Influence of the bonding substrate in dental composite polymerization stress testing

Our objective was to compare the polymerization stress (sigma(pol)) of a series of composites obtained using poly(methyl methacrylate) (PMMA) or glass as bonding substrates, and to compare the results with those from in vitro microleakage of composite restorations. The tested hypothesis was that stress values obtained in a less rigid testing system (i.e. using PMMA) would show a better relationship with microleakage data. Five dental composites were tested: Filtek Z250 (FZ), Z100 (Z1), Concept (CO), Durafill (DU) and Heliomolar (HM). sigma(pol) was determined in 1 mm high specimens inserted between two rods (empty set = 5 mm) of either PMMA or glass. The composite elastic modulus (E) was obtained by three-point bending. sigma(pol) and E data were submitted to a one-way analysis of variance/Tukey test (alpha = 0.05). For the microleakage test (MI), bovine incisors received cylindrical cavities (empty set = 5 mm, h = 2 mm), which were restored in bulk. After storage for 24 h in water, specimens were subjected to dye penetration using AgNO(3) as tracer. Specimens were sectioned twice, perpendicularly, and microleakage was measured (in millimeters) under 20x magnification. Data from MI were submitted to the Kruskal-Wallis test. Means (SD) of sigma(pol) (MPa) using glass/PMMA were FZ: 7.5(1.8)(A)/2.5(0.2)(bc); Z1: 7.3(0.5)(A)/2.8(0.3)(ab); CO: 6.8(1.1)(A)/3.2(0.5)(a); DU: 4.5(0.7)(B)/2.0(0.2)(bc); HM: 3.5(0.2)(B)/2.3(0.3)(c). sigma(pol) obtained using PMMA rods were 34-67% lower than with glass. Means (SD) for tooth average/tooth maximum microleakage were FZ: 0.92(0.19)(B)/1.53(0.30)(a); Z1: 1.19(0.21)(A)/1.75(0.20)(a); CO: 1.26(0.25)(A)/1.78(0.24)(a); DU: 0.83(0.30)(B)/1.68(0.46)(a): HM: 0.81(0.27)(B)/1.64(0.54)(a). The tested hypothesis was confirmed, as the composites showed the same ordering both in the polymerization stress test using PMMA rods and in the microleakage test. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photoinitiator content in restorative composites: Influence on degree of conversion, reaction kinetics, volumetric shrinkage and polymerization stress

Purpose: To determine the influence of rate of polymerization, degree of conversion and volumetric shrinkage on stress development by varying the amount of photoinitiators in a model composite. Methods: Volumetric shrinkage (with a mercury dilatometer), degree of conversion, maximum rate of reaction (RP(max)) (with differential scanning calorimetry) and polymerization stress (with a controlled compliance device) were evaluated. Bis-GMA/TEGDMA (equal mass ratios) were mixed with a tertiary amine (EDMAB) and camphorqpinone, respectively, in three concentrations (wt%): high= 0.8/1.6; intermediate= 0.4/0.8 and low= 0.2/0.4. 80 wt% filler was added. Composites were photoactivated (400 mW/cm(2) x 40 seconds; radiant exposure=16J/cm(2)). A fourth experimental group was included in which the low concentration formulation was exposed for 80 seconds (32 J/cm(2)). Results: For the same radiant exposure, conversion, RP(max) and stress increased with photoinitiator concentration (P< 0.001). When the low concentration group exposed to 32 J/cm(2) was compared with the high and intermediate groups (exposed to 16 J/cm(2)), RPmax Still increased with the photoinitiator concentration between all levels (P< 0.001) but conversion and stress did not vary (P> 0.05). Shrinkage did not vary regardless of the photoinitiator concentration or radiant exposure. For the photoinitiator concentrations used in this study. Polymerization stress was influenced by conversion but not by rate of reaction. (Am J Dent 2009;22:206-210).

Influence of irradiant energy on degree of conversion, polymerization rate and shrinkage stress in an experimental resin composite system

Objective. This study evaluated the degree of conversion (DC), maximum rate of cure (R(p)(max)), and polymerization stress (PS) developed by an experimental dental composite subjected to different irradiant energies (3,6,12, 24, or 48J/cm(2)) under constant irradiance (500 mw/cm(2)). Methods. DC and R(p)(max) were monitored for 10 min on the bottom surface of 2-mm thick disks and on 150-mu m thick films (representing the top of the specimen) using ATR-FTIR. PS was monitored for 10 min in 2-mm thick disks bonded to two glass rods (O = 5 mm) attached to a universal testing machine. One-way ANOVA/Tukey tests were used and differences in DC and R(p)(max) between top and bottom surfaces were examined using Student`s t-test. Statistical testing was performed at a pre-set alpha of 0.05. Results. For a given surface, DC showed differences among all groups, except at the top between 24 and 48 J/cm(2). R(p)(max) was similar among all groups at the same surface and statistically higher at the top surface. PS also showed significant differences among all groups. Data for 48 J/cm(2) were not obtained due to specimen failure at the glass/composite interface. Significance. Increases in irradiant exposure led to significant increases in DC and PS, but had no effect on R(p)(max) (c) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Polymerization stress of resin composites as a function of system compliance

Objectives. Evaluate the effect of testing system compliance on polymerization stress and stress distribution of composites. Methods. Composites tested were Filtek Z250 (FZ), Herculite (HL), Tetric Ceram (TC), Helio Fill-AP (HF) and Heliomolar (HM). Stress was determined in 1-mm thick specimens, inserted between two rods of either poly(methyl methacrylate), PMMA, or glass. Experimental nominal stress (sigma(exp)) was calculated by dividing the maximum force recorded 5 min after photoactivation by the cross-sectional area of the rod. Composites` elastic modulus (E) was obtained by three-point bending. Data were submitted to one-way ANOVA/Tukey`s test (alpha = 0.05). Stress distribution on longitudinal (sigma(y)) and transverse (sigma(x)) axes of models representing the composites with the highest and lowest E (FZ and HM, respectively) were evaluated by finite element analysis (FEA). Results. sigma(exp) ranged from 5.5 to 8.8 MPa in glass and from 2.6 to 3.4 MPa in PMMA. Composite ranking was not identical in both substrates, since FZ showed or sigma(exp) statistically higher than HM in glass, while in PMMA FZ showed values similar to the other composites. A strong correlation was found between stress reduction (%) from glass to PMMA and composite`s E (r(2) = 0.946). FEA revealed that system compliance was influenced by the composite (FZ led to higher compliance than HM). sigma(x) distribution was similar in both substrates, while cry distribution showed larger areas of compressive stresses in specimens built on PMMA. Significance. sigma(exp) determined in PMMA was 53-68% lower than in glass. Composite ranking varied slightly due to differences in substrates` longitudinal and transverse deformation. (c) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of curing protocol on the polymerization of dual-cured resin cements

Objectives. The purpose of this study was to evaluate how curing protocol affects the extent of polymerization of dual-cured resin cements. Methods. Four commercial resin cements were used (DuoLink, Panavia F 2.0, Variolink II and Enforce). The extent of polymerization of the resin cements cured under different conditions was measured using a (1)H Stray-Field MRI method, which also enabled to probe molecular mobility in the kHz frequency range. Results. Resin cements show well distinct behaviours concerning chemical cure. Immediate photo-activation appears to be the best choice for higher filler loaded resin cements (Panavia F 2.0 and Variolink). A photo-activation delay (5 min) did not induce any significant difference in the extent of polymerization of all cements. Significance. The extent of polymerization of dual-cured resin cements considerably changed among products under various curing protocols. Clinicians should optimize the materials choice taking into account the curing characteristics of the cements. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The Effect of Polymerization Cycles on Color Stability of Microwave-Processed Denture Base Resin

Purpose: This study evaluated the effect of different microwave polymerization cycles on the color changes of a microwave-processed denture base resin after accelerated aging and immersion in beverages. Materials and Methods: Specimens of light pink acrylic resin were divided into three groups according to polymerization cycle: (A) 500 W for 3 minutes, (B) 90 W for 13 minutes + 500 W for 90 seconds, and (C) 320 W for 3 minutes + 0 W for 4 minutes + 720 W for 3 minutes. Control groups were a heat-processed acrylic resin (T) and a chemically activated denture repair resin (Q). Eight specimens per group were aged in an artificial aging chamber and evaluated at 20, 192, and 384 hours. Another series of 40 specimens per group were immersed in water, coffee, tea, cola, or red wine and evaluated at 1, 12, and 36 days. Color was measured by a spectrophotometer before and after aging or immersion. Color changes (Delta E) were analyzed by ANOVA/Bonferroni t-test (alpha = 0.05). Results: Mean Delta E (+/- SD) after 384 hours of accelerated aging were (A) 2.51 +/- 0.50; (B) 3.16 +/- 1.09; (C) 2.89 +/- 1.06; (T) 2.64 +/- 0.34; and (Q) 9.03 +/- 0.40. Group Q had a significantly higher Delta E than the other groups. Color changes of immersed specimens were significantly influenced by solutions and time, but the five groups showed similar values. Mean Delta E at 36 days were (water) 1.4 +/- 0.8; (coffee) 1.3 +/- 0.6; (tea) 1.7 +/- 0.5; (cola) 1.4 +/- 0.7; and (red wine) 10.2 +/- 2.7. Results were similar among the five test groups. Conclusions: Color changes of the microwave-polymerized denture base resin tested were not affected by different polymerization cycles after accelerated aging or immersion in beverages. These changes were similar to the conventional heat-polymerized acrylic resin test, but lower than the repair resin after accelerated aging.

Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.

Synthesis of polymer-montmorillonite nanocomposites by in situ intercalative polymerization

Two polymer-montmorillonite (MMT) nanocomposites have been synthesized by in situ intercalative polymerization. The styrene monomer is intercalated into the interlayer space of organically modified MMT, a layered clay mineral. Upon the intercalation, the complex is subsequently polymerized in the confinement environment of the interlayer space with a free radical initiator, 2,2-azobis isobutyronitrile. The aniline monomer is also intercalated and then polymerized within the interlayer space of sodium- and copper-MMT initiated by ammonium peroxodisulphate and interlayer copper cations respectively. X-ray diffraction indicates that the MMT layers are completely dispersed in the polystyrene matrix and an exfoliated structure has been obtained. The resulting polyaniline-MMT nanocomposites show a highly ordered structure of a single polyaniline layer stacked with the MMT layers. Fourier transform infrared spectra further confirm the intercalation and formation of both polymer-MMT nanocomposites.

Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

Molecular mobility of n-ethylene glycol dimethacrylate glass formers upon free radical polymerization

Quando um líquido evita a cristalização durante o arrefecimento, diz-se que entra no estado sobrearrefecido. Se a temperatura continuar a diminuir, o consequente aumento da viscosidade reflecte-se na mobilidade molecular de tal maneira que os tempos característicos se tornam da mesma ordem de grandeza que os tempos acessíveis experimentalmente. Se o arrefecimento continuar, o líquido altamente viscoso acaba por vitrificar, i.e. entra no estado vítreo onde apenas os movimentos locais são permitidos. Os monómeros da família n -etileno glicol dimetacrilato ( n -EGDMA, para n = 1 até 4, que constituem o objecto deste estudo, facilmente evitam a cristalização, sendo pois bons candidatos para estudar a mobilidade molecular nos estados sobrearrefecido e vítreo. A Espectroscopia de Relaxação Dieléctrica (DRS) foi a técnica escolhida para obter informação detalhada sobre a sua dinâmica molecular (Capítulos 1 e 2). A primeira parte deste trabalho consistiu na caracterização dieléctrica dos processos de relaxação existentes acima e abaixo da temperatura de transição vítrea (g T ), a qual aumenta com o aumento do peso molecular (w M ), sendo este resultado confirmado por Calorimetria Diferencial de Varrimento (DSC). No que respeita ao processo cooperativo a , associado à transição vítrea, e ao processo secundário b, observa-se uma dependência com w M , enquanto que o outro processo secundário, g , aparenta ser independente deste factor (Capítulo 3). Nos capítulos seguintes, foram levadas a cabo diferentes estratégias com o objectivo de clarificar os mecanismos que estão na origem destas duas relaxações secundárias (b e g ), assim como conhecer a sua respectiva relação com a relaxação principal (a ). Do estudo, em tempo real, da polimerização isotérmica via radicais livres do TrEGDMA por Calorimetria de Varrimento Diferencial com Modulação de Temperatura (TMDSC), levado a cabo a temperaturas abaixo da g T do polímero final, concluem-se entre outros, dois importantes aspectos: i) que a vitrificação do polímero em formação conduz a graus de conversão relativamente baixos, e ii) que o monómero que está por reagir é expulso da rede polimérica que se forma, dando lugar a uma clara separação de fases (Capítulo 4). Com base nesta informação, o passo seguinte foi estudar separadamente a polimerização isotérmica do di-, tri- e tetra-EGDMA, dando especial atenção às alterações de mobilidade do monómero ainda por reagir. Com as restrições impostas pela formação de ligações químicas, as relaxações a e b detectadas no monómero tendem a desaparecer no novo polímero formado, enquanto que a relaxação g se mantém quase inalterada. Os diferentes comportamentos que aparecem durante a polimerização permitiram a atribuição da origem molecular dos processos secundários: o processo g foi associado ao movimento twisting das unidades etileno glicol, enquanto que a rotação dos grupos carboxilo foi relacionada com a relaxação b (Capítulo 5). No que respeita ao próprio polímero, um processo de relaxação adicional foi detectado, pol b , no poly-DEGDMA, poly-TrEGDMA e poly-TeEGDMA, com características similares ao encontrado nos poli(metacrilato de n -alquilo). Este processo foi confirmado e bem caracterizado aquando do estudo da copolimerização do TrEGDMA com acrilato de metilo (MA) para diferentes composições (Capítulo 6). Para finalizar, o EGDMA, o elemento mais pequeno da família de monómeros estudada, além de vitrificar apresenta uma marcada tendência para cristalizar quer a partir do estado líquido ou do estado vítreo. Durante a cristalização, a formação de uma fase rígida afecta principalmente o processo a , cuja intensidade diminui sem no entanto se observarem modificações significativas na dependência do tempo de relaxação característico com a temperatura. Por outro lado, o processo secundário b torna-se melhor definido e mais estreito, o que pode ser interpretado em termos de uma maior homogeneidade dos micro-ambientes associados aos movimentos locais(Capítulo 7).

Design of a Control Slide for Cyanoacrylate Polymerization : Application to the CA-Bluestar Sequence

Casework expercience has shown that, in some cases, long exposures of surfaces subjected to cyanoacrylate (CA) fuming had detrimental effects on the subsequent application of Bluestar. This study aimed to develop a control mechanism to monitor the amount of CA deposited prior to the subsequent treatment. A control slide bearing spots of sodium hydroxide (NaOH) of known concentrations and volume was designed and validated against both scanning electron microscopy (SEM) observations and latent print examiners' assessments of the quality of the developed marks. The control slide allows one to define three levels of development that were used to monitor the Bluestar reaction on depleting footwear marks left in diluted blood. The appropriate conditions for a successful application of both CA and Bluestar were determined.

Bcl10 controls TCR- and FcgammaR-induced actin polymerization.

Bcl10 plays an essential role in the adaptive immune response, because Bcl10-deficient lymphocytes show impaired Ag receptor-induced NF-kappaB activation and cytokine production. Bcl10 is a phosphoprotein, but the physiological relevance of this posttranslational modification remains poorly defined. In this study, we report that Bcl10 is rapidly phosphorylated upon activation of human T cells by PMA/ionomycin- or anti-CD3 treatment, and identify Ser(138) as a key residue necessary for Bcl10 phosphorylation. We also show that a phosphorylation-deficient Ser(138)/Ala mutant specifically inhibits TCR-induced actin polymerization yet does not affect NF-kappaB activation. Moreover, silencing of Bcl10, but not of caspase recruitment domain-containing MAGUK protein-1 (Carma1) induces a clear defect in TCR-induced F-actin formation, cell spreading, and conjugate formation. Remarkably, Bcl10 silencing also impairs FcgammaR-induced actin polymerization and phagocytosis in human monocytes. These results point to a key role of Bcl10 in F-actin-dependent immune responses of T cells and monocytes/macrophages.

Vida immortal

Poques coses han captivat tan poderosament la imaginació humana com la idea de viure eternament. Però tots sabem que els éssers vius, més tard o més d'hora, moren.

Use of thin films obtained by plasma polymerization for grain protection and germination enhancement

In this work, preliminary results of the use of hydrophobic thin films obtained by plasma deposition to protect grains and seeds are presented: grains coated by the films did not present biological degradation when stored in a saturated water vapor environment, but had their germination accelerated in the presence of water. A model that explains the difference of behavior of the films when exposed to water in vapor form or in liquid form, based on the formation of microchannels within the film that lead to water uptake in seeds, is presented. The model was successfully tested using quartz crystal measurements, which showed that the microchannels within the films can favor the adsorption and permeation of water when the films are immersed in water.