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.     

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.     

Preparation and evaluation of a BisGMA-free dental composite resin based on a novel trimethacrylate monomer

ObjectiveThe use of the BisGMA as base monomer in dental composites has been questioned because of bisphenol A (BPA) is used as raw material in its synthesis, and BPA possess estrogenic potential associated to several health problems. This study describes the synthesis of the trimethacrylate tris(4-hydroxyphenyl)methane triglycidyl methacrylate (TTM) monomer and evaluate its effect when used as base monomer in the formulation of experimental photopolymerizable composite resins.MethodsThe TTM monomer was synthesized by a nucleophilic acyl substitution. Its chemical structure was confirmed via ¹H and ¹³C NMR spectroscopy and FTIR spectroscopy. Experimental composite resins were formulated by mixing TTM, triethyleneglycol dimethacrylate (TEGDMA) and inorganic fillers. A BisGMA/TEGDMA based composite resin was prepared and used as control to compare several physicochemical properties. Cell viability assay was used for cytotoxicity evaluation.ResultsTTM was successfully synthesized with quantitative yields. The results showed that the TTM-based composite resin had similar values of flexural strength, elastic modulus, degree of conversion and polymerization shrinkage than the control (p > 0.05). Water sorption and solubility were statistically significantly higher than the control (p < 0.05), however they complied the requirements stablished by the ISO 4049. Finally, this study shows there were no statistically significant differences for the biocompatibility outcomes (p = 0.345).SignificanceTTM monomer could be potentially useful in the formulation of BisGMA free composite resins, which could mean to minimize the human exposure to BPA.     

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.     

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.     

High performance dental resin composites with hydrolytically stable monomers

Objective

The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications.

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.     

Novel rechargeable calcium fluoride dental nanocomposites

ObjectivesComposite restorations with calcium fluoride nanoparticles (nCaF₂) can remineralize tooth structure through F and Ca ion release. However, the persistence of ion release is limited. The objectives for this study were to achieve long-term remineralization by developing a rechargeable nCaF₂ nanocomposite and investigating the F and Ca recharge and re-release capabilities.MethodsThree nCaF₂ nanocomposites were formulated: (1) BT-nCaF₂:Bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA); (2) PE-nCaF₂:Pyromellitic glycerol dimethacrylate (PMGDM) and ethoxylated bisphenol A dimethacrylate (EBPADMA); (3) BTM-nCaF₂:BisGMA, TEGDMA, and Bis[2-(methacryloyloxy)ethyl] phosphate (Bis-MEP). All formulations contained 15% nCaF₂ and 55% glass particles. Initial flexural strength and elastic modulus, F and Ca ion release, recharge and re-release were tested and compared to three commercial fluoride-containing materials.ResultsBT and BTM nCaF₂ composites were 3–4 times stronger and had elastic modulus 2 times that of resin-modified glass ionomer controls. PE-nCaF₂ had comparable strength to RMGIs. All nCaF₂ composites had significant F and Ca ion release and ion rechargeability. In F and Ca recharging cycles, PE-nCaF₂ had the highest ion recharging capability among nCaF₂ groups, followed by BT-nCaF₂ and BTM-nCaF₂ (p < 0.05). For all recharge cycles, ion release maintained similar levels, demonstrating long-term ion release was possible. Furthermore, after the final recharge cycle, nCaF₂ nanocomposites provided continuous ion release for 42 days without further recharge.SignificanceNovel nCaF₂ rechargeable nanocomposites exhibited significant F and Ca ion release over multiple recharge cycles, demonstrating continuous long-term ion release. These nanocomposites are promising restorations with lasting remineralization potential.     

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.     

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.     

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.     

Mechanical properties of dental resin/composite containing urchin-like hydroxyapatite

ObjectivesTo investigate the reinforcing effect of urchin-like hydroxyapatite (UHA) in bisphenol A glycidyl methacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) dental resin (without silica nanoparticles) and dental composites (with silica nanoparticles), and explore the effect of HA filler morphologies and loadings on the mechanical properties.MethodsUHA was synthesized by a facile method of microwave irradiation and studied by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). Mechanical properties of the dental resin composites containing silanized UHA were tested by a universal mechanical testing machine. Analysis of variance was used for the statistical analysis of the acquired data. The fracture morphologies of tested composites were observed by SEM. Composites with silanized irregular particulate hydroxyapatite (IPHA) and hydroxyapatite whisker (HW) were prepared for comparative studies.ResultsImpregnation of lower loadings (5 wt% and 10 wt%) of silanized UHA into dental resin (without silica nanoparticles) substantially improved the mechanical properties; higher UHA loadings (20 wt% and 30 wt%) of impregnation continuously improved the flexural modulus and microhardness, while the strength would no longer be increased. Compared with silanized IPHA and HW, silanized UHA consisting of rods extending radially from center were embedded into the matrix closely and well dispersed in the composite, increasing filler-matrix interfacial contact area and combination. At higher filler loadings, UHA interlaced together tightly without affecting the mobility of monomer inside, which might bear higher loads during fracture of the composite, leading to higher strengths than those of dental resins with IPHA and HW. Besides, impregnation of silanized UHA into dental composites (with silica nanoparticles) significantly improved the strength and modulus.SignificanceUHA could serve as novel reinforcing HA filler to improve the mechanical properties of dental resin and dental composite.     

Preparation of Zn doped mesoporous silica nanoparticles (Zn-MSNs) for the improvement of mechanical and antibacterial properties of dental resin composites

ObjectiveThe purpose of this work was to explore the enhancement effect of zinc doped mesoporous silica nanoparticles (Zn-MSNs), which could form micromechanical interlocking with resin matrix and sustainably release Zn²⁺, on the mechanical and antibacterial properties of the dental resin composites.MethodsZn-MSNs were prepared by a sol–gel method, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N₂ adsorption/desorption. The mechanical properties of the dental composites reinforced by Zn-MSNs were measured by a universal mechanical testing machine. Antibacterial activities of dental composites were evaluated by both qualitative and quantitative analysis using Streptococcus mutans (S. mutans). The cytotoxicity of the Zn-MSNs filled dental composites was investigated by osteoblasts (OBs).ResultsThe synthesized Zn-MSNs possessed good monodispersity with an average particle size of about 138 nm. The mechanical properties of the composites gradually increased with the increase of the content of Zn-MSNs. The flexural strength, flexural modulus, compressive strength and micro-hardness of the composites containing 15 wt% Zn-MSNs were 31.21%, 50.47%, 53.83% and 26.79% higher than the samples with no Zn-MSNs, respectively. The antibacterial performance was significantly improved by the addition of Zn-MSNs and the antibacterial rate of the composite with 15 wt% of Zn-MSNs reached 100%. Cytotoxicity tests revealed that all the composites were biocompatible during OBs incubation.SignificanceThe prepared Zn-MSNs can effectively improve the mechanical and antibacterial properties of the dental resin composites.     

Resin viscosity determines the condition for a valid exposure reciprocity law in dental composites

ObjectiveTo provide conditions for the validity of the exposure reciprocity law as it pertains to the photopolymerization of dimethacrylate-based dental composites.MethodsComposites made from different mass ratios of resin blends (Bis-GMA/TEGDMA and UDMA/TEGDMA) and silanized micro-sized glass fillers were used. All the composites used camphorquinone and ethyl 4-dimethylaminobenzoate as the photo initiator system. A cantilever beam-based instrument (NIST SRI 6005) coupled with NIR spectroscopy and a microprobe thermocouple was used to simultaneously measure the degree of conversion (DC), the polymerization stress (PS) due to the shrinkage, and the temperature change (TC) in real time during the photocuring process. The instrument has an integrated LED light curing unit providing irradiances ranging from 0.01 W/cm² to 4 W/cm² at a peak wavelength of 460 nm (blue light). Vickers hardness of the composites was also measured.ResultsFor every dental composite there exists a minimum radiant exposure required for an adequate polymerization (i.e., insignificant increase in polymerization with any further increase in the radiant exposure). This minimum predominantly depends on the resin viscosity of composite and can be predicted using an empirical equation established based on the test results. If the radiant exposure is above this minimum, the exposure reciprocity law is valid with respect to DC for high-fill composites (filler contents >50% by mass) while invalid for low-fill composites (that are clinically irrelevant).SignificanceThe study promotes better understanding on the applicability of the exposure reciprocity law for dental composites. It also provides a guidance for altering the radiant exposure, with the clinically available curing light unit, needed to adequately cure the dental composite in question.     

Highly translucent dental resin composites through refractive index adaption using zirconium dioxide nanoparticles and organic functionalization

ObjectivesFor dental resin composites, high translucency is important. Therefore, the aim of the study was to create a biocompatible and highly translucent resin-based composite, and to investigate the effect of material thickness on translucency.MethodsA biocompatible ORMOCER® resin matrix was reinforced with dental glass powder as fillers. To reach a high translucency, refractive index matching of the matrix and fillers was done in the two ways: (1) Highly refractive ZrO₂ nanoparticles were incorporated into the resin. (2) The resin was modified via addition of 4-Methylthiophenol. The corresponding refractive indices were acquired on an Abbe refractometer (n = 5). In both cases, the dental glass powder was added and translucency of the resulting minifilled and nanohybrid composites were measured using spectral photometry (n = 5). Additionally, the translucency of the experimental composites was determined as a function of specimen thickness in the range 10 μm–2 mm (n = 5). One-way ANOVA was performed to determine the significant differences in various optical parameters among different amounts of modifications and thicknesses at α = 0.05. Furthermore, cytotoxicity tests (extract and direct contact tests) were conducted according to ISO 10993 to classify the biocompatibility of the composites (n = 6).ResultsThe translucency values of the composites with 47 wt.-% dental glass powder and a specimen thickness of 2 mm, could be increased from 26% up to 71% by increasing the refractive index of the matrix through incorporating ZrO₂ nanoparticles. Moreover, it can also be increased to 67% via addition of 4-Methylthiophenol. Further results showed that the translucency significantly depended on the sample thickness following an exponential function. The effect of all tested parameters was significant among the materials (p < 0.001). The composites did not show any cytotoxic effect.SignificanceHighly translucent and biocompatible resin composites were developed. They show attractive properties for the use as dental enamel material in direct and indirect restorations.     

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 TEGDMA/BisGMA ratio on stress development and viscoelastic properties of experimental two-paste composites

In this study, we explored the reduction of shrinkage stresses in restored teeth by stimulating viscous flow of adhesive restoratives during curing, by increasing the TEGDMA/BisGMA ratio in the resin of composite restoratives. We studied a series of experimental two-paste composites with different amounts of TEGDMA (30, 50, 70 wt%, respectively) in the resin by mechanical testing, infrared spectroscopy, and dilatometry, to determine how comonomer composition affects the mechanical and chemical properties of the composite during curing. It was found that the polymerization rate of BisGMA-TEGDMA composites is indicative of the viscoelastic behavior during curing: The higher the reactivity, the higher the stiffness and viscosity development. Composites with 50 wt% TEGDMA in the resin displayed the highest maximum polymerization rate. High amounts of TEGDMA in the resin only modestly increased the pre-gel viscous flow (= lowered viscosity) property of composites. Of these composites, high post-gel shrinkage is the decisive factor in high shrinkage stress development.     

牙科纳米氧化铝复合树脂的制备与性能研究

目的 制备一种新型的光固化纳米氧化铝复合树脂,探讨其用于口腔临床的可行性。方法 以双酚A双甲基丙烯酸缩水甘油酯(Bis-GMA)为树脂基质,甲基丙烯酸羟乙酯(HEMA)为活性稀释剂,添加纳米氧化铝填料对树脂基质进行增强增韧改性,制备一种新型牙科纳米氧化铝复合树脂,并表征其固化程度、弯曲强度、硬度、断面形貌、耐磨性、吸水性与水溶解性。结果 添加纳米氧化铝能提高复合树脂材料的刚性和硬度,当添加量达到3wt%时,复合树脂的力学性能、吸水和溶解性能均为最优。结论 复合树脂中加入一定比例的纳米氧化铝可达到增韧和耐磨的效果,该研究为开发新型牙科复合树脂提供了理论和实验基础。     

Towards the development of self-healing and antibacterial dental nanocomposites via incorporation of novel acrylic microcapsules

ObjectiveThe main aim of the current work was to develop the novel self-healing dental composites contained poly(methyl methacrylate) (PMMA) microcapsules. The effects of PMMA microcapsule content in self-healing performance and mechanical properties of dental composites including flexural strength, flexural modulus, and fracture toughness were discussed. The antibacterial activity and non-toxicity properties of optimum self-healing dental composites were also investigated.MethodsNovel acrylic microcapsules were prepared using triethylene glycol dimethacrylate (TEGDMA) as healing agent and PMMA as microcapsule shell via solvent evaporation method. The silica nanoparticles with the mean size of 15–20 nm were treated by 3-methacryloxypropyltrimethoxysilane (MPS) to enhance their adhesion and dispersion within the acrylic matrix of composite. Acrylic microcapsules with mass fractions of 0%, 5%, 10%, and 15% were added into a mixture of acrylic resins and MPS-grafted SiO₂ nanoparticles. The strength and elastic modulus of dental composites were measured by the flexural test. The single edge V-notched beam (SEVNB) method was applied to investigate fracture toughness (K_IC) and healing ef?ciency. The results were then statistically analyzed using one-way analysis of variance (ANOVA) at the con?dence level of 0.95.ResultsAcrylic microcapsules were synthesized with the mean size around 30 µm and the core content of about 15 wt%. The grafting percentage of MPS surface modifier onto SiO₂ nanoparticles was measured 3.2%. The incorporation of PMMA microcapsules into the dental composites had no significant effect on flexural properties. The self-healing dental composites also indicated the high efficient healing performance in the range of 78–121%. The self-healing dental composites also exhibited impressive antibacterial activity against Streptococcus mutans (S. mutans). The MTT assay also revealed that the incorporation of acrylic microcapsules in dental composites has no cytotoxicity effects.Signi?canceIn the current study, for the first time, the self-healing dental nanocomposites contained acrylic microcapsules were prepared with excellent healing performance and antibacterial properties.