Resin-based dental restorative materials contain allergenic methacrylate monomers, which may be released into saliva after restorative treatment. Monomers from resin-based composite materials have been demonstrated in saliva in vitro; however, studies analyzing saliva after restorative therapy are scarce. The aim of this study was to quantify methacrylate monomers in saliva after treatment with a resin-based composite filling material. Saliva was collected from 10 patients at four start points--before treatment, and 10 min, 24 h, and 7 d after treatment--and analysed by combined chromatography/mass spectrometry. The monomers bisphenol-A diglycidyl methacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), and urethane dimethacrylate (UDMA) were detected and quantified in the samples collected shortly (10 min) after treatment. The amounts detected ranged from 0.028 to 9.65 μg ml(-1) for Bis-GMA, from 0.015 to 0.19 μg ml(-1) for HEMA, and from 0.004 to 1.2 μg ml(-1) for UDMA. Triethyleneglycol dimethacrylate (TEGDMA) was detected in four of the samples. Ethoxylated bisphenol-A dimethacrylate (Bis-EMA) was not detected. Monomers were not detected in saliva samples collected before treatment, or 24 h or 7 d after treatment, with the exception of one sample, 24 h after treatment, in which HEMA was detected. In conclusion, monomers from the investigated resin-based composite and adhesive system were present in saliva shortly after treatment. One week after treatment, no monomers could be detected in patients' saliva samples.
Polymer-based dental restorative materials are designed to polymerize in situ. However, the conversion of methacrylate monomer to polymer is never complete, and leakage of the monomer occurs. It has been shown that these monomers are toxic in vitro; hence concerns regarding exposure of patients and dental personnel have been raised. Different monomer methacrylates are thought to cause toxicity through similar mechanisms, and the sequestration of cellular glutathione (GSH) may be a key event. In this study we examined the commonly used monomer methacrylates, 2-hydroxyethylmethacrylate (HEMA), triethylenglycol-dimethacrylate (TEGDMA), bisphenol-A-glycidyl-dimethacrylate (BisGMA), glycerol-dimethacrylate (GDMA) and methyl-methacrylate (MMA). The study aimed to establish monomers' ability to complex with GSH, and relate this to cellular toxicity endpoints. Except for BisGMA, all the monomer methacrylates decreased the GSH levels both in cells and in a cell-free system. The spontaneous formation of methacrylate-GSH adducts were observed for all methacrylate monomers except BisGMA. However, we were not able to correlate GSH depletion and toxic response measured as SDH activity and changes in cell growth pattern. Together, the current study indicates mechanisms other than GSH-binding to be involved in the toxicity of methacrylate monomers.
BPA has been reported to leach from some resin based dental restorative materials and materials used for orthodontic treatment. To confirm and update previous findings, especially in light of the new temporary lower threshold value for tolerable daily BPA intake, we have investigated the leaching of BPA from 4 composite filling materials, 3 sealants and 2 orthodontic bonding materials. The materials were either uncured and dissolved in methanol or cured. The cured materials were kept in deionized water for 24 hours or 2 weeks. Samples were subsequently analyzed by ultra-performance liquid chromatography coupled to mass spectrometry (UPLC-MS-MS). The composite filling material Tetric EvoFlow® and the fissure sealant DELTON® showed significantly higher levels of BPA leaching compared to control samples for all test conditions (uncured, 24 h leaching and 2 weeks leaching). There were no significant differences in amount of leached BPA for any of the tested materials after 24 hours compared to 2 weeks. These results show that BPA is still released from some dental materials despite the general concern about potential adverse effects of BPA. However, the amounts of BPA were relatively low and most likely represent a very small contribution to the total BPA exposure.
Purpose: Some patients experience adverse reactions to poly(methyl methacrylate)-based (PMMA) dentures. Polyamide (PA) as an alternative to PMMA has, however, not been well documented with regard to water sorption and water solubility. The aim of this in vitro study was to measure water sorption and water solubility of two PA materials compared with PMMA, and to evaluate the major components released from the PA materials and the effect on hardness of the materials. Methods: Ten discs (40.0 mm diameter, 2.0 mm thick) of each material (PA: Valplast and Breflex; PMMA: SR Ivocap HIP) were prepared according to manufacturers’ recommendations. The specimens were tested for water sorption and water solubility, according to a modification of ISO 20795-1:2008. Released substances were analysed by gas chromatography/mass spectrometry (GC/MS). Results: There were statistically significant differences among the materials regarding water sorption, water solubility and time to water saturation. Breflex had the highest water sorption (30.4 μg/mm3), followed by PMMA-material (25.8 μg/mm3) and Valplast (13.6 μg/mm3). Both PA materials had statistically significant lower water solubility than the PMMA. Both PA had a net increase in weight. Analysis by GC/MS identified release of the compound 12-aminododecanolactam from the material Valplast. No release was found from the Breflex material. Conclusions: The PA denture materials show differences in water sorption and solubility, but within the limits of the standard requirements. The PA showed a net increase in weight after long-term water sorption. The clinical implications of the findings are not elucidated.
Polymer self-association and thermoreversible gelation in aqueous solutions of poly(N-acetamidoacrylamide) (PAAA) have been investigated by Raman spectroscopy. We found that aqueous solutions of PAAA, even at low concentrations, revealed the presence of polymer−polymer coordination, suggesting formation of polymer clusters. The effect of denaturant (sodium thiocyanate) on the inter- and intramolecular interactions in the system has been also studied. It is shown that the SCN ions destroy the macroscopic hydrogen-bond network of water, as well as reduce the polymer's ability for self-association by occupying the NH groups. The changes observed in the Raman spectra upon the gel transition show that in the gel state the equilibrium of the system is shifted toward polymer−polymer coordination, whereas in the solution it is mostly polymer−water coordination. The influence of the different factors such as polymer concentration, level of denaturant addition, and type of solvent on the gel formation is discussed.
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