自然唾液中介孔生物活性玻璃诱导牙釉质仿生再矿化研究

doi:10.15541/jim20150300

摘要/Abstract

摘要：

将介孔生物活性玻璃用于修复酸蚀的牙釉质, 样品经模拟刷牙后, 浸泡在自然唾液中。通过X射线衍射(XRD)、扫描电镜(SEM)、聚焦离子束(FIB)切割后透射电镜(TEM)观察、X射线能谱分析(EDX)、选区电子衍射(SAED)分析, 及纳米压痕力学测试等表征显示, 经过介孔生物活性玻璃处理后的牙釉质, 在唾液中浸泡6 h, 牙釉质表面形成棒状类骨磷灰石; 浸泡24 h, 表面形成均匀矿化层, 厚度约为100 nm, 且和牙釉质基体结合紧密, 钙磷比接近牙釉质基体。矿化层在300 µN作用下, 出现划痕爆破值, 其显微力学性能为(3.37±0.62) GPa, 弹性模量为(60.48±4.56) GPa, 均达到未酸蚀牙釉质的75%。实验结果表明, 介孔生物活性玻璃可较快地诱导矿化, 有望用于酸蚀牙釉质修复及早期龋齿的预防。

关键词: 牙釉质, 介孔生物活性玻璃, 再矿化

Abstract:

Acidic etched enamel was treated with mesoporous bioactive glass (M58S) to induce enamel remineralization in natural oral saliva. By simulated brushing teeth, the M58S was adhered on the enamel surface. Then the samples were rinsed by water and immersed in natural oral saliva for different periods. Characterized by XRD, SEM, FIB-TEM, EDX, SAED, and nanoindentation, the samples showed that a new mineralized phase appeared on the surface of the treated samples after soaking for 6 h. After soaking for 24 h, a compact and homogeneous mineralized layer at the thickness of about 100 nm formed with similar structure to apatite, and ratio of calcium to phosphate which was close to the enamel’s. Under pressure of 300 µN, mineralized layer showed a scratch limited value with microhardness at (3.37±0.62) GPa and elastic modulus at (60.48±4.56) GPa, both close to 75% value of original enamel. These results indicate that mesoporous bioactive glass can rapidly repair etched enamel and prevent teeth from caries. Therefore, the mesoporous bioactive glass may be used as bionic remineralization materials.

Key words: enamel, mesoporous bioactive glass, remineralization

中图分类号:

TQ174

董志红, 聂志萍, 周长春. 自然唾液中介孔生物活性玻璃诱导牙釉质仿生再矿化研究[J]. 无机材料学报, 2016, 31(1): 88-94.

DONG Zhi-Hong, NIE Zhi-Ping, ZHOU Chang-Chun. Bionic Remineralization of Acidic Etched Enamel Induced by Using Mesoporous Bioactive Glass in Natural Oral Saliva[J]. Journal of Inorganic Materials, 2016, 31(1): 88-94.

图/表 9

图1 制备FIB-TEM 过程中二次电子图像照片

Fig. 1 Secondary electron images of sample in the preparing process by FIB-TEM (a) Platinum protected layer deposited on the enamel surface with the total thickness of about 1 μm; (b) Being digged between the protection layers; (c) Being cut a thin slice with thickness of about 1 μm; (d) The already prepared sample

图2 M58S的小角XRD图谱及TEM 照片

Fig. 2 Small angle XRD pattern and TEM image of M58S

图3 酸蚀的牙釉质(a)、牙釉质原样(b)及M58S处理后浸泡在口腔唾液中24 h(c)样品的XRD 图谱

Fig. 3 XRD patterns of etched enamel (a) original enamel (b) and M58S treated and soaked in natural human saliva for 24 h (c)

图4 牙釉质表面SEM照片

Fig. 4 SEM images of enamel surface (a) Original enamel; (a1) Etched enamel with adhered M58S; (b) Etched enamel; (b1) Etched enamel without M58S soaked in natural oral saliva for 24 h; (c, d) Etched enamel with adhered M58S soaked in natural oral saliva for 6 h and 24 h, respectively; (c1, d1) Magnified images of (c) and (d), respectively

图5 FIB制备的样品在TEM下的矿化层(a)、牙釉质基体(b)及相应的Ca/P比

Fig. 5 TEM image of samples by FIB (a) mineralized layer, (b) enamel matrix, and corresponded Ca/P ratio by EDX

图6 用FIB制备的牙齿样品的HRTEM 照片及选区电子衍射光斑(SAED).

Fig.6 HRTEM image of teeth sample by FIB preparation and selected area electron diffraction (SAED) (a) Mineralized layer of M58S treated for 24 h in natural oral saliva. (b) Enamel matrix.

图7 样品的纳米划痕实验

Fig. 7 Scratch test by nanoindentation machine (a) M58S treated enamel samples soaked in natural oral saliva for 24 h; (b) Enamel original samples

表1 通过纳米压痕仪测试样品的力学强度

Table1 Mechanical properties detected by nanoindentation

Samples	Hardness value (mean±s.d.)/ GPa	Elastic modulus (mean±s.d.)/ GPa
Original	4.21±0.32	80.30±5.20
24 h treated	3.37±0.62*	60.48±4.56*

图8 样品的纳米压痕形貌

Fig. 8 Nanoindentation images of (a) enamel original sample and (b) M58S treated enamel sample soaked in natural oral saliva for 24 h

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