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。
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 com-bined with chitosan and collagen Ⅰwere built through peptide binding reaction using genipin as a crosslinker. The gels self-assembled 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 nucl