Stable silica gel-bound crown ethers. Selective separation of metal ions and a potential for separations of amine enantiomers

Silica gel-bound crown ethers and aza macrocycles have been synthesized with the attaching arm connected to the carbon framework of the macrocycles. The interactions of these bound macrocycles with cations are almost identical to those involving the analogous free macrocycles. This has allowed for predictable cation separation, concentration, and removal processes to be performed on a small scale. Quantum mechanical calculations and NMR measurements indicate that similarly bound chiral macrocycles will be capable of use in separating chiral organic amines.Dedicated to the memory of Professor James J. Christensen who died on 5 September 1987.     

2-(2-Hydroxyaryl)cinnamic amides: a new class of axially chiral molecules

The syntheses of several differently substituted amides formally derived from a chiral amine, either E-2-(2-hydroxyphenyl)cinnamic acid or both E- and Z-2-(2-hydroxynaphthyl)cinnamic acid, are reported. These molecules display a restricted rotation about the C₂-C_aryl bond. The barriers to rotation about the C₂-C_aryl bond were measured by the dynamic ¹H NMR and were found to vary between 11.8 and 24.5 kcal mol⁻¹, depending on the substitution. In particular, E-2-(2-hydroxynapthyl)cinnamic amides, displayed a high barrier to rotation (ΔG_c^‡=24.4 kcal mol⁻¹) and could be isolated in both diastereomerically pure forms at room temperature. The X-ray structure of one E-2-(2-hydroxynapthyl)cinnamic amide, was resolved, enabling for the determination of the absolute configuration of the chiral axis (aR).     

Optimization of the Synthesis of 2,6–Dinitro-4-trifluoromethylphenyl Ether Substituted Cyclodextrin Bonded Chiral Stationary Phases

The comparisons of five different chiral stationary phases (CSPs) based on 2,6-dinitro-4-trifluoromethylphenyl (DNP-TFM) ether substituted β-cyclodextrin are presented. The five CSPs differ from each other in the linkage/spacer chemistry, or on the position of the substituents on β-cyclodextrin, or in the sequence of the synthetic procedure. The results show that there are two optimum combinations: (1) DNP-TFM randomly substituted on the β-cyclodextrin as the chiral selector along with a carbamate linkage chain bonding it to the silica support; and (2) β-cyclodextrin derivatized by DNP-TFM substituents only on the C-2 and C-3 positions of the cyclodextrin with an ether linkage chain anchoring it to the silica gel. These two combinations show complementary separations for some enantiomers. The spacer chain effect is much more pronounced for the CSP based on the β-cyclodextrin derivatives with DNP-TFM substituents only on C-2 and C-3 positions than its randomly substituted counterpart. The sequence of derivatizing the cyclodextrin and attaching it to silica gel also affects its selectivity and efficiency. The β-cyclodextrin should be derivatized before it is linked to the silica gel.     

Chiral separations by capillary electromigration techniques in nonaqueous media. II. Enantioselective nonaqueous capillary electrochromatography

A review on the advantages, peculiarities, and the potential of enantioselective capillary electrochromatography (CEC) in nonaqueous media is presented. Some fundamentals on CEC with particular focus on enantioselective CEC are discussed. The strategies, concepts, preferentially utilized chiral selectors and column technologies that have been utilized to succeed in highly efficient enantiomer separations by nonaqueous CEC are described thoroughly.     

氰戊菊酯立体异构体在手性键合相上的分析

本文介绍了采用高效液相色谱法在(R)-N-3,5-二硝基苯甲酰苯甘氨酸手性键合相上氰戊菊酯的四个立体异构体的分离,以外消旋氰戊菊酯样品为参照,计算了光学活性氰戊菊酯样品的四个立体异构体的百分含量,确定了在手性键合相上氰戊菊酯四个立体异构体构型的流出顺序为SR→RS→SS→RR。     

Systematic optimization of micellar electrokinetic chromatographic separation of flavonoids

Summary A simple and rapid systematic optimization scheme was described for the micellar electrokinetic chromatographic separation of a group of flavonoids. The scheme employed an interpretative optimization approach to predict the optimum conditions for the separation of a group of flavonoids by micellar electrokinetic chromatography. By performing a set of nine pre-planned experiments conducted over the maximum working range for the system, global optimum separation conditions could be determined. To validate the optimization procedure, additional experiments were performed using the optimum experimental conditions derived from the optimization scheme. The results showed that satisfactory separation of all the peaks could be obtained. In addition, the application of the method in micropreparative micellar electrokinetic chromatography of the flavonoids was demonstrated.     

Adsorption separation of terpene lactones from Ginkgo biloba L. extract using glass fiber membranes modified with octadecyltrichlorosilane

In this study porous glass fiber membranes were modified by reaction with octadecyl-trichlorosilane to form C18 hydrophobic membranes. The contact angle and the CH2 vibration bands at 2855 and 2920 cm(-1) found by FTIR measurements verified the successful immobilization of C18 groups on the glass fiber membranes. The resulting C18 hydrophobic membranes were used to adsorb terpene lactones from crude Ginkgo biloba L. extracts. In batch adsorption processes, the modified C18 membranes exhibited a better adsorption performance than commercial C18 solid phase extraction adsorbents. Different desorption solvents were tested and ethyl acetate was found to preferentially desorb terpene lactones from the modified C18 membranes. In flow adsorption experiments at 1 mL/min, terpene lactone contents higher than 6 wt% (the standardized content) could be achieved in the elution step using ethyl acetate.     

Reversible Full‐Range Color Control of a Cholesteric Liquid‐Crystalline Film by using a Molecular Motor

By using a chiral molecular motor as a dopant in a cholesteric liquid‐crystalline film, fully reversible control of the reflection color of this film across the entire visible spectrum is possible. The large difference in helical twisting power between the two isomeric forms of the motor allows efficient light‐ and heat‐induced switching of the helicity of the cholesteric liquid‐crystal superstructure.     

多柱色谱技术进展

在色谱分析过程中，利用串联、并联或串并联结合的方式将多根色谱柱组合起来，可以实现高通量和高分辨的分离效果。相比于传统单柱色谱技术，多柱技术很好地满足了批量样品分析和复杂生物样品分离分析的需求，因此引起了广泛关注。该文对多柱技术在多维分离、芯片色谱、毛细管电泳、固定相筛选以及串联色谱等领域的应用进行了综述，并对其发展前景进行了展望。     

乙烯-甲基丙烯酸共聚物离聚体在聚对苯二甲酸乙二酯中的相分离行为

聚对苯二甲酸乙二酯(PET)结晶速度很慢,通常加入成核剂来提高结晶速度。从专利文献来看,以离子聚合物为成核剂的例子也是很多的。离子聚合物与小分子成核剂的显著差别是:离子聚合物有一个很长的碳氢主链,其侧基为酸基,酸基被部分或全部地中和成盐。很明显,离子聚合物不象小分子成核剂那样能很好地分散在PET基体中,而是以独立的相存在。作为PET体系系列研究的继续,本文报道了离子聚合物Surlyn在PET中的相分离行为。