Chiral Separation of Erythromycin as a New Chiral Selector on CE

Erythromycin as a new chiral selector was first used for chrial separation of four derivatives of biphenyldimethylester enantiomers on CE.The influence of pH,the chiral selector concentration and organic modifiers were preliminarily studied.Experiments show that the erythromycin as chiral selector is useful to CE.     

卡那霉素作为手性选择剂的毛细管电泳手性药物分离研究

建立了一种以天然易得的卡那霉素为手性添加剂，用毛细管区带电泳法快速分离市售对乙肝有良好治疗效果的药物联苯双脂衍生物的方法，拓宽了毛细管电泳中手性选择剂的范围，通过实验研究了卡那霉素、甲醇 含量PH值，磷酸盐缓冲体系和硼硝缓冲体系对手性分离的影响，以及三种有机溶剂（甲醇、乙晴、异丙醇）添加剂对手性分离的影响，结果表明，在含有3％卡那霉素，30mol/L，硼砂缓冲体系（PH＝8．0）添加30％异丙醇是最佳的分离条件。     

Synthesis and Characterization of Water-Soluble Carboxymethyl-Cyclodextrin Polymer as Capillary Electrophoresis Chiral Selector

The water-soluble carboxymethyl-cyclodextrin polymer (CM-CD polymer) was synthesized and used as capillary electrophoresis chiral selector.Verrapamil and thiopentorusodium were well separated using CM-CD polymer as chiral selector.     

Synthesis and Characterisation of Water-Soluble Carboxymethyl-Cyclodextrin Polymer as Capillary Electrophoresis Chiral Selector

Cyclodextrin (CD) and its water-soluble derivatives have been used as chiral selectors incapillary electrophoresis successfully. Among them, the water-soluble CD polymerperforms intramolecular synergistic effect in CE chiral separation and thecarboxymethyl-CD (CM-CD) migrates in the opposite direction of the electroosmoticflow because of its negative charge in water. It is interesting to synthesizecarboxymethyl-CD polymer (CM-CD polymer), which has properties of both the neutralCD poly…     

红霉素作为毛细管区带电泳手性选择剂拆分两种联苯双酯类药物

首次使用大环内酯类抗生素红霉素作为毛细管电泳手性选择剂,采用未涂层石英毛细管分离了两种联苯双酯类保肝药物。实验考察了背景电解质中磷酸盐缓冲液的pH值及浓度、分离电压及温度、红霉素浓度、有机添加剂甲醇含量对手性分离的影响。实验结果表明,磷酸盐浓度为50 mmol/L(pH 5.0)、分离电压为-20 kV、红霉素浓度为30 mmol/L、甲醇的体积分数为50%是最佳分离条件。同时证明红霉素可以作为手性选择剂用于毛细管电泳手性分离中。     

农产品中手性农药对映体残留色谱法分析研究进展

手性农药对映体在对生物体的毒理作用、在生物体内的残留、代谢转化归趋方面存在差别。农产品作为重要的食品来源,与人体健康密切相关,因此区分农产品中手性农药对映体之间的残留,显得尤为重要。该文通过检索近年来发表的有关农产品中手性农药残留分析的文章,从气相色谱法、毛细管电泳法、液相色谱法及合相色谱法等不同色谱技术的应用方面进行归纳、综述、分析和展望,可为后续深入开展农产品中手性农药对映体的相关研究提供借鉴。     

毛细管电泳手性选择剂去硫酸基硫酸软骨素C的研究开发及新药西尼地平对映体的拆分

研究开发了一种新型的毛细管电泳多糖手性选择剂去硫酸基硫酸软骨素C,并用于二氢吡啶类药物对映体的分离。建立了新药西尼地平对映体的拆分方法,同时考察了背景电解质pH值、手性添加剂浓度、工作电压等因素对手性分离的影响。优化的背景电解质pH值 为2.50、手性添加剂的质量浓度为30 g/L,工作电压为10 kV。以去硫酸基硫酸软骨素C为毛细管电泳手性选择剂拆分新药西尼地平对映体,操作简单方便,西尼地平两对映体得到了基线分离,分离度达2.01。     

樟脑酸衍生物构筑的单一手性金属有机骨架化合物的合成、表征及荧光性质

设计合成了一个新的手性樟脑酸衍生物[D-H₂ctba, H₂ctba=4-(3-羧基-2,2,3-三甲基环戊烷酰胺)苯甲酸]. 将其作为配体与硝酸镉通过溶剂热反应得到了新的手性金属有机骨架化合物[Cd₃(ctba)₃·H₂O]_n(1). 通过单晶X射线衍射(XRD)、 粉末X射线衍射(PXRD)、 元素分析、 热重分析(TGA)和圆二色(CD)光谱对该化合物进行了表征. 单晶结构解析表明, 该化合物具有单一手性结构, 以1个六核的Cd羧基簇为基本单元, 簇与簇之间通过羧基相连形成(-Cd-O-C-)_∞棒状次级结构单元, 次级结构单元之间由配体相连, 拓展成为三维的骨架结构. 荧光光谱测试结果表明, 该化合物在室温下具有较强的荧光性质.     

Synthesis, Crystal Structure and Electrochemical Properties of a Novel Phenothiazine Derivative

A new compound 1,1‘-bis(3-pyridyl)-propylene(3,7-diformyl-N-ethylphenothiazinyl)ketone (C30H23N3O2S, Mr = 489.4) has been synthesized, and its crystal structure was determined by single-crystal X-ray diffraction method. The crystal is of orthorhombic, space group Ima2 with a = 27.491 (5), b = 11.942(2), c = 7.389(2) A, V = 2425.8(7) A^3, Z = 8, Dc =1.340 g/cm^3,μ = 0,167 mm ^1, F(000) = 1024, the final R = 0.0363 and wR = 0.0869 for 2054 unique reflections with Rint = 0.0254. The structural determination shows that the molecule assumes a butterfly configuration with nearly planar wings. In addition, the electrochemical study indicates that there is a high electronic delocalization in the molecule.     

Chiral Monolithic Silica-Based HPLC Columns for Enantiomeric Separation and Determination: Functionalization of Chiral Selector and Recognition of Selector-Selectand Interaction

This review draws attention to the use of chiral monolithic silica HPLC columns for the enantiomeric separation and determination of chiral compounds. Properties and advantages of monolithic silica HPLC columns are also highlighted in comparison to conventional particle-packed, fused-core, and sub-2-µm HPLC columns. Nano-LC capillary monolithic silica columns as well as polymeric-based and hybrid-based monolithic columns are also demonstrated to show good enantioresolution abilities. Methods for introducing the chiral selector into the monolithic silica column in the form of mobile phase additive, by encapsulation and surface coating, or by covalent functionalization are described. The application of molecular modeling methods to elucidate the selector–selectand interaction is discussed. An application for enantiomeric impurity determination is also considered.     

单分散树脂键合手性配体交换色谱固定相拆分DL-氨基酸

以单分散交联聚甲基丙烯酸环氧丙酯-甲基丙烯酸乙二醇双酯(PGMA/EDMA)树脂为基质合成了L-脯氨酸键合手性配体交换固定相,并用于DL-氨基酸的直接光学拆分,考察了流动相pH值、金属离子浓度、流速及温度等因素对DL-氨基酸对映体拆分的影响。结果表明,该固定相在配体交换色谱模式下可对多对DL-氨基酸进行良好的拆分。     

Synthesis and Crystal Structure of a Novel Chiral 1-Methylpropargyl Ester Carrying Azobenzene Moiety

A novel chiral methylpropargyl ester containing azobenzene moiety(S)-(-)-3-methyl-3-{4-[4-(n-octyloxy)phenylazophenyl]carbonyl}oxy-1-propyne 3(C25H30N2O3,Mr = 406.51) was synthesized and characterized by IR,NMR and single-crystal X-ray diffraction.The crystal is of monoclinic system,space group P21 with a=6.7610(17),b=7.675(2),c=22.749(7),β=97.613(6)°,V=1170.1(6)3,Z=2,Dc=1.154,F(000)=436,μ=0.076 mm-1,R=0.0544 and wR=0.1569 for 2444 observed reflections with Ⅰ2σ(Ⅰ).Structure analysis proved that the azobenzene presents a trans form,and intermolecular hydrogen bonds yield a 3D framework.The chiral acetylene carrying azobenzene moieties can be a potential alternative nonlinear optical,helical polymer,and liquid crystalline material.     

Multivariate Optimization Approach for Chiral Resolution of Chlorophenoxy Acid Herbicides Using Teicoplanin as Chiral Selector in Capillary LC

In this paper, the selectivity and resolution of enantiomeric separation by capillary liquid chromatography (cLC) of racemates of phenoxy acid herbicides are modelled. The compounds studied were 2-(±)-(2,4,5-trichlorophenoxy)propanoic acid (2,4,5-TP), 2-(±)-(2,4-dichlorophenoxy)propanoic acid (2,4-DP), 2-(±)-(4-chloro-2-methyl)phenoxypropanoic acid (MCPP) and 2-(±)-[4-(2,4-dichlorophenoxy)phenoxy]propanoic acid] (diclofop acid), using a capillary column packed with silica particles modified with teicoplanin as chiral selector. Several mixtures of methanol (MeOH), water and triethylamine acetate (TEAA) buffer at different pHs have been tested as mobile phases, and experimental parameters such as resolution (Rs), retention factor (k) and enantioselectivity factor (α) have been measured in all tested conditions. The chemometric methods used to explore and to model the data were principal component analysis (PCA), stepwise multiple linear regression (stepwise-MLR) and response surface analysis (RSA). The results show that it is possible to quantitatively predict the quality of enantiomeric separations of related compounds in a given chromatographic system.     

含潜在异构手性双臂配体的螺旋组装和手性聚集

采用具有潜在异构手性的双臂配体，双吡啶二甲基联苯-2，2′-二酰肼，合成了4个双核螺旋配合物。配体与CdI₂和Cu(NO₃)₂反应得到双核单螺旋化合物1和2，在化合物2中，由于C-H…π和π…π的协同相互作用沿ab面形成单一手性的二维平面。双核双螺旋化合物3(Ni(Ⅱ))和4(Co(Ⅱ))中的金属中心表现相同的绝对构型，说明含异构手性的配体能够把金属中心的手性从一个中心传递到另一个中心。     

一种芴酮衍生物的合成、晶体结构及其光限幅性能

一种芴酮衍生物的合成、晶体结构及其光限幅性能;芴酮衍生物; 单晶结构; 光限幅性能     

Molecular Complexes for the Study of Enantiodiscriminative Processes

The structure of the molecular complex between the chiral selector (+)1-(3-allylpropyl)-(5R,8S,10R)-N,N-diethyl-N-[6-methylergolin-8-yl]urea, C₂₃H₃₃N₄O, (allyl-terguride) and the more retained (S) isomer of dansyl-serine, C₁₅H₁₉N₂O₅S, has been determined. It is part of a study on the chiral recognition mechanism of ergot alkaloids, when used in chiral stationary phases for the separation of racemic mixture of organic acids by liquid chromatographic methods. At the pH of the crystallization conditions, which mimick those corresponding to the best enantiodiscriminative activity, each molecule of (S)-dansyl-serine is locked by hydrogen bonds between two translation related molecules of allyl-terguride forming a infinite chains in a 1:1 molecular ratio.     

Synthesis and the Crystal Structure of a New Chiral 1D Metal–Organic Coordination Polymer Based on L-Prolineamide-Substituted Diarylacetylenedicarboxylic Acid Derivative

The new homochiral 1D metal–organic coordination polymer [Cu₂(EDPB)•H₂O]_n was synthesized starting from the original 3,3′-ethyne-1,2-diylbis[6-(L-prolylamino)benzoic acid] (H₄EDPB). The unique crystal structure of the new compound was established by powder X-ray diffraction. The [Cu₂(EDPB)•H₂O]_n system shows catalytic activity and enantioselectivity in a Henry reaction of p-nitrobenzaldehyde with nitromethane.     

Synthesis,Characterization, Molecular Structure,and Electrochemistry of a New Ferrocenoyl Derivative

A new organometallic compound containing a heterocyclic amine linked to the ferrocenoyl moiety was synthesized and characterized by elemental analysis (C, H, N), mass spectrometry, IR and ¹HNMR spectroscopy. Its crystal and molecular structure was determined by X‐ray diffraction methods. This compound crystallizes in the monoclinic P2₁ space group, a = 5.80260(10), b = 9.24160(10), c = 12.3510(2) Å, β = 92.8200(10)° and Z = 2. An interesting feature of the crystal structure is the presence of an intermolecular non‐classical hydrogen bonding interaction between a cyclopentadienyl hydrogen atom and a carbonyl oxygen group. The electrochemical behaviour of this compound is characterized by the reversible one‐electron oxidation of the ferrocene moiety.     

Separation and Structure of Chiral S—Malic Acid Hydrate

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｍｅｔｈｏｄｏｆｓｅｐａｒａｔｉｎｇａｒａｃｅｍｉｃｍｉｘｔｕｒｅｉｎｔｏｉｔｓｅｎａｎｔｉｏｍｅｒｓｔｈｒｏｕｇｈｔｈｅｆｏｒｍａｔｉｏｎｏｆｄｉａｓｔｅｒｅｏｍｅｒｉｃｍｏｌｅｃｕｌａｒｃｏｍｐｌｅｘｂｙｒｅａｃｔｉｏｎｗｉｔｈａｎｏｐｔｉｃａｌｌｙａｃｔｉｖｅｃｏｍｐｏｕｎｄｈａｓｂｅｅｎｗｉｄｅｌｙｉｎｖｅｓｔｉｇａｔｅｄ .Ｆｒｏｍｔｈｅｐｏｉｎｔｏｆｖｉｅｗｏｆｃｒｙｓｔａｌｌｏｇｒａｐｈｙ ,ａｎｅｓｓｅｎｔｉａｌｐｒｅｒｅｑｕｉｓｉｔｅｏｆｔｈｅｓｕｃｃ…