手性聚苯胺/二氧化硅核/壳复合物的合成及应用

doi:10.7503/cjcu20170743

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1587.doi: 10.7503/cjcu20170743

手性聚苯胺/二氧化硅核/壳复合物的合成及应用

杨倩, 杨璨瑜, 孙孔春, 侯雯清, 吴乐艳, 沈报春()

昆明医科大学药学院暨云南省天然药物药理重点实验室, 昆明 650500

收稿日期:2017-11-17 出版日期:2018-07-10 发布日期:2018-06-06
作者简介:联系人简介: 沈报春, 女, 博士, 教授, 主要从事手性固定相制备和手性药物对映体分离研究. E-mail: b.shen@kmmu.edu.cn
基金资助:
云南省科技厅-昆明医科大学联合专项重点项目[批准号: 2017FE468(-172)]和昆明医科大学创新团队项目(批准号: CXTD201603)资助.

Synthesis and Application of Chiral Polyaniline/Silica Dioxide Core/Shell Composite^†

YANG Qian, YANG Canyu, SUN Kongchun, HOU Wenqing, WU Leyan, SHEN Baochun^*()

School of Pharmaceutical Science & Yunnan Province Key Laboratory of Pharmacology for Natural Products,Kunming Medical University, Kunming 650500, China

Received:2017-11-17 Online:2018-07-10 Published:2018-06-06
Contact: SHEN Baochun E-mail:b.shen@kmmu.edu.cn
Supported by:
† Supported by the Yunnan Province Applied Basic Research Projects-Union Foundation, China[No. 2017FE468(-172)] and the Kunming Medical University Innovation Team, China(No. CXTD201603).

摘要/Abstract

摘要：

以苯胺为单体, 右旋樟脑磺酸为手性掺杂剂制备了手性聚苯胺[(+)-PANI]; 以(+)-PANI为核, 表面包覆二氧化硅外壳, 得到手性聚苯胺/二氧化硅核/壳复合物[(+)-PANI@SiO₂]. 采用比旋度([α $] D t$ )、紫外-可见光谱(UV-Vis)及圆二色谱(CD)等表征光学活性, 结果表明, (+)-PANI及(+)-PANI@SiO₂均具有手性; 红外光谱(IR)表明, 二氧化硅已经包覆于(+)-PANI表面; 扫描电子显微镜(SEM)结果表明, (+)-PANI@SiO₂为核/壳结构. 将(+)-PANI和(+)-PANI@SiO₂分别用于丙氨酸对映体选择性结晶, L-丙氨酸均优先结晶, 且(+)-PANI@SiO₂手性识别能力更强. 以光学活性聚苯胺为核, 无机二氧化硅为壳的核/壳复合物在手性识别领域具有潜在的应用价值.

关键词: 手性聚苯胺, 二氧化硅, 核/壳复合物, 对映选择性结晶, 丙氨酸

Abstract:

Hybrid core/shell composites, in which an organic core was surrounded by a layer of inorganic material, have been widely investigated both to improve the stability and surface chemistry of the core materials and chemical properties that are not possible from one material alone. This article reports a category of hybrid core/shell composite consist of an organic core(composed of an optically active polyaniline) and a shell(composed of silica dioxide) and thus exhibit optical activities. Chiral polyaniline[(+)-PANI] was synthesized with aniline as monomer and D-camphorsulfonic acid[D-(+)-CSA] as chiral dopant. The silica dioxide was coated on the surface of (+)-PANI by sol-gel approach, thus to obtain the chiral polyaniline/silica dioxide core/shell composite[(+)-PANI@SiO₂]. (+)-PANI and (+)-PANI@SiO₂ were characterized by optical activity and regular morphology. The UV-Vis absorption spectra, circular dichroism and specific rotation demonstrated that the (+)-PANI and(+)-PANI@SiO₂ endowed with optical activity. Fourier transform infrared spectroscopy was used to verify the surface groups and the scanning electron microscopy was used to verify the core/shell conformation. The (+)-PANI and (+)-PANI@SiO₂ were used as chiral selectors for the enantioselective crystallization of alanine racemates, respectively. L-alanine was preferable induced from the racemic solution. More times of inducing, e. e.% value is bigger. The shells could be further cross-linked for improving the properties of organic core. The investigations are of importance not only in chiral studies but also in materials due to the integration of organic helical polymers and inorganic materials in one single material.

Key words: Polyaniline, Silica dioxide, Hybrid core/shell composite, Enantioselective crystallization, Alanine

中图分类号:

TrendMD:

杨倩, 杨璨瑜, 孙孔春, 侯雯清, 吴乐艳, 沈报春. 手性聚苯胺/二氧化硅核/壳复合物的合成及应用. 高等学校化学学报, 2018, 39(7): 1587.

YANG Qian, YANG Canyu, SUN Kongchun, HOU Wenqing, WU Leyan, SHEN Baochun. Synthesis and Application of Chiral Polyaniline/Silica Dioxide Core/Shell Composite^†. Chem. J. Chinese Universities, 2018, 39(7): 1587.

图/表 4

Fig.1 UV-Vis spectrum of(+)-PANI

Fig.2 CD(A) and infrared spectra(B) of (+)-PANI(a) and (+)-PANI@SiO2(b)

Fig.3 SEM images of (+)-PANI(A) and (+)-PANI@SiO2(B)

Fig.4 Microscopic view of crystals of alanine,without any inducer(A), with inducer (+)-PANI(B) and (+)-PANI@SiO2(C)

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手性聚苯胺/二氧化硅核/壳复合物的合成及应用

Synthesis and Application of Chiral Polyaniline/Silica Dioxide Core/Shell Composite^†

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手性聚苯胺/二氧化硅核/壳复合物的合成及应用

Synthesis and Application of Chiral Polyaniline/Silica Dioxide Core/Shell Composite†

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Synthesis and Application of Chiral Polyaniline/Silica Dioxide Core/Shell Composite^†