Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Chemical and morphological features of nanofilled composite resin: Influence of finishing and polishing procedures and fluoride solutions

This study evaluated the influence of finishing and polishing procedures and different fluoride solutions on superficial morphology and chemistry of the nanofilled composite resin Supreme XT (3M) through the EDX analysis and SEM evaluation. Circular specimens (n = 30) of 10 mm diameter and 2 mm thickness were prepared, with half of the sample assays finished and polished with Super-Snap (R) sandpaper. The experimental groups were divided according to the presence or absence of finishing and polishing and solutions (artificial saliva, 0.05% of manipulated sodium fluoride solution, Fluordent Reach, Oral B, Fluorgard). Specimens were immersed in each respective solution for 1 min per day, during 60 days and stored in artificial saliva at 37 +/- 1 degrees C between immersion periods. Topography and chemical analysis was qualitative. It was observed that specimens submitted to finishing and polishing procedures had lower superficial degradation. Fluoride solutions promoted superficial alterations on specimens, being the highest degradation obtained with Fluordent Reach. It can be concluded that finishing and polishing procedures and the immersion media influence the superficial morphology of composite resin tested; the Fluordent Reach was the fluoride solution that most affected the material's surface. Microsc. Res. Tech. 2011., (c) 2011 Wiley Periodicals, Inc.

The influence of "C-factor" and light activation technique on polymerization contraction forces of resin composite

Objectives: This study evaluated the influence of the cavity configuration factor ("C-Factor") and light activation technique on polymerization contraction forces of a Bis-GMA-based composite resin (Charisma, Heraeus Kulzer). Material and Methods: Three different pairs of steel moving bases were connected to a universal testing machine (Emic DL 500): groups A and B - 2x2 mm (CF=0.33), groups C and D - 3x2 mm (CF=0.66), groups E and F - 6x2 mm (CF=1.5). After adjustment of the height between the pair of bases so that the resin had a volume of 12 mm(3) in all groups, the material was inserted and polymerized by two different methods: pulse delay (100 mW/cm(2) for 5 s, 40 s interval, 600 mW/cm(2) for 20 s) and continuous pulse (600 mW/cm(2) for 20 s). Each configuration was light cured with both techniques. Tensions generated during polymerization were recorded by 120 s. The values were expressed in curves (Force(N) x Time(s)) and averages compared by statistical analysis (ANOVA and Tukey's test, p<0.05). Results: For the 2x2 and 3x2 bases, with a reduced C-Factor, significant differences were found between the light curing methods. For 6x2 base, with high C-Factor, the light curing method did not influence the contraction forces of the composite resin. Conclusions: Pulse delay technique can determine less stress on tooth/restoration interface of adhesive restorations only when a reduced C-Factor is present.

A method to investigate the shrinkage stress developed by resin-composites bonded to a single flat surface

Objectives. To purpose a method for predicting the shrinkage stress development in the adhesive layer of resin-composite cylinders that shrink bonded to a single flat surface, by measuring the deflection of a glass coverslip caused by the shrinkage of the bonded cylinders. The correlation between the volume of the bonded resin-composite and the stress-peak was also investigated. Methods. A glass coverslip deflection caused by the shrinkage of a bonded resin-composite cylinder (diameter: d = 8 mm, 4 mm, or 2 mm, height: h = 4 mm, 2 mm, 1 mm, or 0.5 mm) was measured, and the same set-up was simulated by finite element analysis (3D-FEA). Stresses generated in the adhesive layer were plotted versus two geometric variables of the resin-composite cylinder (C-Factor and volume) to verify the existence of correlations between them and stresses. Results. The FEA models were validated. A significant correlation (p < 0.01, Pearson's test) between the stress-peak and the coverslip deflection when the resin-composites were grouped by diameter was found for diameters of 2 and 4 mm. The stress-peak of the whole set of data showed a logarithmic correlation with the bonded resin-composite volume (p < 0.001, Pearson's test), but did not correlate with the C-Factor. Significance. The described method should be considered for standardizing the stress generated by the shrinkage of resin-composite blocks bonded to a single flat surface. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The influence of mouthrinses and simulated toothbrushing on the surface roughness of a nanofilled composite resin

The aim of this study was to determine the influence of mouthrinses on the surface roughness of a nanofilled composite resin after toothbrushing. One hundred nanofilled composite resin specimens were prepared and randomly distributed into two groups-brushed and non-brushed-and then assigned to five subgroups, according to the mouthrinse solutions (n = 10): Colgate Plax Fresh Mint, Oral B, Cepacol, Colgate Plax, and artificial saliva. Each sample was immersed in 20 mL of the mouthrinses for 1 minute, 5 days per week, twice a day, for a 3-week period. The control group used in the study was one in which the specimens were not subjected to brushing and remained only in artificial saliva. Toothbrushing was performed once a week for 1 minute, for 3 weeks. Surface roughness measurements (Ra) were performed after the immersion period and toothbrushing, by means of a profilometer. Data were analyzed by two-way ANOVA and Tukey's test. Analysis revealed that the association between toothbrushing and Colgate Plax Fresh Mint produced the lowest surface roughness (p < 0.05). All other groups tested (Oral B, Cepacol, Colgate Plax, artificial saliva) exhibited no statistically significant differences between surfaces, whether subjected to toothbrushing or not (p < 0.05). It was concluded that the surface roughness of the nanofilled composite resin tested can be influenced by the mouthrinse associated with toothbrushing.

Subcritical crack growth and in vitro lifetime prediction of resin composites with different filler distributions

Objectives. Verify the influence of different filler distributions on the subcritical crack growth (SCG) susceptibility, Weibull parameters (m and sigma(0)) and longevity estimated by the strength-probability-time (SPT) diagram of experimental resin composites. Methods. Four composites were prepared, each one containing 59 vol% of glass powder with different filler sizes (d(50) = 0.5; 0.9; 1.2 and 1.9 mu m) and distributions. Granulometric analyses of glass powders were done by a laser diffraction particle size analyzer (Sald-7001, Shimadzu, USA). SCG parameters (n and sigma(f0)) were determined by dynamic fatigue (10(-2) to 10(2) MPa/s) using a biaxial flexural device (12 x 1.2 mm; n = 10). Twenty extra specimens of each composite were tested at 10(0) MPa/s to determine m and sigma(0). Specimens were stored in water at 37 degrees C for 24 h. Fracture surfaces were analyzed under SEM. Results. In general, the composites with broader filler distribution (C0.5 and C1.9) presented better results in terms of SCG susceptibility and longevity. C0.5 and C1.9 presented higher n values (respectively, 31.2 +/- 6.2(a) and 34.7 +/- 7.4(a)). C1.2 (166.42 +/- 0.01(a)) showed the highest and C0.5 (158.40 +/- 0.02(d)) the lowest sigma(f0) value (in MPa). Weibull parameters did not vary significantly (m: 6.6 to 10.6 and sigma(0): 170.6 to 176.4 MPa). Predicted reductions in failure stress (P-f = 5%) for a lifetime of 10 years were approximately 45% for C0.5 and C1.9 and 65% for C0.9 and C1.2. Crack propagation occurred through the polymeric matrix around the fillers and all the fracture surfaces showed brittle fracture features. Significance. Composites with broader granulometric distribution showed higher resistance to SCG and, consequently, higher longevity in vitro. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Flow-injection spectrophotometric determination of captopril in pharmaceutical formulations using a new solid-phase reactor containing AgSCN immobilized in a polyurethane resin

A simple flow-injection analysis procedure was developed for determining captopril in pharmaceutical formulations employing a novel solid-phase reactor containing silver thiocyanate immobilized in a castor oil derivative polyurethane resin. The method was based on silver mercaptide formation between the captopril and Ag(I) in the solid-phase reactor. During such a reaction, the SCN- anion was released and reacted with Fe3+, which generated the FeSCN2+ complex that was continuously monitored at 480 nm. The analytical curve was linear in the captopril concentration range from 3.0 x 10(-4) mol L-1 to 1.1 x 10(-3) mol L-1 with a detection limit of 8.0 x 10(-5) mol L-1. Recoveries between 97.5% and 103% and a relative standard deviation of 2% for a solution containing 6.0 x 10(-4) mol L-1 captopril (n = 12) were obtained. The sample throughput was 40 h(-1) and the results obtained for captopril in pharmaceutical formulations using this procedure and those obtained using a pharmacopoeia procedure were in agreement at a 95% confidence level.

Effects of curing protocol and storage time on the micro-hardness of resin cements used to lute fiber-reinforced resin posts

Objectives: To determine the micro-hardness profile of two dual cure resin cements (RelyX - U100 (R), 3M-ESPE and Panavia F 2.0 (R), Kuraray) used for cementing fiber-reinforced resin posts (Fibrekor (R) - Jeneric Pentron) under three different curing protocols and two water storage times. Material and methods: Sixty 16mm long bovine incisor roots were endodontically treated and prepared for cementation of the Fibrekor posts. The cements were mixed as instructed, dispensed in the canal, the posts were seated and the curing performed as follows: a) no light activation; b) light-activation immediately after seating the post, and; c) light-activation delayed 5 minutes after seating the post. The teeth were stored in water and retrieved for analysis after 7 days and 3 months. The roots were longitudinally sectioned and the microhardness was determined at the cervical, middle and apical regions along the cement line. The data was analyzed by the three-way ANOVA test (curing mode, storage time and thirds) for each cement. The Tukey test was used for the post-hoc analysis. Results: Light-activation resulted in a significant increase in the microhardness. This was more evident for the cervical region and for the Panavia cement. Storage in water for 3 months caused a reduction of the micro-hardness for both cements. The U100 cement showed less variation in the micro-hardness regardless of the curing protocol and storage time. Conclusions: The micro-hardness of the cements was affected by the curing and storage variables and were material-dependent.

Evaluation of Radiopacity, pH, Release of Calcium Ions, and Flow of a Bioceramic Root Canal Sealer

Introduction: The aim of the present study was to evaluate the physicochemical properties of a bioceramic root canal sealer, Endosequence BC Sealer. Radiopacity, pH, release of calcium ions (Ca2+), and flow were analyzed, and the results were compared with AH Plus cement. Methods: Radiopacity and flow were evaluated according to ISO 6876/2001 standards. For the radiopacity analysis, metallic rings with 10-mm diameter and 1-mm thickness were filled with cements. The radiopacity value was determined according to radiographic density (mm Al). The flow test was performed with 0.05 mL of cement placed on a glass plate. A 120-g weight was carefully placed over the cement. The largest and smallest diameters of the disks formed were measured by using a digital caliper. The release of Ca2+ and pH were measured at periods of 3, 24, 72, 168, and 240 hours with spectrophotometer and pH meter, respectively. Data were analyzed by analysis of variance and Tukey test (P < .05). Results: The bioceramic endodontic cement showed radiopacity (3.84 mm Al) significantly lower than that of AH Plus (6.90 mm Al). The pH analysis showed that Endosequence BC Sealer showed pH and release of Ca2+ greater than those of AH Plus (P < .05) during the experimental periods. The flow test revealed that BC Sealer and AH Plus presented flow of 26.96 mm and 21.17 mm, respectively (P < .05). Conclusions: Endosequence BC Sealer showed radiopacity and flow according to ISO 6876/2001 recommendations. The other physicochemical properties analyzed demonstrated favorable values for a root canal sealer. (J Endod 2012;38:842-845)

56-month clinical performance of Class I and II resin composite restorations

Objective: This study evaluated the 56-month clinical performance of Class I and II resin composite restorations. Filtek P60 was compared with Filtek Z250, which are both indicated for posterior restorations but differ in terms of handling characteristics. The null hypothesis tested was that there is no difference in the clinical performance of the two resin composites in posterior teeth. Material and Methods: Thirty-three patients were treated by the same operator, who prepared 48 Class I and 42 Class II cavities, which were restored with Single Bond/Filtek Z250 or Single Bond/Filtek P60 restorative systems. Restorations were evaluated by two independent examiners at baseline and after 56 months, using the modified USPHS criteria. Data were analyzed statistically using Chi-square and Fisher's Exact tests (alpha=0.05). Results: After 56 months, 25 patients (31 Class I and 36 Class II) were analyzed. A 3% failure rate occurred due to secondary caries and excessive loss of anatomic form for P60. For both restorative systems, there were no significant differences in secondary caries and postoperative sensitivity. However, significant changes were observed with respect to anatomic form, marginal discoloration, and marginal adaptation. Significant decreases in surface texture were observed exclusively for the Z250 restorations. Conclusions: Both restorative systems can be used for posterior restorations and can be expected to perform well in the oral environment.

Effect of Temperature on the Degree of Conversion and Working Time of Dual-Cured Resin Cements Exposed to Different Curing Conditions

Objectives: This study evaluated the degree of conversion (DC) and working time (WT) of two commercial, dual-cured resin cements polymerized at varying temperatures and under different curing-light accessible conditions, using Fourier transformed infrared analysis (FTIR). Materials and Methods: Calibra (Cal; Dentsply Caulk) and Variolink II (Ivoclar Vivadent) were tested at 25 degrees C or preheated to 37 degrees C or 50 degrees C and applied to a similar-temperature surface of a horizontal attenuated-total-reflectance unit (ATR) attached to an infrared spectrometer. The products were polymerized using one of four conditions: direct light exposure only (600 mW/cm(2)) through a glass slide or through a 1.5- or 3.0-mm-thick ceramic disc (A2 shade, IPS e.max, Ivoclar Vivadent) or allowed to self-cure in the absence of light curing. FTIR spectra were recorded for 20 min (1 spectrum/s, 16 scans/spectrum, resolution 4 cm(-1)) immediately after application to the ATR. DC was calculated using standard techniques of observing changes in aliphatic-to-aromatic peak ratios precuring and 20-min postcuring as well as during each 1-second interval. Time-based monomer conversion analysis was used to determine WT at each temperature. DC and WT data (n=6) were analyzed by two-way analysis of variance and Tukey post hoc test (p=0.05). Results: Higher temperatures increased DC regardless of curing mode and product. For Calibra, only the 3-mm-thick ceramic group showed lower DC than the other groups at 25 degrees C (p=0.01830), while no significant difference was observed among groups at 37 degrees C and 50 degrees C. For Variolink, the 3-mm-thick ceramic group showed lower DC than the 1-mm-thick group only at 25 degrees C, while the self-cure group showed lower DC than the others at all temperatures (p=0.00001). WT decreased with increasing temperature: at 37 degrees C near 70% reduction and at 50 degrees C near 90% for both products, with WT reduction reaching clinically inappropriate times in some cases (p=0.00001). Conclusion: Elevated temperature during polymerization of dual-cured cements increased DC. WT was reduced with elevated temperature, but the extent of reduction might not be clinically acceptable.

Influence of Ozone Gas and Ozonated Water Application to Dentin and Bonded Interfaces on Resin-Dentin Bond Strength

Purpose: To assess the influence of ozone gas and ozonated water application to prepared cavity and bonded interfaces on the resin/dentin bond strength of two-step etch-and-rinse adhesive systems (Adper Single Bond 2 [SB2] and XP-Bond [XP]). Materials and Methods: Sixty extracted human third molars were sectioned perpendicularly to their long axes to expose flat occlusal dentin surfaces. In experiment 1, dentin was treated with ozone before the bonding procedure, while in experiment 2, ozone was applied to resin/dentin bonded interfaces. In experiment 1, dentin surfaces were treated either with ozone gas (2100 ppm), ozonated water (3.5 ppm), or distilled water for 120 s, and then bonded with SB2 or XP according to manufacturers' instructions. Hybrid composite buildups were incrementally constructed and the teeth were sectioned into resin-dentin sticks (0.8 mm(2)). In experiment 2, dentin surfaces were first bonded with SB2 or XP, composite buildups were constructed, and bonded sticks obtained. The sticks were treated with ozone as previously described. Bonded sticks were tested under tensile stress at 1 mm/min. Silver nitrate impregnation along the resin/dentin interfaces was also evaluated under SEM. Results: Two-way ANOVA (adhesive and ozone treatment) detected no significant effect for the cross-product interaction and the main factors in the two experiments (p > 0.05), which was confirmed by the photomicrographs. Conclusion: Ozone gas and ozonated water used before the bonding procedure or on resin/dentin bonded interfaces have no deleterious effects on the bond strengths and interfaces.

Qualitative SEM/EDS analysis of microleakage and apical gap formation of adhesive root-filling materials

Objective: The aim of this study was to compare the correspondence between gap formation and apical microleakage in root canals filled with epoxy resin-based (AH Plus) combined or not with resinous primer or with a dimethacrylate-based root canal sealer (Epiphany). Material and Methods: Thirty-nine lower single-rooted human premolars were filled by the lateral condensation technique (LC) and immersed in a 50-wt% aqueous silver nitrate solution at 37 degrees C (24 h). After longitudinal sectioning, epoxy resin replicas were made from the tooth specimens. Both the replicas and the specimens were prepared for scanning electron microscopy (SEM). The gaps were observed in the replicas. Apical microleakage was detected in the specimens by SEM/energy dispersive spectroscopy (SEM/EDS). The data were analyzed statistically using an Ordinal Logistic Regression model and Analysis of Correspondence (alpha=0.05). Results: Epiphany presented more regions containing gaps between dentin and sealer (p<0.05). There was correspondence between the presence of gaps and microleakage (p<0.05). Microleakage was similar among the root-filling materials (p>0.05). Conclusions: The resinous primer did not improve the sealing ability of AH Plus sealer and the presence of gaps had an effect on apical microleakage for all materials.

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.

Impact of filler size and distribution on roughness and wear of composite resin after simulated toothbrushing

Objectives: Nanofilled composite resins are claimed to provide superior mechanical properties compared with microhybrid resins. Thus, the aim of this study was to compare nanofilled with microhybrid composite resins. The null hypothesis was that the size and the distribution of fillers do not influence the mechanical properties of surface roughness and wear after simulated toothbrushing test. Material and methods: Ten rectangular specimens (15 mm x 5 mm x 4 mm) of Filtek Z250 (FZ2), Admira (A), TPH3 (T), Esthet-X (EX), Estelite Sigma (ES), Concept Advanced (C), Grandio (G) and Filtek Z350 (F) were prepared according to manufacturer's instructions. Half of each top surface was protected with nail polish as control surface (not brushed) while the other half was assessed with five random readings using a roughness tester (Ra). Following, the specimens were abraded by simulated toothbrushing with soft toothbrushes and slurry comprised of 2: 1 water and dentifrice (w/w). 100,000 strokes were performed and the brushed surfaces were re-analyzed. Nail polish layers were removed from the specimens so that the roughness (Ra) and the wear could be assessed with three random readings (mu m). Data were analyzed by ANOVA and Tukey's multiple-comparison test (alpha = 0.05). Results: Overall outcomes indicated that composite resins showed a significant increase in roughness after simulated toothbrushing, except for Grandio, which presented a smoother surface. Generally, wear of nanofilled resins was significantly lower compared with microhybrid resins. Conclusions: As restorative materials suffer alterations under mechanical challenges, such as toothbrushing, the use of nanofilled materials seem to be more resistant than microhybrid composite resins, being less prone to be rougher and worn.