壳聚糖/多壁碳纳米管复合膜电化学手性识别色氨酸对映异构体

采用滴涂方式将羧酸化多壁碳纳米管(f-MWCNTs)修饰于玻碳电极(GCE)表面成膜,然后恒电位法在上述修饰电极表面电沉积壳聚糖(CS)膜,形成CS和f-MWCNTs复合膜修饰电极(CS/f-MWCNTs/GCE),并用于色氨酸(Trp)对映异构体的手性识别。采用扫描电子显微镜(SEM)表征了修饰电极表面形貌的差异,电化学阻抗(EIS)和循环伏安法(CV)研究修饰电极的电化学行为差异。差分脉冲伏安法(DPV)用于区别色氨酸(Trp)对映异构体,分离系数可达2.38。研究发现该修饰电极对L-Trp的DPV响应信号强于D-Trp,检测的线性范围为8.0×10~(-6)~4.0×10~(-3)mol/L,检出限(S/N=3)为5.0×10~(-6)mol/L。该方法简单、经济、快速,对发展其它手性化合物的检测方法提供了参考。     

手性识别及氨基酸类手性固定相的研究进展

近年来, 手性识别更加凸现出极其重要的现实意义, 而作为分离手性分子应用的手性固定相自然引起了大家的关注．立足于国内外手性固定相的研究成果, 介绍了手性固定相及其分类, 并重点综述了基于氨基酸的手性固定相的发展及其制备方法. 同时, 简要介绍了作为手性固定相对不同异构体的识别机理.     

手性传感器研究进展

手性工程的崛起对简单、经济、快速、实时、在线的手性检测技术提出了挑战。手性传感器是一个重要的发展趋势。本文综述了近年来在手性电化学传感器、基于石英晶体微天平的手性质量化学传感器及手性光学传感器方面的研究进展,重点介绍了各种传感器的制备及其在手性检测中的应用,并展望了该领域的发展前景。     

手性亚砜类药物的手性识别研究

以L-亮氨酸的衍生物二齿手性氨基醇为主体、氘代氯仿为溶剂、手性亚砜类药物奥美拉唑消旋体和兰索拉唑消旋体为客体,分别考察了主体对两种客体消旋体的手性识别能力,最大化学位移差值(ΔΔδ)分别达到28.5 Hz和14 Hz。     

手性分子识别的质谱研究进展

由于质谱分析速度快以及所需样品量少等特点，使得质谱手性识别技术在现代分析化学、有机化学甚至生物化学等领域得到青睐，阐述了手性分子识别的质谱研究最新动向，对其原理和所使用的手性选择剂作了介绍。     

手性金属有机骨架构筑的电化学传感器对色氨酸对映体的识别

本文将金属离子(Cu(Ⅱ)), 1,10-菲啰啉(Phen)和L-谷氨酸(L-Glu)组装,使用一锅法合成了手性金属有机骨架(L-Glu-Phen-Cu(Ⅱ))。L-Glu-Phen-Cu(Ⅱ)作为一种新型的电化学传感界面,由于具有良好的对映体选择性(IL/ID=2.24),被用于对色氨酸(Trp)对映体的手性识别中。Cu(Ⅱ)和L-Glu配位实现了L-Glu-Phen-Cu(Ⅱ)立体选择性的构建,Cu(Ⅱ)和Phen配位增强了电化学信号,实现了L-Glu-Phen-Cu(Ⅱ)高对映选择性的构建。本研究不仅为高效的Trp对映体检测提供了一种易于调节、低成本的传感界面,而且将直接合成的手性MOFs用于手性识别提供了一种可行的新思路。     

基于手性冠醚的对映选择性识别研究进展

介绍了冠醚类化合物的结构特点及络合性能、冠醚的络合作用和识别分子的新进展.冠醚类化合物因其稳定的构象和易于修饰的特点,成为研究最为广泛的主体分子之一,其中大量的文献报道了能够用于对映选择性识别和检测的手性冠醚.在分子识别的研究中,核磁、荧光、紫外和质谱是四种最常见的研究方法,总结了近年来手性冠醚运用这四种方法在对映选择性识别领域的最新研究进展并对手性冠醚的发展前景作了展望.     

超分子化学方法研究环糊精的手性识别

本文论述了环糊精（ｃｙｌｄｅｘｔｒｉｎ，ＣＤ）的主体结构，并引进了超分子化学和概念，讨论了基于ＣＤ的特殊结构及在手性分离中的分子识别机理。     

氨基酸及其衍生物的手性识别研究进展

本文综述了近年来开拓的多种人工受体模型对氨基酸及其衍生物的对映选择性识别性能，并做了相互比较，从中总结出手性识别的几个基本原则，预期了其应用前景。     

Comparative Analysis of Proline Enantiomer in Chiral Recognition of Biological Macromolecule in Immunoassay

An interesting phenomenon of the stereoselective interaction between biological macromolecule and amino acid enantiomorphous was described. Firstly, proline enantiomer (L‐ and D‐proline) was assembled on the glassy carbon electrode surface. Then carcinoembryonic antibody (anti‐CEA) was loaded to the enantiomer surface, electrochemical impedance spectroscopy (EIS) was used to monitor the growth of amino acid film. The assembly process was characterized by cyclic voltammetry (CV) and atomic force microscopy (AFM) was applied to image the chiral films. Finally, the developed electrodes had interacted with carcinoembryonic antigen (CEA) in varying concentration solutions. The AFM and amperometric results revealed that the proline enantioner had the chiral recognition function to antibody.     

Chiral Recognition of Penicillamine Enantiomers Based on DNA‐MWNT Complex Modified Electrode

Double‐stranded DNA and multiwalled carbon nanotube (MWNT) complex modified glassy carbon electrodes (DNA‐MWNT‐GCE) were employed to discriminate penicillamine (PA) enantiomers. Cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and ultraviolet‐visible spectroscopy were used to characterize the enantioselective phenomenon. The results indicated that the binding effect between L ‐PA and DNA‐MWNTs was stronger than that of D ‐PA and DNA‐MWNTs. In addition, the influencing factors of the modified electrodes were systematically investigated. The modified electrodes exhibited a linear response towards PA enantiomers from 1.0×10^?1 to 1.0×10^?8 mol L^?1 and detection limits of 3.1×10^?9 and 3.3×10^?8 mol L^?1 for L ‐PA and D ‐PA, respectively.     

Electrochemical Recognition of Chiral Molecules with Poly(4‐bromoaniline) Modified Gold Electrode

A poly(4‐bromoaniline) (PBA) film is electrochemically synthesized on a gold electrode for the recognition of amino acids enantiomers. Scanning electron microscopy measurements show that the porous PBA films are made up of nano‐ribbons. At the PBA modified Au electrode differential pulse voltammograms of L ‐ and D ‐glutamic acids not only have very different current densities, but also produce different waveforms, providing an intuitive way to differentiate the two chiral molecules. Similar results are obtained in analyzing L ‐ and D ‐aspartic acids. Control experiments suggest that the observed sensing behavior arises from synergistic interactions between Au and the PBA film, where polymerization at the meta‐position creates a steric structure needed for differentiating chiral molecules.     

手性离子液体修饰纳米金粒子用于酪氨酸对映体的手性识别

本文以手性离子液体1-乙基-3-甲基咪唑L-酒石酸盐(EMIML-Tar)为修饰剂合成了EMIML-Tar修饰的金纳米粒子(EMIML-Tar-AuNPs)。采用透射电镜、紫外-可见分光光度计对EMIML-Tar-AuNPs进行了表征。合成的EMIML-Tar-AuNPs平均粒径约为6.5nm,其紫外-可见吸收光谱的最大吸收波长为520nm。进一步将EMIML-Tar-AuNPs用于酪氨酸(Tyr)对映体的手性识别,观察添加不同浓度D-Tyr和L-Tyr的EMIML-Tar-AuNPs的颜色变化及其紫外-可见吸收光谱。结果表明,经过D-Tyr和L-Tyr处理的EMIML-Tar-AuNPs胶体的颜色不同,而且紫外-可见光谱图也存在明显差异。对各浓度光谱图在650nm和520nm处的吸光度比值进行比较,结果发现各浓度D-Tyr的吸光度比值均较低且差别不大,而L-Tyr的吸光度比值均较高,且随着浓度的增大会出现大幅度增加。     

2-N-邻苯二甲酰亚胺壳聚糖基手性固定相的制备及手性识别能力研究

为了开发具有高效手性识别能力的新型多糖类手性固定相,合成了5种糖单元2-位具有邻苯二甲酰亚胺,而3,6-位同时具有4种不同苯基氨基甲酸酯基团(2-氯、3-氯、4-氯和3,5二氯取代的苯基氨基甲酸酯)和一种无取代的苯基氨基甲酸酯基团的壳聚糖类衍生物,并将其涂覆在氨丙基硅胶表面制备成HPLC手性固定相.利用红外光谱和核磁氢谱对所合成的衍生物进行结构表征与分析,并应用HPLC法评价其对10种对映体的手性识别能力.研究结果表明:这些新型壳聚糖类手性固定相的手性识别能力受苯基氨基甲酸酯取代基中芳环上侧基的引入位置、数量和空间位阻的影响较大.同时色谱测试中所使用流动相的成分对该类手性固定相的识别能力也具有较大影响.进一步探讨了这些衍生物的氨基甲酸酯残基核磁氢谱中N—H质子的化学位移和红外光谱中N—H波数与手性识别能力之间的关系.     

New Chiral Calixarene Derivatives： Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.     

Chiral Recognition and Resolution Based on Helical Polymers

Helical polymers have attracted a great deal of attention and been extensively investigated due to their various applications.One of the most important applications of helical polymers is chiral recognition and resolution of enantiomers for the reason that a pair of enantiomers is commonly with different physiological and toxicological behaviors in biological systems.Helical polymers usually present unexpected high chiral recognition ability to a variety of racemic compounds.What's more,the chiral recognition and resolution abilities of the system are dependent on the highly ordered helical structures of the helical polymers.This mini review mainly focuses on the recent progress in chiral recognition and resolution based on helical polymers.The synthetic methodology for helical polymers is firstly discussed briefly.Then recent advances of chiral recognition and resolution systems based on helical polymers,especially polyacetylenes and polyisocyanides,are described.We hope this mini review will inspire more interest in developing helical polymers and encourage further advances in chiral-related disciplines.     

Chiral Recognition of Tryptophan Enantiomers Based on β‐Cyclodextrin‐platinum Nanoparticles/Graphene Nanohybrids Modified Electrode

The nanohybrids which based on β‐cyclodextrin, platinum nanoparticles and graphene (β‐CD‐PtNPs/GNs) were successfully synthesized and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT‐IR) and electrochemical impedance spectroscopy (EIS). Then they were used to construct a simple and reliable chiral sensing platform to interact with tryptophan (Trp) enantiomers. Differential pulse voltammetry (DPV) was used to investigate the stereo selectivity of β‐CD‐PtNPs/GNs to Trp enantiomers. After interaction, the obvious difference of peak currents of L‐Trp and D‐Trp was obtained, indicating this strategy could be employed to chiral recognition of Trp enantiomers. Under the optimum conditions, the chiral sensor exhibited a good linear response to Trp enantiomers in a linear range of 5.0×10^?5 to 5.0×10^?3 M with a low limit of detection of 1.7×10^?5 M (S/N=3). This approach provided a new available platform to recognize and determine Trp enantiomers.     

芳香取代基结构对螺旋聚乙炔高效液相色谱手性固定相手性识别性能的影响

设计合成了3种源于脯氨酸的手性乙炔基单体——(S)-2-乙炔基-N-芳香胺基甲酰基吡咯烷. 在氯化降冰片二烯铑二聚体{[Rh(nbd)Cl]₂}-三乙胺催化下, 3种单体被转化为相应的光学活性螺旋聚合物. 用高效液相色谱评估了3种聚合物作为手性固定相(CSPs)对9种底物的手性识别性能. 以正己烷/异丙醇(体积比9∶1)为流动相时, 3种聚合物对3对种氢键给体分子苯偶姻(α=1.35~1.44)、 三氟-1-(9-蒽基)乙醇(α=1.11~1.53)、 2,2′-二羟基-1,1′-联萘(α=1.09~1.11)及乙酰丙酮钴(α=1.84~2.38)表现出很好的手性识别能力; 当以正己烷为流动相时, 3种聚合物都能立体选择性地识别氢键给体分子2,2-二甲基-1-苯基-1-丙醇(α=1.12~1.22), 聚[(S)-2-乙炔基-N-(2′-萘基胺基甲酰基)吡咯烷]能识别氢键受体分子2-苯基环己酮(α=1.11). 结合核磁共振波谱、 拉曼光谱、 旋光测试、 紫外吸收光谱和圆二色光谱及液相色谱等方法, 系统研究了芳香侧基结构与连接位置对聚合物螺旋构象和对映体选择性拆分能力的影响. 分子对接模拟结果表明, 1-萘基的空间位阻大于2-萘基且可促进形成更强的分子内氢键, 不利于大尺寸底物(如联萘酚)的手性拆分. 与苯基相比, 引入萘基有利于增强聚合物与底物间的π-π相互作用, 提高聚合物的立体选择性和手性识别能力.     

石英晶体微天平在手性识别中的应用

石英晶体微天平(QCM)是一类重要的质量型检测器,因具有灵敏度高、分析速度快、检测成本低等优点而具有极好的应用前景,现已广泛应用于环境监测、药物分析、食品质量控制等诸多领域。手性工程的崛起对简单、快速、在线的手性检测技术提出了挑战,QCM手性传感器就是其中一个重要的发展分支。该文简要介绍了QCM的典型实验装置和基本传感原理,详细综述了近年来QCM在手性识别领域的研究进展,包括以环糊精衍生物、分子印迹聚合物、氨基酸衍生物等为手性主体的QCM在手性识别中的应用,并对其今后的发展进行了展望。