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齐齐哈尔大学藏雨 /郑州大学张伟 Polym. Sci. Technol. | 基于硫醇-烯点击化学构筑三维交联手性分离膜实现高选择性高渗透性对映体拆分

  • 2026-06-01 13:31:48
齐齐哈尔大学藏雨 /郑州大学张伟 Polym. Sci. Technol. | 基于硫醇-烯点击化学构筑三维交联手性分离膜实现高选择性高渗透性对映体拆分

英文原题:Surface-Initiated Thiol-Ene Click Polymerization for Fabricating 3D Cross-Linked Chiral Composite Membranes with Enhanced Enantioselectivity and Permeability

作者:Yu Zang* Jingwen Zhang Shuang Xia Jianjun Wang Liang Xu Jiao Liu Xiangming Fu Ruyan Xie and Wei Zhang*

通讯作者:藏雨,齐齐哈尔大学化学与化学工程学院;张伟,郑州大学化学学院

研究背景

手性是自然界的本质属性,对制药、生命及材料科学都至关重要。临床超过50%的药物为手性化合物,其对映体在药效、代谢及毒性上常表现各不相同,“沙利度胺悲剧”便深刻警示了这种差异的致命风险,使得获取光学纯药物成为保障用药安全的核心。相比成熟的结晶与色谱技术,膜分离因低耗、连续及易放大的优势,被视为大规模手性分离的潜力方向。然而,该领域长期受困于“选择性-渗透性权衡效应”,提升选择性往往导致渗透性骤降,难以实现二者兼得,这形成了当前手性分离膜实际应用的主要挑战。

目前,手性分离膜研究面临两大难题:传统线性结构手性聚合物膜虽有良好成膜性和一定识别能力,但运行中链段易溶胀,导致分离性能衰减,选择性及长期稳定性难保;而金属有机框架(MOFs)、共价有机骨架(COFs)等多孔晶体材料虽具有可调孔道与高比表面积优势,却因其固有的纳米或微米级晶体或颗粒在膜制备中易形成晶界或界面缺陷,影响机械强度和分离选择性;另外,其与聚合物基底界面粘附力弱,长期运行或在压力下易分层导致性能下降。因此,开发兼具链段柔性与骨架刚性的新型膜材料,通过界面高密度均匀稳定构建手性识别位点、精准调控微观结构以打破“权衡效应”,成为该领域突破的关键。

文章简介

齐齐哈尔大学藏雨与郑州大学张伟团队基于硫醇-烯点击化学的表面引发原位聚合法,在多孔二氧化硅(SiO2)基底上成功构建了具有三维交联网络结构的手性复合膜(P-SiO2)。该研究首先利用硅烷偶联剂对SiO2基底进行巯基功能化(SiO2-SH),随后通过紫外光引发手性奎宁单体(A1)、三官能团烯单体(A3)与二硫醇交联剂(B2R1/B2R2)之间的点击反应,实现了分离层的原位生长。通过精确调控交联剂类型刚性芳香族B2R1 和柔性脂肪族B2R2、基底孔径(G3型,4.3-9.0 μm)及反应物浓度与配比,团队将膜厚控制在18-45 μm范围内,形成了致密连续且具有均匀手性识别位点的界面结构,解决了传统线性聚合物膜易溶胀及多孔晶体材料易产生晶界缺陷的问题。

图1. P-SiO2复合膜的合成及手性分离。

D,L-苯丙氨酸体系的分离测试中,该三维交联手性膜展现出良好的分离性能。当采用刚性交联剂B2R1、反应浓度为0.20 mol/L,总反应量为0.40 mmol时,复合膜在渗透系数高达1.97×10-10 m2/h的同时,对映体过量值(ee%)达到了98.3%,成功打破了手性分离领域长期存在的“选择性-渗透性权衡效应”。机理研究表明,该膜的分离过程遵循“延迟传输机制”,通过静态吸附实验与分子动力学模拟证实,聚合物PR1L-苯丙氨酸具有更强的吸附亲和力(结合能为-20.48 kcal/mol),这源于L-苯丙氨酸的氨基与奎宁单元芳香氮原子之间形成的N-H···N氢键。这种特异性吸附导致L-对映体在膜内传输被“阻滞”,而D-对映体因相互作用较弱得以优先透过,从而在渗透侧实现高效拆分。该研究提出的“延迟传输机制”深入阐释了手性识别位点与对映体间的特异性相互作用,为理性设计兼具高渗透过性和高选择性的手性分离膜提供了坚实的理论依据与全新的构筑策略。

图2. (a) 复合膜聚合物层厚度L与单体浓度c之间的关系;(b) 反应浓度c与渗透率P及对映体过量ee%之间的关系;(c) 复合膜聚合物层厚度L与反应体系中物质总含量n之间的关系;(d) 反应体系中物质总含量n与渗透率P及对映体过量ee%之间的关系。

作者团队

藏雨,本文通讯作者

藏雨,齐齐哈尔大学教授,长期从事功能高分子材料的设计、合成及其在膜分离技术中的应用研究,尤其专注于手性膜分离技术的开发。近年主持多项国家自然科学基金项目,在Chem. Eng. J.、Sci. China Mater.、Sep. Purif. Technol.等国内外顶尖期刊发表高水平研究论文100余篇。

张伟,本文通讯作者

张伟,男,博士,教授。2001年本科毕业于安徽大学,2006年在苏州大学获有机化学专业博士学位并留校工作,2013年破格晋升为教授。2009年4月-2011年3月日本奈良先端科学技术大学院大学JSPS博士后。2015年11月-2016年2月,北海道大学访问教授。教育部“101”计划《高分子化学与物理》教材骨干教师。截止目前,以通讯作者/第一作者在Chem、J. Am. Chem. Soc.和Angew. Chem. Int. Ed.等杂志发表学术论文137篇,参与撰写专著6部,授权美国和中国发明专利30余项。共主持包括国家自然科学基金重点项目、重大研究计划集成项目课题、重大研究计划培育项目、面上项目等7项。获安徽省杰青年基金基金,中国化工学会科学技术基础研究成果一等奖和教育部自然科学二等奖等奖项多项。

扫描二维码阅读英文原文

Polym. Sci. Technol. 2026, ASAP

https://doi.org/10.1021/polymscitech.6c00030

Published April 16, 2026

 © 2026 The Authors. Co-published by Changchun Institute of Applied Chemistry, Chinese Academy of Sciences; American Chemical Society. 

关于Polymer Science &Technology

Polymer Science & Technology 旨在发表高分子科学与技术及其跨学科领域的前沿创新成果,利用高分子研究为全球性挑战发掘可持续方案。该期刊聚焦于高分子合成与加工、可持续高分子、高分子循环与增值回收、先进功能高分子、高分子物理与表征、人工智能赋能等重要领域。期刊将涵盖多种类型文章,包括研究论文(Article)、研究快报(Letter)、综述(Review)、前瞻观点(Perspective)、评论(Comment)和社论(Editorial)。

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  1. CONNECT:[ UseTime:0.001075s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001643s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000788s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000741s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001316s ]
  6. SELECT * FROM `set` [ RunTime:0.000614s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001450s ]
  8. SELECT * FROM `article` WHERE `id` = 547858 LIMIT 1 [ RunTime:0.001121s ]
  9. UPDATE `article` SET `lasttime` = 1780312119 WHERE `id` = 547858 [ RunTime:0.001613s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000685s ]
  11. SELECT * FROM `article` WHERE `id` < 547858 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.001236s ]
  12. SELECT * FROM `article` WHERE `id` > 547858 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001041s ]
  13. SELECT * FROM `article` WHERE `id` < 547858 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.002413s ]
  14. SELECT * FROM `article` WHERE `id` < 547858 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.002660s ]
  15. SELECT * FROM `article` WHERE `id` < 547858 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.005399s ]
0.162893s