手性共价有机框架材料的研究进展与应用

共价有机框架材料(covalent organic frameworks, COFs)是一类是由各种有机小分子单体通过共价键有序连接而成的有机多孔材料.手性是一种在自然界中普遍存在的现象,手性化合物在医学、药学、农业等方面有重要应用.近几年,手性COFs引起了广大科研工作者的注意.手性COFs由于具有永久多孔、隧道型孔道、结构可预测、结构稳定、可循环利用等特点,在手性催化、手性分离等领域具有广泛的潜在应用.合成手性COFs材料的一种方案是通过各种不同的手性构筑单元直接连接而成,所以通过设计不同结构的手性构筑单元和合成具有功能性基团的手性单体可以得到结构多样的手性COFs材料.手性COFs材料的另一种合成方案是利用后修饰的方法将金属粒子或者有机小分子修饰到手性COFs骨架上从而对结构进行功能性调控.     

氨基酸功能化晶态多孔聚合物的研究进展

以金属有机框架（metal-organic frameworks,MOFs）和共价有机框架（covalent organic frameworks,COFs）为代表的晶态多孔聚合物,具有高比表面积、多样的结构、开放的孔道、丰富的官能团、易功能化等特点,在气体储存和分离、催化、储能、光电器件等领域都有着广泛的应用前景.氨基酸是构成多肽和蛋白质的基本结构单元,不仅具有重要的生物学功能,还在药物生产、生物降解塑料、手性催化剂等工业应用中发挥重要作用.将氨基酸引入到MOFs和COFs体系中,可赋予其柔性化骨架、特殊的孔道环境、手性识别位点等特征,并且在一定程度上提高框架材料的生物相容性、可降解性,进一步丰富晶态多孔聚合物的功能和应用.本综述概括了利用氨基酸功能化MOF和COF材料的制备策略,主要包括以氨基酸及其衍生物作为构筑单元、骨架共价修饰氨基酸、以氨基酸作为调节剂;并重点介绍了这些材料在手性拆分、催化、吸附以及质子传导等领域的应用.最后,本综述分析了当前氨基酸功能化的晶态多孔聚合物面临的困难与挑战,并对其未来研究方向进行了展望.     

手性组装材料及其在对映体分离中的应用

手性组装材料作为一种新型功能复合材料,已经引起众多科学研究领域的广泛关注,尤其是其在对映体分离方面的潜在应用成为当前的研究热点。本文首先从手性来源角度对手性组装材料的构建机制进行了分类探讨,包括手性诱导、手性放大、手性传递和手性转录4个主要途径,其中具有手性的多孔金属有机骨架、纳米笼是基于手性诱导和手性传递机制构建的组装材料,手性凝胶的形成是基于手性放大机制,而手性转录机制主要用于手性多孔无机材料、螺旋纳米结构的构建。其次,介绍了手性组装材料的对映体识别功能,主要针对金属有机骨架化合物(MOFs)、手性凝胶和纳米笼三类手性组装材料在对映体分离中的应用进行了综述。阐述了天然生物大分子DNA的手性自组装特性及其对对映体的立体选择性识别功能,并介绍了DNA螺旋组装结构在手性等离子材料、非对称催化剂设计等方面的应用。最后,归纳了金属有机骨架化合物、手性凝胶、纳米笼和DNA等手性组装材料各自的优势,并对DNA在手性拆分领域的应用前景进行了展望。     

基于手性有机框架材料制备气相色谱固定相的研究进展

对映异构体通常具有不同的药理学、毒理学和生理学性质，获得单一手性化合物对人类健康和环境的可持续发展均具有重要意义。目前，色谱是分离对映异构体的主要方式之一，色谱分离的关键在于固定相的选择。有机框架材料作为一类新兴的结晶多孔材料，具有结构高度有序、孔隙丰富、孔结构和尺寸可调及易于功能化等优点，在对映异构体的色谱分离方面受到广泛关注。通过后修饰或自下而上的合成策略，一系列具有高结晶度和丰富手性识别位点的有机框架材料已经被成功研制。基于动态涂覆或原位生长等方法，手性有机框架材料可被成功固定于气相色谱柱的内表面，从而实现多种对映异构体混合物的高分辨分离；与商用手性色谱柱相比，部分自制的手性有机框架材料色谱柱具有更优异的选择因子和分离度。本文首先介绍了有机框架材料在分离领域所展现出的优势，之后分别论述了手性有机框架材料的合成方式、相应色谱固定相的制备方法及手性有机框架材料对对映异构体的分离性能，最后总结了手性有机框架材料在未来手性材料领域的突出优势和面临的挑战。     

手性金属有机骨架材料的合成及其在对映异构体选择性分离中的应用

手性现象在自然界中广泛存在,手性分离在药物研发、农用化学、药理学、环境科学和生物学等诸多领域具有重要意义。手性金属有机骨架化合物材料(MOFs)是一类具有特殊拓扑结构和可设计的孔道结构的新型多孔材料,加之其比表面积高、孔隙率大、热稳定性良好和溶剂耐受性好等特性,使得MOFs在分析化学领域的应用与研究日益深入。本文简要综述了手性MOFs的合成方法,着重讨论了手性MOFs在对映异构体选择性分离方面的应用及相关机理,最后对该类材料的发展前景做了展望。     

手性共价有机骨架用于高效液相色谱固定相拆分13种外消旋化合物

共价有机骨架材料(COFs)作为一种新型的晶体多孔材料,在手性分离领域得到了广泛的关注。本文以1,3,5-三醛基间苯三酚(Tp)和(+)-二乙酰基-L-酒石酸酐反应合成的CTp作为手性有机单体和2,5-二甲基-1,4-苯二胺(Pa-2)发生席夫碱反应,制备了一种手性共价有机骨架材料CTpPa-2。将该手性COF材料CTpPa-2与C_(18)硅胶混合均匀作为固定相,成功制备了高效液相色谱手性柱。以正己烷/异丙醇作为流动相,在一定的色谱条件下,考察了该手性柱对一系列外消旋化合物的拆分性能。实验结果表明,基于手性COF材料CTpPa-2的新型高效液相色谱固定相对13种手性化合物具有较好的对映选择分离能力。将该手性柱与之前我们课题组报道的手性MOF[Ni(L)(bpe)_2(H_2O)_2]H_2O柱和商品AD柱进行比较,该手性柱表现出较好的手性拆分互补作用。     

金属有机框架色谱固定相的研究进展

金属有机框架(MOFs)是由金属离子或金属簇与有机配体通过配位作用自组装形成的一类新型多孔材料. MOFs具有独特的拓扑结构、丰富的孔隙结构、可调的孔道尺寸、巨大的比表面积以及灵活的表面修饰等特征,是色谱分离领域颇受关注的一类新型固定相. 综述了近几年MOFs材料作为固定相在气相色谱、液相色谱及手性拆分等领域应用的研究进展,展现MOFs材料在色谱分离领域的优异性能和应用潜力,并对MOFs材料在色谱固定相领域今后的发展进行了展望.     

手性毛细管电色谱研究进展

手性化合物的分离分析一直是分析化学领域的一个重要研究课题。对映异构体在非手性环境中具有相同的化学和物理性质,但在生物体系中会展现出不同的生物和生理活性。因此,手性对映体的有效拆分对于医药、生物领域有着重大的意义。本文就近年来毛细管电色谱技术及其对手性化合物的拆分研究进行归纳及综述,介绍了基于不同材料,包括多糖衍生物、纳米材料、多孔有机骨架材料以及生物材料作为手性固定相的毛细管电色谱柱制备和应用。最后对手性毛细管电色谱的未来发展方向进行了展望。     

基于共价－有机骨架固定相的色谱分离应用研究进展

共价－有机骨架材料（COFs）是一类由轻质元素通过共价键形成的多孔材料,具有比表面积大、稳定性好、孔径可调、功能多样、结构可修饰等特点,在分析化学领域如样品前处理和色谱分离等方面显示出了良好的应用前景。其中COFs作为新颖色谱固定相在高效液相色谱、气相色谱和毛细管电色谱分离应用研究也逐渐引起了人们的关注。色谱分离所用COFs均具有良好的化学稳定性,但比表面积、孔径和性质各异,适用于分离不同类型的目标物如有机小分子、同分异构体和手性化合物等。该文综述了近年来以COFs为固定相的色谱分离应用研究进展,包括基于COFs的色谱固定相/色谱柱的制备及其色谱分离应用,并对其进行了展望。     

多孔高分子材料对二氧化碳的捕获与转化

在温和的条件下,运用化学技术进行有效的碳捕获和碳转换是减少人为CO_2排放的重要途径。近年来,多孔有机聚合物(Porous organic polymers,POPs)由于其优异的CO_2吸附性能,被视为最具潜力的CO_2捕获材料而引起了广泛的关注。本文介绍了4种POPs的最新研究进展,包括金属有机骨架材料(Metalorganic frameworks,MOFs)、沸石咪唑酯骨架材料(Zeolitic Imidazolate Frameworks,ZIFs)、共轭微孔聚合物(Conjugated microporous polymers,CMPs)、共价有机骨架材料(Covalent organic frameworks,COFs),并对MOFs和CMPs作为催化剂和吸附剂在室温条件下CO_2的捕获与转化过程的相关实验研究工作进行了综述。     

Recent advances of application of porous molecular cages for enantioselective recognition and separation

Porous materials with well‐defined pore structures have received considerable attention in the past decades due to their unique structures and wide applications. Most porous materials such as zeolites, metal‐organic frameworks, covalent organic frameworks, and porous organic polymers are extended to infinite frameworks or networks by robust covalent or coordination bonds. Porous molecular cages composed of discrete molecules with permanent cavities are an emerging class of porous material and the discrete molecules assemble into solids by weak intermolecular interaction. In comparison to porous extended solids such as metal‐organic frameworks and covalent organic frameworks, porous molecular cage solids are generally soluble in organic solvents thus allowing solution processing, making them more convenient to apply in many fields. This review mainly focuses on the recent advances of application of porous molecular cages (porous organic cages and metal‐organic cages) for enantioselective recognition and separation from 2010 to present, including gas chromatography, capillary electrochromatography, chiral fluorescent recognition, chiral potentiometric sensing, and enantioselective adsorption. Furthermore, the two important family members of porous molecular cages, porous organic cages and metal‐organic cages, are also discussed.     

Recent development trends for chiral stationary phases based on chitosan derivatives,cyclofructan derivatives and chiral porous materials in high performance liquid chromatography

The separation of enantiomers by chromatographic methods, such as gas chromatography, high‐performance liquid chromatography and capillary electrochromatography, has become an increasingly significant challenge over the past few decades due to the demand of pharmaceutical, agrochemical, and food analysis. Among these chromatographic resolution methods, high‐performance liquid chromatography based on chiral stationary phases has become the most popular and effective method used for the analytical and preparative separation of optically active compounds. This review mainly focuses on the recent development trends for novel chiral stationary phases based on chitosan derivatives, cyclofructan derivatives, and chiral porous materials that include metal‐organic frameworks and covalent organic frameworks in high‐performance liquid chromatography. The enantioseparation performance and chiral recognition mechanisms of these newly developed chiral selectors toward enantiomers are discussed in detail.     

Recent Advances of Covalent Organic Frameworks for Chiral Separation

Covalent organic frameworks(COFs), orderly assembled from the building blocks via covalent bonds, are a novel type of porous materials with rich functional sites and permanent porosity. At present, most of COFs are achiral networks, nevertheless, chiral COFs(CCOFs) have become a research hotspot in recent years, due to their unique chiral sites and microenvironment. As one of the most important applications of CCOFs, chiral separation has attracted huge attention for the convenient, rapid and efficient feature. In this review, recent progresses of covalent organic frameworks for chiral separation are covered. And we also present the challenges and outlooks of CCOFs in the future for this field.     

金属有机框架材料在分离分析领域的研究进展

金属有机框架材料是由金属离子节点和有机配体通过配位键连接形成的具有序多孔骨架的材料, 因其具有比表面积大、 孔隙可调及表面性质可控等优点而备受关注. 通过对有机配体和金属离子进行选择及对金属有机框架材料进行后修饰处理, 可实现对金属有机框架材料表面性质的调控, 以提升其选择性吸附及特异性识别等性能, 进而拓展其在分离分析等领域的应用. 本文从金属有机框架材料的表面性质调控出发, 介绍了其表面性质与分离分析性能的关系, 总结了近年来该领域的代表性工作, 并展望了金属有机框架材料在分离分析领域的应用前景.     

A homochiral porous organic cage with large cavity and pore windows for the efficient gas chromatography separation of enantiomers and positional isomers

Porous organic cages composed of discrete cage molecules have attracted considerable recent attention as gas adsorption materials and separation media. In this study, we report a homochiral porous organic cage CC5 with a large cavity and pore windows as a novel stationary phase for high‐resolution gas chromatographic separations. The capillary column was prepared by a static coating method. A large number of racemic compounds have been resolved on the coated capillary column, including derivatized amino acids, alcohols, alcohol amines, esters, ethers, ketones, and epoxides. It is interesting that the CC5‐coated capillary column exhibits significant chiral recognition complementarity to a commercial β‐DEX 120 column and a previously reported homochiral porous organic cage CC3‐R‐coated column, which could expand the range of the analytes amenable to separation on porous organic cage‐based capillary columns. Moreover, the fabricated column also shows excellent selectivity for the separation of positional isomers, including the challenging ethylbenzene and xylene isomers. Experimental results demonstrate an excellent separation performance and stability of the CC5‐coated column, making it promising for gas chromatography applications.     

金属有机骨架及其复合材料在分离领域中的应用进展

金属有机骨架（MOFs）是一类由无机金属离子与有机配体自组装形成的新型有机-无机杂化多孔材料,因具有比表面积超高、结构多样、热稳定性良好、孔道尺寸和性质可调等优势,在分离领域表现出重要的应用价值。然而,采用传统方法制备的MOFs多为粒径在微米或亚微米尺度的晶体,且颗粒形貌不规则,因此限制了MOFs在样品前处理和色谱固定相等领域的应用和发展。构建基于MOFs的复合材料是弥补MOFs应用缺陷的一项有效措施,有望在保留MOFs优越的分离特性的同时,引入基体材料的特定性能。该文简要综述了近年来MOFs及其复合材料在吸附、样品前处理和色谱固定相等分离领域中的应用进展,并对MOFs在分离科学中的应用前景做出展望。     

Recent trends on the implementation of reticular materials in column-centered separations

Advances in the development of column-based analytical separations are strongly linked to the development of novel materials. Stationary phases for chromatographic separation are usually based on silica and polymer materials. Nevertheless, recent advances have been made using porous crystalline reticular materials, such as metal-organic frameworks and covalent organic frameworks. However, the direct packing of these materials is often limited due to their small crystal size and nonspherical shape. In this review, recent strategies to incorporate porous crystalline materials as stationary phases for liquid-phase separations are covered. Moreover, we discuss the potential future directions in their development and integration into suitable supports for analytical applications. Finally, we discuss the main challenges to be solved to take full advantage of these materials as stationary phases for analytical separations.     

衍生多孔碳材料在固相微萃取中的应用研究进展

固相微萃取是一种集采样、萃取、富集和进样于一体的样品前处理技术,其萃取效果与涂层材料密切相关。多孔碳材料具有比表面积大、多孔结构可控、活性位点多和化学稳定性好等优点,广泛应用于电池、超级电容器、催化、吸附和分离等领域,也是一种热门的用作固相微萃取探针的涂层材料。衍生多孔碳材料因种类丰富、可设计性强被广泛研究,研究主要集中在对衍生多孔碳材料的结构优化方面。但是衍生多孔碳材料在固相微萃取中的应用还存在如下问题:(1)共价有机框架衍生多孔碳材料的制备已取得较大进展,但将其应用于固相微萃取领域的研究仍较少;(2)有待进一步明确制备出的衍生多孔碳材料用作固相微萃取涂层表现出优异提取能力的机理;(3)有待进一步深入研究将衍生多孔碳材料用作固相微萃取涂层以实现对不同物理化学性质污染物的广谱高灵敏度分析。文章综述了近3年衍生多孔碳材料在固相微萃取中的应用研究,并展望了未来衍生多孔碳材料在固相微萃取中的研究前景。引用文献共56篇,主要来源于Elsevier。     

Chiral covalent organic frameworks for asymmetric catalysis and chiral separation

Covalent organic frameworks (COFs), covalently assembled from the condensation reactions of organic building blocks, are a fascinating class of functional porous materials with two- or three-dimensional crystalline organic structures. Generally, it is preferable to use symmetric and rigid building blocks to construct highly crystalline COFs with desired topology. On the other hand, the incorporation of chiral functional moieties in the building blocks would open up new applications such as asymmetric catalysis and chiral separation. This mini review highlights the principle strategies in the design and synthesis of chiral COFs. The interesting and potential applications of these chiral COFs for asymmetric catalysis and chiral separation are also summarized. This mini review aims to provide an up-to-date advancement of chiral COFs for asymmetric catalysis and chiral separation.