bisphenol-A Glycidyl Dimethacrylate Research Articles

Light-curable urushiol enhanced bisphenol A glycidyl dimethacrylate dentin bonding agent

ObjectivesThe low durability of composite resin restorations can be attributed to the degradation of the resin dentin bonding interface. Owing to the presence of hydrophilic components in the adhesive, the integrity of the resin dentin bonding interface is easily compromised, which, in turn, leads to a reduction in bond strength. The hydrophilic nature of the adhesive leads to water sorption, phase separation, and leaching of the resin component. Therefore, hydrophobic adhesives could effectively be used to stabilize the integrity and durability of the resin dentin bonding interface. MethodsWe synthesized a novel hydrophobic dentin adhesive by partially replacing bisphenol A glycidyl dimethacrylate (Bis-GMA) with a light-curable urushiol monomer. The properties of the produced adhesive, including the degree of conversion, viscosity, contact angle, water sorption/solubility, and mechanical strength, were comprehensively examined and compared to those of the commercially adhesive Adper Single Bond2 as a positive control. The adhesive properties were determined using microtensile bond strength measurements, laser confocal microscopy, scanning electron microscopy observations, and nanoleakage tests. Finally, the novel adhesive was subjected to biocompatibility testing to determine its potential cytotoxicity. ResultsAt a light-curable urushiol content of 20 %, the synthesized adhesive exhibited high degrees of conversion and hydrophobicity, low cytotoxicity, good mechanical properties, and outstanding adhesive strength. ConclusionsThe introduction of the light-curable urushiol into dentin adhesives can significantly enhance their hydrophobic, mechanical, and bonding properties, demonstrating potential to significantly improve restoration longevity. Clinical significanceThe integration of light-curable urushiol has endowed the experimental adhesives with several enhanced functionalities. These notable benefits underscore the suitability of this monomer for expanded applications in clinical practice.

Enhanced anti-bacterial adhesion effect of FDMA/SR833s based dental resin composites by using 1H,1H-heptafluorobutyl methacrylate as partial diluent

With the purpose of further reducing surface free energy to achieve better anti-bacterial adhesion effect of fluorinated dimethacrylate (FDMA)/tricyclo (5.2.1.0) decanedimethanol diacrylate (SR833s) based dental resin composites (DS), 1H,1H-heptafluorobutyl methacrylate (FBMA) was used to partially replace SR933s as reactive diluent. According to the degree of substitution, the obtained resin composites were marked as DSF-1 (20 wt.% of SR833s was replaced by FBMA), DSF-2 (40 wt.% of SR833s was replaced by FBMA), and DSF-3 (60 wt.% of SR833s was replaced by FBMA). Bisphenol A glycidyl dimethacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) based resin composite (BT) was used as control. The influence of FBMA concentration on double bond conversion (DC), contact angle, surface free energy, anti-bacterial adhesion effect against Streptococcus mutans (S. mutans), volumetric shrinkage (VS) and shrinkage stress (SS), flexural strength (FS) and modulus (FM), water sorption (WS) and solubility (SL) were investigated. The results showed that FBMA addition could reduce surface free energy from 44.6 mN/m for DS to 32.9 mN/m for DSF-3, and lead to better anti-bacterial adhesion effect (the amounts of adherent bacteria decreased from 2.03 × 105 CFU/mm2 for DS to 6.44 × 104 CFU/mm2 for DSF-3). The FBMA had no negative effects on DC, VS, SS, WS, and SL. Too high a concentration of FBMA reduced FS and FM before water immersion, but the values were still higher than those of BT.

Development of a Boron Nitride-Filled Dental Adhesive System.

There is a dearth of adhesive systems capable of forming stable bonds between restorative materials and tooth surfaces. To address the concern, this study determined the effects of using methacrylate-functionalized boron nitride nanosheets (BNNSs) in a polymeric dental adhesive system. The bisphenol A glycidyl dimethacrylate (BisGMA):2 hydroxyethyl methacrylate (HEMA) (60:40) adhesive monomer blend with a photoinitiator was filled with 0 wt% (control), 0.1 wt%, and 1 wt% BNNSs and light cured. Fourier transform infrared spectroscopy was performed to determine the conversion degree of monomer double bonds (DoC). Water absorption and solubility were measured. Flexural strength and Youngs's modulus were evaluated to determine the mechanical properties of the composite adhesive system. Finally, dentin bond strength degradation and fracture mode were quantified with a microtensile bond test to confirm the bonding ability of the developed adhesive system. Results showed that the incorporation of BNNSs increased DoC (9.8% and 5.4% for 0.1 and 1 wt%, respectively), but it did not affect water sorption (101.9-119.72 (µg/mm3)), solubility (2.62-5.54 (µg/mm3)), Young's modulus (529.1-1716.1 MPa), or microtensile bond strength (46.66-54.72 MPa). Further studies are needed with varying BNNS loading percentages from 0.1 wt% to 1 wt% in order to more comprehensively determine the effect of BNNSs on dental adhesives.

Elution of Monomers From CAD-CAM Materials and Conventional Resin Composite in Distilled Water and Artificial Saliva.

The purpose of this study was to evaluate the leaching pattern of different types of polymer computer-aided design and computer-aided manufacturing (CAD-CAM) materials with a conventional resin composite. Specimens of three representatives by type of polymer CAD-CAM blocks and one conventional resin composite were suspended using a silk thread in distilled water and artificial saliva. After one day, seven days, 14 days, 30 days, and 60 days, the analysis of the eluates for the detection of bisphenol A (BPA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGDMA) and bisphenol A-glycidyl dimethacrylate (Bis-GMA) was quantified by utilizing high-performance liquid chromatography (HPLC). TEGDMA was the main eluted monomer for the polymer CAD-CAM materials for both solutions. However, there was a decreasing pattern throughout the tested period. On the contrary, there was a constant release of monomers from the conventional resin composite. Bisphenol-A was released only by the conventional resin composite and in both solutions chosen. Different types of polymer CAD-CAM materials release minimal or no monomers compared to the conventional resin composite material. The methods of fabrication of polymer CAD-CAM materials produces better properties than the conventional resin composite with a dramatic decrease of monomer elution.

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.

Evaluation of Monomer Elution and Surface Roughness of a Polymer-Infiltrated Ceramic Network CAD–CAM Material After Er,Cr:YSGG Laser-assisted Tooth Bleaching

The aim of this in vitro study was to examine the effect of Er,Cr:YSGG laser-assisted tooth bleaching treatment on the elution of monomers and surface roughness of a hybrid computer-aided design-computer-aided manufacturing (CAD-CAM) material, and to compare it with a resin composite for direct restorations. Forty specimens of a hybrid CAD-CAM material (Enamic) and forty of a conventional resin composite (Tetric) were fabricated and randomly divided into four groups (n=10). Half of the specimens of each material were stored in distilled water and the other half in artificial saliva for 7 days. At the end of this period, the storage medium was analyzed by high-performance liquid chromatography (HPLC), and the surface roughness parameters of the specimens were evaluated by optical imaging noncontact interferometric profilometry. Afterwards, half of the specimens of each tested material received a conventional in-office tooth bleaching treatment and the other half an Er,Cr:YSGG laser-assisted bleaching treatment, and then they were again incubated in distilled water and artificial saliva for an additional 7-day time period. At the end of this period, the effect of the bleaching treatments on elution of monomers and surface roughness of the tested materials was evaluated. Bisphenol A (BPA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGDMA), and bisphenol A-glycidyl dimethacrylate (BisGMA) were eluted from the conventional resin composite into both the solutions tested. Only TEGDMA was eluted from the hybrid CAD-CAM material. However, no statistically significant differences were found among the surface roughness parameters of both materials. Both the conventional and Er,Cr:YSGG laser-assisted tooth bleaching treatments affected the monomer elution from the composite resin. However, there were no statistically significant differences (p<0.05) between the treatments. According to the results of this study, tooth bleaching with Er,Cr:YSGG laser or conventional technique is safe, even if the bleaching agent comes in contact with hybrid CAD-CAM restorations.

Alternative Co-Initiators for Photocurable Biomaterials: Polymerisation, Quantum Yield of Conversion and Cytotoxicity

Cyclic acetals such as 1,3 benzodioxole (BZD), piperonyl alcohol (PA), and N-phenyl glycine (NPG) are naturally occurring compounds capable of acting as co-initiators during free-radical polymerisation, and potentially serve to offer non-allergic and biologically less toxic alternatives to conventional (tertiary) amines. The current study aimed to evaluate the use of cyclic acetals in concentrations of 0.5-6.0 mol % for photopolymerisation of an unfilled model dimethacrylate resin system, bisphenol-A-glycidyldimethacrylate (BisGMA), and triethylene glycol dimethacrylate (tegDMA), 1:1 wt.%) using the photosensitiser camphorquinone (CQ; λmax = 469 nm) in concentrations of 0.5-1.5 mol %. Conventional tertiary amines, namely, ethyl-4-dimethyamino benzoate (EDMAB) (aromatic) and dimethylaminoethyl methacrylate (DMAEMA) (aliphatic) were utilised for comparison purposes. Real-time degree of conversion (DC) was evaluated using Fourier transform near-infrared spectroscopy. To measure the effectiveness of these alternative compounds in facilitating CQ photon absorption, quantum yield of conversion of CQ per absorbed photon was calculated using UV-Vis spectroscopy. Cytotoxicity of NPG and cyclic acetals were assessed using MTT and Calcien AM to determine metabolic activity and cell viability, respectively. The result indicated that cyclic acetals were capable of facilitating free radical polymerisation as co-initiators at all three CQ concentrations (0.5, 1.0 and 1.5 mol %). Further, the use of NPG as a co-initiator resulted in post-irradiation DC values that were comparable to both EDMAB and DMAEMA across all three CQ concentrations. Based on the quantum yield of conversion of CQ, alternative compounds facilitated the hydrogen abstraction process, which provided high conversion of CQ molecules. UV-Vis absorption and quantum yield data revealed that NPG exhibited competitive effects in absorbing blue light photons, which might be attributed to the photolytic degradation of NPG and the formation of N-methylaniline. Indirect treatment of human dental pulp cells (HDPCs) with eluted extracts of NPG, BZD and PA exhibited relatively lower cytotoxicity when compared with HDPCs groups treated with no eluted extracts. The relative cytotoxicity of DMAEMA was comparable to that of PA. However EDMAB, CQ and the neat model resin media extracts resulted in significant cytotoxicity, with highest relative reduction in the number of viable cells observed in groups treated with neat model resin extracts, suggesting that bisGMA and tegDMA monomers played significant role in the overall cytotoxicity of photocurable systems involving HDPCs.

Novel calcium phosphate ion-rechargeable and antibacterial adhesive to inhibit dental caries.

This study aimed to develop an antibacterial and calcium (Ca) and phosphate (P) rechargeable adhesive and investigate the effects of dimethylaminododecyl methacrylate (DMAHDM) and nanoparticles of amorphous calcium phosphate (NACP) on dentin bonding, biofilm response, and repeated Ca and P ion recharge and re-release capability for the first time. Pyromellitic glycerol dimethacrylate (PMGDM), ethoxylated bisphenol A dimethacrylate (EBPADMA), 2-hydroxyethyl methacrylate (HEMA), and bisphenol A glycidyl dimethacrylate (BisGMA) formed the adhesive (PEHB). Three groups were tested: (1) Scotchbond (SBMP, 3M) control, (2) PEHB + 30% NACP, and (3) PEHB + 30% NACP + 5% DMAHDM. Specimens were tested for dentin shear bond strength, and Ca and P ion release, recharge, and re-release. Biofilm lactic acid production and colony-forming units (CFU) on resins were analyzed. The four groups had similar dentin shear bond strengths (p > 0.1). Adhesive with DMAHDM showed significant decrease in metabolic activity, lactic acid production, and biofilm CFU (p < 0.05). The adhesives containing NACP released high levels of Ca and P ions initially and after being recharged. This study developed the first Ca and P ion-rechargeable and antibacterial adhesive, achieving strong antibacterial activity and Ca and P ion recharge and re-release for long-term remineralization. Considering the restoration-tooth bonded interface being the weak link and recurrent caries at the margins being the primary reason for restoration failures, this novel calcium phosphate-rechargeable and antibacterial adhesive is promising for a wide range of tooth-restoration applications to inhibit caries.

Methacrylate peak determination and selection recommendations using ATR-FTIR to investigate polymerisation of dental methacrylate mixtures.

Investigation of polymerisation kinetics using ATR-FTIR systems is common in many dental studies. However, peak selection methods to calculate monomer-polymer conversion can vary, consequently affecting final results. Thus, the aim of this study is to experimentally confirm which method is less prone to systematic errors. Three commercial restorative materials were tested–Vertise Flow (VF), Constic and Activa Bioactive Restorative Kids. Firstly, Attenuated Total Reflectance Fourier Transform Infra-Red (ATR-FTIR) (Spectrum One, Perkin-Elmer, UK) spectra of monomers were acquired—10-methacryloyloxy decyl dihydrogen phosphate (10-MDP), bisphenol-A glycidyl dimethacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), triethyelene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) to investigate proportionality of methacrylate peak heights versus concentration. Spectral changes upon light exposure of 2 mm discs of the restorative materials (irradiated for 20 s, LED curing unit 1100–1330 mW/cm2) were assessed to study polymerisation kinetics (n = 3), with continuous acquisition of spectra, before, during and after light exposure. Peak differences and degrees of conversion (DC %) were calculated using 1320/1336, 1320/1350 and 1636/1648 cm-1 as reaction/reference peaks. Inferential statistics included a MANOVA and within-subjects repeated measures ANOVA design (5% significance level). Proportionality of methacrylate peak height to concentration was confirmed, with the 1320/1352 cm-1 peak combination showing the lowest coefficient of variation (8%). Difference spectra of the polymerisation reaction showed noise interference around the 1500–1800 cm-1 region. Across the different materials, DC % results are highly dependent upon peak selection (p<0.001), with higher variability associated to the 1636 cm-1. Significant differences in the materials were only detected when the 1320 cm-1 peak was used (p<0.05). Within the same materials, methods were significantly different for Constic and Activa (p<0.05). It is possible to conclude that the 1320 cm-1 peak is more adequate to assess polymerisation of methacrylates and is therefore recommended.

Development of a novel resin for provisional prostheses using hyperbranched polyurethane acrylate and triethylene glycol dimethacrylate - An in vitro study.

To develop a novel resin for provisional prostheses using hyperbranched polyurethane acrylate (HBPUA) and triethylene glycol dimethacrylate (TEGDMA) with promising mechanical properties and low volumetric shrinkage. Four groups including TIH3-0 (100 wt% TEGDMA), TIH3-30 (30 wt% HBPUA + 70 wt% TEGDMA), TIH3-60 (60 wt% HBPUA + 40 wt% TEGDMA), and TB-60 (60 wt% bisphenol A-glycidyl dimethacrylate + 40 wt% TEGDMA) were prepared and commercial Luxatemp (DMG) was used for comparison. Fourier transform infrared spectroscopy and gel permeation chromatography were used for material characterization. Mechanical properties including microhardness, flexural strength, flexural modulus, and load energy were measured before and after water immersion. Physical properties measurement included weight changes, solubility, water absorption, surface hydrophobicity, and volumetric shrinkage. Finally, biocompatibility was evaluated using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. The number- and weight-average molecular weights of the HBPUA were approximately 870 and 1480, respectively. The addition of HBPUA to TEGDMA increased the mechanical strength considerably. Although the weight changes and water absorption of TIH3-60 were higher than those of Luxatemp, the microhardness, flexural strength, flexural modulus, load energy, solubility, shrinkage, and biocompatibility of TIH3-60 were either comparable or superior to those of Luxatemp. Based on the findings of the present study, TIH3-60 has potential for development as a new provisional material.

Dental composites - a low-dose source of bisphenol A?

Dental composite materials often contain monomers with bisphenol A (BPA) structure in their molecules, e.g. bisphenol-A glycidyl dimethacrylate (Bis-GMA). In this study, it was examined whether dental restorative composites could be a low-dose source of BPA or alternative bisphenols, which are known to have endocrine-disrupting effects. Bis-GMA-containing composites Charisma Classic (CC) and Filtek Ultimate Universal Restorative (FU) and "BPA-free" Charisma Diamond (CD) and Admira Fusion (AF) were examined. Specimens (diameter 6 mm, height 2 mm, n=5) were light-cured from one side for 20 s and stored at 37 °C in methanol which was periodically changed over 130 days to determine the kinetics of BPA release. BPA concentrations were measured using a dansyl chloride derivatization method with liquid chromatography - tandem mass spectrometry detection. The amounts of BPA were expressed in nanograms per gram of composite (ng/g). BPA release from Bis-GMA-containing CC and FU was significantly higher compared to "BPA-free" CD and AF. The highest 1-day release was detected with FU (15.4+/-0.8 ng/g), followed by CC (9.1+/-1.1 ng/g), AF (2.1+/-1.3 ng/g), and CD (1.6+/-0.8 ng/g), and the release gradually decreased over the examined period. Detected values were several orders of magnitude below the tolerable daily intake (4 microg/kg body weight/day). Alternative bisphenols were not detected. BPA was released even from "BPA-free" composites, although in significantly lower amounts than from Bis-GMA-containing composites. Despite incubation in methanol, detected amounts of BPA were substantially lower than current limits suggesting that dental composites should not pose a health risk if adequately polymerized.

Rutin-protected BisGMA-induced cytotoxicity, genotoxicity, and apoptosis in macrophages through the reduction of the mitochondrial apoptotic pathway and induction of antioxidant enzymes.

Bisphenol-A-glycidyldimethacrylate (BisGMA) is a resin monomer frequently used in dentin restorative treatments. The leakage of BisGMA monomer from BisGMA-based polymeric resins can lead to cytotoxicity in macrophages. Rutin has various beneficial bioeffects, including antioxidation and antiinflammation. In this study, we found that pretreatment of RAW264.7 macrophages with rutin-inhibited cytotoxicity induced by BisGMA in a concentration-dependent manner. BisGMA-induced apoptosis, which was detected by levels of phosphatidylserine from the internal to the external membrane and formation of sub-G1, and genotoxicity, which was detected by cytokinesis-blocked micronucleus and single-cell gel electrophoresis assays, were inhibited by rutin in a concentration-dependent manner. Rutin suppressed the BisGMA-induced activation of caspase-3 and -9 rather than caspase-8. Rutin inhibited the activation of the mitochondrial apoptotic pathway, including cytochrome C release and mitochondria disruption, after macrophages were treated with BisGMA. Finally, BisGMA-induced reactive oxygen species (ROS) generation and antioxidant enzyme (AOE) deactivation could be reversed by rutin. Parallel trends were observed in the elevation of AOE activation and inhibition of ROS generation, caspase-3 activity, mitochondrial apoptotic pathway activation, and genotoxicity. These results suggested that rutin suppressed BisGMA-induced cytotoxicity through genotoxicity, the mitochondrial apoptotic pathway, and relatively upstream factors, including reduction of ROS generation and induction of AOE.

Novel CaF2 Nanocomposites with Antibacterial Function and Fluoride and Calcium Ion Release to Inhibit Oral Biofilm and Protect Teeth.

(1) Background: The objective of this study was to develop a novel dental nanocomposite containing dimethylaminohexadecyl methacrylate (DMAHDM), 2-methacryloyloxyethyl phosphorylcholine (MPC), and nanoparticles of calcium fluoride (nCaF2) for preventing recurrent caries via antibacterial, protein repellent and fluoride releasing capabilities. (2) Methods: Composites were made by adding 3% MPC, 3% DMAHDM and 15% nCaF2 into bisphenol A glycidyl dimethacrylate (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) (denoted BT). Calcium and fluoride ion releases were evaluated. Biofilms of human saliva were assessed. (3) Results: nCaF2+DMAHDM+MPC composite had the lowest biofilm colony forming units (CFU) and the greatest ion release; however, its mechanical properties were lower than commercial control composite (p < 0.05). nCaF2+DMAHDM composite had similarly potent biofilm reduction, with mechanical properties matching commercial control composite (p > 0.05). Fluoride and calcium ion releases from nCaF2+DMAHDM were much more than commercial composite. Biofilm CFU on composite was reduced by 4 logs (n = 9, p < 0.05). Biofilm metabolic activity and lactic acid were also substantially reduced by nCaF2+DMAHDM, compared to commercial control composite (p < 0.05). (4) Conclusions: The novel nanocomposite nCaF2+DMAHDM achieved strong antibacterial and ion release capabilities, without compromising the mechanical properties. This bioactive nanocomposite is promising to reduce biofilm acid production, inhibit recurrent caries, and increase restoration longevity.

The polymerization efficiency of a bulk-fill composite based on matrix-modification technology.

ObjectivesTo evaluate the polymerization efficiency of a matrix-modified bulk-fill composite, and compare it to a conventional composite which has a similar filler system. The degree of conversion (DC%) and monomer elution were measured over different storage periods. Additionally, fillers' content was examined.Materials and MethodsCylindrical specimens were prepared, in bulk and incrementally, from Filtek Bulk Fill (B) and Filtek Supreme XTE (S) composites using a Teflon mold, for each test (n = 6). Using attenuated total reflection method of Fourier transformation infrared spectroscopy, DC% was measured after 24 hours, 7 days, and 30 days. Using high-performance liquid chromatography, elution of hydroxyethyl methacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, and bisphenol-A glycidyl dimethacrylate was measured after 24 hours, 7 days and 30 days. Filler content was examined by scanning electron microscopy (SEM). Data were analyzed using 2-way mixed-model analysis of variance (α = 0.05).ResultsThere was no significant difference in DC% over different storage periods between B-bulk and S-incremental. Higher monomer elution was detected significantly from S than B. The elution quantity and rate varied significantly over storage periods and between different monomers. SEM images showed differences in fillers' sizes and agglomeration between both materials.ConclusionsMatrix-modified bulk-fill composites could be packed and cured in bulk with polymerization efficiency similar to conventional composites.

Novel rechargeable nano-CaF2 orthodontic cement with high levels of long-term fluoride release

ObjectivesFluoride-containing orthodontic cements are used to combat white spot lesions (WSLs) in enamel. However, the fluoride (F) ion releases from these cements are relatively low and short-term. The objectives of this study were to develop a novel rechargeable orthodontic cement with nanoparticles of calcium fluoride (nCaF2) to provide long-term and high levels of F release, and to investigate F recharge and physical and cytotoxic properties. MethodsThe nCaF2 with a mean particle size of 58 nm were synthesized using a spray-drying method. Pyromellitic glycerol dimethacrylate (PMGDM), ethoxylated bisphenol A dimethacrylate (EBPADMA), 2-hydroxyethyl methacrylate (HEMA) and bisphenol A glycidyl dimethacrylate (BisGMA) were used to prepare the cements (denoted PE and PEHB resins). A resin-modified glass ionomer (RMGI) served as control. Enamel shear bond strength (SBS), cytotoxicity, and F ion recharge and re-release were evaluated. ResultsnCaF2 cements had good SBS and excellent biocompatibility that were comparable to RMGI (p > 0.1). After a recharge for 1 min, the F re-release from PEHB + 30%nCaF2 cement was 80% higher than RMGI (p < 0.05). Increasing nCaF2 content from 20% to 30% greatly increased the F ion re-release (p < 0.05). The F ion re-release of nCaF2 cements did not decrease with increasing the number of recharge and re-release cycles (p > 0.1). ConclusionsA novel F ion-rechargeable orthodontic cement containing nCaF2 was developed with clinically acceptable enamel SBS, good biocompatibility, and sustained F ion recharge and re-release that were 1.8 folds that of a commercial RMGI. Clinical SignificanceNovel rechargeable nCaF2 orthodontic cement is promising to provide the needed long-term and high levels of F ion releases to inhibit WSLs in orthodontics.

Evaluation of monomers derived from resorcinol as eluents of bisphenol A glycidyl dimethacrylate for the formulation of dental composite resins

ABSTRACTThe objective of this work was to synthesize two bio‐based monomers, using the resorcinol as raw material, and its effect as bisphenol A glycidyl dimethacrylate (Bis‐GMA) eluents on different chemical–physical and biological properties of experimental photopolymerizable composite resins. The acrylic 1,3‐phenylen diacrylic (1,3‐FDA) and methacrylic 1,3‐phenylen dimethacrylic (1,3‐FDMA) monomers were synthesized and fully characterized through FTIR and 1H‐NMR spectroscopies. Experimental photopolimerizable composites were formulated using Bis‐GMA/1,3‐FDA or Bis‐GMA/1,3‐FDMA as organic matrix. The materials were compared with a Bis‐GMA/TEGDMA resin‐based composite used as control. Polymerization kinetics was evaluated by means of FTIR spectroscopy. Polymerization stress was directly measured through a polymerization stress tester. The cell viability of the composites was evaluated using the MTT assay. One‐way analysis of variance and Tukey's test were used for statistical analysis. The materials formulated with the 1,3‐FDA monomer showed higher Rpmax values and lower polymerization stress values (p &lt; 0.05), while the flexural strength, water sorption, and solubility remained similar to the TEGDMA composite. Conversely, the materials formulated with the 1,3‐FDMA monomer showed a lower degree of conversion and statistically lower flexural strength (p &lt; 0.05). All materials exhibited a cellular viability close to 100%. Concerning the study conditions, the acrylic 1,3‐FDA monomer could be considered an alternative to TEGDMA in the formulation of photopolymerizable dental composite resins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48576.

Influence of N-(2-hydroxyethyl)acrylamide addition in light- and dual-cured resin cements

ObjectiveTo develop experimental light-cured (L) and dual-cured (D) resin cements containing N-(2-hydroxyethyl)acrylamide and evaluate the physicochemical and optical properties. MethodsExperimental resin cements were formulated using bisphenol A-glycidyl dimethacrylate (70%) and 2-hydroxyethyl methacrylate (30%), in the control groups, and, bisphenol A-glycidyl dimethacrylate (70%) and N-(2-hydroxyethyl)acrylamide (30%). Polymerization kinetics were evaluated by differential scanning calorimetry (n = 3), softening in solvent (ΔKHN) evaluated by the difference of Knoop microhardness before (KHN1) and after (KHN2) ethanol solution immersion (n = 5), radiopacity in mmAl (n = 5), film thickness (n = 3) and color stability were evaluated. Mechanical properties as ultimate tensile strength (UTS) and micro-shear bond strength (μSBS) were analyzed immediately and after 6 months. Results were analyzed using ANOVA, Tukey’s test and Student’s t-test (α = 0.050). ResultsThe LHEAA1 group had no statistical difference from the control group regarding polymerization kinetics, KHN1, ΔKHN and color stability (p > 0.050). In dual-cured cements, the acrylamide groups presented a lower degree of conversion and higher ΔKHN than the DHEMA0.6 group, which obtained a higher rate of polymerization (p < 0.050). There was no statistical difference in radiopacity and film thickness (p > 0.050). Dual-cured cements with N-(2-hydroxyethyl)acrylamide showed higher color change than methacrylates. Immediate mechanical properties were lower for acrylamide groups (p < 0.050), with higher hydrolytic stability. ConclusionsThe addition of N-(2-hydroxyethyl)acrylamide negatively affected the properties of the dual-cured resin cements. LHEAA1 did not differ in physicochemical and optical properties from the control, with higher hydrolytic stability. Clinical significanceThe results of the study indicate that acrylamides increased mechanical properties over time independently of the curing system mode, with more hydrolytic stability. The clinical performance of experimental resin cements should be evaluated.

Short-term and long-term release of monomers from newly developed resin-modified ceramics and composite resin CAD-CAM blocks

Statement of problemMonomer leaching from restorations may affect the oral mucosa and general health; however, information on monomer leaching from chairside computer-aided design and computer-aided manufacturing (CAD-CAM) restorative materials is lacking. PurposeThe purpose of this in vitro study was to investigate the leaching of monomers from newly introduced resin-modified ceramics and composite resin CAD-CAM blocks that were immersed in water and ethanol for short-term and long-term incubation periods. Material and methodsTen square-shaped specimens of 5 newly introduced CAD-CAM blocks were suspended by means of a silk thread in distilled water and in 75% ethanol. After 1 day, 7 days, 30 days, and 60 days, the eluates bisphenol A (BPA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGDMA), N, N-dimethylacrylamide (DMA), bisphenol A-glycidyl dimethacrylate (Bis-GMA), and bisphenol A ethoxylate dimethacrylate (Bis-EMA) were analyzed by means of high-performance liquid chromatography (HPLC). Additional specimens of each material, before and after immersion in the solutions, were investigated by scanning electron microscopy, and elemental analysis was performed by energy-dispersive X-ray spectrometry. ResultsTEGDMA and UDMA were the main monomers eluted from all the materials tested. A pattern of declining release was detected for all the monomers. Bisphenol-A was not released by any of the investigated ceramic-composite or composite resin blocks either in water or ethanol. ConclusionsCAD-CAM blocks release less monomer when they are immersed in aqueous solutions in the short-term and long-term periods than conventional resin composite materials. The amount of monomer release declined until no monomer could be detected.

In vitro remineralization of artificial enamel caries with resin composites containing calcium phosphate particles.

The aim of the study was to evaluate the effect of experimental composites containing dicalcium phosphate dihydrate (DCPD) on remineralization of enamel lesions. Five resin-based composites containing equal parts (in mols) of bisphenol-A glycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), and 60 vol % of fillers were manipulated. Filler phase was constituted by silanized barium glass and 0, 10, or 20 vol % of DPCD particles, either functionalized (F) or nonfunctionalized (NF) with TEGDMA. Artificial subsurface lesions were produced in human enamel fragments and divided according to the resin composite applied on the lesion (no DCPD, 20% NF, 20% F, 10% NF, 10% F) plus a group without composite build-up (nontreated, NT). Fragments were exposed to 16 days of pH cycling. Specimens were evaluated using transverse microradiography (TMR). Calcium and phosphate concentrations in pH-cycling solutions were determined by spectrophotometry. TMR and ionic concentrations were analyzed using one-way ANOVA/Tukey and Kruskal-Wallis/Dunn test, respectively (alpha: 0.05). All composite groups showed enamel remineralization (3%-23%). Higher mineral recovery in the middle (7%-11%) and bottom (2%-7%) thirds of the lesion was observed in groups with DCPD-containing composites compared to the "no DCPD" group (middle: 1%, bottom: -3%). Lesion depth was significantly reduced in groups using DCPD-containing composites compared to NT group. No noticeable increase in calcium and phosphate ions was observed in the pH-cycling solutions due to the presence of DCPD in the composites. In conclusion, composites with DCPD fractions as low as 10%, regardless of functionalization, were able to promote mineral recovery and reduce lesion depth of enamel lesions. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1542-1550, 2019.

Synthesis, characterization and evaluation of a fluorinated resin monomer with low water sorption

A fluorinated acrylate monomer (4-TF-PQEA) without BPA (bisphenol-A) structure was synthesized and mixed with triethylene glycol dimethacrylate (TEGDMA) to used as dental resin system in order to achieve lower water sorption and reduce human exposure to BPA derivatives. Double bond conversion (DC) was measured using Fourier transform infrared spectroscopy (FTIR). Water sorption (WS), water solution (WL) and depth of cure (DOC) were evaluated according to ISO 4049:2009. Water contact angle (CA) was measured using contact angle analyzer. Polymerization shrinkage (PS) was evaluated according to the Archimedes' principle and ISO 17304:2013. Flexural strength (FS) and flexural modulus (FM) were measured by three-point bending test with a universal testing machine according to ISO 4049:2009. Comprehensive strength (CS) and vickers microhardness (VM) were also investigated. Thermal stability test was measure by Thermogravimetric analyzer. Cytotoxicity of three resin systems was tested through MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromid) cytotoxicity method according to the ISO 10993-5:2009. Bisphenol-A glycidyl dimethacrylate (Bis-GMA)/ TEGDMA resin system was used as a control. The results show that 4-TF-PQEA/TEGDMA resin system had lower PS, lower WS and higher DC values than those of Bis-GMA/TEGDMA resin system except some mechanical properties, such as FS, FM and CS. Moreover, properties of other 4-TF-PQEA-containing resin systems were also comparable with those of Bis-GMA/TEGDMA resin system. In particular, the overall performance of resin system consisted of 4-TF-PQEA/Bis-GMA/TEGDMA is optimized when the mixture ratio is 30/40/30(wt/wt/wt). Therefore, the 4-TF-PQEA has potential to be used as resin monomer for dental resin composites to achieve lower water sorption.