磷酸酯粘结剂诱导生成羟基磷灰石晶体的实验研究
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摘要
牙体龋坏和缺损目前的治疗方法有很多隐患,可能造成牙本质过敏、继发龋等,粘结剂与牙体组织之间还存在边缘微渗漏问题。仿生材料学日新月异的研究进展给牙体疾病的治疗带来了新的思路,如能采用仿生矿化合成类似牙体硬组织结构的生物材料,引导牙体损伤组织的自愈性修复,以上问题将有可能得到彻底的解决。
目的：依据生物矿化中有机大分子调控无机晶体生长的理论,以光固化在载玻片和牙本质上的牙本质粘结剂为有机聚合物大分子模板,通过摄取模拟体液中的钙磷等离子,诱导羟基磷灰石晶体的矿化,并通过含磷酸酯粘接剂与不含磷酸酯粘接剂诱导生成羟基磷灰石晶体能力的对比,为牙体硬组织的粘接修复和生物矿化修复提供研究思路。
方法：首先分别将CLEARFIL S3 BOND和3M Adper Single Bond 2两种牙本质粘接剂涂布到载玻片上,光固化后浸入模拟体液,37℃恒温水浴箱孵育7天,每天更换1次。分别用SEM,XRD,FTIR观察羟基磷灰石形貌,确定其性质和组成；再用相同方法观察两种粘接剂在牙本质片上诱导羟基磷灰石的矿化的情况,用SEM观察磷灰石形貌,用EDS测定磷灰石元素组成；最后评价两种粘接剂诱导羟基磷灰石矿化的能力,分析其形成机制和影响因素。
结果：矿化后载玻片标本上两种粘接剂表面都有白色不透明物质生成；扫描电子显微镜下观察到：含磷酸酯粘接剂矿化7天后生成的晶体直径约1～2μm,呈簇状,球状；X射线衍射出现羟基磷灰石晶体的特征峰；傅立叶红外光谱显示矿化后有矿化前没有的磷酸根基团和碳酸根基团振动吸收峰,说明含磷酸酯的粘接剂CLEARFIL S3 BOND在模拟体液中可以诱导生成含碳酸根的羟基磷灰石晶体；而不含磷酸酯粘接剂3M Adper Single Bond 2没有出现以上结果,说明没有诱导生成羟基磷灰石晶体。
牙本质片标本上两种粘接剂矿化7天后,两种粘接剂表面都有白色不透明物质生成,扫描电子显微镜下含磷酸酯的粘接剂CLEARFIL S3 BOND表面生成直径约10μm云层片状磷灰石；用能谱仪测定生成物是含多种离子的羟基磷灰石；而3M Adper Single Bond 2没有观察到羟基磷灰石晶体生成。
结论：综上所述,以含磷酸酯的牙本质粘接剂为模板,在模拟体液中能够诱导羟基磷灰石晶体矿化,这为牙羟基磷灰石的仿生矿化提供了新的依据。
There are many hidden dangers in the present treatment of dental caries and defects,which may cause hypersensitivity, secondary caries and other symptoms, and there is still a problem to be resolved,adhesives and dental organizations are still have marginal microleakage. Rapid progress in biomimetic materials science has brought new ideas to the treatment of dental disease that if biological materials similar to dental hard tissue structure can be biomimetic synthesized which can guide the damage dental tissue repaired themselves, then the above problems will be completely resolved.
Objective:This study is based on biomineralization theory that organic molecules regulate and control inorganic crystal growth.The dental adhesive light-cured on glass slide and dentin was used as the organic polymer molecules template, through intake calcium and phosphorus in plasma from simulated body fluid, and the mineralization of hydroxyapatite (HAP) crystals was induced..And the capacity of generating HAP crystals by intake of calcium and phosphorus in simulated body fluid is compared between adhesives containing and without phosphate, in order to provide a basis for repairing dental hard tissue with bonding and biomimetic mineralization.
Methods:Firstly, CLEARFIL S3 BOND and3M Adper Single Bond 2 two kinds of adhesive is coated to the glass slide respectively, and then immersed in simulated body fluid(SBF)after light-curing,then incubated for 7days in 37℃constant temperature water bath and SBF is changed once a day. Morphology is observed by scanning electron microscopy(SEM); X-ray diffraction(XRD) and Fourier transform infrared spectrometer (FTIR) respectively, to determine the nature and composition.Then, HAP on dentin is observed with the same method, morphology of the product is observed with SEM, the elemental composition is measured by EDS. Finally ability to induce mineralization of HAP by two adhesive is evaluated and formation mechanisms and influencing factors is analyzed.
Results:The results showed that white opaque material is appeared on both two adhesives surface after mineralization; The crystal products of the adhesive containing phosphate mineraled after7days have a diameter of about 1～2μm, were clustered, globular; the characteristic peaks of hydroxyapatite crystals is observed by XRD; the vibration absorption peak of PO43+ and CO32+ is showed after mineralization by FTIR;it's all said that CLEARFIL S3BOND can be induced to be HAP crystals in SBF, but 3M Adper Single Bond 2 doesn't have these results.
There also have white opaque material generation on the dentin speciments of the two adhesives which mineralized 7days; The crystal products'diameter are about 10μm by scanning electron microscopy(SEM); HAP with a variety of ion was showed by Energy dispersive spectrometer (EDS);But the 3M Adper Single Bond 2 did not observe formation of HAP crystals.
Conclusion:HAP crystals can be induced to minerralize in simulated body fluid.as the dental adhesive with phosphate for the template, this provides a new theoretical basis.for biomimetic mineralization of tooth-like HAP.
目的：依据生物矿化中有机大分子调控无机晶体生长的理论,以光固化在载玻片和牙本质上的牙本质粘结剂为有机聚合物大分子模板,通过摄取模拟体液中的钙磷等离子,诱导羟基磷灰石晶体的矿化,并通过含磷酸酯粘接剂与不含磷酸酯粘接剂诱导生成羟基磷灰石晶体能力的对比,为牙体硬组织的粘接修复和生物矿化修复提供研究思路。
方法：首先分别将CLEARFIL S3 BOND和3M Adper Single Bond 2两种牙本质粘接剂涂布到载玻片上,光固化后浸入模拟体液,37℃恒温水浴箱孵育7天,每天更换1次。分别用SEM,XRD,FTIR观察羟基磷灰石形貌,确定其性质和组成；再用相同方法观察两种粘接剂在牙本质片上诱导羟基磷灰石的矿化的情况,用SEM观察磷灰石形貌,用EDS测定磷灰石元素组成；最后评价两种粘接剂诱导羟基磷灰石矿化的能力,分析其形成机制和影响因素。
结果：矿化后载玻片标本上两种粘接剂表面都有白色不透明物质生成；扫描电子显微镜下观察到：含磷酸酯粘接剂矿化7天后生成的晶体直径约1～2μm,呈簇状,球状；X射线衍射出现羟基磷灰石晶体的特征峰；傅立叶红外光谱显示矿化后有矿化前没有的磷酸根基团和碳酸根基团振动吸收峰,说明含磷酸酯的粘接剂CLEARFIL S3 BOND在模拟体液中可以诱导生成含碳酸根的羟基磷灰石晶体；而不含磷酸酯粘接剂3M Adper Single Bond 2没有出现以上结果,说明没有诱导生成羟基磷灰石晶体。
牙本质片标本上两种粘接剂矿化7天后,两种粘接剂表面都有白色不透明物质生成,扫描电子显微镜下含磷酸酯的粘接剂CLEARFIL S3 BOND表面生成直径约10μm云层片状磷灰石；用能谱仪测定生成物是含多种离子的羟基磷灰石；而3M Adper Single Bond 2没有观察到羟基磷灰石晶体生成。
结论：综上所述,以含磷酸酯的牙本质粘接剂为模板,在模拟体液中能够诱导羟基磷灰石晶体矿化,这为牙羟基磷灰石的仿生矿化提供了新的依据。
There are many hidden dangers in the present treatment of dental caries and defects,which may cause hypersensitivity, secondary caries and other symptoms, and there is still a problem to be resolved,adhesives and dental organizations are still have marginal microleakage. Rapid progress in biomimetic materials science has brought new ideas to the treatment of dental disease that if biological materials similar to dental hard tissue structure can be biomimetic synthesized which can guide the damage dental tissue repaired themselves, then the above problems will be completely resolved.
Objective:This study is based on biomineralization theory that organic molecules regulate and control inorganic crystal growth.The dental adhesive light-cured on glass slide and dentin was used as the organic polymer molecules template, through intake calcium and phosphorus in plasma from simulated body fluid, and the mineralization of hydroxyapatite (HAP) crystals was induced..And the capacity of generating HAP crystals by intake of calcium and phosphorus in simulated body fluid is compared between adhesives containing and without phosphate, in order to provide a basis for repairing dental hard tissue with bonding and biomimetic mineralization.
Methods:Firstly, CLEARFIL S3 BOND and3M Adper Single Bond 2 two kinds of adhesive is coated to the glass slide respectively, and then immersed in simulated body fluid(SBF)after light-curing,then incubated for 7days in 37℃constant temperature water bath and SBF is changed once a day. Morphology is observed by scanning electron microscopy(SEM); X-ray diffraction(XRD) and Fourier transform infrared spectrometer (FTIR) respectively, to determine the nature and composition.Then, HAP on dentin is observed with the same method, morphology of the product is observed with SEM, the elemental composition is measured by EDS. Finally ability to induce mineralization of HAP by two adhesive is evaluated and formation mechanisms and influencing factors is analyzed.
Results:The results showed that white opaque material is appeared on both two adhesives surface after mineralization; The crystal products of the adhesive containing phosphate mineraled after7days have a diameter of about 1～2μm, were clustered, globular; the characteristic peaks of hydroxyapatite crystals is observed by XRD; the vibration absorption peak of PO43+ and CO32+ is showed after mineralization by FTIR;it's all said that CLEARFIL S3BOND can be induced to be HAP crystals in SBF, but 3M Adper Single Bond 2 doesn't have these results.
There also have white opaque material generation on the dentin speciments of the two adhesives which mineralized 7days; The crystal products'diameter are about 10μm by scanning electron microscopy(SEM); HAP with a variety of ion was showed by Energy dispersive spectrometer (EDS);But the 3M Adper Single Bond 2 did not observe formation of HAP crystals.
Conclusion:HAP crystals can be induced to minerralize in simulated body fluid.as the dental adhesive with phosphate for the template, this provides a new theoretical basis.for biomimetic mineralization of tooth-like HAP.
引文
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