衍生化环糊精键合固定相对N-苄氧甲酰基-α-氨基膦 酸酯化合物色谱保留和手 性识别机理的研究

正相条件下,一系列N-苄氧甲酰基-α-氨基膦酸二苯酯化合物首次在苯基氨基甲酸酯衍生化β环糊精键合硅胶固定相上实现了高效液相色谱手性拆分,结合热力学模型,对手性分离过程的热力学行为进行了讨论。探索运用定量结构-对映异构体选择性保留关系的方法,将对映异构体的色谱保留和溶质分子描述参数相关性闻系建立定量方程,从超热力学模型的角度研究了色谱保留和手性识别机理。     

衍生化环糊精键合固定相色谱保留和手性识别机理的研究(Ⅰ)

合成了苯基氨基甲酸酯衍生化β-环糊精键合固定相,14个α-氨基膦酸酯类化合物首次在该固定相和商品化的(S)-(+)-萘乙基氨基甲酸酯衍生化β-环糊精固定相上进行液相色谱手性拆分.通过定量结构-对映异构体保留关系对比研究了两种不同的环糊精类固定相上可能的色谱保留和手性识别机理.     

衍生化环糊精键合固定相色谱保留和手性识别机理的研究(Ⅱ)

合成了苯基氨基甲酸酯衍生化β-环糊精键合固定相CSP1和CSP2，在正相色谱条件下，一系列α-氨基膦酸酯化合物首次在这类衍生化β-环糊精固定相上实现了手性拆分。探索运用定量结构-对映异构体选择性保留关系的方法，将对映异构体的色谱保留和溶质子描述参数进行相关性联系建立定量方程，对比研究了该类苯基氨基甲酸酯生化β-环糊精键合固定相上可能的液相色谱保留和手性识别机理。     

3，5-二硝基苯甲酰化β-环糊精键合硅胶手性固定相的合成及高效液相色谱中的手性分离研究

合成了3,5-二硝基苯甲酰化β-环糊精键合硅胶手性固定相,并用红外光谱和X射线光电子能谱进行了表征.制备了相应的高效液相色谱柱,在高效液相色谱中,考察了该手性柱的柱效和对于一些位置异构体和对映异构体的手性分离能力.结果表明,该固定相对于一些位置异构体和对映异构体具有较好的分离能力.     

新型衍生化β-环糊精键合硅胶手性固定相的合成与性能研究

合成了苯基氨基甲酸酯全衍生化β-环糊精键合硅胶手性固定相.在正相色谱条件下,对系列2-(噻唑基)-α-氨基膦酸酯化合物进行了有效的手性拆分研究.结果表明,所有化合物都得到基线分离,对映异构体选择性α>1.2,为制备型液相色谱的手性拆分提供条件.     

有机磷化合物高效液相色谱保留和手性识别机理的研究

在正相条件下,对一系列手性磷有机化合物进行了高效液相色谱拆分,探索运用定量结构-对映异构体选择性保留关系的方法,将对映异构体的色谱保留和溶质分子描述参数相关性联系建立定量方程,研究了色谱保留和手性识别机理,结果表明:在Sumichiral OA4700手性固定相上,对硫代磷酰胺酯类化合物色谱保留贡献最大的是其LUMO参数,即相应的氢键和(或)π-π相互作用;手性识别与logP和LUMO相应的作用力相关.     

衍生化环糊精键合固定相色谱保留和手性识别机理的研究（I）

合成了苯基氨基甲酸酯衍生化β－环糊精键合固定相,１４个α－氨基膦酸酯类化合物首次在该固定相和商品化的（Ｓ）－（＋）－萘乙基氨基甲酸酯衍生化β－环糊精固定相上进行液相色谱手性分拆。通过定量结构－对映异构体保留关系对比研究了两种不同的环糊精类固定相上可能的色谱保留和手性识别机理。     

高效液相色谱的4种商品手性柱对38种手性化合物的拆分研究

采用纤维素-三(3,5-二甲基苯基氨基甲酸酯)涂敷型手性固定相(Chiralcel OD柱)、直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)涂敷型手性固定相(Chiralpak AD柱)、直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)键合型手性固定相(Chiralpak IA柱)和Pirkle型的(S,S)-Whelk-01手性固定相对38种外消旋体化合物进行手性拆分。实验结果表明,4种固定相的手性识别能力为:OD>AD>IA>(S,S)-Whelk-01,OD固定相的手性识别率达到60%,并且它们之间的手性识别性能还具有一定的互补性。本研究对4种常用手性固定相的拆分能力进行了对比,为拆分手性化合物时有的放矢地选择手性固定相提供了参考。     

高效液相色谱手性固定相的研究VI. 间隔基结构对L-缬氨酸玻丁酰胺型手性固定相拆分效果的影响

本文合成一系列含不同结构间隔基的L-缬氨酸叔丁酰胺型键合硅胶手性固定相, 将其用于高效液相色谱拆分α-氨基烃基膦酸衍生物, N-乙酰基-β-二茂铁基丙氨酸乙酯、N-叔丁氧羰基亮氨酰亮氨酸甲酯、N-乙酰基-α-氨基酸甲酯等对映异构体。结果表明: 制得的固定相对以上化合物对映异构体均有不同程度的拆分效果。间隔基刚性增强, 一般对拆分产生不利影响。间隔基为旋光活性酒石酰基的固定相拆分化合物范围减少, 但对某些类化合物对映体的拆分效果有所增强。     

手性有机磷农药对映体在衍生化环糊精类手性固定相上的分离

正相色谱条件下,首次在两种新型衍生化β-环糊精键合硅胶手性固定相上,对系列2-(噻唑基)-α-氨基膦酸酯化合物进行了有效的手性拆分研究,对映异构体选择性α达1.812,Rs高达4.072,为该类化合物的制备型拆分提供了一条行之有效的方法.探讨了化合物结构、流动相组成及流速对拆分的影响及其相应的手性识别机理.     

Structural optimization of a chiral selector for use in preparative enantioselective chromatography

Utilizing the immobilized-target strategy, the structure of a proline-derived chiral stationary phase was optimized for use in the preparative chromatographic separation of the enantiomers of two chiral selectors used in commercial chiral stationary phases. In this study, various N-acylated proline anilides were prepared and chromatographed on the commercial Pirkle-1J and -Burke 2 chiral stationary phases. The analyte which displayed the greatest retention without sacrifice of enantioselectivity (the 3,5-dimethoxyanilide of N-undecenoyl proline) was chosen for incorporation into the preparative chiral stationary phase. Once prepared, this phase shows increased analyte retention and enantioselectivity comparable to that of earlier phases derived from 3,5-dimethyl anilides of proline. The increased retention allows one to use mobile phases in which the target analytes are more soluble, hence greatly facilitating an increase in the through-put of a column of a given size.     

β-环糊精键合手性固定相分离苯并恶嗪类对映体

研究了在反相高效液相色谱模式下,基于点击化学的β-环糊精手性固定相对苯并恶嗪类对映体的手性分离情况。考察了流动相中有机改性剂的类型和比例、缓冲盐的浓度和pH值对分离的影响。考察结果表明: 乙腈作为有机改性剂比甲醇更有利于苯并恶嗪对映体的分离;乙酸三乙胺缓冲盐体积分数从0.1%增大到1.0%时,苯并恶嗪对映体的保留时间和分离度都随之减小,在pH 4.1时苯并恶嗪对映体具有最大分离度。因此确定乙腈和体积分数为0.1%的乙酸三乙胺缓冲盐流动相(pH 4.1)为最佳分离条件。分离机理研究结果表明,固定相和样品之间的包容络合相互作用以及样品和固定相之间的氢键作用,是样品得以分离的基础。本研究为进一步深入研究β-环糊精固定相提供了实验基础,同时也证明了点击化学在手性环糊精固定相制备中具有极大潜力。     

Thin-layer chromatography enantioseparations on chiral stationary phases: a review

The current state of chiral separations by thin-layer chromatography using chiral stationary phases is reviewed. Both stationary phases essentially constituted by the chiral selector and those obtained by the impregnation of achiral plates with appropriate chiral selectors are described. Particular attention is paid to commercial and non-commercial cellulose and cellulose-derivative plates, as well as commercially available Chiralplate?, which are currently the most widely used. Some of the most important results obtained to date are reported and discussed; the examples provided illustrate the very wide range of structurally different solutes that can be readily resolved into their enantiomers by planar chromatographic methods. Special attention is paid to the discussion of the retention and resolution factors that influence chiral discrimination. The quantitative analysis of enantiomers is also discussed, especially from the point of view of determination of enantiomeric purity.     

High-performance liquid chromatography of α-amino acid enantiomers on eremomycin-modified silica

The chromatographic behavior of enantiomers of α-amino acids was studied on new chiral stationary phases based on silica gel with macrocyclic glycopeptide antibiotic eremomycin and its aglycone immobilized on the surface. The retention of adsorbates and enantioselectivity of their separation were studied as functions of the structure of the side group of α-amino acids, eluant pH, concentration of organic modifier in the eluant, and temperature. The mechanism of the chiral recognition of α-amino acid enantiomers is discussed.     

在多糖衍生物类色谱柱上手性拆分乙炔基氮杂环丙烷类化合物

在以正己烷－异丙醇为移动相的体系中，用ＣｈｉｒａｌｐａｋＡＤ和ＣｈｉｒａｌｃｅｌＯＤ作为手性固定相对１５种乙炔基氮杂环丙烷类化合物对映体进行了ＨＰＬＣ手性拆分。这些化合物至少在一支柱上能基线级分离。     

在多糖衍生物类色谱柱上手性拆分β-氨基醇及β-羟基 硫醚类化合物

在以正己烷-异丙醇为移动相的体系中,用ChiralcelOD,ChiralcelOJ及ChiralpakAD作为手性固定相对13种β-氨基醇及β-羟基硫醚类化合物对映体进行HPLC手性拆分,这些化合物至少能在一支柱上得到基线级分离。考察了它们于不同浓度配比的这类洗脱体系中在柱上的色谱行为。实验表明化合物取代基的性质明显影响它们在手性柱上的拆分。手性固定相与外消旋样品上的极性基团之间的氢键作用和π-π作用可能是进行手性识别的主要原因。方法已用于非手性环氧化合物不对称开环反应产物β-氨基醇及β-羟基硫醚类化合物的光学纯度鉴定。     

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.     

Unusual effects of separation conditions on chiral separations

Unusual effects in liquid chromatographic separations of enantiomers on chiral stationary phases are reviewed with emphasis on polysaccharide phases. On protein phases and Pirkle phases reversal of the elution order between enantiomers due to variation of temperature and mobile phase composition has been reported. Most of the nonanticipated observations have dealt with the widely used polysaccharide phases. Reversed retention order and other stereoselective effects have been observed by variation of temperature, organic modifier and water content in nonpolar organic mobile phases.