手性污染物的色谱分离与分析

手性化合物的对映体选择性分离与检测发展异常迅速.本文全面总结评述了近年来手性污染物的色谱分离分析技术(包括气相、液相、薄层、超临界色谱和毛细管电泳)的发展.环境中手性污染物-农药在土壤-水环境中的降解与作用具有对映体选择性,对其的分离与分析文中分类作了较为深入的介绍.     

手性药物分析方法研究进展

从手性药物的概念入手,阐述了高效液相色谱法、毛细管电泳法、分子印迹技术、高速逆流色谱法、超临界流体色谱法和生物酶法等几种常用的手性药物分析技术的原理、特点及研究实例,以期为手性药物分离技术提供指导。     

中药生物碱成分的毛细管电泳分析

介绍了毛细管电泳的发展、分离模式及特点,综述了近10年来毛细管电泳在中药生物碱成分分析中的应用.     

毛细管电泳在基因突变检测中的应用

简述了毛细管电泳的技术原理,综述了毛细管电泳在基因突变检测中的应用,包括CE-RFLP、CE-SSCP、CE-HA、CE-PEX、CE-CMC等。     

植物源性食品中手性农药残留检测技术的研究进展

手性农药存在一个或多个对映体,其空间构型不同,药效作用、降解时间、毒性大小等都有较大的差异,为更好地发挥农药的药效,最大程度地减小其对非靶向目标物的毒副作用,分析手性农药在植物源食品中残留状况有充分的必要性。目前,植物源食品中农药残留检测更多地关注某种农药残留的总量,这与法规的要求有关,当能够充分分析植物源食品中手性农药的残留量时,限量标准的指向性及检测方法的针对性势必引起重视。综述了植物源食品中手性农药残留检测技术的现状,目前应用得较多的检测方法有液相色谱法、气相色谱法、毛细管电泳法,毛细管电色谱法也会应用于手性农药的拆分,强超临界流体色谱和超高效合相色谱在手性农药分离方面也有应用研究,植物源食品中手性农药残留检测技术研究仍处于探索阶段。     

浅谈毛细管电泳的基本原理及相关技术

毛细管电泳是新型液相分离分析技术,具有高效、快速、灵敏、试剂和样品用量少等特点。在介绍毛细管电泳分析分离基本原理的基础上,阐述了毛细管电泳的分离形式及应用范围,包括毛细管区带电泳、毛细管凝胶电泳、毛细管胶束电动色、毛细管等电聚焦及毛细管等速电泳形式及应用范围等,并探讨了毛细管电泳的几种检测方法,包括紫外检测器检测、激光诱导荧光检测、CE-MS联用检测及电化学检测器检测等。     

毛细管电泳在食品添加剂检测中的应用

毛细管电泳(CE)具有样品预处理简单、可同时分离测定多组分等优点,在食品分析中的应用日益广泛.综述了近年来毛细管电泳在一系列食品添加剂,包括色素、防腐剂、抗氧化剂、甜味剂等检测中的应用,重点是实际样品的分析.     

植物源性食品中手性农药残留检测技术的研究进展

手性农药存在一个或多个对映体,其空间构型不同,药效作用、降解时间、毒性大小等都有较大的差异,为更好地发挥农药的药效,最大程度地减小其对非靶向目标物的毒副作用,分析手性农药在植物源食品中残留状况有充分的必要性.目前,植物源食品中农药残留检测更多地关注某种农药残留的总量,这与法规的要求有关,当能够充分分析植物源食品中手性农药的残留量时,限量标准的指向性及检测方法的针对性势必引起重视.综述了植物源食品中手性农药残留检测技术的现状,目前应用得较多的检测方法有液相色谱法、气相色谱法、毛细管电泳法,毛细管电色谱法也会应用于手性农药的拆分,强超临界流体色谱和超高效合相色谱在手性农药分离方面也有应用研究,植物源食品中手性农药残留检测技术研究仍处于探索阶段.     

电泳峰中相关因素对人工神经网络分析的影响

采用人工神经网络方法对重叠的毛细管电泳谱图中的相关组分进行了定量分析。结果表明,随着毛细管电泳谱图噪声水平的增大,2种神经网络模型定量分析重叠的毛细管电泳谱图中相关组分的能力下降;随着毛细管电泳谱图总分离度的增大,多层感知器神经网络模型定量分析重叠的毛细管电泳谱图中相关组分的能力提高。     

离子液体在萃取和色谱分析技术中的应用

总结了近年来离子液体在萃取和色谱分析技术中的应用,主要包括在液液萃取、微萃取以及在毛细管电泳色谱、液相色谱、气相色谱中的应用。     

Chiral fiber gratings

Chiral gratings with double helix symmetry were produced by twisting glass optical fiber with a noncircular core cross section as it passed through a miniature oven. We observed polarization-selective transmission in chiral fibers with pitches of tens of micrometers. Two modes of optical interaction were differentiated. In chirallong-period gratings, dips in transmission were observed at wavelengths associated with scattering into distinct cladding modes mediated by the chiral grating. In chiral intermediateperiod gratings, a broad scattering band was observed. These gratings can be used to produce sharp or broad polarization-selective filters.     

Chiral metal complexes as discriminating molecular catalysts

As molecular recognition continues to gain importance in the biological and physical sciences as well as in the technologies of molecular electronics and optics, so has the need for efficient syntheses of chiral molecules. Chemists are fulfilling this need through use of chiral organometallic molecules. These chiral metal complexes precisely discriminate between enantiotopic atoms, groups, or faces in achiral molecules and catalyze production of a broad array of natural or unnatural substances of excellent enantiomeric purity. Because of their ability to efficiently multiply chirality, even on an industrial level, these catalysts promise to exert a general impact on molecular science and engineering.     

手性咪唑啉的合成及应用研究

以1,2-二苯基乙二胺和邻羟基苯乙酸以及脯氨酸为原料,设计并合成了咪唑啉-酚,四氢吡咯-咪唑啉两类手性催化剂,初步研究了它们在催化不对称Michael加成反应中的催化活性．     

Chiral symmetry breaking in sodium chlorate crystallizaton

Sodium chlorate (NaClO(3)) crystals are optically active although the molecules of the compound are not chiral. When crystallized from an aqueous solution while the solution is not stirred, statistically equal numbers of levo (L) and dextro (D) NaClO(3) crystals were found. When the solution was stirred, however, almost all of the NaClO(3) crystals (99.7 percent) in a particular sample had the same chirality, either levo or dextro. This result represents an experimental demonstration of chiral symmetry breaking or total spontaneous resolution on a macroscopic level brought about by autocatalysis and competition between L- and D-crystals.     

Formation of Chiral Interdigitated Multilayers at the Air-Liquid Interface Through Acid-Base Interactions

Thin interdigitated films composed of a long-chain, water-insoluble chiral acid (p-pentadecylmandelic acid of absolute configuration R) and a water-soluble chiral base (phenylethylamine, R') were constructed at the air-solution interface. The (R, R') structure was characterized to near-atomic resolution by grazing-incidence x-ray diffraction (GIXD). The two diastereomeric systems, (R, R') and (R, S'), demonstrate similar surface pressure-molecular area isotherms, but their structures are completely different on the molecular level, as monitored by GIXD. Complementary data on these two architectures were provided by atomic force microscopy.     

高效液相色谱在手性农药分析分离上的应用研究进展

随着人类社会可持续发展的需要,环境中手性农药的污染日渐受到人们的重视,因此手性农药的拆分也得到越来越多的重视.高效液相色谱是一门适用于手性分离的研究技术.本文综述了近年来高效液相色谱在手性农药拆分中的应用研究,并对该方法的发展前景进行了讨论.     

呋虫胺在有机溶剂和水中的手性稳定性

【目的】在人工氙灯光照、室内自然光照和避光培养条件下,探究呋虫胺外消旋体（Rac-呋虫胺）及其对映体（S-呋虫胺和R-呋虫胺）在甲醇、乙醇、异丙醇、乙酸乙酯、乙腈、二氯甲烷、超纯水以及β-环糊精水溶液中的手性稳定性,为大宗用量的手性新烟碱类杀虫剂呋虫胺的准确检测分析、药效和环境安全的正确评价提供依据。【方法】培养周期内分段取样,以直链淀粉-三（3, 5-二甲基苯基氨基甲酸酯）为手性固定相,正己烷/甲醇/乙醇（85/10/5, v/v/v）为流动相,柱温为30℃,流速为1.0 mL?min^-1,紫外检测波长为270 nm,进样量为20 µL,高效液相色谱/二极管阵列检测器（HPLC/DAD）进行分离分析,S-呋虫胺和R-呋虫胺的保留时间分别为8.3和9.7 min。外标法定量。【结果】人工氙灯光照、室内自然光照和避光培养条件下,S-呋虫胺和R-呋虫胺在甲醇、乙醇、异丙醇、乙酸乙酯、乙腈、二氯甲烷、超纯水以及β-环糊精水溶液中均不存在相互转化现象;配对样品t-test分析Rac-呋虫胺在每种溶剂中两个对映体的降解残留量,证实无对映体选择性降解。对映体浓度比值（EF值）为0.4746-0.5116。但在人工氙灯光照下,Rac-呋虫胺、S-呋虫胺和R-呋虫胺迅速降解,顺序为二氯甲烷＞乙腈＞乙酸乙酯≈异丙醇≈乙醇＞甲醇＞超纯水＞β-环糊精水溶液。相比水溶液,呋虫胺在有机溶剂中更容易降解,半衰期分别为3.3-3.6 h和1.2-2.3 h。光解动态符合一级动力学模型,相关系数为0.9550-0.9959。室内自然光照与避光培养条件下,Rac-呋虫胺、S-呋虫胺和R-呋虫胺在二氯甲烷、乙腈、乙酸乙酯、异丙醇、乙醇、甲醇、超纯水和β-环糊精水溶液中无明显降解,实测浓度和相对标准偏差分别为9.5-10.4 mg?L^-1,1.0%-3.2%和9.5-10.5 mg?L^-1,1.4%-2.8%。【结论】在（25±2）℃人工氙灯光照、室内自然光照和避光条件下,呋虫胺在甲醇、乙醇、异丙醇、乙酸乙酯、乙腈、二氯甲烷、超纯水以及β-环糊精水溶液中手性构型稳定,在此条件下进行定性定量分析、药效和环境安全评价是准确的。     

新手性吡啶类配体的合成及其不对称诱导性能研究

以2,6-二甲基吡啶和2,6-二溴吡啶为原料,经锂试剂分别与光学活性的樟脑、薄荷酮和3-甲酰基蒎烷反应合成了4个新的手性吡啶类化合物。测定了它们在苯甲醛和二乙基锌加成反应中的不对称诱导性能。     

Chiral amplification of oligopeptides in two-dimensional crystalline self-assemblies on water

Differences in the two-dimensional packing arrangements of racemic and enantiomeric crystalline self-assemblies on the water surface of amphiphilic activated analogs of lysine and glutamic acid have been used to prepare oligopeptides of homochiral sequence and oligopeptides of single handedness from chiral nonracemic mixtures. The crystalline structures on the water surface were determined by grazing incidence x-ray diffraction and the diastereomeric composition of the oligopeptides by matrix-assisted laser desorption time-of-flight mass spectrometry with enantio-labeling. These results suggest that reactivity of ordered clusters at interfaces might have played a role in the generation of early homochiral biopolymers.     

四种手性农药在CHIRALPAK AS-H柱上的直接拆分

采用高效液相色谱手性固定相在CHIRALPAK AS-H柱上对三唑醇、戊唑醇、烯唑醇和顺式高效氯氟氰菊酯4种手性农药进行了直接拆分,同时考察了流动相中极性改性剂醇的种类及含量对手性拆分的影响.结果表明:在室温及0.5mL·min-1流速下,4个手性农药样品均获得基线分离,其中三唑醇的最佳拆分条件为V正己烷:V乙醇=95:5,Rs=2.00;戊唑醇、烯唑醇和顺式高效氯氟氰菊酯的最佳拆分条件均为V正己烷:V异丙醇=90:10,Rs分别为1.40、2.76和1.80.