The effect of storage medium on the elution of monomers from composite materials

The aim of this study was to evaluate the effect of four different storage media on the elution of monomers from two composite materials. Samples (n = 10, diameter: 4.5 mm, thickness: 2 mm) of two different composite materials (Ceram X? & Filtek? Supreme XT) were stored after polymerization in four different media (NaCl, saliva, ethanol 75% & acetone) for 24 h, 7 days, and 28 days. From the storage medium of each tested time period, samples were prepared and analyzed by LC-MS/MS, for the elution of BisGMA, TEGDMA, HEMA, Bisphenol A, and two types of UDMA. No monomers were detected in the samples of Ceram X?, independently of the storage medium used. In the samples of Filtek? Supreme XT, no Bisphenol A, HEMA, and UDMA 1 were found. BisGMA was detected only in the ethanol and acetone samples. The amount of BisGMA eluted in acetone was significant higher compared with ethanol 75% (p < 0.0001). TEGDMA was the only monomer that could be detected in all tested storage media. Storage in acetone resulted in higher release of TEGDMA when compared with other media. The amount of TEGDMA released in saliva was similar to the one released in ethanol 75%. It can be concluded that acetone is not a suitable medium for elution experiments and although ethanol 75% can simulate saliva concerning the elution of TEGDMA, it does not represent a laboratory substitute of saliva with respect to the elution of monomers like BisGMA.     

Thermal expansion characteristics of light-cured dental resins and resin composites

The thermal expansion characteristics of dental resins prepared by light-curing of Bis-GMA, TEGDMA, UDMA, Bis-EMA(4) or PCDMA dimethacrylate monomers and of commercial light-cured resin composites (Z-100 MP, Filtek Z-250, Sculpt-It and Alert), the organic matrix resin of which is based on different combinations of the above monomers, were studied by thermomechanical analysis (TMA). This study showed the existence of a glass transition temperature at around 35-47 degrees C for the resins and 40-45 degrees C for the composites; then the coefficient of linear thermal expansion (CLTE) was calculated at the temperature intervals 0-60 degrees C, 0-T(g) and T(g)-60 degrees C. The CLTE values of Bis-GMA, TEGDMA and UDMA resins are similar and lower than those of Bis-EMA (4) and PCDMA resins. The CLTE values of the composites indicated that the major factor that affects the CLTE of a composite is the filler content, but it also seems to be affected by the chemical structure of the matrix resin. TMA on water-saturated samples showed that water desorption takes place during the measurement and that the residual water acts as a plasticizer decreasing the T(g) and increasing the CLTE values. Furthermore, TMA on post-heated samples for 1, 3 or 6h showed, only for the resins, an initial decrease of CLTE and increase of the T(g) after 1h that was not significantly changed after 6h of heating.     

Study of water sorption,solubility and modulus of elasticity of light-cured dimethacrylate-based dental resins

Polydimethacrylate resins were prepared by photopolymerization of Bis-GMA, TEGDMA, UDMA or Bis-EMA (4) monomer, initiated by camphoroquinone/N,N-dimethylaminoethyl methacrylate system. The study of physical properties of these resins showed that TEGDMA seems to create the most dense polymer network, which however is the most flexible (0.74GPa), absorbs the highest amount of water (6.33 wt%) and releases the lowest amount of unreacted monomer (2.41 microg/mm(3)). UDMA and Bis-EMA (4) create more rigid networks, which absorb lower water and release higher unreacted monomer than TEGDMA. Bis-EMA (4) absorbs the lowest water amount (1.79 wt%) and releases the highest amount of unreacted monomer (14.21 microg/mm(3)). Bis-GMA leads to the formation of the most rigid network (1.43 GPa), which absorbs lower water than the resin made by TEGDMA but higher than the resin made by UDMA and Bis-EMA (4). Copolymers of Bis-GMA with the other monomers were also prepared, using various monomer combinations and molar ratios. Copolymers Bis-GMA/TEGDMA (50/50 and 70/30 wt%) showed significantly higher values for Young's modulus (1.83 and 1.78 GPa) than those predicted by the linear dependence of the values on the copolymer composition. Gradual replacement of TEGDMA with UDMA or/and Bis-EMA (4) in copolymerization with Bis-GMA resulted in more flexible resins with lower water sorption and higher solubility values, depending on the TEGDMA content.     

Elution study of unreacted Bis-GMA, TEGDMA, UDMA, and Bis-EMA from light-cured dental resins and resin composites using HPLC

In the present work the elution of residual monomers from light-cured dental resins and resin composites into a 75% ethanol:water solution was studied using High-Performance Liquid Chromatography (HPLC). The resins studied were made by light-curing of bisphenol A glycol dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), ethoxylated bisphenol A glycol dimethacrylate [Bis-EMA(4)] and mixtures of these monomers. The resin composites were made from two commercial light-cured restorative materials (Z100 MP and Filtek Z250), the resin matrix of which is based on copolymers of these monomers. The effect of the curing time on the amount of monomers eluted was investigated. The concentration of the extractable monomers was determined at several immersion periods from 3 h to 30 days. For all the materials studied, it was observed that the chemical structure of the monomers used for the preparation of the resins, which defines the chemical and physical structure of the corresponding resin, directly affects the amount of eluted monomers, as well as the time needed for the elution of this amount. In the case of composites, it seems that the elution process it is not influenced by the presence of filler.     

Thermal analysis of dental resins cured with blue light-emitting diodes (LEDs)

Thermal analysis was used to measure the characteristics of dental resins cured with the use of a new light-activation unit equipped with high illuminant blue light-emitting diodes (LEDs). The characteristics were compared with those of resins cured with the use of two conventional halogen lamp units. The prepared base monomer consisted of a mixture of Bis-GMA and TEGDMA (60:40 by weight), with 0.5 wt% CQ/DMPT or CQ/DMAEMA. The two experimental visible-light-cured resins were polymerized for 40 s. Differential scanning calorimetry (DSC) was used to examine the thermal characteristics of the cured resins. The activation energy for the decomposition of the dental resin was calculated from the peaks of the endothermic curves obtained when the specimens were heated at three different rates (5, 10, and 15 C/min) during DSC. The activation energies calculated for the LED-cured specimens were more than 220 kJ/mol; specimens cured with the use of the halogen units had activation energies of less than 192 kJ/mol. The Knoop hardness number (KHN) of the same specimens was measured, and was higher with the blue LED units than with halogen lamp units. Therefore, dental resins cured using blue LEDs have a higher degree of polymerization and more stable three-dimensional structures than those cured with halogen lamps.     

Sorption kinetics of ethanol/water solution by dimethacrylate-based dental resins and resin composites

In the present investigation the sorption-desorption kinetics of 75 vol % ethanol/water solution by dimethacrylate-based dental resins and resin composites was studied in detail. The resins examined were made by light-curing of bisphenol A glycol dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), bisphenol A ethoxylated dimethacrylate (Bis-EMA), and mixtures of these monomers. The resin composites were prepared from two commercial light-cured restorative materials (Z100 MP and Filtek Z250), the resin matrix of which is based on copolymers of the above-mentioned monomers. Ethanol/water sorption/desorption was examined in both equilibrium and dynamic conditions in two adjacent sorption-desorption cycles. For all the materials studied, it was found that the amount of ethanol/water sorbed or desorbed was always larger than the corresponding one reported in literature in case of water immersion. It was also observed that the chemical structure of the monomers used for the preparation of the resins directly affects the amount of solvent sorbed or desorbed, as well as sorption kinetics, while desorption rate was nearly unaffected. In the case of composites studied, it seems that the sorption/desorption process is not influenced much by the presence of filler. Furthermore, diffusion coefficients calculated for the resins were larger than those of the composites and were always higher during desorption than during sorption. Finally, an interesting finding concerning the rate of ethanol/water sorption was that all resins and composites followed Fickian diffusion kinetics during almost the whole sorption curve; however, during desorption the experimental data were overestimated by the theoretical model. Instead, it was found that a dual diffusion-relaxation model was able to accurately predict experimental data during the whole desorption curve. Kinetic relaxation parameters, together with diffusion coefficients, are reported for all resins and composites.     

ESR study of camphorquinone/amine photoinitiator systems using blue light-emitting diodes

New light-activation units equipped with high-illuminant blue light-emitting diodes (LEDs) have recently been proposed as a replacement for the halogen units that are widely used in dentistry to polymerize light-cured resins. The photoinitiators in light-cured dental resins, typified by the camphorquinone (CQ)/amine photoinitiator system, generate primary radicals with light irradiation that attack the double bonds of resin monomers. The physical properties of the cured resins are affected by the generation of primary radicals during the initial stage of polymerization. This study examined two types of photoinitiator systems, CQ/DMPT and CQ/DMAEMA, and three types of curing units, a new LED unit and two conventional halogen units. The primary radicals generated by irradiation were quantified using electron spin resonance (ESR) spectroscopy with a trapping method, using phenyl-tert-butyl nitrone as the trapping agent. The energy efficiencies of the LED and halogen units were compared by quantifying the generated radicals and emitted light energy (J/cm(2)). The energy required to generate a given amount of radicals using the LED unit was smaller than that using the halogen units (p<0.05). These results suggest that the new LED unit performs better than conventional halogen units with respect to light energy.     

Interactions between resin monomers and commercial composite resins with human saliva derived esterases

Cholesterol esterase (CE) and pseudocholinesterase (PCE) have been reported to degrade commercial and model composite resins containing bisphenylglycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA) or the latter in combination with urethane modified BisGMA monomer systems. In addition, human saliva has been shown to contain esterase like activities similar to CE and PCE. Hence, it was the aim of the current study to determine to what extent human saliva could degrade two common commercial composite resins (Z250 from 3M Inc. and Spectrum TPH from L.D. Caulk) which contain the above monomer systems. Saliva samples from different volunteers were collected, processed, pooled, and freeze-dried. TEGDMA and BisGMA monomers were incubated with human saliva derived esterase activity (HSDEA) and their respective hydrolysis was monitored using high performance liquid chromatography (HPLC). Both monomers were completely hydrolyzed within 25 h by HSDEA. Photopolymerized composites were incubated with buffer or human saliva (pH 7.0 and 37 C) for 2, 8 and 16 days. The incubation solutions were analyzed using HPLC and mass spectrometry. Surface morphology characterization was carried out using scanning electron microscopy. Upon biodegradation, the Z250 composite yielded higher amounts of BisGMA and TEGDMA related products relative to the TPH composite. However, there were higher amounts of ethoxylated bis-phenol A released from the TPH material. In terms of total mass of products released, human saliva demonstrated a greater ability to degrade Z250. In summary, HSDEA has been shown to contain esterase activities that can readily catalyze the biodegradation of current commercial composite resins.     

Synthesis and characterization of new dimethacrylate monomer and its application in dental resin

In this study, a dimethacrylate monomer, 1,4-Bis[2-(4-(2′-hydroxy-3′-methacryloyloxy-propoxy)phenyl)-2propyl]benzene (BMPPB) was synthesized to replace 2,2-bis[4-(2′-hydroxyl-3′-methacryloyloxy-propoxy)phenyl]propane (Bis-GMA) as one component of dental restorative materials. The structure of BMPPB and its intermediate product 1,4-bis[2-(4-(oxiranylmethoxy)phenyl)-2propyl]benzene (BOPPB) were confirmed by Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance spectroscopy (¹H-NMR), and elemental analysis. In order to evaluate the possibility of replacing Bis-GMA with BMPPB in dental resin, double bond conversion (DC), polymerization shrinkage, contact angle, water sorption (WS) and solubility (SL), and flexural strength (FS) and modulus of BMPPB/tri(ethylene glycol)dimethacrylate (TEGDMA) (50/50?wt) resin system and Bis-GMA/BMPPB/TEGDMA (25/25/50?wt) resin system were studied. Commercially used Bis-GMA/TEGDMA (50/50?wt) dental resin system was used as reference. The results showed that BMPPB-contained copolymer had higher DC, higher WS and SL than the copolymer that only contained Bis-GMA (p?<?0.05). All of the copolymers had nearly the same contact angle (p?>?0.05). BMPPB/TEGDMA resin system had lower polymerization shrinkage, higher FS and modulus (p?<?0.05) than Bis-GMA/TEGDMA resin system. There was no significant difference on polymerization shrinkage, FS and modulus (p?>?0.05) between Bis-GMA/BMPPB/TEGDMA resin system and Bis-GMA/TEGDMA resin system. Before and after water immersion, both FS and modulus of every copolymer did not change significantly (p?>?0.05). Therefore, BMPPB had potential to be used to replace Bis-GMA as base resin in dental restorative materials, but many studies should be undertaken further.     

A new resin matrix for dental composite having low volumetric shrinkage

The applications of dental restorative composite resins containing 2,2 bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), as a base resin, and triethylene glycol dimethacrylate (TEGDMA), as a diluent, are often limited in dentistry due to the relatively large amount of volumetric shrinkage that occurs during the curing reaction. In this study, various new resin matrices were examined for use as dental composites in order to reduce the amount of volumetric shrinkage that occurs in dental composites as a result of curing. Bis-GMA derivatives were synthesized by substituting methyl groups for hydrogen on the phenyl ring. The derivatives of TEGDMA with different chain lengths or reactive groups were also examined. The molecular structural changes in the TEGDMA derivatives were not effective in reducing the level of volumetric shrinkage. The resin matrix containing a Bis-GMA derivative and TEGDMA showed a reduced amount of volumetric shrinkage in proportion to the number of methyl groups on the phenyl rings. Polymerization with a mixture of Bis-GMA, its derivatives and a diluent is a promising strategy for obtaining a polymer with a low amount of volumetric shrinkage. A comparison of the volumetric shrinkage of dental composites containing Bis-GMA, TMBis-GMA (2,2-bis[3,5-dimethyl, 4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane)), and TEGDMA with that prepared from a Bis-GMA and TEGDMA mixture showed that the volumetric shrinkage reduction in the new resin was approximately 50%. Furthermore, the mechanical strength of the former was higher than that of the latter.     

Biodegradation of a dental composite by esterases: dependence on enzyme concentration and specificity

Studies have shown that inflammatory (cholesterol esterase, CE) and salivary (pseudo-cholinesterase, PCE) enzymes can cause the breakdown of bisphenol-A diglycidyl dimethacrylate (bisGMA) and triethylene glycol dimethacrylate (TEGDMA) components from composite resins. Based on the above consideration, it was desired to show how CE- and PCE-catalyzed hydrolysis of resin components was dependent on the enzymes' concentration and to determine their distinct specificities (if any) towards resin components. Photopolymerized model composite resin samples (60% weight fraction silanated barium glass filler) based on bisGMA and TEGDMA monomers (55/45 weight ratio of the matrix, respectively) were incubated with PBS and either 0.01, 0.05, 0.1 or 1 unit/ml of CE or PCE for 16 days (pH 7.0, 37 degrees C). Incubation solutions were analyzed by high-performance liquid chromatography (HPLC), UV spectroscopy and mass spectrometry. The composite samples were characterized by scanning electron microscopy (SEM). Degradation rates of bisGMA and TEGDMA monomers were assessed. The results showed that CE had a greater specificity towards cleaving bisGMA while PCE showed a greater specificity towards TEGDMA. A strong enzyme concentration dependence was observed which suggests that the level of degradation products generated for a material will depend on the esterase make-up of an individual's saliva in combination with the specific formulation of monomer components used.     

Effects of long-term sub-lethal concentrations of dental monomers on THP-1 human monocytes

Studies have shown that monomers from dental resins are acutely cytotoxic, but little is known of their long-term effects at sub-lethal concentrations. The current study determined the long-term effects of sub-lethal concentrations of TEGDMA (triethyleneglycol dimethacrylate) and Bis-GMA (bisphenol-glycidylinethacrylate), two common dental monomers, on the in vitro cellular proliferation, succinic dehydrogenase activity, and total cellular protein production of monocytes. Human THP-1 monocytes were exposed to concentrations of 100, 200, and 400 micromol l(-1) of TEGDMA or 1, 5, and 25 micromol l(-1) Bis-GMA for 5 weeks. Controls received only vehicle solutions of ethanol. Each week cellular proliferation (hemocytometer), succinic dehydrogenase (SDH) activity (MTT) and total cellular protein (bicinchoninic acid) were assessed. The results were compared with ANOVA and Tukey intervals (alpha = 0.05). TEDGMA had no proliferative or cellular protein effects, but increased SDH activity 20-60% in week 1 (p < 0.05). SDH activity then decreased 40% in week 2, followed by a gradual increase of 30-40% over week 3-5 (p < 0.05). Bis-GMA reduced proliferation by 40-60% from 1-5 weeks exposure (p < 0.05). However, SDH activity and total protein per cell were not affected. There was some indication of increased SDH activity after 5 weeks (20-30%, p < 0.05). Sub-lethal concentrations of TEGDMA and Bis-GMA have significant long-term effects on monocytes at low-dose 5-week exposures in vitro. Each monomer acted differently.     

Biodegradation of a dental composite by esterases: dependence on enzyme concentration and specificity

Studies have shown that inflammatory (cholesterol esterase, CE) and salivary (pseudocholinesterase, PCE) enzymes can cause the breakdown of bisphenol-A diglycidyl dimethacrylate (bisGMA) and triethylene glycol dimethacrylate (TEGDMA) components from composite resins. Based on the above consideration, it was desired to show how CE- and PCE-catalyzed hydrolysis of resin components was dependent on the enzymes' concentration and to determine their distinct specificities (if any) towards resin components. Photopolymerized model composite resin samples (60% weight fraction silanated barium glass filler) based on bisGMA and TEGDMA monomers (55/45 weight ratio of the matrix, respectively) were incubated with PBS and either 0.01, 0.05, 0.1 or 1 unit/ml of CE or PCE for 16 days (pH 7.0, 37°C). Incubation solutions were analyzed by high-performance liquid chromatography (HPLC), UV spectroscopy and mass spectrometry. The composite samples were characterized by scanning electron microscopy (SEM). Degradation rates of bisGMA and TEGDMA monomers were assessed. The results showed that CE had a greater specificity towards cleaving bisGMA while PCE showed a greater specificity towards TEGDMA. A strong enzyme concentration dependence was observed which suggests that the level of degradation products generated for a material will depend on the esterase make-up of an individual's saliva in combination with the specific formulation of monomer components used.     

Effects of long-term sub-lethal concentrations of dental monomers on THP-1 human monocytes

Studies have shown that monomers from dental resins are acutely cytotoxic, but little is known of their long-term effects at sub-lethal concentrations. The current study determined the long-term effects of sub-lethal concentrations of TEGDMA (triethyleneglycol dimethacrylate) and Bis-GMA (bisphenol-glycidylmethacrylate), two common dental monomers, on the in vitro cellular proliferation, succinic dehydrogenase activity, and total cellular protein production of monocytes. Human THP-1 monocytes were exposed to concentrations of 100, 200, and 400 μmol l^-1 of TEGDMA or 1, 5, and 25 μmol l^-1 Bis-GMA for 5 weeks. Controls received only vehicle solutions of ethanol. Each week cellular proliferation (hemocytometer), succinic dehydrogenase (SDH) activity (MTT) and total cellular protein (bicinchoninic acid) were assessed. The results were compared with ANOVA and Tukey intervals (α =0.05). TEDGMA had no proliferative or cellular protein effects, but increased SDH activity 20-60% in week 1 (p < 0.05). SDH activity then decreased 40% in week 2, followed by a gradual increase of 30-40% over week 3-5 (p < 0.05). Bis-GMA reduced proliferation by 40-60% from 1-5 weeks exposure (p < 0.05). However, SDH activity and total protein per cell were not affected. There was some indication of increased SDH activity after 5 weeks (20-30%, p < 0.05). Sub-lethal concentrations of TEGDMA and Bis-GMA have significant long-term effects on monocytes at low-dose 5-week exposures in vitro. Each monomer acted differently.     

Residual monomers and degree of conversion of partially bioresorbable fiber-reinforced composite

The aim of this study was to evaluate the total quantity of residual monomer (bis-phenyl glycidyl dimethacrylate, i.e. Bis-GMA, and triethylene glycol dimethacrylate, i.e. TEGDMA), residual monomer release into water and the degree of monomer conversion (DC%) of glass fiber-reinforced composites (FRC) with a partially bioresorbable polymer matrix. Another aim was to find out whether the curing mode affects the quantity of residual monomer and degree of conversion. Glass fibers were preimpregnated with a bioresorbable poly(hydroxyproline) amide and non-resorbable Bis-GMA-TEGDMA resin system. Specimens were immersed in water for 1, 3 or 7 days (37 degrees C) to determine the quantity of leached residual monomers, or in the solvent tetrahydrofuran for 3 days to determine the total quantity of residual monomers by high performance liquid chromatography. DC% was measured by Fourier transform infrared spectroscopy. The quantity of residual monomer of the specimens decreased when the specimens contained glass fibers, and/or poly(hydroxyproline) amide, and/or when it was post-cured. The majority of the residual monomers were leached out during the first 24 h of immersion in water. The DC% of the specimens increased when post-cured. Also glass fibers in the composite increased the DC% in contrast to Bis-GMA-TEGDMA resin only. In conclusion, use of poly(hydroxyproline) amide as a sizing of the glass fibers in FRC does not increase the quantity of residual monomers. These results suggest that this new kind of partially bioresorbable FRC has potential for biomedical applications.     

Mutual influence of cholesterol esterase and pseudocholinesterase on the biodegradation of dental composites

It has been demonstrated that human saliva contains cholesterol esterase (CE)- and pseudocholinesterase (PCE)-like hydrolase activities. While PCE has been shown to preferentially degrade triethylene glycol dimethacrylate (TEGDMA) and its derivatives, CE has a greater catalytic effect on the breakdown of bis-phenol-A-diglycidyl dimethacrylate (bisGMA) components in composite dental resins. The current study seeks to determine if there is a mutual influence between the different esterases with respect to the biodegradation of resin composite. Photopolymerized model composite resin samples (containing 60% by weight fraction of silanated barium glass filler) based on bisGMA/TEGDMA (bis) or urethane-modified bisGMA/TEGDMA/bisEMA (ubis) monomers were incubated in buffer, CE and/or PCE solutions (pH=7.0, 37 degrees C) for 8 and 16 days. The incubation solutions were analyzed for degradation products using high-performance liquid chromatography, UV spectroscopy and mass spectrometry. In the bis system, higher amounts (p<0.05) of a bisGMA derived product, bishydroxy-propoxyphenyl-propane (bisHPPP), were detected in the combined enzyme group as compared to the sum of the two individual enzyme groups. In the ubis system, similar comparisons showed that higher levels (p<0.05) of bisHPPP were detected in the combined group at 8 days while higher amounts (p<0.05) of a bisEMA derived product, ethoxylated bis-phenol A, were detected in the combined group at 16 days. The study concluded that CE and PCE act synergistically to increase the biodegradation of both composite resin materials.     

流动纳米树脂预防性窝沟龋充填

背景：预防性树脂充填术由于不采用传统的预防性扩展,只去除少量的龋坏组织后即用复合树脂或玻璃离子材料充填龋洞,而未患龋的窝沟使用封闭剂保护。 目的：通过应用美国3M公司生产的Filtek Z350流动纳米树脂对窝沟可疑龋、初龋磨除后进行预防性充填,观察并评价其临床效果,探索预防性充填治疗早期窝沟龋的新方法。 方法：对196例6~25岁患者磨牙的牙合 面窝沟龋在去除龋坏的牙体组织后,采用Eadper prompt自酸蚀粘结技术,用Filtek Z350流动纳米树脂对整个牙面进行预防性充填术,并采用对侧同名牙或邻牙也有窝沟龋者用同一公司生产的ClinproTM可见光固化变色窝沟封闭剂充填作对照研究。 结果与结论：随治4年后发现该方法涂膜保留率高,能有效阻止龋病的进一步发展。实验组与对照组在术后1,2年时的涂膜保留率差异无显著性意义,而在第3,4年时差异有显著性意义(P < 0.01、P < 0.05)。龋病发生率在1,2年时差异无显著性意义,而在3,4年时差异有显著性意义(P < 0.05)。提示Filtek Z350流动纳米树脂预防性窝沟充填是一种有效阻止窝沟早期龋进一步发展的方法。     

Bis-GMA／（SiO2-ZrO2）纳米复合树脂的制备与性能研究

目的：通过添加纳米无机填料对树脂基质进行增强增韧改性,来满足修复性牙科材料的要求,解决树脂基质耐磨性较差、强度低的问题,制备出合适的临床牙科修复材料。方法：采用原位分散法,双酚A-甲基丙烯酸缩水甘油酯（Bis-GMA）和双甲基丙烯酸二缩三乙二醇酯（TEGDMA）共同作为树脂基质,混合加入经过硅烷偶联剂（KH-570）表面处理的纳米氧化硅（SiO2）和二氧化锆（ZrO2）制备新型复合树脂,同时使用高速搅拌和超声分散等制备工艺来改善纳米填料分散体系,运用X射线衍射（XRD）、扫描电子显微镜（SEM）等实验手段对Bis—GMA纳米复合树脂材料进行性能测试及结构表征。结果：使用高速搅拌和超声分散技术可使经过表面处理的纳米SiO2和ZrO2均匀分散在树脂基质中,达到了纳米级原生粒子分散效果,发挥了不同无机填料间的相互作用,能够有效的提高复合树脂材料的机械性能。结论：该方法制备出的高性能Bis—GMA／nano（SiO2-ZrO2）复合树脂牙科材料,能充分满足临床牙科修复学需要。     

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.     

Shrinkage strain-rates of dental resin-monomer and composite systems

The purpose of this study was to investigate the shrinkage strain rate of different monomers, which are commonly used in dental composites and the effect of monomer functionality and molecular mass on the rate. Bis-GMA, TEGDMA, UDMA, MMA, HEMA, HPMA and different ratios of Bis-GMA/TEGDMA were mixed with Camphorquinone and Dimethyl aminoethyle methacrylate as initiator system. The shrinkage strain of the samples photopolymerised at Ca. 550 mW/cm2 and 23 degrees C was measured using the bonded-disk technique of Watts and Cash (Meas. Sci. Technol. 2 (1991) 788-794), and initial shrinkage-strain rates were obtained by numerical differentiation. Shrinkage-strain rates rose rapidly to a maximum, and then fell rapidly upon vitrification. Strain and initial strain rate were dependent upon monomer functionality, molecular mass and viscosity. Strain rates were correlated with Bis-GMA in Bis-GMA/TEGDMA mixtures up to 75-80 w/w%, due to the higher molecular mass of Bis-GMA affecting termination reactions, and then decreased due to its higher viscosity affecting propagation reactions. Monofunctional monomers exhibited lower rates. UDMA, a difunctional monomer of medium viscosity, showed the highest shrinkage strain rate (P < 0.05). Shrinkage strain rate, related to polymerization rate, is an important factor affecting the biomechanics and marginal integrity of composites cured in dental cavities. This study shows how this is related to monomer molecular structure and viscosity. The results are significant for the production, optimization and clinical application of dental composite restoratives.