氰醇类化合物对映体的气相色谱分离

对ＣＹＤＥＸ－β全甲基化β－环糊精毛细管柱上，对１４种手性氰醇对映体的乙酰化和三氟乙酰化衍生物，进行了气相色谱分离研究，比较了两种衍生方法的拆分效果，测定了实际合成样品的ｅ．ｅ．值，并对对映体拆分机理进行了一些探讨。     

手性气相色谱分离α-醇腈和α-羟基酸对映体

以３－丙酰基－２,６－Ｏ－二戊基－γ－环糊精和３－三氟乙酰基－２,６－Ｏ－二戊基－γ－环糊精为手性固定相,利用气相色谱进行了α－醇腈化合物、α羟基酸以及二共存时的对映体分离。系统观察了影响对映体分离的主要因素,优化了十种α－醇腈和七种α－羟基酸拆分条件,３－三氟乙酰基－２,６－Ｏ－二戊基－γ－环糊精毛细管柱的分离因子达到１．０５～３．１２,对α－羟基酸,并对分离的机理进行了初步分析。     

两种新型手性冠醚聚硅氧烷用于毛细管气相色谱法分离对映体

两种新型手性冠醚聚硅氧烷用于毛细管气相色谱法分离对映体周喜春，严慧，吴采樱，陈远荫（武汉大学化学系武汉４３００７２）手征性冠醚是在大醚环上兼连有手征性中心的冠醚。由于手性中心的引入，使其对客体分子具有独特的结构选择性和手征性选择。我们在多年研究冠醚聚...     

高效液相色谱手性固定相对氨基酸衍生物对映体分离研究

利用高效液相色谱手性固定相对光学异构体分离分析日益受到人们的重视。高效液相色谱氨基酸酰胺型手性固定相对拆分对映异构体具有较好的效果。本文为了探讨该类手性固定相对氨基酸的拆分影响,用L-异亮氨酸叔丁酰胺型手性固定相,对6种DL氨基酸(丙氨酸、2-氨基-n-丁酸、缬氨酸、亮氨酸、苯丙氨酸和蛋氨酸)的18种衍生物进行了拆分,并讨论了其衍生物取代基对手性拆分的影响及从立体化学角度提出了手性拆分机理。实验结果表明,这种手性固定相对外消旋氨基酸衍生物有较好的拆分能力。 1 实验部分 1.1 仪器和试剂 Varian 2010型高效液相色谱仪(美国);2050型紫外检测器及HP3394型积分仪(美国);L-异亮氨酸叔丁酰胺型手性柱(TBILS,上海药物研究所),粒度10μm,柱长100mm、内径4mm的不锈钢柱。 异丙醇(分析纯)用前重蒸,石油醚(60～90℃)分析纯,重蒸收集69℃镏分,用前全经过0.5μm薄膜并脱气。DL-氨基酸衍生物[丙氨酸(Ala),2-氨基-n-丁酸(Buty),缬氨酸(Val),亮氨酸(Leu),苯丙氨酸(Phe),蛋氨酸(Met)]用相应DL-氨基酸参考文献方法进行N-乙酰化及酯化。衍生物经元素分析合格,配制成5mg/mL溶液。     

两种新型手性冠醚聚硅氧烷用于毛细管气相色谱法分离对映体

 两种新型手性冠醚聚硅氧烷用于毛细管气相色谱法分离对映体周喜春，严慧，吴采樱，陈远荫（武汉大学化学系武汉４３００７２）手征性冠醚是在大醚环上兼连有手征性中心的冠醚。由于手性中心的引入，使其对客体分子具有独特的结构选择性和手征性选择。我们在多年研究冠醚聚硅氧烷固定液的基础上，设计合成了两种含末端烯基的手性冠醚，并采用硅氢加成技术将其键合在聚硅氧烷链上，制得了两种高分子化的手性冠醚固定相，并初步考察了其气相色谱性能。研究结果表明：这两种手性冠醚裹硅氧烷固定液均具有普通冠醚聚硅氧烷固定液的良好柱性能.。     

多维气相色谱直接分离食品中的光学活性γ－内酯

应用多维气相色谱方法对市售桃罐头、杏罐头和蜜桃汁饮料中的某些光学活性γ－内酯进行了直接对映体拆分。样品抽提物先经一根ＳＥ－５４玻璃毛细管柱预分离，然后将γ－内酯组分相应切割进入一根α－环糊精衍生物作固定相的玻璃毛细管柱上进行对映体拆分。结果表明，多维气相色谱技术不仅能够简化分析步骤，减少样品污染及保护手性柱免受污染或损害，而且提供了一种能够简便、快捷地区分食品中天然香料和人工合成香料的较好方法。     

用手性高效液相色谱对β—羟基酯化合物进行对映体分离

本文利用手性ＯＤ柱在高效液相色谱上对光活性β－羟基酯类化合物进行了对映体分离，达到了较好的分离效果，并通过讨论手性ＯＤ涂附物的结构与该类化合物的作用方式，解释了不同的该类化合物的色谱分离效果。     

几种拟除虫菊酸甲酯对映体的毛细管气相色谱手性拆分

4种酰基化环糊精衍生物（2，6－二－O－戊基－3－O－丁酰基－β－CD、2，6－二－O－戊基－3－O－戊酰基－β－CD、2，6－二－O－戊基－3－O－庚酰基-β－CD和2，6－二－O－戊基－3－O－辛酰基－β－CD）用作毛细管气相色谱固定相，对顺式－和反式－3－（2－甲基丙烯基）－2，2－二甲基环丙烷羧酸甲酯（菊酸甲酯）、顺式－和反式－3－（2，2－二氯乙烯基）－2，2－二甲基环丙烷羰酸甲酯（二氯菊酸甲酯）、2－（4－氯苯基）－3－甲基丁酸甲酯（戊菊酸甲酯）和顺式－3－（2－氯－3，3，3－三氟丙烯基）－2，2－二甲基环丙烷羧酸甲酯（功夫菊酸甲酯）等6种拟除虫菊酸甲酯对映体进行了拆分，结果表明：所合成的4种环糊精衍生物可将顺式－和反式－菊酸甲酯、顺式－和反式－二氯菊酸甲酯、戊菊酸甲酯及顺式－功夫菊酸甲酯等6种菊酸甲酯对映体较好分离。发现不同的环糊精衍生物手性分离能力不同，溶质的结构变化对分离结果也有较大影响。     

气相色谱对映体标记法测定实际样品中氨基酸

]本文在自制的手性（OV-225-L-缬氨酰-叔丁胺）交联毛细管柱上,用对映体标记法测定了豆浆水、海参水解液、裸腹蚤鲫鱼血、鲫鱼蛋白和轮虫等实际样品中的氦基酸含量,取得了较好的结果,其中,用对映体标记的氨基酸含量测定相对偏差小于5％。     

Gas Chromatographic Enantiomer Separation of Atropisomeric PCBs Using Modified Cyclodextrins as Chiral Phases

Columns containing different types of cyclodextrin derivatives have been evaluated for chiral gas chromatographic separation of atropisomeric PCBs, o,p´‐DDT and o,p´‐DDD. Separation was attempted on columns containing mixed chiral selectors, and the performance of two closely related selectors was also examined. The cyclodextrins were: permethylated‐β‐CD (PM‐β‐CD), heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐butyldimethylsilyl)‐β‐CD (2,3‐M‐6‐TBDMS‐β‐CD), heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD (2,3‐M‐6‐THDMS‐β‐CD), and heptakis(2,3‐di‐O‐ethyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐cyclodextrin (2,3‐E‐6‐THDMS‐β‐CD). The cyclodextrins were dissolved in OV‐1701 or in a dimethylsiloxane/silarylene copolymer containing 5% phenyl in the backbone. The application of mixed chiral selectors led to improved separations, however; at most eleven PCB congeners were separated on a single column. Chiral resolution of o,p´‐DDD was achieved. The use of a dimethylsiloxane/silarylene copolymer as a matrix for the cyclodextrins is a promising approach. With such a matrix, blocking of the CD cavities by silicone substituent groups can be avoided, and a reasonable CD solubility can be provided. The selectivity of heptakis(2,3‐di‐O‐ethyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD and heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD was quite different, the former selector could separate four congeners, while the latter separated ten congeners.     

多维气相色谱法检测酒中甲醇

建立了多维气相色谱检测酒中甲醇含量的方法.采用自动进样器将酒类样品直接注入气相色谱进样口,依次经过非极性RTX-5ms色谱柱和极性HP-INNOWax色谱柱,由气相色谱质谱选择离子监测技术进行测定与确证.甲醇在1～10000 mg/L范围内呈线性相关;方法检出限为1 mg/L.各种酒类样品在5,50,250,400和8...     

Investigation of Enantiomer Separation by LC with a New Bonded Cellulose 3,5-Dimethylphenylcarbamate Chiral Stationary Phase

A chiral stationary phase has been prepared from the 3,5-dimethylphenylcarbamate of cellulose chemically bonded to 3-aminopropylsilica gel at the 6-positions of the glucose units. The phase has been used to study direct liquid chromatographic enantioselective separation of five racemates. The effects on resolution of modifiers (alcohols, THF, and chloroform), flow rate, and temperature were investigated. It was found that the concentration and structure of the alcohol modifier can affect the separation; enantiomer separations were improved to different extents by addition of THF or chloroform to the mobile phase. Flow rate and temperature can also effect the resolution of racemates. In the range 10–40°C there was a linear relationship between ln k (or ln α) and 1/T (r > 0.98) for four of the compounds. These results indicate retention mechanism does not change as a function of temperature.     

胶束电动毛细管色谱法拆分肾上腺素对映体

胶束电动毛细管色谱法拆分肾上腺素对映体;电化学检测;对映体拆分     

Determination of Enantiomer Ratios of Bornane Congeners in Biological Samples Using Heart-Cut Multidimensional Gas Chromatography

The enantiomeric ratios of the chlorinated bornanes, 2-exo, 5,5,9,9,10, 10-heptachlorobornane (B[20030]-(022)), 2-endo,3-exo,5-endo,6-exo,8, 8,10,10-octachlorobornane (B[12012]-(202), Parlar No. 26), 2-exo,3-endo,6-endo,8,9,10,10-heptachlorobornane (B[21001]-(112)), 2,2,5,5,9,9, 10,10-octachlorobornane (B[30030]-(022), Parlar No. 38), 2-endo,3-exo,5-endo6-exo,8,8,9,10,10-nonachlorobornane (B[12012]-(212), Parlar No. 50), and 2,2,5,5,8,9,9,10,10-nonachlorobornane (B[30030]-(122), Parlar No. 62) were determined in a hake liver (Merluccius merluccius) and in two whitebeaked dolphin blubber (Lagenorynchus albirostris) samples. The analysis was performed by heart-cut multidimensional gas chromatography using an electron capture detector (ECD). Ultra 2 (5%-phenyl-95%-methylsilicone) was used as stationary phase in the first column and enantioselectivity was obtained in the second column with a phase consisting of a mixture of OV-1701 and heptakis(2,3,6-O-tert- butyldimethylsilyl)-β-cyclodextrin (10 : 1). All reference standards were also tested on the enantioselective column alone. The comparison of the two systems showed that deviations of ±0.12 from the racemic enantiomer ratio can be observed for the single column due to co-eluting impurities which are present in the reference standards. In most of the heart-cut chromatograms of the biota samples about 15 peaks could be found, showing the importance of a multidimensional separation system for an interference-free quantification by ECD. In all biological samples a significant deviation from the racemic enantiomer ratio was found for B[30030]-(022) (Parlar No. 38) and for B[30030]-(122) (Parlar No. 62). This indicates that an enantioselective disposition of the congeners occurs. In addition, considerations are presented concerning the relationship between congener structure and enantiomeric disposition.     

柱色谱/气相色谱分析Fischer-Tropsch合成液相产物

以两步柱液体色谱法对F-T合成(Fischer-Tropsch synthesis)液相产物冷阱油进行预处理,获得烷烃、烯烃及有机含氧化合物的族分离,并采用高分辨毛细管柱气相色谱对各族成分进行分离鉴定。组分定性采用以纯物质为基准,色谱保留值比较并辅以碳数保留值规律法;定量采用峰面积校正因子归一法。本文提供了冷阱油中63个组分的测定结果,占总含量达80%以上     

Determination of Enantiomer Excess of Asymmetric Hydroesterification Reaction by Hplc using A Cellulose Tribenzoate Chiral Column

Abstract

The preparation of cellulose tribenzoate (CTB) chiral stationary phases coated on a small-particle (5 μ m, 120A°) spherical silica support, according to a process that is reported, is presented. The products of asymmetric hydroesterification of norbornene are resolved on the cellulose tribenzoate chiral stationary phases.     

几种环糊精衍生物手性固定相与OV－1701或OV－7混和离析氨基酸、羟基酸等对映体

本实验合成了２，６－０－二丁基－３－０－三氟乙酰基－γ－环糊精、２，６－０－二戊基－３－０－三氟乙酰基－β－环糊精、全戊基－β－ＣＤ。分离了一些氨基酸酯、羟基酸酯、卤代酸酯、卤代烃、醇等对映体。比较了ＯＶ－７和ＯＶ－１７０１作混合固定相稀释液对离析性能的影响。     

超临界流体色谱法分离手性药物

对超临界流体色谱技术（SFC）在手性药物分离方面的研究与应用状况做了评述,对超临界流体色谱手性分离的分离方式、操作条件及影响因素作了介绍。