Elution of substances from a silorane-based dental composite

Kopperud HM, Schmidt M, Kleven IS. Elution of substances from a silorane-based dental composite. Eur J Oral Sci 2010; 118: 100–102. © 2010 The Authors. Journal compilation © 2010 Eur J Oral Sci
Previous studies have shown that residual monomers, initiators, and additives are eluted from methacrylate-based dental composite materials. Recently, a composite material (Filtek Silorane), based on a new resin chemistry, was introduced. The purpose of this study was to investigate substances eluted from Filtek Silorane in water and ethanol. Polymerized specimen discs of the material were immersed in either distilled water or 75 vol% ethanol at 37°C, and the solutions were analyzed using liquid chromatography-mass spectrometry after 1, 4, 24, and 72 h eluting time. No substances were found to leach from Filtek Silorane in water, whereas silorane monomers and an initiator component were eluted from the material into the ethanol solution.     

Physical and mechanical properties of an experimental dental composite based on a new monomer.

OBJECTIVE: The purpose of this study was to investigate the physical and mechanical properties of a dental composite based on BTDMA, a new dimethacrylate monomer based on BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), and to compare these with the properties of a composite based on commonly used Bis-GMA monomer. METHODS: Experimental composites were prepared by mixing the silane-treated filler with the monomers. The prepared pastes were inserted into the test molds and heat-cured. Light-cured composites were also prepared using camphorquinone and amine as photoinitiator system. Degree of conversion of the light-cured and heat-cured composites was measured using FTIR spectroscopy. The flexural strength, flexural modulus, diametral tensile strength (DTS), water sorption, water contact angle, microhardness and thermal expansion coefficient of the prepared composites were measured and compared. Water uptake of the monomers was also measured. RESULTS: The results showed that the mechanical properties of the new composite are comparable with the properties of the Bis-GMA-based composite but its water sorption is higher. BTDMA as a monomer containing aromatic rings and carboxylic acid groups in its structure gives a composite with good mechanical properties. There is a close relation between the contact angle, water sorption of the cured composite and water uptake of their monomers. SIGNIFICANCE: Finding new monomers as alternatives for Bis-GMA have been a challenge in the field of dental materials and any investigation into the properties of new composites would be beneficial in the development of dental materials.     

Monomer release from direct and indirect adhesive restorations: A comparative in vitro study

ObjectivesIndirect dental restorations produced by computer-aided design and computer-aided manufacturing (CAD/CAM) are relatively new in daily dental practice. The aim of the present study was to compare the monomer release between direct composite restorations and indirect CAD/CAM produced restorations (composite, ceramic and hybrid).MethodsIdentical crown restorations were prepared from three indirect materials (Cerasmart, Vitablocs Mark II and Vita Enamic) and one composite material (Clearfil AP-X). For each restoration, eight crown restorations were luted onto tooth samples and immersed into 2.5 mL of an aqueous extraction solvent. Additionally, three nonluted crowns of each restoration type were also immersed in the extraction solvent, and served as controls. Every week, the extraction solvent was collected and refreshed, during a period of 8 weeks. The released monomers were quantified using ultra-performance liquid chromatography-tandem mass spectrometry.ResultsIndirect restorations release significantly lower quantities of residual monomers than direct restorations, and the monomers released by the luted indirect restorations are mainly derived from the composite material used for cementation. The quantity of monomers released by direct restorations greatly depended on the time of light polymerization.SignificanceIn terms of monomer release, indirect restorations are a good alternative to direct restorations to limit patient exposure to residual monomers. It is important to ideally design the fit of indirect restoration so that the cement layer is as thin as possible and the monomer release from this cement layer remains as low as possible.     

Analysis of eluate extracted from dental filling resin by high performance liquid chromatography (author's transl)]

Since the residual monomer of cured filling resin has been implicated in toxicological effects, a high performance liquid chromatography (HPLC) was used to analyze the eluate of bisphenol A diglycidylmethacrylate (Bis-GMA) and methyl methacrylate (MMA) type resins presently used. The main chemicals of the eluate from resin into three kinds of solution, water, 85% methanol water solution and 100% methanol were the residual monomers which formely were Bis-GMA, triethylenglycol dimethacrylate and latterly MMA. Residual initiators, benzoyl peroxide and hydroquinone were also determined. This investigation has shown that HPLC is rapid, reliable and an acurate method to analyze the residual monomers of cured dental filling resins.     

Effects of 1,4-butanediol dimethacrylate and urethane dimethacrylate on HL-60 cell metabolism

The polymerization of methacrylic monomers present in dental composite resins never reaches completion and therefore the leakage of residual monomers into the oral cavity and into biological fluids can cause local and systemic adverse effects. This work was carried out to study the in vitro biochemical interactions of urethane dimethacrylate and 1,4-butanediol dimethacrylate monomers with HL-60 cells, a cell line assumed as an experimental model for simulating granulocyte behaviour. Our main finding was that both monomers induce cell differentiation at toxic concentrations and that cytotoxicity seems to be caused by alterations of glucose metabolism arising from mitochondrial dysfunction rather than from oxidative stress, which could not be altogether verified under our experimental conditions. Our study could be considered as a useful approach to investigate the biochemical mechanisms that contribute to the cytotoxicity of methacrylate compounds and it underlines the importance of assessing such parameters for testing biocompatibility in order to promote the development of better and safer dental materials.     

Evaluation of residual monomer elimination methods in three different fissure sealants in vitro

The aim of this study was to determine the concentration of residual monomers and to evaluate the effectiveness of elimination methods of residual monomers in three different fissure sealant materials (Helioseal F, Filtek Flow and EXM-510). The sealant materials were divided into four subgroups because of the treatment methods used; one control group and three experimental groups (cotton roll, rubber cup and prophylaxis paste in cup). High performance liquid chromatography was used to determine the concentrations of residual monomers. Results of the study showed that residual Bis-glycidyl dimethacrylate elution was the highest in Helioseal F and the lowest in Filtek Flow with the three methods tested. For triethleneglycol dimethacrylate, EXM-510 eluted the highest residual monomer. It was also found that although the three tested methods were insufficient for removing all of the residual monomers and rubbing with cotton rolls was more effective than other two methods.     

Synthesis of radiopaque cyclophosphazene monomers, properties of bulk polymers and their application to composite resin.

A series of studies was conducted on the synthesis of polyfunctional cyclophosphazene monomers having radiopacity and a polymerization group in the same molecule, and their properties and applicability to composite resin were examined. Using octachlorocyclotetraphosphazene, P4N4Cl8 (4PNC), monomers were synthesized by replacing the 1-4 of chlorine (Cl) with p-bromophenol (BrC6H4OH, BrPh), and replacing the residual number of Cl, 7-4, with 2-hydroxyethyl methacrylate [CH2:C(CH3)COOCH2CH2OH](HEMA), so as to obtain four kinds of transparent monomer having radiopacity and a polymerization group in the same molecule. We then analyzed these monomers and examined their physical properties after bulk-polymerization. Next, we prepared an organic composite filler using 4PN-(BrPh)3-(EMA)5 monomer, which showed comparatively good radiopacity, to produce a new experimental radiopaque composite resin. Although radiopacity improved in accordance with the increase in the number of BrPh molecules replaced, the mechanical properties of the polymer became poorer. Similarly it was proved that the radiopacity of composite resin made with 4PN-(BrPh)3-(EMA)5 monomer was equivalent or even superior, compared with the radiopacity of the front tooth. Consequently, it was shown that these synthesized monomers can be applied to visible light-cured radiopaque composite resin.     

Durability of commercial composite resin. Chronological change in transverse strength and transverse elastic modulus of composite resin immersed in MeOH

The durability of visible light-cured composite resin was examined. Five kinds of commercial redox type composite resin and 7 kinds of visible light-cured composite resin were used and their base monomers were analyzed by HPLC. After the set products were immersed in MeOH, transverse strength and transverse elastic modulus were measured. Furthermore, the MeOH sorption, solubility in MeOH and main soluble component were examined. The main component of the base monomer in all 5 kinds of redox type was Bis-GMA. Seven kinds of visible light-cured composite resin consisted of 4 kinds of Bis-GMA (including BMPEPP) and 3 kinds of UDMA. Both cases of redox type and visible light-cured type of composite resin, when they were immersed in MeOH, transverse strength and transverse elastic modulus decreased. In the case of redox type (Clearfil posterior new bond), the decrease of transverse strength and transverse elastic modulus was small, that is, its base monomer was Bis-GMA, and large quantities of hybrid type filler were mixed. In the case of redox type, transverse strength and transverse elastic modulus showed a tendency to decrease with the increase of MeOH sorption. Solubility of 12 kinds of these composite resins was 0.25-4.78% and its main component in Pyrofil light bond A was BMPEPP, the residual were coincident with the main component of base monomer.     

Sorption, solubility and residual monomers of a dental adhesive cured by different light-curing units

The aim of this study was to assess polymerization ability of three light-curing units by evaluating the influence of the light source, curing regimen and permeant (water or ethanol) on sorption, solubility and amount of residual monomers of a dental adhesive. Specimens of Adper Single Bond 2 were fabricated using a stainless steel circular matrix (8 mm x 1 mm). One quartz-tungsten-halogen (QTH) lamp and two light-emitting diode (LED) device at three different curing regimes (L1 = 12 J; L2 = 24 J; L3 = 24 J) were used to cure the specimens. Specimens were stored in two types of permeants - deionized water or 75% ethanol - for two storage times (G1 =7 days; G2 = 30 days). The specimens underwent water sorption and solubility tests, according to ISO 4049:2000 standard. After storage, residual monomers were identified and quantified by high performance liquid chromatography (HPLC). For sorption, L1 showed the highest values and QTH, the lowest. For solubility, in ethanol-stored groups, L1 had also the highest values, and QTH, the lowest, and findings were significantly different from the other curing regimens. L1 leached significantly more monomers than the others, and QTH had the lowest results. In conclusion, the type of light source, the curing regimen and the permeant affected sorption, solubility and amount of residual monomers of the adhesive under study.     

The application of fluorinated aromatic dimethacrylates and diacrylates to light-cured composite resins. 1. Improvement of transmittance of composite

To improve the transmittance of light-cured composite resins, the matching of the refractive indices of the matrix monomer and filler were examined. Eight fluorinated aromatic dimethacrylates and diacrylates with a low refractive index were synthesized. Three of these monomers had a poor solubility to TEGDMA. The depths of cure and the other physical properties of eight experimental composites prepared from one of five fluorinated monomers, TEGDMA and UDMA were determined compared with those of the control composites prepared from Bis-GMA or Bis-MEPP/ and TEGDMA in the same ratio. These composites contained 70 wt% of silanized silica filler. The depths of cure of the experimental composites except for one were significantly greater than those of the control composites. The mechanical properties of the experimental composites were comparable to those of the control composites with a few exceptions, but the difference in the mechanical properties between these exceptional composites and the control was small. The water sorption of the experimental composites was markedly lower than that of the composite containing Bis-GMA and comparable to that of the composite containing Bis-MEPP. These five fluorinated monomers are considered useful as the matrix monomer of light-cured composite resins.     

Residual monomer (Bis-GMA) of composite resins

A method of measuring residual monomer (Bis-GMA) is described. In addition, the percentage of residual monomer eluted into water from composite resins after setting was compared for several commercial products.     

Resin composite monomers alter MTT and LDH activity of human gingival fibroblasts in vitro.

OBJECTIVES: Substances such as monomers may be released from composite resin systems and may induce adverse effects in biological tissues. The aim of this study is to investigate the cytotoxic concentrations of resin composite monomers on cultures of human gingival fibroblasts. METHODS: A range of dilutions of five resin composite monomers (HEMA, HPMA, DMAEMA, TEGDMA, and Bis-GMA) were added to the culture medium of human gingival fibroblasts for 24 h. Their cytotoxic effects were measured by using two colorimetric functional assays, mitochondrial dehydrogenase activity (MTT) and lactate dehydrogenase activity (LDH) assay. The logP values (water/octanol partition) of test monomers were also calculated computationally. RESULTS: Mitochondrial reducing activity assessed with the MTT test was inhibited by all monomers and all the monomers increased the LDH release in a reproducible dose dependent manner. A wide range of TC 50 values (concentrations altering MTT and LDH activity by 50%) (0.32-5.8 mM by MTT assay and 0.36-6.7 mM by LDH assay) was observed. Ranking of composite resin monomer cytotoxicities (TC 50) were similar for both the MTT and LDH assays, (Bis-GMA>TEGDMA>DMAEMA>HPMA >HEMA). However, the MTT assay was found to be more sensitive than the LDH assay, particularly when lower doses of the tested monomers were determined. The ranking of TC 50 concentrations correlated with the calculated logP values. SIGNIFICANCE: Monomers used in dental restorative materials show a variety of toxic effects on gingival fibroblasts. A combination approach using MTT and LDH assays provides valuable information about their toxic effects.     

Water sorption and solubility of dental composites and identification of monomers released in an aqueous environment

Water sorption and solubility of six proprietary composite resin materials were assessed, and monomers eluted from the organic matrix during water storage identified. Water sorption and solubility tests were carried out with the following storage times: 4 h, 24 h and 7, 60 and 180 days. After storage, water sorption and solubility were determined. Eluted monomers were analysed by high performance liquid chromatography (HPLC). Correlation between the retention time of the registered peak and the reference peak was observed, and UV-spectra confirmed the identity. The results showed an increase in water sorption until equilibrium for all materials with one exception. The solubility behaviour of the composite resin materials tested revealed variations, with both mass decrease and increase. The resin composition influences the water sorption and solubility behaviour of composite resin materials. The HPLC analysis of eluted components revealed that triethyleneglycol dimethacrylate (TEGDMA) was the main monomer released. Maximal monomer concentration in the eluate was observed after 7 days. During the test period, quantifiable quantities of urethanedimethacrylate (UEDMA) monomer were observed, whereas 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]propane (Bis-GMA) was only found in detectable quantities. No detectable quantities of bisphenol-A were observed during the test period.     

Water sorption, solubility, MeOH sorption and THF sorption of visible light cured resin--on resin using cyclophosphazene monomers and commercial monomers

Studies were done to decrease both the water sorption and solubility of visible light cured resin. As monomer, three kinds of cyclophosphazene monomers and three kinds of commercial monomers were prepared to the visible light cured unfilled resins. When these set products were immersed in water, MeOH and THF, water sorption and solubility in water, MeOH sorption and solubility in MeOH, THF sorption, and mechanical properties were examined. Water sorption was increased by degrees for all the monomers. In the cases of 4 PN-(EMA)8, 4 PN-(TF)1-(EMA)7, 4 PN-(TF)2-(EMA)6, Tri-EDMA, BMPEPP and Bis-GMA + Tri-EDMA, the value of solubility in water after 30 days, was 0.16, 0.20, 0.51, 0.65, 0.17 and 0.81% respectively. MeOH sorption showed a tendency to increase, except for Bis-GMA + Tri-EDMA and 4 PN-(TF)2-(EMA)6. Solubility in MeOH after 30 days, for cyclophosphazene monomers and commercial monomers, was 0.09-0.36% and 1.36-5.40%. THF sorption after 30 days, for cyclophosphazene monomers, was small in comparison with that of commercial monomers. Compressive strength was 230-275 MPa in all cases. But, transverse strength, for all the cyclophosphazene monomers, was 45 MPa or below. In the cases of commercial monomers, the value of transverse strength was 55-90 MPa.     

Oxidative stress and cytotoxicity generated by dental composites in human pulp cells

Dental composites are a source of residual monomers that are released into the oral environment. Since monomers act on cultured cells through reactive oxygen species (ROS), we hypothesized that composites generate ROS associated with cytotoxicity. Human pulp-derived cells were exposed to extracts of methacrylate-based materials including triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate-free composites (Tetric Ceram, Tetric EvoCeram, els, els flow, Solitaire 2) and a silorane-based composite (Hermes III). The materials were polymerized in the presence and absence of a polyester film and then extracted in culture medium. The generation of ROS was measured by flow cytometry, and cytotoxicity was determined as well. Methacrylate-based composites reduced cell survival but varied in efficiency. Undiluted extracts of Solitaire 2 specimens prepared in the absence of a polyester film reduced cell survival to 26% compared with untreated cultures. Cytotoxicity was reduced when specimens were covered with a polyester film during preparation. Cytotoxicity of the composites was ranked as follows: Solitaire 2 >> els flow > Tetric Ceram = Tetric EvoCeram = els > Hermes III. The generation of ROS followed the same pattern as detected with cytotoxic effects. A positive correlation was found between ROS production and cell survival caused by extracts made from materials not covered with a polyester film. These findings suggest that components released from composites affect cellular signaling networks through ROS formation. Regenerative and reparative capacities of the dentine–pulp complex may be impaired by biologically active resin monomers released from composite restorations.     

Direct and indirect eluates from bulk fill resin-based-composites

ObjectivesTo compare elutable substances directly released from bulk-fill (BF) resin-based composites (RBCs) with indirect elution from teeth restored with a BF composite. In addition to (co)monomers, the analytical focus was on other potentially toxic ingredients or impurities. Furthermore, the barrier function of the residual dentin/adhesive layer was studied.MethodsSix BF-RBC materials were studied. For each material subgroup, ten human third molar teeth with standard Class-I occlusal cavities were prepared and provided with a three-step adhesive system and the respective composite restoration (tooth groups). Same sized control specimens of the restorative material were prepared (‘direct BF-RBC’ groups). Each specimen was placed in an elution chamber such that the elution media (ethanol/water, 3:1) only contacted the tooth root or ¾ height of each specimen. They were incubated at 37 °C for up to 7 d. Samples of eluate were taken after 1, 2, 4 and 7 d and were analysed by high-temperature gas chromatography/mass spectrometry.Results(Co)monomers such as Bisphenol A ethoxylate dimethacrylate (bisEMA) or tetraethylene glycol dimethacrylate (TEEGDMA) were mostly found in the eluates of the ‘direct BF-RBC’ groups in statistically significantly greater amounts than in the eluates of the ‘tooth groups’. The residual dentin and/or adhesive layers acted as a diffusion barrier for most of the substances except for triethylene glycol dimethacrylate (TEGDMA) or diethylene glycol dimethacrylate (DEGDMA). For TEGDMA up to 3 orders of magnitude more were found in the ‘tooth groups’ compared to the ‘direct BF-RBC’ groups, evidently released by the adhesive system.Substances of Very High Concern (SVHC) including TINUVIN® 328 and BPA were found mainly in the eluates of ‘direct BF-RBC’ groups.SignificanceFor estimation of biocompatibility, a total system, specifically BF-RBC + adhesive, should always be investigated since individual considerations, such as only elution from a BF-RBC, do not correctly reflect the total clinical situation. The focus of elution tests should not only be on the co(monomers), but also on other ingredients or impurities that may be released.     

光固化复合树脂释放成分的检测方法及评价

光固化复合树脂是临床广泛使用的牙体修复材料,在光照发生聚合固化时,有部分单体未发生聚合,成为残余单体,残余单体在口腔环境中进行浸出释放,唾液、酶等也会引起树脂的生物降解从而释放一些成分,这些成分可能对机体组织形成一定的影响。目前有多种检测释放单体的方法,包括高效液相色谱法、液相色谱-质谱联用法、高效液相色谱-质谱联用法、气相色谱-质谱联用法等。该文从残余单体释放的原因及其对人体的影响、检测方法等方面作一综述。     

Bis-GMA/TEGDMA树脂水解产物分析

目的检测Bis-GMA/TEGDMA树脂片经去离子水浸泡后的水解产物。方法 Bis-GMA/TEGDMA单体加入CQ/DMAEMA后光照聚合制备树脂片,将树脂片经37℃恒温去离子水浸泡24 h,其中在1h、3 h、6 h和24 h四个时间点各取1 mL浸泡液,用乙酸乙酯萃取、旋蒸,通过高效液相色谱质谱法(HPLC/MS)检测分析,确定树脂水解产物。结果树脂片的水解产物为双酚A-二甘油醚(Bis-GMA-2MA)、双酚A-二氧代丙基醚(Bis-GMA-2MA-2H2O)、单甲基丙烯酸二缩三乙二醇酯(TEGDMA-MA)和二缩三乙二醇(TEGDMA-2MA)。结论 Bis-GMA/TEGDMA树脂片经去离子水浸泡后树脂可发生水解,水解产物及残余Bis-GMA/TEGDMA树脂单体可析出并释放到去离子水中。     

Disintegration of visible light-cured composite resins caused by long-term water immersion

The purpose of this study is to clarify a cause of disintegration of composite resins by long-term immersion in distilled water. Three kinds of visible light-cured composite resins (Heliosit, Plurafil Super and Visio Dispers) and one conventional composite resin (Clearfil F II) were prepared as the specimens with a 20 mm diameter and 1 mm thickness. These specimens were immersed in distilled water at 37 +/- 1 degree C for 3 years. These specimens were analysed and observed by a comprehensive multi analyzer and scanning electron microscope. The other hand residues in distilled water were analysed by infrared (IR) and nuclear magnetic resonance (NMR) spectrometers. The surface layer of all four composite resins showed signs of disintegration. The composite resins with abundant dissolved substances had disintegrated markedly, and such disintegration occurred deep inside the specimens. In IR and 1H-NMR spectra of dissolved substances, two visible light-cured composite resins (Heliosit and Plurafil Super) could be detected unreacted monomers, but one visible light-cured composite resin (Visio Dispers) and one conventional composite resin (Clearfil F II) could not be detected them. In 1H-NMR spectra of dissolved substances of all four composite resins, new signals not composed originally were observed. The progress of disintegration were demonstrated clearly. The dissolved substances were shown as the disintegrated substance between resin matrixs and silane coupling agents. It is suggested that the disintegration of composite resins by long-term water immersion is derived from hydrolysis.     

Mechanical properties and cure depth of UDMA-based composite resins

Mechanical properties and cure depth of visible light-cured composite resins based on six types of UDMA (IP-HEMA, IP-HPMA, XY-HPMA, MC-HPMA, UEDMA and UPDMA) monomers were investigated. Under wet conditions, the mechanical properties of the composite resins based on aliphatic UDMA (UEDMA and UPDMA) monomers were inferior to those based on the other UDMA monomers containing aromatic or cyclohexane rings in their chemical structures. The cure depth for these UDMA-based composite resins increased with increasing irradiation time. The composite resin based on the XY-HPMA monomer showed a cure depth and transmission coefficient superior to the other composite resins.