Camphorquinone Concentrations Research Articles

Achieving property enhancements in dental resin composites via reduced concentrations of camphorquinone within a ternary initiator system

ObjectivesThe study aimed to assess the impact of diphenyliodonium hexafluorophosphate (DPI) on the physicochemical properties of experimental resin composites (ECRs) featuring reduced concentrations of camphorquinone (CQ)/amine. MethodsFive concentrations of CQ (0.125, 0.25, 0.5, 0.75, and 1 mol%) with dimethylaminoethyl amine benzoate (EDAB) in a 1:2 mol% ratio (CQ:EDAB) were incorporated into a 50:50 mass% monomer blend of bisphenol glycidyl methacrylate (BisGMA) and triethyleneglycol dimethacrylate (TEGDMA). An additional 5 groups with the same CQ:EDAB concentrations had 0.5 mol% DPI added. Each resin group contained 60 wt% of 0.7 µm barium-alumino-silicate glass. Light transmission (n = 3), real-time degree of polymerization (n = 3), temperature change during polymerization (n = 5), polymerization shrinkage strain (n = 3), flexural strength, and modulus (n = 12), as well as water sorption and solubility (n = 5), were evaluated. Data were analyzed using two-way ANOVA and Tukey's post-hoc test (α = 0.05). ResultsLight transmission was reduced in groups containing 0.125 and 0.25 mol% of CQ without DPI. DPI increased temperature, degree and rate of polymerization, despite the reduction in CQ/amine concentration. Additionally, there was an increase in polymerization shrinkage strain, flexural strength and modulus, and a reduction in water sorption and solubility in ECRs with DPI, even with lower concentrations of CQ/EDAB. SignificanceDPI improved the assessed properties of composites across various concentrations of CQ/EDAB, showing the benefit of reducing the quantity of CQ used without compromising the properties and curing of the resin composites.

Alternative co-initiators for photocurable dental resins: Polymerisation, quantum yield of conversion and cytotoxicity

ObjectiveCyclic acetals such as are naturally occurring compounds capable of acting as co-initiators during free-radical polymerisation, and potentially serve to offer non-allergic and biologically less toxic alternatives to conventional (tertiary) amines. The current study aimed to evaluate the polymerisation efficiency and potential toxicity of cyclic acetals compared with conventional photoinitiator systems in photocurable dental resins. MethodsBoth, 1,3 benzodioxole (BZD) and piperonyl alcohol (PA) were used in 0.5, 1.0, 1.5, 2.0, 3.0, 4.0 and 6.0 mol% concentrations. Whereas, N-phenyl glycine (NPG) was utilised in 0.5, 1.0, 1.5, 2.0, 3.0, 4.0 mol% concentrations for photopolymerisation of an unfilled model resin system, BisGMA and TEGDMA (1:1 mass %), involving three separate camphorquinone (CQ) concentrations of 0.5 (Low), 1.0 (Intermediate) and 1.5 (High) mol%. Conventional tertiary amines; ethyl-4-dimethyamino benzoate (EDMAB) and dimethylaminoethyl methacrylate (DMAEMA) were utilised for comparison. Real-time degree of conversion (DC, %) was evaluated using Fourier transform near-infra-red spectroscopy and quantum yield of conversion of CQ was calculated using UV-Vis spectroscopy. Cytotoxicity of NPG and cyclic acetals were assessed using MTT to determine metabolic activity of human dental pulp cells (HDPCs). ResultsThe cyclic acetals were capable of facilitating free radical polymerisation as co-initiators at all three CQ concentrations. Furthermore, the use of NPG as a co-initiator resulted in post-irradiation DC (%) that were comparable to both EDMAB and DMAEMA for all CQ concentrations. Alternative compounds facilitated the hydrogen abstraction process, which provided high conversion of CQ molecules. Quantum yield increased from 0.009 ± 0.0001 (0.5 mol%) to 0.03 ± 0.006 (6.0 mol%), and 0.01 ± 0.0003 (0.5 mol%) to 0.04 ± 0.001 (6.0 mol%), for respective BZD and PA formulations involving 1.0 mol% CQ. The use of NPG led to relatively higher quantum yield values (Up to 0.09 ± 0.007 at 4.0 mol%), though it exhibited competitive effects in absorbing blue light, which might be attributed to the photolytic degradation of NPG and the formation of N-methylaniline. MTT assay indicated alternative co-initiators to be comparatively less cytotoxic than EDMAB and CQ. Relative metablic activity of HDPCs treated with BZD, PA, and NPG eluates were 58.3 ± 15.7, 57.5 ± 17.4 and 64.6 ± 12.2 %, when compared with untreated HDPCs group (Control), respectively. Exposure to DMAEMA-based eluate led to relative metabolic activity (60.0 ± 0.5 %) that was comparable to that of cyclic acetals. Treatment with neat model resin eluate displayed the highest relative reduction in metabolic activity (28.9 ± 22.4) (P < 0.05), suggesting bisGMA and TEGDMA monomers played significant role in the overall cytotoxicity of photocurable systems involving HDPCs. SignificanceCyclic acetals were capable of facilitating photo-induced free radical polymerisation reactions with relatively less cytotoxicity compared with their amine counterparts, which might realise reduced cytotoxicity of photocurable materials used for dentistry and biomaterial applications.

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.

Effect of Camphorquinone Concentration in Physical-Mechanical Properties of Experimental Flowable Resin Composites.

The aim of this study was to evaluate the effect of camphorquinone concentration in physical-mechanical properties of experimental flowable composites in order to find the concentration that results in maximum conversion, balanced mechanical strength, and minimum shrinkage stress. Model composites based on BISGMA/TEGDMA with 70% wt filler loading were prepared containing different concentrations of camphorquinone (CQ) on resin matrix (0.25%, 0.50%, 1%, 1.50%, and 2% by weight). Degree of conversion was determined by FTIR. Surface hardness was assessed before and after 24 h ethanol storage and softening rate was determined. Depth of cure was determined by Knoop hardness evaluation at different depths. Color was assessed by reflectance spectrophotometer, employing the CIE-Lab system. Flexural strength and elastic modulus were determined by a three-point bending test. Shrinkage stress was determined in a Universal Testing Machine in a high compliance system. Data were submitted to ANOVA and Tukey's test (α = 0.05). The increase in CQ concentration caused a significant increase on flexural strength and luminosity of composites. Surface hardness was not affected by the concentration of CQ. Composite containing 0.25% wt CQ showed lower elastic modulus and shrinkage stress when compared to others. Depth of cure was 3 mm for composite containing 1% CQ and 2 mm for the other tested composites. Degree of conversion was inversely correlated with softening rate and directly correlated with elastic modulus and shrinkage stress. In conclusion, CQ concentration affects polymerization characteristics and mechanical strength of composites. The concentration of CQ in flowable composite for optimized polymerization and properties was 1% wt of the resin matrix, which allows adequate balance among degree of conversion, depth of cure, mechanical properties, and color characteristics of these materials.

Diphenyl-iodonium modulating properties of resins with low concentrations of camphorquinone

Diphenyl-iodonium modulating properties of resins with low concentrations of camphorquinone

Influence of Different Concentration and Ratio of a Photoinitiator System on the Properties of Experimental Resin Composites.

The aim in this study was to evaluate the influence of different ratio of camphorquinone/tertiary amine concentration on the flexural strength (FS), elastic modulus (EM), degree of conversion (DC), yellowing (YL), water sorption (WS) and water solubility (WSL) of experimental composites. Thus, acrylate blends were prepared with different camphorquinone (CQ) and amine (DABE) concentrations and ratios by weight: (CQ/DABE%): 0.4/0.4% (C1), 0.4/0.8% (C2), 0.6/0.6% (C3), 0.6/1.2% (C4), 0.8/0.8% (C5), 0.8/1.6% (C6), 1.0/1.0% (C7), 1.0/2.0% (C8), 1.5/1.5% (C9), 1.5/3.0% (C10). For the FS and EM, rectangular specimens (7x2x1 mm, n=10) were photo-activated by single-peak LED for 20 s and tested at Instron (0.5 mm/min). Then, the same specimens were evaluated by FTIR for DC measurement. For YL, disks (5x2 mm, n=10) were prepared, light-cured for 20 s and evaluated in spectrophotometer using the b aspect of the CIEL*a*b* system. For WS and WSL, the volume of the samples was calculated (mm³). For WS and WSL, composites disks (5x0.5 mm, n=5) were prepared. After desiccation, the specimens were stored in distilled water for 7 days and again desiccated, in order to measure the WS and WSL. Data were submitted to one-way ANOVA and Tukey's test (5%). The groups C8, C9 and C10 showed higher DC, EM and YL means, compared to other composites. Therefore, the FS and WS values were similar among all groups. Also, C1, C2 and C3 presented higher WSL in 7 days, compared to other composites. In general, higher concentrations of camphorquinone promoted higher physical-mechanical properties; however, inducing higher yellowing effect for the experimental composites.

3D-human small intestinal tissue to study ligand-induced acute and chronic inflammation in the gastrointestinal tract

Camphorquinone (CQ) is the most important photoinitiator used in dental composite resins. Sparse data indicate a mutagenic potential of CQ. Therefore, it was aim of this study to evaluate the cytotoxicity, genotoxicity, and mutagenicity of CQ in L5178Y TK+/− mouse lymphoma cells.L5178Y/TK+/− cells were exposed to different concentrations of non-irradiated CQ (0.25–2.5 mM). Cytotoxicity was evaluated by propidium iodide assay, determination of suspension growth rate, relative total growth and the mitotic index. Intracellular levels of reactive oxygen/nitrogen species (ROS/RNS) were quantified by 2′,7′-dichlorofluoresceine diacetate (DCFH-DA). Early induction of DNA strand breaks and oxidative DNA base lesions was assessed using the 8-hydroxyguanine DNA-glycosylase 1 (hOGG1)-modified alkaline comet assay, whereas mutagenicity of CQ was determined in the mouse lymphoma TK assay (MLA), according to OECD Guideline No. 490.CQ (0.5–2.5 mM) induced concentration- and time-dependent inhibition of cell growth associated with increased ROS/RNS production, amounting to 2342% ± 1108% of controls after 90 min at 2.5 mM. Additionally, CQ concentration-dependently caused direct DNA-damage, i.e. formation of DNA strand breaks and 8-hydroxy-2′-deoxyguanosine. Whereas the MLA indicated lack of mutagenicity of CQ after a 4 h of treatment, CQ concentration-dependently increased total mutant frequency (MF) after 24 h (about 2-fold at 2.5 mM). But, based on the global evaluation factor concept, increase in MF did not reach biologically relevance.CQ induced concentration-dependent, cytotoxic and genotoxic effects in L5178Y/TK+/− cells, most likely due to oxidative stress, but without mediating obvious biological relevant mutagenicity.

Effects of camphorquinone concentrations on resins containing diphenyliodonium hexafluorphosphate

Effects of camphorquinone concentrations on resins containing diphenyliodonium hexafluorphosphate

Genotoxic effects of camphorquinone and DMT on human oral and intestinal cells

ObjectiveReleased components of oral biomaterials can leach into the oral cavity and may subsequently reach the gastrointestinal tract. Camphorquinone (CQ) is the most common used photoinitiator in resinous restorative materials and is often combined with the co-initiator N,N-dimethyl-p-toluidine (DMT). It has been shown that CQ exerts cytotoxic effects, at least partially due to the generation of reactive oxygen species (ROS). Objective of this study was to examine the cytotoxic and genotoxic potential of CQ in human oral keratinocytes (OKF6/TERT2) and immortalized epithelial colorectal adenocarcinoma cells (Caco-2). Furthermore, the effects of visible-light irradiation and the co-initiator DMT were investigated as well as the generation of ROS, the potential protective effect of glutathione (GSH) and a recovery period of CQ-treated Caco-2 cells. MethodsThe alkaline comet assay was used to determine DNA damage. Additionally, an enzyme modified comet assay was applied, which detects 7,8-dihydro-8-oxoguanine (8-oxoguanine), a reliable marker for oxidative stress. ResultsOur data revealed that high concentrations of CQ induced DNA lesions in OKF6/TERT2 cells. This DNA damage is at least partly caused by the generation of 8-oxoguanine. In addition, CQ and DMT increased ROS formation and induced DNA damage in Caco-2 cells. CQ-treatment resulted in generation of 8-oxoguanine. The antioxidant GSH efficiently prevented CQ-associated DNA damage. Furthermore, a recovery following CQ-treatment significantly reduced DNA damage. SignificanceWe conclude that CQ-induced DNA damage is caused by oxidative stress in oral and intestinal cells. These lesions can be prevented and possibly repaired by GSH-treatment and recovery of cells after the photoinitiator is removed from cultures.

Mapping camphorquinone consumption, conversion and mechanical properties in methacrylates with systematically varied CQ/amine compositions

ObjectivesTo evaluate conversion, bulk mechanical properties and camphorquinone (CQ) consumption in methacrylate resins, comprising a range of overall initiator concentrations and CQ/amine ratios. MethodsBisGMA (Bisphenol-A glycidyl dimethacrylate), TEGDMA (triethyleneglycol dimethacrylate) and UDMA (urethane dimethacrylate) were mixed at a 1:1:1 molar ratio. CQ was used as the visible light photosensitizer, in combination with EDMAB (Ethyl p-dimethylamino benzoate), at 3:1, 2:1, 1:1, 1:2 and 1:3 weight ratios, at 0.5, 1.0, 1.5, 2.0 and 3.0wt% overall initiator concentration. Butylhydroxytoluene was added at 0.05wt% as an inhibitor. Unfilled resins were photoactivated with a dental light source (VIP Jr, Bisco) for 60s at 600mW/cm2. Flexural strength/modulus were assessed in 2×1×10mmbars, tested in three-point bending. Degree of conversion was assessed at the bottom of the same specimens using FT-RAMAN. CQ consumption was measured using a UV–vis spectrometer. Data were analyzed with two-way ANOVA/Tukey test (α=5%). ResultsLower conversion and inferior mechanical properties were observed with lower overall initiator concentrations and higher amine/CQ ratios. The lowest overall initiator concentration (0.5%) presented the statistically lowest conversion/properties results, except for the 1:3 amine/CQ ratio. For overall concentrations equal or greater to 1.5%, the amine/CQ ratio did not influence conversion or mechanical properties. CQ consumption was less efficient for the highest overall initiator concentrations and lower amine/CQ ratios. Clinical relevanceAbove 1.5wt% overall initiator concentration, the conversion and general mechanical properties were independent of the initiator concentration. Therefore, there seems to be no benefit to increasing the initiator concentration above that level. At higher camphorquinone concentrations, light transmission and photosensitizer consumption becomes impaired, which could lead to decreased depth of cure and yellowing of the restoration.

Oxidative stress is responsible for genotoxicity of camphorquinone in primary human gingival fibroblasts

The photoinitiator camphorquinone (CQ), used in dental restorative materials, was found to be cytotoxic in cell cultures. Previously, we have shown that CQ induces alkali labile sites and DNA strand breaks in human gingival fibroblasts (HGF) associated with an increase of intracellular reactive oxygen species (ROS). Therefore, the objective of our study was to evaluate if DNA damage in HGF cells is caused by the generation of ROS. HGF cells were treated with different concentrations (0.5-2.5 mM) of CQ. The cell viability was assessed using propidium iodide (PI) assay. Oxidative DNA damage was evaluated by an enzyme-modified comet assay using human 8-hydroxyguanine DNA-glycosylase 1 (hOGG1), which converts oxidized 7,8-dihydro-8-oxoguanine (8-oxoguanine) into DNA strand breaks and functions as a marker for oxidative modified DNA. The results showed that CQ induced DNA damage in HGF cells without cytotoxic effects for the chosen treatment time. CQ treatment led to the generation of 8-oxoguanine in DNA, which can be shown by a significant increase in tail moment after CQ treatment by the enzyme-modified comet assay. It may be concluded that DNA damage due to CQ is caused by oxidative stress in gingival fibroblasts. A more detailed insight into genotoxic mechanisms in oral cells can be of great importance for a better understanding of the biocompatibility of CQ.

Colloidal platinum nanoparticles increase mitochondrial stress induced by resin composite components

Components of dental composites have been implicated as metabolic and oxidative stressors in cells. Antioxidant colloidal platinum nanoparticles (CPtN) could be useful as nanofillers that reduce cellular stress caused during placement and exposure to unpolymerized composite components. Yet, CPtN may have pro- or anti-oxidative properties depending on the chemical environment in which they are used. This study investigated the ability of CPtN to mitigate mitochondrial or oxidative stress induced by camphorquinone (CQ) and dimethylaminoethyl methacrylate (DMAEM), two components of dental composites that initiate light-activated addition polymerization. THP-1 human monocytic cells were exposed to subtoxic concentrations of CQ and DMAEM, then blue light for 0-60 s. Mitochondrial and oxidative stress were estimated 0, 6, or 24 h after irradiation by measuring cellular ATP or GSH levels, respectively. CPtN (0-20 ppm) were added prior to blue light irradiation. Statistically significant effects were determined by ANOVA with Tukey post-hoc analysis (α = 0.05). Light alone did not alter THP-1 activity, but CQ and DMAEM induced 120% increases in cell ATP levels, which was increased further (50%) by CPtN. Blue light irradiation caused a 50% drop in ATP levels, which increased to 75% when CPtN were added. GSH levels were suppressed by CQ/DMAEM and blue light, and CPtN increased suppression by 20-30%. CPtN did not mitigate mitochondrial or oxidative stress in THP-1, but amplified these stresses under the conditions tested.

Photopolymerization of vinyl ether networks using an iodonium initiator—The role of photosensitizers

AbstractPhoto‐differential scanning calorimetry (photo‐DSC) and UV‐visible spectrometry were used to investigate the photocuring kinetics of visible light initiated cationic photopolymerization of triethyleneglycol divinyl ether with a diphenyl iodonium salt and three photosensitizers, 1‐chloro‐4‐propoxy‐9H‐thioxanthen‐9‐one (CPTXO), acridine orange (AO), and camphorquinone (CQ). Although all photosensitizers were effective in causing photopolymerization, CPTXO and AO photo‐reacted during the irradiation; whereas CQ was not significantly consumed during the timescale of the photo‐DSC experiment. This difference in photo‐reactivity has not been reported previously, and indicates that the reaction of the iodonium ion with CPTXO and AO results in the formation of the photosensitizer radical cation, whereas the CQ mechanism involves the reduction of the CQ excited state to a ketyl radical by a H‐donor (monomer) followed by the oxidation of the ketyl radical by the iodonium salt and thus regeneration of the CQ. For the CPTXO and AO systems, the photopolymerization rate was retarded by a radical inhibitor but the CQ system was unaffected, which confirms that different mechanisms are involved. The cure rate was found to be proportional to the concentrations of CPTXO and CQ but appeared to follow an approximately square root dependence on the AO concentration. Mechanisms to explain these differences were presented. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5474–5487, 2009

Non-irradiated campherquinone induces DNA damage in human gingival fibroblasts

Objectives Camphorquinone (CQ) is cytotoxic in cell cultures. The mechanism of this toxic action, however, is not yet clearly understood. Aim of this investigation was to analyze the effects of non-irradiated CQ on intracellular formation of reactive oxygen species (ROS), intracellular glutathione (GSH) content, and the integrity of DNA in cultured primary human gingival fibroblasts (HGF). Methods Cells were exposed to CQ at concentrations ranging between 0.05 mM and 2.5 mM. Intracellular levels of ROS were detected by the fluorescent probe 2′,7′-dichlorofluorescein diacetate (DCFH-DA) and GSH was determined by the fluorescent probe monobromobimane (MBBr). Genotoxicity was measured quantitatively by the alkaline comet assay. The cytotoxic effects of CQ were investigated by means of the fluorescent dye propidium iodide and the Cytotoxicity Detection Kit. Results CQ generated an increase of intracellular ROS, a depletion of intracellular GSH level, decreased cells’ viability and total cell number dependent on the applied CQ concentration: 0.5–2.5 mM (ROS↑, GSH↓) and 0.125–2.5 mM CQ (cytotoxicity↑). Increased DNA damage was observed at all concentrations (0.05–2.5 mM, p < 0.05). The ROS-scavenger N-acetylcysteine (NAC) reduced CQ-induced ROS formation at CQ concentrations higher than 0.5 mM ( p < 0.05). Significance Our data indicate that non-irradiated CQ induces oxidative stress, DNA damage and cytotoxicity as well in primary HGF.

Phosphorescence for Sensitive Enantioselective Detection in Chiral Capillary Electrophoresis

Enantioselective phosphorescence lifetime detection was combined with chiral cyclodextrin-based electrokinetic chromatography for the analysis of camphorquinone (CQ). A time-gated detection system based on a pulsed light-emitting diode for excitation at 465 nm was developed for the online lifetime determination. The background electrolyte for the chiral separation consisted of 20 mM alpha-cyclodextrin (alpha-CD), 10 mM carboxymethyl-beta-CD, and 25 mM borate buffer at pH 9.0. The separation of (+)-CQ and (-)-CQ is caused by a difference in association constants of these enantiomers with alpha-CD. Under the separation conditions, different phosphorescence lifetimes were obtained for (+)-CQ and (-)-CQ (tau = 384 +/- 8 and 143 +/- 5 micros, respectively), which could be used to distinguish the enantiomers. This selectivity in detection is based on a difference in protection of the enantiomers against phosphorescence quenching after their complexation with alpha-CD. Concentration detection limits were 2 x 10(-7) and 1 x 10(-6) M for (+)-CQ and (-)-CQ, respectively. After correction for the lifetime shortening by triplet-triplet annihilation at higher CQ concentrations, a linear dynamic range was obtained from the detection limit up to 2 mM. The system was used to determine the enantiomeric impurity levels of commercial samples of (+)-CQ and (-)-CQ; 0.2% and 0.1%, respectively.

The Role of Amines in the Camphorquinone Photoinitiated Polymerization of Multifunctional Monomer

The influence of the camphorquinone (CQ) concentration and thirteen amines on the rate of polymerization of trimethyleneglycol dimethacrylate (TEGDMA) was investigated. As shown, the rate of polymerization of TEGDMA increases with the increasing of the camphorquinone concentration. However, over 6×10−2 M it deviation from the linearlity is observed. Some of the amines decrease the rate of polymerization and some of them increase the rate. The acceleration effect on CQ photoinitiated polymerization of TEGDMA is caused by amines radicals formed by the direct hydrogen atom abstraction from amines by triplet 3CQ*, rather than by the electron–proton transfer reaction.

ROS formation and glutathione levels in human oral fibroblasts exposed to TEGDMA and camphorquinone

Glutathione (GSH) is important for the self-protection of cells against oxidative stress and toxic xenobiotics, whereas reactive oxygen species (ROS) at elevated concentrations may cause detrimental alterations of cell membranes, DNA, and other cellular structures. The present investigation addressed the effects of triethylene-glycoldimethacrylate (TEGDMA) and camphorquinone (CQ) on glutathione metabolism and the formation of ROS in oral cells. Primary human pulp fibroblasts were exposed to various concentrations of TEGDMA and CQ (0.1-5 mM). Subsequently, GSH concentration and ROS formation were analyzed with the use of the monobromobimane assay (GSH) and 2',7'-dichlorofluorescein diacetate (DCFH-DA) (ROS). The endogenous ROS hydrogen peroxide (H2O2) was used as a positive control (0.02-2 mM). TEGDMA significantly decreased GSH at concentrations between 0.5 and 5 mM (p<0.05), but did not elevate ROS levels. Contrary, CQ increased ROS formation at concentrations>or=1 mM, but had only a moderate effect on GSH at the highest test concentration. Hydrogen peroxide increased ROS and simultaneously decreased GSH at concentrations of >or=0.2 mM. These data show that the investigated substances may cause cell damage due to various mechanisms, GSH decrease and/or ROS increase. As a consequence, TEGDMA and CQ released into an aqueous environment from resinous materials might interact, thus generating significant cytotoxic effects even at low concentrations.

Effects of sub-toxic concentrations of camphorquinone on cell lipid metabolism

The biological effects of camphorquinone (CQ), an initiator for light-polymerized resins, have been reported to relate to its ability to generate free radicals and cause radical-induced membrane damage via lipid peroxidation. However, the effects of CQ on lipids other than peroxidation may result in unfavorable tissue responses especially at concentrations that are not overtly toxic to cells. The purpose of the current study was to examine the effects of CQ on cell lipid metabolism at sub-toxic concentrations, with or without visible light irradiation. HCP and THP-1 cells were exposed to CQ with or without light irradiation under clinically relevant conditions and lipid metabolism was analyzed using 14C-labeling and thin-layer chromatography. We found that CQ increased synthesis of neutral lipids, such as triglycerides, from 7 to nearly 15% of the total and diglycerides from 2% to about 3% of the total in HCP cells, while synthesis of phospholipids, such as sphingomyelin, was decreased by 1–1.5%. In THP-1 cells cholesterol synthesis increased more than 2-fold and cholesterol ester synthesis increased more than 5-fold. Light-activated CQ did not differ significantly in terms of its bioactivity compared to no-light conditions. We conclude that CQ significantly altered the metabolism of several important structural lipids in two cell types at sub-toxic concentrations that are clinically relevant. These changes in lipid metabolism may in turn affect membrane integrity and permeability and possibly lead to significant changes in cell responses.

Shear bond strength of experimental methacrylated beta-cyclodextrin-based formulations

Previous studies have shown that methacrylated beta-cyclodextrins (MCDs) can be used as comonomers in resin-based dental composites. These MCDs by virtue of having several polymerizable methacrylate groups and hydrophilic hydroxyl groups, may also promote bonding of dental composites to dentin. This study evaluated MCDs as adhesive comonomers, and optimized comonomer and polymerization initiator concentrations for maximum shear bond strength (SBS). Experimental MCD-based bonding formulations in acetone were prepared by mixing 33 mass fraction % MCDs with (10, 20, 30, 40, or 50) mass fraction % of 2-hydroxyethyl methacrylate (HEMA). The MCD/HEMA-based solutions were activated with varied amounts of camphorquinone (CQ) and ethyl 4-dimethylamino benzoate (4E). Samples for SBS were prepared by bonding a composite resin to acid-etched dentin surfaces of extracted human molars with the experimental bonding solutions. The specimens were immersed in 37 °C water for 24 h and bond strengths were determined in shear mode. With increasing HEMA concentration, the SBS values of MCD-bonding solutions increased to 16 MPa at a composition of 33% MCD, 30% HEMA, and 37% acetone by mass. Also, SBS values of MCD-bonding solutions varied as a function of the CQ and 4E concentrations and passed through a maximum SBS at 21 MPa, which was comparable to that of a commercial control. This preliminary study indicated that nonacidic MCD monomers could be used as an adhesion-promoting comonomer. Additional modification of MCDs having both polymerizable groups and anionic ligand groups, e.g., polymerizable acidic cyclodextrin derivatives should increase the SBS even further.

Photocurable biodegradable liquid copolymers: synthesis of acrylate-end-capped trimethylene carbonate-based prepolymers, photocuring, and hydrolysis.

Various photocurable liquid biodegradable trimethylene carbonate (TMC)-based (co)oligomers were prepared by ring-opening (co)polymerization of TMC with or without L-lactide (LL) using low molecular weight poly(ethylene glycol) (PEG) (mol wt 200, 600, or 1000) or trimethylolpropane (TMP) as an initiator. Resultant (co)oligomers were pastes, viscous liquids, or liquids at room temperature, depending on the monomer composition and monomer/initiator ratio. Liquid (co)oligomers were subsequently end-capped with acrylate groups. Upon visible-light irradiation in the presence of camphorquinone as a radical generator, rapid liquid-to-solid transformation occurred to produce photocured solid. The photocuring yield increased with photoirradiation time, photointensity, and camphorquinone concentration. The photocured polymers derived from low molecular weight PEG (PEG200) and TMP exhibited much reduced hydrolysis potential compared with PEG1000-derived polymers in terms of weight loss, water uptake, and swelling depth. Force-distance curve measurements by nanoindentation using atomic force microscopy clearly showed that Young's moduli of the photocured polymer films decreased with increasing hydrolysis time. Their potential biomedical applications are discussed.