华西口腔医学杂志

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通过自生长方式实现壳聚糖—胶原聚合物引导的牙体硬组织仿生再矿化

任迅1 姚静2 杜芹1 廖楚航1 田鲲1   

  1. 1.四川省医学科学院•四川省人民医院口腔科,成都 610072;2.遵义医学院口腔学院,遵义 563003
  • 出版日期:2014-10-01 发布日期:2014-10-01
  • 通讯作者: 田鲲,副主任医师,博士,E-mail:tiankun78@hotmail.com
  • 作者简介:任迅,主治医师,学士,E-mail:13980018335@139.com
  • 基金资助:

    国家自然科学基金资助项目(81100786);四川省科技支撑计划基金资助项目(2013SZ0020)

Chitosan-collagen polymer induced remineralization of tooth hard tissue through self-growing methods

Ren Xun1, Yao Jing2, Du Qin1, Liao Chuhang1, Tian Kun1.   

  1. 1. Dept. of Stomatology, Sichuan Medical Science Academy and Sichuan Provincial People’s Hosptial, Chengdu 610072, China; 2. School of Dentistry, Zunyi Medical College, Zunyi 563003, China
  • Online:2014-10-01 Published:2014-10-01

摘要:

目的 以改良的壳聚糖、胶原等生物大分子作为矿化模板,引导釉质实现类似自生长的再矿化。方法 通过对天然聚阳离子多糖——壳聚糖进行磷酸化本体改性,生成其聚阴离子衍生物磷酸化壳聚糖;以京尼平为交联剂将磷酸化壳聚糖与聚阳离子的Ⅰ型胶原交联改性,构建双性聚电解质复合物水凝胶作为生物矿化的大分子模板,以紫外光辐射激发其在惰性牙体表面的化学组装,仿生唾液提供矿化离子,调控磷灰石晶体在牙体原位的形成与组装,生成羟磷灰石。结果 红外光谱检测证实,PO43−官能团(3 446 cm-1)成功引入壳聚糖,扫描电子显微镜下双性聚电解质复合物水凝胶呈现多孔并存,孔孔交通的级联结构。水凝胶原位接枝能够生成白色晶体,X射线衍射证实新生的晶体为羟磷灰石,该沉积层与原有釉质同质结合,类似釉柱平行排列;新生晶体直径30~60 nm,硬度接近牙本质。结论 取材容易、操作便利的双性聚离子凝胶能够在一定程度上模仿釉质矿化模板,实现羟磷灰石的自生长,这对釉质结构仿生的发展有重要意义。

关键词: 羟磷灰石, 釉质, 壳聚糖, 聚合物

Abstract:

Objective To modify biomacromolecules, such as chitosan and collagen, to synthesize a mineralized template that will induce self-growing remineralization of tooth enamel. Methods Natural polycation polysaccharide chitosan was modified through phosphorylation to synthesize the polyanion derivative of phosphorylated chitosan. Parent hydrogels combined with chitosan and collagen Ⅰ were built through peptide binding reaction using genipin as a crosslinker. The gels selfassembled on the tooth’s inert surface, which was stimulated by ultraviolet radiation. The bionic saliva provided mineralized ion, and then the hydroxyapatite assembled and grew in situ on the tooth. Results The functional group PO43− (3 446 cm−1) was grafted on chitosan as confirmed by the Fourier transform infrared spectroscopy. The porous polyelectrolyte complex hydrogel formed by the interaction between the polycation chitosan and the polyanion phosphorylated chitosan could induce hydroxyapatite crystal nucleation and growth on the hydrogel fiber surfaces. The neonatal crystal was hydroxyapatite as confirmed by X-ray diffraction and was tightly connected to the tooth. A continuous structure of column crystals with sizes ranging from 30 nm to 60 nm was observed. The structure was in parallel direction similar to the direction of the enamel rod, and its hardness was close to dentin. Conclusion The parent hydrogels that were easily obtained and controlled could mimic the template of the enamel mineralization and induce a self-growing hydroxyapatite, which is an important step in the structural bionics of enamel.

Key words: hydroxyapatite, enamel, chitosan, polymer