New dimethacrylate monomers based on phenolphthalein and resveratrol for the application of dental materials.

Potential estrogenic effects and changes in fertility are some of the health problems associated with bisphenol A (BPA) derivatives used to produce some polymers, including dental materials that contain Bis-GMA. Those issues drove this study proposing the synthesis of methacrylate resveratrol and phenolphthalein monomers that, combined with diluent monomers, generate copolymers. Their key characteristics were determined and analyzed on the chemical structure-property perspective considering monomer planarity and flexibility based on molecular dynamic simulations. METHODS: Methacrylate resveratrol ((E)-5-(4-(methacryloyloxy)styryl)-1,3-phenylenebis(2-methylacrylate)), EMPM) and methacrylate phenolphthalein ((3-oxo-1,3-dihydroisobenzofuran-1,1-diyl)bis(4,1-phenylene)bis(2-methylacrylate)), DIFPM) were synthesized through the reaction of precursors with methacryloyl chloride. After monomers purification and spectroscopic characterization (FTIR and NMR), the following copolymers were produced: DIFPM/TEGDMA and Bis-GMA/TEGDMA, EMPM/HEMA and Bis-GMA/HEMA. Microhardness, degree of conversion, water sorption and contact angle data were statistically analyzed through one-way ANOVA and Tukey's test (p ≤ 0.05). RESULTS: The DIFPM molecular structure's reduced flexibility proved to be an important factor to inhibit TEGDMA cyclization. In turn, the EMPM molecule's high planarity modified the spatial organization of the HEMA copolymer, altering the water diffusion and, therefore, the water sorption when compared to Bis-GMA copolymers. CONCLUSION: The scientific findings contribute to better understand the effect of monomer chemical structures, molecular geometry, and planarity on some physicochemical properties of copolymers. Knowledge that can contribute to the design of new monomers to replace Bis-GMA.

Synthesis and characterization of experimental endodontic sealers containing bioactive glasses particles of NbG or 45S5.

OBJECTIVE: This study evaluated the influence of adding bioactive glasses particles [Niobophosphate (NbG) or bioglass (45S5)] into endodontic cements in relation to physical, chemical and biological properties. METHODS: The following commercial cements were used as comparison: AH Plus (Dentsply), Endofill (Dentsply), MTA Fillapex (Angelus) and EndoSequence (BC Sealer, Brasseler). Setting time, radiopacity, flow rate, weight loss/variation, alkaline capacity (pH) at different time-intervals (24h/48h/7d/14d/28d), bioactivity (assessed under SEM/EDS, FTIR/ATR and XDR) and cell viability were measured. Data were analyzed by One-way ANOVA/Holm-Sidak post-test (α = 5%) (normal distribution) and Kruskal-Wallis/Students-Newman-Keuls post-test (α = 5%) (non-normal distribution). RESULTS: Bioactive endodontic experimental cements (containing NbG or 45S5) had high alkalinization capacity. The experimental cements presented high weight loss/variation (p < 0.001). 45S5 experimental cement did not present radiopacity (p < 0.001). AH Plus had the lowest cell cytotoxicity when compared to the other tested cements (p < 0.001). Regarding bioactivity, SEM/EDS analyses showed precipitates with high concentrations of Ca/P for 45S5 and NbG, as well as for MTA Fillapex and BC Sealer. AH plus and Endofill did not present bioactive precipitates. FTIR/ATR and XDR analyses found hydroxyapatite precursors for NbG, 45S5, MTA Fillapex and BC Sealer. SIGNIFICANCE: The incorporation of bioactive particles (NbG or 45S5) into endodontic cements had potential to neutralize acidic environments and induced formation of hydroxyapatite precursors. Clinically, these would produce a cement that is bactericidal and have the potential to improve tissue healing. The improved radiopacity and flowability would facilitate the visualization of the material in the radiograph and the filling of anatomical complexities during root canal obturation. As drawbacks, the excessive weight loss and post-setting cytotoxicity could result in clinical degradation of the cement and adjacent tissue irritation for the patient.

Bioactive bacterial cellulose membrane with prolonged release of chlorhexidine for dental medical application.

Bioabsorbable barrier membrane is desired in dental medicine for treatment of periodontal diseases caused by different types of bacteria. Bioactive and bioabsorbable bacterial cellulose (BC) is a promising material for such application. However, a key challenge to implement this approach is produce BC membranes selectively oxidized and loaded with a bactericide, in order to modulate bioabsortion time and bactericide effect, respectively. In the present study, the drug model chlorhexidine (CHX) was chosen and NaIO4 was used as oxidizing agent. To modulate CHX release and efficacy, inclusion complexes of CHX with ß-cyclodextrin (CHX:ßCD) were synthesized. A linear dependence between degree of oxidation (DO) and oxidant concentration was found (DO = 2.07 + 45 [NaIO4]). CHX has strong chemical interaction with cellulose structure, contributing for its significant retention. The association of membrane oxidation and formation of the inclusion complex with ßCD causes a 10-fold increase in CHX release rate compared to unmodified cellulose. Thus, validating the concept that CHX release can be modulated using these two strategies. All membranes loaded with CHX inhibited S. aureus, E. coli and C. albicans growth, but DABC+CHX:ßCD showed greater inhibition zone (p < 0.05). That, associated with other results, indicates potential application as bioactive and bioabsorbable membrane.

Bioactivity and properties of an adhesive system functionalized with an experimental niobium-based glass.

OBJECTIVE: This study evaluated the incorporation of niobophosphate bioactive glass (NbG) fillers into a commercial adhesive resin. MATERIALS AND METHODS: The silanized (NbGs) or non-silanized (NbG) NbG was added to the commercial adhesive system One Step (OS) at 30% by weight; unfilled adhesive served as control. The bioactivity of adhesives was analyzed by SEM and FTIR/ATR after 28 days in PBS. The adhesives were evaluated as regards microtensile bond strength immediately and after six months (n = 6); degree of conversion (n = 3), microhardness (n = 5); and radiopacity (n = 3). Data from each test were submitted to ANOVA and Tukey tests (P <0.05). RESULTS: FTIR/ATR analysis showed phosphate and carbonate precipitates on the NbG adhesive specimen surface. Statistical analysis of microtensile bond strength values showed that material x time interaction was not significant, but NbG group values were similar to those of unfilled adhesive (p <0.05). Addition of NbG did not alter the degree of conversion, but did increase microhardness and radiopacity values of the adhesive systems compared with those of the control group (OS). Incorporation of NbG into the adhesive system did not compromise the properties of the adhesive. CONCLUSION: A smart adhesive system with bioactive properties, high radiopacity, microhardness, and similar bond strength and degree of conversion was obtained by incorporating 30% by weight of NbG.

Adhesives Doped with Bioactive Niobophosphate Micro-Filler: Degree of Conversion and Microtensile Bond Strength.

To evaluate the effect of incorporating niobium phosphate bioactive glass (NbG) into commercial etch-and-rinse adhesive systems, with and without silane, on their degree of conversion (DC) (%) and microtensile bond strength (µTBS). The NbG micro-filler was added to two etch-and-rinse adhesive systems: One Step (OS) and Prime & Bond (PB) at 40% concentration. The following groups were formed: control without glass addition OS; addition of unsilanized NbG (OSNbG); addition of silanized NbG (OSNbGS); control without glass PB; addition of unsilanized NbG (PBNbG); addition of silanized NbG (PBNbGS). The DC was determined using total Fourier spectroscopy reflection (FTIR/ATR). For µTBS testing, 48 human third molars (n=8) were restored and sliced to obtain specimens (0.8 mm2) and they were tested at two different time intervals: immediately and after 6 months. The fracture mode was evaluated with a stereoscopic loupe (40×) and by scanning electron microscopy (SEM). The data were subjected to ANOVA and Tukey tests (a=0.05). NbG addition did not compromise the adhesive system DC values (p>0.05). Furthermore, the NbG added to the adhesive systems did not affect µTBS values (p>0.05). Fracture occurred predominantly at the dentin-adhesive interface. NbG bioactive glass did not affect the DC or microtensile bond strength results.

Adhesives Doped with Bioactive Niobophosphate Micro-Filler: Degree of Conversion and Microtensile Bond Strength

Abstract To evaluate the effect of incorporating niobium phosphate bioactive glass (NbG) into commercial etch-and-rinse adhesive systems, with and without silane, on their degree of conversion (DC) (%) and microtensile bond strength (μTBS). The NbG micro-filler was added to two etch-and-rinse adhesive systems: One Step (OS) and Prime & Bond (PB) at 40% concentration. The following groups were formed: control without glass addition OS; addition of unsilanized NbG (OSNbG); addition of silanized NbG (OSNbGS); control without glass PB; addition of unsilanized NbG (PBNbG); addition of silanized NbG (PBNbGS). The DC was determined using total Fourier spectroscopy reflection (FTIR/ATR). For μTBS testing, 48 human third molars (n=8) were restored and sliced to obtain specimens (0.8 mm2) and they were tested at two different time intervals: immediately and after 6 months. The fracture mode was evaluated with a stereoscopic loupe (40×) and by scanning electron microscopy (SEM). The data were subjected to ANOVA and Tukey tests (a=0.05). NbG addition did not compromise the adhesive system DC values (p>0.05). Furthermore, the NbG added to the adhesive systems did not affect μTBS values (p>0.05). Fracture occurred predominantly at the dentin-adhesive interface. NbG bioactive glass did not affect the DC or microtensile bond strength results.

Resumo Avaliar o efeito da incorporação de vidro niobofosfato bioativo (NbG, 40% em peso) em dois sistemas adesivos simplificados convencionais (One Step [OS] e Prime & Bond {PB}) com e sem silano, no grau de conversão (%) e resistência de união (RU) após 6 meses. Os seguintes grupos foram testados: Controle OS: sem adição de partículas; OS e adição de NbG sem silano (OSNbG); OS e adição de partículas silanizadas NbG (OSNbGS); Controle PB: sem adição de partículas; PB e adição de partículas de NbG sem silano (PBNbG); PB e adição de partículas silanizadas NbG (PBNbGS). O grau de conversão (GC) foi determinado utilizando espectroscopia de Fourier (FTIR/ATR). Para RU, 48 terceiros molares humanos (n=8) foram restaurados e cortados para obter corpos-de-prova (0,8 mm2) e, em seguida, testados em dois momentos: imediato e após seis meses. O padrão de fratura foi avaliado com lupa estereoscópica (40×) e microscópio eletrônico de varredura (MEV). Os dados foram submetidos à análise de variância e Tukey (a=0,05). NbG não comprometeu valores de GC dos sistemas adesivos (p>0,05). Além disso, a adição de NbG aos sistemas adesivos não afetou os valores de RU (p>0,05). O padrão de fratura ocorreu predominantemente na interface dentina-adesivo. NbG não afetou os resultados de GC e RU.

Influence of the base and diluent monomer on network characteristics and mechanical properties of neat resin and composite materials.

This study evaluated the effect of the combination of two dimethacrylate-based monomers [bisphenol A diglycidyl dimethacrylate (BisGMA) or bisphenol A ethoxylated dimethacrylate (BisEMA)] with diluents either derived from ethylene glycol dimethacrylate (ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate) or 1,10-decanediol dimethacrylate (D3MA) on network characteristics and mechanical properties of neat resin and composite materials. The degree of conversion, maximum rate of polymerization and water sorption/solubility of unfilled resins and the flexural strength and microhardness of composites (after 24 h storage in water and 3 months storage in a 75 vol% ethanol aqueous solution) were evaluated. Data were analyzed with two-way ANOVA and Tukey's test (α = 0.05). The higher conversion and lower water sorption presented by BisEMA co-polymers resulted in greater resistance to degradation in ethanol compared with BisGMA-based materials. In general, conversion and mechanical properties were optimized with the use of long-chain dimethacrylate derivatives of ethylene glycol. D3MA rendered more hydrophobic materials, but with relatively low conversion and mechanical properties.

Influence of silane content and filler distribution on chemical-mechanical properties of resin composites

This study investigated the influence of silane concentration and filler size distribution on the chemical-mechanical properties of experimental composites. Experimental composites with silane contents of 0%, 1% and 3% (in relation to filler mass) and composites with mixtures of barium glass particles (median size = 0.4, 1 and 2 μm) and nanometric silica were prepared for silane and filler analyses, respectively. The degree of conversion (DC) was analyzed by FTIR. Biaxial flexural strength (BFS) was tested after 24-h or 90-d storage in water, and fracture toughness, after 24 h. The data were subjected to ANOVA and Tukey’s test (p = 0.05). The DC was not significantly affected by the silane content or filler distribution. The 0% silane group had the lowest immediate BFS, and the 90-d storage time reduced the strength of the 0% and 3% groups. BFS was not affected by filler distribution, and aging decreased the BFS of all the groups. Silanization increased the fracture toughness of both the 1% and 3% groups, similarly. Significantly higher fracture toughness was observed for mixtures with 2 μm glass particles. Based on the results, 3% silane content boosted the initial strength, but was more prone to degradation after water storage. Variations in the filler distribution did not affect BFS, but fracture toughness was significantly improved by increasing the filler size.

Mechanical properties and modeling of drug release from chlorhexidine-containing etch-and-rinse adhesives.

OBJECTIVES: To evaluate the effects of chlorhexidine (CHX) addition in different concentrations into simplified etch-and-rinse adhesives on the ultimate tensile strength (UTS), water sorption (WS), solubility (SO) and the rate of CHX release over time. METHODS: We added CHX diacetate to Ambar [AM] (FGM) and XP Bond [XP] (Dentsply) in concentrations of 0, 0.01, 0.05, 0.1 and 0.2 wt%. For UTS (n=10 for each group), adhesive specimens were constructed in an hourglass shape metallic matrix with cross-sectional area of 0.8 mm(2). Half of specimens were tested after 24 h and the other half after 28 days of water storage in tension of 0.5 mm/min. For WS and SO (n=10 for each group), adhesive discs (5.8 mm×1.0 mm) were prepared into a mold. After desiccation, we weighed and stored the cured adhesive specimens in distilled water for evaluation of the WS, SO and the cumulative release of CHX over a 28-day period. For CHX release (n=10 for each group), spectrophotometric measurements of storage solution were performed to examine the release kinetics of CHX. We subjected data from each test to ANOVA and Tukey' test (α=0.05). RESULTS: XP Bond adhesive showed significantly more WS and SO and lower UTS than Ambar. In general, the addition of CHX did not alter WS, SO and UTS of the adhesives. XP showed a higher CHX release than AM (p<0.05) in all concentrations and the final amount of CHX release was directly proportional to the initial CHX concentration added to the adhesives. After 28 days of water storage, approximately 20% of CHX was released from XP and 8.0-12.0% from AM. CONCLUSIONS: Addition of CHX to commercial adhesive is a feasible method to provide a controlled release of CHX over time without jeopardizing WS, SO and UTS of the adhesives. SIGNIFICANCE: Manufacturers should consider adding CHX to commercial adhesives to provide a controlled release of CHX over time.

Effects of adding barium-borosilicate glass to a simplified etch-and-rinse adhesive on radiopacity and selected properties.

PURPOSE: To evaluate the radiopacity, ultimate tensile strength (UTS), microhardness (KHN), degree of conversion (DC), water sorption (WS) and solubility (SL) of experimental adhesives. MATERIALS AND METHODS: Five experimental adhesives with different concentrations of barium-borosilicate oxide microfillers [0% (R0), 30% (R30), 40% (R40), 50% (R50), 60% (R60)] were formulated based on the adhesive system Ambar (FGM). The adhesive Adper Single Bond 2 (SB, 3M ESPE) was used as commercial reference. For the radiopacity (n = 5), KHN (n = 5), WS (n = 10), and SL (n = 10) tests, adhesive disks were constructed (5.0 mm in diameter and 1.0 mm thick), while for UTS (n = 5), hourglass-shaped specimens with a cross-sectional area of 0.8 mm2 were used. The FTIR spectra of unpolymerized and polymerized adhesives were used to determine the DC. Data were submitted to a one-way ANOVA and Tukey's test (α = 0.05). RESULTS: All experimental adhesives showed radiopacity similar to enamel, except those of R0 and SB. Filler addition did not jeopardize the UTS, KHN, or WS of the filled adhesives in comparison with the unfilled version. Except for R40, filler addition reduced the SL. The filled adhesives showed lower DC when compared with R0, but the DC was similar or higher when compared with SB. CONCLUSIONS: The addition of barium-borosilicate glass up to 50% did not jeopardize the mechanical properties of the adhesive layer and seems to reduce its solubility.

Effects of zirconia nanoparticles addition to experimental adhesives on radiopacity and microhardness

AIM: To evaluate the radiopacity and microhardness (KHN) of experimental dental adhesives (EX). The experimental adhesive resins of the present study were formulated based on the simplified adhesive system Ambar (FGM). METHODS: Five EX with different concentrations of zirconia nanoparticles [0(EX0), 15(EX15), 25(EX25), 30(EX30) e 50%(EX50)] were incorporated in a UDMA/HEMA adhesive (control). Adper Single BondTM 2 (SB, 3M ESPE) was used as a commercial reference. For the radiopacity (n=5), KHN (n=5), adhesive specimens were fabricated using a stainless steel mold. Data were submitted to one-way ANOVA and Tukey's test (α=0.05). RESULTS: The filler addition on the EX showed radiopacity similar to enamel and higher than SB. The EX25, EX35 and EX50 showed higher KHN values when compared to the commercial SB. EX25, EX35 and EX50 showed higher KHN values when compared to the commercial SB. CONCLUSIONS: The results of the present investigation suggest that the addition of zirconia nanoparticles seems to be a good alternative to produce radiopaque adhesives with increased microhardness.

Improvement of exposure times: effects on adhesive properties and resin-dentin bond strengths of etch-and-rinse adhesives.

PURPOSE: This study evaluated the effect of prolonged polymerization times on the microtensile resin-dentin bond strength (µTBS), degree of conversion of adhesive films (DC) and silver nitrate uptake (SNU) for an ethanol/water- (Adper Single Bond 2, [SB]) and an acetone-based (One Step Plus, [OS]) etch-and-rinse adhesive. MATERIALS AND METHODS: Thirty caries-free extracted molars were included in this study. The occlusal enamel of all teeth was removed by wet grinding the occlusal enamel on 180-grit SiC paper. Adhesives were applied according to the manufacturer's instructions, but they were light cured for 10, 20 and 40 s at 600 mW/cm2. Bonded sticks (0.6 mm2) were tested in tension (0.5 mm/min). Two bonded sticks from each tooth were immersed in an ammoniacal solution of silver nitrate (24 h), photodeveloped (8 h), and analyzed by SEM. The DC of the adhesives was evaluated under Fourier Transformed Infra-Red spectroscopy (FTIR). Data for each property were analyzed by two-way ANOVA and Tukey's test (α = 0.05). RESULTS: Statistically higher µTBS and DC were observed for SB and OS when both adhesives were light cured for 40 s in comparison with 10 s. For OS, the µTBS in the 20- and 40-s groups did not differ statistically, while for SB it did. Higher prolonged exposure times did not prevent nanoleakage within the hybrid layer for all groups regardless of the adhesive. CONCLUSION: This study supports the hypothesis that exposure times longer than those recommended can improve the degree of conversion of adhesive films and the immediate resin-dentin bonds. The prolonged curing times (20 and 40 s) for polymerization of simplified adhesives resulted in an increase in the degree of conversion of the adhesive films and resin-dentin bond strengths but did not reduce the nanoleakage within the hybrid layer.

Evaporating solvents with a warm air-stream: effects on adhesive layer properties and resin-dentin bond strengths.

OBJECTIVES: This study evaluated the effect of a warm or cold air-dry stream for solvent evaporation on the microtensile resin-dentin bond strength (muTBS), nanoleakage pattern (SEM), degree of conversion (DC) and solvent evaporation rates (SE) of an ethanol/water- (Adper Single Bond, [SB] 3MESPE) and an acetone-based (Prime & Bond 2.1, [PB] Dentsply), two-step etch-and-rinse adhesive system. MATERIALS AND METHODS: Adhesives were applied on demineralized dentin surfaces. For SE, a warm or cold air-dry stream (10 s) was applied prior to light-activation (10 s). Bonded sticks (0.8mm2) were tested in tension (0.5 mm/min). Two bonded sticks from each tooth were immersed in a 50% (w/v) solution of silver nitrate (24 h), photodeveloped (8 h) and analyzed by SEM. The DC and solvent evaporation rate of the adhesives were evaluated under FTIR and analytical balance, respectively. Data were analyzed by two-way ANOVA and Tukey test (alpha=0.05). RESULTS: Higher muTBS and lower nanoleakage were observed when the SE step was performed with warm air-dry stream. However, the DC of the adhesives was not altered by the use of a warm air-dry. CONCLUSIONS: The use of a warm air-dry stream seems to be a clinical tool to improve the bond strength and the quality of the hybrid layer (less nanoleakage infiltration), since it might reduce the number of pores within the adhesive layer.