Effects of ethanol addition on the water sorption/solubility and percent conversion of comonomers in model dental adhesives

ObjectivesThis study evaluated the kinetics of water uptake and percent conversion in neat versus ethanol-solvated resins that were formulated to be used as dental bonding agents.MethodsFive methacrylate-based resins of known and increasing hydrophilicities (R1, R2, R3, R4 and R5) were used as reference materials. Resins were evaluated as neat bonding agents (100% resin) or they were solvated with absolute ethanol (95% resin/5% ethanol or 85% resin/15% ethanol). Specimens were prepared by dispensing the uncured resin into a circular mold (5.8 mm × 0.8 mm). Photo-activation was performed for 80 s. The water sorption/diffusion/solubility was gravimetrically evaluated, while the degree of conversion (DC) was calculated by Fourier-transform infrared spectroscopy.ResultsWater sorption increased with the hydrophilicity of the resin blends. In general, the solvated resins exhibited significantly higher water sorption, solubility and water diffusion coefficients when compared to their corresponding neat versions (p < 0.05). The only exception was resin R1, the least hydrophilic resin, in which neat and solvated versions exhibited similar water sorption (p > 0.05). Addition of ethanol increased the DC of all resins tested, especially of the least hydrophilic, R1 and R2 (p < 0.05). Despite the increased DC of ethanol–solvated methacrylate-based resins, it occurs at the expense of an increase in their water sorption/diffusion and solubility values.SignificanceNegative effects of residual ethanol on water sorption/solubility appeared to be greater as the hydrophilicity of the resin blends increased. That is, the use of less hydrophilic resins in dental adhesives may create more reliable and durable bonds to dentin.     

Excretion of dental resin monomers and metabolic intermediates via urine in guinea pigs

ObjectiveMonomers like BisGMA (Bisphenol-A-glycidyldimethacrylate) and comonomers like TEGDMA (triethyleneglycoldimethacrylate) are used in dental restorative materials in order to build up the three-dimensional network of filling materials. Since earlier investigations revealed uptake and subsequent metabolism of unpolymerized remainders of (co)monomers, the present experiment investigates the metabolic urine pattern of guinea pigs (n = 4) after application of TEGDMA or BisGMA (each dose = 0.02 mmol/kg body weight = 100%), respectively.MethodsFor the investigations BisGMA was pre-dissolved in DMSO and subsequently diluted with 0.9% NaCl solution (final DMSO concentration 1%) and TEGDMA was dissolved in 0.9% NaCl solution. The solutions were administered with a gastric tube into the animals. Control animals received either 0.9% NaCl or 0.9% NaCl solution with 1% DMSO solution.ResultsAfter 24 h in collected urine the following metabolites were identified. After administration of TEGDMA (mean relative concentration of administered substances) ± s.d. [%]; n = 4): unchanged TEGDMA: 12 ± 1.5%, MA: 2.4 ± 0.8%, and triethyleneglycol: 35 ± 2.2%. After administration of BisGMA (mean ± s.d. [%]; n = 4): unchanged BisGMA: 11.4 ± 2.7%, MA: 2.2 ± 0.6%, and bisphenol-A-bis(2,3-dihydroxypropyl)ether: 60.1 ± 5.2%).ConclusionNo further metabolites like the previously identified intermediate 2,3-epoxymethacrylic acid and derived reaction products were identified in the urine, indicating that these metabolites must have reacted further.     

Evaluation of polymerization characteristics and penetration into enamel caries lesions of experimental infiltrants

ObjectivesTo evaluate the properties of experimental infiltrant blends by comparing them with the commercial infiltrant Icon^® and penetration homogeneity into enamel caries lesions.MethodsGroups were set up as follows: G1 (TEGDMA 100%); G2 (TEGDMA 80%, Ethanol 20%); G3 (TEGDMA 80%, HEMA 20%); G4 (TEGDMA 75%, BisEMA 25%); G5 (TEGDMA 60%, BisEMA 20%, Ethanol 20%); G6 (TEGDMA 60%, BisEMA 20%, HEMA 20%); G7 (TEGDMA 75%, UDMA 25%); G8 (TEGDMA 60%, UDMA 20%, Ethanol 20%); G9 (TEGDMA 60%, UDMA 20%, HEMA 20%) and Icon^®. Ten specimens were comprised by each group for the following tests (n = 10): degree of conversion (DC), elastic modulus (EM), Knoop hardness (KH), and softening ratio (SR). Infiltrant penetration was evaluated using confocal microscopy (CLSM). Data were subjected to two-way ANOVA and a Tukey's test (5%). Data comparing experimental materials and Icon^® were analysed using ANOVA and Dunnett's test (5%).ResultsThe highest DC values were found in G1, G7, G8, and G9. The lowest DC values were found in G2, G4, G5, and G6. EM and KHN were significantly lower in HEMA and with ethanol addition for all blends, except for G9. There was no significant difference among the groups regarding SR, and it was not possible to take KHN readings of G2, G5, and G8 after storage. There was no significant difference among groups for infiltrant penetration into enamel lesions.ConclusionsThe addition of hydrophobic monomers and solvents into TEGDMA blends affected DC, EM, and KHN. UDMA added to TEGDMA resulted in an increase in DC, EM, and KHN. Overall, solvents added to monomer blends resulted in decreased properties. The addition of hydrophobic monomers and solvents into TEGDMA blends does not improve the penetration depth of the infiltrants.     

Effect of resin matrix composition on the translucency of experimental dental composite resins

ObjectivesThe purpose of this study was to investigate the effect of the resin matrix composition on the translucency of experimental dental composite resins.MethodsThree types of unfilled resin matrices (TEGDMA-, UDMA- and BisGMA-based) were formulated and light cured. In addition, six different experimental dental composite resins with constant filler loading but varying in the type of monomer and the content of BisGMA were fabricated. Discs of each test material with 15.5 mm diameter and 1.0 mm thickness were prepared (N = 3) and light cured. Total and diffuse transmittance values for each sample were measured using a UV/VIS spectrophotometer with the range of readings from 380 to 700 nm. Difference in color was measured using the CIE Lab system.ResultsStatistical analysis by one-way ANOVA followed by Tukey's test showed that there was no statistically significant difference in transmittance values between the three unfilled resins. However, with the addition of filler, BisGMA-containing composite resins showed significantly higher transmittance values than the UDMA- and TEGDMA-based composite resins. Regression analysis revealed that there was a linear correlation between the percentage of BisGMA in the resin matrix and the total and diffuse translucency.SignificanceThe amount of BisGMA used in the resin matrix has a significant effect on the translucency of silica filler-containing dental composite resins.     

Acrylamides and methacrylamides as alternative monomers for dental adhesives

Objective

Synthesize and characterize a methacrylamide monomer for adhesive system and evaluate the physicochemical properties of the adhesive resin.

Influence of curing protocol on selected properties of light-curing polymers: Degree of conversion, volume contraction, elastic modulus, and glass transition temperature

ObjectivesThe purpose of this study was to investigate the effect of light-curing protocol on degree of conversion (DC), volume contraction (C), elastic modulus (E), and glass transition temperature (T_g) as measured on a model polymer. It was a further aim to correlate the measured values with each other.MethodsDifferent light-curing protocols were used in order to investigate the influence of energy density (ED), power density (PD), and mode of cure on the properties. The modes of cure were continuous, pulse-delay, and stepped irradiation. DC was measured by Raman micro-spectroscopy. C was determined by pycnometry and a density column. E was measured by a dynamic mechanical analyzer (DMA), and T_g was measured by differential scanning calorimetry (DSC). Data were submitted to two- and three-way ANOVA, and linear regression analyses.ResultsED, PD, and mode of cure influenced DC, C, E, and T_g of the polymer. A significant positive correlation was found between ED and DC (r = 0.58), ED and E (r = 0.51), and ED and T_g (r = 0.44). Taken together, ED and PD were significantly related to DC and E. The regression coefficient was positive for ED and negative for PD. Significant positive correlations were detected between DC and C (r = 0.54), DC and E (r = 0.61), and DC and T_g (r = 0.53). Comparisons between continuous and pulse-delay modes of cure showed significant influence of mode of cure: pulse-delay curing resulted in decreased DC, decreased C, and decreased T_g. Influence of mode of cure, when comparing continuous and step modes of cure, was more ambiguous.SignificanceA complex relationship exists between curing protocol, microstructure of the resin and the investigated properties. The overall performance of a composite is thus indirectly affected by the curing protocol adopted, and the desired reduction of C may be in fact a consequence of the decrease in DC.     

Effects of monomer ratios and highly radiopaque fillers on degree of conversion and shrinkage-strain of dental resin composites

ObjectivesThe degree of conversion (DC) and polymerization shrinkage of resin composites are closely related manifestations of the same process. Ideal dental composite would show an optimal degree of conversion and minimal polymerization shrinkage. These seem to be antagonistic goals, as an increase in monomer conversion leads to a high polymerization shrinkage. This paper aims to determine the effect of opaque mineral fillers and monomer ratios on the DC and the shrinkage-strain of experimental composites based on (BisGMA/TEGDMA) monomers (traditionally used monomers). A relationship between the shrinkage-strain and the degree of conversion values was also investigated. The radiopacity of these experimental composites has been investigated in a previous paper.MethodsExperimental resin composites were prepared by mixing different monomer ratios of (BisGMA/TEGDMA) with Camphoroquinone and dimethyl aminoethyl methacrylate (DMAEMA) as photo-initiator system. Five different radiopacifying filler agents: La₂O₃, BaO, BaSO₄, SrO and ZrO₂ at various volume fractions ranging from 0 to 80 wt.% were added to the mixture. The degree of conversion of experimental composites containing different opaque fillers contents was measured using FTIR/ATR spectroscopy. The shrinkage-strain of specimens, photopolymerized at circa 500 mW/cm², was measured using the bonded-disk technique at room temperature with respect to time.ResultsThe result revealed that the DC and the shrinkage-strain decrease slightly with the increasing of opaque fillers loadings, but this decrease is not significant. However, these two properties are closely related to the monomer concentration of the organic matrix. The results have also showed a linear correlation between the shrinkage-strain and DC of experimental composites investigated.SignificanceThe nature and the volume effects of the opaque fillers on the DC and shrinkage of the experimental composites investigated were not significant. However, this study has confirmed the importance of viscosity in the system and shrinkage behavior of dimethacrylate monomers studied. Then we confirmed that direct relationships linked the shrinkage and the DC of filled dental resin composites.     

Effect of proanthocyanidin incorporation into dental adhesive resin on resin-dentine bond strength

ObjectivesThis study evaluated the effect of proanthocyanidin (PA) incorporation into experimental dental adhesives on resin–dentine bond strength.MethodsFour experimental hydrophilic adhesives containing different PA concentrations were prepared by combining 50 wt% resin comonomer mixtures with 50 wt% ethanol. Proanthocyanidin was added to the ethanol-solvated resin to yield three adhesives with PA concentrations of 1.0, 2.0 and 3.0 wt%, respectively. A PA-free adhesive served as the control. Flat dentine surfaces from 40 extracted third molars were etched with 32% phosphoric acid. The specimens were randomly assigned to one of the four adhesive groups. Two layers of one of the four experimental adhesives were applied to the etched dentine and light-cured for 20 s. Composite build-ups were performed using Filtek Z250 (3M ESPE). After storage in distilled water at 37 °C for 24 h, twenty-four bonded teeth were sectioned into 0.9 mm × 0.9 mm beams and stressed to failure under tension for bond strength testing. Bond strength data were evaluated by one-way ANOVA and Tukey's test (α = 0.05). Interfacial nanoleakage was examined in the remaining teeth using a field-emission scanning electron microscope and analysed using the Chi-square test (α = 0.05).ResultsNo significant difference in bond strength was found amongst PA-free, 1% and 2% PA adhesives. However, incorporation of 3% PA into the adhesive significantly lowered bond strength as demonstrated by a greater number of adhesive failures and more extensive nanoleakage along the bonded interface.ConclusionIncorporation of 2% proanthocyanidin into dental adhesives has no adverse effect on dentine bond strength.Clinical significanceThe addition of proanthocyanidin to an experimental adhesive has no adverse effect on the immediate resin–dentine bond strength when the concentration of proanthocyanidin in the adhesive is less than or equal to 2%.     

Epigallocatechin-3-gallate (EGCG) enhances the therapeutic activity of a dental adhesive

ObjectivesThe purpose of this study was to evaluate the antibacterial potential and physicochemical properties of a dental adhesive incorporated with epigallocatechin-3-gallate (EGCG) in different concentration over time.MethodsEGCG was incorporated at a ratio of 100, 200, and 300 μg/ml into a dental adhesive. The effects of the cured adhesives on the growth of Streptococcus mutans were determined by direct contact test immediately or one month later and by scanning electron microscopy (SEM), respectively. Microtensile bond strength (μTBS) test was used to test the mechanical property of the adhesives immediately or six months later. The degree of conversion (DC) of the adhesives was evaluated by Fourier Transform Infrared Spectroscopy (FTIR).ResultsCompared with negative control, the 200 μg/ml and 300 μg/ml EGCG-incorporated dental adhesive were found to exhibit inhibitory effect on the growth of S. mutans. The μTBS of the EGCG-incorporated dental adhesive was higher than the control. The DC of the adhesive system was not affected by the addition of EGCG.Conclusions200 μg/ml EGCG incorporated dental adhesives could accomplish therapeutic goals that play in antimicrobial function whilst keeping the durability of resin–dentine bond.     

Chlorhexidine-modified nanotubes and their effects on the polymerization and bonding performance of a dental adhesive

ObjectivesThe purpose of this study was to synthesize chlorhexidine (CHX)-encapsulated aluminosilicate clay nanotubes (Halloysite®, HNTs) and to incorporate them into the primer/adhesive components of an etch-and-rinse adhesive system (SBMP; Scotchbond Multipurpose, 3M ESPE) and to test their effects on degree of conversion, viscosity, immediate and long-term bonding to dentin.MethodsCHX-modified HNTs were synthesized using 10% or 20% CHX solutions. The primer and the adhesive components of SBMP were incorporated with 15 wt.% of the CHX-encapsulated HNTs. Degree of conversion (DC) and viscosity analyses were performed to characterize the modified primers/adhesives. For bond strength testing, acid-etched dentin was treated with one of the following: SBMP (control); 0.2%CHX solution before SBMP; CHX-modified primers + SBMP adhesive; SBMP primer + CHX-modified adhesives; and SBMP primer + CHX-free HNT-modified adhesive. The microtensile bond strength test was performed after immediate (24 h) and long-term (6 months) of water storage. Data were analyzed using ANOVA and Tukey (α = 5%) and the Weibull analysis.ResultsDC was greater for the CHX-free HNT-modified adhesive, whereas the other experimental adhesives showed similar DC as compared with the control. Primers were less viscous than the adhesives, without significant differences within the respective materials. At 24 h, all groups showed similar bonding performance and structural reliability; whereas at the 6-month period, groups treated with the 0.2%CHX solution prior bonding or with the CHX-modified primers resulted in greater bond strength than the control and superior reliability.SignificanceThe modification of a primer or adhesive with CHX-encapsulated HNTs was an advantageous approach that did not impair the polymerization, viscosity and bonding performance of the materials, showing a promising long-term effect on resin-dentin bonds.     

Effects of residual ethanol on the rate and degree of conversion of five experimental resins

ObjectivesThis study examined the extent of ethanol retention in five comonomer blends of experimental methacrylate-based dental adhesives, containing (10, 20, or 30 wt.%) ethanol, after solvent evaporation, as well as observing the effect of residual ethanol and exposure duration on degree of conversion (DC). The null hypothesis that was tested was that residual, unevaporated ethanol has no effect on the rate or extent of DC of polymerized adhesive resins.MethodsA known mass of each mixture was placed in glass wells and evaporated for 60 s. The mass of the mixtures before and after evaporation was measured, allowing calculation of the gravimetric ethanol loss/retention.ResultsThe concentration of retained ethanol increased significantly with ethanol concentration (p < 0.01): 1.1–1.9 mole/L for 10% ethanol/90% comonomers, 2.2–3.5  mole/L for 20% ethanol, and 2.6–3.7 mole/L for 30% ethanol/70% comonomers. As ethanol is evaporated from solvated comonomer mixtures, the molar concentration of comonomers increases, reducing the vapor pressure of the remaining ethanol. Thus, the fractional loss of ethanol solvent decreases as the comonomer concentration increases. The DC of 10, 20, and 30 wt.% ethanol blends increased with ethanol concentration in four of the five experimental resins (p < 0.05), increasing by 30–45% when 10 or 20 wt.% ethanol was added to neat resins, regardless of exposure duration. Depending on the resin system, inclusion of 30% ethanol lowered DC at 20 s but increased DC after 40–60 s of light exposure.SignificanceSince 10 and 20 wt.% ethanol–resin blends increased the DC of solvated resins by 30–45% over neat resins, the test null hypothesis is rejected. Even with prolonged evaporation, 4–9% residual ethanol concentration can remain in 90/10 (wt./wt.) comonomer–ethanol mixtures. This is thought to be because comonomers lower the vapor pressure of ethanol. This amount of residual ethanol facilitates DC but lowers the rate of polymerization.     

Release of monomers from different core build-up materials

ObjectiveThe aim of the present study was to evaluate and compare the elution of monomers from three different core build-up composite materials and correlate it with the degree of conversion.MethodsThree different core build-up composite materials (a chemically cured, a photo-cured, and a dual-cured) were tested. Ten samples (diameter: 4.5 mm and thickness: 2 mm) of each material were fabricated to evaluate the release of monomers. The photo-cured samples were polymerized for 40 s and the dual-cured samples for 20 s. The samples remained undisturbed for 10 min and then were stored in 1 ml of 75% ethanol at room temperature, and the storage medium was renewed after 24 h, 7 and 28 days. From the storage medium that was removed, samples were prepared and analyzed by LC–MS/MS. Additionally, four samples of each material were tested for the degree of conversion by using a FT-IR spectrometer.ResultsThe three composite materials differed significantly concerning the elution of monomers (BisGMA: p < 0.0001; TEGDMA: p < 0.0001; and Bisphenol A: p < 0.0001). A significantly higher amount of BisGMA and TEGDMA was released from the chemically cured composite compared to the other two materials. Between the photo-cured and the dual-cured material the latter eluted significantly higher amounts of BisGMA and TEGDMA. During the storage of the samples, the amounts of the eluted substances decreased. The degree of conversion of the chemically cured composite was significantly lower compared to the other two materials.SignificanceUsing the present parameters, the photo-cured material released less monomer and therefore they might be less dangerous with respect to toxicological effects.     

Alternative monomer for BisGMA-free resin composites formulations

ObjectiveWater sorption, high volumetric shrinkage, polymerization stress, and potential estrogenic effects triggered by leached compounds are some of the major concerns related to BisGMA-TEGDMA co-monomer systems used in dental composites. These deficiencies call for the development of alternative organic matrices in order to maximize the clinical lifespan of resin composite dental restorations. This study proposes BisGMA-free systems based on the combination of UDMA and a newly synthesized diurethane dimethacrylate, and evaluates key mechanical and physical properties of the resulting materials.Methods2EMATE-BDI (2-hydroxy-1-ethyl methacrylate) was synthesized by the reaction between 2-hydroxy-1-ethyl methacrylate with a difunctional isocyanate (1.3-bis (1- isocyanato-1-methylethylbenzene) – BDI). The compound was copolymerized with UDMA (urethane dimethacrylate) at 40 and 60 wt%. UDMA copolymerizations with 40 and 60 wt% TEGDMA (triethylene glycol dimethacrylate) were tested as controls, as well as a formulation based in BisGMA (bisphenol A-glycidyl methacrylate)-TEGDMA 60:40% (BT). The organic matrices were made polymerizable by the addition of DMPA (2.2-dimethoxyphenoxy acetophenone) and DPI-PF6 (diphenyliodonium hexafluorophosphate) at 0.2 and 0.4 wt%, respectively. Formulations were tested as composite with the addition of 70 wt% inorganic content consisting of barium borosilicate glass (0.7 μm) and fumed silica mixed in 95 and 5 wt%, respectively. All photocuring procedures were carried out by a mercury arc lamp filtered to 320–500 nm at 800 mW/cm². The experimental resin composites were tested for kinetics of polymerization and polymerization stress in real time. Flexural strength, elastic modulus, water sorption, and solubility were assessed according to ISO 4049. Biofilm formation was analyzed after 24 h by luciferase assay. Data were statistically analyzed by one-way ANOVA and Tukey's test (α ≤ 0.05).ResultsIn general, the addition of 2EMATE-BDI into the formulations decreased the maximum rate of polymerization (RP_MAX), the degree of conversion at RP_MAX (DC at RP_MAX), and the final degree of conversion (final DC). However, these reductions did not compromise mechanical properties, which were comparable to the BT controls, especially after 7-day water incubation. The incorporation of 60 wt% 2EMATE-BDI reduced water sorption of the composite. 2EMATE-BDI containing formulations showed reduction in polymerization stress of 30% and 50% in comparison to BT control and TEGDMA copolymerizations, respectively. Biofilm formation was similar among the tested groups.SignificanceThe use of the newly synthesized diurethane dimethacrylate as co-monomer in dental resin composite formulations seems to be a promising option to develop polymers with low-shrinkage and potentially decreased water degradation.     

Evaluation of alternative photoinitiator systems in two-step self-etch adhesive systems

ObjectiveThe aim of this study was to evaluate the effect of different photoinitiator systems on the cell viability and physico-chemical properties of an experimental adhesive resin of a two-step self-etch adhesive system.MethodsEight photoinitiators and coinitiators were evaluated, camphorquinone (CQ); ethyl-dimethylamino benzoate (EDAB); diphenyliodonium hexafluorophosphate (DPIHFP); 1,3-benzodioxole (BDO); piperonyl alcohol (AP); 1,3-diethyl-2-thiobarbituric acid (TBA); bisphenyl phosphinic oxide (BAPO); and diphenyl phosphinic oxide (TPO). Seven experimental adhesive resins (Bis-GMA:TEGDMA – 1:1 by wt%) were formulated by varying the initiation systems: R_CQ+EDAB (control), R_{CQ+EDAB+DPHFP}, R_CQ+BDO, R_CQ+AP, R_CQ+TBA, R_BAPO and R_TPO. The cell viability of the different photoinitiators in their isolated form and after being incorporated into the adhesive resins was evaluated using the MTT assay. The degree of conversion within the hybrid layer (DC in situ) was evaluated by micro-Raman spectroscopy; the polymerization kinetics, by FTIR spectroscopy. The water sorption (Wsp) and solubility (Wsl) were calculated by using percentage of gain and loss of mass. Data were analyzed using One-way ANOVA and Kruskal-Wallis tests (α = 0.05).ResultsWhen evaluated in their isolated form, the DPIHFP was considered cytotoxic in all concentrations evaluated. When incorporated into and adhesive resin, R_CQ+TBA presented higher cell viability values than control and the highest values of DC in situ (p < 0.05). Additionally, the use of CQ + TBA showed a higher cell viability when compared with the conventional CQ + EDAB system.SignificanceThe pair CQ + TBA could be potentially useful in the development of materials with improved biocompatibility.     

Effect of oxalate desensitizer on the bonding durability of adhesive resin cements to dentin

PurposeThis study investigated whether the tubular occluding effect of oxalate desensitizer (OX) during adhesive cementation improved bonding of a self-etch and two etch-and-rinse resin cements to dentin after 6 months.MethodsA flat dentin surface was prepared on 120 extracted premolars, which were randomly divided into six groups of 20 teeth each according to the adhesive resin cement system used: ED primer II/Panavia F2.0, Excite DSC (Ex DSC)/Variolink II, and One-Step Plus (OS Plus)/Duolink, with or without OX (BisBlock) application. After cementation of an indirect composite rod, two subgroups (n = 10) were tested after 24 h and 6 months of water storage plus thermocycling, and shear bond strengths were recorded in MPa.ResultsStatistical tests showed that although oxalate had a borderline significant negative effect on initial bonding of ED primer II/Panavia F2.0, it significantly improved bonding durability (p < 0.05). OX severely compromised the initial bond strength of Ex DSC/Variolink II (p < 0.001) but had no effect on the reduction in bonding after aging. OX was compatible with OS Plus/Duolink and did not affect the loss of bonding strength after 6 months (p > 0.05).ConclusionCombining an oxalate desensitizer with three types of resin cements had different effects on bond strength to dentin after aging, depending on the interaction of oxalate with the adhesive system associated to the resin cement.     

The addition of nanostructured hydroxyapatite to an experimental adhesive resin

ObjectivesWas produced nanostructured hydroxyapatite (HA_nano) and evaluated the influence of its incorporation in an adhesive resin.MethodsHA_nano was produced by a flame-based process and was characterized by scanning electron microscopy. The surface area, particle size, micro-Raman and cytotoxicity were evaluated. The organic phase was formulated by mixing 50 wt.% Bis-GMA, 25 wt.% TEGDMA, and 25 wt.% HEMA. HA_nano was added at seven different concentrations: 0; 0.5; 1; 2; 5; 10 and 20 wt.%. Adhesive resins with hydroxyapatite incorporation were evaluated for their radiopacity, degree of conversion, flexural strength, softening in solvent and microshear bond strength. The data were analyzed by one-way ANOVA and Tukey's post hoc test (α = 0.05), except for softening in solvent (paired t-test) and cytotoxicity (two-way ANOVA and Bonferroni).ResultsHA_nano presented 15.096 m²/g of specific surface area and a mean size of 26.7 nm. The radiopacity values were not different from those of 1-mm aluminium. The degree of conversion ranged from 52.2 to 63.8%. The incorporation of HA_nano did not influence the flexural strength, which ranged from 123.3 to 143.4 MPa. The percentage of reduction of the microhardness after immersion in the solvent became lower as the HA_nano concentration increased. The addition of 2% nanostructured hydroxyapatite resulted in a higher value of microshear bond strength than the control group (p < 0.05).ConclusionsThe incorporation of 2% of nanostructured hydroxyapatite into an adhesive resin presented the best results.Clinical significanceThe incorporation of nanostructured hydroxyapatite increases the adhesive properties and may be a promising filler for adhesive resin.     

Effect of proanthocyanidins and photo-initiators on photo-polymerization of a dental adhesive

ObjectivesTo evaluate the effects of proanthocyanidins (PA) and photoinitiator type on the degree of conversion (DC) and polymerization rate (PR) of a model dental adhesive.MethodsThree types of photo-initiation systems were introduced into the Bis-GMA/HEMA co-monomer mixture, resulting in four resin formulations including CQ/A (0.5 wt% CQ and EDMAB), CQ/A/I-1 (0.5 wt% CQ, EDMAB and DPIHP), CQ/A/I-2 (1.0 wt% CQ, EDMAB and DPIHP), and TPO (2.1 wt% TPO). For each resin formulation, adhesives containing 0%, 2.5%, 5% and 10% of PA with respect to the weight of resin were produced after mixing the resin with various amount of PA/ethanol solution. When light-cured, the RP and DC of each adhesive was determined using ATR-FTIR spectroscopy.ResultsAcross and within the initiator groups, the DC followed the general trend of CQ/A < CQ/A/I-1 < CQ/A/I-2 < TPO and 0-PA > 2.5-PA > 5-PA > 10-PA, respectively. The change of PR with respect to photo-initiation systems and PA content was in a similar but less pronounced pattern.ConclusionPA hampered the polymerization of all adhesives regardless of photoinitiators used. The initiator formulations CQ/A/I-2 and TPO are better fit for PA-containing adhesives, both leading to >65% DC in the presence of 5% PA.Clinical significanceThe inclusion of PA in dental adhesives has been limited by its interference with the light-curing of adhesive resins. This study found photo-initiation formulations that could maintain a satisfactory degree of monomer conversion while a significant amount of PA is incorporated.     

Long-term nanomechanical properties and gelatinolytic activity of titanium tetrafluoride-treated adhesive dentin interface

ObjectiveThis study investigated the effects of dentin pretreatment with 2.5% titanium tetrafluoride (TiF₄) on nanomechanical properties, and the in situ gelatinolytic activity of the dentin–resin interface, for up to 6 months.MethodsTwenty-four human teeth were prepared by exposing occlusal flat dentin surfaces, and were randomly assigned to experimental groups, according to application or non-application of a TiF₄ pretreatment, and to the adhesive systems (Clearfil SE Bond or Scotchbond Universal). Resin composite (Filtek Supreme Ultra) was built up incrementally on the teeth in all the groups. Then, the specimens were sectioned and randomly selected for evaluation at 24 h, 3 months and 6 months of storage time. The reduced modulus of elasticity (E_r) and the nanohardness of the underlying dentin, as well as the hybrid layer and the adhesive layer were measured using a nanoindenter. Gelatinolytic activity at the dentin–resin interfaces was assessed by in situ zymography using quenched fluorescein-conjugated gelatin at 24 h and 6 months. Statistical analyses were performed with ANOVA and Tukey’s tests.ResultsThere were no differences in E_r and nanohardness values between adhesives systems and pretreatment (p = 0.1250). In situ zymography showed significantly higher gelatinolytic activity after 6 months for all the experimental groups (p = 0.0004), but no differences between the adhesive systems (p = 0.7708) and the surface pretreatment (p = 0.4877). Significance: Dentin pretreatment with 2.5% TiF₄ followed by self-etching adhesive systems did not influence nanomechanical properties or gelatinolytic activity of the adhesive–dentin interface layers, over time.     

Effect of the addition of thiourethane oligomers on the sol⿿gel composition of BisGMA/TEGDMA polymer networks

ObjectivesThiourethane oligomers have been shown to increase the fracture toughness and reduce the polymerization stress of methacrylate-based materials. However, network formation has not been elucidated in these materials yet. The aim of this study was to evaluate how the addition of a thiourethane oligomer (TU) influences the sol/gel composition and network structure of methacrylate-based materials using dynamic mechanical analysis and extraction methods.Materials and methodsBisGMA/TEGDMA at systematically varied mass ratios (20/80 to 80/20 wt%) were mixed with pre-polymerized thiourethane oligomers at 0 (control) or 20 wt%, synthesized by combining pentaerythritol tetra-3-mercaptopropionate with dicyclohexylmethane 4,4⿲-Diisocyanate, at 1:2 isocyanate:thiol. 0.1 wt% of 2,2-Dimethoxy-2-phenylacetophenone was added as the photoinitiator and 0.3 wt% of 2,6-di-tert-butyl-4-methylphenol was added as a free radical inhibitor. Disk specimens (0.8 ÿ 10 mm in diameter, n = 3) were photoactivated at 270 mW/ (320⿿500 nm) for 1 min. The degree of conversion (DC) was measured in near-IR (˿6165 cm^⿿1). Specimens were immersed in two different solvents (water for 7 days or dicholoromethane for 48 h). Water sorption (WS) and solubility (SL) were obtained according to ISO 4049. The leachates for both solutions were analyzed with ¹H-NMR (400 MHz, CDCL₃). Bar specimens (1 ÿ 3 ÿ 25 mm, photocured and then post-processed at 180 °C for 8 h to DC > 95%) were subjected to dynamic mechanical analysis (⿿30 to 230 °C) to obtain glass transition temperature (Tg), tan delta curves and crosslinking density (ν). Data was analyzed with two-way ANOVA/Tukey⿿s test (95%).ResultsIn general, the presence of TU increased the overall conversion. The WS was similar for all groups, but the SL decreased by 2-fold with the addition of the TU oligomer for all compositions, except BisGMA/TEGDMA 80/20. The BisGMA concentration of the leachates increased with increasing BisGMA in the initial mixture, and with the presence of thiourethane. This compositional drift of the gel with the presence of TU was attributed to the preferential dissolution of TEGDMA into the TU network. Tg and ν decreased with the addition of TU, as expected. The addition of TU produced more homogeneous networks, as evidenced by narrower breadth of the tan delta curve.ConclusionThe addition of TU affected the composition of the sol/gel in crosslinked networks, which were more homogeneous and presented 2-fold less potentially toxic leachates than the methacrylate controls.Clinical significanceThe addition of TU may produce less cytotoxic materials based on the increased conversion and reduced amount of unreacted extractables from its network after water storage.     

Bond strength durability of a resin composite on a reinforced ceramic using various repair systems

ObjectivesThis study compared the durability of repair bond strength of a resin composite to a reinforced ceramic after three repair systems.MethodsAlumina-reinforced feldspathic ceramic blocks (Vitadur-α^®) (N = 30) were randomly divided into three groups according to the repair method: PR-Porcelain Repair Kit (Bisco) [etching with 9.5% hydrofluoric acid + silanization + adhesive]; CJ-CoJet Repair Kit (3M ESPE) [(chairside silica coating with 30 μm SiO₂ + silanization (ESPE^®-Sil) + adhesive (Visio?-Bond)]; CL-Clearfil Repair Kit [diamond surface roughening, etching with 40% H₃PO₄ + Clearfil Porcelain Bond Activator + Clearfil SE Bond)]. Resin composite was photo-polymerized on each conditioned ceramic block. Non-trimmed beam specimens were produced for the microtensile bond strength (μTBS) tests. In order to study the hydrolytic durability of the repair methods, the beam specimens obtained from each block were randomly assigned to two conditions. Half of the specimens were tested either immediately after beam production (Dry) or after long-term water storage (37 °C, 150 days) followed by thermocyling (12,000 cycles, 5–55 °C) in a universal testing machine (1 mm/min). Failure types were analyzed under an optical microscope and SEM.ResultsμTBS results were significantly affected by the repair method (p = 0.0001) and the aging conditions (p = 0.0001) (two-way ANOVA, Tukey's test). In dry testing conditions, PR method showed significantly higher (p < 0.001) repair bond strength (19.8 ± 3.8 MPa) than those of CJ and CL (12.4 ± 4.7 and 9.9 ± 2.9, respectively). After long-term water storage and thermocycling, CJ revealed significantly higher results (14.5 ± 3.1 MPa) than those of PR (12.1 ± 2.6 MPa) (p < 0.01) and CL (4.2 ± 2.1 MPa) (p < 0.001). In all groups when tested in dry conditions, cohesive failure in the composite accompanied with adhesive failure at the interface (mixed failures), was frequently observed (76%, 80%, 65% for PR, CJ and CL, respectively). After aging conditions, while the specimens treated with PR and CJ presented primarily mixed failure types (52% and 87%, respectively), CL group presented mainly complete adhesive failures at the interface (70%).SignificanceHydrolytic stability of the repair method based on silica coating and silanization was superior to the other repair strategies for the ceramic tested.