聚多巴胺修饰的介孔二氧化硅微球的合成及其用于负载左旋薄荷醇凉味剂

doi:10.15541/jim20160486

摘要/Abstract

摘要：

介孔二氧化硅材料具有巨大的孔隙率、开放的孔道结构、易于改性的孔道表面以及良好的生物相容性, 广泛用于药物传递、吸附分离以及催化等领域。本研究通过非极性溶剂辅助共组装法合成了具有较大孔径(6.9 nm)和比表面积(615 m²/g)的介孔二氧化硅微球。采用纳米浇铸的方法, 成功地将左旋-薄荷醇负载到该材料的孔内。进一步通过界面聚合的方法, 在所得微球的表面涂覆一层聚多巴胺(PDA)涂层, 从而将薄荷醇封装在微球的孔道内。利用PDA作为半透膜, 研究了复合微球在不同温度的空气吹扫下释放薄荷醇的行为, 发现在相对适宜的温度下PDA涂层有利于薄荷醇的可控缓慢释放。这些研究结果表明基于聚多巴胺修饰的介孔二氧化硅材料有望用于开发食品和医药等领域的缓释制剂。

关键词: 介孔二氧化硅, 聚多巴胺, 薄荷醇, 缓释

Abstract:

Ordered mesoporous silica materials (OMS) possess high specific surface areas, large pore volume, open channel structure, easily tunable surface functionalities, and good biocompatibility. They have great potential for application in various fields, such as drug delivery, enzyme immobilization, and catalysis. In this study, ordered mesoporous silica microspheres with large pore sizes were synthesized via a non-polar solvent assisted co-assembly method in a water- n-hexane biliquid solution. The obtained mesoporous silica microspheres possess large pore size of 6.9 nm and high surface area of 615 m²/g. Through a nanocasting method, L-menthol was successfully loaded into the mesopores. Through an interface polymerization of dopamine, polydopamine (PDA) was deposited on the external surface of the composite microspheres. By monitoring the weight change of the composite microspheres during treatment by hot air flow, the menthol release behavior was evaluated. As a result of the presence of permeable PDA in shell, the composite microspheres were found to release L-menthol in a controllable way, especially at an appropriate temperature of about 50℃. This study provides an important primary guideline for potential applications of mesoporous silica functionalized with PDA in bio-medicine, adsorption and separation, and so on.

Key words: mesoporous silica, polydopamine, L-menthol, controlled release

中图分类号:

TQ174

白家峰, 王希庆, 陈义昌, 邓勇辉, 李志华, 刘鸿, 刘绍华. 聚多巴胺修饰的介孔二氧化硅微球的合成及其用于负载左旋薄荷醇凉味剂[J]. 无机材料学报, 2017, 32(8): 845-850.

BAI Jia-Feng, WANG Xi-Qing, CHEN Yi-Chang, DENG Yong-Hui, LI Zhi-Hua, LIU Hong, LIU Shao-Hua. Synthesis of Polydopamine Modified Mesoporous Silica Microspheres for Encapsulation of L-menthol[J]. Journal of Inorganic Materials, 2017, 32(8): 845-850.

图/表 8

图1 正己烷辅助下的液-液界面共组装法合成介孔二氧化硅微球以及后续负载左旋薄荷醇

Fig. 1 The synthetic route to polydopamine functionalized mesoporous silica microspheres for loading L-menthol(a) Synthesis of ordered mesoporous silica microspheres with pseudo core-shell structure via non-polar solvent assisted co-assembly approach; (b) Loading L-menthol through “nanocasting” method; (c) Polymerization of dopamine on the surface of microspheres with embedded L-menthol

图2 表面包覆PDA 前(a)和后(b)的介孔二氧化硅微球(mSiO2)的FESEM照片和相应的TEM照片(见插图)

Fig. 2 FESEM and TEM (inset) images of the mesoporous silica (mSiO2) before (a) and after (b) coating with PDA

图3 介孔二氧化硅微球的氮气吸-脱附等温线及其对应的孔径分布曲线(插图)

Fig. 3 Nitrogen adsorption-desorption isotherm and pore size distribution curves of mSiO2 (inset)

图4 (a)脱除CTAB之前的CTAB-silica 复合微球, (b)脱除CTAB后获得介孔二氧化硅微球, (c)负载薄荷醇后的mSiO2- menthol微球, (d)进一步包覆PDA后得到的mSiO2-menthol@PDA 微球的傅里叶变换红外吸收光谱

Fig. 4 FTIR spectra of (a) SiO2-CTAB microsphere and (b) mSiO2 after removing CTAB, (c) mSiO2-menthol microsphere, (d) mSiO2- menthol@PDA microsphere

图5 (a)左薄荷醇和(b)通过纳米浇铸法制备的薄荷醇-介孔二氧化硅微球复合物广角XRD图谱

Fig. 5 Wide-angle XRD patterns of the commercial L-menthol crystal (a) and mSiO2 loaded with L-menthol (b)

图6 在30℃空气吹扫条件下, (a)mSiO2-menthol和(b)mSiO2- menthol@PDA的薄荷醇释放率随时间变化曲线

Fig. 6 Release curves of L-menthol as a function of time in mSiO2-menthol (a) and mSiO2-menthol@PDA (b) in air flow at 30℃

图7 在50℃空气吹扫条件下(a)mSiO2-menthol和(b)mSiO2- menthol@PDA的薄荷醇释放率随时间变化曲线

Fig. 7 Release rate of L-menthol as a function of time in mSiO2- menthol (a) and mSiO2-menthol@PDA (b) in air flow at 50℃

图8 在80℃空气吹扫条件下(a)mSiO2-menthol和(b)mSiO2- menthol@PDA的薄荷醇释放率随时间变化曲线

Fig. 8 Release rate of L-menthol as a function of time in mSiO2- menthol (a) and mSiO2-menthol@PDA (b) in air flow at 80℃

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