Influence of the base and diluent methacrylate monomers on the polymerization stress and its determinants

The aim of this study was to evaluate the effect of the association between bisphenol-A diglycidyl dimethacrylate (BisGMA) or its ethoxylated version (BisEMA) with diluents derived from the ethylene glycol dimethacrylate (EGDMA), with increasing number of ethylene glycol units (1: EGDMA, 2: DEGDMA, 3: TEGDMA, or 4: TETGDMA), or trimethylol propane trimethacrylate (TMPTMA) or 1,10-decanediol dimethacrylate (D3MA) on polymerization stress, volumetric shrinkage, degree of conversion, maximum rate of polymerization (Rpmax), and elastic modulus of experimental composites. BisGMA containing formulations presented lower shrinkage and stress but higher modulus and Rpmax than those containing BisEMA. TMPTMA presented the lowest stress among all diluents, as a result of lower conversion. EGDMA, DEGDMA, TEGDMA, and TETGDMA presented similar polymerization stress which was higher than the stress presented by D3MA and TMPTMA. D3MA presented similar conversion when copolymerized with both base monomers. The other diluents presented higher conversion when associated with BisEMA. EGDMA showed similar shrinkage compared with DEGDMA and higher than the other diluents. The lower conversion achieved by TMPTMA did not jeopardize its elastic modulus, similar to the other diluents. Despite the similar conversion presented by D3MA in comparison with EGDMA and DEGDMA, its lower elastic modulus may limit its use. Rather than proposing new materials, this study provides a systematic evaluation of off the shelf monomers and their effects on stress development, as highlighted by the analysis of conversion, shrinkage and modulus, to aid the optimization of commercially available materials. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Six-month evaluation of a resin/dentin interface created by methacrylate and silorane-based materials

Objectives: This study aimed to compare the micro-tensile bond strength of methacrylate resin systems to a silorane-based restorative system on dentin after 24 hours and six months water storage. Material and Methods: The restorative systems Adper Single Bond 2/Filtek Z350 (ASB), Clearfil SE Bond/Z350 (CF), Adper SE Plus/Z350 (ASEP) and P90 Adhesive System/Filtek P90 (P90) were applied on flat dentin surfaces of 20 third molars (n=5). The restored teeth were sectioned perpendicularly to the bonding interface to obtain sticks (0.8 mm2) to be tested after 24 hours (24 h) and 6 months (6 m) of water storage, in a universal testing machine at 0.5 mm/min. The data was analyzed via two-way Analysis of Variance/Bonferroni post hoc tests at 5% global significance. Results: Overall outcomes did not indicate a statistical difference for the resin systems (p=0.26) nor time (p=0.62). No interaction between material × time was detected (p=0.28). Mean standard-deviation in MPa at 24 h and 6 m were: ASB 31.38 (4.53) and 30.06 (1.95), CF 34.26 (3.47) and 32.75 (4.18), ASEP 29.54 (4.14) and 33.47 (2.47), P90 30.27 (2.03) and 31.34 (2.19). Conclusions: The silorane-based system showed a similar performance to methacrylate-based materials on dentin. All systems were stable in terms of bond strength up to 6 month of water storage.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Epiphany root canal sealer prepared with resinous solvent is irritating to rat subcutaneous tissues

Objective: This study assessed the biocompatibility of the Epiphany endodontic sealer prepared with resinous solvent of Epiphany system (Thinning resin) in rat subcutaneous tissues. Study Design: Polyethylene tubes were filled with the sealer and 4 groups were established: GI, Epiphany prepared with 1 drop of resinous solvent (RS); GII, Epiphany prepared with 1 drop of RS and photoactivated; GIII, Epiphany associated with self-etch primer and prepared with 1 drop of RS; GIV, Epiphany associated with self-etch primer, prepared with 1 drop of RS and photoactivated. The filled tubes were implanted into 4 different regions of the dorsum of 20 adult male rats. Results: After 7, 14 and 21 days, all groups presented a moderate to severe chronic inflammation, necrosis and foreign-body giant cells. At 42 days, although the intensity of chronic inflammatory reaction decreased, the other features still were observed. Conclusion: The Epiphany sealer prepared with the RS was irritating to rat subcutaneous tissues.

Effects of the antimycobacterial compound 2-phenoxy-1-phenylethanone on rat hepatocytes and formation of metabolites

Context: Neolignans are usually dimers formed by oxidative coupling of allyl and propenyl phenols, and the neolignan analogue, 2-phenoxy-1-phenylethanone (LS-2) is a promising antimycobacterial compound showing very weak cytotoxicity in mammalian cells and lack of acute toxicity in murine models. Objectives: To investigate the mechanism of action of LS-2 in rat hepatocytes by evaluating the activity levels of enzymes related to oxidation status and drug-metabolizing activity. Materials and methods: Hepatocytes were treated with LS-2 from 0.05 up to 1 mM, for 24 and 48 h, and reduced glutathione (GSH), lipid peroxidation and cytochrome P450 enzyme (CYP450) activity were assayed. A homologous series of phenoxazone ethers were used as substrates to measure the enzymatic profile. The biotransformation of LS-2 was studied in hepatocytes by gas chromatography-mass spectrometry (GC-MS) for detection and analysis of possible metabolites. Results: Hepatocytes treated with LS-2 up to 1 mM for 24 or 48 h did not induce the formation of GSH and lipid peroxidation. O-Dealkylation activities of the isoenzymes CYP4501A1, CYP4501A2, CYP4502B1 and CYP4502B2 were also not detected in the hepatocytes treated with LS-2 for 24 or 48 h. Discussion and conclusion: The results indicate that LS-2 or its two detected metabolites, 2-phenoxy-1-phenylethanol and 2,4-(2-hydroxy-2-phenylethoxy) phenol, are not cytotoxic to rat hepatocytes. These compounds maintain a balance between the production of pro-oxidant agents and their respective antioxidant systems. The data show that enzymes related to oxidation status and drug-metabolizing activities are not involved in the mechanism of action of LS-2.

Photophysical properties of a fluorene-bipyridine copolymer and its complexes with europium

The synthesis and structural characterization of a europium complexed fluorene-bipyridine copolymer are described. A level of ion insertion of 80% in molar basis was achieved, and theoretical calculations showed that it required a twist of 179 degrees (49 kJ) between the pyridine units. Spectroscopy data showed that no electronic coupling between the main backbone and the complexation sites had occurred, but these hindered the interchain aggregation observed in the non complexed polymer. Preliminary electroluminescence studies showed that the EL and PL spectra are consistent, and that the ion had a trapping effect in the charge transport. (C) 2011 Elsevier B.V. All rights reserved.

Ceramic Primer Heat-Treatment Effect on Resin Cement/Y-TZP Bond Strength

The purpose of this study was to evaluate the effect of different heat-treatment strategies for a ceramic primer on the shear bond strength of a 10-methacryloyloxydecyl-dihydrogen-phosphate (MDP)-based resin cement to a yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic. Specimens measuring 4.5 x 3.5 x 4.5 mm(3) were produced from Y-TZP presintered cubes and embedded in polymethyl methacrylate (PMMA). Following finishing, the specimens were cleaned using an ultrasound device and distilled water and randomly divided into 10 experimental groups (n=14) according to the heat treatment of the ceramic primer and aging condition. The strategies used for the experimental groups were: GC (control), without primer; G20, primer application at ambient temperature (20 degrees C); G45, primer application + heat treatment at 45 degrees C; G79, primer application + heat treatment at 79 degrees C; and G100, primer application + heat treatment at 100 degrees C. The specimens from the aging groups were submitted to thermal cycling (6000 cycles, 5 degrees C/55 degrees C, 30 seconds per bath) after 24 hours. A cylinder of MDP-based resin cement (2.4 mm in diameter) was constructed on the ceramic surface of the specimens of each experimental group and stored for 24 hours at 37 degrees C. The specimens were submitted to a shear bond strength test (n=14). Thermal gravimetric analysis was performed on the ceramic primer. The data obtained were statistically analyzed by two-way analysis of variance and the Tukey test (alpha=0.05). The experimental group G79 without aging (7.23 +/- 2.87 MPa) presented a significantly higher mean than the other experimental groups without aging (GC: 2.81 +/- 1.5 MPa; G20: 3.38 +/- 2.21 MPa; G100: 3.96 +/- 1.57 MPa), showing no difference from G45 only (G45: 6 +/- 3.63 MPa). All specimens of the aging groups debonded during thermocycling and were considered to present zero bond strength for the statistical analyses. In conclusion, heat treatment of the metal/zirconia primer improved bond strength under the initial condition but did not promote stable bonding under the aging condition.

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.

Solvation in aqueous binary mixtures: consequences of the hydrophobic character of the ionic liquids and the solvatochromic probes

Information on the solvation in mixtures of water, W, and the ionic liquids, ILs, 1-allyl-3-R-imidazolium chlorides; R = methyl, 1-butyl, and 1-hexyl, has been obtained from the responses of the following solvatochromic probes: 2,6-dibromo-4-[(E)-2-(1-R-pyridinium-4-yl)ethenyl] phenolate, R = methyl, MePMBr2; 1-octyl, OcPMBr(2), and the corresponding quinolinium derivative, MeQMBr(2). A model developed for solvation in binary mixtures of W and molecular solvents has been extended to the present mixtures. Our objective is to assess the relevance to solvation of hydrogen-bonding and the hydrophobic character of the IL and the solvatochromic probe. Plots of the medium empirical polarity, E-T(probe) versus its composition revealed non-ideal behavior, attributed to preferential solvation by the IL and, more efficiently, by the IL-W hydrogen-bonded complex. The deviation from linearity increases as a function of increasing number of carbon atoms in the alkyl group of the IL, and is larger than that observed for solvation by W plus molecular solvents (1-propanol and 2-(1-butoxy)ethanol) that are more hydrophobic than the ILs investigated. This enhanced deviation is attributed to the more organized structure of the ILs proper, which persists in their aqueous solutions. MeQMBr(2) is more susceptible to solvent lipophilicity than OcPMBr(2), although the former probe is less lipophilic. This enhanced susceptibility agrees with the important effect of annelation on the contributions of the quinonoid and zwitterionic limiting structures to the ground and excited states of the probe, hence on its response to both medium composition and lipophilicity of the IL.

Compatibilization of polypropylene/poly(3-hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3-hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene-g-maleic anhydride) (PPMAH), poly (ethylene-co-methyl acrylate) [P(EMA)], poly(ethylene-co-glycidyl methacrylate) [P(EGMA)], and poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) [P(EMAGMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(EMAGMA) > P(EMA) > P(EGMA) > PP-MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 3511-3519, 2012

Antimicrobial Properties and Cytotoxicity of an Antimicrobial Monomer for Application in Prosthodontics

Purpose: This study aimed to investigate the antimicrobial properties and cytotoxicity of the monomer methacryloyloxyundecylpyridinium bromide (MUPB), an antiseptic agent capable of copolymerizing with denture base acrylic resins. Materials and Methods: The antimicrobial activity of MUPB was tested against the species Candida albicans, Candida dubliniensis, Candida glabrata, Lactobacillus casei, Staphylococcus aureus, and Streptococcus mutans. The minimum inhibitory and fungicidal/bactericidal concentrations (MIC, MFC/MBC) of MUPB were determined by serial dilutions in comparison with cetylpyridinium chloride (CPC). The cytotoxic effects of MUPB at concentrations ranging from 0.01 to 1 g/L were assessed by MTT test on L929 cells and compared with methyl methacrylate (MMA). The antimicrobial activity of copolymerized MUPB was tested by means of acrylic resin specimens containing three concentrations of the monomer (0, 0.3, 0.6% w/w). Activity was quantified by means of a disc diffusion test and a quantification of adhered planktonic cells. Statistical analysis employed the Mann-Whitney test for MIC and MFC/MBC, and ANOVA for the microbial adherence test (a= 0.05). Results: MUBP presented lower MIC values when compared with CPC, although differences were significant for C. dubliniensis and S. mutans only (p= 0.046 and 0.043, respectively). MFC/MBC values were similar for all species except C. albicans; in that case, MUPB presented significantly higher values (p= 0.046). MUPB presented higher cytotoxicity than MMA for all tested concentrations (p < 0.001) except at 0.01 g/L. Irrespective of the concentration incorporated and species, there was no inhibition halo around the specimens. The incorporation of MUPB influenced the adhesion of C. albicans only (p= 0.003), with lower CFU counts for the 0.6% group. Conclusions: It was concluded that non-polymerized MUPB has an antimicrobial capacity close to that of CPC and high cytotoxicity when compared with MMA. The antimicrobial activity of MUPB after incorporation within a denture base acrylic resin did not depend on its elution, but was shown to be restricted to C. albicans.

Femtosecond Laser in Polymeric Materials: Microfabrication of Doped Structures and Micromachining

The use of laser light to modify the material's surface or bulk as well as to induce changes in the volume through a chemical reaction has received great attention in the last few years, due to the possibility of tailoring the material's properties aiming at technological applications. Here, we report on recent progress of microstructuring and microfabrication in polymeric materials by using femtosecond lasers. In the first part, we describe how polymeric materials' micromachining, either on the surface or bulk, can be employed to change their optical and chemical properties promising for fabricating waveguides, resonators, and self-cleaning surfaces. In the second part, we discuss how two-photon absorption polymerization can be used to fabricate active microstructures by doping the basic resin with molecules presenting biological and optical properties of interest. Such microstructures can be used to fabricate devices with applications in optics, such as microLED, waveguides, and also in medicine, such as scaffolds for tissue growth.

Hofmeister effects on the colloidal stability of poly(ethylene glycol)-decorated nanoparticles

The colloidal stability of poly(ethylene glycol)-decorated poly(methyl methacrylate), PMMA/Tween-20, particles was investigated by means of phase separation measurements, in the presence of sodium fluoride (NaF), sodium chloride, sodium bromide, sodium nitrate, or sodium thiocyanate (NaSCN) at 1.0 mol L-1. Following Hofmeister's series, the dispersions of PMMA/Tween-20 destabilized faster in the presence of NaF than with NaSCN. After the phase separation, the systems were homogenized and except for the dispersions in NaF, re-dispersed particles took longer to destabilize, indicating that anions adsorbed on the particles, creating a new surface. Except for F- ions, the adsorption of anions on the polar outmost shell was evidenced by means of tensiometry and small-angle X-ray scattering measurements. Fluoride ions induced the dehydration of the polar shell, without affecting the polar shell electron density, and the formation of very large aggregates. A model was proposed to explain the colloidal behavior in the presence of Hofmeister ions.

Effect of Prior Photodegradation on the Biodegradation of Polypropylene/Poly(3-hydroxybutyrate) Blends

In this work, the effect of blend composition and previous photodegradation on the biodegradation of polypropylene/ poly(3-hydroxybutyrate) (PP/PHB) blends was studied. The individual polymers and blends with or without the addition of poly(ethylene-co-methyl acrylate- co-glycidyl methacrylate) [P(E-MA-GMA)] as a compatibilizer (in the case of 80/20 blend) were exposed to UV light for 4 weeks and their biodegradation was evaluated. The biodegradation of PHB phase within the blends was hindered as PHB was the dispersed phase and PP fibrous particles were observed at the surface of the blend samples after biodegradation. Previous photodegradation lessened PHB biodegradation but enhanced the biodegradation of PP and the blends within the biodegradation time studied. Photodegradation resulted in cracks at the surface of PP and the blends, which probably facilitated the biotic reactions due to an easier access of the enzymes to deeper polymer layers. It also resulted in a decrease of molecular weight of PP phase and formation of carbonyl and hydroxyl groups which were consumed during biodegradation. Size exclusion chromatography analysis revealed that only the short chains of PP were consumed during biodegradation.