羟丙基-β-环糊精固载相薄层色谱法拆分盐酸克伦特罗对映体

以羧甲基纤维素钠为交联剂,将羟丙基-β-环糊精固载在硅胶GF254板上,作为固定相制成层析薄板,成功用于拆分盐酸克伦特罗对映异构体。考察了展开剂对层析薄板分离效果的影响,发现展开剂中醇的种类和比例对拆分效果有很大的影响,含4个碳的醇类包括正丁醇、仲丁醇、叔丁醇可使盐酸克伦特罗得以拆分。确定了实验的最佳条件：V（乙腈）：V（叔丁醇）=50：50,展开时间约为12min。     

手性选择体涂敷薄层色谱拆分盐酸普萘洛尔

采用手性选择体涂敷薄层色谱方法,拆分了盐酸普萘洛尔对映体,考察了β-环糊精、羟丙基-β-环糊精以及（2R,3R）-酒石酸-二-烷基酯等多种手性选择体拆分效果,得到手性选择体涂敷薄层色谱拆分盐酸普萘洛尔对映体最佳条件：采用β-环糊精、羟丙基-β-环糊精涂敷薄层色谱,以乙腈-仲丁醇混合溶剂作展开剂,展开剂中乙腈体积分数大于30%时,室温下展开均可拆分盐酸普萘洛尔对映体,并实现基线分离.实验同时发现,采用（2R,3R）-酒石酸-二-烷基酯涂敷薄层色谱拆分不能实现拆分.通过比较手性选择体结构,探讨了拆分机理.     

酒石酸酯固载薄层色谱法拆分盐酸克伦特罗对映异构体

药物对映体的各个单体通常具有不同的生物活性、药理活性,所以需要对它们进行拆分以得到旋光单体。D-和L-酒石酸是廉价的手性原料,（2R,3R）-酒石酸可直接从自然界获取。选择酒石酸衍生物例如酒石酸二酯、酒石酸单酰胺、酒石酸二酰胺等用于对映体拆分,效果比较令人满意。本工作将（2R,3R）-酒石酸-二环己酯固载在硅胶GF254板上,成功地拆分了盐酸克伦特罗对映体,并对其拆分机理进行了探讨。     

聚谷氨酸苄酯掺杂硅胶用于拆分氧氟沙星对映体

通过将聚谷氨酸苄酯（PBLG）掺杂在硅胶中,建立了一种分离手性物质氧氟沙星对映体的方法。以壳聚糖为引发剂,利用开环聚合方法合成了PBLG。将PBLG掺杂在硅胶G中制备薄层色谱板,实现了对氧氟沙星外消旋体的拆分。考察了展开溶剂体系、不同比例溶剂、展开温度和展开时间对手性拆分氧氟沙星对映异构体的影响。结果表明,该薄层色谱板拆分氧氟沙星对映异构体的最佳条件为：0.5 g PBLG掺杂在2 g硅胶G中,以乙腈-甲醇（V/V=2∶1）混合溶剂为展开体系,35℃下展开30 min。氧氟沙星对映体单体在薄层色谱板上的手性分离因子（α）范围为2.62～6.12,实现了基线分离。     

薄层色谱法拆分手性药物对映体

用性能稳定的薄层色谱用β-环糊精(β-CD)、硅胶手性固定相拆分手性药物对映体.在适当比例的乙腈-1%乙酸三乙胺(TEAA)、己烷-异丙醇、乙腈-甲醇-乙酸-三乙胺、甲醇-1%TEAA及乙腈-1%TEAA-三乙胺溶剂系统中展开,8种临床常用的手性药物对映体得到有效分离,对映异构体之间的相对比移值α为1.53～4.89.     

两种薄层色谱直接拆分美托洛尔的方法研究

β-受体阻断药物美托洛尔有两个对映异构体,其药理学、毒理学及药代动力学具有极大的差异。研究建立了以D-10樟脑磺酸铵作为流动相手性离子对添加剂拆分美托洛尔对映体的薄层色谱方法,其最佳色谱条件为:D-10-樟脑磺酸铵溶液(0.17mmol/L,pH7.5)/二氯甲烷/甲醇(0.3/2.06/0.64,V/V/V),室温(15℃)下预饱和30m in,样品pH为8.0;研究建立了以β-环糊精固载薄层色谱拆分美托洛尔的方法,最佳色谱条件为:按硅胶GF254∶β-环糊精质量为30∶1的比例铺板,甲醇/二氯甲烷(0.87/2.13,V/V),室温(17℃)。两种方法均具有操作简便、经济、重现性好、结果可靠的特点。     

用薄层色谱法分离芳香醇胺药物对映体

用D－10-樟脑磷酸铵作为手性离子对试剂添加到流动相中,在硅胶GF254薄层板上分离了两种芳香醇胺类药物对映体。     

Pirkle型手性固定相拆分盐酸克伦特罗对映体

建立并优化了高效液相色谱手性固定相分离盐酸克伦特罗对映体的方法。使用两种Pirkle型手性固定相(α-Burke-2和Pirkle-1J)拆分了盐酸克伦特罗对映体,考察了缓冲盐添加剂,有机溶剂种类和浓度,以及柱温对保留行为和分离的影响。当流动相为二氯甲烷-乙醇(19:1,V/V)含5 mmol/L乙酸铵,流速2.0 mL/min,柱温20℃时,盐酸克伦特罗对映体在α-Burke-2色谱柱上能实现较好的分离,分离度可达1.85;在Pirkle-1J色谱柱上,分离度可达0.64。盐酸克伦特罗对映体与Pirkle型固定相之间的π-π主客体相互作用和氢键作用是实现对映体分离的最主要分离机制。方法可用于盐酸克伦特罗对映体的质量控制及立体选择性药代动力学的研究。     

用环糊精合成楔筒状主体分子新模型

用四醋酸铅将七元（6-O-二甲基叔丁基硅基）-β-环糊精选择氧化、并用三氟 化硼乙醚脱硅基保护基后,再经分离、纯化,可获得具有“楔筒状”空腔的单-2, 3-二醛基-β-环糊精。单-2,3-二醛基-β-环糊精较β-环糊精有更好的水溶性。 用单-2,3-二醛基-β-环糊精作TLC流动相手性添加剂时,可将肾上腺素对映体在 硅胶薄层板上有效拆分。     

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     

Quantitative determination of clenbuterol enantiomers in human plasma by high-performance liquid chromatography using the macrocyclic antibiotic chiral stationary phase teicoplanin

We report a method for the high-performance liquid chromatographic (HPLC) chiral separation of racemic clenbuterol in human plasma. Human plasma was spiked with stock solutions of clenbuterol hydrochloride and practolol as the internal standard. Following a liquid-liquid extraction procedure with 10% (+/-)-2-butanol/isopropyl ether under alkaline conditions, the dried samples were reconstituted in methanol and chromatographed using a macrocyclic antibiotic chiral stationary phase (CSP) known as Chirobiotic T(trade mark) (teicoplanin). The mobile phase composition was methanol:acetonitrile (70:30, v/v), containing 0.3% (v/v) acetic acid and 0.2% (v/v) triethylamine. The resulting chromatogram achieved baseline separation for the clenbuterol enantiomers. Calibration curves (peak area ratio vs plasma concentration, n = 10) were constructed for the (-)-R-and (+)-S-clenbuterol enantiomers with a plasma concentration range of 0. 25-10 microM. The correlation coefficient (r) range was 0.99988-0. 99999 (mean = 0.99999). The lowest concentration measured was 0.25 microM. Inter- and intra-assay variation was determined for the lowest, medium and highest plasma concentration (0.25, 2 and 10 microM) by calculating the analytical recoveries with a range of 96-104%. The percentage recoveries for the clenbuterol enantiomers were 88.4-102% over the concentration range used. Detailed methodology is presented.     

Resolution of enantiomers of DL-amino acids on silica gel plates impregnated with optically pure (-)-quinine.

TLC resolution of enantiomers from racemic amino acids was achieved on silica gel plates impregnated with optically pure (-)-quinine. The successful solvent systems were butanol-chloroform-acetic acid (3:7:5, v/v) for DL-methionine; 6:8:4, v/v for alanine; 10:1:4; v/v for threonine; and ethyl acetate-carbon tetrachloride-propionic acid (10.5:6.5:3.5, v/v) for valine. Minimum detection limits were found to be different for each of the amino acid, ranging between 0.9 and 3.7 microg. The effects of concentration of impregnating reagent, temperature and pH on resolution of enantiomers have been studied in details.     

Direct TLC resolution of atenolol and propranolol into their enantiomers using three different chiral selectors as impregnating reagents

Direct resolution of racemic atenolol and propranolol into their enantiomers was achieved by normal phase TLC on silica gel plates impregnated with optically pure L-tartaric acid, (R)-mandelic acid and (-)-erythromycin as chiral selectors. Different solvent systems were worked out to resolve the enantiomers. Spots were detected using iodine vapour. The TLC method was validated for linearity, limit of detection and limit of quantification. The influence of pH, temperature and concentration of chiral selector was studied.     

Reversed-Phase TLC of 3d Metal Ions on Silica Gel GF254 Impregnated with Silicone Fluid DC200, Tri-Aryl Phosphate,and Tri-n-Butyl Phosphate and with DMSO-HNO3 Mobile Phases

JPC – Journal of Planar Chromatography – Modern TLC - The reversed-phase thin-layer chromatographic behavior of 3d metal ions has been studied on silica gel GF254 layers impregnated...     

Resolution of (+/-)-ibuprofen using (-)-brucine as a chiral selector by thin layer chromatography

The enantiomeric resolution of (+/-)-ibuprofen into its enantiomers was achieved by TLC on silica gel plate using optically pure (-)-brucine as a chiral selector and acetonitrile-methanol (5:1, v/v) as the solvent system. Spots were located in an iodine chamber. The detection limit was 4.9 microg. The effect of concentration of the chiral selector, temperature and pH on resolution has been studied.     

TLC resolution of enantiomeric mixtures of amino acids

Summary Resolution of enantiomeric mixtures of DL-amino acids (Nine) using silica gel layers impregnated with (-)-bruncine is reported. The solvent system used was Butanol: Acetic acid: Chloroform (3∶1∶4). The diastereomers were formed and hydrolysed, by dilute HCl spray, on the chromatogram only and the amino acids thus resolved were located by ninhydrin spray. The cross resolution possibilities of enantiomers were also calculated.     

Modified Diatomaceous earth as a principal stationary phase component in TLC

Modified natural diatomaceous earth (DE) is a principal component of the stationary phase in normal thin-layer chromatography (TLC) applications and is mixed with commercial silica gel 60GF254 (Si-60GF254). Modification is carried out by flux calcination and refluxing with acid. Natural DE, modified DEs [flux calcinated (FC)DE and FCDE-I), and Si-60GF254 are characterized by scanning electron microscopy and Fourier-transform-IR spectroscopy. Particle size, specific surface area, pore distribution, pore volume, and surface hydroxyl group density parameters of materials are determined by various techniques. FCDE-I and Si-60GF254 are investigated for their usefulness in the stationary phase of TLC both individually and in composition. Commercially available red and blue ink samples are run on layers of Si-60GF254 and FCDE-I individually, and on various FCDE-I and Si-60GF254 mixtures. Butanol-ethanol-2M ammonia (3:1:1, v/v) and butanol-acetic acid-water (12:3:5, v/v) mixtures are used as mobile phases. The polarities of stationary phases decrease, and the retention factor (Rf) values of ink components increase when the FCDE-I content of the stationary phase increases. The properties of the stationary phase can be optimized by adding FCDE-I to Si-60GF254. This study may be useful in understanding both the systematic effects of stationary phase properties [e.g., specific surface area and surface hydroxyl group density, aOH(s)] and those of the mobile phase (e.g., polarity and acidity) on Rf values and the separability of components.     

同位素稀释质谱法测定猪肉中克伦特罗含量的国际比对APMP. QM-S6

建立了同位素稀释质谱法（IDMS）测定猪肉中克伦特罗含量的高准确度方法,并应用于亚太计量规划组织（Asia Pacific Metrology Programme,APMP）开展的国际比对“猪肉中克伦特罗含量测定”（APMP. QM-S6）。本研究考察了影响测定结果的喷雾电压值、流动相、色谱柱、提取条件、净化条件等主要因素并进行了优化,并对测定结果的不确定度进行了评定。结果表明:流动相组成以及pH值会影响克伦特罗的质谱响应以及最优的电喷雾电压值;样品溶剂会影响克伦特罗的色谱保留,甲醇溶剂会引起严重的溶剂效应,甚至导致峰分裂;克伦特罗易在固相萃取柱及亲水性滤膜上吸附,且吸附材料和滤膜上吸附的杂质有可能被洗脱,引起基质效应,干扰测定。提取效率最高的方法是采用0.1%（v/v）甲酸乙腈溶液为提取溶剂,通过匀浆进行提取。方法检出限（以信噪比大于3计）为0.2 μg/kg。比对样品中克伦特罗的含量为5.18 μg/kg±0.50 μg/kg（k=2）,比对结果与参考值等效一致,取得国际互认。该方法准确可靠,可为猪肉中克伦特罗的日常检测提供参考。     

Stereospecific analysis of lorazepam in plasma by chiral column chromatography with a circular dichroism-based detector

The chiral separation of lorazepam was achieved on a chiral column with UV and circular dichroism (CD) detection. The good resolution of lorazepam enantiomers was obtained on the column of beta-cyclodextrin derivative immobilized silica gel under reversed-phase conditions. The enantiomeric separation and identification of lorazepam were succeeded by CD detector. The method described allows the quantitation of the stereoisomers of lorazepam in human plasma following the administration of a therapeutic dose of the racemic drug. Chiroptical detection is useful for the pharmacokinetic study of chiral drugs.     

Indirect reversed‐phase high‐performance liquid chromatographic and direct thin‐layer chromatographic enantioresolution of (R,S)‐Cinacalcet

Enantioresolution of the calcimimetic drug (R,S)‐Cinacalcet was achieved using both indirect and direct approaches. Six chiral variants of Marfey's reagent having l ‐Ala‐NH₂, l ‐Phe‐NH₂, l ‐Val‐NH₂, l ‐Leu‐NH₂, l ‐Met‐NH₂ and d ‐Phg‐NH₂ as chiral auxiliaries were used as derivatizing reagents under microwave irradiation. Derivatization conditions were optimized. Reversed‐phase high‐performance liquid chromatography was successful using binary mixtures of aqueous trifluoroacetic acid and acetonitrile for separation of diastereomeric pairs with detection at 340 nm. Thin silica gel layers impregnated with optically pure l ‐histidine and l ‐arginine were used for direct resolution of enantiomers. The limit of detection was found to be 60 pmol in HPLC while in TLC it was found to be in the range of 0.26–0.28 µg for each enantiomers. Copyright © 2010 John Wiley & Sons, Ltd.