Photoinduced free radical-releasing systems and their anticancer properties.

Cancer has been a serious threat and impact on the health and life of human. Phototherapy is considered as a promising therapeutic method to replace the traditional treatment in clinic owing to its noninvasive nature and high efficiency. Photoinitiators have long been used in the field of photopolymerization; however, few studies have been carried out on their potential as anticancer agents under light irradiation. In this study, the effect of a photoinitiator, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide (TPO), on breast cancer is investigated and the related mechanism is elucidated. It is found that TPO has low dark toxicity and significant phototoxicity. TPO can inhibit cell growth and development and promote cell apoptosis through a mitochondrial pathway under light irradiation. Further studies show that cell apoptosis is induced by free radicals produced from the photolysis of TPO to activate JNK phosphorylation. Overall, we identify the antitumor effects of TPO in vitro for the first time, and provides a proof of concept for its application as a novel photolatent therapeutic drug.

Effect of Light-Curing Unit Type and Bulk-Fill Composite Resins with Different Photoinitiators on Marginal Gaps of Class II Restorations

Abstract Objective: To evaluate the effect of two types of light-curing units (second and third generations) and two types of bulk-fill composite resins with different photoinitiators - Tetric N-Ceram Bulk Fill (TNCB) and Xtra Fil (XTF) on gap formation at the gingival margins of Cl II restorations. Material and Methods: Fifty-six standard Cl II cavities were prepared on the mesial and distal surfaces of premolar teeth, with the gingival margin of the cavities 1 mm apical to the CEJ. The samples were randomly assigned to two groups based on the composite resin type and two subgroups based on the light-curing unit type and restored. After 5000 rounds of thermocycling, gingival margin gap in each sample was measured in µm under an electron microscope at ×2000 magnification. Data were analyzed by two-way ANOVA and Tukey tests (α=0.05). Results: Marginal gaps of TNCB composite resin were significantly smaller than those of XTF composite resin (p<0.001). There were no significant differences between the two light-curing units in each group (p=0.887 with XTF and p=0.999 with TNCB). Conclusion: The gaps at gingival margins of Cl II cavities with TNCB bulk-fill composite were smaller than XTF composite resin. Both composite resins can be cured with both the second- and third-generation LEDs (AU).

Cytotoxicity and genotoxicity of DMABEE, a co-photoinitiator of resin polymerization, on CHO-K1 cells: Role of redox and carboxylesterase.

The 4-dimethylaminobenzoic acid ethyl ester (DMABEE) is an important co-initiator for resin polymerization in dental resinous materials. As a radical forming chemical with high lipophilicity, the genotoxicity and cytotoxicity of DMABEE deserve prudent investigation. In this study, we found that DMABEE reduced the viability and proliferation of Chinese hamster ovary (CHO-K1) cells in a dose-dependent manner, and altered cell morphology at higher concentrations. G0/G1 cell cycle arrest was induced by DMABEE at 0.25-0.75 mM, and cell proportion of sub-G0/G1 phase was significantly elevated at 1 mM while cell apoptosis was observed. Genotoxic effect was noted when cells were treated by 0.1 mM DMABEE, as revealed by increase of micronucleus formation. Reactive oxygen species overproduction was observed as cells treated with 0.75 and 1 mM, while elevation of intracellular glutathione was noticeable since 0.1 mM. Contrary to our expectation, pretreatment by N-acetyl-l-cysteine enhanced the toxicity of DMABEE on CHO-K1 cells. Catalase mildly reduced the toxic effect and carboxylesterase showed obvious ability to reverse the toxicity of DMABEE. These findings highlight the mechanism of DMABEE toxicity and provide clues for safety improvement of its application in clinical dental treatment.

Light curing resin cements containing iodonium salts promote suitable apical bonding of posts to radicular dentin.

The aim of this study was to analyze the efficiency of experimental light-curing resin cements (ERCs) with a ternary photo-initiator system containing diphenyliodonium hexafluorphosphate (DPI) and different amines on retention of glass-fiber posts to dentin (GFP). ERCs formulations: a 1:1 mass ratio of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenylpropane and triethyleneglycol dimethacrylate. Camphorquinone was used as initiator. Six experimental groups were established according to the amine used: [ethyl-4-(dimethylamino)benzoate-EDMAB or 2-(dimethylamino)ethyl methacrylate-DMAEMA] and the concentration of DPI (0, 0.5 mol%, 1 mol%). The resin cements Variolink II (dual- and light-cured versions) were used as commercial reference. Eighty recently extracted bovine incisors (n = 10) were selected for this study. The roots were prepared and the fiber posts were cemented with the resin cement specified for each experimental group. Specimens from coronal, middle, and apical thirds of the root were subjected to push-out bond strength test 24 hours after bonding. Data were subjected to split-plot ANOVA and the Tukey test (p = 0.05). ERCs containing DPI showed statistically significant higher bond strengths compared with ERCs without DPI. ERCs containing DPI were statistically similar to VARIOLINK II - dual-cured and superior to VARIOLINK II - light-cured (except for EDMAB - 1DPI in the medium third and DMAEMA - 1DPI in the coronal third). Different amines did not influence post retention. The apical root region showed the lowest bond strength for the groups EDAB-0DPI, DMAEMA-0DPI and VARIOLINK II light-cured. Light-cured ERCs containing DPI were efficient for GFP retention to radicular dentin, with similar behaviour to that of dual-curing commercial resin cement.

Structure-properties relationships in dental adhesives: Effect of initiator, matrix monomer structure, and nano-filler incorporation.

OBJECTIVES: This is a confirmatory study to evaluate the effect of photoinitiator type and concentration, matrix monomer chemical structure, and nanoparticle incorporation on the physical and mechanical properties of an experimental dentin bonding agent. MATERIALS AND METHODS: Different concentrations of camphorquinone-amine (CQ-A) system, butanedione (BD), and phenylpropanedione (PPD), as photoinitiator, BTDMA, as a comonomer containing carboxylic acid groups, and silica nanoparticles as reinforcing inorganic filler were incorporated into a methacrylate base experimental dental adhesive. The effect of these ingredients, as independent variables, on the shrinkage kinetics, flexural strength and modulus, and microshear bond strength of the adhesives were then investigated. The results were analyzed using one-way ANOVA and Tukey's post-hoc test at the significance level of 0.05. RESULTS: The results indicate that the efficiency of CQ-A initiator system is diminished in the presence of the acidic monomer BTDMA while the photopolymerization is efficiently progressed with BD as initiator. PPD shows the lowest efficiency in the photopolymerization of the adhesives. BTDMA as a monomer with the capability of interaction with tooth structure provides adhesive with improved microshear bond strength to dentin. Incorporation of silica nanoparticles at low concentrations enhances the flexural and microshear strength of the dentin bonding agent. SIGNIFICANCE: Understanding the structure-property relationship in dental adhesives may help the material selection in clinical dentistry. The study elucidates the relationship between monomer structure, initiator type, and nanofiller and physical and mechanical properties in dental adhesives.

Polymerization efficiency affects interfacial fracture toughness of adhesives.

OBJECTIVE: To evaluate the effect of the kind and concentration of photo-initiator on the degree of conversion (DC) of adhesives on dentin/glass substrates and their mini-interfacial fracture toughness (mini-iFT) to dentin. METHODS: We tested the adhesive Clearfil S3 Bond Plus and 4 derived experimental 'LUB' ('Leuven Univesity Bond') adhesives (all from Kuraray Noritake), namely 'LUB-CQ/amine_high', 'LUB-CQ/amine_low', 'LUB-TPO_high', and 'LUB-TPO_low', respectively containing 2.0wt% camphorquinone (CQ) and 2.0wt% EDMAB (amine), 0.35wt% CQ and 0.35wt% amine, 2.0wt% TPO, and 0.35wt% TPO. For DC, each adhesive was applied onto glass or dentin prior to being cured (Bluephase 20i; Ivoclar Vivadent: "high mode") for 10s. DC was measured at 5min, 10min, 1h, 24h and 1 week using micro-Raman spectroscopy (SENTERRA; BrukerOptik). For mini-iFT, each adhesive was bonded to 320-grit SiC-paper ground dentin and covered with composite (Z100; 3M ESPE). The restored teeth were cut in sticks (1.5×2.0×16mm), after which a single-gradient notch was prepared at the adhesive-dentin interface using a 150-µm diamond blade. The micro-specimens were loaded until failure in a 4-point bending test and the mini-iFT in term of KQvM was calculated. RESULTS: DC was higher on dentin than on glass. All adhesives were adequately polymerized at 1 week, except for LUB-TPO_low. DC at 5min was significantly higher for LUB-TPO_high than for both CQ/amine-based adhesives. The highest and most reliable mini-iFT was measured for LUB-CQ/amine_high, despite its 5-min DC was relatively low. No correlation between DC and mini-iFT was found. SIGNIFICANCE: Curing of TPO-based adhesives is faster, but the dark cure of the CQ/amine-containing adhesives is more efficient. The differences in curing profiles do affect the mechanical properties of the resultant interfaces at dentin.

Light curing resin cements containing iodonium salts promote suitable apical bonding of posts to radicular dentin

Abstract The aim of this study was to analyze the efficiency of experimental light-curing resin cements (ERCs) with a ternary photo-initiator system containing diphenyliodonium hexafluorphosphate (DPI) and different amines on retention of glass-fiber posts to dentin (GFP). ERCs formulations: a 1:1 mass ratio of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenylpropane and triethyleneglycol dimethacrylate. Camphorquinone was used as initiator. Six experimental groups were established according to the amine used: [ethyl-4-(dimethylamino)benzoate-EDMAB or 2-(dimethylamino)ethyl methacrylate-DMAEMA] and the concentration of DPI (0, 0.5 mol%, 1 mol%). The resin cements Variolink II (dual- and light-cured versions) were used as commercial reference. Eighty recently extracted bovine incisors (n = 10) were selected for this study. The roots were prepared and the fiber posts were cemented with the resin cement specified for each experimental group. Specimens from coronal, middle, and apical thirds of the root were subjected to push-out bond strength test 24 hours after bonding. Data were subjected to split-plot ANOVA and the Tukey test (p = 0.05). ERCs containing DPI showed statistically significant higher bond strengths compared with ERCs without DPI. ERCs containing DPI were statistically similar to VARIOLINK II - dual-cured and superior to VARIOLINK II - light-cured (except for EDMAB - 1DPI in the medium third and DMAEMA - 1DPI in the coronal third). Different amines did not influence post retention. The apical root region showed the lowest bond strength for the groups EDAB-0DPI, DMAEMA-0DPI and VARIOLINK II light-cured. Light-cured ERCs containing DPI were efficient for GFP retention to radicular dentin, with similar behaviour to that of dual-curing commercial resin cement.

Light curing in dentistry and clinical implications: a literature review.

Contemporary dentistry literally cannot be performed without use of resin-based restorative materials. With the success of bonding resin materials to tooth structures, an even wider scope of clinical applications has arisen for these lines of products. Understanding of the basic events occurring in any dental polymerization mechanism, regardless of the mode of activating the process, will allow clinicians to both better appreciate the tremendous improvements that have been made over the years, and will also provide valuable information on differences among strategies manufacturers use to optimize product performance, as well as factors under the control of the clinician, whereby they can influence the long-term outcome of their restorative procedures.

Light curing in dentistry and clinical implications: a literature review

Abstract Contemporary dentistry literally cannot be performed without use of resin-based restorative materials. With the success of bonding resin materials to tooth structures, an even wider scope of clinical applications has arisen for these lines of products. Understanding of the basic events occurring in any dental polymerization mechanism, regardless of the mode of activating the process, will allow clinicians to both better appreciate the tremendous improvements that have been made over the years, and will also provide valuable information on differences among strategies manufacturers use to optimize product performance, as well as factors under the control of the clinician, whereby they can influence the long-term outcome of their restorative procedures.

Light-emitting Diode Beam Profile and Spectral Output Influence on the Degree of Conversion of Bulk Fill Composites.

OBJECTIVES: To evaluate the beam profile and the spectral output of monowave and polywave light-emitting diodes (LEDs) and their influence on the degree of conversion (DC) of bulk fill composites. METHODS: A monowave LED (Smartlite Focus, Dentsply) and a polywave LED (Valo Cordless, Ultradent) were characterized using a resin calibrator and a laser beam profile analyzer. Two bulk fill composites, Sonic Fill 2 (SF) containing camphorquinone (CQ) and Tetric EvoCeram Bulk Fill (TEB) containing CQ associated with alternative photoinitiators, were placed in custom-designed molds (n=3) and photoactivated by the monowave or polywave LED with 20 J/cm2. To map the DC, longitudinal cross sections (0.5 mm thick) from the center of the restoration were evaluated using FT-NIR microscopy. SF and TEB light transmittances (n=3) through 4-mm-thick specimens were evaluated during curing. Data were analyzed using a split-plot analysis of variance and Tukey test (α=0.05; ß=0.2). RESULTS: The monowave LED had a radiant emittance of 20 ± 0.5 J/cm2 over 420-495 nm, and the polywave LED had an emittance of 15.5 ± 0.4 J/cm2 over 420-495 nm and of 4.5 ± 0.2 J/cm2 over 380-420 nm. The total radiant exposure at the bottom of TEB was 2.2 ± 0.2 J/cm2 with the monowave LED and 1.6 ± 0.3 J/cm2 with the polywave LED, and for SF it was 0.4 ± 0.1 J/cm2 for both LEDs. There were no differences in the curing profiles produced either by the monowave or the polywave LED (p=0.9), according to the regions under influence of blue and/or violet emission at the same depth. There was no statistical difference in the DC for SF using the monowave or polywave LED at any depth (p=0.29). TEB had a higher DC at up to 2 mm in depth when the polywave LED was used (p<0.004), but no differences were found when starting at 2.5 mm. CONCLUSIONS: Monowave and polywave LEDs emitted nonhomogeneous light beams, but this did not affect the DC homogeneity of bulk fill composites. For composites containing CQ associated with alternative photoinitiators, polywave LEDs had a higher DC, but only at the top part of the restoration; lower wavelength absorption photoinitiators were ineffective in deeper areas.

Effects of radiant exposure values using second and third generation light curing units on the degree of conversion of a lucirin-based resin composite.

OBJECTIVE: Using Fourier transform infrared analysis (FTIR) in vitro, the effects of varying radiant exposure (RE) values generated by second and third generation LED LCUs on the degree of conversion (DC) and maximum rate of polymerization (Rpmax) of an experimental Lucirin TPO-based RC were evaluated. MATERIAL AND METHODS: 1 mm or 2 mm thick silicon molds were positioned on a horizontal attenuated total reflectance (ATR) unit attached to an infrared spectroscope. The RC was inserted into the molds and exposed to varying REs (18, 36 and 56 J/cm2) using second (Radii Plus, SDI) and third generation LED LCUs (Bluephase G2/Ivoclar Vivadent) or a quartz tungsten based LCU (Optilux 501/SDS Kerr). FTIR spectra (n=7) were recorded for 10 min (1 spectrum/s, 16 scans/spectrum, resolution 4 cm-1) immediately after their application to the ATR. The DC was calculated using standard techniques for observing changes in aliphatic to aromatic peak ratios both prior to, and 10 min after curing, as well as during each 1 second interval. DC and Rpmax data were analyzed using 3-way ANOVA and Tukey's post-hoc test (p=0.05). RESULTS: No significant difference in DC or Rpmax was observed between the 1 mm or 2 mm thick specimens when RE values were delivered by Optilux 501 or when the 1 mm thick composites were exposed to light emitted by Bluephase G2, which in turn promoted a lower DC when 18 J/cm2 (13 s) were delivered to the 2 mm thick specimens. Radii Plus promoted DC and Rpmax values close to zero under most conditions, while the delivery of 56 J/cm2 (40 s) resulted in low DC values. CONCLUSIONS: The third generation LCU provided an optimal polymerization of Lucirin TPO-based RC under most tested conditions, whereas the second generation LED-curing unit was useless regardless of the RE.

Effects of radiant exposure values using second and third generation light curing units on the degree of conversion of a lucirin-based resin composite

Abstract Alternative photoinitiators with different absorption wavelengths have been used in resin composites (RCs), so it is crucial to evaluate the effectiveness of light-curing units (LCUs) on these products. Objective Using Fourier transform infrared analysis (FTIR) in vitro, the effects of varying radiant exposure (RE) values generated by second and third generation LED LCUs on the degree of conversion (DC) and maximum rate of polymerization (Rpmax) of an experimental Lucirin TPO-based RC were evaluated. Material and Methods 1 mm or 2 mm thick silicon molds were positioned on a horizontal attenuated total reflectance (ATR) unit attached to an infrared spectroscope. The RC was inserted into the molds and exposed to varying REs (18, 36 and 56 J/cm2) using second (Radii Plus, SDI) and third generation LED LCUs (Bluephase G2/Ivoclar Vivadent) or a quartz tungsten based LCU (Optilux 501/SDS Kerr). FTIR spectra (n=7) were recorded for 10 min (1 spectrum/s, 16 scans/spectrum, resolution 4 cm-1) immediately after their application to the ATR. The DC was calculated using standard techniques for observing changes in aliphatic to aromatic peak ratios both prior to, and 10 min after curing, as well as during each 1 second interval. DC and Rpmax data were analyzed using 3-way ANOVA and Tukey’s post-hoc test (p=0.05). Results No significant difference in DC or Rpmax was observed between the 1 mm or 2 mm thick specimens when RE values were delivered by Optilux 501 or when the 1 mm thick composites were exposed to light emitted by Bluephase G2, which in turn promoted a lower DC when 18 J/cm2 (13 s) were delivered to the 2 mm thick specimens. Radii Plus promoted DC and Rpmax values close to zero under most conditions, while the delivery of 56 J/cm2 (40 s) resulted in low DC values. Conclusions The third generation LCU provided an optimal polymerization of Lucirin TPO-based RC under most tested conditions, whereas the second generation LED-curing unit was useless regardless of the RE.

Influence of Different Photoinitiators on Polymerization Kinetics and Marginal Microleakage in Restorations using Photopolymerizable Dental Composites

Objective: To evaluate the influence of four different photoinitiators on the polymerization kinetics and marginal microleakage in class V restorations using photopolymerizable dental composites. Material and Methods: Four photopolymerizable dental composites based on Bis-GMA (14.5 wt %), UDMA (6.5 wt %) and silanized filler particles (79 wt %) containing different photoinitiators were formulated. Camphorquinone (CQ)/amine, phenyl-propanedione (PPD), monoacylphosphine oxide (Lucirin® TPO) and bisacylphosphine oxide (Irgacure® 819) were used as photoinitiators. Sixteen intact human third molars were selected and divided into four groups. All teeth received class V cavity preparations in their buccal and lingual surfaces and were submitted to a dye leakage test. Data were independently analyzed for both enamel and dentin, and the results were assessed by a Kruskal-Walis test. The polymerization reactions of the four composites were evaluated by differential scanning calorimeter coupled with photocalorimeter accessory. Results: Lucirin® TPO presented the highest scores for microleakage in enamel, whereas the other photoinitiators have not demonstrated statistical differences. The lowest scores were obtained for PPD in dentin while the highest scores have been achieved by Irgacure® 819 and Lucirin® TPO. Photocalorimetric measurements demonstrated a correlation between polymerization reaction rate and marginal leakage, showing that faster reactions cause greater marginal leakage. Conclusion: Marginal microleakage scores in photopolymerizable dental composites can be greatly influenced by different types of photoinitiators through their distinct reaction rates.

Evaluation of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental dental resin-based materials

ABSTRACT Objective To evaluate the influence of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental resin-based materials photoactivated using different light curing units (LCUs). Material and Methods Experimental resin-based materials with the same organic matrix (60:40 wt% BisGMA:TEGDMA) were mechanically blended using a centrifugal mixing device. To this blend, different photoinitiator systems were added in equimolar concentrations with aliphatic amine doubled by wt%: 0.4 wt% CQ; 0.38 wt% PPD; or 0.2 wt% CQ and 0.19 wt% PPD. The degree of conversion (DC), flexural strength (FS), Young’s modulus (YM), Knoop hardness (KNH), crosslinking density (CLD), and yellowing (Y) were evaluated (n=10). All samples were light cured with the following LCUs: a halogen lamp (XL 2500), a monowave LED (Radii), or a polywave LED (Valo) with 16 J/cm2. The results were analysed by two-way ANOVA and Tukey’s test (α=0.05). Results No statistical differences were found between the different photoinitiator systems to KNH, CLS, FS, and YM properties (p≥0.05). PPD/CQ association showed the higher DC values compared with CQ and PPD isolated systems when photoactivated by a polywave LED (p≤0.05). Y values were highest for the CQ compared with the PPD systems (p≤0.05). Conclusion PPD isolated system promoted similar chemical and mechanical properties and less yellowing compared with the CQ isolated system, regardless of the LCU used.

High-performance 3D printing of hydrogels by water-dispersible photoinitiator nanoparticles.

In the absence of water-soluble photoinitiators with high absorbance in the ultraviolet (UV)-visible range, rapid three-dimensional (3D) printing of hydrogels for tissue engineering is challenging. A new approach enabling rapid 3D printing of hydrogels in aqueous solutions is presented on the basis of UV-curable inks containing nanoparticles of highly efficient but water-insoluble photoinitiators. The extinction coefficient of the new water-dispersible nanoparticles of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) is more than 300 times larger than the best and most used commercially available water-soluble photoinitiator. The TPO nanoparticles absorb significantly in the range from 385 to 420 nm, making them suitable for use in commercially available, low-cost, light-emitting diode-based 3D printers using digital light processing. The polymerization rate at this range is very fast and enables 3D printing that otherwise is impossible to perform without adding solvents. The TPO nanoparticles were prepared by rapid conversion of volatile microemulsions into water-dispersible powder, a process that can be used for a variety of photoinitiators. Such water-dispersible photoinitiator nanoparticles open many opportunities to enable rapid 3D printing of structures prepared in aqueous solutions while bringing environmental advantages by using low-energy curing systems and avoiding the need for solvents.

Photopolymerization study and adhesive properties of self-etch adhesives containing bis(acyl)phosphine oxide initiator.

OBJECTIVE: This paper investigates the photo-co-polymerization behavior of a blend of a diacrylamide (DEBAAP) with a phosphonylated acidic monomer using either bis(acyl)phosphine oxide or camphorquinone/amine as photo-initiator and studies the effect of variation of the structure of the phosphonylated acidic monomer on the shear bond strength to human dentin. METHODS: Photopolymerization kinetics has been assessed through the use of photo-DSC with either initiating system and with and without a phosphonic acid monomer, while the shear bond strengths (SBS) of dentin bonding agents formulated with several phosphonylated acidic monomers have been evaluated by macro SBS testing on human dentin. RESULTS: Photo-DSC results show that bis(acyl)phosphine oxide initiates a faster polymerization than camphorquinone/amine and that both photopolymerizations are accelerated by the phosphonic acid monomer. Similar results were obtained between adhesives based on camphorquinone/amine and a commercial adhesive (AdheSE, Ivoclar-Vivadent, Schaan, Liechtenstein). The best performances were obtained when BAPO was used as the initiator, in many cases far better than the commercial adhesive. Adhesive SEA6 based on difluoromethylphosphonic acid C demonstrated the best adhesion results of this study. Significance The bis(acyl)phosphine oxide photo-initiator causes faster photopolymerization of two-step self-etching dental adhesive, and its use could yield better bonding performance.

Influência dos sistemas fotoiniciadores sobre as propriedades físicas e mecânicas de cimentos resinosos fotoativados por diferentes fontes de luz / Effect of light curing units on the physical and mechanical properties of lutting resin cements containing different photoinitiators systems

A utilização de sistemas iniciadores alternativos na composição de cimentos resinosos fotoativados tem por objetivo melhorar as propriedades químicas, mecânicas e estéticas dos agentes de cimentação odontológicos, reduzindo os aspectos desfavoráveis do sistema iniciador convencional, canforoquinona/amina. Para isso, um correto relacionamento entre o espectro de emissão da fonte de luz e o espectro de absorção do fotoiniciador é fundamental. O presente estudo tem como objetivo, através de uma revisão de literatura, avaliar as possíveis alterações físicas e mecânicas atribuídas a agentes de cimentação resinosos fotoativados, contendo diferentes sistemas fotoiniciadores sob efeito de diferentes tipos de fonte de luz...

The use of alternative initiator systems in the composition of luting resin cements aims to improve chemical, mechanical, and aesthetic properties of dental cementation agents, reducing the drawbacks aspects of the conventional initiator system, canphorquinone/amine. Therefore the proper interaction between the light-curing units emission spectrum and the photo-initiator absorption spectrum is r. This study presents a literature review with the objective of evaluating the possible physical and mechanical changes on photoactivated resin cements, containing different photo-iniciators systems under the effect of different types of light sources...

Probing the dual function of a novel tertiary amine compound in dentin adhesive formulations.

OBJECTIVES: A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The synthesis, photopolymerization kinetics, and leaching were examined in an earlier study using this novel compound as the co-initiator (0.5 and 1.75wt% based on the total resin mass). The objective of this work was to investigate the potential of TUMA (8-(2-(((2-(methacryloyloxy)ethyl)carbamoyl)oxy)propyl)-6,10-dimethyl-4,12-dioxo-5,11-dioxa-3,8,13-triazapentadecane-1,15-diyl bis(2-methylacrylate)) to serve simultaneously as a co-initiator and co-monomer (15-45wt% based on the total resin mass) in dentin adhesive formulations. The polymerization kinetics, water sorption and dynamic mechanical properties of these novel formulations were determined. MATERIALS AND METHOD: The monomer system contained Bisphenol A glycerolate dimethacrylate (BisGMA), 2-hydroxyethylmethacrylate (HEMA) and TUMA (synthesized in our lab) at the mass ratio of 45/(55-x)/x. Two photoinitiator (PI) systems were compared. One initiator system contains three components: camphorquinone (CQ), diphenyliodonium hexafluorophosphate (DPIHP) and ethyl-4-(dimethylamino) benzoate (EDMAB) and the second initiator system contains CQ and DPIHP. The control adhesive formulations are: C0-3: HEMA/BisGMA 45/55 (w/w) and 3-component PI and C0-2: HEMA/BisGMA 45/55 (w/w) and 2-component PI. These controls were used as a comparison to the experimental adhesive resins (Ex-3 or Ex-2), in which x represents the weight percentage of synthesized co-monomer (TUMA) to replace part of BisGMA. The control and experimental adhesive formulations were photo-polymerized and compared with regard to the degree of conversion (DC), polymerization rate (Rp), water sorption and dynamic mechanical analysis (DMA) under both dry and wet conditions. RESULTS: C0-3 and Ex-3 formulations had similar DC, while the DC of Ex-2 formulation was higher than C0-2. The DC was similar when comparing the two- component with the three-component photoinitiator system when TUMA was used at the same concentration. DMA under dry conditions shows higher rubbery storage modulus for all experimental formulations, while storage modulus at rubbery region under wet conditions was decreased as compared with control (C0-3). There was no statistically significant difference for the DMA results under both dry and wet conditions when comparing two- and three-component initiator systems with the same TUMA concentration. SIGNIFICANCE: The newly synthesized TUMA could serve simultaneously as a co-monomer and co-initiator in the absence of commercial co-initiator. This study provides information for the future development of new co-monomer/co-initiator for dentin adhesives and dental composites.

Effect of resin and photoinitiator on color, translucency and color stability of conventional and low-shrinkage model composites.

OBJECTIVE: To study the effect of a low-shrinkage methacrylate monomer and monoacylphosphine oxide photoinitiator on color, translucency, and color stability of model resin-based composites (RBCs). METHODS: Four micro-hybrid RBCs were prepared containing barium-glass fillers in bisphenol A-glycidyl-methacrylate (BisGMA) and triethyleneglycol-dimethacrylate (TEGDMA) or urethane-based low-shrinkage monomer FIT-852 (FIT; Esstech Inc.) and TEGDMA matrix. Camphorquinone (CQ)/amine or Lucirin TPO were used as photoinitiators. Commercial low-shrinkage RBCs (Charisma Diamond, Heraeus Kulzer and N'Durance, Septodont) and conventional RBCs (Tetric EvoCeram, Ivoclar Vivadent and Filtek Z250, 3M ESPE) were used as controls. Color and translucency were measured using Thermo Scientific Evolution (Thermo Fisher Scientific) and SpectroShade™ Micro (MHT Optic Research) spectrophotometers. Color stability was evaluated after immersion in black tea (pure, with milk or lemon) and distilled water. Data were analyzed using analyses of variance with Tukey's post-test (α=0.05). RESULTS: Photoinitiators had no significant effect on baseline color. Initially whiter FIT-based RBCs showed greater staining in all staining solutions than BisGMA-based RBCs. TPO-containing RBCs showed better color stability than CQ-containing RBCs irrespective of the base monomer. Tea and tea with lemon induced greatest color changes. Adding milk to tea significantly reduced material staining. SIGNIFICANCE: Urethane-based low-shrinkage monomer FIT and conventional BisGMA affected color, translucency and color stability of their respective RBCs. Despite being used in posterior teeth, low-shrinkage RBCs are expected to have favorable optical and esthetic properties. Manufacturers are urged to provide information on optical properties of monomers and monomer mixtures in their low-shrinkage RBCs to allow understanding of interaction with fillers and photoinitiators.

Evaluation of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental dental resin-based materials.

OBJECTIVE: To evaluate the influence of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental resin-based materials photoactivated using different light curing units (LCUs). MATERIAL AND METHODS: Experimental resin-based materials with the same organic matrix (60:40 wt% BisGMA:TEGDMA) were mechanically blended using a centrifugal mixing device. To this blend, different photoinitiator systems were added in equimolar concentrations with aliphatic amine doubled by wt%: 0.4 wt% CQ; 0.38 wt% PPD; or 0.2 wt% CQ and 0.19 wt% PPD. The degree of conversion (DC), flexural strength (FS), Young's modulus (YM), Knoop hardness (KNH), crosslinking density (CLD), and yellowing (Y) were evaluated (n=10). All samples were light cured with the following LCUs: a halogen lamp (XL 2500), a monowave LED (Radii), or a polywave LED (Valo) with 16 J/cm2. The results were analysed by two-way ANOVA and Tukey's test (α=0.05). RESULTS: No statistical differences were found between the different photoinitiator systems to KNH, CLS, FS, and YM properties (p≥0.05). PPD/CQ association showed the higher DC values compared with CQ and PPD isolated systems when photoactivated by a polywave LED (p≤0.05). Y values were highest for the CQ compared with the PPD systems (p≤0.05). CONCLUSION: PPD isolated system promoted similar chemical and mechanical properties and less yellowing compared with the CQ isolated system, regardless of the LCU used.