Release of Monomers from Dental Composite Materials into Saliva and the Possibility of Reducing the Toxic Risk for the Patient.

Background and Objectives: The objective of this study was (1) to measure the amount of monomers released into the saliva depending on the time elapsed after the hardening of the composite and on the type of monomer used; and (2) with the prolongation of the light-curing procedure, to publish information on whether it would be possible to influence the level of leached monomers. Materials and Methods: HPLC technique was used to monitor the levels of the unpolymerized monomers Bis-GMA, Bis/EMA, TEGDMA, and UDMA from the four commonly used composite materials, released into the saliva of a volunteer with intact dentition. The levels were monitored in 3 time periods during 24 h after composite hardening. From every composite material, 4 samples were formed and cured with an LED lamp for 10 s, 20 s, 40 s, and 60 s. After the light curing, the same polishing procedure was used and the samples were leached in blank saliva samples. Results: We observed that every monitored composite material eluted monomers into the saliva after its application. The amount of monomers depended on the time elapsed after the curing of the composite and on the type of composite used. A 40 s LED curing procedure can reduce the amount of leached monomers in comparison with the standard 20 s procedure, especially for monomers of higher molecular weight. Conclusions: Our study confirmed the hypothesis that the release of monomers gradually decreases with increasing time after the hardening of the composite filling.

Release of monomers from orthodontic adhesives.

INTRODUCTION: Most composite resins release both bisphenol A (BPA), which disrupts the endocrine balance, and triethylene glycol dimethacrylate (TEGDMA), which has high risks for human health: eg, allergies and cytotoxicity. The aim of this study was to characterize monomers released from orthodontic adhesives. METHODS: We studied samples of orthodontic adhesives by associating 2 techniques: gas phase chromatography and mass spectrometry. RESULTS: The in-vitro analysis detected significant quantities of BPA, TEGDMA, and other monomers in orthodontic adhesives used in daily practice: Transbond XT, Transbond Supreme LV (both, 3M Unitek, Monrovia, Calif), Blugloo (Ormco, Orange, Calif), and MonoLok 2 (Rocky Mountain Orthodontics, Denver, Colo). CONCLUSIONS: Clinicians should consider that orthodontic adhesives contain BPA, an endocrine disruptor; TEGDMA, an allergic and a cytotoxic compound; and carcinogenic genotoxic compounds. These molecules are not mentioned in the material safety data sheets. Manufacturers should declare all components of dental composites to identify these substances that may result in allergic or undesirable side effects for patients and dental staff.

Detection and quantification of monomers in unstimulated whole saliva after treatment with resin-based composite fillings in vivo.

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.

Release of monomers from four different composite materials after halogen and LED curing.

PURPOSE: To evaluate the release of monomers from four different composite materials (Ceram X, Filtek Supreme XT, Tetric Flow, Tetric EvoCeram), polymerized using either halogen or LED unit. METHODS: Ten specimens were made for each material/unit combination. Each specimen was stored in 1 ml 75% ethanol. The storage medium was renewed after 1, 7 and 28 days. Aliquots of this medium were analyzed by LC-MS/MS. RESULTS: The effect of the curing unit on monomers' release differed significantly among the materials (P < 0.0001). The amount of BisGMA and TEGDMA released from Ceram X was not influenced by the unit used (P > 0.05). Curing with LED reduced the amount of Bisphenol A released from Ceram X compared to halogen. For Filtek Supreme XT, the type of unit exerted a significant effect on the elution of BisGMA (P < or = 0.05). LED curing resulted in a higher release of TEGDMA and UDMA compared to halogen (P < or = 0.05). For Tetric Flow, LED curing resulted in lower monomer release (P < 0.0001). For Tetric EvoCeram, the amounts of BisGMA, UDMA and Bisphenol A were higher when polymerizing with LED compared to halogen. The release of substances was more material dependent and less influenced by the curing unit used.

Evaluation of Residual Monomers Eluted from Pediatric Dental Restorative Materials.

Unreacted monomers eluted from resin-based restorative materials have been considered a reason of local and systemic adverse reactions. This study was designed to determine the effect of finishing and polishing procedures on the elution of Bis-GMA, TEGDMA, UDMA, and HEMA monomers from compomer and bulk-fill composite resins. Bulk-fill composite (3M ESPE GmbH, Seefeld, Germany) and compomer (Dentsply DeTrey GmbH, Konstanz, Germany) specimens with 3 × 4 mm diameters were prepared. The specimens were randomly divided into two groups, and finishing-polishing procedures were applied only to the experimental groups. Release of residual monomers was analyzed by using High-Performance Liquid Chromatography (HPLC) after 24, 48, and 72 hours. Repeated measures ANOVA and Tukey post hoc tests were used for comparisons. Finishing and polishing procedures had a significant effect on reducing the quantity of UDMA release in the Filtek™ Bulk Fill composite and Bis-GMA, HEMA, and TEGDMA in the Dyract XP compomer (p < 0.05). The restorative materials investigated here are not chemically stable after polymerization, and concentrations of eluted monomers may reach critical toxicity levels even after one restoration placement. Finishing and polishing procedures are mandatory to reduce residual monomers.

Elution of residual monomers from dental composite materials.

AIM: This study was designed to determine the type and amount of the monomers leached from the different particle sizes of the composite materials. MATERIALS AND METHODS: Three different disk sizes (2, 4, 6 mm) prepared for each material group (Filtek Flow, Filtek A110, Filtek P60 and Filtek Supreme) were polymerised by LED and halogen light; the specimens were then placed in artificial saliva. The monomer release in 30 min and 24 hrs from the specimens was analyzed in HPLC calibrated for the monomer extracts before. RESULTS: TEGDMA release was detected in all material groups after 30 min and after 24 hrs. BisGMA and BisEMA were not determined in any groups and UDMA was detected only in Filtek Supreme. Significant differences in release of TEGDMA and UDMA were obtained between the different sizes of discs. Significantly high amount of TEGDMA and UDMA monomer release was obtained in LED than Halogen groups. Lower amount of monomer release was obtained in species of 30 min than 24 hrs. CONCLUSION: Data has revealed that the monomer release could be detected significantly high from the composite materials polymerized by a lower output curing light device; and higher elution of monomers was determined as the composite thickness has increased. Therefore, the clinical applications of composite materials and the type of curing units have very important effects on the success of restorations and in the decrease of potential side effects.

Examination of composite resins with electron microscopy, microhardness tester and energy dispersive X-ray microanalyzer.

This study was conducted to examine the ultrastructures of eight recently improved light-cure restorative composite resins with scanning and transmission electron microscopes (SEM and TEM). Additionally, Vickers hardness, volume/weight fraction of filler, and chemical composition were analyzed. Composite resins selected for evaluation were Beautifil II, Clearfil AP-X, Clearfil Majesty, Estelite sigma, Filtek Supreme, Filtek Z250, Solare, and Synergy. SEM and TEM images revealed a great diversity in ultrastructure, and Vickers hardness test showed significant differences amongst all the composite resins (except between Clearfil Majesty and Estelite sigma, and between Filtek Supreme and Filtek Z250). By means of EDX, similar elements such as C, O, and Si were detected, but the concentration was different in every composite resin. Results obtained in this study served to validate that the methods employed in this study SEM and TEM at high magnification--were useful in examining the ultrastructures of composite resins. It was also found that the ultrastructure, size of filler particles, volume/weight fraction of filler, and chemical composition of the composite resins had an effect on Vickers hardness. Given the great diversity of ultrastructures amongst the composite resins, which stemmed from the different revolutionary technologies used to manufacture them, further studies are warranted in the search of clinical applications that optimally match the differing properties of these materials.

Analysis of the degradation of a model dental composite.

UNLABELLED: Dental composites undergo material property changes during exposure to the oral environment and may release compounds of potential toxicity, such as bisphenol A. Degradation of dental composites was studied in a simplified overlayer model in which bisphenol A diglycidyl methacrylate (BisGMA) was covalently bound to a porous silicon oxide surface. It was hypothesized that the chemical structure of this overlayer would allow release of bisphenol A, BisGMA, and the decomposition products thereof, upon exposure to water for an extended period. Liquid chromatography mass spectrometry found leaching of intact BisGMA and several degradation products that contained the bisphenol A moiety from the overlayer into distilled water after 2 wks of aging. The absence of bisphenol A release from the overlayer reduces concerns regarding its potential health risk in dental composites. Nevertheless, health concerns might arise with respect to BisGMA and the leached degradation products, since they all contain the bisphenol A moiety. ABBREVIATIONS: BisGMA, bisphenol A diglycidyl methacrylate; HPLC, high-performance liquid chromatography; LCMS, liquid chromatography mass spectrometry; MA, methacrylic acid; MPS, 3-(trimethoxysilyl) propyl methacrylate; m/z, mass-to-charge ratio; and TIC, total ion chromatogram.

Distribution and excretion of BisGMA in guinea pigs.

Bisphenol-A-glycidyldimethacrylate (BisGMA) is used in many resin-based dental materials. It was shown in vitro that BisGMA was released into the adjacent biophase from such materials during the first days after placement. In this study, the uptake, distribution, and excretion of [(14)C]BisGMA applied via gastric and intravenous administration (at dose levels well above those encountered in dental care) were examined in vivo in guinea pigs to test the hypothesis that BisGMA reaches cytotoxic levels in mammalian tissues. [(14)C]BisGMA was taken up rapidly from the stomach and intestine after gastric administration and was widely distributed in the body following administration by each route. Most [(14)C] was excreted within one day as (14)CO(2). The peak equivalent BisGMA levels in guinea pig tissues examined were at least 1000-fold less than known toxic levels. The peak urine level in guinea pigs that received well in excess of the body-weight-adjusted dose expected in humans was also below known toxic levels. The study therefore did not support the hypothesis.

Assessment of monomer release from 3 different fissure sealants.

BACKGROUND: Light-activated resin-based dental fissure sealants are the most widely accepted among clinicians. The objective of this study was to determine monomer release of 3 different light-curing fissure sealants in vitro: Control Seal (Voco, Germany), Fissurit FX (Voco, Germany) and R&D Series Fissured Nova (Imicrly, Turkey). METHODS: Each material was polymerized with a curing light: Valo Cordless (Ultradent) LED in standard mode for 20 seconds (n = 27) and 40 seconds (n = 27) and in Xtra power mode (plasma arc) for 3 seconds (n = 27). High-performance liquid chromatography (HPLC) was used to measure the amount of monomers released over 1, 3 and 7 days. RESULTS: Plasma arc groups showed the highest release of monomers at 1, 3 and 7 days in the 3 fissure sealant groups (p<0.001). The greatest release of bisphenol A glycidyl methacrylate (bis-GMA) determined for R&D Series Fissured Nova both with LED 20 seconds and LED 40 seconds and for Control Seal was with the plasma arc. With time, release of the monomer was reduced for all polymerization systems. CONCLUSIONS: Efficiency of the polymerization system and applying the recommended curing time for light-activated resin-based dental materials are very important to protect the patient from potential hazards of residual monomers.

Elution of monomers from two conventional dental composite materials.

OBJECTIVE: The aim of this study was to determine the elution of monomers of two conventional resin composite materials after different polymerization and storage times. METHODS: Two resin composites (a hybrid and a flowable) were used. Four groups (n=10, diameter: 4.5mm, thickness: 2mm) of each material were fabricated, one for each polymerization time of: 0s, 20s, 40s, and 80s. The samples were stored in 1ml of 75% ethanol at room temperature, and the storage medium was renewed after 24h, 7 days, and 28 days. From the storage medium that was removed, samples were prepared and evaluated, with LC-MS/MS. RESULTS: Bisphenol A and UDMA were not detected in the samples. Regardless of the polymerization time, the material or the storage time, a higher amount of BisGMA was eluted compared to TEGDMA. The amount of monomer that was released from the polymerized samples of the hybrid resin composite (Tetric Ceram) was significantly higher (p<0.0001) compared to the flowable (Tetric Flow). No significant difference was found between samples polymerized for 20s compared to 40s concerning the elution of monomers. Only a polymerization time of 80s resulted in a decreased release of monomers. The release of TEGDMA decreased after 28 days; however, the elution of BisGMA remained at high levels. SIGNIFICANCE: The release of monomers remains at a high level for a long time (7-28 days) after polymerization. The 40s that are usually used for the polymerization of resin composites seems insufficient in order to prevent a high release of monomers.

Evaluation of the dentinal tubule penetration of an endodontic bioceramic sealer after three final irrigation protocols

Introduction: This study aimed to evaluate the dentinal tubule penetration of an endodontic bioceramic sealer, Sealer Plus BC, after three final irrigation protocols. Methods: Thirty distobuccal roots of maxillary molars were selected. Root canal preparation was performed up to an #40.06 instrument (X1 Blue) under 2.5% sodium hypochlorite irrigation. Specimens were randomly divided into three groups (n=10), according to the final irrigation protocol: G-NaOCl (2.5% sodium hypochlorite + PUI), G-SS (0.9% saline solution + PUI) and G-H20 (Deionized water + PUI). After final irrigation protocols, all specimens were irrigated with phosphate buffer solution. Root canal obturation was performed using the single cone technique and Sealer Plus BC, stained with a specific fluorophore. Specimens were transversely sectioned and each root third was evaluated in a confocal scanning laser microscopy. Images obtained were analyzed for sealer penetration in the dentinal tubules. Results: Dentinal tubule penetration of Sealer Plus BC was not observed in any root third, regardless of the final irrigation protocol investigated. Conclusions: Sealer Plus BC dentinal tubule penetration was not observed after none of the protocols tested. Dentinal tubule penetrability of Sealer Plus BC may be related to other factors rather than the final irrigation protocol.

Morphological and immunohistochemical analysis of the biocompatibility of resin-modified cements.

The aim of this double-blind randomized study was to evaluate the biocompatibility of resin-modified glass ionomer cements (RMGIC) by means of morphological and immunohistochemical analyses. RMGICs were selected and divided into four groups: Group CK (Crosslink Orthodontic Band Cement); Group RS (Resilience Light Cure Band Cement) Group RMO (RMO Band Cement), Group TP (Transbond Plus Light Cure Band), and Group C (Control-polyethylene). The materials were implanted in rat subcutaneous tissues, randomly selected for this study. After time intervals of 7, 15, and 30 days the tissues were submitted to morphological analysis. In immunohistochemical analysis, the immuno-marking of antibody CD68 was evaluated. The results obtained were statistically analyzed by the Kruskal-Wallis and Dunn tests (p < .05). In the morphological analysis after 7 days, Groups RS, RMO and TP showed more intense inflammatory infiltrate (p = .004) and only Group RMO presented greater intensity of multinucleated giant cells (p = .027). In the immunohistochemical analysis, Groups RMO and RS were observed to present a larger quantity of CD68+ (p = .004) in the time interval of 7 days and only Group RMO presented statistically significant difference for this parameter after 15 days (p = .026). In the time interval of 30 days, Group RMO presented the largest quantity of multinucleated giant cells (p < .004). The RMGICS Crosslink and Transbond Plus provided significantly better tissue biocompatibility than the Resilience and RMO Cements.

Development of highly reactive mono-(meth)acrylates as reactive diluents for dimethacrylate-based dental resin systems.

Reactive diluents such as triethyleneglycol-dimethacrylate (TEGDMA) have been widely used with bisphenol-A-glycidyl-dimethacrylate (Bis-GMA) to achieve restorative resins with appropriate viscosity and higher conversion. However, additional water sorption and polymerization shrinkage were also introduced. The aim of this work is to investigate whether the cure and material properties can be improved in dental resins containing novel mono-(meth)acrylates as reactive diluents so that these Bis-GMA-based copolymers have reduced polymerization shrinkage but higher overall double bond conversion. Several ultra-high-reactivity mono-(meth)acrylates that contain secondary functionalities have been synthesized and investigated. The polymerization rate and double bond conversion were monitored using photo-FTIR. Polymerization shrinkage, dynamic mechanical analysis, and flexural strength were characterized. Compared with the Bis-GMA/TEGDMA control, the Bis-GMA/mono-methacrylate systems studied showed higher final conversions, faster curing rates, and decreased polymerization shrinkage. Our optimum system Bis-GMA/morpholine carbamate methacrylate achieved 86% final conversion (vs. 65%), a polymerization rate 3.5 times faster, and a 30% reduction in polymerization volumetric shrinkage. These results indicate that certain highly reactive, novel mono-(meth)acrylates possess very promising potential to replace TEGDMA as reactive diluents and can readily be applied to develop superior dental resins.

Development of high-viscosity, two-paste bioactive bone cements.

Self-curing two-paste bone cements have been developed using methacrylate monomers with a view to formulate cements with low polymerization exotherm, low shrinkage, better mechanical properties, and improved adhesion to bone and implant surfaces. The monomers include bis-phenol A glycidyl dimethacrylate (bis-GMA), urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) as a viscosity modifier. Two-paste systems were formulated containing 60% by weight of a bioactive ceramic, hydroxyapatite. A methacroyloxy silane (A174) was used as a coupling agent due to its higher water stability in comparison to other aminosilanes to silanate the hydroxyapatite particles prior to composite formulation. A comparison of the FT-infrared spectrum of hydroxyapatite and silanated hydroxyapatite showed the presence of the carbonyl groups ( approximately 1720 cm(-1)), -C=C-( approximately 1630 cm(-1)) and Si-O- (1300-1250 cm(-1)) which indicated the availability of silane groups on the filler surface. Two methods of mixing were effected to form the bone cement: firstly by mixing in an open bowl and secondly by extruding the two pastes by an auto-mixing tip using a gun to dispense the pastes. Both types of cements yielded low polymerization exotherms with good mechanical properties; however, the lower viscosity of UDMA allowed better extrusion and handling properties. A biologically active apatite layer formed on the bone cement surface within a short period after its immersion in simulated body fluid, demonstrating in vitro bioactivity of the composite. This preliminary data thus suggests that UDMA is a viable alternative to bis-GMA as a polymerizable matrix in the formation of bone cements.

High-pressure infrared and FT-Raman investigation of a dental composite.

Composite resins are often used as filling materials on load-bearing surfaces of teeth. As masticatory stresses can be high, here, we study the effect of pressure on the behaviour of a dental composite. Using a polymerized wafer, the IR and FT-Raman spectra of a zirconia-containing proprietary composite (Z100, 3M, Minneapolis, MN, USA) were recorded. The high-pressure IR spectra were also recorded. Band assignments were made for the main peaks of both organic and inorganic components. Breaks in the pressure dependences (dv/dP) of the organic components were found at 22 kbar. Different pressure dependences for different vibrational modes of inorganic components were also observed. These data suggest that the network structure of the composite is compacted under high pressure and that both the atomic distance and bonding angles in the network are altered.

Estrogenicity of fissure sealants and adhesive resins determined by reporter gene assay.

It is controversial whether the dental resinous materials containing 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), which is synthesized from the estrogenic compound bisphenol A (BPA), include unreacted BPA and/or can mimic the effects of natural steroid hormones. In the present study, the estrogenic activities of 3 fissure sealants and 5 adhesive resins, which were all unpolymerized, were determined by means of a reporter gene assay, and the relevance of the components to the estrogenicity was investigated. Two commercially available sealants were confirmed to have estrogenic activity, although none of the tested materials contained BPA. In contrast, hydrophobic monomer bisphenol A dimethacrylate (BPA-DMA), which is also estrogenic, was found to be included in these estrogenic sealants in an amount greater than the minimum concentration to show estrogenicity. This suggests that the estrogenicity of the two proprietary sealants was associated with BPA-DMA rather than with BPA.

Movement of resin cement components through acid-treated dentin during crown cementation in vitro.

This study examined the hypothesis that components of crown cements may be forced through acid-treated dentin during cementation. Freshly extracted, human third molar teeth were prepared to accept full crowns. Roots were removed to allow irrigation of the pulp chamber with saline before, during, and after crown placement with resin dentin bond and resin composite cement. Saline samples were collected and analyzed by high performance liquid chromatography to identify and quantify resin components arriving in the pulp space. Two components of the bond-cement system used were identified in the pulp space samples immediately after crown cementation. These were 2-hydroxyethylmethacrylate and 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane. The amounts of these components in the pulp space decreased when the bonding agent was cured prior to crown placement. The results of this study supported the hypothesis that crown cementing components may flow through acid-treated dentin during crown cementation.

A study of component release from resin pit and fissure sealants in vitro.

OBJECTIVE: A recent study reported that an estrogenic chemical, bisphenol-A, was released from a fissure sealant. The aim of this study was to identify and quantify the major (or detectable) components released from any of seven commercially-available, light-cured pit and fissure sealants in vitro. METHODS: The fissure systems of ten extracted, third molar teeth were filled with sealant, light-activated and immersed in separate containers of distilled water. Separate, cylindrical stainless steel molds were filled with sealant which was then light-activated and immersed. Each mold or tooth with sealant was moved to a new container of water at defined times and each remaining water sample (eluate) then analyzed by high performance liquid chromatography (HPLC). RESULTS: Triethylene glycol dimethacrylate (TEGDMA) was present in all eluates from each of the sealants tested. 2,2-bis[4'-(2'-hydroxy-3'-methacryloyloxy)phenyl]propane (BisGMA) was detected at much lower levels (about one thousand-fold less) in eluates from one sealant only. Bisphenol-A was not detected in any eluates. The rates of TEGDMA and BisGMA release were highest on first immersion and decreased thereafter. The total amount of TEGDMA released was on the order of 0.25 mg per tooth. Most release occurred during the first day. SIGNIFICANCE: Because bisphenol-A release could not be detected from any of the seven sealants tested, these results call into question earlier concerns expressed about possible adverse effects of bisphenol-A released from resin sealants.

The effect of post-cure heating on residual, unreacted monomer in a commercial resin composite.

OBJECTIVES: This paper examined the influence of post-cure temperature on the amount of unreacted monomer remaining in a commercial light-cured resin composite restoration following initial light-curing and subsequent post-cure heating. METHODS: Discs of composite were light-cured and then subjected to immediate post-cure heating (50, 75, 100, or 125 degrees C for 7 min) or were left unheated (control). They were then placed in a solvent for two weeks at 37 degrees C to extract the unreacted monomer. HPLC analysis was used to determine the amounts of TEGDMA, BIS-GMA, and ethoxylated BIS-GMA remaining after the different treatments. The amounts of each monomer leaching were compared using ANOVA with respect to the different curing treatments. RESULTS: Even the lowest post-cure heat treatment (50 degrees C) resulted in 80% reduction in remaining, unreacted TEGDMA, 75% reduction in BIS-GMA, and 77% lower ethoxylated BIS-GMA than the light-cured only control. Post-cure heating at 75 degrees C and above resulted in the lowest amount of each type monomer remaining uncured in the polymer and did not significantly decrease with an increase in post-cure temperature for the most part. SIGNIFICANCE: One of the main benefits of post-cure heating of resin composite restorations could be the enhancement of biocompatibility of these restorations as a result of the significant decrease in potentially leachable, unreacted monomer.