Camphorquinone Research Articles

Carbazolyl α-diketones as novel photoinitiators in photopolymerization under LEDs

Novel photoinitiators (α-DKs) bearing α-dicarbonyl groups as initiating group and aromatic groups as chromophore group were synthesized and developed as visible light type I photoinitiators with high performance for radical photopolymerization of acrylate. α-DKs exhibit good absorption at 405 nm and higher initiation efficiency compared with commercial initiator camphorquinone (CQ) under LED sources. Meanwhile, α-DKs were found to efficiently photosensitize bis (4-methylphenyl) hexafluorophosphate (ION) and initiate both free radical polymerization and cationic polymerization.

Synthesis and Characterization of New Dental Composite for Dentistry Based on Unsaturated Monomers and Nano-fillers by Photopolymerization

In this study, dental nano-composite specimens were prepared by dispersion of various amounts of nano-sized fillers (HA, ZrO2, and SiO2) in a monomer system containing 60% Bis-GMA and 40% TEGDMA. 2,2 propyl bis-phenyl glycidyldimethacrylate (Bis-GMA) with unsaturated monomers were prepared. Camphor Quinone (CQ) of 1 wt %, 2-DiMethyl Amino Ethyl Methacrylate (DMAEMA) of 1 wt % have been applied in photo-initiation system for the purpose of initiating matrix resins’ co-polymerization. Wear resistance, flexural strength, hardness and compressive strength were measured. The results indicated an increase in the mechanical properties in the samples containing nano-size filler particles. It is interesting to note that, this improvement was observed at much lower nano-size filler content. Physicochemical properties, such as Solubility (SL), Water Sorption (WS) as well as the Volumetric Shrinkage (VS) have been examined. FT-IR as well as SEM have been utilized for implementing the characterization. SEM has been applied for showing particle size distribution as well as the particle agglomeration that is related to the treated nano-fillers in nano-composites. FT-IT is initially applied for identifying qualitative compositions regarding the nano-composites’ compositions. The Thermal stability of all dental nano-ocomposites was also studied using TGA and DSC techniques.

1,2‐Diketones as photoinitiators of both cationic and free‐radical photopolymerization under UV (392 nm) or Blue (455 nm) LEDs

ABSTRACTThe photoinitiation abilities of three 1,2‐diketones [i.e., acenaphthenequinone (ANPQ), aceanthrenequinone (AATQ), and 9,10‐phenanthrenequinone (PANQ)]‐based photoinitiating systems [PISs, with additives such as iodonium salt, N‐vinylcarbazole (NVK), tertiary amine, and phenacyl bromide (R‐Br)] for cationic photopolymerization and free‐radical photopolymerization under the irradiation of ultraviolet (UV; 392 nm) or blue (455 nm) light‐emitting diode (LED) bulb are investigated. All 1,2‐diketones studied exhibit ground state absorption that match with the emission spectra of UV (392 nm) or blue LED (455 nm) better than that of the well‐known blue‐light‐sensitive photoinitiator camphorquinone (CQ). In particular, AATQ/iodonium salt/NVK can show high photoinitiating ability (with epoxide conversion yield >70%) under the UV light irradiation due to the effect of NVK. In addition, 1,2‐diketone/iodonium salt (and optional NVK) systems are capable of initiating free‐radical photopolymerization of methacrylates, with conversions of 50–58%. Furthermore, some 1,2‐diketone/tertiary amine (and optional R‐Br) combinations are found to demonstrate high efficiency to initiate free‐radical photopolymerization, and 71% of methacrylate conversion can be achieved with PANQ/tertiary amine/R‐Br PIS. Some 1,2‐ketone‐based PISs can even exhibit higher efficiency than the CQ‐based systems. The photochemical mechanism of the radical generation from the 1,2‐diketone‐based PISs is investigated and found to be consistent with the related photopolymerization efficiency. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 792–802

Difference in Cell Viability between with and without Visible Light-irradiation by Camphorquinone (CQ)-containing Medium

Difference in Cell Viability between with and without Visible Light-irradiation by Camphorquinone (CQ)-containing Medium

Evaluation of alternative photoinitiator systems in two-step self-etch adhesive systems

ObjectiveThe aim of this study was to evaluate the effect of different photoinitiator systems on the cell viability and physico-chemical properties of an experimental adhesive resin of a two-step self-etch adhesive system. MethodsEight photoinitiators and coinitiators were evaluated, camphorquinone (CQ); ethyl-dimethylamino benzoate (EDAB); diphenyliodonium hexafluorophosphate (DPIHFP); 1,3-benzodioxole (BDO); piperonyl alcohol (AP); 1,3-diethyl-2-thiobarbituric acid (TBA); bisphenyl phosphinic oxide (BAPO); and diphenyl phosphinic oxide (TPO). Seven experimental adhesive resins (Bis-GMA:TEGDMA – 1:1 by wt%) were formulated by varying the initiation systems: RCQ+EDAB (control), RCQ+EDAB+DPHFP, RCQ+BDO, RCQ+AP, RCQ+TBA, RBAPO and RTPO. The cell viability of the different photoinitiators in their isolated form and after being incorporated into the adhesive resins was evaluated using the MTT assay. The degree of conversion within the hybrid layer (DC in situ) was evaluated by micro-Raman spectroscopy; the polymerization kinetics, by FTIR spectroscopy. The water sorption (Wsp) and solubility (Wsl) were calculated by using percentage of gain and loss of mass. Data were analyzed using One-way ANOVA and Kruskal-Wallis tests (α=0.05). ResultsWhen evaluated in their isolated form, the DPIHFP was considered cytotoxic in all concentrations evaluated. When incorporated into and adhesive resin, RCQ+TBA presented higher cell viability values than control and the highest values of DC in situ (p<0.05). Additionally, the use of CQ+TBA showed a higher cell viability when compared with the conventional CQ+EDAB system. SignificanceThe pair CQ+TBA could be potentially useful in the development of materials with improved biocompatibility.

Sulfinates and sulfonates as high performance co-initiators in CQ based systems: Towards aromatic amine-free systems for dental restorative materials

ObjectiveThe aim of our study is to develop amine-free photoinitiating systems (PISs) for the polymerization of representative dental methacrylate resins under blue light irradiation. PISs based on camphorquinone (CQ)/sulfinate and CQ/sulfonate, eventually in combination with an iodonium salt, are proposed and compared to the well-established CQ/amine system. The polymerization performances of thick (1.4 mm) samples of different methacrylate blends upon exposure to a commercial blue LED centered at 477 nm under air are described. Finally, the performances of the new developed PISs are evaluated for dental composites application. MethodsFTIR is used to monitor the photopolymerization profiles. ESR spectroscopy and electrochemical experiments are used to identify the radicals generated. Mechanical properties measurements and color stability measurements are carried out to determine the key properties of the dental composites prepared. Results and SignificianceThe performances of the new proposed PISs for the photopolymerization of thick (1.4 mm) samples of methacrylate upon exposure to a blue dental LED under air are excellent. Similar or better performances and bleaching properties are obtained with the new proposed amine-free systems compared to those reached with the CQ/amine reference system. Dental composites with excellent mechanical properties and exceptional color stability are obtained. The involved chemical mechanisms for the initiation step were also established.

Biocompatibility and cytotoxicity of novel photoinitiator π-conjugated dithienophosphole derivatives and their triggered polymers

Photoinitiators have widely been applied to industry, and now increasingly to clinical therapy. A novel high-performance photoinitiation system based on π-conjugated dithienophosphole derivatives (DTPs), including Ph-DTP and TPA-DTP, has recently been developed with high extinction coefficients and amazing polymerization initiating abilities at a relatively low dose in both the near-UV and visible light ranges, and TPA-DTP has better absorption characteristics than Ph-TPA. The purpose of this study was to evaluate cytotoxicity of DTPs and cytocompatibility of their initiated polymers by a MTT assay and calcein AM/propidium iodide staining. The cytotoxicity of Ph-DTP or TPA-DTP exposed to non-irradiation or irradiation is lower than bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BAPO) applied widely to industry. No obvious cytotoxicity was observed in the TPA-DTP-treated primary cells and various cell lines, while the activated Ph-DTP inhibited the cell viability and resulted in the massive cellular apoptosis and necrosis. Compared to camphorquinone (CQ) applied widely to clinical dental prosthetic restoration, the cytocompatibility of DTPs-photopolymerized BisGMA/TEGDMA polymers was inferior to CQ although their extracts exhibited low toxicity, indicating that TPA-DTP but not Ph-DTP is more suitable for industrial application. These results provide a novel insight into underlying potential application of DTPs to industrial deep polymerization or clinical tissue engineering rehabilitation.

Gelatin Type A from Porcine Skin Used as Co-Initiator in a Radical Photo-Initiating System.

In the present study, a different approach for the preparation of poly(ethylene glycol) diacrylate-gelatin (PEGDA-gelatin) hydrogels was investigated. Gelatin type A from porcine skin was used as the co-initiator of a radical photo-initiating system instead of the traditional aliphatic or aromatic amines. This became possible because, upon visible-light irradiation, the amine sequences within gelatin generate initiating free-radicals through the intermolecular proton transfer in a Norrish type II reaction with camphorquinone (CQ). PEGDA-gelatin hydrogels were prepared by visible-light-induced photopolymerization. The gelatin content in the precursor formulations was varied. The influence of gelatin on the kinetics of the photocuring reaction was investigated, and it was found that gelatin fastened the rate of polymerization at all concentrations. The covalent attachment of gelatin segments within the cross-linked hydrogels was evaluated by means of attenuated total reflectance-infrared spectroscopy (ATR-FTIR) spectroscopy after solvent extraction. The thermo-mechanical properties, as well as the swelling behavior and gel content, were also investigated.

Effect of diphenyliodonium hexafluorphosphate in the yellowing and properties of experimental resin cements

Aim: The yellowing effect is undesirable and can occur in the dental restoration margins when light-cured resin cements containing camphorquinone as photoinitiator is used. This study aimed to evaluate the effect of diphenyliodonium hexafluorphosphate (DPI) in photoinitiator systems that contained different concentrations of camphorquinone (CQ) and dimethylamino ethyl benzoate (EDAB) on resin cements. Methods: A base (1:1) of bisphenol A diglycidyl methacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) was obtained, and 60wt% of glass fillers was added. Eight formulations were obtained: RC1 (0.5mol% CQ / 1mol% EDAB), RC2 (0.5mol% CQ / 2mol% EDAB), RC3 (1mol% CQ / 1mol% EDAB), RC4 (1mol% CQ / 2mol% EDAB), and RC5 to RC8, which contained the same bases plus 0.5mol% DPI. Experimental resin cements were evaluated by the degree of conversion (DC), L*a*b* color analysis, water sorption (WS) and solubility (S), flexural strength, and Elastic Modulus. The data were analyzed by three-way ANOVA, Tukey’s and Mann-Whitney tests (α = 0.05). Results: The combination of DPI and 0.5mol% CQ increased DC in RC6 and L* in RC5 without increasing the WS and a* b* values. CQ at 1mol% showed higher values of b* and lower values of a*, except for RC3. Groups with 2mol% EDAB showed higher DC. Conclusion: The addition of DPI reduces CQ, generating a decreased yellowing effect, while maintaining adequate properties in the resin cements, especially with 2mol% EDAB.

Aryliodonium Ylides as Novel and Efficient Additives for Radical Chemistry: Example in Camphorquinone (CQ)/Amine Based Photoinitiating Systems

Diaryliodonium salts are well-established compounds in free radical chemistry and are already used as photoinitiators (free radical or cationic polymerization), but the presence of counter anions is a strong drawback. Indeed, a counter anion is always required (e.g., SbF6−) leading to potential toxicity issues or release of HF. In the present paper, counter anion-free and fluoride-free aryliodonium salts are proposed, that is, aryliodonium ylides (AY) are studied here as new and efficient additives for radical chemistry and an example is provided for the camphorquinone (CQ)/amine based photoinitiating systems (PISs) for the polymerization of thick (1.4 mm) and thin (20–13 µm) methacrylates under air and blue light irradiation. The newly proposed PISs, for example, CQ/amine/AY, presented excellent polymerization performances and good bleaching properties were obtained after polymerization. Real-time Fourier transform infrared spectroscopy (RT-FTIR) was used to monitor the photopolymerization profiles. The chemical mechanisms involved were investigated using electron spin resonance (ESR).

Synthesis and quantitative analyses of acrylamide-grafted poly(lactide-co-glycidyl methacrylate) amphiphilic copolymers for environmental and biomedical applications.

Bio-degradable/bio-compatible poly(lactide-co-glycidyl methacrylate), P(LA-co-GMA), a copolymer has been synthesized. The material contains curable CC groups, which enable its self-curing and grafting reactions with other vinyl monomers. The copolymer was grafted with a pH-responsive polyacrylamide (PAAm), by UV-assisted reactions using acrylamide (AAm) and N,N'-methylene bisacrylamide monomers, and various photoinitiator systems. The original copolymer and its partially-cured counterpart were employed in the grafting reaction. Chemical structures and properties of the resulting materials were characterized. Standard quantitative analysis techniques for measurement of the grafted AAm content and the degree of CC conversion have been developed by 1H NMR and FTIR spectroscopy. FTIR offers more advantages, in terms of non-destructive analysis, ease of operation, and lower cost of analysis. The results show that the grafted products from pre-cured P(LA-co-GMA) copolymers contain higher grafted AAm contents than their uncured counterparts. The highest grafted AAm content was obtained by using benzophenone (BP) as an initiator, while camphorquinone (CQ) led to the lowest content. In contrast, the degree of CC conversion of the copolymer from the two initiator systems shows a reverse trend. These amphiphilic and pH-responsive grafted copolymers with tunable AAm contents have a high potential for use in various applications, especially in biomedical and environmental fields.

Mechanical properties of experimental resin cements containing different photoinitiators and co-initiators.

AimThe aim of this study was to evaluate the influence of different concentrations of two photoinitiators and one co-initiator on the flexural strength (FS) and elastic modulus (E) of experimental resin cements.Materials and methodsA mixture containing BisGMA, TEGDMA, and barium-aluminum-silicate (BaAlSi) and silanized colloidal silica (SiO2) filler particles was prepared with two photoinitiators, viz. camphorquinone (CQ) and bisacylphosphine oxide (BAPO). Dimethylaminoethyl methacrylate (DMAEMA) was used as co-initiator. Thirty groups (n=10) were formulated with different photoinitiator systems (CQ/DMAEMA and BAPO/DMAEMA) and concentrations (wt%) of photoinitiator and co-initiator. The photoactivation was carried out for 20 s with a light-emitting diode (LED, Bluephase, Ivoclar Vivadent) with irradiance of 1200 mW/cm2. The FS and E were obtained in a three-point bending test on a universal testing machine (0.5 mm/min). Data were subjected to the Kolmogorov-Smirnov normality test, followed by two-way ANOVA and Tukey’s test (α=0.05).ResultsNo polymerization occurred in the CQ groups without DMAEMA (0 wt%). DMAEMA 0.5 %wt and 1 %wt groups showed statistically similar FS and E results for CQ and BAPO, except for CQ 0.3 wt% (FS), CQ 0.9wt% (E) and BAPO 1.76 wt% (FS and E) for DMAEMA 0.5 %wt. No significant difference was found for FS and E values for different concentrations of photoinitiators, except for CQ 0.25 wt% (FS and E) and BAPO 0.25 wt% (E) that showed the lowest values.ConclusionThe wt% of the photoinitiators and co-initiator influenced the mechanical properties and the performance of CQ was dependent on the DMAEMA concentration. BAPO can be used as substitute for the conventional CQ/DMAEMA photoinitiator system.

Airborne exposure to gaseous and particle‐associated organic substances in resin‐based dental materials during restorative procedures

Dental composite dust has been shown to act as a vehicle for methacrylates in vivo/in vitro. The objective of this study was to assess airborne exposure of dental personnel to gaseous and particle-associated organic constituents from resin-based dental materials in a simulated clinic. Sampling of total aerosol fractions and gaseous substances was performed by dental students carrying particle filters and gas sorbents attached to a personal pump during preclinical restorative procedures in phantom models (n=13). Water from the phantoms was sampled. Organic substances were extracted from the sampled water, particle filters, and gas sorbents. Qualitative and quantitative analyses were performed by gas chromatography-mass spectrometry (GC-MS) and ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MS). The methacrylates 2-hydroxyethyl methacrylate (HEMA) and triethylene glycol dimethacrylate (TEGDMA) and the additives camphorquinone (CQ), butylated hydroxytoluene (BHT), and ethyl 4-(dimethylamino)benzoate (DMABEE), were quantified in the gas and particle fractions sampled. A positive-control experiment was conducted. No methacrylates were detected in the gas or particle fractions sampled, whereas strong signals for methacrylates were detected in the positive controls, matching the analysis of the uncured material. In addition, TEGDMA and DMABEE were quantified in the sampled water. Airborne exposure to constituents in resin-based dental materials was below the detection limit. However, the extent of exposure is probably dependent on the procedure, preventive measures, and type of materials used.

Iodonium sulfonates as high‐performance coinitiators and additives for CQ‐based systems: Toward aromatic amine‐free photoinitiating systems

ABSTRACTIodonium sulfonates are proposed here as a new class of high‐performance coinitiators for camphorquinone (CQ)‐based systems for the polymerization of methacrylates under blue light irradiation. When combined with CQ, the new proposed coinitiators present excellent polymerization performances and are excellent candidates for the replacement of tertiary aromatic amines subjected to toxicological concerns in the well‐established CQ/amine photoinitiating system (PIS). Remarkably, good bleaching properties are obtained after polymerization. The use of the new PIS for dental adhesives is also investigated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1664–1669

Diethoxyacetate Salts as Co‐initiators for Radical Photosensitive Resins: Towards Aromatic Amine‐Free Systems?

AbstractDiethoxyacetate salts are investigated as new co‐initiators for the free radical polymerization (FRP) of (meth)acrylates upon visible light exposure, with light emitting diodes (LEDs; 405 nm, 477 nm) being employed for this purpose. Interestingly, the impact of the counter cation on their initiating ability is clearly highlighted. When these co‐initiators are combined with commercial photoinitiators such as 2‐isopropylthioxanthone (ITX) or camphorquinone (CQ), good to excellent free radical polymerization initiating performances are found and high final reactive function conversions are achieved. In the absence of these co‐initiators, no or poor polymerization occurs, clearly highlighting the importance of these co‐initiators for an efficient process. These systems can be interesting for the replacement of aromatic amines opening the way for amine‐free Type II photoinitiating systems.

Blue Light Initiated Photopolymerization: Kinetics and Synthesis of Superabsorbent and Robust Poly(N,N′-dimethylacrylamide/Sodium Acrylate) Hydrogels

The kinetics of blue light and camphorquinone (CQ)/diphenyl iodonium hexafluorophosphate (DPI) initiated photopolymerization of N,N′-dimethylacrylamide (DMMA)/sodium acrylate (SA) was studied using...

Effect of Beam Profiles From Different Light Emission Tip Types of Multiwave Light-emitting Diodes on the Curing Profile of Resin-based Composites.

Light activation is an important clinical step for achieving success in restorative procedures. This study evaluated the influence of beam profile from different light emission tip types of multiwave light-emitting diodes (LEDs) on the curing profile of resin-based composites. Experimental composites were produced containing either camphorquinone (CQ) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. Multiwave LEDs with either a bundle light guide tip (Bluephase G2, Ivoclar Vivadent) or a microlens tip (VALO Cordless, Ultradent) were characterized using a beam profiler. Block-shaped samples (5×5×3 mm depth) of the two composites were cured in a custom-designed mold with the multiwave LEDs positioned to compare the regions exposed to the 420-495 nm (blue) and 380-420 nm (violet) emittances. To map the curing profile, the degree of conversion (DC) of longitudinal thin cross sections from each block was evaluated using transmission FT-NIR. Radiant exposure transmitted through the composites during curing was evaluated at different thicknesses. Data were analyzed using analysis of variance and Tukey test (α=0.05; β=0.2). The results indicated that there were differences in the beam profile and the overall radiant exposures transmitted through the composites using each multiwave LED (p<0.01, df=1 F=73.18). However, there were no differences in the curing profiles provided by the two multiwave LEDs (p=0.89, df=12 F=0.52), and similar effects were found according to the different LED emittance regions (p=0.09, df=5, F=2.11). When considering up to 1 mm in depth, no differences in the DC were found between the composites containing either photoinitiators. Starting at 2 mm in depth, the composite containing TPO showed a decrease in DC in the 420-495 nm emittance region, while the composite containing CQ showed a similar decrease in cure efficiency only at 3-mm depth under both 380-420 nm and 420-495 nm emittance regions. Thus, despite the fact that the nonuniform light beam emitted from the two multiwave LEDs was visually distinctly different when delivering 24 J/cm2, this difference did not seem to affect the curing profile of the composites. However, light transmission within 380-420 nm seems to be reduced with depth, directly affecting the curing profile of composites containing a photoinitiator with absorbance falling within this emission range.

The Use of Different Photoinitiator Systems in Photopolymerizing Resin Cements Through Ceramic Veneers.

To evaluate the effect of different photoinitiator systems on photopolymerizing resin cements through ceramic veneers with different thickness on microshear bond strength (μSBS), flexural strength (FS), and ultimate tensile strength (UTS) and verify the light attenuation through these ceramic veneers. Four photopolymerizing experimental resin cements were produced with the same resin matrix and associated with four different photoinitiator systems: camphorquinone (CQ), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), Ivocerin, and TPO + Ivocerin. Eighty disc-shaped ceramic veneers (IPS Empress Esthetic, Ivoclar Vivadent) were fabricated (10-mm diameter) in two different thicknesses: 0.7 and 1.5 mm. A previously characterized multiwave LED (Bluephase G2, Ivoclar Vivadent) was standardized for 40 seconds of photoactivation. Light transmittance through each ceramic veneer thickness (n=5) was measured using a spectrometer (USB 2000, Ocean Optics). The μSBS of each resin cement (n=15) to the ceramic veneer was evaluated using 0.5-mm cylinders with 0.7-mm diameters photoactivated through the different ceramic veneer thicknesses. Samples for FS and UTS tests were made either with or without ceramics veneers (0.7 and 1.5 mm) fixed to the light-curing tip. Data were submitted to two-way analysis of variance and the Tukey test (α=0.05). The multiwave LED emitted higher irradiance into the blue wavelength spectra than into the violet wavelength spectra (p=0.0001). Light transmittance through the ceramic veneers was reduced in a systematic manner based on thickness regardless of the wavelength spectra emitted from the multiwave LED (p=0.00037). The μSBS was reduced in a systematic manner based on thickness regardless of the photoinitiator system (p<0.05). However, resin cements with CQ and Ivocerin showed higher bond strength values in comparison to the resin cement with TPO regardless of the ceramic veneer thickness (p<0.05). The FS and UTS means decreased (p<0.05) with the interposition of 0.7- and 1.5-mm ceramic veneers for all resin cements. The resin cement containing only TPO showed the lowest FS and UTS means (p<0.05) for all ceramic veneers. The thickness of the ceramic veneers reduced the irradiance of the multiwave LED in all wavelength spectra. Ivocerin alone or associated with TPO showed to be an effective alternative photoinitiator to substitute for CQ. The resin cement containing only TPO had lower bond strength values in comparison to resin cements with CQ, Ivocerin, and Ivocerin + TPO.

Cytotoxic and genotoxic potential of the type I photoinitiators BAPO and TPO on human oral keratinocytes and V79 fibroblasts

ObjectivesPhenylbis(acyl) phosphine oxide (BAPO) and diphenyl(acyl) phosphine oxide (TPO) are alternative photoinitiators to camphorquinone (CQ) in dental resinous materials. Aim of this study was to investigate their cytotoxic/genotoxic potential in human oral keratinocytes (OKF6/Tert2) and Chinese hamster lung fibroblasts (V79) in comparison to CQ. MethodsCells were exposed to different concentrations of BAPO and TPO (1–50μM). Cytotoxicity was evaluated using H33342 and MTT assay, cell proliferation by BrdU proliferation assay and microscopy. Effects on cellular redox homeostasis were assessed by detecting intracellular levels of reactive oxygen/nitrogen species (ROS/RNS) using the DCFH2 assay and by quantification of mRNA expression of oxidatively regulated, cyto-protective enzymes. Genotoxic potential was determined by use of micronucleus (MN) assay. ResultsBAPO and TPO induced a concentration-dependent decrease of cell number. BAPO and TPO showed 50- to 250-fold higher cytotoxicity than CQ. In contrast to CQ, both photoinitiators revealed no increase of intracellular ROS/RNS. However, BAPO (10μM) at least significantly induced mRNA-expression of redox-regulated proteins after 24h similar to 2.5mM CQ. Additionally, BAPO significantly raised the number of micronuclei, but only in V79 cells (10μM: 12±1, 2.5mM CQ: 15±1, medium control: 6±3). However, it also significantly decreased proliferation of these cells (10μM BAPO: 19.8%±7.3% compared to controls). SignificanceBAPO and TPO revealed concentration-dependent cytotoxic effects in human oral keratinocytes and V79 cells. However, in contrast to CQ, no generation of intracellular ROS/RNS was found. Only BAPO induced genotoxicity in V79 cells.

Effect of adhesive-monomers and photoinitiator on C=C conversion and color stability of model self-adhesive flowable composites

The aim of this study was to determine the influence of the monomer type and photoinitiator systems on the degree of C=C conversion and color stability of model self-adhesive flowable composites (SAFCs). Three sets of flowable composites were formulated varying the monomer type: set 1 (control), with bisphenol-A glycidyl methacrylate and triethylene glycol dimethacrylate (BisGMA/TEGDMA) at 50/50 wt%; set 2, with BisGMA/TEGDMA/bis[2(methacryloyloxy)ethyl]phosphate (2MP) at 30/30/40 wt%; and set 3, with BisGMA/TEGDMA/4-ethyl-methacryloxy-trimetilato anhydride (4-META) at 30/30/40 wt%. For each set, different initiator systems were added: camphorquinone (CQ) + ethyl-4-dimethylamino benzoate (EDMAB); diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO); phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO); and the combinations CQ + EDMAB + TPO and CQ + EDMAB + BAPO. Degree of C=C conversion was determined by Fourier-transformed infrared spectroscopy with an attenuated total reflectance device (ATR-FTIR). The color stability was determined by CIE00 color difference formula (∆E*00), after water (T1) and coffee (T2) storages for 30 days. Data was submitted to two-way analysis of variance (ANOVA) followed by Student-Newman-Keuls test (α = 0.05). Degree of conversion and color stability were dependent on the resin matrix composition and the photoinitiator system. The 2MP-based set showed the highest DC, but also the poorest color stability. For the 4-META-base set, TPO and BAPO produced the highest degree of C=C conversion. The use of BAPO produced the best color stability for the acidic-monomer-based sets.