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Objective: Bisphenol A glycidyl methacrylate (Bis-GMA) is of great importance for dental materials as the preferred monomer. However, the presence of bisphenol-A (BPA) core in Bis-GMA structure causes potential concerns since it is associated with endocrine diseases, developmental abnormalities, and cancer lesions. Therefore, it is desirable to develop an alternative replacement for Bis-GMA and explore the intrinsic relationship between monomer structure and resin properties., Methods: Here, the betulin maleic diester derivative (MABet) was synthesized by a facile esterification reaction using plant-derived betulin and maleic anhydride as raw materials. Its chemical structure was confirmed by 1 H and 13 C NMR spectra, FT-IR spectra, and HR-MS, respectively. The as-synthesized MABet was then used as polymerizable comonomer to partially or completely substitute Bis-GMA in a 50:50 Bis-GMA: TEGDMA resin (5B5T) to formulate dental restorative resins. These were then determined for the viscosity behavior, light transmittance, real-time degree of conversion, residual monomers, mechanical performance, cytotoxicity, and antibacterial activity against Streptococcus mutans (S. mutans) in detail., Results: Among all experimental resins, increasing the MABet concentration to 50 wt% made the resultant 5MABet5T resin have a maximum in viscosity and appear dark yellowish after polymerization. In contrast, the 1MABet4B5T resin with 10 wt% MABet possessed comparable shear viscosity and polymerization conversion (46.6 ± 1.0% in 60 s), higher flexural and compressive strength (89.7 ± 7.8 MPa; 345.5 ± 14.4 MPa) to those of the 5B5T control (48.5 ± 0.6%; 65.7 ± 6.7 MPa; 223.8 ± 57.1 MPa). This optimal resin also had significantly lower S. mutans colony counts (0.35 ×10 8 CFU/mL) than 5B5T (7.6 ×10 8 CFU/mL) without affecting cytocompatibility., Significance: Introducing plant-derived polymerizable MABet monomer into dental restorative resins is an effective strategy for producing antibacterial dental materials with superior physicochemical property., Competing Interests: Declaration of Competing Interest We hereby confirm that all of the authors have read this manuscript, and no related work is in the press with any other journal. There are no known potential conflicts of interest with this work., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The current study focuses on the fabrication of calcium hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ) (HA) in a nanorange having whiskers- and cubic-shaped uniform particle morphology. The synthesized HA particles hold a promising feature as reinforcement fillers in dental acrylic resin composite. They increase the efficacy of reinforcement by length and aspect ratio, uniformity, and monodispersity. Therefore, the acrylic resin was reinforced with the as-synthesized monodispersed HA filler particles (0.2-1 Wt%). The presence of filler particles in the composite had a noticeable effect on the tribological and mechanical properties of the dental material. The morphological effect of HA particles on these properties was also investigated, revealing that cubic-shaped particles showed better results than whiskers. The as-fabricated composite (0.4 Wt%) of the cubic-shaped filler particles showed maximum hardness and improved antiwear/antifriction properties. Particle loading played its part in determining the optimum condition, whereas particle size also influenced the reinforcement efficiency. The current study revealed that particle morphology, particle size, uniformity, etc., of HA fillers, greatly influenced the tribological and mechanical properties of the acrylic resin-based nanocomposite. Improvement in the tribological properties of HA particle-reinforced acrylic resin composites (HA-acrylic resin) followed the trend as AR < C m C < WC < CC., (© 2021. The Author(s).)

Six novel urethane-dimethacrylate analogues (QAUDMAs) were synthesized and characterized. They consisted of the 2,4,4,-trimethylhexamethylene diisocyanate (TMDI) core and two methacrylate-terminated wings containing quaternary ammonium groups substituted with alkyl chains of 8, 10, 12, 14, 16, or 18 carbon atoms. QAUDMAs, due to the presence of quaternary ammonium groups, may have possible antibacterial effects. Since they showed satisfactory physicochemical properties, they will be subjected to further research towards the development of dental composites with a capacity to reduce secondary caries. The synthesis of QAUDMAs included three stages: (i) transesterification of methyl methacrylate (MMA) with N -methyldiethanolamine (MDEA), (ii) N -alkylation of the tertiary amino group with alkyl bromide, and (iii) addition of TMDI to the intermediate achieved in the second stage. The formation of QAUDMAs was confirmed by 1 H and 13 C NMR. They were characterized for density ( d m ), viscosity ( η ), refractive index ( RI ), glass transition temperature ( T g ), polymerization shrinkage ( S ), and degree of conversion ( DC ). QAUDMAs were yellow, viscous resins (the η values ranged from 1.28 × 10 3 to 1.39 × 10 4 Pa·s, at 50 °C). Their RI ranged from 1.50 to 1.52, T g from -31 to -15 °C, DC from 53 to 78%, and S from 1.24 to 2.99%, which is appropriate for dental applications.

In response to the demand for high-performance materials, epoxy thermosetting and its composites are widely used in various industries. However, their poor toughness, resulting from the high crosslinking density of the epoxy network, must be improved to expand their application to the manufacturing of flexible products. In this study, ductile epoxy thermosetting was produced using thiol compounds with functionalities of 2 and 3 as curing agents. The mechanical properties of the epoxy were further enhanced by incorporating fumed silica into it. To increase the filler dispersion, epoxide-terminated polydimethylsiloxane was synthesized and used as a composite component. Thanks to the polysiloxane-silica interaction, the nanosilica was uniformly dispersed in the epoxy composites, and their mechanical properties improved with increasing fumed silica content up to 5 phr (parts per hundred parts of epoxy resin). The toughness and impact strength of the composite containing 5 phr nanosilica were 5.17 (±0.13) MJ/m 3 and 69.8 (±1.3) KJ/m 2 , respectively.

In the frame of developing sustainable, eco-friendly and high performance materials, microcrystalline cellulose modified through silane coupling agent (MCC Si) is used as a reinforcing agent of benzoxazine resin to manufacture composites at different loadings of 5, 10, 15, 20 wt%. The structural, morphological and crystallinity characterizations of the modified MCC were initially performed to scrutinize the changes and confirm the modification. Then, an investigation on the crosslinking process of the prepared composites was held through curing kinetic study employing isoconversional methods. The kinetic data revealed a decrease in the average values of activation energy and the pre-exponential factor, particularly for composite supplemented with 10% MCC Si, whereas all samples disclosed a tendency of an autocatalytic curing mechanism. Furthermore, the study of the dynamic mechanical properties and degradation features of the cured specimens, respectively, indicated a superior stiffness attributable to the good interaction between BA-a and MCC Si, and enhanced thermal stability for the composites compared to pristine resin., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Rigid polyurethane (PUR) foams reinforced with 1, 2, and 5 wt.% of salvia filler (SO filler) and montmorillonite-modified salvia filler (MMT-modified SO filler) were produced in the following study. The impact of 1, 2, and 5 wt.% of SO filler and MMT-modified SO filler on the morphological, chemical, and mechanical properties of PUR composites were examined. In both cases, the addition of 1 and 2 wt.% of SO fillers resulted in the synthesis of PUR composites with improved physicomechanical properties, while the addition of 5 wt.% of SO fillers resulted in the formation of PUR composites with a less uniform structure and, therefore, some deterioration in their physicomechanical performances. Moreover, the results showed that the modification of SO filler with MMT improved the interphase compatibility between filler surface and PUR matrix. Therefore, such reinforced PUR composites were characterized by a well-developed closed-cell structure and improved mechanical, thermal, and flame-retardant performances. For example, when compared with reference foam, the addition of 2 wt.% of MMT-modified SO filler resulted in the formation of PUR composites with greater mechanical properties (compressive strength, flexural strength) and improved dynamic-mechanical properties (storage modulus). The PUR composites were characterized by better thermal stability as well as improved flame retardancy-e.g., decreased peak rate of heat release (pHRR), reduced total smoke release (TSR), and increased limiting oxygen index (LOI).

Despite all the advances in adhesive dentistry, dental bonds are still fragile due to degradation events that start during application of adhesive agents and the inherent hydrolysis of resin-dentin bonds. Here, we combined two outstanding processing methods (electrospinning and cryomilling) to obtain bioactive (antimicrobial and anti-metalloproteinase) fiber-based fillers containing a potent matrix metalloproteinase (MMP) inhibitor (doxycycline, DOX). Poly(ε)caprolactone solutions containing different DOX amounts (0, 5, 25, and 50 wt%) were processed via electrospinning, resulting in non-toxic submicron fibers with antimicrobial activity against Streptococcus mutans and Lactobacillus. The fibers were embedded in a resin blend, light-cured, and cryomilled for the preparation of fiber-containing fillers, which were investigated with antibacterial and in situ gelatin zymography analyzes. The fillers containing 0, 25, and 50 wt% DOX-releasing fibers were added to aliquots of a two-step, etch-and-rinse dental adhesive system. Mechanical strength, hardness, degree of conversion (DC), water sorption and solubility, bond strength to dentin, and nanoleakage analyses were performed to characterize the physico-mechanical, biological, and bonding properties of the modified adhesives. Statistical analyses (ANOVA; Kruskal-Wallis) were used when appropriate to analyze the data (α = 0.05). DOX-releasing fibers were successfully obtained, showing proper morphological architecture, cytocompatibility, drug release ability, slow degradation profile, and antibacterial activity. Reduced metalloproteinases (MMP-2 and MMP-9) activity was observed only for the DOX-containing fillers, which have also demonstrated antibacterial properties against tested bacteria. Adhesive resins modified with DOX-containing fillers demonstrated greater DC and similar mechanical properties as compared to the fiber-free adhesive (unfilled control). Concerning bonding performance to dentin, the experimental adhesives showed similar immediate bond strengths to the control. After 12 months of water storage, the fiber-modified adhesives (except the group consisting of 50 wt% DOX-loaded fillers) demonstrated stable bonds to dentin. Nanoleakage was similar among all groups investigated. DOX-releasing fibers showed promising application in developing novel dentin adhesives with potential therapeutic properties and MMP inhibition ability; antibacterial activity against relevant oral pathogens, without jeopardizing the physico-mechanical characteristics; and bonding performance of the adhesive.

A simple and efficient separation method of carrier-free 47 Sc from neutron irradiated titanium target using a novel chitosan-acrylic acid/multiwalled carbon nanotubes (CS-AA/MWCNTs) composite was established. The synthesis of the CS-AA/MWCNTs composite was achieved using gamma radiation-induced template polymerization. The grafting efficiency (GE%) of AA on CS onto the surface of f-MWCNTs reached a maximum of~84% under the optimized conditions (30 wt% CS, 1.0 wt% AA, 0.15 wt% f-MWCNTs, >0.2 wt% N,N'-Methylenebisacrylamide (NMBA), and irradiation dose ~25 kGy). Different analyses (FT-IR, SEM, TGA and DTA) were examined for confirming the structural morphology and mechanical properties of the new synthesized composite. Interestingly, the CS-AA/MWCNTs composite depicted a selective adsorption of Sc(III) rather than Ti(IV) ions at pH 5 with adsorption efficiency of ~93.93%. The ionic exchange separation of no-carrier-added (NCA) 47 Sc(III) from irradiated TiO 2 target on CS-AA/MWCNTs composite packed column efficiently eluted 47 Sc(III) by 91 ± 0.8% using 1 M HCl solution. The quality control tests (radionuclidic, radiochemical, and chemical purities) for the eluted 47 Sc(III) clarified its high purity and validity for cancer theranostics., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Fiber-reinforced composite (FRC) retainers are an aesthetic alternative to conventional Stainless Steel splints. They are generally used with a full bonded technique, but some studies demonstrated that they could be managed with a spot bonding technique to significantly decrease their rigidity. In order to propose this FRC spot bonding technique for clinical use, the aim of this study was to evaluate mechanical properties and surface wear of fibers left uncovered. Tests were made by simulating tooth brushing, comparing FRC spot bonding technique splints with stainless steel and FRC traditional technique splints. Specimens were tested both at 0.1 mm of deflection and at maximum load, showing higher values of rigidity for the FRC full bonded technique. After tooth brushing, no significant reduction in values at 0.1 mm deflection was reported, while we found a similar reduction in these values for the Stainless Steel and FRC spot bonding technique at maximum load, and no significant variation for the FRC full bonded technique. SEM images after tooth brushing showed wear for FRC fibers left uncovered, while no relevant wear signs in metal and conventional FRC fibers were noticed. Results showed that FRC spot bonding technique has advantages in mechanical properties when compared to the FRC traditional full bonding technique, also after tooth brushing. However, the surface wear after tooth brushing in the FRC spot bonding technique is considerable and other tests must be performed before promoting this technique for routine clinical use.

The biofilm accumulation over the composite resin restorations can contribute to the formation of secondary caries. In this way, antibacterial restorative composite resins are highly desired. Then, the purpose of this study was to modify a composite resins using Ag doped ZnO nanoparticles (NPs), evaluate the antibacterial and mechanical properties of the modified composite resin. The ZnO/AgNPs were synthesized by two different routes, polymeric precursor and coprecipitation methods, and characterized by thermal decomposition, X-ray diffraction, specific surface area by N 2 desorption/desorption and scanning electron microscopy (SEM). Antibacterial activity of composite resin specimens (4 mm in height and 2 mm in diameter; n = 15) modified by ZnO/Ag nanoparticles was performed against 7-days Streptococcus mutans biofilm. Colony forming units (CFU/mL) were used to evaluate the bacterial activity. Additionally, the morphology and the bacteria adherence area were analyzed by SEM images. Cylindrical specimens (6 mm in height and 4 mm in diameter; n = 20) of the composite resin containing ZnO/Ag NPs were prepared to perform compressive strength in a universal mechanical test machine, and the surface of fractured specimens was analyzed by EDX element mapping to verify NPs homogeneity. The normal distribution was confirmed and the two-way analysis of variance (ANOVA) and Tukey's test for pair comparison were performed. The nanospheres of ZnO/Ag lead to a better biofilm inhibition, than nanoplates. No difference on compressive strength was found for the composite resin modified by ZnO/Ag nanoplates. Based on these results, this material could be a good option as a new restorative material., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Objectives: To evaluate the antibacterial activity, bacterial viability, cytotoxicity, and mechanical/physical properties of a novel methacrylate triclosan-derivative monomer (TM) incorporated in dental resin composite., Methods: TM was synthesized by esterification and, after characterization by FT-IR, was added to an experimental composite. Samples were divided into two groups according to TM presence, i.e., C1 (control) and C2 (C1 + 14.4% TM). Microbiological properties: Specimens (C1 and C2) were prepared and placed on bacterial suspensions of Streptococcus mutans. Antibacterial activity, MTT, and live/dead bacterial viability were used to test the resin composites. All assays were performed in triplicates. Mechanical properties: Specimens underwent compression (CS) and flexural strength (FS) tests conducted in an Instron universal testing machine at a crosshead speed of 0.5 mm/min. Physical properties: Specimens were assessed for Knoop hardness (KHN) and crosslink density (CD). Fourier transform infrared spectroscopy allowed the degree of conversion (DC) to be evaluated. Data were subjected to appropriate statistical tests according to data distribution and assay (p < 0.05)., Results: Microbiological properties: C2 showed the lowest biofilm accumulation and the highest membrane-compromised bacteria in the biofilm. Mechanical/physical properties: For CS, FS, KHN, and DC, there was no significant difference between groups C1 and C2; however, significant difference was observed for the CD assay., Conclusions: The triclosan methacrylate reduces bacterial adhesion of S. mutans and decreased the formation of bacterial biofilm without affecting important polymer properties. The triclosan methacrylate incorporated in resin composite could greatly reduce the live bacterial adhesion of S. mutans and decrease the formation of bacterial biofilm without affecting important polymer properties., Clinical Significance: The resin composites containing triclosan methacrylate could greatly reduce the bacterial adhesion and biofilm formation. That might prevent the secondary caries round the margins of the restorations.

Objective: The aim of this study is to explore the reinforcing effect and the antimicrobial activity of the core-mesoporous shell structured ZnO@m-SiO 2 , which possesses the micromechanical resin matrix/filler interlocking in dental composites, and to investigate the effect of filler compositions on their physical-mechanical properties., Methods: ZnO@m-SiO 2 was synthesized by a simple self-assembly method and then characterized by electron microscopy, X-ray diffraction (XRD) and N 2 adsorption/desorption measurements. Mechanical properties of dental composites reinforced with ZnO@m-SiO 2 and nonporous SiO 2 particles were measured with a universal mechanical testing machine. Fracture morphologies of these composites were observed by field-emission scanning electron microscopy (FE-SEM), and their antimicrobial activities were evaluated according to the ASTM E 2180-07 (2012) method. Resin composites containing unimodal silanized SiO 2 were served as the control group., Results: The impregnation of lower loading of ZnO@m-SiO 2 (≤7wt%) into dental composites including silanized SiO 2 substantially increased their mechanical properties. Among all composites, the optimal composite Z 7 S 63 (ZnO@m-SiO 2 : silanized SiO 2 =7:63, wt/wt, total filler loading 70wt%) demonstrated the best flexural strength, flexural modulus and compression strength, which were increased by 121.2, 67.1 and 32.5%, respectively, in comparison with the control composite Z 0 S 70 . In addition, this optimal composite also exhibited superior antimicrobial activity (>99.9%) and acceptable degree of conversion, polymerization shrinkage and curing depth., Significance: The incorporation of ZnO@m-SiO 2 and silanized SiO 2 as bimodal fillers led to the design and formulation of dental composites with excellent comprehensive performance, especially the improved mechanical properties and the superior antimicrobial activity., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Objective: There has been no report on the effect of incorporating protein repellent 2-methacryloyloxyethyl phosphorylcholine (MPC) into a composite containing nanoparticles of amorphous calcium phosphate (NACP) on calcium (Ca) and phosphate (P) ion rechargeability. The objectives of this study were to develop a Ca and P ion-rechargeable and protein-repellent composite for the first time, and investigate the effects of MPC and NACP on mechanical properties, protein-repellency, anti-biofilm effects, and Ca and P ion recharge and re-release., Methods: NACP were synthesized using a spray-drying technique. The resin contained ethoxylated bisphenol A dimethacrylate (EBPADMA) and pyromellitic glycerol dimethacrylate (PMGDM). Three NACP composites were made with 0 (control), 1.5%, and 3% of MPC. NACP (20%) and glass particles (50%) were also added into the resin. Protein adsorption was measured using a micro-bicinchoninic acid (BCA) method. A human saliva microcosm biofilm model was used to determine biofilm metabolic activity, lactic acid, and colony-forming units (CFU). Ca and P ion recharge and re-release were measured using a spectrophotometric method., Results: Flexural strengths and moduli of CaP-rechargeable composites matched those of a commercial composite without CaP rechargeability (p>0.1). Adding 1.5% and 3% MPC reduced protein adsorption to 1/3 and 1/5, respectively, that of commercial composite (p<0.05). Adding 3% MPC suppressed biofilm metabolic activity and lactic acid production, and reduced biofilm CFU by nearly 2 logs. All three NACP composites had excellent ion rechargeability and higher levels of ion re-releases. One recharge yielded continuous ion release for 21 days. The release was maintained at the same level with increasing number of recharge cycles, indicating long-term ion release. Incorporation of MPC did not compromise the CaP ion rechargeability., Significance: Incorporating 3% MPC into NACP nanocomposite greatly reduced protein adsorption, biofilm growth and lactic acid, decreasing biofilm CFU by nearly 2 logs, without compromising Ca and P recharge. This protein-repellent NACP-MPC rechargeable composite with long-term remineralization is promising for tooth restorations to inhibit secondary caries., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

The aim of this laboratory study was to evaluate the monomer leaching and degree of conversion (DC) from experimental bioactive resin composites (RBCs) and to do comparison with commercial bulkfill and packable resin composites. Experimental dimethacrylatebased resin composites were reinforced with silanated nano-hydroxyapatite (30 and 45 wt%). The ion leaching and DC of these resin composites were compared and contrasted with SDR™ and Filtek P60™ by using the high performance liquid chromatography (HPLC) and Fourier transform infrared spectroscopy (FTIR), respectively. A significant difference was found in elution of monomer between the resin composites. SDR™ showed significantly high monomer elution and structural changes compared to other resin composites. The DC of bioactive RBCs showed the highest conversion rate after polymerization. Resin composite with nano-hydroxyapatite with the presence of a bioactive component might provide biomimetic approach for the material. Moreover, a low concentration of nanohydroxyapatite nano-fillers have shown better properties than micro-fillers based resin composites.

Objective: Synthesize a new BPA-free monomer for use in methacrylate-based materials and evaluate critical properties of resin and composite materials based on the monomer., Methods: Bis-EFMA was synthesized through reaction between 9,9-bis[4-(2-hydroxyethoxy)-phenyl]fluorene and 2-(methacryloyloxy)ethyl isocyanate. Experimental Bis-EFMA-based resin (Bis-EFMA/TEGDMA=50/50, wt./wt.) and composite were prepared. Critical properties were investigated according to standard or referenced methods Bis-GMA/TEGDMA (50/50, wt./wt.) resin system, Bis-GMA-based composite and 3M ESPE Filtek™ Z250 were used as controls., Results: FT-IR and 1 H NMR spectra confirmed the structure of Bis-EFMA monomer. Cured resin materials: Bis-EFMA-based and Bis-GMA-based resins had nearly the same degree of conversion (p>0.05); Bis-EFMA-based resin had significantly lower shrinkage, water sorption and solubility, and cytotoxicity than Bis-GMA-based resin (p<0.05); flexural properties of Bis-EFMA-based resin were all higher than those of Bis-GMA-based resin (p<0.05). Cured composite materials: There was no significant difference in conversion (p>0.05); Bis-EFMA-based composite had significantly lower shrinkage and solubility (p<0.05); water sorption of Bis-EFMA-based composite and Z250 were similar (p>0.05), but lower compared to Bis-GMA-based composite (p<0.05); Bis-EFMA-based composite had the deepest curing depth (p<0.05); Before water immersion, there was no significant difference in flexural strength between Bis-EFMA-based composite and each control composite (p>0.05), while FS became lower than that of Z250 (p<0.05), but higher than that of Bis-GMA-based composite (p<0.05) after water immersion; Flexural modulus of Bis-EFMA-based composite and Z250 were nearly the same (p>0.05), higher than that of Bis-GMA-based composite (p<0.05); Bis-EFMA-based composite showed less cytotoxicity than Bis-GMA-based composite and Z250 (p<0.05)., Significance: Bis-EFMA has potential as a substitute for Bis-GMA to prepare Bis-GMA-free dental composites., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Current commercially available dental composite materials have certain limitations for their use, including high monomer viscosity and high polymerization shrinkage, resulting in residual stresses and interfacial gaps. This study focused on the chemical modification of resin monomer bisphenol A-glycidyl methacrylate (bisGMA), so as to reduce the viscosity and polymerization shrinkage. In this design, the hydroxyl groups of bisGMA were transformed into ester groups with various alkyl chain length and branching. The modified monomers showed promising properties including reduced viscosity, reduced polymerization shrinkage, increased hydrophobicity, increased degree of double bond conversion, and improved mechanical properties of the resulting dental resin composites. The structure/property relationships of the new monomers were investigated, and optimal monomer structures were identified for dental composites with improved properties., (Copyright © 2018. Published by Elsevier B.V.)

Several new urethane-based dimethacrylates were synthesized, characterized and used to formulate the resin composites. Compressive strength (CS) was used as a screen tool to evaluate the mechanical property of the formed composites. Flexural strength, diametral tensile strength, water sorption, degree of conversion and shrinkage of the composites were also evaluated. The results show that most of the synthesized urethane-based dimethacrylates were solid, which are not suitable to dental filling restorations. However, it was found that liquid urethane-based dimethacrylates could be derivatized using asymmetrical methacrylate synthesis. Not only the newly synthesized urethane-based dimethacrylates showed lower viscosity values but also their constructed composites exhibited higher mechanical strengths. Without triethyleneglycol dimethacrylate (TEGDMA) addition, the new urethane-constructed composites showed significantly lower water sorption and shrinkage.

Objectives: This study describes the synthesis of brushite nanoparticles (CaHPO 4 ·2H 2 O) functionalized with triethylene glycol dimethacrylate (TEGDMA) and their application in dental restorative composites with remineralizing capabilities., Methods: Nanoparticles were synthesized, with TEGDMA being added to one of the precursor solutions at three different molar ratios (0:1, 0.5:1 and 1:1, in relation to the ammonium phosphate precursor). Then, they were added (10 vol%) to a photocurable dimethacrylate matrix containing 50 vol% of reinforcing glass particles. The resulting composites were tested for degree of conversion, biaxial flexural strength and elastic modulus (after 24h and 28days in water), and ion release (over a 28-day period). Commercial composites (one microhybrid and one microfilled) were tested as controls., Results: The final TEGDMA content in the functionalizing layer was modulated by the molar ratio added to the precursor solution. Functionalization reduced nanoparticle size, but did not reduce agglomeration. Improved mechanical properties were found for the composite containing nanoparticles with higher TEGDMA level in comparison to the composite containing non-functionalized nanoparticles or those with a low TEGDMA level. All brushite composites presented statistically significant reductions in strength after 28 days in water, but only the material with high-TEGDMA nanoparticles retained strength similar to the microhybrid commercial control. Overall, ion release was not affected by functionalization and presented steady levels for 28 days., Significance: Though agglomeration was not reduced by functionalization, the improvement in the matrix-nanoparticle interface allowed for a stronger material, without compromising its remineralizing potential., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Objective: Two leading causes contributing to dental restoration replacement are the marginal breakdown at the composite/dentin interface and secondary caries mediated by bacteria. The objective of the present study was to synthesize oligomers which incorporated enhanced bio-stability but would also be able to generate antimicrobial function if they underwent degradation., Methods: Stability was incorporated into the oligomers by generating structural features that would physically hinder the availability of hydrolytically sensitive groups in the oligomers. As a proof-of concept for the antibacterial feature, antimicrobial function was achieved by covalently incorporating Ciprofloxacin (CF) into the backbone of cross-linking divinyl oligomers (referred to as EDV and HLH-CFPEG). The hydrolytic stability of the oligomers was studied in simulated human salivary esterase and compared to the commercial monomer 2,2-bis[4(2-hydroxy-3-methacryloxypropoxy)-phenyl]propane (BisGMA)., Results: Both drug oligomers were found to be significantly more stable than BisGMA. Upon degradation, both drug oligomers released CF differentially in free form. Polymer synthesis from resin formulations containing 15wt% HLH-CFPEG showed a high degree of vinyl group conversion and gel content, and under hydrolytic conditions showed the release of CF during a 28-day monitoring study period., Significance: HLH-CFPEG can be used in dental resin adhesive systems for local delivery of CF to the marginal interface. Minimizing the growth of Streptococcus mutans at the marginal site can improve longevity by reducing esterase activity derived specifically from S. mutans., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Objectives: To functionalize novel chlorhexidine (CHX) particles with iron oxide (Fe 3 O 4 ) nanoparticles and control their release kinetics in a dental resin using an external magnetic field., Methods: Fe 3 O 4 nanoparticles were synthesized and incorporated into spherical CHX particles and the powder was freeze dried. Resin disc specimens were produced using a UDMA-HEMA resin mixed with freeze dried spherical Fe 3 O 4 -CHX particles (5wt.%), which were placed into a Teflon mould (10mm diameter×1mm depth) and covered with a Mylar strip. A MACS magnet was left in contact for 0min (Group 1), 5min (Group 2) or 10min (Group 3) and the resin discs subsequently light cured (Bluedent LED pen, Bulgaria) for 60s per side. The resin discs were immersed in deionized water at various time points up to 650h. UV-Vis absorbance was used to determine the CHX content. CHX released for each time point was determined. The functionalized CHX particles and resin discs were characterized using TEM, TGA, EDX and SEM., Results: Fe 3 O 4 nanoparticles (20nm) incorporated into the spherical CHX particles led to a mean (SD) particle size reduction from 17.15 (1.99)μm to 10.39 (2.61)μm. The presence of Fe 3 O 4 nanoparticles in the spherical CHX particles was confirmed with SEM, EDX, and TGA. SEM of Group 1 resin discs (no magnetic exposure) showed functionalized CHX spheres were homogeneously distributed within the resin discs. For resin discs which had magnetic exposure (5 or 10min) the particles started to cluster nearer the surface (Group 2: 43.7%, Group 3: 57.3%), to a depth of 94μm. UV-Vis absorbance revealed Group 1 resin discs had a cumulative CHX release of 4.4% compared to 5.9% for Group 2 and 7.4% for Group 3 resin discs, which had magnetic exposure (5, 10min)., Significance: Fe 3 O 4 nanoparticle functionalized CHX spheres demonstrated a magnetic field responsive property. A magnetic field responsive release of CHX may be useful in clinical situations where the drug can be directed to give a tailored release at the site of infection., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

Objective: The aim was to evaluate the effect of short glass-fiber/filler particles proportion on fracture toughness (FT) and flexural strength (FS) of an experimental flowable fiber-reinforced composite (Exp-SFRC) with two methacrylate resin formulations. In addition, we wanted to investigate how the fracture-behavior of composite restorations affected by FT values of SFRC-substructure., Methods: Exp-SFRC was prepared by mixing 50wt% of dimethacrylate based resin matrix (bisGMA or UDMA based) to 50wt% of various weight fractions of glass-fiber/particulate filler (0:50, 10:40, 20:30, 30:20, 40:10, 50:0wt%, respectively). FT and FS were determined for each experimental material following standards. Specimens (n=8) were dry stored (37°C for 2 days) before they were tested. Four groups of posterior composite crowns (n=6) composed of different Exp-SFRCs as substructure and surface layer of commercial particulate filler composite were fabricated. Crowns were statically loaded until fracture. Failure modes were visually examined. The results were statistically analysed using ANOVA followed by post hoc Tukey's test., Results: ANOVA revealed that ratio of glass-fiber/particulate filler had significant effect (p<0.05) on tested mechanical properties of the Exp-SFRC with both monomer systems. Exp-SFRC (50wt%) had significantly higher FT (2.6MPam 1/2 ) and FS (175.5MPa) (p<0.05) compared to non-reinforced material (1.3MPam 1/2 , 123MPa). Failure mode analysis of crown restorations revealed that FT value of the substructure directly influenced the failure mode., Significance: This study shows that short glass-fibers can significantly reinforce flowable composite resin and the FT value of SFRC-substructure has prior importance, as it influences the crack arresting mechanism., (Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

The objective of this study was to investigate several physicochemical properties of an experimental discontinuous S2-glass fiber-reinforced resin composite. The experimental composite was prepared by mixing 10 wt% of discontinuous S2-glass fibers with 27.5 wt% of resin matrix and 62.5 wt% of particulate fillers. Flexural strength (FS) and modulus (FM), fracture toughness (FT), work of fracture (WOF), double bond conversion (DC), Vickers hardness, volume shrinkage (VS) and fiber length distribution were determined. These were compared with two commercial resin composites. The experimental composite showed the highest FS, WOF and FT compared with two control composites. The DC of the experimental composite was comparable with controls. No significant difference was observed in VS between the three tested composites. The use of discontinuous glass fiber fillers with polymer matrix and particulate fillers yielded improved physical properties and substantial improvement was associated with the use of S2-glass fiber.

Objective: Investigate physical and chemical properties of model composites formulated with quaternary ammonium salt monomers (QAS) at different concentrations and alkyl chains lengths METHODS: QAS with 12 dimethylaminododecyl methacrylate (DMADDM) and 16 dimethylaminohexadecyl methacrylate (DMAHDM) chains lengths were synthesized and incorporated at 5 and 10% in model composites, resulting in four groups: G12.5 (DMADDM 5%), G12.10 (DMADDM 10%), G16.5 (DMAHDM 5%), G16.10 (DMAHDM 10%). One group was used as control group (CG 0%). Degree of conversion (DC); water sorption (WS) and solubility (SL); hygroscopic expansion (HE); degradation temperature (DT); glass transition temperature (T g ) and polymerization shrinkage (PS) were determined. Knoop hardness (KNH), flexural strength (FS) and elastic modulus (EM) were measured before and after storage Data were submitted to ANOVA and Tukey's test (p≤0.05)., Results: DC ranged between 76.1 (G12.10) and 70.7 (G16.5) %; CG had the lowest WS, SL and HE. There was no statistical difference for PS and FS. KHN values ranged between 30.2 (GC) and 25 (G16.10) and after storage the performance was depended on QAS concentration and chain length. For EM, CG had the highest values before and after storage and no difference was observed in the QAS groups before storage. After storage, the results were dependent on QAS concentration (3.5-4.3GPa)., Significance: In general, the addition of QAS increased composite's degradation compared with the CG. In the tested QAS, the addition of DMADDM at 5% concentration resulted in a less degradable material., (Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objective: Development of antibacterial dental composites is the ultimate goal to decrease carious disease occurrence and increase the restoration longevity. For this purpose, the quaternary ammonium dimethyl-hexadecyl-methacryloxyethyl-ammonium iodide (DHMAI) and the methacryloyloxyethylphosphorylcholine (MPC) have been incorporated in experimental methacrylate-based composite resins. This aims to first investigate the effect of each alone and then their combined effect., Methods: Synthesized DHMAI and commercial MPC were added either alone or combined at different concentrations to experimental dental composite. Flexural strength (FS) and modulus (FM) were tested to select the optimal concentrations. Only selected composites were evaluated for Vickers hardness (HV) and the degree of conversion (DC) using fourier transform infrared spectroscopy analysis (FTIR-ATR). Antibacterial activity was assessed using tests on colony-forming unit (CFU), scanning electron microscopy (SEM) and Alamarblue assay to measure the metabolic activity. Streptococcus mutans biofilm was chosen to be grown on the composite surfaces during 96h at 37°C., Results: Incorporation of 7.5% DHMAI in composite improved the degree of conversion and gave a strong antibacterial effect with a reduction of (∼98%) in CFU and (∼50%) of metabolic activity with acceptable mechanical properties. Addition of MPC to DHMAI affects mechanical properties of composites without providing a better antibacterial activity., Significance: Composites with DHMAI greatly reduced S. mutans biofilm and improved the degree of conversion without scarifying the composites' mechanical properties. DHMAI may have wide applicability to other dental materials in order to inhibit caries and improve the longevity of restorations., (Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objective: To incorporate an antibacterial agent derived deep eutectic solvent (DES) into a dental resin composite, and investigate the resulting mechanical properties and antibacterial effects., Method: The DES was derived from benzalkonium chloride (BC) and acrylic acid (AA) and was incorporated into the dental resin composite through rapid mixing. A three-point bending test was employed to measure the flexural strength of the composite. An agar diffusion test was used to investigate antibacterial activity. Artificial (accelerated) aging was undertaken by immersing the composites in buffer solutions at an elevated temperature for up to 4 weeks. UV-vis spectrophotometry and NMR analysis were conducted to study BC release from the composite. Finally, the biocompatibility of the composite materials was evaluated using osteoblast cell culture for 7 days. Results were compared to those of a control composite which contained no BC., Result: The DES-incorporated composite (DES-C) displayed higher flexural strength than a similar BC-incorporated composite BC (BC-C) for the same level of BC. The inclusion of BC conferred antibacterial activity to both BC-containing composites, although BC-C produced larger inhibition halos than DES-C at the same loading of BC. Control composites which contained no BC showed negligible antibacterial activity. After artificial aging, the DES-C composite showed better maintenance of the mechanical properties of the control compared with BC-C, although a decrease was observed during the three-point bending test, particularly upon storage at elevated temperatures. No BC release was detected in the aged solutions of DES-C, whereas the BC-C showed a linear increase in BC release with storage time. Significantly, cell viability results indicated that DES-C has better biocompatibility than BC-C., Significance: The incorporation of a BC-based DES into a dental resin composite provides a new strategy to develop antibacterial dental materials with better biocompatibility and longer effective lifetimes without sacrificing the intrinsic mechanical properties of the composite structure., (Copyright © 2017. Published by Elsevier Ltd.)

Poly-methyl methacrylate (PMMA)-based dental resins with strong and long-lasting antifungal properties are critical for the prevention of denture stomatitis. This study evaluated the antifungal effects on Candida albicans ATCC90028, the cytotoxicity toward human dental pulp cells (HDPCs), and the mechanical properties of a silver bromide/cationic polymer nano-composite (AgBr/NPVP)-modified PMMA-based dental resin. AgBr/NPVP was added to the PMMA resin at 0.1, 0.2, and 0.3 wt%, and PMMA resin without AgBr/NPVP served as the control. Fungal growth was inhibited on the AgBr/NPVP-modified PMMA resin compared to the control (P < 0.05), and the antifungal activity increased as the incorporation of the AgBr/NPVP antimicrobial composite increased. Confocal laser scanning microscopy (CLSM) showed that the number of fungal cells attached to the modified PMMA resin was considerably lower than in the control. The relative growth rate of HDPCs of modified groups were higher than 75%. The flexural strength (FS) and flexural modulus (FM) were not significantly different (P > 0.05) between the experimental and control groups. These data indicate that the incorporation of AgBr/NPVP conferred strong and long-lasting antifungal effects against Candida albicans to the PMMA resin, and it has low toxicity toward HDPCs, and its mechanical properties were not significantly affected.

Objective: In this study, we designed and synthesized a novel macromolecule (tetramethyl bisphenol F acrylate, TMBPF-Ac) with low viscosity, excellent mechanical properties, and good biocompatibility. It could be used as a monomer for dental resin composites, which could reduce the risk of human exposure to bisphenol A derivatives in the oral environment. In addition, the monomer could be used without diluent, thereby avoiding the negative effect of a diluent METHODS: TMBPF-Ac was synthesized by a multistep condensation reaction. Its structure was confirmed by 1 H NMR spectra. Different resin mixtures were prepared, and then a number of performance and cytotoxicity tests were performed on these specimens., Results: 1 H NMR spectra showed that the structure of TMBPF-Ac was in accordance with the design. The viscosity of TMBPF-Ac was obviously lower than that of bisphenol-A diglycidyl methacrylate. The three kinds of resins used in this study were in line with ISO 4049:2009 and ISO 10993-5:2009. TMBPF-Ac-based resin had better physical and biological properties., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

With the aim of reducing human exposure to Bisphenol A (BPA) derivatives in dentistry, a fluorinated dimethacrylate monomer was synthesized to replace 2,2-bis[4-(2-hydroxy-3-methacryloy-loxypropyl)-phenyl]propane (Bis-GMA) as the base monomer of dental resin. After mixing with reactive diluent triethyleneglycol dimethacrylate (TEGDMA), fluorinated dimethacrylate (FDMA)/TEGDMA was prepared and compared with Bis-GMA/TEGDMA in physicochemical properties, such as double bond conversion (DC), volumetric shrinkage (VS), water sorption (WS) and solubility (WSL), flexural strength (FS) and modulus (FM). The results showed that, when compared with Bis-GMA based resin, FDMA-based resin had several advantages, such as higher DC, lower VS, lower WS, and higher FS after water immersion. All of these revealed that FDMA had potential to be used as a substitute for Bis-GMA. Of course, many more studies, such as biocompatibility testing, should be undertaken to prove whether FDMA could be applied in clinic., Competing Interests: The authors declare no conflict of interest.

Polyhydroquinone-graphene composite as a new redox species was synthesized simply by a microwave-assisted one-pot method through oxidative polymerization of hydroquinone by graphene oxide, which exhibited excellent electrochemical redox activity at 0.124 V and can remarkably promote electron transfer. The as-prepared composite was used as immunosensing substrate in a label-free electrochemical immunosensor for the detection of cytokeratins antigen 21-1, a kind of biomarker of lung cancer. The proposed immunosensor showed wide liner range from 10 pg mL(-1) to 200 ng mL(-1) with a detection limit 2.3 pg mL(-1), and displayed a good stability and selectivity. In addition, this method has been used for the analysis of human serum sample, and the detection results showed good consistence with those of ELISA. The present substrate can be easily extended to other polymer-based nanocomposites.

Synthetic composite materials that mimic the structure and composition of mammalian tooth enamel were prepared by mixing fluoroapatite rods (diameter 2-3 μm, thickness about 0.5 μm) and methylmethacrylate (MMA), followed by polymerization either during or immediately after ultracentrifugation, using either a tertiary amine/radical initiator for polymerization at room temperature or a radical initiator for thermal polymerization. This led to mineral-rich composites (mineral content between 50 and 75 wt%). To enhance the mechanical stability and the interaction between fluoroapatite and polymer matrix, small amounts of differently functionalized MMA monomers were added to the co-monomer mixture. Another approach was the coating of the fluoroapatite rods with silica and the polymerization in the presence of a siloxane-functionalized MMA monomer. The hardness of the composites was about 0.2-0.4 GPa as determined by Vickers indentation tests, about 2 times higher than the polymer matrix alone. The composites had a good resistance against acids (60 min at pH 3, 37 °C).

Objective: The effect of filler content in dental restorative composites on the polymerization shrinkage stress (PS) is not straightforward and has caused much debate in the literature. Our objective in this study was to clarify the PS/filler content relationship based on analytical and experimental approaches, so that guidelines for materials comparison in terms of PS and clinical selection of dental composites with various filler content can be provided., Methods: Analytically, a simplified model based on linear elasticity was utilized to predict PS as a function of filler content under various compliances of the testing system, a cantilever beam-based instrument used in this study. The predictions were validated by measuring PS of composites synthesized using 50/50 mixtures of two common dimethacrylate resins with a variety of filler contents., Results: Both experiments and predictions indicated that the influence of filler content on the PS highly depended on the compliance of the testing system. Within the clinic-relevant range of compliances and for the specific sample configuration tested, the PS increased with increasing filler content at low compliance of instrument, while increasing the compliance caused the effect of filler content on the PS to gradually diminish. Eventually, at high compliance, the PS inverted and decreased with increasing filler content., Significance: This compliance-dependent effect of filler content on PS suggests: (1) for materials comparison in terms of PS, the specific compliance at which the comparison being done should always be reported and (2) clinically, composites with relatively lower filler content could be selected for such cavities with relatively lower compliance (e.g. a Class-I cavity with thick tooth walls or the basal part in a cavity) and vice versa in order to reduce the final PS., (Published by Elsevier Ltd.)

Composites containing nanoparticles of amorphous calcium phosphate (NACP) remineralize tooth lesions and inhibit caries. A recent study synthesized quaternary ammonium methacrylates (QAMs) with chain lengths (CLs) of 3-18 and determined their effects on a bonding agent. This study aimed to incorporate these QAMs into NACP nanocomposites for the first time to simultaneously endow the material with antibacterial and remineralizing capabilities and to investigate the effects of the CL on the mechanical and biofilm properties. Five QAMs were synthesized: DMAPM (CL3), DMAHM (CL6), DMADDM (CL12), DMAHDM (CL16), and DMAODM (CL18). Each QAM was incorporated into a composite containing 20% NACP and 50% glass fillers. A dental plaque microcosm biofilm model was used to evaluate the antibacterial activity. The flexural strength and elastic modulus of nanocomposites with QAMs matched those of a commercial control composite (n = 6; P > 0.1). Increasing the CL from 3 to 16 greatly enhanced the antibacterial activity of the NACP nanocomposite (P < 0.05); further increasing the CL to 18 decreased the antibacterial potency. The NACP nanocomposite with a CL of 16 exhibited biofilm metabolic activity and acid production that were 10-fold lesser than those of the control composite. The NACP nanocomposite with a CL of 16 produced 2-log decreases in the colony-forming units (CFU) of total microorganisms, total streptococci, and mutans streptococci. In conclusion, QAMs with CLs of 3-18 were synthesized and incorporated into an NACP nanocomposite for the first time to simultaneously endow the material with antibacterial and remineralization capabilities. Increasing the CL reduced the metabolic activity and acid production of biofilms and caused a 2-log decrease in CFU without compromising the mechanical properties. Nanocomposites exhibiting strong anti-biofilm activity, remineralization effects, and mechanical properties are promising materials for tooth restorations that inhibit caries.

Polyacrylic acid (PAA) is an important industrial chemical, which has been extensively applied in various fields, including for several biomedical purposes. In this study, we report the synthesis and modification of this polymer with various phenol imides, such as succinimide, phthalimide and 1,8-naphthalimide. The as-synthesized derivatives were used to prepare polymer metal composites by the reaction with Zn(+2). These composites were characterized by using various techniques, including NMR, FT-IR, TGA, SEM and DSC. The as-prepared PAA-based composites were further evaluated for their anti-microbial properties against various pathogens, which include both Gram-positive and Gram-negative bacteria and different fungal strains. The synthesized composites have displayed considerable biocidal properties, ranging from mild to moderate activities against different strains tested.

Objective: To evaluate the ability of thio-urethane oligomers to improve the properties of restorative composite resins., Methods: Oligomers were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 0-20 wt% to BisGMA-TEGDMA (70-30 wt%). Silanated inorganic fillers were added (70 wt%). Materials were photoactivated at 800 mW/cm(2) filtered to 320-500 nm. Near-IR was used to follow degree of methacrylate conversion (DC). Mechanical properties were evaluated in three-point bending with 2 mm × 2 mm × 25 mm bars for flexural strength/modulus and toughness (FS/E, and T) according to ISO 4049, and 2 mm × 5 mm × 25 mm notched specimens for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Results were analyzed with ANOVA/Tukey's test (α=5%)., Results: Significant increase in DC was observed in thio-urethane-containing materials especially for the group with 20 wt% of aliphatic version. Materials composed by oligomers also promoted higher FS, E, and KIC in comparison to controls irrespective of thio-urethane type. A significant increase in toughness was detected by ANOVA, but not distinguished in the groups. The PS was significantly reduced by the presence of thio-urethane for almost all groups., Conclusions: The use of thio-urethane oligomer to compose methacrylate-based restorative composite promote increase in DC, FS, E and KIC while significant reduces PS., Significance: A simple additive was shown to reduce stress while increasing convrersion and mechanical properties, mainly fracture toughness. This has he potential of increasing the service life of dental composites, without changing current operatory procedures., (Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objectives: Calcium phosphate (CaP) composites with Ca and P ion release can remineralize tooth lesions and inhibit caries. But the ion release lasts only a few months. The objectives of this study were to develop rechargeable CaP dental composite for the first time, and investigate the Ca and P recharge and re-release of composites with nanoparticles of amorphous calcium phosphate (NACP) to achieve long-term inhibition of caries., Methods: Three NACP nanocomposites were fabricated with resin matrix of: (1) bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) at 1:1 mass ratio (referred to as BT group); (2) pyromellitic glycerol dimethacrylate (PMGDM) and ethoxylated bisphenol A dimethacrylate (EBPADMA) at 1:1 ratio (PE group); (3) BisGMA, TEGDMA, and Bis[2-(methacryloyloxy)ethyl] phosphate (BisMEP) at 2:1:1 ratio (BTM group). Each resin was filled with 20% NACP and 50% glass particles, and the composite was photo-cured. Specimens were tested for flexural strength and elastic modulus, Ca and P ion release, and Ca and P ion recharge and re-release., Results: NACP nanocomposites had strengths 3-fold of, and elastic moduli similar to, commercial resin-modified glass ionomer controls. CaP ion recharge capability was the greatest for PE group, followed by BTM group, with BT group being the lowest (p<0.05). For each recharge cycle, CaP re-release reached similarly high levels, showing that CaP re-release did not decrease with more recharge cycles. After six recharge/re-release cycles, NACP nanocomposites without further recharge had continuous CaP ion release for 42 d., Significance: Novel rechargeable CaP composites achieved long-term and sustained Ca and P ion release. Rechargeable NACP nanocomposite is promising for caries-inhibiting restorations, and the Ca and P ion recharge and re-release method has wide applicability to dental composites, adhesives, cements and sealants to achieve long-term caries-inhibition., (Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objective: Bulk fracture is one of the primary reasons for resin-based dental restoration failures. To date, there has been no report on the use of polymerizable dental monomers with acceptable biocompatibility to develop a resin with substantial self-healing capability. The objectives of this study were to: (1) develop a self-healing resin containing microcapsules with triethylene glycol dimethacrylate (TEGDMA)-N,N-dihydroxyethyl-p-toluidine (DHEPT) healing liquid in poly(urea-formaldehyde) (PUF) shells for the first time, and (2) determine the physical and mechanical properties, self-healing efficiency, and fibroblast cytotoxicity., Methods: Microcapsules of polymerizable TEGDMA-DHEPT in PUF were prepared via an in situ polymerization method. Microcapsules were added into a BisGMA-TEGDMA resin at microcapsule mass fractions of 0%, 5%, 10%, 15% and 20%. A flexural test was used to measure composite strength and elastic modulus. A single edge V-notched beam method was used to measure fracture toughness KIC and self-healing efficiency., Results: Flexural strength and elastic modulus (mean±sd; n=6) of resin containing 5-15% microcapsules were similar to control without microcapsules (p>0.1). Adding microcapsules into the resin increased the virgin KIC, which was about 40% higher at 15% microcapsules than that with 0% microcapsules (p<0.05). Specimens were fractured and healed, then fractured again to measure the healed KIC. A self-healing efficiency of about 65% in KIC recovery was obtained with 10-20% microcapsules. All specimens with 0-20% microcapsules had fibroblast viability similar to control without resin eluents (p>0.1)., Significance: Self-healing dental resin containing microcapsules with polymerizable TEGDMA-DHEPT healing liquid in PUF shells were prepared for the first time with excellent self-healing capability. These microcapsules and self-healing resins containing them may be promising for dental restorations to heal cracks/damage and increase durability., (Copyright © 2015 Academy of Dental Materials. All rights reserved.)

A novel biocompatible resin monomer 4&mdash;3&mdash;(acryloyloxy)&mdash;2&mdash;hydroxypropoxy) phenyl 4&mdash;(3&mdash;(acryloyloxy)&mdash;2&mdash;hydroxypropoxy) benzoate, as an oral restorative &mdash; acrylate liquid crystalline resin monomer (ALCRM) was synthesized. The intermediate product and the final product were characterized by differential scanning calorimetry (DSC), polarized optical microscope (POM), and nuclear magnetic resonance (NMR). A resin matrix which has a potential application in dental composites was prepared by photopolymerizing ALCRM and triethylene glycol dimethacrylate (TEGDMA) as a primary and diluted monomer with a photosensitizer of camphorquinone (CQ) and 2&mdash;(Dimethylamino)ethyl methacrylate (DMAEMA) mixture. The molar ratio of ALCRM and TEGDMA was 7:3. The properties such as the curing depth, curing time, and the volumetric shrinkage of the resin matrix were investigated and compared with a traditional composite resin matrix Bis&mdash;GMA. After photocuring polymerization, the conversion degree of the resin matrix is 68.06%, higher than Bis&mdash;GMA/TEGDMA; the curing time is 4.08±0.20min, the curing depth is 2.10±0.17mm, and the volumetric shrinkage is 3.62%±0.26%. All the properties exhibit a better performance of the prepared resin matrix than Bis&mdash;GMA.

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe(3+) additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe-catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives.

The selection of a light-curing unit for the curing composite resins is important to achieve best outcomes. The purpose of the present study was to test lasers of 457 and 473 nm alone or in combination under different light conditions with respect to the cure of composite resins. Four different composite resins were light cured using five different laser combinations (530 mW/cm(2) 457 nm only, 530 mW/cm(2) 473 nm only, 177 mW/cm(2) 457 + 177 mW/cm(2) 473 nm, 265 mW/cm(2) 457 + 265 mW/cm(2) 473 nm, and 354 mW/cm(2) 457 + 354 mW/cm(2) 473 nm). Microhardness and polymerization shrinkage were evaluated. A light-emitting diode (LED) unit was used for comparison purposes. On top surfaces, after aging for 24 h, microhardness achieved using the LED unit and the lasers with different conditions ranged 42.4-65.5 and 38.9-67.7 Hv, respectively, and on bottom surfaces, corresponding ranges were 25.2-56.1 and 18.5-55.7 Hv, respectively. Of the conditions used, 354 mW/cm(2) 457 nm + 354 mW/cm(2) 473 nm produced the highest bottom microhardness (33.8-55.6 Hv). On top and bottom surfaces, microhardness by the lowest total light intensity, 354 (177 × 2) mW/cm(2), ranged 39.0-60.5 and 18.5-52.8 Hv, respectively. Generally, 530 mW/cm(2) at 457 nm produced the lowest polymerization shrinkage. However, shrinkage values obtained using all five laser conditions were similar. The study shows the lasers of 457 and 473 nm are useful for curing composite resins alone or in combination at much lower light intensities than the LED unit.

N-bromo-dimethylhydantoin polystyrene beads were synthesized and tested as antimicrobial agents for water microbial decontamination. Optimization of synthetic process was thoroughly investigated, including solvents used, ratio of reactants and reaction conditions, kilogram scale production, and detailed spectral analysis. The microbial inactivation efficiency was studied according to the NSF-231 Guide Standard and Protocol for Testing Microbiological Water Purifiers against Escherichia coli and MS2 phage. The tested resins maintained their activity for 550 L. Thus, N-bromo-dimethylhydantoin-polystyrene beads synthesized under optimized conditions at kilogram quantities have a potential use in water purification filters.

One of the leading causes for the failure of dental composite restorations is secondary caries. Effectively inhibiting cariogenic biofilms and reducing secondary caries could extend the service life of composite restorations. Dental composites releasing antibacterial agents such as chlorhexidine (CHX) have shown biofilm-inhibitory efficacy, but they usually have poor physical and mechanical properties. Herein, we present a study of a new method to encapsulate and release CHX from dental composite using mesoporous silica nanoparticles (MSNs). SBA-15 MSNs were synthesized according to a reported procedure. CHX (62.9 wt%) was encapsulated into dried MSN from 0.3 M CHX ethanol solution. The dental composites containing 0% (control), 3%, 5%, and 6.3% CHX or the same amounts of CHX entrapped in MSN (denoted as CHX@MSN) were fabricated with methacrylate monomers and silanized glass fillers (CHX or CHX@MSN + glass filler particle = 70 wt%). The monomer mixture consisted of bisphenol A glycidyl methacrylate (BisGMA), hexanediol dimethacrylate (HDDMA), ethoxylated bisphenol A dimethacrylate (EBPADMA), and urethane dimethacrylates (UEDMA) at a weight ratio of 40:30:20:10. The composites were tested for CHX release and recharge, flexural strength and modulus (at 24 hr and 1 mo), surface roughness, in vitro wear, and antibacterial activity against Streptococcus mutans and Lactobacillus casei (in both planktonic growth and biofilm formation). The results showed that the composites with CHX@MSN largely retained mechanical properties and smooth surfaces and showed controlled release of CHX over a long time. In contrast, the composites with directly mixed CHX showed reduced mechanical properties, rough surfaces, and burst release of CHX in a short time. The composites with CHX either directly mixed or in MSN showed strong inhibition to S. mutans and L. casei. This research has demonstrated the successful application of MSNs as a novel nanotechnology in dental materials to inhibit oral biofilm without sacrificing materials' mechanical properties and surface integrity., (© International & American Associations for Dental Research.)

Calcium phosphate (CaP) materials have a wide range of applications, including biomaterials, adsorbents, chemical engineering materials, catalysts and catalyst supports and mechanical reinforcements. The size and shape of CaP crystals and aggregates play critical roles in their applications. The main inorganic building blocks of human bones and teeth are nanocrystalline CaPs; recently, much progress has been made in the application of CaP nanocrystals and their composites for clinical repair of damaged bone and tooth. For example, CaPs with special micro- and nanostructures can better imitate the biomimetic features of human bone and tooth, and this offers significantly enhanced biological performances. Therefore, the design of CaP nano-/microcrystals, and the shape and hierarchical structures of CaPs, have great potential to revolutionize the field of hard tissue engineering, starting from bone/tooth repair and augmentation to controlled drug delivery devices. Previously, a number of reviews have reported the synthesis and properties of CaP materials, especially for hydroxyapatite (HAp). However, most of them mainly focused on the characterizations and physicochemical and biological properties of HAp particles. There are few reviews about the control of particle size and size distribution of CaPs, and in particular the control of nano-/microstructures on bulk CaP ceramic surfaces, which is a big challenge technically and may have great potential in tissue engineering applications. This review summarizes the current state of the art for the synthesis of CaP crystals with controlled sizes from the nano- to the macroscale, and the diverse shapes including the zero-dimensional shapes of particles and spheres, the one-dimensional shapes of rods, fibers, wires and whiskers, the two-dimensional shapes of sheets, disks, plates, belts, ribbons and flakes and the three-dimensional (3-D) shapes of porous, hollow, and biomimetic structures similar to biological bone and tooth. In addition, this review will also summarize studies on the controlled formation of nano-/microstructures on the surface of bulk ceramics, and the preparation of macroscopical bone grafts with 3-D architecture nano-/microstructured surfaces. Moreover, the possible directions of future research and development in this field, such as the detailed mechanisms behind the size and shape control in various strategies, the importance of theoretical simulation, self-assembly, biomineralization and sacrificial precursor strategies in the fabrication of biomimetic bone-like and enamel-like CaP materials are proposed., (Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Background/purpose: Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins., Methods: Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group., Results: The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group., Conclusion: Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins., (Copyright © 2012. Published by Elsevier B.V.)

The aim of this study was to prepare urethane dimethacrylates containing quaternary alkyl (C16, C12) ammonium and polyethylene glycol short sequences (Mn, 400 g/mol) and to investigate their behaviour in some experimental formulations in order to evaluate their potential applicability in the dental composites field. The structure of urethane dimethacrylates has been confirmed by (1)H ((13)C) NMR and FTIR spectra, as well as by electrospray ionization tandem mass spectroscopy, and gel permeation chromatography measurements. The effects of the cationic macromers on the properties of the filled/non-filled composites were examined through FTIR, photoDSC, and specific measurements as volumetric polymerization shrinkage, water sorption/solubility, contact angle, mechanical parameters, and morphology. The monomer compositions based on cationic dimethacrylate (6.88-27.52 wt%), BisGMA-analogue (48.18-68.82 wt%) and TEGDMA (23.3 wt%) showed a good photoreactivity in terms of double bond conversion (DC, 50.07-68.81 %) and polymerization rate (Rp, 0.099-0.141 s(-1)) measured by photoDSC compared to a control sample (BisGMA-1/TEGDMA: DC, 45.91 %; Rp, 0.162 s(-1)), while the polymerization shrinkage increased in acceptable limits (5.37-7.74 vol%). The mechanical properties (compressive, flexural and diametral tensile strength) of the composite resin incorporating 70 wt% silanized zirconium silicate micro/nanopowder can be modulated by the initial co-monomer concentrations.

The purpose of this study was to investigate the effect of fiber orientation of a fiber-reinforced composite (FRC) made of poly-methyl-methacrylate (PMMA) and E-glass to the surface fabrication process by solvent dissolution. Intention of the dissolution process was to expose the fibers and create a macroporous surface onto the FRC to enhance bone bonding of the material. The effect of dissolution and fiber direction to the bone bonding capability of the FRC material was also tested. Three groups of FRC specimens (n = 18/group) were made of PMMA and E-glass fiber reinforcement: (a) group with continuous fibers parallel to the surface of the specimen, (b) continuous fibers oriented perpendicularly to the surface, (c) randomly oriented short (discontinuous) fibers. Fourth specimen group (n = 18) made of plain PMMA served as controls. The specimens were subjected to a solvent treatment by tetrahydrofuran (THF) of either 5, 15 or 30 min of time (n = 6/time point), and the advancement of the dissolution (front) was measured. The solvent treatment also exposed the fibers and created a surface roughness on to the specimens. The solvent treated specimens were embedded into plaster of Paris to simulate bone bonding by mechanical locking and a pull-out test was undertaken to determine the strength of the attachment. All the FRC specimens dissolved as function of time, as the control group showed no marked dissolution during the study period. The specimens with fibers along the direction of long axis of specimen began to dissolve significantly faster than specimens in other groups, but the test specimens with randomly oriented short fibers showed the greatest depth of dissolution after 30 min. The pull-out test showed that the PMMA specimens with fibers were retained better by the plaster of Paris than specimens without fibers. However, direction of the fibers considerably influenced the force of attachment. The fiber reinforcement increases significantly the dissolution speed, and the orientation of the glass fibers has great effect on the dissolving depth of the polymer matrix of the composite, and thus on the exposure of fibers. The glass fibers exposed by the solvent treatment enhanced effectively the attachment of the specimen to the bone modeling material.

Objectives: The aim of this study was to use high-pressure high-temperature (HP/HT) polymerization to produce urethane dimethacrylate (UDMA)-triethylene glycol dimethacrylate (TEGDMA) based resin composite blocks (RCB) suitable for dental computer-aided design/manufacture (CAD/CAM) applications and to compare their physical/mechanical properties to those of a commercial dental RCB. The null hypotheses tested were: (1) there are no differences in the physical/mechanical properties between HP/HT polymerized UDMA-TEGDMA RCB and a commercial RCB; (2) volume fraction filler (Vf) does not affect the physical/mechanical properties of HP/HT polymerized RCB., Methods: Four UDMA-based experimental RCB were manufactured under HP/HT conditions. A RCB manufactured under the same HP/HT conditions from a commercial resin composite (Z100) and its commercial counterpart CAD/CAM RCB (Paradigm MZ100) were used as controls. Flexural strength (σf), fracture toughness (KIC), and hardness were determined. The results were analyzed using one-way ANOVA, Scheffé multiple means comparisons (α=0.05), and Weibull statistics (for σf). Scanning electron microscopy was used to characterize fractured surfaces., Results: All HP/HT polymerized RCB had superior σf, KIC, and Weibull modulus compared to the commercial dental RCB. The experimental RCB had similar or superior properties compared to HP/HT polymerized Z100 RCB. Fewer and smaller porosities (not quantified) were apparent in HP/HT polymerized RCB. The experimental RCB that contained 65% Vf showed higher porosity, suggesting practical difficulties in filler incorporation beyond a certain Vf., Conclusions: The results of this study suggested that RCB suitable for dental CAD/CAM applications could be obtained by HP/HT polymerization of resin composites based on pure UDMA., (Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objectives: To determine and identify correlations between flexural strength, strain at failure, elastic modulus and hardness versus ceramic network densities of a range of novel polymer-infiltrated-ceramic-network (PICN) materials., Methods: Four ceramic network densities ranging from 59% to 72% of theoretical density, resin infiltrated PICN as well as pure polymer and dense ceramic cross-sections were subjected to Vickers Indentations (HV 5) for hardness evaluation. The flexural strength and elastic modulus were measured using three-point-bending. The fracture response of PICNs was determined for cracks induced by Vickers-indentation. Optical and scanning electron microscopy (SEM) was employed to observe the indented areas., Results: Depending on the density of the porous ceramic the flexural strength of PICNs ranged from 131 to 160MPa, the hardness values ranged between 1.05 and 2.10GPa and the elastic modulus between 16.4 and 28.1GPa. SEM observations of the indentation induced cracks indicate that the polymer network causes greater crack deflection than the dense ceramic material. The results were compared with simple analytical expressions for property variation of two phase composite materials., Significance: This study points out the correlation between ceramic network density, elastic modulus and hardness of PICNs. These materials are considered to more closely imitate natural tooth properties compared with existing dental restorative materials., (Copyright © 2013 Academy of Dental Materials. All rights reserved.)

Objective: Development of high strength dental composites with adhesive, antibacterial and re-mineralizing potential., Materials: Urethane and triethylene glycol dimethacrylates were combined with HEMA (10 or 20wt%) and 2MP (2 or 10wt%), antibacterial chlorhexidine (2.5wt%) and chemical cure initiators. Reactive mono/tri calcium phosphate (CP) mixed with silica/silicon carbide nanoparticles (S) (CP:S weight ratio 1:2 or 2:1) was added (50wt%)., Results: Decreasing CP/S ratio and HEMA content reduced monomer conversion at 15min from 93 to 63%. Conversely, decreasing CP/S increased initial "dry" compressive (137-203MPa) and flexural (79-116MPa) strength. With high HEMA content, these decreased by ∼15-20MPa upon 24h water storage. With low HEMA content, average decline was <8MPa due to reduced water sorption. Early water sorption induced mass increase, volume expansion, mono calcium phosphate dissolution and chlorhexidine release, were proportional to the initial calcium phosphate content. Furthermore, they increased ∼1.5 fold upon raising HEMA wt%. These diffusion controlled processes and strength decline slowed after 24h as phosphates reaction bound water within the materials. Increasing 2MP concentration reduced calcium release but did not affect strength. Formulations with high CP/S indicated greater antibacterial activity in agar diffusion and in vitro biofilm tests., Significance: New material use beneath a conventional composite could potentially reduce high failure rates associated with residual caries and bacterial microleakage., (Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objective: Conventional dental composites with randomly dispersed inorganic particles within a polymer matrix fail to recapitulate the aligned and anisotropic structure of the dentin and enamel. The aim of the study was to produce a biomimetic composite consisting of a ceramic preform with graded and continuously aligned open pores, infiltrated with epoxy resin., Methods: The freeze casting technique was used to obtain the hierarchically structured architecture of the ceramic preforms. Optical and scanning electron microscopy (SEM) and differential thermal analysis and thermogravimetry (TG-DTA) were used to characterize the samples. Three point bending test and compression test were also performed., Results: All analysis confirmed that the biomimetic composite was characterized by a multi-level hierarchical structure along the freezing direction. In the bottom layers close to the cooling plate (up to 2mm thick), a randomly packed ceramic with closed pores were formed, which resulted in incomplete infiltration with resin and resultant poor mechanical propertiesof the composite. Above 2mm, all ceramic samples showed an aligned structure with an increasing lamellae spacing (wavelength) and a decreasing wall thickness. Mechanical tests showed that the properties of the composites made from ceramic preforms above 2mm from cooling plate are similar to those of the dentin., Significance: The fabrication processing reported in this work offers a viable route for the fabrication of biomimetic composites, which could be potentially used in a range of dental restorations to compete with the current dental composites and ceramics., (Copyright © 2012 Academy of Dental Materials. All rights reserved.)

A series of renewable bis(cyanate) esters have been prepared from bisphenols synthesized by condensation of 2-methoxy-4-methylphenol (creosol) with formaldehyde, acetaldehyde, and propionaldehyde. The cyanate esters have been fully characterized by infrared spectroscopy, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These compounds melt from 88 to 143 °C, while cured resins have glass transition temperatures from 219 to 248 °C, water uptake (96 h, 85 °C immersion) in the range of 2.05-3.21%, and wet glass transition temperatures from 174 to 193 °C. These properties suggest that creosol-derived cyanate esters may be useful for a wide variety of military and commercial applications. The cure chemistry of the cyanate esters has been studied with FTIR spectroscopy and differential scanning calorimetry. The results show that cyanate esters with more sterically demanding bridging groups cure more slowly, but also more completely than those with a bridging methylene group. In addition to the structural differences, the purity of the cyanate esters has a significant effect on both the cure chemistry and final Tg of the materials. In some cases, post-cure of the resins at 350 °C resulted in significant decomposition and off-gassing, but cure protocols that terminated at 250-300 °C generated void-free resin pucks without degradation. Thermogravimetric analysis revealed that cured resins were stable up to 400 °C and then rapidly degraded. TGA/FTIR and mass spectrometry results showed that the resins decomposed to phenols, isocyanic acid, and secondary decomposition products, including CO2. Char yields of cured resins under N2 ranged from 27 to 35%, while char yields in air ranged from 8 to 11%. These data suggest that resins of this type may potentially be recycled to parent phenols, creosol, and other alkylated creosols by pyrolysis in the presence of excess water vapor. The ability to synthesize these high temperature resins from a phenol (creosol) that can be derived from lignin, coupled with the potential to recycle the composites, provides a possible route to the production of sustainable, high-performance, thermosetting resins with reduced environmental impact.