Maximizing the utility of bio-based diisocyanate and chain extenders in crystalline segmented thermoplastic polyester urethanes: effect of polymerization protocol

High molecular weight semi crystalline thermoplastic poly(ester urethanes), TPEUs, were prepared from a vegetable oil-based diisocyanate, aliphatic diol chain extenders and poly(ethylene adipate) macro diol using one-shot, pre-polymer and multi-stage polyaddition methods. The optimized polymerization reaction achieved ultra-high molecular weight TPEUs (>2 million as determined by GPC) in a short time, indicating a very high HPMDI diol reactivity. TPEUs with very well controlled hard segment (HS) and soft segment (SS) blocks were prepared and characterized with DSC, TGA, tensile analysis, and WAXD in order to reveal structure property relationships. A confinement effect that imparts elastomeric properties to otherwise thermoplastic TPEUs was revealed. The confinement extent was found to vary predictably with structure indicating that one can custom engineer tougher polyurethane elastomers by "tuning" soft segment crystallinity with suitable HS block structure. Generally, the HPMDI-based TPEUs exhibited thermal stability and mechanical properties comparable to entirely petroleum-based TPEUs. (C) 2014 Elsevier Ltd. All rights reserved.

Effect of postpolymerization method on the color stability of composite resins submitted to ultraviolet aging

The aim of this research was to evaluate the effect of postpolymerization method on the color stability of resin-based composites. Samples of direct and indirect restorative materials were polymerized with two photo-curing units (Visio photo-curing oven system and LED Elipar Freelight 2). All samples were submitted to an initial chromatic analysis using a spectrometer and submitted to ultraviolet-accelerated artificial aging. The direct material showed less color change than the indirect material, independent of the photo-activation method used. Samples photo cured with the LED system showed less change than those photo cured with the Visio system. The postpolymerization oven did not improve the color stability of direct and indirect resin-based composites.

Abrasion resistance of direct and indirect resins as a function of a sealant veneer

Abrasive wear is one of the most common type of wear that not only affect teeth, as also dental restorations. Thus to investigate one of the etiological factors as tooth brushing procedure is clinical relevant in order to select the best material combination that may prevent damage of resin dental restoration's abrasion. This study evaluated the influence of tooth brushing on mass loss and surface roughness of direct Venus (Vs) and indirect Signum (Sg) resin composites, with and without a surface sealant, Fortify (F). Twenty-four specimens were prepared with each resin composite, using their proprietary curing units, according to manufacturer's instructions. All the specimens were polished and ultrasonically cleaned in distilled water for 5 minutes. Half of the specimens of each resin (n = 12) were covered with F (Vs F and Sg F ), except for the control (C) specimens (Vs C and Sg C ), which were not sealed. Mass loss (ML) as well as surface roughness (Ra ) was measured for all the specimens. Then, the specimens were subjected to toothbrush-dentifrice abrasion, using a testing machine for 67.000 brushing strokes, in an abrasive slurry. After brushing simulation, the specimens were removed from the holder, rinsed thoroughly and blot dried with soft absorbent paper. The abrasion of the material was quantitatively determined with final measurements of ML and surface roughness, using the method described above. ML data were analyzed by two-way analysis of variance (ANOVA) and the analysis indicated that resin composites were not statistically different; however, the specimens sealed with F showed higher ML. Ra mean values of the groups Vs F and Sg F significantly increased. Tooth brushing affects mainly the roughness of the direct and indirect resin composites veneered with a sealant.

In vitro enamel remineralization capacity of composite resins containing sodium trimetaphosphate and fluoride

This study evaluated the in vitro enamel remineralization capacity of experimental composite resins containing sodium trimetaphosphate (TMP) combined or not with fluoride (F). Bovine enamel slabs were selected upon analysis of initial surface hardness (SH1) and after induction of artificial carious lesions (SH2). Experimental resins were as follows: resin C (control-no sodium fluoride (NaF) or TMP), resin F (with 1.6 % NaF), resin TMP (with 14.1 % TMP), and resin TMP/F (with NaF and TMP). Resin samples were made and attached to enamel slabs (n = 12 slabs per material). Those specimens (resin/enamel slab) were subjected to pH cycling to promote remineralization, and then final surface hardness (SH3) was measured to calculate the percentage of surface hardness recovery (%SH). The integrated recovery of subsurface hardness (ΔKHN) and F concentration in enamel were also determined. Data was analyzed by ANOVA and Student-Newman-Keuls test (p < 0.05). Resins F and TMP/F showed similar SH3 values (p = 0.478) and %SH (p = 0.336) and differed significantly from the other resins (p < 0.001). Considering ΔKHN values, resin TMP/F presented the lowest area of lesion (p < 0.001). The presence of F on enamel was different among the fluoridated resins (p = 0.042), but higher than in the other resins (p < 0.001). The addition of TMP to a fluoridated composite resin enhanced its capacity for remineralization of enamel in vitro. The combination of two agents with action on enamel favored remineralization, suggesting that composite resins containing sodium trimetaphosphate and fluoride could be indicated for clinical procedures in situations with higher cariogenic challenges.

Chromatic stability of acrylic resins of artificial eyes submitted to the accelerated aging and polishing

Esthetics and durability of materials used to fabricate artificial eyes has been an important issue since artificial eyes are essential to restore esthetics and function, protect the remaining tissues and help with patients' psychological therapy. However, these materials are submitted to degrading effects of environmental agents on the physical properties of the acrylic resin. OBJECTIVE: This study assessed the color stability of acrylic resins used to fabricate sclera in three basic shades (N1, N2 and N3) when subjected to accelerated aging, mechanical and chemical polishing. MATERIAL AND METHODS: Specimens of each resin were fabricated and submitted to mechanical and chemical polishing. Chromatic analysis was performed before and after accelerated aging through ultraviolet reflection spectrophotometry. RESULTS: All specimens revealed color alteration following polishing and accelerated aging. The resins presented statistically significant chromatic alteration (p<0.01) between the periods of 252 and 1008 h. CONCLUSIONS: Both polishing methods presented no significant difference between the values of color derivatives of resins.

Análise da efetividade de polimerização, adaptação marginal e interna de restaurações Classe II de resinas compostas de inserção em bloco utilizando diferentes matrizes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Biodegradation of Thermoplastic and hermosetting Polyesters from Z-Protected Glutamic Acid

In a previous article,1 the development and molecular characterization of three polyesters from N-carbobenzyloxy-L-glutamic acid (ZGluOH) were reported. The polymers were a linear, heterochain polyester (ZGluOH and ethylene glycol), a crosslinked heterochain polyester (ZGluOH and diglycidyl ether of 1,4-butanediol), and a crosslinked, heterochain aromatic polyester (ZGluOH and diglycidyl ether of bisphenol A). In this manuscript, results of biodegradation studies are reported. The three polymers hydrolyzed to low molecular weight oligomers similar to the monomers with lipase. When exposed to a mixed culture of micro-organisms, the first two resins degraded to biomass and respiratory gases. The crosslinked heterochain aromatic polyester resisted microbial degradation.

Purification of coagulation factor VIII using chromatographic methods. Direct chromatography of plasma in anion exchange resins

Coagulation factor VIII (FVIII) concentrates are used in the treatment of patients with Hemophilia A. Human FVIII was purified directly from plasma using anion exchange chromatography followed by gel filtration. Three Q-Sepharose resins were tested, resulting in 40% recovery of FVIII activity using Q-Sepharose XL resin, about 80% using Q-Sepharose Fast Flow and 70% using the Q-Sepharose Big Beads. The vitamin K-dependent coagulation factors co-eluted with FVIII from the anion exchange columns. In the second step of purification, when Sepharose 6FF was used, 70% of FVIII activity was recovered free from vitamin K-dependent factors.

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

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, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and R-p(max) values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an R-p(max) value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity. Significance. Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The filler content of the dental composite resins and their influence on different properties

The purpose of this study was to compare the inorganic content and morphology of one nanofilled and one nanohybrid composite with one universal microhybrid composite. The Vickers hardness, degree of conversion and scanning electron microscope of the materials light-cured using LED unit were also investigated. One nanofilled (Filtek (TM) Supreme XT), one nanohybrid (TPH (R) 3) and one universal microhybrid (Filtek (TM) Z-250) composite resins at color A2 were used in this study. The samples were made in a metallic mould (4 mm in diameter and 2 mm in thickness). Their filler weight content was measured by thermogravimetric analysis (TG). The morphology of the filler particles was determined using scanning electron microscope equipped with a field emission gun (SEM-FEG). Vickers hardness and degree of conversion using FT-IR spectroscopy were measured. Filtek (TM) Z-250 (microhybrid) composite resin shows higher degree of conversion and hardness than those of Filtek (TM) Supreme XT (nanofilled) and TPH (R) 3 (nanohybrid) composites, respectively. The TPH3 (R) (nanohybrid) composite exhibits by far the lowest mechanical property. Nanofilled composite resins show mechanical properties at least as good as those of universal hybrids and could thus be used for the same clinical indications as well as for anterior restorations due to their high aesthetic properties. Microsc. Res. Tech. 75:758765, 2012. (C) 2011 Wiley Periodicals, Inc

Degree of conversion of nanofilled and microhybrid composite resins photo-activated by different generations of LEDs

Objective: This study aimed at evaluating the degree of conversion (DC) of four composite resins, being one nanofilled and 3 microhybrid resins, photo-activated with second- and third-generation light-emitting diodes (LEDs). Material and methods: Filtek (TM) Z350 nanofilled composite resins and Amelogen (R) Plus, Vit-l-escence (TM) and Opallis microhybrid resins were photo-activated with two second-generation LEDs (Radii-cal and Elipar Free Light (TM) 2) and one third-generation LED (Ultra-Lume LED 5) by continuous light mode, and a quartz halogen-tungsten bulb (QHT, control). After 24 h of storage, the samples were pulverized into fine powder and 5 mg of each material were mixed with 100 mg of potassium bromide (KBr). After homogenization, they were pressed, which resulted in a pellet that was evaluated using an infrared spectromer (Nexus 470, Thermo Nicolet) equipped with TGS detector using diffuse reflectance (32 scans, resolution of 4 cm(-1)) coupled to a computer. The percentage of unreacted carbon-carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm-1) against internal standard before and after curing of the specimen: aromatic C-C (peak at 1610 cm-1). Results: The ANOVA showed a significant effect on the interaction between the light-curing units (LCUs) and the composite resins (p<0.001). The Tukey's test showed that the nanofilled resin (Filtek (TM) Z350) and Opallis when photo-activated by the halogen lamp (QTH) had the lowest DC compared with the other microhybrid composite resins. The DC of the nanofilled resin (Filtek (TM) Z350) was also lower using LEDs. The highest degrees of conversion were obtained using the third-generation LED and one of second-generation LEDs (Elipar Free Light (TM) 2). Conclusions: The nanofilled resin showed the lowest DC, and the Vit-l-escence (TM) microhybrid composite resin showed the highest DC. Among the LCUs, it was not possible to establish an order, even though the second-generation LED Radii-cal provided the lowest DC.

Evaluation of the flexural strength and elastic modulus of resins used for temporary restorations reinforced with particulate glass fibre

Objective: The flexural strength and the elastic modulus of acrylic resins, Dencor, Duralay and Trim Plus II, were evaluated with and without the addition of silanised glass fibre. Materials and methods: To evaluate the flexural strength and elastic modulus, 60 test specimens were fabricated with the addition of 10% ground silanised glass fibres for the experimental group, and 60 without the incorporation of fibres, for the control group, with 20 test specimens being made of each commercial brand of resin (Dencor, Duralay and Trim Plus II) for the control group and experimental group. After the test specimens had been completed, the flexural strength and elastic modulus tests were performed in a universal testing device, using the three-point bending test. For the specimens without fibres the One-Way Analysis of Variance and the complementary Tukey test were used, and for those with fibres it was not normal, so that the non-parametric Mann-Whitney test was applied. Results: For the flexural strength test, there was no statistical difference (p > 0.05) between each commercial brand of resin without fibres [Duralay 84.32(+/- 8.54), Trim plus 85.39(+/- 6.74), Dencor 96.70(+/- 6.52)] and with fibres (Duralay 87.18, Trim plus 88.33, Dencor 98.10). However, for the elastic modulus, there was statistical difference (p > 0.01) between each commercial brand of resin without fibres [Duralay 2380.64 (+/- 168.60), Trim plus 2740.37(+/- 311.74), Dencor 2595.42(+/- 261.22)] and with fibres (Duralay 3750.42, Trim plus 3188.80, Dencor 3400.75). Conclusion: The result showed that the incorporation of fibre did not interfere in the flexural strength values, but it increased the values for the elastic modulus.

Evaluation of the biocide activity of phosphorylated and sulfophosphorylated resins

Phosphorylated poly(styrene-co-divinylbenzene) copolymers prepared by aromatic electrophilic substitution reaction with PCl3/AlCl3 were reacted with carbon dissulfite in order to introduce sulfophosphorylated groups into copolymers. These modifications were characterized by FTIR, elemental analysis, spectrophotometry, optical and scanning electron microscopy. The antibacterial activities of the phosphorylated and sulfophorylated copolymers were assessed against Escherichia coli ATCC25922 suspensions (10(3)-10(7) cells mL(-1)) using a column system. The unmodified copolymers did not have antibacterial activity against the E. coil suspensions but the phosphorylated and sulfophorylated copolymers showed significant bactericidal action for all E. coli concentrations. The sulfophosphorylated copolymers had higher antibacterial activity than the phosphorylated ones, mainly for high concentrations of E. coli cells. Published by Elsevier B.V.

Tannin-phenolic resins: Synthesis, characterization, and application as matrix in biobased composites reinforced with sisal fibers

A tannin-phenolic resin (40 wt% of tannin, characterized by H-1 nuclear magnetic resonance (NMR) and C-13 NMR, Fourier transform infrared, thermogravimetry, differential scanning calorimetry) was used to prepare composites reinforced with sisal fibers (30-70 wt%). Inverse gas chromatography results showed that the sisal fibers and the tannin-phenolic thermoset have close values of the dispersive component and also have predominance of acid sites (acid character) at the surface, confirming the favoring of interaction between the sisal fibers and the tannin-phenolic matrix at the interface. The Izod impact strength increased up to 50 wt% of sisal fibers. This composite also showed high storage modulus, and the lower loss modulus, confirming its good fiber/matrix interface, also observed by SEM images. A composite with good properties was prepared from high content of raw material obtained from renewable sources (40 wt% of tannin substituted the phenol in the preparation of the matrix and 50 wt% of matrix was replaced by sisal fibers). (C) 2012 Elsevier Ltd. All rights reserved.