Adhesion and optics: The challenges of esthetic oral rehabilitation on varied substrates-Reflections based on a clinical report.

Patients with challenging prosthodontic conditions require rehabilitation with a biological, functional, and esthetic approach. When one or more teeth are badly discolored, their restoration is problematic because poor appearance affects not only the crown but also the periodontal tissues. This clinical report describes a complex esthetic rehabilitation with conservative tissue management and ceramic restorations. Subepithelial connective tissue graft surgery and the replacement of a cast metal post with a glass fiber post addressed the problem of a discolored maxillary central incisor. The discolored right maxillary incisor was restored with a combination of a medium-opaque, lithium-disilicate ceramic coping to mask the dark root and to approximate the color of the other incisors. Subsequently, 6 ceramic veneers were placed. A knowledge of the materials' optical properties and adhesion possibilities helped solve this complex problem.

Luting laminate veneers: Do resin-composites produce less polymerization stress than resin cements?

OBJECTIVES: Regular composites could produce less polymerization stress than resin cements when luting laminate veneers but there is no proper evidence to support this theory. The current study aimed to determine the degree of conversion, volumetric shrinkage, polymerization stress and the resultant elastic moduli of materials currently used for adhesive cementation and to determine possible correlations. METHODS: The study considered (i) regular resin composites (Admira Fusion, Gradia, Grandioso, Palfique, Sirius Z, Viscalor and Z100) at room and pre-warmed (PW) at 69ºC, (ii) flowable composites (Sigma Flow and Grandioso Flow); (iii) solely light-activated cements (AllCem Veneer, Variolink Esthetic and RelyX Veneer); and (iv) one dual-activated resin cement (SpeedCEM). Degree of conversion (DC, n = 3) was accessed with FTIR 1 h after irradiation. Bonded-disk and Bioman II instruments were used to access polymerization shrinkage strain and shrinkage stress, respectively, for 60 min at 23 ± 1◦C (n = 3). The elastic modulus was determined by 3-point bending flexural test (n = 6). The results were submitted to analyse s of variance, Tukey's, and correlation tests. RESULTS: For regular composites, the pre-warming did not affect DC, shrinkage and modulus but significantly increased the stress magnitude. Correlation tests indicated a significant relationship only between stress and polymerization shrinkage (r = 0.811343). SIGNIFICANCE: Regular composites can produce less polymerization stress than resin cements when luting laminate veneers. Polymerization stress was dependent on the shrinkage magnitude, but not on the degree of conversion nor the elastic modulus.

Influence of resin matrix on the rheology, translucency, and curing potential of experimental flowable composites for bulk-fill applications.

OBJECTIVE: To propose monomer formulations that show an optimal degree of conversion as a function of depth for bulk-fill applications. METHODS: Four resin blends were formulated with methacrylate-based monomers: BisGMA + TEGDMA (control); BisEMA + BisGMA + TEGDMA (BisEMA-based); UDMA + BisGMA + TEGDMA (UDMA-based) and BisEMA + UDMA + BisGMA + TEGDMA (BisEMA + UDMA-based). For each material, a photoinitiating system and silanized filler particles were added. The rheological analyses were performed with a rotational rheometer using the cone/plate geometry. CIELab coordinates were assessed over black and white backgrounds using a bench spectrophotometer (SP60, X-Rite) to calculate the translucency parameter (TP) for samples with 0.5, 4, and 6 mm thickness. The degree of CC conversion (DC) was determined by infrared spectroscopy (FTIR/ATR) at 0.05 mm (top), 4, and 6 mm depths (bottom), and the bottom-to-top ratio was considered. A broad spectrum-based LED was used for light activation. Analysis of variance and Tukey's test (95%) were performed on the results. RESULTS: The materials tested showed pseudoplastic and thixotropic behavior and a predominance of viscous effects over elastics. The control resin yielded the lowest viscosity for the entire shear rate investigated, followed by the BisEMA-based, BisEMA + UDMA-based, and UDMA-based group, which had the highest viscosity. The UDMA-based material showed the lowest TP as a function of thickness. Both the materials' formulations and depths significantly influenced the DC. The UDMA-based group promoted the highest DC ​​on the top (71 ± 1%) and 4 mm depth (68 ± 1%) but exhibited lower bottom-to-top DC ratio. The BisEMA + UDMA-based material promoted the highest bottom-to-top DC ratio at 4 mm (99%) and 6 mm (97%). SIGNIFICANCE: The resin matrix interferes in the rheological behavior, translucency parameter, and polymerization capacity as a function of depth. The material formulated with the addition of UDMA and BisEMA demonstrated the highest curing potential as a function of depth and can be useful for bulk-fill applications.

Physicochemical properties and biological effects of quaternary ammonium methacrylates in an experimental adhesive resin for bonding orthodontic brackets.

METHODOLOGY: Fixed orthodontic appliances may lead to biofilm accumulation around them that may increase caries risk. This study aimed to evaluate the influence of quaternary ammonium methacrylates (QAMs) on the physicochemical properties, cytotoxicity, and antibacterial activity of adhesive resins for orthodontic purposes. A base resin was prepared with a comonomer blend and photoinitiator/co-initiator system. Two different QAMs were added to the base adhesive: dimethylaminododecyl methacrylate at 5 wt.% (DMADDM) or dimethylaminohexadecyl methacrylate (DMAHDM) at 10 wt.%. The base adhesive, without QAMs, (GC) and the commercial Transbond™ XT Primer 3M (GT) were used as control. The resins were tested immediately and after six months of aging in the water regarding the antibacterial activity and shear bond strength (SBS). The antibacterial activity was tested against Streptococcus mutans via metabolic activity assay (MTT test). The groups were also tested for the degree of conversion (DC) and cytotoxicity against keratinocytes. RESULTS: The resins containing QAM showed antibacterial activity compared to the commercial material by immediately reducing the metabolic activity by about 60%. However, the antibacterial activity decreased after aging (p<0.05). None of the groups presented any differences for SBS (p>0.05) and DC (p>0.05). The incorporation of DMADDM and DMAHDM significantly reduced the keratinocyte viability compared to the GT and GC groups (p<0.05). CONCLUSION: Both adhesives with QAMs showed a significant reduction in bacterial metabolic activity, but this effect decreased after water aging. Lower cell viability was observed for the group with the longer alkyl chain-QAM, without significant differences for the bonding ability and degree of conversion. The addition of QAMs in adhesives may affect the keratinocytes viability, and the aging effects maybe decrease the bacterial activity of QAM-doped materials.

Curing potential and color stability of different resin-based luting materials.

PURPOSE: To determine the curing potential and color stability of resin-based luting materials for aesthetic restorations. MATERIAL AND METHODS: Four resin-based luting agents were tested: traditional dual-activated resin cement (RelyX ARC, ARC), amine-free dual-activated resin cement (RelyX Ultimate, ULT), light-activated resin cement (RelyX Veneer, VEN), and pre-heated restorative resin composite (Filtek Supreme, PHC). Degree of C=C conversion was determined by infrared spectroscopy (n=3) with direct light exposure or with interposition of 1.5-mm-thick ceramic (e.max Press HT) between the luting material and light. The curing potential considered the ratio between these two scenarios. Color difference (n=6) was determined by CIELAB (ΔEab) and CIEDE2000 (ΔE00) methods, by spectrophotometer measurements made 24h after photoactivation and 90 days after storage in water. Data was submitted to ANOVA and Tukey's test (α=0.05). RESULTS: The luting agents affected both conversion and color stability. With ceramic, ARC produced the highest conversion among the tested groups (75±1%) and the pre-heated composite (PHC) the lowest one (51±3%), but the curing potential was similar for all materials. ULT produced lower ΔEab than ARC. PHC presented the lowest color difference when considered both CIELAB and CIE2000 methods (ΔEab 2.1±0.4; ΔE00 1.6±0.2). SIGNIFICANCE: All luting strategies presented high curing potential. Amine-free dual-activated material was able to reduce color difference than that formulated with the amine component. Pre-heated composite produced the least color variation after storage.

Effect of storage and compressive cycles on the bond strength after collagen removal.

This study verified the influence of storage and compressive loads on the microtensile bond strength (microtbs) of an adhesive system when using the conventional technique or collagen removal treatment. Twenty bovine teeth were separated into four groups: G1) adhesive system Prime & Bond NT (PBNT) in accordance with the manufacturer's instructions, G2) PBNT after deproteinization with 10% sodium hypochlorite (NaOCl), G3) PBNT in accordance with the manufacturer's instructions + 50,000 compressive cycles and G4) PBNT after deproteinization + 50,000 compressive cycles. After 24 hours, the teeth were sectioned and half of the specimens were stored in water (37 degrees C) for further evaluation (after 60 days). The failure mode was evaluated by scanning electron microscopy (SEM). The bond strength values were separately submitted to two-way ANOVA for each period and the differences among groups were determined by Tukey's test (p = 0.05). Comparisons between 24 hours and 60 days were determined by multiple paired Student's t-tests (5%). The evaluation at 24 hours revealed that deproteinization did not affect microtbs for the non-cycled groups (G1 = 47.8 +/- 4.7 and G2 = 52.4 +/- 11.32). For the groups tested after the mechanical cycles, deproteinization produced higher microtbs (G3 = 32.7 +/- 9.6 and G4 = 43.3 +/- 16.7). At 60 days, deproteinization produced higher microtbs than the manufacturers' recommendations for the cycled and non-cycled groups (G1 = 31.5 +/- 5.8; G2 = 48.8 +/- 7.7; G3 = 17.1 +/- 7.2 and G4 = 48.8 +/- 12.2). In conclusion, the deproteinized groups were less susceptible to degradation than the groups restored with the conventional technique.

Physicochemical Properties and Microshear Bond Strength of Experimental Self-adhesive Resin Cements to Dentin or Yttria-stabilized Tetragonal Zirconia Polycrystal.

PURPOSE: To determine the degree of conversion (DC), physicochemical properties, and microshear bond strength (µSBS) of experimental self-adhesive resin cements (SARCs) to dentin and yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic. MATERIALS AND METHODS: Dual-curing cements were formulated with UDMA, HEMA, bis-GMA, and TEG-DMA as the organic matrix. 2MP (bis 2-(methacryloyloxy)-ethyl-phosphate) and GDMAP (1,3-glycerol dimethacrylate phosphate) were added to impart self-adhesive characteristics. A control group was formulated without self-etch methacrylates. Silanized particles were incorporated. Photoactivation was carried out using an LED light-curing unit (1200 mW/cm2) for 20 s. Infrared spectroscopy assessed the DC immediately and after 24 h. pH was analyzed in real time and recorded after 48 h. Water sorption (Wsp), water solubility (Wsl), and film thickness measurements followed ISO 4049. µSBS of the cements to dentin and Y-TZP was evaluated immediately and after 3 months of water storage. Y-TZP was also tested without a surface treatment and after tribochemical silica coating with subsequent application of a silane agent. The fractures patterns were classified as adhesive, cohesive, and mixed. Data were submitted to analyses of variance and Tukey's tests (α = 0.05). RESULTS: Control (91.7%) and 2MP (92.0%) groups generated the highest DC after 24 h. 2MP (pH = 3.6) showed the lowest pH followed by GDMAP (pH = 4.7) and control (pH = 6.4) after 48 h. The control cement exhibited lower Wsp (41.0 µg/mm3) and Wsl (4.3 µg/mm3) than the other groups. Film thickness was statistically similar (p = 0.266) for all cements. Control (27.0 MPa) and GDMAP (24.1 MPa) showed higher µSBS to dentin than 2MP (13.7 MPa) after water storage. Mixed fractures were predominant in dentin. For all cements, the µSBS to Y-TZP was < 3.0 MPa after water storage, independent of the surface treatment. CONCLUSION: The results of DC, pH, Wsp and Wsl were material dependent. Only the film thickness was statistically similar for all groups. The cement formulated with GDMAP maintained the bond strengths to dentin even after aging. However, none of the groups were able to generate satisfactory bond strength to Y-TZP, independent of the surface treatment.

Influence of photoinitiator type on the rate of polymerization, degree of conversion, hardness and yellowing of dental resin composites.

OBJECTIVES: To evaluate the degree of conversion (DC), maximum rate of polymerization (Rpmax), Knoop hardness (KHN) and yellowing (b-value) of resin composites formulated with phenylpropanedione (PPD), camphorquinone (CQ), or CQ/PPD at different concentrations. The hypotheses tested were (i) PPD or CQ/PPD would produce less Rpmax and yellowing than CQ alone without affecting DC and KHN, and (ii) Rpmax, DC, and KHN would be directly related to the absorbed power density (PDabs). METHODS: CQ/amine, PPD/amine and CQ/PPD/amine were used at low, intermediate and high concentrations in experimental composites. Photoinitiator absorption and halogen-light emission were measured using a spectrophotometer, Rp with differential scanning calorimetry (DSC), DC with DSC and FTIR, KHN with Knoop indentation; and color with a chromameter. The results were analyzed with two-way analysis of variance (ANOVA)/Student-Newman-Keul's test (p<0.05). Correlation tests were carried out between PDabs and each of DC, Rpmax and KHN. RESULTS: The PDabs increased with photoinitiator concentration and PPD samples had the lowest values. In general, maximum DC was comparable at intermediate concentration, while Rpmax and KHN required higher concentrations. DC was similar for all photoinitiators, but Rpmax was lower with PPD and CQ/PPD. PPD produced the lowest KHN. Yellowing increased with photoinitiator concentration. PPD did not reduce yellowing at intermediate and/or high concentrations, compared to CQ-formulations. PDabs showed significant correlations with DC, Rpmax and KHN. CONCLUSION: PPD or CQ/PPD reduced Rpmax in experimental composites without affecting the DC. The use of PPD did not reduce yellowing, but reduced KHN. DC, Rpmax and KHN were dependent on PDabs.

Cross-link density evaluation through softening tests: effect of ethanol concentration.

OBJECTIVES: The aim of this study was to investigate whether the ethanol concentration used would influence the outcomes obtained through softening tests when comparing light-activation modes. METHODS: Disc specimens (n=20) of Filtek Z250 and Filtek Z100 (3M ESPE) were light activated by standard (S) and pulse-delay (PD) modes. Initial Knoop hardness (KHN) measurements were performed 24h after dry storage at 37 degrees C. Half of the specimens (n=10) of each resin-composite were stored in absolute ethanol (100%) and the other half in 75% ethanol solution, for 24h at room temperature, and KHN was determined anew. Initial hardness data were submitted to Student's t-test (p=0.05). Percentages of hardness decrease were analyzed by two-way ANOVA followed by pairwise Tukey's test (p=0.05). The statistical analyses were performed separately for each resin-composite. RESULTS: No statistically significant differences were observed between standard and pulse-delay modes for initial Knoop hardness values. After storage in 75% ethanol solution, KHN was decreased in all cases but no significant differences were detected between light-activation modes (Filtek Z250: PD=12.6%, S=13.5%; Filtek Z100: PD=13.5%, S=11.8%) regardless of the resin-composite tested. After absolute ethanol storage, higher decrease in KHN were observed. Samples light-activated by the PD mode (Filtek Z250=20.4% and Filtek Z100=16.9%) exhibited significantly higher percentage decrease of KHN than specimens light-activated by the standard mode (Filtek Z250=14.1% and Filtek Z100=8.8%), regardless of the resin-composite tested. CONCLUSION: The ethanol concentration affected the outcomes of the softening test.

Influence of Photoinitiator System on Physical-Chemical Properties of Experimental Self-Adhesive Composites.

The aim of this study was to determine the influence of photoinitiator systems on physical-chemical properties of flowable composites. Conventional (CFC), composed by bisphenol-glycidyl dimethacrylate (BisGMA)+triethyleneglycol dimethacrylate (TEGDMA), and self-adhesive (SAFC), composed by BisGMA+TEDGMA+bis{2-(methacryloyloxy) ethyl} phosphate (2MP), flowable composites were developed. Five photoinitiator systems were tested: camphorquinone (CQ), ethyl-4-dimethylaminobenzoate (EDMAB), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), phenylbis (2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), CQ+EDMAB+TPO and CQ+EDMAB+BAPO. A two-peak LED was used; degree of conversion (DC) and the maximum polymerization rate (RPmax) were determined by near infrared spectroscopy. For the yellowing degree a spectrophotometer was used. Water sorption (Wsp) was obtained after 30 days of water storage (n=5). Data were submitted to two-way analysis of variance and Tukey's test (a=0.05). BAPO presented the highest DC and RPmax values for both series. SAFCs presented lower DC and RPmax for CQ+EDMAB-based materials. Greater yellowing was observed for SAFCs compared with CFCs, except for BAPO. Greater Wsp was observed for SAFCs compared with CFCs. The photoinitiator did not influence Wsp for CFCs, but TPO and BAPO presented the highest Wsp in SAFCs. The photoinitiator system affected differently the physical-chemical properties of CFCs and SAFCs.

Effect of monomer type on the CC degree of conversion, water sorption and solubility, and color stability of model dental composites.

OBJECTIVE: This study has investigated the influence of BisGMA, BisEMA, BisEMA 30, and two UDMA-based monomers (UDMA and Fit 852), with TEGDMA as co-monomer, on the degree of conversion, water sorption, water solubility, and optical properties of experimental dental composites. METHODS: Materials were formulated at 70/30 molar rations using BisGMA, BisEMA, BisEMA 30, UDMA or FIT 852, as base monomers, combined with TEGDMA. 60wt% of silanated-glass particles was added. Degree of conversion (DC) and polymerization kinetics were monitored using Fourier-transformed infrared spectroscopy in the near-IR range. Water sorption (Wsp) and solubility (Wsl) were assessed using mass variation after 60days water storage. Color was evaluated using a digital spectrophotometer, applying the CIELab parameters 24h after dry storage and 60days after water immersion to calculate ΔE values. All data were analyzed using ANOVA and Tukey's test (pre-set alpha=0.05). RESULTS: The BisGMA-based co-monomer mixture presented the lowest DC (62±1%), whereas BisEMA 30 had the highest DC value (95±2%). The highest Wsp was observed for BisEMA 30 (12.2±0.8%), and the lowest for BisEMA (0.4±0.1%). BisEMA has shown the lowest Wsl (0.03±0.01%) and BisEMA 30 the highest one (0.97±0.1%). The ΔE values showed that BisEMA 30 (7.3 color units) and Fit 852 (3.8 color units) altered the color stability providing ΔE>3.3, which is considered clinically unacceptable. CONCLUSIONS: The chemical composition and structure of the base monomer influenced the degree of conversion, water sorption, water solubility, and color stability. Considering the overall results, it is possible to state that the base monomer BisEMA mixed with the co-monomer TEGDMA presented the best performance in terms of all the parameters tested. SIGNIFICANCE: The resin matrix composition might influence physical property degradation processes and color stability of dental resin composites. Formulations based on BisEMA seem most promising for materials' development.

Physicochemical properties and biological effects of quaternary ammonium methacrylates in an experimental adhesive resin for bonding orthodontic brackets

Abstract Fixed orthodontic appliances may lead to biofilm accumulation around them that may increase caries risk. This study aimed to evaluate the influence of quaternary ammonium methacrylates (QAMs) on the physicochemical properties, cytotoxicity, and antibacterial activity of adhesive resins for orthodontic purposes. Methodology: A base resin was prepared with a comonomer blend and photoinitiator/co-initiator system. Two different QAMs were added to the base adhesive: dimethylaminododecyl methacrylate at 5 wt.% (DMADDM) or dimethylaminohexadecyl methacrylate (DMAHDM) at 10 wt.%. The base adhesive, without QAMs, (GC) and the commercial Transbond™ XT Primer 3M (GT) were used as control. The resins were tested immediately and after six months of aging in the water regarding the antibacterial activity and shear bond strength (SBS). The antibacterial activity was tested against Streptococcus mutans via metabolic activity assay (MTT test). The groups were also tested for the degree of conversion (DC) and cytotoxicity against keratinocytes. Results: The resins containing QAM showed antibacterial activity compared to the commercial material by immediately reducing the metabolic activity by about 60%. However, the antibacterial activity decreased after aging (p<0.05). None of the groups presented any differences for SBS (p>0.05) and DC (p>0.05). The incorporation of DMADDM and DMAHDM significantly reduced the keratinocyte viability compared to the GT and GC groups (p<0.05). Conclusion: Both adhesives with QAMs showed a significant reduction in bacterial metabolic activity, but this effect decreased after water aging. Lower cell viability was observed for the group with the longer alkyl chain-QAM, without significant differences for the bonding ability and degree of conversion. The addition of QAMs in adhesives may affect the keratinocytes viability, and the aging effects maybe decrease the bacterial activity of QAM-doped materials.

Influence of surface treatments to repair recent fillings of silorane-and methacrylate-based composites.

PURPOSE: The aim of this study was to evaluate the tensile bond strength (TBS) of repairs in recent fillings of methacrylate- (MBC) or silorane-based composites (SBC) subsequent to different surface treatments. MATERIALS AND METHODS: Fifty slabs of Filtek P60 (3M ESPE, St Paul, USA) and Filtek P90 (3M ESPE) were stored for 10 days in distilled water at 37°C. The surface of adhesion was abraded with a 600-grit silicone paper and repaired using each respective composite: G1, no treatment (control); G2, application of adhesive; G3, application of silane and adhesive; G4, sandblasting (Al2O3) and adhesive; and G5, sandblasting (Al2O3), silane, and adhesive. Further 10 slabs of each composite were also evaluated for cohesive strength (G6). After 30 days immersion in distilled water at 37°C, the TBS was determined. RESULTS: TBS results were higher for MBC than for SBC (P = 0.00012). The experimental groups were similar for SBC and the TBS was 27% of its cohesive strength. For P60, sandblasting significantly improved the TBS compared to other groups. With MBC, G4 and G5, the TBS was approximately 47% of its cohesive strength. CONCLUSION: Sandblasting (Al2O3) improves the repair-strength of MBC, whilst for the SBC all treatments succeed. MBC presents higher repair strength than SBC.

Influence of photoinitiator system and nanofiller size on the optical properties and cure efficiency of model composites.

OBJECTIVE: To establish the relationship between photoinitiator system and nanofiller size on the optical properties and cure efficiency of model composites. METHODS: Model composites based on BisGMA/TEGDMA (60:40mol%) were loaded with 40wt% of 7nm or 16nm-sized filler particles. One of the following photoinitiator systems was added: camphorquinone (CQ) associated with an amine (EDMAB), monoacylphosphine oxide (TPO), or bysacylphosphine oxide (BAPO). The optical properties of disk-shaped specimens were measured 24h after curing and repeated after storage in water for 90 days and coffee for 15 days. A large spectrum LED unit (Bluephase G2, Ivoclar Vivadent) was used for photoactivation. CIE L*a*b* parameters, color difference (ΔE), and translucency parameter (TP) were calculated. Knoop hardness readings were taken at top and bottom composite surfaces. Cure efficiency was determined by bottom/top hardness ratio. Data were statistically analyzed at α=0.05 significance level. RESULTS: Composites formulated with 16nm particles had higher CIE L* than those with 7nm particles in all storage conditions. BAPO-based composites generally had lower CIE a* than the other composites. The group TPO+16nm before storage and all groups with 16nm-sized particles after storage had lower CIE b* (i.e. lower degree of yellowing) than the other groups. TPO-based materials had higher color stability. The cure efficiency was not significantly affected by photoinitiator system or particle size. CQ+7nm had the lowest and BAPO+16nm the highest hardness values. SIGNIFICANCE: Combination of photoinitiator system and filler particle size might affect the optical properties of composites, with low influence on cure efficiency.

The influence of nanoscale inorganic content over optical and surface properties of model composites.

OBJECTIVES: To investigate the influence of nanoscale inorganic content over optical and surface properties of model composites before and after ageing. METHODS: Three model composites were formulated with silica fillers in nanoscale of 7 nm (G1), 12 nm (G2) and 16 nm (G3), at 45.5% by weight in a matrix of BisGMA/TEGDMA 1:1. Color coordinates (CIE L*a*b* parameters), color difference (ΔE*), translucency parameter (TP), surface gloss (SG) and surface roughness (SR) were measured before and after ageing procedures of immersion in water and toothbrush abrasion. Surface hardness (SH) were evaluated before and after immersion in absolute ethanol. Results were submitted to two-way ANOVA followed by Tukey's post hoc test performed at a pre-set alpha of 0.05. RESULTS: Regarding CIE L*a*b* parameters, a darkening, a redness and a blueness effect, were respectively detected after water storage for all groups. Smaller filler sizes (G1) had the highest CIE b* values, whereas medium (G2) (p<0.05) had higher values than larger fillers (G3) (p<0.05) either before or after water immersion. Toothbrush abrasion did not produce any significant effect on CIE a* and CIE b* values, however increased CIE L*, decreased TP in addition to produce rougher and matte surfaces in all groups. Filler size did not influence ΔE* (p>0.05), although a tendency towards lower values in smaller filler materials was observed. Ageing after immersion in absolute ethanol decreased SH for all model composites. CONCLUSIONS: Filler sizes and ageing procedures influenced the optical and surface properties of the nanostructured composites evaluated in this study. CLINICAL SIGNIFICANCE: Filler size influenced optical and surface properties of resin composites. Materials containing smaller filler size offered improved optical stability and surface properties that can lead to longer maintenance of the restoration's appearance in the oral environment.

Color stability, conversion, water sorption and solubility of dental composites formulated with different photoinitiator systems.

OBJECTIVES: The aim of this study was to formulate materials with high color stability and reduced degradation by using photoinitiator systems derived from phosphine oxides alternative to the traditional camphorquinone (CQ)/amine system. METHODS: Materials were formulated with the monomers BisGMA and TEGDMA as organic matrix. The photoinitiators tested were CQ+amine (EDMAB), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), BAPO+EDMAB, diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO) and TPO+EDMAB. A 60% mass of silanated glass filler particles was added. Degree of CC conversion was evaluated by Fourier-transformed infrared spectroscopy 10min after photopolymerization. The color properties were evaluated by a digital spectrophotometer, applying the CIELab parameters, either before photoactivation, immediately after photoactivation, 24h after dry storage, and one month after water immersion. Water sorption and solubility were assessed by mass gain or loss after storage in water for 30 days. Data were analyzed using ANOVA and Tukey's test (5%). RESULTS: Degree of conversion did not differ statistically among all the tested formulations. Regarding color, only groups with TPO presented satisfactory color stability after one month of water storage (ΔE<3.3). Water sorption and water stability did not differ among the groups. CONCLUSIONS: Degree of conversion, water sorption and water solubility did not differ among all the tested groups. The TPO-based groups were the only materials with satisfactory color stability after one month of water storage. CLINICAL SIGNIFICANCE: The use of a photoinitiator system containing TPO might improve the color stability of resin composites compared with the traditional CQ/amine system while attaining similar physico-chemical properties for the composite.

Curing efficiency of dental resin composites formulated with camphorquinone or trimethylbenzoyl-diphenyl-phosphine oxide.

OBJECTIVES: Since photoinitiator systems for dental resins based on camphorquinone (CQ) present color disadvantages, trimethylbenzoyl-diphenyl-phosphine oxide (TPO) has been proposed as an alternative. However, there are remaining considerations about its curing efficiency. The aims of the present investigation were: to characterize the relationship between the photoinitiator absorption spectra and the light spectrum emitted from a QTH light (absorbed power density, PD(abs)); to evaluate the kinetics of polymerization, and the depth of cure for filled dimethacrylate resins formulated with different photoinitiator systems. METHODS: CQ+EDMAB (control); TPO and TPO+EDMAB were used in 50:50 Bis-GMA/TEGDMA resins. Photoinitiator absorption and QTH-light emission were evaluated using a spectrophotometer and kinetics of polymerization with differential scanning calorimetry (DSC) (n=3). Depth of cure was analyzed by the scraping method (n=5), as recommended by ISO4049. One-way ANOVA/Tukey's (p<0.05) was used to analyze the results. RESULTS: CQ presented higher PD(abs) than TPO (364 and 223 mW/cm(3), respectively). The DSC revealed that TPO and TPO+EDMAB produced a faster reaction than CQ+EDMAB. Composite formulated with CQ+EDMAB produced higher depth of cure (6.3±0.4 mm) than those with TPO (4.3±0.1) or TPO+EDMAB (4.2±0.3). SIGNIFICANCE: Although CQ presented higher PD(abs) than TPO, formulations containing TPO exhibited higher reactivity than that with CQ. On the other hand, materials formulated with TPO demonstrated lower depth of cure than that with CQ. Therefore, its use as an alternative photoinitiator requires further investigation, with higher concentrations.

Influence of Photoinitiator System on Physical-Chemical Properties of Experimental Self-Adhesive Composites

Abstract The aim of this study was to determine the influence of photoinitiator systems on physical-chemical properties of flowable composites. Conventional (CFC), composed by bisphenol-glycidyl dimethacrylate (BisGMA)+triethyleneglycol dimethacrylate (TEGDMA), and self-adhesive (SAFC), composed by BisGMA+TEDGMA+bis{2-(methacryloyloxy) ethyl} phosphate (2MP), flowable composites were developed. Five photoinitiator systems were tested: camphorquinone (CQ), ethyl-4-dimethylaminobenzoate (EDMAB), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), phenylbis (2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), CQ+EDMAB+TPO and CQ+EDMAB+BAPO. A two-peak LED was used; degree of conversion (DC) and the maximum polymerization rate (RPmax) were determined by near infrared spectroscopy. For the yellowing degree a spectrophotometer was used. Water sorption (Wsp) was obtained after 30 days of water storage (n=5). Data were submitted to two-way analysis of variance and Tukey’s test (a=0.05). BAPO presented the highest DC and RPmax values for both series. SAFCs presented lower DC and RPmax for CQ+EDMAB-based materials. Greater yellowing was observed for SAFCs compared with CFCs, except for BAPO. Greater Wsp was observed for SAFCs compared with CFCs. The photoinitiator did not influence Wsp for CFCs, but TPO and BAPO presented the highest Wsp in SAFCs. The photoinitiator system affected differently the physical-chemical properties of CFCs and SAFCs.

Resumo O objetivo do estudo foi determinar a influência do sistema fotoiniciador sobre as propriedades físico-químicas de compósitos fluidos. Os compósitos convencionais foram compostos por bisfenol-glicidil dimetacrilato (BisGMA) + trietilenoglicol dimetacrilato (TEGDMA), e os autoadesivos, apresentavam BisGMA +TEGDMA+ Bis2(metacriloiloxi)etil fosfato (2 MP). Cinco sistemas fotoiniciadores foram testados: canforquinona + etil-4- dimetilamino benzoato (CQ+EDMAB), óxido mono-alquil fosfínico (TPO) e óxido bis-alquil fosfínico (BAPO), CQ+EDMAB+TPO e CQ+EDMAB+BAPO. LED de amplo espectro foi usado; o grau de conversão (GC) e a taxa de polimerização (TP) foram determinados por espectroscopia próximo ao infravermelho; o grau de amarelo foi mensurado por um espectrofotômetro e absorção de água foi obtida após 30 dias de armazenamento em água (n=5). Os dados foram submetidos a análise de variância de dois fatores e teste de Tukey (?=0,05). BAPO apresentou os maiores valores de GC e TP nos compósitos convencionais e autoadesivos. Compósitos autoadesivos apresentaram menor GC e TP quando CQ+EDMAB foi usado. Maior amarelecimento foi observado nos compósitos autoadesivos em relação aos convencionais, exceto para BAPO. Compósitos autoadesivos promoveram maior absorção de água. Não houve influência dos fotoiniciadores nos compósitos convencionais, no entanto TPO e BAPO apresentaram os maiores valores de absorção de água nos compósitos autoadesivos. Os sistemas fotoiniciadores influenciaram de maneira diferente as propriedades físico-químicas dos compósitos convencionais e autoadesivos.

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins.

OBJECTIVES: The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. METHODS: A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R(p)(max)) profile of the model resin. RESULTS: In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ+EDAB exhibited higher DC and R(p)(max) values. In formulations that contained ternary initiator systems, the group CQ+QTX+EDAB was the only one of the investigated experimental groups that exhibited an R(p)(max) value greater than that of CQ+EDAB. The groups QTX+EDAB+DPIHFP and QTX+DPIHFP+SULF exhibited values similar to those of CQ+EDAB with respect to the final DC; however, they also exhibited lower reactivity. SIGNIFICANCE: Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations.

Surface integrity of solvent-challenged ormocer-matrix composite.

OBJECTIVE: To investigate the surface integrity of solvent-challenged ormocer-matrix composites, photoactivated by different light exposure modes, through surface-hardness measurements at different periods of time; and to compare such behavior with dimethacrylate-based materials. METHODS: One hundred percent ormocer-based matrix (experimental ormocer (ORM)), a commercial mixed dimethacrylate-ormocer-based matrix (Admira (ADR)) and two commercial dimethacrylate-based matrix composites (experimental controls, (Grandio (GRD) and Premise (PRE)) were evaluated. Disk specimens (4 mm × 2 mm) were prepared from each material and light-activated using either a standard (S) or soft-start (SS) light exposure protocol with an LED-curing unit. Top, irradiated surface Knoop hardness (KHN) was measured within the following experimental groups (n=5): Group 1: immediately after exposure; Group 2: after dry and dark storage, Group 3: after storage in distilled water, and Group 4: immersion in absolute ethanol. Hardness of Groups 2-4 were measured after 7 days storage. Immediate hardness values were submitted to Student's t-tests separately for each material. Hardness values after treatments were submitted to two-way ANOVA and Tukey's post hoc test to compare values among different storage media and light exposure mode protocols. Comparisons among materials were described using percentage of hardness change. Statistical testing was performed at a pre-set alpha of 0.05. RESULTS: Immediate hardness values were not affected by the light exposure mode, regardless of the material. In general, exposure mode did not significantly affect hardness after 7 days storage, regardless of storage media or material. After 7 days dry storage, hardness values increased for all materials relative to immediate testing, and decreased after water and ethanol storage, with ethanol showing the greatest effect. The experimental ormocer-based material had the lowest percentage hardness change and thus proved more resistant to solvent degradation than the other materials, regardless of the light exposure method. SIGNIFICANCE: Irradiated surface hardness values and surface integrity were unaffected by light exposure mode, regardless of the material tested. The experimental ormocer-based material presented the least change in hardness as a result of solvent challenge than any of the commercial products: ormocer or conventional resin-based, and thus showed better surface integrity.