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超组装手性介孔杂化膜用于智能和灵敏的对映体加速拆分。

Super-Assembled Chiral Mesostructured Heteromembranes for Smart and Sensitive Couple-Accelerated Enantioseparation.

机构信息

Shanghai Key Lab of Molecular Catalysis and Innovative Materials, iChEM, Department of Chemistry, Fudan University, Shanghai 200438, P. R. China.

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, P. R. China.

出版信息

J Am Chem Soc. 2022 Aug 3;144(30):13794-13805. doi: 10.1021/jacs.2c04862. Epub 2022 Jul 13.

Abstract

In the context of sustainable development, chirality, especially chiral drugs, has attracted great interest in the pharmaceutical industry, yet the smart and sensitive separation of enantiomers still presents a major scientific challenge. Herein, inspired by supramolecular templating chiral transcription nanoparticles, an artificial chiral nanochannel membrane with asymmetric structure, porosity, and abundant chiral surface is fabricated for smart and sensitive enantiomer recognition and separation. Constructed from chiral transcript mesoporous silica (CMS) super-assembled on a porous anode alumina oxide (AAO) support, the obtained heterostructured chiral membrane (CMS/AAO) exhibits enhanced enantioseparation (approximately 170% compared to the supramolecular-templated nanoparticles) among a series of amino acids with various isoelectric points (PIs). Especially for amino acids with a PI greater than 7, the couple-accelerated enantioseparation (CAE) can be achieved for the first time. Further analysis using an osmotic energy conversion test and simulations based on the Poisson-Nernst-Planck (PNP) equations confirm that the heterostructure and charge polarity are the key to achieve chiral amino acids and ion separation. We expect this work will inspire the development of multifunctional membrane systems for more sustainable and energy-efficient enantioseparation.

摘要

在可持续发展的背景下,手性,特别是手性药物,在制药行业引起了极大的兴趣,但对映异构体的智能和灵敏分离仍然是一个重大的科学挑战。在此,受超分子模板手性转录纳米粒子的启发,我们制备了一种具有不对称结构、多孔性和丰富手性表面的人工手性纳滤膜,用于智能和灵敏的对映体识别和分离。该纳滤膜由手性转录介孔硅(CMS)在多孔阳极氧化铝(AAO)基底上超组装而成,所得的杂化结构手性膜(CMS/AAO)在手性分离方面表现出增强的性能(与超分子模板纳米粒子相比,约提高了 170%),可以分离具有不同等电点(PI)的一系列氨基酸。特别是对于 PI 值大于 7 的氨基酸,可以首次实现偶联加速的对映体分离(CAE)。进一步使用渗透压能量转换测试和基于泊松-纳诺-普朗克(PNP)方程的模拟分析证实,杂化结构和电荷极性是实现手性氨基酸和离子分离的关键。我们期望这项工作将激发多功能膜系统的发展,以实现更可持续和节能的对映体分离。

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