Synthesis of chemically modified BisGMA analog with low viscosity and potential physical and biological properties for dental resin composite

ObjectivesThe currently available commercial dental resin composites have limitations in use owing to the high viscosity and water sorption of Bisphenol A glycidyl methacrylate (BisGMA). The objective of this study was to obtain a BisGMA analog with reduced viscosity and hydrophilicity for potential use as an alternative to BisGMA in dental resin composites.MethodsThe targeted chlorinated BisGMA (Cl-BisGMA) monomer was synthesized via the Appel reaction. The structural modification was confirmed via ¹H- and ¹³C nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and mass spectrometry. Five resin mixtures (70:30 wt.%: F1 = BisGMA/TEGDMA; F2 = Cl-BisGMA/TEGDMA; F3 = Cl-BisGMA only; F4 = Cl-BisGMA/BisGMA; F5 contained 15% TEGDMA with equal amounts of BisGMA and Cl-BisGMA) were prepared. The viscosity, degree of double-bond conversion (DC), water sorption (W_SP), and solubility (W_SL) were tested. Cell viability and live/dead assays, as well as cell attachment and morphology assessments, were applied for cytotoxicity evaluation.ResultsCl-BisGMA was successfully synthesized with the viscosity reduced to 7.22 (Pa s) compared to BisGMA (909.93, Pa s). Interestingly, the DC of the F2 resin was the highest (70.6%). By the addition of equivalence concentration of Cl-BisGMA instead of BisGMA, the W_SP was decreased from 2.95% (F1) to 0.41% (F2) with no significant change in W_SL. However, the W_SL increased with high Cl-BisGMA content. Biological tests revealed that all the resins were biocompatible during CL1 incubation.SignificanceThe experimental resins based on Cl-BisGMA exhibited improved properties compared with the control samples, e.g., biocompatibility and lower viscosity, indicating that Cl-BisGMA can be considered as a potential monomer for application in dental resin composites.     

Evaluation of a photo-initiated copper(I)-catalyzed azide-alkyne cycloaddition polymer network with improved water stability and high mechanical performance as an ester-free dental restorative

ObjectiveThe objective is to develop and characterize an ester-free ether-based photo-CuAAC resin with high mechanical performance, low polymerization-induced stress compared with common BisGMA/TEGDMA (70/30) resins, and improved water stability in comparison to previously developed urethane-based photo-CuAAC resins.MethodsTriphenyl-ethane-centered ether-linked tri-azide monomers were synthesized and co-photopolymerized with ether-linked tri-alkyne monomers under visible light irradiation using a copper(II) pre-catalyst and CQ/EDAB as the initiator. The ether-based CuAAC formulation was investigated for thermo-mechanical properties, polymerization kinetics and shrinkage stress, and flexural properties with respect to a conventional BisGMA/TEGDMA (70/30) dental resin. In addition, both the ether-based CuAAC resin and the urethane-based CuAAC resin were examined for their water stability using the BisGMA/TEGDMA (70/30) resin as a control.ResultsThe ether-based CuAAC network (AK/AZ-1) exhibited a slightly lower glass-transition temperature compared with the BisGMA/TEGDMA network (108 °C vs 128 °C), but because of its much sharper glass transition, the AK/AZ-1 CuAAC-network maintained storage modulus higher than 1 GPa up to 100 °C. In addition, the ether-based AK/AZ-1 network exhibited reduced shrinkage stress (0.56 MPa vs 1.0 MPa) and much higher flexural toughness (7.6 MJ/m³ vs 1.6 MJ/m³) while showing slightly lower flexural modulus and slightly higher flexural strength compared with the BisGMA/TEGDMA network. Moreover, the ether-based AK/AZ-1 CuAAC network displayed comparable water stability in comparison to the BisGMA/TEGDMA network with slightly higher water sorption (46 μg/mm³ vs 38 μg/mm³) and much lower water solubility (2.3 μg/mm³ vs 4.4 μg/mm³).SignificanceEmploying the ether-based hydrophobic CuAAC formulation significantly improved the water stability of the CuAAC network compared with previously developed urethane-based CuAAC networks. Furthermore, compared with the conventionally used BisGMA/TEGDMA formulation, the reduced shrinkage stress, comparable flexural strength/flexural modulus, and the superior flexural toughness of the ether-based CuAAC network make it a promising ester-free alternative to the currently widely-used methacrylate-based dental restoratives.     

Evaluation of highly reactive mono-methacrylates as reactive diluents for BisGMA-based dental composites

ObjectivesThis study evaluates the performance of highly reactive novel monomethacrylates characterized by various secondary moieties as reactive diluent alternatives to TEGDMA in BisGMA filled dental resins. We hypothesize that these monomers improve material properties and kinetics over TEGDMA because of their unique polymerization behavior.MethodsThe cure rates and final double bond conversion of the resins were measured using real-time FTIR spectroscopy. The glass transition temperature and storage modulus of the formed polymers were measured using dynamic mechanical analysis. Flexural modulus and flexural strength values were obtained using a three-point bending flexural test.ResultsPolymerization kinetics and polymer mechanical properties were evaluated for the novel resin composites. It was observed that upon the use of novel monomethacrylates as reactive diluents, polymerization kinetics increased by up to 3-fold accompanied by increases in the extent of cure from 5% to 13% as compared to the BisGMA/TEGDMA control. Polymer composites formed from resins of BisGMA/novel monomethacrylates exhibited comparable T_g values to the control, along with 27–37% reductions in the glass transition half widths indicating the formation of more homogeneous polymeric networks. The BisGMA/monomethacrylate formulations exhibited equivalent flexural modulus and flexural strength values relative to BisGMA/TEGDMA.SignificanceFormulations containing novel monovinyl methacrylates exhibit dramatically increased curing rates while also exhibiting superior or at least comparable composite polymer mechanical properties. Thus, these types of materials are attractive for use as reactive diluent alternatives to TEGDMA in dental formulations.     

Bisphenol A as degradation product of monomers used in resin-based dental materials

ObjectiveThere is still much debate about the release of bisphenol-A (BPA) from dental materials. Therefore, this study aimed to quantify BPA present as an impurity in both BPA-based and non-BPA-based monomers and to evaluate whether these monomers may degrade to BPA upon salivary, bacterial, and chemical challenges.MethodsBPA was determined in three different amounts (1, 2, and 3 μmol) of each monomer (TEGDMA, UDMA, mUDMA, BisGMA, BisEMA-3, -6, -10, -30, BisPMA, EBPADMA urethane, BADGE, and BisDMA). Next, the monomers (3 μmol) were immersed in whole human pooled saliva collected from adults, Streptococcus mutans (2 × 10⁷ CFU/mL), and acidic (0.1 M HCl), alkaline (0.1 M NaOH), and control media. The amount of BPA was quantified using a specific and highly sensitive UPLC–MS/MS method including derivatization of BPA by pyridine-3-sulfonyl chloride.ResultsThe monomers BisGMA and BisEMA-3 contained trace amounts (0.0006% and 0.0025%, respectively) of BPA as impurities of their synthesis process. BPA concentrations increased when the monomers BisGMA, BisEMA-3, BisEMA-6, BisEMA-10, BisPMA and BADGE were exposed to saliva and S. mutans, indicating degradation of a small amount of monomer into BPA. In addition, BisPMA and BADGE degraded into BPA under alkaline conditions. The conversion rate of the monomers into BPA ranged between 0.0003% and 0.0025%.SignificanceImpurities and degradation of BPA-based monomers may account for the release of BPA from resin-based dental materials. Even though the detected amounts of BPA due to monomer impurity were small, manufacturers of dental materials can reduce the BPA content by using only monomers of the highest purity. Considering the overall current trend towards BPA-free materials, it may be recommendable to investigate whether non-BPA based monomers can be used in dental resin-based materials.     

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.     

Physicochemical properties of dental resins formulated with amine-free photoinitiation systems

ObjectiveTo assess the mechanical properties of two different dimethacrylate resin blends containing the photosensitizer camphorquinone (CQ) alone or in combination with one or more synergists including an amine and/or an iodonium.MethodsTwo co-monomer resin blends were formulated using Bis-GMA/TEGDMA and UDMA/TEGDMA, both at 1:1 mass ratio. Each resin blend was divided into four groups, comprising the following four photoinitiation systems: (1) CQ + 2-(dimethylamino)ethyl methacrylate (DMAEMA); (2) CQ + DMAEMA + bis(4-methyl phenyl)iodonium hexafluorophosphate (BPI); (3) CQ; and (4) CQ + BPI. Materials were evaluated for polymerisation kinetics, water sorption, solubility, flexural strength and modulus.ResultsBisGMA/TEGDMA with CQ showed minimal and insignificant degree of conversion and was not tested for water sorption/solubility and mechanical properties. The ternary system (i.e., CQ + DMAEMA + BPI), promoted the highest degree of conversion for each monomer blend. The resins containing amine had higher mechanical properties than the amine free. However, the UDMA amine free resins exhibited greater flexural strength and modulus than the corresponding amine free BisGMA resins. BisGMA/TEGDMA containing CQ + DMAEMA or CQ + BPI had significantly higher water sorption and solubility than the other groups.SignificanceResins containing amine presented better properties than the amine-free systems. The addition of iodonium salt (BPI) improved the degree of conversion of the resins, even without an amine co-initiator. The amine-free initiator system (CQ + BPI) was more effective when used with UDMA versus BisGMA based-resins respectively.     

Dynamic covalent chemistry (DCC) in dental restorative materials: Implementation of a DCC-based adaptive interface (AI) at the resin–filler interface for improved performance

ObjectiveDental restorative composites have been extensively studied with a goal to improve material performance. However, stress induced microcracks from polymerization shrinkage, thermal and other stresses along with the low fracture toughness of methacrylate-based composites remain significant problems. Herein, the study focuses on applying a dynamic covalent chemistry (DCC)-based adaptive interface to conventional BisGMA/TEGDMA (70:30) dental resins by coupling moieties capable of thiol–thioester (TTE) DCC to the resin–filler interface as a means to induce interfacial stress relaxation and promote interfacial healing.MethodsSilica nanoparticles (SNP) are functionalized with TTE-functionalized silanes to covalently bond the interface to the network while simultaneously facilitating relaxation of the filler–matrix interface via DCC. The functionalized particles were incorporated into the otherwise static conventional BisGMA/TEGDMA (70:30) dental resins. The role of interfacial bond exchange to enhance dental composite performance in response to shrinkage and other stresses, flexural modulus and toughness was investigated. Shrinkage stress was monitored with a tensometer coupled with FTIR spectroscopy. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine.ResultsA reduction of 30% in shrinkage stress was achieved when interfacial TTE bond exchange was activated while not only maintaining but also enhancing mechanical properties of the composite. These enhancements include a 60% increase in Young’s modulus, 33% increase in flexural strength and 35% increase in the toughness, relative to composites unable to undergo DCC but otherwise identical in composition. Furthermore, by combining interfacial DCC with resin-based DCC, an 80% reduction of shrinkage-induced stress is observed in a thiol–ene system “equipped” with both types of DCC mechanisms relative to the composite without DCC in either the resin or at the resin–filler interface.SignificanceThis behavior highlights the advantages of utilizing the DCC at the resin–filler interface as a stress-relieving mechanism that is compatible with current and future developments in the field of dental restorative materials, nearly independent of the type of resin improvements and types that will be used, as it can dramatically enhance their mechanical performance by reducing both polymerization and mechanically applied stresses throughout the composite lifetime.     

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.     

Influence of resin matrix on the rheology,translucency, and curing potential of experimental flowable composites for bulk-fill applications

ObjectiveTo propose monomer formulations that show an optimal degree of conversion as a function of depth for bulk-fill applications.MethodsFour resin blends were formulated with methacrylate-based monomers: BisGMA + TEGDMA (control); BisEMA + BisGMA + TEGDMA (BisEMA-based); UDMA + BisGMA + TEGDMA (UDMA-based) and BisEMA + UDMA + BisGMA + TEGDMA (BisEMA + UDMA-based). For each material, a photoinitiating system and silanized filler particles were added. The rheological analyses were performed with a rotational rheometer using the cone/plate geometry. CIELab coordinates were assessed over black and white backgrounds using a bench spectrophotometer (SP60, X-Rite) to calculate the translucency parameter (TP) for samples with 0.5, 4, and 6 mm thickness. The degree of CC conversion (DC) was determined by infrared spectroscopy (FTIR/ATR) at 0.05 mm (top), 4, and 6 mm depths (bottom), and the bottom-to-top ratio was considered. A broad spectrum–based LED was used for light activation. Analysis of variance and Tukey’s test (95%) were performed on the results.ResultsThe materials tested showed pseudoplastic and thixotropic behavior and a predominance of viscous effects over elastics. The control resin yielded the lowest viscosity for the entire shear rate investigated, followed by the BisEMA-based, BisEMA + UDMA-based, and UDMA-based group, which had the highest viscosity. The UDMA-based material showed the lowest TP as a function of thickness. Both the materials’ formulations and depths significantly influenced the DC. The UDMA-based group promoted the highest DC ??on the top (71 ± 1%) and 4 mm depth (68 ± 1%) but exhibited lower bottom-to-top DC ratio. The BisEMA + UDMA-based material promoted the highest bottom-to-top DC ratio at 4 mm (99%) and 6 mm (97%).SignificanceThe resin matrix interferes in the rheological behavior, translucency parameter, and polymerization capacity as a function of depth. The material formulated with the addition of UDMA and BisEMA demonstrated the highest curing potential as a function of depth and can be useful for bulk-fill applications.     

Assessing the estrogenic activity of chemicals present in resin based dental composites and in leachates of commercially available composites using the ERα-CALUX bioassay

ObjectiveThe biocompatibility of resin based dental composites has not yet been fully characterized even though certain monomers used in these composites are synthesized from Bisphenol A (BPA), a well-known estrogenic endocrine disruptor. As a result, they show structural relationship to BPA and can contain it as an impurity. Therefore, the estrogenic activity of 9 monomers, 2 photoinitiators, one photostabilizer and leachates of 4 commercially available composites was determined.MethodsThe ERα-CALUX bioassay was used to determine both agonistic and antagonistic estrogenic activities of the pure compounds (BPA, BisDMA, BisGMA, BisEMA(3), BisEMA(6), BisEMA(10), TEGDMA, TCD-DI-HEA, BADGE, UDMA, HMBP, DMPA, CQ) and the leachates of cured composite disks. The leachates of 4 commercially available composites (Solitaire 2, Ceram.x Spectra ST, G-ænial Posterior and Filtek Supreme XTE) in water and 0.1 M NaOH (pH = 13, ‘worst-case scenario’) were tested for estrogenic activity (pooled leachates from 10 cured composite disks).ResultsAgonistic estrogenic activity was found for the monomer BisDMA, the photostabilizer HMBP and photoinitiator DMPA. All leachates from the 4 tested composites showed significant agonistic estrogenic activity higher than the DMSO control, and the highest activity (potency and efficacy) was found for Solitaire 2, followed by Ceram.x Spectra ST. Furthermore, antagonistic estrogenic activity was found in the leachates from G-ænial Posterior.SignificanceThese results show that significant estrogenic activity was found in all leachates of the cured composite disks, and that this estrogenicity is most likely due to a mixture effect of multiple estrogenic compounds (including BPA, HMBP and DMPA). This indicates that further research into the endocrine activity of all the compounds that are present in these composites (even at low quantities) and their possible mixture effect is warranted to guarantee their safe use.     

Relocation and reinforcement of the adhesive/composite interface with spontaneous amine-peroxide interfacial polymerization

ObjectivesThis study demonstrates a spontaneous redox polymerization process located at the adhesive-composite interface that precedes photocure of the composite with the intent to improve bonding.MethodsAn aromatic amine and benzoyl peroxide redox initiator system was partitioned between BAPO-photoinitiated BisGMA/HEMA adhesive and BisGMA/TEGDMA resin-composites. The composite was placed on the photocured adhesive layer with a brief delay before photopolymerization of the composite layer. Micro-tensile bond strength between the adhesive and composite was assessed in comparison with the non-redox active control materials.ResultsThe presence of amine or peroxide in these resins without the redox initiation contribution enhanced both the rate and the final conversion of the BAPO-based photopolymerizations. Control formulations using redox-only initiation showed active polymer formation starting at approximately 30 s when physical mixing of the redox components was involved; however, simply by waiting 60 s between composite placement and photocure provided adequate time for passive interfacial diffusion of benzoyl peroxide from the pre-cured adhesive into the overlaid aromatic amine-containing composite such that a sufficient degree of redox initiated interfacial polymerization occurred prior to the composite photocure. The result was a significant increase in the adhesive to composite micro-tensile bond strength with the failure site moved away from the mainly interfacial failure noted for the control.SignificanceThe stress-free autonomous pre-conversion of a redox-initiated thin film of composite that then provides a compositionally homogeneous interface for composite photopolymerization offers a means to enhance at least short-term bond strength between the adhesive and composite phases during restorative placement.     

Preparation and evaluation of novel bio-based Bis-GMA-free dental composites with low estrogenic activity

ObjectiveAlthough bisphenol Aglycidyl methacrylate (Bis-GMA) are widely used in the dental composite, its raw materials include the petroleum-based product bisphenol A (BPA) with high estrogenic activity (EA). In this study, two new BPA-free dimethacrylate monomers from bio-based material creosol were synthesized and evaluated.MethodsThe renewable bisphenol monomer 5, 5'-methylenedicreosol (BCF) was prepared from bio-based material creosol. By the human breast cancer cells (MCF-7 cells) proliferation assay, a risk assessment of BCF was performed to determine if BCF possessed reduced EA in comparison to BPA. Then, the novel monomers 5, 5'-methylenedicreosol diglycidyl ether diacrylate (BCF-EA) and 5, 5'-methylenedicreosol diglycidyl ether dimethacrylate (BCF-GMA) were synthesized from BCF with epichlorohydrin and (meth)acrylate. All products were investigated by ¹H NMR and FT-IR spectra. The control resin was a mixture based on Bis-GMA and tri(ethyleneglycol) dimethacrylate (TEGDMA) with a weight ratio of 5:5 (5B5T). Similarly, experimental resin matrix was a mixture based on BCF-EA/TEGDMA (5E5T) and BCF-GMA/TEGDMA (5G5T). And their corresponding composites were then prepared with corresponding resin matrices and hybrid SiO₂ (5E5TC, 5G5TC and 5B5TC). The properties of these composites were investigated according to the standard or referenced methods. Each sample was evaluated for double bond conversion (DC), shrinkage stress (SS) and volumetric polymerization shrinkage (VS). Water sorption (WS), water solubility (SL), mechanical properties and cytotoxicity were also measured.Results¹H NMR and FT-IR spectra confirmed the chemical structure of each monomer. EA test revealed that bio-based bisphenol monomer BCF as the precursor of BCF-EA and BCF-GMA showed lower EA than BPA. Cured resin matrix: Both 5E5T and 5G5T had nearly the same DC (p < 0.05), which was higher than 5B5T (p < 0.05); 5E5T and 5G5T had lower VS, SL and cytotoxicity than 5B5T (p < 0.05); mechanical properties of 5E5T and 5G5T were all better than those of 5B5T (p < 0.05). Cured composite: There was no significant difference in conversion (p < 0.05); 5E5TC and 5G5TC had significantly lower VS (p < 0.05); WS of 5E5TC and 5G5TC were similar (p < 0.05), but higher compared to 5B5TC (p < 0.05); 5E5TC and 5G5TC had the deeper depth of cure (p > 0.05); before water immersion, there was no significant difference in flexural strength between 5E5TC and 5G5TC (p > 0.05), and higher than 5B5TC (p < 0.05); 5E5TC and 5G5TC showed less cytotoxicity than 5B5TC (p < 0.05).SignificanceThe new BPA-free di(meth)acrylates are promising photocurable dental monomers owning to bio-based raw material, high degree of conversion coupled with low curing shrinkage and good mechanical properties. Therefore, BCF-EA and BCF-GMA has a potential to be used as the substitution for Bis-GMA to prepare Bis-GMA-free dental composite.     

Influence of intermediate resin on the bond strength of light-curing composite resin to polymer substrate

Objectives. The aim of this study was to examine the effect of intermediate resin (IMR) of different monomer compositions and viscosities on the shear bond strength between polymer substrate and light-curing composite. Methods. The substrate used in the study was an autopolymerizing polymethyl methacrylate (PMMA) based polymer. The substrate was treated with the IMR for 3 min before application of light polymerizable particulate filler composite resin. The monomers of the IMR were either bisphenol-A-glycidyl dimethacrylate (BisGMA) and triethyleneglycol dimethacrylate (TEGDMA) or BisGMA and methyl methacrylate (MMA). The shear bond strength of the IMR treated substrate to the particulate filler composite was evaluated after storing the specimens dry and after thermocycling the specimens in water. Light microscope examination was accomplished to determine the swelled layer of the substrate. Results. Significant differences were found between the shear bond strength values of the IMRs (p < 0.001). The bond strengths were generally higher in the BisGMA-MMA groups than in the BisGMA-TEGDMA groups. Two-way ANOVA revealed significant effects of type of IMR (p < 0.001) and thermocycling (p = 0.017) on the shear bond strength. No interaction was found between these variables (p > 0.05). Conclusions. The results suggest that the monomer composition and ratio of the IMRs used in the study influence the shear bond strength of the polymer substrate to the new resin.     

Modified POSS nano-structures as novel co-initiator-crosslinker: Synthesis and characterization

ObjectiveTo synthesize an amine-modified polyhedral oligomeric silsesquioxane (POSS) nano-structure as a novel co-initiator-crosslinker (co-Ini-Linker) and to determine the effect of the co-Ini-linker on the physical and mechanical behavior of an experimental dental composite.MethodsThe amine-methacrylate POSS nano-structures (AMA-POSS) were chemically synthesized by anchoring a tertiary amine functionality on the methacrylate POSS (MA-POSS) branches. Three types of AMA-POSS, having different amine branches in their structures, were synthesized through the Aza Michael reaction. The chemical structure of AMA-POSSs were evaluated by¹H-NMR spectroscopy. Afterward, the AMA-POSS was incorporated into a dental resin system composed of Bis-GMA, TEGDMA, and photo-initiator. Three resin systems with different AMA-POSS types were then prepared, and their properties were compared with a resin containing DMAEMA as a conventional co-initiator. The degree of conversion evaluated by FTIR spectroscopy and the shrinkage kinetics of the resins were determined through the bonded-disk technique. The flexural properties of the photopolymerized resins were also investigated. The distribution of nano-structures in the matrix resin was analyzed using EDX analysis.ResultsThe modified POSS structure and the number of amine branches were confirmed with¹H-NMR spectroscopy. The resin containing 8 amine branches (P8) showed the same degree of conversion (DC%) as the resin containing DMAEMA (P > 0.05). Decreasing the amine branches in the POSS structure, however, revealed an increasing trend in DC%. The resin containing P8 showed the lowest shrinkage strain. By incorporating AMA-POSS into the resin system, the water sorption significantly decreased (P < 0.05). The flexural strength and modulus increased by adding P3 into the resin system (P < 0.05). EDX Si-map revealed that the co-Ini-linker was well dispersed in the resin matrix.SignificanceThe synthesized novel amine-methacrylate POSS nanostructures not only act as an amine co-initiator but also work as a reinforcing filler and a cross-linking agent.     

Influence of composition on rate of polymerization contraction of light-curing resin composites

A slow contraction may result in reduced gap formation when a restorative resin polymerizes in a dental cavity. It was the aim in the present work to investigate the rate of contraction in relation to composition of experimental light-curing resin composites. The monomer of the resin composites consisted of mixtures of BisGMA, TEGDMA, and in one series HEMA. The resins contained varying amounts of initiators, co-initiators, and inhibitor, and were made composite by adding a silanized glass filler to a content of 74% by weight of the composite paste. The polymerization contraction up to 120 sec was determined by means of the bonded-disk method. Within the ranges studied, the concentration of initiator and co-initiator in the monomer mixture had only an insignificant influence on rate of polymerization. In comparison to camphorquinone, the initiators 1-phenyl-1,2-propanedione and benzil reduced the rate of polymerization without affecting the final contraction. In comparison to N,N-dimethyl- p -aminobenzoic acid ethyl ester, N,N-cyanoethyl methylaniline was as effective, while N,N-diethanol- p -toluidine was less effective as co-initiator. A relatively high content of the inhibitor methoxyhydroquinone reduced the initial rate but not the final polymerization contraction. The rate of polymerization increased with the level of HEMA and TEGDMA in the monomer mixture. It was concluded that intrinsic slow cure may be obtained with certain compositions of resin composites without impairing the final extent of polymerization.     

Influence of chlorhexidine on the degree of conversion and E-modulus of experimental adhesive blends

ObjectivesThis study examined the effect of chlorhexidine (CHX) content on degree of conversion (DC) and E-modulus of experimental adhesive blends. The hypothesis tested was that increasing concentrations of CHX result in decreased DC and E-modulus in relation to adhesive hydrophilicity.MethodsExperimental adhesive blends with increasing hydrophilicity R2 (70% bisGMA, 28.75% TEGDMA); R3 (70% BisGMA, 28.75% HEMA); R4 (40% BisGMA, 30% TCDM, 28.75% TEGDMA); R5 (40% BisGMA, 30% BisMP, 28.75% HEMA) and different CHX concentrations (1 and 5%) were analyzed. 5% CHX could not be dissolved in R2. A differential scanning calorimeter was used to measure the DC of resin blends. Photopolymerized disks of the experimental comonomer mixtures (n = 10/gp) were used to measure the E-modulus of each specimen using a biaxial flexure test. Data were analyzed with two-way ANOVA (resin type and CHX concentration) and Tukey's post hoc test.ResultsThe addition of 1% CHX did not significantly alter the DC of R2 and R3. Significant decrease in R3 DC values was observed when 5% CHX was added. CHX significantly increased the DC of R4 and R5. 1% CHX reduced the E-modulus of all resins (p < 0.05) except for R2, in which the E-modulus was significantly increased (p < 0.05). 5% CHX significantly reduced the E-modulus of resins R3 to R5 (p < 0.05).SignificanceIn conclusion, increasing concentrations of CHX dissolved in resin blends had little adverse effect on DC but decreased the E-modulus 27–48% compared to controls. Solvation of CHX in ethanol prior to incorporation of CHX into R2 may permit higher CHX concentrations without lower polymer stiffness.     

Mucotoxicity of dental composite resins on a tissue-engineered human oral mucosal model

OBJECTIVE: Tissue-engineered human oral mucosal models have been developed for biocompatibility assessment of biomaterials. The aim of this study was to evaluate the biological effects of three different composite resin systems on a three-dimensional human oral mucosal model. METHODS: Full-thickness oral mucosal models were engineered by air/liquid interface culture of a human oral keratinocyte cell line on a lamina propria composed of oral fibroblasts seeded into a porous scaffold. The surface of the tissue models was exposed to three types of experimental composite resins: a TEGDMA-based, a UDMA-based, and a BisGMA/TEGDMA (80:20)-based composite resin for 24h. The response of the engineered oral mucosa to the test materials was assessed using routine histology, the Alamar Blue tissue viability assay and IL-1beta release measured by ELISA. RESULTS: Compared to the other materials tested, the TEGDMA-based composite resin caused significant damage to the oral mucosal model. Statistical analysis by one-way ANOVA followed by Tukey's analysis showed that there was a significant decrease in the viability of tissue models after 24h exposure to TEGDMA-based composite resin. Also exposure to TEGDMA-based composite resin significantly increased the amount of IL-1beta released from the oral mucosal model. CONCLUSION: The 3D human oral mucosal model has the potential to be a more relevant and more informative model than monolayer cell culture systems for biocompatibility testing of dental materials. The results obtained from multiple-endpoint analysis of the oral mucosal model indicate significant mucotoxicity of high TEGDMA-containing composite resins.     

BisGMA/TEGDMA dental composite containing high aspect-ratio hydroxyapatite nanofibers

Objectives

The objectives of this study are to investigate the properties of high aspect-ratio hydroxyapatite (HAP) nanofibers and the reinforcing effect of such fibers on bisphenol A glycidyl methacrylate (BisGMA)/triethylene glycol dimethacrylate (TEGDMA) dental resins (without silica microparticle filler) and dental composites (with silica microparticle filler) with various mass fractions (loading rates).

Methods

HAP nanofibers were synthesized using a wet-chemical method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermal gravimetric analysis (TGA). Biaxial flexural strength (BFS) of the HAP nanofibers reinforced dental resins without any microsized filler and dental composites with silica microparticle filler was tested and analysis of variance (ANOVA) was used for the statistically analysis of acquired data. The morphology of fracture surface of tested dental composite samples was examined by SEM.

Results

The HAP nanofibers with aspect-ratios of 600 to 800 can be successfully fabricated with a simple wet-chemical method in aqueous solution. Impregnation of small mass fractions of the HAP nanofibers (5 wt% or 10 wt%) into the BisGMA/TEGDMA dental resins or impregnation of small mass fractions of the HAP nanofibers (2 wt% or 3 wt%) into the dental composites can substantially improve the biaxial flexural strength of the resulting dental resins and composites. A percolation threshold of HAP nanofibers, beyond which more nanofibers will no longer further increase the mechanical properties of dental composites containing HAP nanofibers, was observed for the dental composites with or without silica microparticle filler. Our mechanical testing and fractographic analysis indicated that the relatively good dispersion of HAP nanofibers at low mass fraction is the key reason for the significantly improved biaxial flexural strength, while higher mass fraction of HAP nanofibers tends to lead to bundles that cannot effectively reinforce the dental resins or composites and may even serve as defects and thus degrade the resulting dental resin and composite mechanical properties.

Significance

The incorporation of small mass fraction of HAP nanofibers with good dispersion can improve the mechanical property of dental resins and dental composites.     

Photopolymerization shrinkage-stress reduction in polymer-based dental restoratives by surface modification of fillers

ObjectivesThis research explores the use of polymer brushes for surface treatment of fillers used in polymer-based dental restoratives with focus on shrinkage stress reduction. The influence of interfacial reactive groups on shrinkage stress is explored.MethodsOligomers of varying lengths and with varying number of reactive groups along the length were synthesized by modifying commercial oligomers. Surface of silica fillers (OX50) was treated with methylaminopropyltrimethoxysilane and this was further reacted with the synthesized oligomers to obtain a series of polymer brushes on the surface. Fillers modified with γ-methacryloxypropyltrimethoxysilane were used as a control. Filler surface treatment was confirmed using diffuse reflectance spectroscopy and thermogravimetric analysis. Fillers were added at 30 wt % to a resin made of BisGMA/TEGDMA and polymerization kinetics, shrinkage stress, volumetric shrinkage, flexural strength and modulus, viscosity were measured.ResultsComposites with polymer brush functionalized fillers showed up to a 30 % reduction in shrinkage stress as compared to the control, with no reduction in flexural strength and modulus. Shrinkage stress reduced with increasing length of the polymer brush and increased with increase in number of reactive groups along the length of the polymer brush.SignificanceThe interface between inorganic fillers and an organic polymer matrix has been utilized to reduce shrinkage stress in a composite with no compromise in mechanical properties. This study gives insights into the stress development mechanism at the interface.     

Multifunctional monomer acts as co-initiator and crosslinker to provide autonomous strengthening with enhanced hydrolytic stability in dental adhesives

ObjectiveThe purpose of this study was to evaluate a new synthesized multifunctional monomer, aminosilane functionalized methacrylate (ASMA), containing polymerizable methacrylate, tertiary amine, and methoxysilane functionalities in dental adhesive formulations, and to investigate the polymerization kinetics, leachates, thermal and mechanical properties of copolymers.MethodsAdhesive contained HEMA/BisGMA (45/55, w/w) was used as a control, and mixtures based on HEMA/BisGMA/ASMA at the mass ratio of 45/(55-x)/x were used as experimental adhesive. Adhesives were characterized with regard to water miscibility, photo-polymerization behavior (Fourier transform infrared spectroscopy, FTIR), leached co-monomers (high performance liquid chromatography, HPLC), thermal properties (modulated differential scanning calorimeter, MDSC), and mechanical properties (dynamic mechanical analyzer, DMA). Stress relaxation times and the corresponding moduli, obtained from stress relaxation tests, are used in a simulated linear loading case.ResultsAs compared to the control, ASMA-containing adhesives showed higher water miscibility, lower viscosity, improved monomer-to-polymer conversion, significantly greater T_g and rubbery modulus. HPLC results indicated a substantial reduction of leached HEMA (up to 85 wt%) and BisGMA (up to 55 wt%) in ethanol. The simulation reveals that the ASMA-containing adhesive becomes substantially stiffer than the control.SignificanceASMA monomer plays multiple roles, i.e. it serves as both a co-initiator and crosslinker while also providing autonomous strengthening and enhanced hydrolytic stability in the adhesive formulations. This multifunctional monomer offers significant promise for improving the durability of the adhesive at the composite/tooth interface.