环糊精及其衍生物在手性识别中的应用

详细地论述了环糊精及其衍生物在手性识别中的应用,并对环糊精超分子体系手性识别中的进一步研究提供了依据。     

Molecular Dynamic Study for Chiral Discrimination of α-Phenylethylamine by Modified Cyclodextrin in Gas Chromatography

IntroductionAfter the introduction of modified cyclodextrins (CDs) as a new type ofchiral stationaryphases, great progress has been made in enantioselective gas chromatography, which hasraised many questions about the mechanism of chiral recognition and intermolecularinteractionsl. Theoretical computational methods in conjunction with modellingprocedures have been extensively used to investigate the nature of binding processesresponsible for inclusion complex formation2'3. It is of interest t…     

Structure and Molecular Recognition of Chiral Amino-Cyclodextrin: One-dimensional Array by Self-assembly in Solid and Chiral Discrimination in Solution

Abstract

The crystal structure and molecular recognition behaviour of a new chiral-amino cyclodextrin are reported; van der Waals interaction, hydrogen bond and the electrostatic interactions play an important role in the self-assembling process and chiral recognition for (R)-(-)-and (S)-(+)-mandelic acid.     

改性环糊精气相色谱手性固定相拆分对映体的选择性及拆分机理的讨论

改性环糊精气相色谱手性固定相拆分对映体的选择性及拆分机理的讨论周昕，万宏，欧庆瑜（中国科学院兰州化学物理研究所兰州７３００００）１前言自１９８８年Ｋｏｎｉｇ￣［１］等人成功地将改性环糊精用于毛细管气相色谱固定相拆分对映体以来，环糊精衍生物以其高选择性...     

毛细管电泳手性拆分中的二元环糊精体系

二元环糊精体系常对复杂难分离手性体系表现出很好的拆分能力并对一些手性药物有极好的拆分效果, 一般情况下它又与一元体系有不尽相同的拆分机理, 本文就该体系在手性物质拆分中的应用及相应理论研究作一概述。     

β—环糊精对D／L—酪氨酸对映体的手性识别及超分子包合物的合成

利用圆二色谱研究了β－环糊精（β－ＣＤ）对Ｄ／Ｌ酪氨酸的手性识别行为，制备出了β－ＣＤ与Ｌ－酪氨酸（Ｌ－Ｔｙｒ）的固体超分子化合物，并用元素分析、薄层分析、Ｘ射线粉末衍射及热分析对包合物进行了表征，用荧光光谱法测定了包合物的形成常数．实验结果表明，β－ＣＤ具有选择包结Ｌ－酪氨酸的特性；主客体形成１１的包合物，其组成为Ｌ－Ｔｙｒ／β－ＣＤ·１２Ｈ２Ｏ；稳定常数为５．１３×１０３Ｌ／ｍｏｌ；包合物的热稳定性比主客体皆有改善     

环糊精在手性药物分离分析研究中的应用

环糊精由于自身特殊的手性环境和结构特征,已广泛运用于手性化合物的对映体拆分及分析。对近年来环糊精在各种色谱、质谱及核磁等分析方法中的应用进行了归纳总结,综述了环糊精及其衍生物在手性药物的分离分析方面的研究进展。     

分子模型及其在手性识别机理研究上的应用

介绍了近十几年来在色谱手性识别机理研究中的分子模型。在这些模型中,采用量子力学、分子力学和分子动力学等方法计算了手性选择试剂与对映体之间的相互作用,并借助X射线晶体学、核磁共振技术和计算机模拟等技术建立了各种分子模型,研究在手性化合物分离过程中的手性识别机理。     

环糊精衍生物气相色谱手性毛细管柱的制备与考察

合成了３种新的含长烷基链的β－环糊精衍生物手性固定相。实验表明，随着烷基链长的增加，对手性卤代烃和酯的立体选择性有所提高；以ＯＶ－７为手性固定相的稀释剂对多数手性化合物的拆分效果好于ＯＶ－１７０１。２，６－Ｏ－二辛基－３－Ｏ三氟乙酰－β－环糊精／ＯＶ－７柱应用于不对称合成及催化中对映体的分离与测定和白酒中乳酸乙酯对映体含量的测定。     

2,3-Di-O-pentyl-6-O-tert-butyldimethylsilyl-β-cyclodextrin as a Chiral Stationary Phase in Capillary Gas Chromatography

2,3-Di-O-pentyl-6-O-tert-butyldimethylsilyl-β-cyclodextrin has been evaluated as an enantioselective stationary phase for capillary gas chromatography. Experimental results show a good enantioselectivity towards compounds with different functional groups (haloalkanes, alcohols, esters, terpenoids, amino acid derivatives, and heterocycles). Column stability improves mixing the chiral phase with polysiloxane SE-54 (1 : 1).     

新型手性酪氨酸修饰的锌卟啉对氨基酸酯的分子识别研究

合成并表征了一种L型Boc酪氨酸修饰的自由卟啉(L-BocTyrTAPP)及其锌卟啉配合物Zn(L-BocTyr)TAPP.通过紫外-可见光谱滴定法,研究了手性锌卟啉配合物与四对对映异构的手性氨基酸酯客体在CHCl₃中的分子识别行为.实验结果表明,在分子识别的过程中,缔合常数顺序均为D型略大于L型,且按K(PheOMe)>K(AIaOMe)>K(ValOMe)>K(LeuOMe)的顺序依次减小.同时,利用园二色光谱进一步阐述手性分子识别过程.此外,采用分子力学方法搜索了主客体体系的最低能量构象,从理论上对实验本质进行较深入的探讨.     

Molecular Recognition of Aliphatic Alcohols and Carboxylic Acid by Chromophoric Cyclodextrins

Abstract

Molecular recognition behavior of eight cyclodextrin derivatives, i.e. mono(6-pyridinio-6-deoxy)-α-cyclodextrin (1α), mono(6-pyridinio-6-deoxy)-β-cyclodetrin (1β), mono(6-pyridinio-6-deoxy)-γ-cyclodextrin (1γ), mono[6-(p-picolinio)-6-deoxy]-β-cyclodextrin (2β), mono(6-anilino-6-deoxy)-β-cyclodextrin (3β), mono[6-(m-toluidino)-6-deoxy]-β-cyclodextrin (4β), mono[6-O-(8-quinolyl)]-β-cyclodextrin (5β), and novel mono[6-(2-naphthylamino)-6-deoxy]-β-cyclodextrin (6β), with a series of aliphatic alcohols and carboxylic acid has been investigated spectroscopically. Using the appended aromatic group as a spectral probe, spectroflurometric or spectropolarimetric titrations have been performed at 25°C in aqueous phosphate buffer solution (pH 7.20, 0.1 M) to determine the complex stability constants (K_s ) and Gibbs free energy changes (-δG°) for the stoichiometric 1:1 inclusion complexation of cyclodextrin derivatives with the guests. The results obtained demonstrate that the modified cyclodextrins are highly sensitive to the size/shape and hydrophobicity of guest molecules, and particularly 5β gives an excellent molecular selectivity up to 215 for 1-adamantanol/cyclohexanol. The binding ability and selectivity of the modified cyclodextrins (1α, 1β, and 1β-6β) are discussed from the view points of size/shape-fit concept, induced-fit interaction, and the multiple recognition mechanisms.     

液相色谱手性拆分机理的热力学方法研究

手性识别是分子识别的一个重要组成部分。液相色谱手性拆分机理研究有助于色谱条件的优化和新型手性固定相的设计,也有助于理解手性识别机制。本文就线性色谱与非线性色谱条件下手性拆分过程对应热力学参数的推求方法进行了评述,阐述了相关热力学参数的涵义及其在色谱保留及手性拆分机理探讨中的应用,并展望了该领域的研究前景。     

液相色谱手性拆分机理的热力学方法研究

手性识别是分子识别的一个重要组成部分。液相色谱手性拆分机理研究有助于色谱条件的优化和新型手性固定相的设计,也有助于理解手性识别机制。本文就线性色谱与非线性色谱条件下手性拆分过程对应热力学参数的推求方法进行了评述,阐述了相关热力学参数的涵义及其在色谱保留及手性拆分机理探讨中的应用,并展望了该领域的研究前景。     

气相色谱手性固定相研究进展

本文评述了气相色谱手性分离的发展过程,介绍了氨基酸、二肽、金属配合物、环糊精、多糖、手性离子液体、环肽、键合以及交联类气相色谱手性固定相以及各类型的拆分机理,展望了气相色谱手性固定相的研究前景。     

Functionalization of Macroporous Organic Polymer Monolith Based on Succinimide Ester Reactivity for Chiral Capillary Chromatography: A Cyclodextrin Click Approach

Macroporous cross‐linked organic polymer based on N‐acryloxysuccinimide (NAS) and ethylene dimethacrylate (EDMA) was prepared inside 75 µm id fused silica capillary as a functionalizable monolithic stationary phase for chromatographic applications. Succinimide groups on the monolith surface provide reactive sites able to react readily through standard electrophile–nucleophile chemistry. Propargylamine was used to prepare alkyne functionalized poly(NAS‐co‐EDMA). Onto this azido‐reactive polymer surface was grafted β‐cyclodextrin (CD) via a triazole ring utilizing the copper(I)‐catalyzed 1,3‐dipolar cyclo‐addition reaction. Chemical characterization was performed in situ after each synthetic step by means of Raman spectroscopy. Good enantioseparations of flavanone enantiomers, chosen as test chiral compound, were achieved under reversed phase conditions by both capillary electrochromatography and nano‐liquid chromatography (nano‐LC) techniques. These results demonstrate the potentiality and usefulness of click chemistry in the preparation of β‐CD containing chiral organic polymer monolith.

     

Simultaneous Chiral SeparationUsing a Combinatorial Molecular Imprinting Phase

Molecular imprinting is a technology by which specific recognition sites can be producedby using a template molecule in the polymerization procedure. In recent years,molecular imprinting has become an important approach for the preparation of chiralstationary phase with predetermined selectivity'-'. So far, the commonly atilizedfunctional monomers include methacrylic acid', acrylamide' and 4-vinylpyridine',combined functional monomers such as methacrylic acid 2-vinylpyridine'-' andacrylamide…     

环糊精衍生物作为气相色谱固定相的发展及应用

从环糊精及其衍生物作为气相色的分离机理出发介绍了影响这固定相的因素及其分离应用的近期发展,共评述56篇文章。     

General Mechanism for Chiral Recognition by Native and Modified Cyclodextrins

A general mechanism for chiral recognition by native and modified cyclodextrins hasbeen proposed by reconsidering the data reported so far. Cyclodextrins in aqueoussolution adopt asymmetrically twisted structures, which seems to be the origin of chiralrecognition.     

2-呋喃甲硫醇修饰环糊精形成互锁式螺旋柱状超分子的自组装行为

利用单-(6-氧-对甲基苯磺酰基)-β-环糊精和2-呋喃甲硫醇反应得到单修饰环糊精, 单[6-硫-6-(2-甲基呋喃)]-β-环糊精. 通过X-ray衍射分析及核磁光谱等方法研究了其在溶液和固态中形成线状超分子的分子自组装行为. 结果表明, 化合物在固态中通过呋喃基团从第二面羟基连续插入到另一个环糊精的空腔, 形成了互锁式螺旋柱状超分子, 而且在溶液中也显示了相似的自组装行为, 其键合常数K及聚合度n分别为450 mol^-1·L和1.9.