手性膜材料及分离机制研究进展

手性膜分离法作为一种新兴的手性分离技术，具有高效、简便、低能耗、可连续操作等特点，在手性分离领域具有巨大的潜力。但近几十年的研究表明，传统手性聚合物材料选择性差、渗透通量低、稳定性差，且难以打破选择性与渗透通量之间的制约关系。这是膜拆分性能无法大幅提高的症结所在，导致膜分离领域长时间处于发展的瓶颈期。近年来，已有许多学者针对这些问题，寻找手性位点更加丰富、稳定性更强、能够提供更多分子通道的新型材料。重点介绍了近5年来基于碳纳米材料、金属有机框架(MOF)、共价有机框架(COF)、改良手性聚合物和一些其他无机材料的新型手性固体膜的合成和应用，并对这些材料的优缺点进行了总结和讨论，以期推动固体膜手性分离技术的进步。另外，还对膜分离机制的研究进展进行了总结，并特别讨论了新材料在手性膜中的作用机制，为进一步改善膜拆分性能提供理论基础。     

基于甲壳素的手性分离材料

甲壳素是一种丰富的可再生资源,将甲壳素在碱性条件下脱去乙酰基得到壳聚糖,甲壳素和壳聚糖分子骨架有大量的手性碳原子存在,且含有较多的羟基、乙酰氨基或氨基活性官能团,容易进行化学改性得到有较好手性识别能力的衍生物,且它们能以膜、纤维、凝胶及微球等不同形式出现,可作为各种手性分离介质。概述了近年来甲壳素衍生物作为手性分离介质的重要研究进展,主要包括甲壳素及其衍生物的色谱手性固定相、手性分离膜、分子印迹聚合物。重点介绍了这些手性分离介质的结构、制备及性能,并展望了甲壳素衍生物手性分离介质的研究前景。     

刷型手性固定相及其在手性化合物分离中的应用

对映体的分离在有机合成、动力学、药理学、药效学及农业化学等许多学科领域内具有重要的意义,液相色谱手性固定相法拆分对映体的方法被认为最准确、方便的方法之一,刷型手性固定相是液相色谱中非常重要的一类手性固定相。本文介绍了目前常用的几种刷型手性固定相及其在手性化合物分离中的应用情况。     

膜拆分法分离制备手性药物

手性是自然界的一种普遍现象,天然存在的手性化合物很多,构成生物体的基本物质如氨基酸、糖类和蛋白质等也都是手性分子.外消旋体药物的手性拆分目前在单一手性药物的制备上仍占有极其重要的地位.手性拆分膜包括基于对映体间亲和性差异的固体膜和基于选择性萃取的液膜两大类.膜分离技术具有能耗低、易于连续操作等优点,被普遍认为是进行大规模手性拆分非常有潜力的方法之一,具有良好的应用前景.手性拆分膜技术引起了国内外研究者们的广泛关注,并成为膜学界研究的新热点.     

手性聚苯胺的研究进展

手性聚苯胺是一种特殊的导电聚合物,在分子识别、手性拆分、吸波材料等方面有着潜在的应用.合成高手性聚苯胺的研究方法已成为近年来的研究热点.综述了手性聚苯胺的研究进展,详细介绍了手性聚苯胺的制备方法,包括原位化学氧化聚合法、电化学聚合法、二次掺杂法、模板法、自组装法和低聚物辅助法等,展望了未来的发展方向.     

手性吸波材料研究进展

手性吸波材料是近年来发展起来具有良好吸波性能的隐身材料,它具有手性参数可调、吸波频带宽等优点。通过对材料手性参数的调整,可以达到预期吸波效果,使吸波材料的制作更具有针对性。对手性吸波材料的吸波机理进行了阐述,综述了3种常见的手性吸波材料——金属手性微体、螺旋炭纤维和手性导电高聚物的研究进展,并对其发展前景进行了展望。     

用手性选择性阳离子交换膜分离DL-苯甘氨酸

以聚乙烯醇为基材,加入β环糊精作为手性选择剂,加入聚丙烯酸促进离子传递,制得具有手性选择性的阳离子交换膜.通过电渗析过程分离DL-苯甘氨酸.改变原料中D-苯甘氨酸与L-苯甘氨酸的比例,一级电渗析实验结果表明均为D-苯甘氨酸优先通过手性阳膜,分离系数1.05,且基本不随原料组成变化.二级电渗析可以把过程的分离系数提高到1.10左右.     

具有手性分离功能的MOCPs的构建

就手性在药物分离中的重要性及手性分离剂的分离机制进行了概述.以此为基础,对一类在手性分离领域有巨大发展潜力的功能材料--金属有机络合聚合物(MOCPs)在分子设计和合成方面的研究现状进行了综述.MOCPs优异的理化性能、孔结构特性和手性分离功能可通过其构建分子的选择和修饰进行设计,其手性结构可通过手性配体与非手性配体进行构建.MOCPs有望在手性分离,特别是在手性药物分离领域形成新的研究和应用的热点.     

用手性选择性阳离子换膜分离DL-苯甘氨酸

以聚乙烯醇为基材,加入β环糊精作为手性选择剂,加入聚丙烯酸促进离子传递,制得具有手性选择性的阳离子交换膜.通过电渗析过程分离DL-苯甘氨酸.改变原料中D-苯甘氨酸与L-苯甘氨酸的比例,一级电渗析实验结果表明均为D-苯甘氨酸优先通过手性阳膜,分离系数1.05,且基本不随原料组成变化.二级电渗析可以把过程的分离系数提高到1.10左右.     

淀粉苯基氨基甲酸酯类手性固定相的制备及用于HPLC手性体分离性能的研究

合成了含有3,5-二甲基和3,5-二氯取代基团的混合型淀粉(苯基氨基甲酸酯)衍生物(CSP-2),并作为手性体分离材料涂敷在氨丙基化多孔硅胶表面,制得新型高效液相色谱(HPLC)用手性固定相;通过1H核磁共振(1H NMR)和红外光谱(IR)表征衍生物结构;以正己烷-异丙醇(9∶1,v/v)为流动相,对多种手性对映体进行了拆分;结果表明,CSP-2综合了单一取代基团淀粉(苯基氨基甲酸酯)衍生物的手性拆分性能,具有优越的手性分离能力,同时固定相的稳定性大大增强。     

Single-molecule chiral recognition on a surface by chiral molecular tips

Chiral surfaces attract increasing interest due to their vital role in a variety of scientific fields, such as chiral separation and heterogeneous enantioselective catalysis. The most urgent issue in research on such two-dimensional chirality is a lack of methodologies that recognize molecular chirality on a surface. Here we show that the chiral molecular tips enable for the first time discrimination of enantiomers on a single-molecule basis. The chiral selectivity is attributed to favorable chemical interactions that the molecular tips form with only one of two enantiomers. The stereoselective observation reveals spatial distribution of the enantiomers on a surface at the molecular level. The chiral molecular tips open a way for control of organization of enantiomers toward the advanced functionality of these chiral surfaces through knowledge on pivotal roles of chirality on molecular assemblies as shown here.     

Determination of the refractive index and the chiral parameter of a chiral solution based on chiral reflection equations and heterodyne interferometry

This study develops a method for determining the chiral parameter and the refractive index of an isotropic chiral medium using chiral reflection equations and critical angle phenomena. Linearly polarized light propagates back and forth in a parallelogram prism between two parallel compartments with chiral solutions. A beam splitter then divides the light that emerges from the prism into a reflected light beam and a transmitted light beam. The two beams pass through a compensator and an analyzer, respectively, to cause phase compensation and interference of s and p polarizations. The phase difference between the two interference signals are initially optimized by a suitable optical arrangement and subsequently measured by heterodyne interferometry. Additionally, the refractive index of the solution is determined from the critical angle that occurred at the discontinuity of the phase difference between the two interference signals. These results are substituted into derived equations to calculate the chiral parameter. The approach has the merits of both common-path interferometry and heterodyne interferometry.     

Spontaneously resolved chiral arylsulfonamides

Our recent studies have shown that cocrystallization of 1:1 solutions of (R)-X and (S)-X′ (where X and X′ represent two sterically similar molecules) often form quasiracemic crystals, in which approximately centrosymmetric molecular pairs cocrystallize in an arrangement that resembles a “true” racemic structure. As part of an ongoing study of the influence of molecular shape on crystal packing, the present work centers on the design, synthesis and X-ray structure determination of four homologous N-(α-methylbenzyl)-4-substituted benzenesulfonamides. Crystallization of a solution of these (±)-arylsulfonamides unexpectedly yields enantiomerically pure crystals via a Pasteurian-type resolution process. This mode of crystallization presumably also deters the cocrystallization of different, but structurally similar, arylsulfonamides to form quasiracemates. The X-ray crystal structures of the four sulfonamides reveal the dominance of N–H⋅⋅⋅O–S hydrogen bonds that form infinite helical C(4) molecular chains. For three of the structures this pattern is extended by short inter- and intramolecular π⋅⋅⋅π interactions to form two-dimensional molecular architectures.     

Three-dimensional chiral plasmonic oligomers

The living world is chiral. Chirality or the handedness of a structure or molecule is at the heart of life itself. Recently, it has been shown that plasmonic structures exhibit unprecedented and gigantic chiral optical responses. Here we show that truly three-dimensional arrangements of plasmonic "meta-atoms" only exhibit a chiral optical response if similar plasmonic "atoms" are arranged in a handed fashion as we require resonant plasmonic coupling. Moreover, we demonstrate that such particle groupings, similarly to molecular systems, possess the capability to encode their three-dimensional arrangement in unique and well-modulated spectra making them ideal candidates for a three-dimensional chiral plasmon ruler. Our results are crucial for the future design and improvement of plasmonic chiral optical systems, for example, for ultrasensitive enantiomer sensing on the single molecule level.     

Molecular dynamics study of chiral recognition for the whelk-O1 chiral stationary phase

In this article, we examine the docking of 10 analytes on the Whelk-O1 stationary phase. A proper representation of analyte flexibility is essential in the docking analysis, and analyte force fields have been developed from a series of B3LYP calculations. Molecular dynamics simulations of a representative Whelk-O1 interface, in the presence of racemic analyte and solvent, form the basis of the analysis of chiral selectivity. The most probable docking arrangements are identified, the energy changes upon docking are evaluated, and separation factors are predicted. From comparisons between the analytes, the mechanism of chiral selectivity is divided into contributions from hydrogen bonding, ring-ring interactions, steric hindrance, and molecular flexibility. We find that both hydrogen bonding and ring-ring interactions are necessary to localize the analyte within the Whelk-O1 cleft region. We also identify one docking mechanism that is often dominant and analyze the conditions that lead to alternate docking modes.     

A sensitivity-enhanced field-effect chiral sensor

Organic thin-film transistor sensors have been recently attracting the attention of the plastic electronics community for their potential exploitation in novel sensing platforms. Specificity and sensitivity are however still open issues: in this respect chiral discrimination-being a scientific and technological achievement in itself--is indeed one of the most challenging sensor bench-tests. So far, conducting-polymer solid-state chiral detection has been carried out at part-per-thousand concentration levels. Here, a novel chiral bilayer organic thin-film transistor gas sensor--comprising an outermost layer with built-in enantioselective properties-is demonstrated to show field-effect amplified sensitivity that enables differential detection of optical isomers in the tens-of-parts-per-million concentration range. The ad-hoc-designed organic semiconductor endowed with chiral side groups, the bilayer structure and the thin-film transistor transducer provide a significant step forward in the development of a high-performance and versatile sensing platform compatible with flexible organic electronic technologies.     

Molecular recognition in chiral discrimination

The importance of obtaining reliable detection systems for enantiomers' assays increases with the necessity of chiral discrimination between the enantiomers of raw materials from the pharmaceutical industry. The utilization of electrochemical sensors in molecular recognition of chiral substances becomes a very accurate and precise alternative for the structural analysis as well as for the chromatographic techniques. The reliability of the response characteristics as well as of the analytical information obtained by using electrochemical sensors is strictly correlated with the design of the sensors. The most reliable design is that of carbon paste based sensors; this design was adopted for the construction of potentiometric, enantioselective membrane electrodes as well as for the construction of the amperometric biosensors, and immunosensors. However, it is also necessary to look for more reliable chiral selectors.     

Electric line source illumination of a chiral cylinder placed in another chiral background medium

An electric line source illumination of a chiral cylinder embedded in a chiral background medium is considered. The field expressions inside and outside of a chiral cylinder have been derived using the wave field decomposition approach. The effects of various chiral cylinders, chiral background media and source locations upon the scattering gain pattern have been investigated. It is observed that the chiral background reduces the backward scattering gain as compared to the free space background for a dielectric cylinder. It is also studied that by moving a line source away from a cylinder reduces the backward scattering gain for a chiral cylinder placed in a chiral background under some specific conditions. A unique phenomenon of reduced scattering gain has been observed at a specific observation angle for a chiral cylinder placed in a chiral background having an electric line source location of unity free space wavelength. An isotropic scattering gain pattern is observed for a chiral nihility background provided that if cylinder is chiral or chiral nihility type. It is also observed that this isotropic behaviour is independent of background and cylinder chirality.