, Andrew B; Mcleary, James B; Moad, Graeme; Monteiro, Michael J; Sanderson, Ronald D; Tonge, Matthew
Fonte: Wiley-VCH Verlag GMBH Publicador: Wiley-VCH Verlag GMBH
Tipo: Artigo de Revista Científica
Relevância na Pesquisa
48.14055%
Investigations into the kinetics and mechanism of dithiobenzoate-mediated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the rate coefficients associated with the RAFT equilibrium is discussed and methods for obtaining RAFT-specific rate coefficients are detailed. In addition, mechanistic studies are presented, which target the elucidation of the fundamental cause of rate retarding effects. The experimental and theoretical data existing in the literature are critically evaluated and apparent discrepancies between the results of different studies into the kinetics of RAFT polymerizations are discussed. Finally, recommendations for further work are given.

Computational Studies of RAFT Polymerization - Mechanistic Insights and Practical Applications

Coote, Michelle; Krenske, Elizabeth; Izgorodina, Ekaterina
Fonte: Wiley-VCH Verlag GMBH Publicador: Wiley-VCH Verlag GMBH
Tipo: Artigo de Revista Científica
Relevância na Pesquisa
47.809316%
Computational chemistry is a valuable complement to experiments in the study of polymerization processes. This article reviews the contribution of computational chemistry to understanding the kinetics and mechanism of reversible addition fragmentation chain transfer (RAFT) polymerization. Current computational techniques are appraised, showing that barriers and em:halpies can now be calculated with kcal accuracy. The utility of computational data is then demonstrated by showing how the calculated barriers and enthalpies enable appropriate kinetic models to be chosen for RAFT. Further insights are provided by a systematic analysis of structure-reactivity trends. The development of the first computer-designed RAFT agent illustrates the practical utility of these investigations.

Ring-opening polymerization of lactides by (pyrazol-1-ylmethyl)pyridine Zn(II) and Cu(II) complexes: Kinetics, mechanism and tacticity studies

Ojwach,Stephen O.; Zaca,Thembisile P.
Fonte: South African Journal of Chemistry Publicador: South African Journal of Chemistry
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/01/2015 EN
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The kinetics, mechanism and polymer microstructure studies of ring-opening polymerization (ROP) of lactides (LA) by Zn(II) and Cu(II) complexes of (pyrazolylmethyl)pyridine ligands, 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1) and 2-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L2) is described. The complexes [Zn(Ac)2(L1)] (1), [Cu(Ac)2(L1)] (2), [Zn(Ac)2(L2)] (3) and [Cu2(Ac)4(L2)2](4) form active initiators in the ROP of D,L-LA and L-LA monomers. Generally Zn(II) complexes 1 and 3 exhibit higher activities compared to the corresponding Cu(II) complexes 2 and 4. Polymerization kinetics of D,L-LA show higher rates compared to the L-LA reactions. All the polymerization reactions follow pseudo first-order kinetics with respect to monomer while 1 shows second-order dependency on the polymerization reactions. Molecular weights of the polymers range from 813 g mol-1 to 9207 g mol-1 and exhibit relatively narrow molecular weight distributions between 1.2 to 1.6. While poly(D,L-LA) are predominantly atactic, poly(L-LA) are largely isotactic. All polymerization reactions proceed through coordination insertion mechanism followed by hydrolysis of the end groups.