"Fatigue-Crack Propagation Behavior in Microcapsule-Containing Self-Healing Polymeric Networks".

Over the last years, research on the design of dental self-healing polymers has grown dramatically. It is related to the promising potential of maximizing the clinical lifespan of dental restorations that this strategy holds. In this manuscript, the microcapsule-based strategy is innovated by incorporating the high toughness component N,N-Dimethylacrylamide (DMAM) into the healing agent systems and analyzing in-depth the change in crack propagation behavior induced by the addition of microcapsules into the highly crosslinked polymeric network. In general, the addition of the hydrophilic and high vapor pressure DMAM into the healing agent systems imposed a challenge for the microencapsulation, which highlighted the importance of tailoring the properties of the capsules' shells according to the core composition. The addition of DMAM as cushioning agent proved to be a successful strategy since it resulted in increased G'/G" crossover time from 0.06 (control) to 0.57 s and decreased storage modulus from 8.0 (control) to 0.5GPa. In addition, the incorporation of microcapsules within the polymerized networks provided obstacles to crack propagation, which translated to an overall reinforcement of the polymeric network, as evidenced by the increase in toughness up to 50 % and energy required to propagate cracks up to 100 % in systems containing DMAM at 20 wt%.

Methacrylate saccharide-based monomers for dental adhesive systems.

The aim of this in vitro study was to synthesize three new methacrylate monomers based on the modification of saccharides structures (glucose-Gluc, sucrose-Sucr and chitosan-Chit) with glycidyl methacrylate, and to use them in the composition of dental adhesives. Three methacrylate saccharide monomers were synthesized and characterized by mid-IR, 1H and 13C NMR, antioxidant activity and cytotoxic effect. Monomers included: one monosaccharide - Gluc-MA; one disaccharide - Sucr-MA; and one polysaccharide - Chit-MA. Primers containing HEMA, methacrylate saccharide monomers at concentrations of 0 (control), 1, 2 or 4 wt%, 60 wt% ethanol aqueous solution (pH3.0) and initiator system were formulated. Primers were used in conjunction with a bond step and composite paste to restore caries-free third molars, and dentin bond strength (24 hours and 6 month of storage in water), and antimicrobial activity (Alamar Blue test) were tested. Degree of conversion (DC) and maximum rate of polymerization (Rpmax) of the primers themselves were also analyzed. The mid-IR, 1H and 13C spectrum confirmed the presence of vinyl group on the structure of saccharides. Chit-MA showed low antioxidant activity and did not present a cytotoxic effect. Gluc-MA and Sucr-MA possess antioxidant and cytotoxic activity, concentration dependent. In the presence of methacrylate saccharide monomers, the primers showed DC comparable to the control group, except Gluc-MA4%, Sucr-MA4% and Chit-MA1%, which showed a range of 64.6 from 58.5 %DC. Rpmax was not statistically different for all the groups (p = 0.01). The bond strength of Sucr-MA1% increased from 25.7 (±2.8) to 40.6 (±5.3) MPa after 6 months of storage. All the synthesized monomers showed some antimicrobial activity after polymerization. Gluc-MA and Chit-MA 4% and Sucr-MA 1, 2 and 4% led to decrease bacterial metabolism. Sucr-MA 1% showed better results regarding the decrease in bacterial metabolism and increasing the bond strength after 6 months of storage.

Effect of shade, opacity and layer thickness on light transmission through a nano-hybrid dental composite during curing.

OBJECTIVE: The aim of this study was to investigate the effect of shade and opacity on the change in light transmission through different thicknesses of a nano-hybrid composite during curing. MATERIALS AND METHODS: Twelve different shades of Venus Diamond (Heraeus Kulzer) were placed in disk shaped molds with thickness of 1, 2, and 3 mm (n = 3 per group) and cured with an LED light-curing unit. Initial, final and average irradiance, and the total amount of energy passing through the specimen were measured using the MARC Resin Calibrator at every 10s for a total of 40s. The translucency parameter and the contrast ratio were obtained using a chromameter. Results were analyzed with ANOVA/Tukey's test (α = 0.05). RESULTS: All shades and all thicknesses (up to 3 mm) experienced an increase in light transmittance during curing. The majority of the increase occurred during the initial 10s exposure, with significant increase occurring from subsequent exposures only in thicker specimens (i.e., 3 mm). The increase in irradiance at the bottom during curing was dependent on shade, with darker shades and greater depths of material showing less increase. CONCLUSIONS: For one specific resin composite formulation, an increase in translucency occurs as cure progresses, and the increase is enhanced for composites with greater lightness and lower contrast ratio. CLINICAL SIGNIFICANCE: Composites demonstrate increased light transmittance as curing progress, which may improve depth of cure. The thicker composite showed the least increase in light transmission within the same shade. The increase in translucency is enhanced for composites with great lightness and lower contrast ratio.

Effectiveness of high-power LEDs to polymerize resin cements through ceramics: An in vitro study.

STATEMENT OF PROBLEM: The cementation of ceramic veneers using light-polymerized resin cement is largely dependent on the proper light activation of the cement. Light activation using high irradiance could shorten the time required to lute multiple restorations. PURPOSE: The purpose of this in vitro study was to evaluate the light transmission of dental light-polymerizing units through ceramic cylinders and its effect on the polymerization kinetics of a resin cement. MATERIAL AND METHODS: Ceramic ingots (IPS Empress Esthetic, shade ET1) were sectioned to produce cylinders 0.5, 1.0, and 2.0 mm thick. Two light-emitting diode units were evaluated: SmartLite Focus and Valo Cordless, the latter used in either Standard or Xtra Power (XP) modes. Light transmission (average of irradiance, total energy, and light-emission profile) through the cylinders was measured (n=3). The polymerization kinetics of a resin cement light polymerized through the ceramic was monitored for 5 minutes (n=3). The degree of conversion was measured again after 72 hours. Data were individually analyzed with 2-way ANOVA and the Tukey HSD test (α=.05). RESULTS: Valo at XP presented the highest values of irradiance and SmartLite the lowest, irrespective of the ceramic thickness. Regarding the total energy, XP showed the lowest values. The total energy and irradiance lessened with the increase in ceramic thickness. In general, except for Valo at XP, the ceramic thickness did not affect the degree of conversion. Valo at XP and interposing 2.0 mm ceramic resulted in the lowest values of Rpmax. CONCLUSIONS: The reduction of total energy and irradiance by ceramic interposition had only a slight effect on polymerization kinetics.

The potential use of glycosyl-transferase inhibitors for targeted reduction of S. mutans biofilms in dental materials.

Streptococcus mutans is the primary oral caries-forming bacteria, adept at producing "sticky" biofilms via the synthesis of insoluble extracellular polysaccharides (EPS), catalyzed by glucosyltransferases (GTFs). To circumvent the use of broad-spectrum antibiotics to combat these bacteria, this study sought to modify existing EPS-targeting small molecules with the ultimate goal of producing anti-biofilm polymer surfaces specifically targeting S. mutans. To achieve this, a known GTF inhibitor (G43) was modified with methoxy or tetraethyleneglycol substitutions in different positions (nine derivatives, tested at 50-µM) to pinpoint potential sites for future methacrylate functionalization, and then assessed against single-species S. mutans biofilms. As expected, the compounds did not diminish the bacterial viability. In general, the compounds with methoxy substitution were not effective in reducing EPS formation, whereas the tetraethyleneglycol substitution (G43-C3-TEG) led to a decrease in the concentration of insoluble EPS, although the effect is less pronounced than for the parent G43. This aligns with the reduced GTF-C activity observed at different concentrations of G43-C3-TEG, as well as the consequent decrease in EPS formation, and notable structural changes. In summary, this study determined that G43-C3-TEG is non-bactericidal and can selectively reduce the biofilm formation, by decreasing the production of EPS. This molecule will serve to functionalize surfaces of materials to be tested in future research.

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems.

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously.The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials.

Strategies to design extrinsic stimuli-responsive dental polymers capable of autorepairing.

Objectives: For many years, the requirements for dental polymers were limited to inertially filling the cavity and restoring form, function, and esthetics. Inorganic filler systems were widely enhanced to maximize the mechanical properties and optimize finishing and polishing procedures. The development of alternative photoinitiator systems also improved the carbon-carbon double bond conversion, increasing biocompatibility, wear, and stain resistance. However, despite laudable progress, the clinical life span of dental restorations is still limited, and their replacement is the most common procedure in dental offices worldwide. In the last few years, the development of materials with the potential to adapt to physiological stimuli has emerged as a key step to elevating dental polymers to a higher excellence level. In this context, using polymeric networks with self-healing properties that allow for the control of the propagation of microcracks is an appealing strategy to boost the lifetime of dental restorations. This review aims to report the current state-of-the-art of extrinsic self-healing dental polymers and provide insights to open new avenues for further developments. General classification of the self-healing polymeric systems focusing on the current extrinsic strategies used to inhibit microcracks propagation in dental polymers and recover their structural integrity and toughness are presented. Search Strategy: An electronic search was perfomed using PubMed, Google Scholar, and Scopus databases. Only studies published in English on extrinsic self-healing polymeric systems were included. Overall Conclusions: Self-healing materials are still in their infancy in dentistry, and the future possibilities are almost limitless. Although the mouth is a unique environment and the restorative materials have to survive chemical, physical, and mechanical challenges, which limits the use of some strategies that might compromise their physicochemical performance, there are countless untapped opportunities to overcome the challenges of the current systems and advance the field.

Engineering a new generation of thermoset self-healing polymers based on intrinsic approaches.

Objectives: The development of thermosetting polymers with autonomic reparability has become an important research topic since it has the potential to benefit several fields such as biomaterials, tissue engineering, paint and coating technologies, electronics, and soft robotics. In dentistry, the development of restorative materials capable of inhibiting the propagation of microcracks caused by masticatory forces and thermal stress may represent a crucial expansion of the limited clinical lifespan of dental restorations, which is a pressing challenge. Biological systems have inspired the underlying concepts and designs of synthetic polymeric self-healing systems, and different strategies have been used to impart autonomous repair capability in polymers. In this review, the most relevant intrinsic strategies are categorized based on the reaction mechanisms. In general, these strategies rely on the incorporation of latent functionalities capable of undergoing reversible chemical bonds within the polymeric structure (chemically or compositionally tuned). Search Strategy: The searches were conducted in the databases Scopus, PubMed, and Google Scholar and limited to articles that were written in English and published during the last ten years. A few additional articles were included by complementing the database searches with manual review of the reference lists. Overall Conclusions: Although intrinsic approaches remain underexplored in dentistry, a wide variety of elegant chemistries with tremendous translational potential employed in other fields to promote autonomic repair are highlighted in this review.

Delayed Gelation Through Chain-Transfer Reactions: Mechanism For Stress Reduction In Methacrylate Networks.

Chain-transfer reactions from thiols to methacrylates are expected to delay gelation and possibly reduce stress at the bonded interface of dental restorations. Thiol additives with varying structures were combined with a dimethacrylate commonly used in dental materials. Polymerization stress/modulus development were monitored by a tensometer/rheometer, respectively, both coupled with RT-NIR. For all thiol-modified materials, conversion and modulus were 5-25 % higher than the control, and maximum reaction rate was 25-50 % lower. Gel point conversions were 12-22 % (control=5 %), and deceleration was observed at later stages in conversion (30-60 %; control=15 %). Consequently, even with increased conversion/modulus, stress values were either equal or reduced compared to the control. This approach does not require any modification in the bonding/photoactivation procedures, and seems promising for stress management not only in polymeric dental materials, but also for other applications of glassy, crosslinked photopolymers, as long as thiol volatility is addressed.

Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites.

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials.

Effect of side-group methylation on the performance of methacrylamides and methacrylates for dentin hybridization.

The stability of the bond between polymeric adhesives to mineralized substrates is crucial in many biomedical applications. The objective of this study was to determine the effect of methyl substitution at the α- and ß-carbons on the kinetics of polymerization, monomer hydrolytic stability, and long-term bond strength to dentin for methacrylamide- and methacrylate-based crosslinked networks for dental adhesive applications. METHODS: Secondary methacrylamides (α-CH3 substituted=1-methyl HEMAM, ß-CH3 substituted=2-methyl HEMAM, and unsubstituted=HEMAM) and OH-terminated methacrylates (α- and ß-CH3 mixture=1-methyl HEMA and 2-methyl HEMA, and unsubstituted=HEMA) were copolymerized with urethane dimethacrylate. The kinetics of photopolymerization were followed in real-time using near-IR spectroscopy. Monomer hydrolysis kinetics were followed by NMR spectroscopy in water at pH 1 over 30 days. Solvated adhesives (40 vol% ethanol) were used to bond composite to dentin and microtensile bond strength (µTBS) measured after 24h and 6 months storage in water at 37°C. RESULTS: The rate of polymerization increased in the following order: OH-terminated methacrylates≥methacrylamides>NH2-terminated methacrylates, with minimal effect of the substitution. Final conversion ranged between 79% for 1-methyl AEMA and 94% for HEMA. 1-methyl-HEMAM showed the highest and most stable µTBS, while HEMA showed a 37% reduction after six months All groups showed measurable degradation after up to 4 days in pH 1, with the methacrylamides showing less degradation than the methacrylates. Additionally, transesterification products were observed in the methacrylamide groups. SIGNIFICANCE: Amide monomers were significantly more stable to hydrolysis than the analogous methacrylates. The addition of a α- or ß-CH3 groups increased the rate of hydrolysis, with the magnitude of the effect tracking with the expected base-catalyzed hydrolysis of esters or amides, but opposite in influence. The α-CH3 substituted secondary methacrylamide, 1-methyl HEMAM, showed the most stable adhesive interface. A side reaction was observed with transesterification of the monomers studied under ambient conditions, which was not expected under the relatively mild conditions used here, which warrants further investigation.

Improvement on properties of experimental resin cements containing an iodonium salt cured under challenging polymerization conditions.

OBJECTIVE: The use of resin cements in clinical practice entails photopolymerization through prosthetic devices, which precludes light penetration. The objective of this study was to modify experimental resin cements (ERCs) with diphenyliodonium hexafluorophosphate (DPI) in an attempt to improve chemical and mechanical properties of materials cured with reduced irradiance and final radiant exposure. METHODS: A co-monomer base containing a 1:1 mass ratio of 2.2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (bis-GMA) and triethyleneglycol dimethacrylate (TEGDMA) was prepared, with 1mol% of camphorquinone and 2mol% of ethyl 4-(dimethylamino)benzoate as initiator system. The resin was divided into 4 fractions according to the DPI concentrations (0, 0.5, 1 and 2mol%). The challenging polymerization condition was simulated performing the light activation (12, 23 and 46s) through a ceramic block (3mm thick). The irradiance was assessed with a calibrated spectrometer (1320mW/cm2), resulting in three levels of radiant exposure (0.58, 1.1 and 2.2J/cm2). The polymerization kinetics was evaluated in real-time using a spectrometer (Near-IR). Water sorption and solubility was analyzed and the cohesive strength of resins obtained through the microtensile test. Polymerization stress was assessed by Bioman method. RESULTS: Resins containing DPI had higher degree of conversion and rate of polymerization than the control (without DPI). The use of DPI reduced water sorption and solubility, and led to higher cohesive strength compared to resins without the iodonium salt. However, the stress of polymerization was higher for experimental resins with DPI. SIGNIFICANCE: Even under remarkably reduced irradiance, cements containing a ternary initiating system with an iodonium salt can present an optimal degree of conversion and chemical/mechanical properties.

Improper Light Curing of Bulkfill Composite Drives Surface Changes and Increases S. mutans Biofilm Growth as a Pathway for Higher Risk of Recurrent Caries around Restorations.

How dentists cure a resin-based material has deleterious effects on the material's properties and its interaction with surrounding dental tissues. Biofilm accumulation has been implicated in the pathogenesis of carious lesions around dental restorations, with its composition manifesting expressed dysbiosis in patients suffering from dental caries. To evaluate the influence of varying radiant exposure on the degree of conversion (DC%), Streptococcus mutans biofilm growth, and surface roughness of bulk-fill composites under different light-curing conditions. Two light-curing units (LCU) at 600 and 1000 mW/cm2 were used to simulate curing conditions with different angulations (∢20° and ∢35°) or 2 mm-distance displacements of the LCU tip. The radiant exposure (RE) was assessed, and the composites were analyzed for DC%. Biofilm formation was induced over the bulk-fill composites and analyzed via colony-forming units counting and scanning electron microscopy (SEM). The surface roughness was analyzed via a profilometer and SEM after biofilm formation. Curing conditions with different angulation or displacement decreased RE compared to the "optimal condition". The moderately (∢35°) angulated LCU tip and low (600 mW/cm2) radiant emittance significantly reduced the DC% (p < 0.05). The difference in DC% between the top and bottom of the composites ranged from 8 to 11% for 600 mW/cm2 and 10 to 20% for 1000 mW/cm2. Greater S. mutans biofilm and surface changes were found in composites with non-optimal RE delivery (e.g., tip displacement and angulation) (p < 0.05). Inadequate polymerization of bulk-fill composites was associated with more biofilm accumulation and surface topography changes. Overall, non-optimally performed curing procedures reduced the amount of delivered RE, which led to low DC%, more biofilm formation, and higher surface roughness. The improper light-curing of bulk-fill composites compromises their physicochemical and biological properties, which could lead to inferior clinical performance and reduced restorative treatments' longevity.

Development of dual-cured resin cements with long working time, high conversion in absence of light and reduced polymerization stress.

OBJECTIVE: This study evaluated the properties of experimental dual-cured cements containing thiourethane (TU) and low concentrations of p-Tolyldiethanolamnie (DHEPT) and benzoyl peroxide (BPO) as chemical initiators. METHODS: BisGMA/TEGDMA-based dual-cured cement was formulated with 1.0 wt% DHEPT and 0.75 wt% BPO as initiators and used as control. The concentration of BPO was adjusted to 0.1 wt% in catalyst paste of experimental cements, and two base pastes containing TU and 0.5 wt% or 0.25 wt% of DHEPT were formulated. The rheological behavior and kinetics of polymerization of cements were assessed in the absence of light activation. The kinetics of polymerization was also evaluated for cements light-activated immediately or 5 min after the start of mixing. Polymerization stress, flexural strength and elastic modulus (n = 5) were also evaluated under these conditions. RESULTS: Cements with TU presented lower viscosity than the control, improved working time (0.25% DHEPT > 0.5% DHEPT) and higher conversion in the absence of light-activation. Delaying the light-activation reduced the maximum rate of polymerization (Rpmax) but did not affect the conversion or stress. The addition of TU increased the Rpmax and conversion, and reduced the stress when compared to the control, without affecting the flexural strength. Except for the control with delayed light-activation (highest values), the other experimental conditions yielded similar modulus. SIGNIFICANCE: Adding TU and using a low concentration of DHEPT/BPO resulted in dual-cured cements with longer working time, reduced polymerization stress and increased conversion even in the absence of light, with no significant effect on the mechanical properties.

Methacrylamide-methacrylate hybrid monomers for dental applications.

OBJECTIVES: The susceptibility of methacrylates to hydrolytic and enzymatic degradation may be a contributing factor limiting the clinical lifespan of resin composite restorations. The elimination of labile ester bonds is a potential advantage of methacrylamides, which have been shown to produce more stable restorative interfaces. The rationale of this study is to design hydrolytically and enzymatically stable adhesive monomers, with the added benefit of being able to form crosslinked networks. The objective of this study was to synthesize difunctional, hybrid methacrylate-methacrylamide monomers, and evaluate them as potential monomers for dental adhesives. MATERIALS AND METHODS: HEMA, TEGDMA (controls) or secondary methacrylamides (HEMAM - commercially available, 2EM and 2dMM - newly synthesized) either bearing a hydroxyl group or a methacrylate functionality (Hybrids-Hy), were added at 40mass% to bisGMA. The photoinitiator system consisted of 2-dimethoxyphenyl acetophenone (DMPA) and diphenyl iodonium hexafluorophosphate (DPI-PF6) at 0.2 and 0.4mass%, respectively. Polymerization kinetics were followed in real-time by near-IR spectroscopy during light activation at 630mW/cm2 for 300s. Water sorption and solubility (WS, SL) were measured according to ISO 4049. Storage modulus in shear (G') for 300s was obtained by oscillatory rheometry. For the microtensile bond strength (µTBS), fully formulated adhesives containing 40vol% ethanol were used to restore caries-free human third molars. Bonded specimens with 1mm2 cross-sectional area were tested after 48h and 6 months storage in water at 37°C. Single bond (SB) was tested as a commercial control. Data were analysed with one-way ANOVA and Tukey's test and Student's t-test (α=0.05). RESULTS: In general, hybrid versions showed lower polymerization rate and degree of conversion, whereas the methacrylate controls, HEMA and TEGDMA, showed the highest values. The hybrid versions showed lower values of WS and SL than their monofunctional versions. HEMAM Hy showed the highest values of G' and TEGDMA, 2EM, and 2dMM-Hy the lowest. The µTBS values between 48h and 6 months were statistically reduced only for the HEMA and both 2dMM materials. The formulation containing the monofunctional methacrylamide (HEMAM) showed only 9% reduction in µTBS after 6 months of aging, while the other groups showed a decrease ranging between 18% and 33%. CONCLUSION: Overall, hybrid monomers showed lower reactivity than their analogous monofunctional versions, but had markedly lower water sorption. Shear storage modulus was affected differently by the addition of the second functionality. HEMAM-containing systems were able to maintain stable long-term dentin bond strength, which demonstrates that bonding stability is a result of the complex interplay among the factors studied. CLINICAL SIGNIFICANCE: The novel monomers showed here are potential alternatives to the current methacrylate adhesives, with selected formulations presenting greater bond stability.

Synthesis of di- and triacrylamides with tertiary amine cores and their evaluation as monomers in dental adhesive interfaces.

PURPOSE/AIM: In an attempt to increase the service life of dental adhesive interfaces, more hydrolytically and enzymatically-stable methacrylate alternatives, such as methacrylamides, have been proposed. The aim of this study was to investigate polymerization behavior, as well as mechanical and biological properties of experimental adhesives containing multi-functional acrylamides. MATERIALS AND METHODS: Multi-functional acrylamides (N,N-Bis[(3-methylaminoacryl)propyl]methylamine - BMAAPMA, Tris[(2-methylaminoacryl)ethyl]amine - TMAAEA, N,N'-bis(acrylamido) 1,4-diazepane - BAADA, N,N-Diethyl-1,3-bis(acrylamido)propane - DEBAAP) or HEMA (2-Hydroxyethyl methacrylate - control) were added at 40 wt% to UDMA. 0.2 wt% DMPA and 0.4 wt% DPI-PF6 were used as initiators. Polymerization kinetics was followed in real-time in near-IR during photoactivation (320-500 nm, at 630 mW/cm2). Water sorption/solubility and flexural strength/modulus were measured according to ISO 4049. 1H NMR was used to assess monomer degradation kinetics. MTT assay was used to assess cytotoxicity against OD-21 and DPSC cells. Biofilm formation and adhesion were assessed by Luciferase Assay and Impingement technique, respectively. Solvated adhesives (40 vol% ethanol) were used to test interfacial adhesion strength. The results were analyzed by ANOVA/Tukey's test (α = 0.05). RESULTS: In general, the pure methacrylate mixture had higher rate of polymerization (Rpmax), degree of conversion (DC) at Rpmax, and final DC than the acrylamides. Flexural properties after water storage decreased between 11 and 65%, more markedly for acrylamides. Interfacial bond strength was greater and more stable long-term for the newly synthesized acrylamide formulations (less than 4% reduction at 6 months) compared to the methacrylate experimental control (42% reduction at 6 months). HEMA degraded by almost 90%, while the acrylamides showed no degradation in acidic conditions. Cytotoxicity and biofilm formation, in general, were similar for all groups. CONCLUSIONS: Despite demonstrating high water sorption, the acrylamide-containing materials had similar mechanical and biological properties and enhanced interfacial bond strength stability compared to the methacrylate control.

Strategies for Potential Toughening of Acrylic Denture Bases Polymerized With Microwave Energy.

Thiourethane additives have been shown to improve properties in several dental polymer applications. The aim of this study was to verify the effect of the addition of thiourethane oligomers and acrylamide or isobornyl-based plasticizers on the physical properties of the denture base acrylic resin polymerized with microwaves. Thiourethane oligomer (TU) was synthetized and added to microwaved acrylic resin in proportions varying between 3 and 14 wt%. Separate experimental groups included the addition of dimethyl acrylamide (DMAM) and isobornyl methacrylate as plasticizers, at concentrations varying from 5 to 20 wt%. Samples were polymerized using microwave energy at 500 Watts for 3 min, deflasked at room temperature, stored in water at 37 °C for 24 h, and evaluated for: linear dimensional change, gloss, Knoop hardness, surface roughness, impact strength, yield strength, elastic modulus, toughness, yield strength, viscosity, glass transition temperature and network heterogeneity, and water sorption/solubility. Data were analyzed with ANOVA/Tukey's post-hoc test (a=5%). The addition of TU led to properties that were similar or worse than the materials to which it was not added, except for dimensional stability. The impact on properties was statistically significant for all materials above 20% addition of TU. The addition of DMAM at 5 wt% or isobornyl methacrylate at 10 wt% improved yield strength and modulus, but increased water sorption and solubility. Except for dimensional stability, the addition of thiourethane oligomers to acrylic denture base materials compromised most tested properties. The use of DMAM and isobornyl methacrylate improved properties for selected compositions.

Alternative monomer for BisGMA-free resin composites formulations.

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

Photoinitiator content in restorative composites: influence on degree of conversion, reaction kinetics, volumetric shrinkage and polymerization stress.

PURPOSE: To determine the influence of rate of polymerization, degree of conversion and volumetric shrinkage on stress development by varying the amount of photoinitiators in a model composite. METHODS: Volumetric shrinkage (with a mercury dilatometer), degree of conversion, maximum rate of reaction (RPmax) (with differential scanning calorimetry) and polymerization stress (with a controlled compliance device) were evaluated. Bis-GMA/TEGDMA (equal mass ratios) were mixed with a tertiary amine (EDMAB) and camphorquinone, respectively, in three concentrations (wt%): high = 0.8/1.6; intermediate = 0.4/0.8 and low = 0.2/0.4. 80 wt% filler was added. Composites were photoactivated (400 mW/cm2 x 40 seconds; radiant exposure = l6 J/cm2). A fourth experimental group was included in which the low concentration formulation was exposed for 80 seconds (32 J/cm2). RESULTS: For the same radiant exposure, conversion, RPmax and stress increased with photoinitiator concentration (P < 0.001). When the low concentration group exposed to 32 J/cm2 was compared with the high and intermediate groups (exposed to 16 J/cm2), RPmax still increased with the photoinitiator concentration between all levels (P < 0.001) but conversion and stress did not vary (P > 0.05). Shrinkage did not vary regardless of the photoinitiator concentration or radiant exposure. For the photoinitiator concentrations used in this study. Polymerization stress was influenced by conversion but not by rate of reaction.

Toughening of Dental Composites with Thiourethane-Modified Filler Interfaces.

Stress of polymerization is one of the most significant drawbacks of dental resin composites, since it is related to poor marginal adaptation, postoperative pain, and secondary caries. Previous studies have shown that thiourethane oligomers incorporated into the organic matrix represents a promising strategy to reduce stress and increase fracture toughness in dental composites. However, this strategy promotes a significant increase of the viscosity system, which may represent a challenge for clinical application. The objective of this study was to functionalize the surface of inorganic filler particles with thiouretanes and evaluate the impact on mechanical properties and kinetics of polymerization. Our results showed that composites filled with thiourethane-silanized inorganic fillers showed up to 35% lower stress while doubling mechanical properties values. This was achieved with no prejudice to the viscosity of the material and following a clinically acceptable photoactivation protocol.