制备手性色谱拆分氧氟沙星光学异构体

利用配合交换原理,采用手性流动相添加剂方法,在反相高效液相色谱（ＲＰ－ＨＰＬＣ）制备柱上,拆分了氧氟沙星的两种对映体。流动相组成为手性添加剂溶液（含６ｍｍｏｌ／ＬＬ－苯丙氨酸和３ｍｍｏｌ／ＬＣｕＳＯ４）－ＣＨ３ＯＨ（８４：１６）,流速４．６ｍＬ／ｍｉｎ,紫外检测波长２９３ｎｍ。经提取纯化后,确证首先洗脱的是Ｓ－（＋）－氧氟沙星,后一个洗脱的是Ｒ－（＋）－氧氟沙星。经对映体选择性分析方法测定,制备获得的两种对映体的光学纯度均大于９９％。     

一种新型L-脯氨酸衍生的高效液相色谱手性固定相

设计和制备了一种用于手性化合物的高效液相色谱拆分的新型手性固定相（ＣＳＰ）。该固定相以构象刚性的Ｌ－脯氨酸为手性选择子,经引入保护基、萘酰胺化、加氢脱保护基、酰胺化和与ＬｉＣｈｒｏｓｏｒｂＮＨ２５μｍ微粒硅胶偶联等５步反应而制得。在此ＣＳＰ结构中引入萘酰胺,可增强ＣＳＰ和手性溶质之间的π－π相互作用,以提高该ＣＳＰ的对映体选择性。报道了４种Ｎ－３,５－二硝基苯甲酰－ＤＬ－氨基酸甲酯对映体色谱拆分的初步结果,对映体选择性在１．０４～１．１８之间。色谱拆分条件的优化和该固定相的应用将有待于进一步研究。     

高效液相色谱法对反式-1,2-二取代环丙烷类化合物的手性拆分

在ＣｈｉｒａｌｃｅｌＯＤ和ＣｈｉｒａｌｃｅｌＯＪ柱上,以各种配比的正己烷／异丙醇为洗脱剂,对１３种反式－１,２－二取代环丙烷类化合物的对映体进行了手性拆分。考察了这些外消旋物在这两种柱上的色谱行为。实验表明带芳环的反式－１,２－二取代环丙烷类化合物在ＯＤ及ＯＪ柱上的拆分能力明显地与芳环上取代基的性质和位置有关。另一方面,一些带有脂族取代基的反式－１,２－二取代环丙烷类化合物也能在这两种柱上得到拆分。     

α－取代苯甲醇类化合物对映体的高效液相色谱法分离

 采用高效液相色谱法，用ＯＤ手性色谱柱直接分离α－取代苯甲醇类化合物的对映异构体。研究了流动相组成比例的改变对化合物对映体的分离色谱保留行为的影响，并将已知标准旋光的手性化合物采用高效液相色谱法拆分数据计算出的对映体过量百分值（ｅ．ｅ．％）与旋光仪测得的过量百分值（Ｏ．Ｐ％）进行了比较。     

α－取代苯甲醇类化合物对映体的高效液相色谱法分离

采用高效液相色谱法，用ＯＤ手性色谱柱直接分离α－取代苯甲醇类化合物的对映异构体。研究了流动相组成比例的改变对化合物对映体的分离色谱保留行为的影响，并将已知标准旋光的手性化合物采用高效液相色谱法拆分数据计算出的对映体过量百分值（ｅ．ｅ．％）与旋光仪测得的过量百分值（Ｏ．Ｐ％）进行了比较。     

γ－环糊精－SDS胶束电动色谱法分离十八甲基炔诺酮光学异构体

 研究了ＣＤ－ＳＤＳ胶束电动色谱（ＣＤ－ＭＥＫＣ）对电中性及疏水性的手性化合物的分离，并讨论了不同类型ＣＤ的手性识别作用。使用γ－ＣＤ可以有效地拆分十八甲基块诺酮（ＮＯＧ）旋光异构体。选择了最佳分离条件，通过调节ＣＤ和ＳＤＳ浓度以及其它操作条件可以把ＮＯＧ异构体很好的分离。     

γ－环糊精－SDS胶束电动色谱法分离十八甲基炔诺酮光学异构体

研究了ＣＤ－ＳＤＳ胶束电动色谱（ＣＤ－ＭＥＫＣ）对电中性及疏水性的手性化合物的分离，并讨论了不同类型ＣＤ的手性识别作用。使用γ－ＣＤ可以有效地拆分十八甲基块诺酮（ＮＯＧ）旋光异构体。选择了最佳分离条件，通过调节ＣＤ和ＳＤＳ浓度以及其它操作条件可以把ＮＯＧ异构体很好的分离。     

高效液相色谱手性流动相法拆分甲状腺素对映体

运用高效液相色谱手性流动相法（ＨＰＬＣ－ＣＭＰ）对影响甲状腺素对映体（Ｄ－,Ｌ－Ｔ４）分离方法的因素：三乙胺（ＴＥＡ）浓度,流动相ｐＨ值,铜离子（Ｃｕ２＋）浓度,Ｌ－脯氨酸（Ｌ－ｐｒｏ）浓度,柱温以及流动相的流速进行了系统的研究。同时,考察了色谱方法分离Ｔ４对映体的线性关系,精密度和准确度。线性响应范围为０．６～３．２　ｎｍｏｌ　（Ｄ－,Ｌ－Ｔ４）,线性相关系数为ｒＤ－Ｔ４＝０．９９８０,ｒＬ－Ｔ４＝０．９９９０,日内和日间的精密度分别为ＲＳＤ＜２．３％（ｎ＝６）,ＲＳＤ＜３．１５％（ｎ＝５）。结果表明本实验所得的色谱条件较文献报道的优越,分离条件简单,重现性好。ＨＰＬＣ－ＣＭＰ法测定甲状腺素对映体其意义在于该方法可为定量测定药品及人体血液中Ｄ－,Ｌ－Ｔ４两种异构体,为治疗药物监测（ＴＤＭ）和药物不良反应监测（ＡＤＲｓ）提供了依据。     

用铜（Ⅱ）—L—精氨酸配体交换薄层色谱拆分氨基酸对映体

报道了一种新的配体交换薄层色谱拆分氨基酸对映体的方法。以醋酸铜－Ｌ－精氨酸的络合物为配体交换剂，用浸渍的方法吸附在硅胶薄层板上，制成配体交换薄层，用ＰＲＩＳＭＡ优化法选择出展开剂的最佳组成为：甲醇／乙腈／四氢呋喃／水＝８０：８．２：５．８：６，在此色谱条件下，十对氨基酸对映体得到良好的分离，Ｄ－和Ｌ－氨基酸的相对比移值在１．０９－２．４０之间。文中对配体交换薄层的制备方法，样品的分子结构及色谱行为     

不同稀释剂对改性环糊精手性分离的影响

用α－苯乙胺、反式－二氯菊酸甲酯做手性试剂,考察了５种稀释剂稀释２,６－二－Ｏ－Ｔ基－３－Ｏ＝丁酰基－β－环糊精的对映体拆分效果。结果表明,用ＳＰ－７９做知释剂与ＯＶ－７、ＯＶ－１７０１、ＳＥ－５４、ＰＥＧ－２０Ｍ等相比,前者有基本相同的柱效、略高或基本一致的对映体选择性。通过焓熵关系分析发现,选用所述不同稀释剂不改变手性拆分机制。     

RP-HPLC拆分普萘洛尔对映体的洗脱顺序及其荧光响应研究

应用反相高效液相色谱法,以（Ｒ,Ｒ）－Ｏ,Ｏ－二乙酰基酒石酸酐（ＤＡＴＡＡＮ）为手性衍生化试剂,拆分了普萘洛尔（ｐｒｏｐｒａｎｏｌｏｌ）对映体。实验结果显示：普萘洛尔对映体经衍生化而生成的两个非对映异构体分子的空间结构有着明显的差异,即（Ｒ,Ｒ,Ｒ）－异构体中存在着分子内氢键,而（Ｒ,Ｒ,Ｓ）－异构体中却没有,这种结构上的区别不仅成为控制洗脱顺序的主要因素,而且对其荧光响应也产生重要的影响。     

Enantioselective drug monitoring of (R)- and (S)- propranolol in human plasma via derivatization with optically active (R,R)-O,O-diacetyl tartaric acid anhydride

A sensitive high-performance liquid chromatographic method was developed for the stereoselective assay of (R)- and (S)-propranolol in human plasma. The method involves diethyl ether extraction of the drugs and a racemic internal standard, N-tert.-butylpropranolol, followed by derivatization of the compounds with the chiral reagent (R,R)-O,O-diacetyl tartaric acid anhydride. The resulting diastereomeric derivatives were separated isocratically on a reversed-phase column. Quantitation was achieved by the peak-height ratio method with reference to the internal standard. The assay was accurate and reproducible in the concentration range 1-100 ng of (R)- and (S)-propranolol per ml plasma, using fluorescence detection at lambda ex 290 nm and lambda em 335 nm. The applicability of this method was demonstrated for the determination of concentration-time profiles of propranolol enantiomers in the course of comparative pharmacokinetic studies.     

Enantiomeric separation of D,L-tryptophan and D,L-kynurenine by HPLC using pre-column fluorescence derivatization with R(-)-DBD-PyNCS

The enantiomeric separation of d ,l ‐tryptophan (Trp) and d ,l ‐kynurenine (KYN) was investigated by high‐performance liquid chromatography using pre‐column fluorescence derivatization with a chiral fluorescent labeling reagent, R(−)‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐ (N,N‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole [R(−)‐DBD‐PyNCS]. Using an octadecylsilica column, namely, an Inertsil ODS‐3 column (250 × 2.0 mm; i.d., 3 µm), four fluorescence peaks of D‐ and l ‐Trp as well as d ‐ and l ‐KYN derivatized with R(−)‐DBD‐PyNCS were clearly observed, and their chemical structures were confirmed by HPLC–time‐of‐flight–mass spectrometry. Simultaneous separation was achieved under the mobile phase condition of 1.5% acetic acid in H₂O–CH₃CN (60:40), and the separation factors of d ,l ‐Trp and d ,l ‐KYN derivatized with R(−)‐DBD‐PyNCS were 1.22 and 1.19, respectively. Fluorescence detection was carried out by setting the emission wavelength at 565 nm, and the excitation wavelength at 440 nm, and the detection limits were approximately 0.3–0.5 pmol (signal‐to‐noise ratio of 3). Copyright © 2010 John Wiley & Sons, Ltd.     

硼-姜黄素络合物的高效液相色谱研究及应用

本文研究了在非水体系中硼与质子化的姜黄素形成的络合物以无水甲醇为溶剂,在C18色谱柱上用甲醇-水(80:20 V/V)作流动相(1.00mL/min)分离并检测.硼的校正曲线线性范围为 0.4～3.2μg/25mL,硼的校测限为 0.08ng.此法用于复合硼肥的分析,结果令人满意.     

(3R,4R)-欧洲榆小蠹聚集信息素的合成

欧洲榆小蠹原产欧洲榆树生长区,美国、加拿大及非洲北部也有分布,其成虫及幼虫蛀食榆树皮,并能传播榆疫病,从而影响榆树生长．Ｐｅａｒｃｅ等分离出其聚集信息素并鉴定其分子结构为（—）４甲基３庚醇（１）［１］,Ｍｏｒｉ等研究结果确定出其天然产物构型为...     

快速柱前衍生HPLC法检测曲格列汀中(R)-3-氨基哌啶

以邻苯二甲醛(OPA)和3-巯基丙酸为衍生试剂,建立了柱前衍生高效液相色谱(HPLC)测定曲格列汀中(R)-3-氨基哌啶含量的分析方法.(R)-3-氨基哌啶与衍生剂在碱性(pH 10.5)条件下于室温反应30s,进行柱前衍生,并利用高效液相色谱-质谱对衍生产物进行定性分析.采用YMC-Triart C18色谱柱(150...     

水/有机溶剂双相中杏仁醇腈酶促不对称合成(R)-苯乙氰醇

 研究了水／有机溶剂双相中来源于杏仁的（R）－醇腈酶催化苯\r\n甲醛与HCN不对称合成（R）－苯乙氰醇,系统探讨了有机溶剂、水相与\r\n有机溶剂相体积比、水相pH值和反应温度对反应速度、转化率和产物光\r\n学纯度的影响．结果表明,上述因素对醇腈酶促不对称合成（R）－苯\r\n乙氰醇反应均有显著影响．异丙醚为该反应最好的有机溶剂,水相与有\r\n机溶剂相体积比以1／2为宜,适宜的pH值为3．4,最佳反应温度为0～\r\n5℃．在该优化反应条件下,反应转化率和产物的光学纯度均高达99％\r\n以上．     

Development and Validation of an HPLC Method for the Determination of Dexamethasone, Dexamethasone Sodium Phosphate and Chloramphenicol in Presence of Each Other in Pharmaceutical Preparations

An HPLC method for the determination of dexamethasone, dexamethasone sodium phosphate and chloramphenicol in presence of each other in pharmaceutical preparations has been developed using a Shim-Pack CLC-ODS column (6.0 × 150 mm²). These analytes were separated under isocratic conditions. Various chromatographic parameters including linearity, precision and accuracy have been evaluated. The method was found to be suitable for analysis of these drug substances in presence of each other. The run time was less than 15 min. This method is suitable for application to various dosage forms.     

Analytical and semi-preparative HPLC enantioseparation of novel pyridazin-3(2H)-one derivatives with α-aminophosphonate moiety using immobilized polysaccharide chiral stationary phases

The direct HPLC enantioseparation of a novel series of chiral pyridazin-3(2H)-one derivatives with α-aminophosphonate moiety was performed on two immobilized polysaccharide chiral stationary phases (Chiralpak IA, Chiralpak IC) using n-hexane (n-Hex)/dichloromethane (DCM) mobile phase with 5% alcohol additive. Good baseline separation of the enantiomers was achieved using amylose tris-(3,5-dimethylphenylcarbamate) chiral stationary phases (Chiralpak IA) on analytical scale. The analytical method was further scaled up to semi-preparative loading to obtain small amounts of both the enantiomers of pyridazin-3(2H)-one derivative. The semi-preparative resolution of all compounds was successfully achieved with n-hexane/dichloromethane/ethanol (EtOH) as mobile phase using a semi-preparative Chiralpak IA column. The first fractions were isolated with purities of >99.9% (enantiomeric excess (e.e.), and the second fractions were obtained with purities of >98.2% (enantiomeric excess). The assignment of the absolute configuration was established for the F1 fraction of compound a-2 by single-crystal X-ray diffraction method.     

Synthesis and Crystal Structure of 5（R）-（1R,2S,5R）-Menthoxy-4（R）- N-cyclohexylaminobutyrolactone

1INTRODUCTION Substitutedγ-butyrolactones are a group of impor-tant compounds containing unique carbon skeleton of butyrolactone which is widely present in many natural products and have received considerable interest because of their biological and medicinal properties[1～4].Therefore,much attention has been paid to the new asymmetric methods for synthesi-zing these interesting compounds[5～11].The prece-ding results led us to explore the possibility of using cyclohexylamine to convert5(…