核壳结构羟基磷灰石/介孔二氧化硅纳米颗粒的制备及其药物释放研究

doi:10.15541/jim20170361

摘要/Abstract

摘要：

核壳纳米颗粒是一种具有独特结构和性能的复合纳米材料, 在催化、生物医学和光子晶体等领域具有重要应用前景。本工作以羟基磷灰石(HAp)纳米颗粒作为核体、十六烷基三甲基溴化铵(CTAB)作为介孔模板剂, 采用改进的Stöber包覆法制备具有介孔结构的核壳HAp@mSiO₂新型纳米颗粒。通过控制正硅酸四乙酯(TEOS)的浓度及其水解和缩合动力学, 可以有效调控HAp表面包覆的mSiO₂壳层厚度。经TEM、EDS、XRD、FT-IR及BET一系列测试可知, 制备得到的HAp@mSiO₂纳米颗粒具有比表面积大、孔径尺寸窄且分布均匀等特点。同时, 以布洛芬作为模板药物, 将制备得到的材料应用于药物释放实验, 发现该核壳材料还具有良好的药物控制性能和pH响应特性, 且可以通过改变mSiO₂壳层厚度对药物释放速率进行有效调控。

关键词: 核壳结构, 羟基磷灰石, 介孔二氧化硅, 药物释放, pH响应

Abstract:

Core-shell nanoparticle is a kind of composite nanomaterials with unique structure and properties, which has important application prospects in the fields of catalysis, biomedicine and photonic crystal, etc. A new kind of materials, core-shell structured HAp@mSiO₂ nanoparticles with mesoporous were prepared by improved Stöber coating method using hydroxyapatite (HAp) nanoparticles as core and cetyltrimethylammonium bromide (CTAB) as mesoporous template. By controlling concentration of tetraethyl orthosilicate (TEOS) and its hydrolysis and condensation kinetics, the thickness of mSiO₂shell coating on the core HAp surface could be well regulated. The results of TEM, EDS, XRD, FT-IR, and BET testing show that the prepared HAp@mSiO₂ nanoparticles have the characteristics of high specific surface area, narrow pore size and uniform distribution. And using the Ibuprofen as model drug, the prepared materials were tested for drug adsorption and release experiments. It is found that the obtained core-shell structured materials also have good drug control properties and pH response characteristics, and can effectively control the drug release rate and release amount through altering the mSiO₂ shell thickness.

Key words: core-shell structure, hydroxyapatite, mesoporous silica, drug release, pH response

中图分类号:

TQ1741

宋晶晶, 陈波, 林开利. 核壳结构羟基磷灰石/介孔二氧化硅纳米颗粒的制备及其药物释放研究[J]. 无机材料学报, 2018, 33(6): 623-628.

SONG Jing-Jing, CHEN Bo, LIN Kai-Li. Core-shell Structured Hydroxyapatite/Mesoporous Silica Nanoparticle: Preparation and Application in Drug Delivery[J]. Journal of Inorganic Materials, 2018, 33(6): 623-628.

图/表 8

图1 内核HAp及包覆不同壳层的HAp@mSiO2的TEM照片

Fig. 1 TEM images of the kernel HAp and HAp@mSiO2 coated with different shells(a, b) HAp; (c, d) HAp@mSiO2-1; (e, f) HAp@mSiO2-2; (g, h) HAp@mSiO2-3

图2 介孔二氧化硅包覆后HAp@mSiO2-2的EDS图谱

Fig. 2 EDS pattern of HAp@mSiO2-2 after mesoporous silica coating

图3 核HAp及不同壳层厚度HAp@mSiO2的XRD图谱

Fig. 3 XRD patterns of core HAp and HAp@mSiO2 with different shell thicknesses(a) HAp; (b) HAp@mSiO2-1; (c) HAp@mSiO2-2; (d) HAp@mSiO2-3

图4 核HAp及不同壳层厚度HAp@mSiO2的红外谱图

Fig. 4 FT-IR spectra of core HAp and HAp@mSiO2 with different shell thicknesses(a) HAp; (b) HAp@mSiO2-1; (c) HAp@mSiO2-2; (d) HAp@mSiO2-3

表1 内核HAp及不同HAp@mSiO2样品的孔径、比表面积及壳层厚度比较

Table 1 Pore size, specific surface area, and shell thickness for kernel HAp and different HAp@mSiO2 samples

Samples	V_p/(cm³·g^-1)	S_BET/(m²·g^-1)	D_p/nm	Shell thickness/nm
HAp	1.024	69.7	1.689	—
HAp@mSiO₂-1	0.608	653.4	1.929	9.59
HAp@mSiO₂-2	0.591	666.6	2.188	10.01
HAp@mSiO₂-3	0.467	714.1	2.450	12.97

图5 内核HAp及不同壳层厚度HAp@mSiO2的N2-吸脱附图

Fig. 5 N2 adsorption/desorption isotherms for core HAp and HAp@mSiO2 with different shell thicknesses(a) HAp; (b) HAp@mSiO2-1; (c) HAp@mSiO2-2; (d) HAp@mSiO2-3

图6 核HAp及不同壳层厚度HAp@mSiO2吸附IBU后的累计释放量

Fig. 6 Cumulative IBU release from core HAp and HAp@mSiO2 with different shell thicknesses in the release media of PBS (pH=7.4)

图7 HAp@mSiO2-2在不同pH的释放介质下吸附IBU后的累计释放量

Fig. 7 Cumulative IBU release from HAp@mSiO2-2 in the release media of PBS with different pH

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