A Chiral Recognition Mechanism Proposed for Resolving π-Acidic Racemates on π-Acidic Chiral Stationary Phases Derived from (S)-Leucine

A chiral recognition mechanism which can rationalize the resolution of N-(3,5-dinitrobenzoyl)-α-amino amides on chiral stationary phases (CSPs) obtained from N-(3,5-dinitrobenzoyl)leucine amide derivatives has been proposed on the basis of the chromatographic resolution behavior of various N-(3,5-dinitrobenzoyl)-α-amino acid derivatives and N-(various benzoyl)leucine N-propyl amides. The proposed chiral recognition mechanism utilizes two hydrogen bonding interactions between the CSP and the analyte and a π-π donor-acceptor interaction between the N-(3,5-dinitrobenzoyl) groups of the CSP and the analyte. From the chiral recognition mechanism proposed, it has been concluded that the resolution of π-acidic N-(3,5-dinitrobenzoyl)-α-amino acid derivatives on π-acidic CSPs derived from N-(3,5-dinitrobenzoyl)leucine amide delivatives is not unusual, but is merely the extension of the resolution of the π-basic racemates on π-acidic CSPs. However, the chromatographic behavior of the resolution of N-(3,5-dinitrobenzoyl)phenylglycine derivatives on CSPs derived from N-(3,5-dinitrobenzoyl)leucine amide derivatives is different from that of the resolution of other N-(3,5-dinitrobenzoyl)-α-amino acid derivatives. To rationalize this exceptional behavior, a second chiral recognition mechanism which utilizes two hydrogen bonding interactions (which are different from those of the first chiral recognition mechanism) between the CSP and the analytes and a π-π donor-acceptor interaction between the N-(3,5-dinitrobenzoyl) group of the CSP and the phenyl group of the analytes has been proposed to compete with the first chiral recognition mechanism. In this instance, it has been proposed that the separation factors and the elution orders of the resolution of N-(3,5-dinitrobenzoyl)phenylglycine derivatives are dependent on the balance of the two competing chiral recognition mechanisms.     

疏水性L-酒石酸酯立体选择性萃取分离氯噻酮对映体

研究了氯噻酮对映体在含有疏水性L-酒石酸酯手性选择体的水-1,2-二氯乙烷两相系统萃取分配行为,考察了pH、L-酒石酸酯烷基链长度、L-酒石酸酯浓度和磷酸盐浓度对分配系数和分离因子的影响。实验表明：L-酒石酸酯与氯噻酮I( )-对映体比与Ⅱ(-)-对映体形成更稳定的非对映体复合物;随着L-酒石酸酯取代烷基链长的增长,分配系数和分离因子增大;随着pH增大,分配系数增大,而分离因子降低;同时,L-酒石酸酯和磷酸盐浓度影响也比较大。     

Spectral and chemical determination of copolymer composition of poly (butyl acrylate-co-glycidyl methacrylate) from emulsion polymerization

Batch emulsion polymerization was used for preparing poly(butyl acrylate-co-glycidyl methacrylate) with different copolymer compositions at 75 °C with potassium persulfate as an initiator. Solubility and gel content of the prepared copolymers were studied. Four different spectral (¹H-NMR and FTIR) and chemical (elemental analysis and titration) methods were used to determine the copolymer composition. The epoxy was used as a key functional group, particularly in FTIR and titration methods of quantification. Results obtained from the chemical methods showed good agreement with those of the spectral methods. Effects of some probable phenomena occurring during copolymerization were investigated to account for differences of data obtained from the different analytical methods. Finally, the methods were compared and ¹H-NMR and elemental analysis were recognized as preferred approaches for the copolymer composition determination.     

Chirality in the Absence of Rigid Stereogenic Elements: The Absolute Configuration of Residual Enantiomers of C3‐Symmetric Propellers

Two new tris(aryl)phosphane oxides existing as configurationally stable residual enantiomers have been synthesised and their racemates resolved by semipreparative HPLC on a chiral stationary phase (CSP HPLC). One of them, recognised as a conglomerate, could be resolved by fractional crystallisation at a preparative scale level. In this case, the absolute configuration of the propeller‐shaped molecule was determined by anomalous X‐ray scattering. The problem of the correlative assignment of the absolute configuration to all known C₃‐symmetric three‐bladed propeller‐shaped molecules existing as stable residual enantiomers is discussed. The configurational stability of the new chiral phosphane oxides and of the corresponding phosphanes was evaluated by CD signal decay kinetics and dynamic ¹H NMR spectroscopy. The racemisation barriers in phosphanes were found about 10 kcal mol^?1 lower than those found for the corresponding oxides, though geometry and inter‐ring gearing would be very similar in the two series. Configurational stability of residual tris(aryl)phosphanes was found to be influenced by the electronic availability of the phosphorus centre, as evaluated by electrochemical CV experiments.     

磺丁基醚-β-环糊精手性流动相添加剂法分离兰索拉唑对映体

采用磺丁基醚-β-环糊精(SBE-β-CD)为手性流动相添加剂,建立了兰索拉唑对映体的高效液相色谱分离分析方法.对影响兰索拉唑对映体分离的主要因素:环糊精种类和浓度、缓冲溶液pH以及有机改性剂种类和含量进行考察.确定最优色谱条件:色谱柱为Spherigel C18 (150 mm×4.6 mm,5 μm),流动相为V(乙腈):V(水相)=20:80(水相含10 mmol/L SBE-β-CD、 10 mmol/L NaH2PO4缓冲液、 pH 2.5),流速为0.9 mL/min,检测波长为288 nm.在此条件下,兰索拉唑对映体的保留时间分别为14.4和15.8 min,分离度为2.0.两对映体质量浓度在0.2～50 μg/mL范围内线性关系良好(r≥0.9996),保留时间的RSD分别为0.27%和0.26%,峰面积的RSD分别为0.65%和0.68%.     

毛细管电泳氨类手性药物对映体拆分机理研究

手性药物及其对映体在药理上可表现出较大的差异,对它们进行研究将具有重要的理论意义和实用价值[1,2].毛细管区带电泳因其分离效率高、药品和试剂用量少、方法简单而成为目前手性拆分鉴定的重要方法之一[3].     

双水相手性萃取拆分扁桃酸外消旋体

研究了扁桃酸(MA)对映体在含β-环糊精(β-CD)手性选择剂的聚乙二醇(PEG)/(NH_4)_2SO_4双水相体系中的萃取分配行为.考察了pH、PEG和(NH_4)_2SO_4的质量分数、β-CD的浓度、MA的浓度与萃取温度等因素对拆分效果的影响.实验结果表明:双水相手性萃取具有很强的手性分离能力,β-CD对L-MA对映体的识别能力大于对D-MA对映体的识别能力;当温度为30℃、pH=1.0、PEG2000质量分数为30%、(NH_4)_2SO_4质量分数为20%、β-CD的浓度为0.008 mol/L、扁桃酸的浓度为0.05 mol/L时,分离因子(α)达到2.46,上、下相对映体过剩值(e.e.%)分别为42.13%和40.43%.     

高效液相色谱手性流动相添加剂法分离3种黄酮类化合物对映体

采用反相高效液相色谱法(RP-HPLC),以磺丁基醚-β-环糊精(SBE-β-CD)作为手性流动相添加剂,建立了二氢黄豆苷原(dihydrodaidzein)、雌马酚(equol)和山姜素(alpinetin)3种黄酮类化合物的手性拆分方法。考察了环糊精的种类和浓度、有机相的种类和比例、缓冲盐的种类和浓度以及pH对3种化合物手性拆分效果的影响。结果表明:采用Kromasil 100-5C₁₈(250 mm×4.6 mm, 5 μm)色谱柱,流动相为乙腈-10 mmol/L SBE-β-CD水溶液(含20 mmol/L KH₂PO₄, pH值到4.0)(体积比为20:80)的条件下,二氢黄豆苷原、雌马酚和山姜素的对映体都达到了基线分离,分离度分别为1.8, 1.9和1.4。该方法简便,分离效果好,对黄酮类化合物的拆分具有应用价值。     

生物法制备2,3-丁二醇的最新进展

2,3-丁二醇及其衍生物作为重要的液体燃料和化工原料,具有广阔的工业应用前景。高效、经济的2,3-丁二醇生物制备方法,对我国低碳经济和循环经济的建设具有重要的促进作用。针对近三年间生物法制备2,3-丁二醇领域的最新研究成果,本文综述了当前国内外学者在该领域研究的热点,即关键基因和酶的鉴定、新菌种的开发和代谢工程改造、同步糖化和共培养等发酵条件的优化、耦合工艺等分离纯化技术改进等。使用非致病的高产单一2,3-丁二醇手性异构体的代谢工程菌株,作为细胞炼制工厂,利用廉价的非粮原料作底物,采用经济、简单、环保的分离纯化方式,是2,3-丁二醇产业化发展的可靠保障。