Enantioselective Partitioning of Racemic Ibuprofen in a Biphasic Recognition Chiral Extraction System

Enantioselective partitioning of ibuprofen enantiomers in a biphasic recognition chiral extraction system was studied. A combination of hydrophobic L‐isobutyl tartrate in organic phase and hydrophilic β‐cyclodextrin derivative in aqueous phase is necessary to establish a biphasic recognition chiral extraction system. The studies performed involve an enantioselective extraction in a biphasic system, where ibuprofen enantiomers form four complexes with the β‐cyclodextrin derivative in aqueous phase and the D(L)‐isobutyl tartrate in organic phase, respectively. In these biphasic resolutions, the types and the concentrations of the extractants, pH and temperature all exert a considerable influence on the biphasic recognition process. Good enantioselectivities for ibuprofen enantiomers were obtained at pH≦2.5 and a ratio of 2:1 of [L‐isobutyl tartrate] to [HP‐β‐CD]. Biphasic recognition chiral extraction is of strong chiral separation ability, and may be very helpful to optimize the extraction systems and realize the large‐scale production of enantiomers.     

独立重尾随机变量随机和的大偏差估计

本文研究了一类独立重尾随机变量随机和S（t)∧=∑k=1^N(t)Xk,t≥0的大偏差概率，其中{N(t),t≥0}是一放大晨负整数值随机变量；{Xn,n≥1}是非负，独立随机变量序列，并与{N(t),t≥０}独立。本文的结果将{Xn,n≥１}为独立同分布情形推广到了独立不同分布情形。     

Enantioselective extraction of terbutaline enantiomers with <Emphasis Type="Italic">β</Emphasis>-cyclodextrin derivatives as hydrophilic selectors

Hydrophilic β-cyclodextrin (β-CD) and its derivatives are not soluble in organic liquids but they are highly soluble in water and can interact with enantiomers selectively to form diastereomeric complexes which enable their use as chiral selectors in chiral solvent extraction. In this paper, terbutaline enantiomers were extracted by hydrophilic β-CD derivatives in an aqueous/organic biphasic solvent system with racemic terbutaline in the organic phase and β-CD in the aqueous phase. Five β-CD derivatives, namely: methyl-β-cyclodextrin (Me-β-CD), hydroxyethyl-β-cyclodextrin (HE-β-CD), 2-hydroxyethyl-β-cyclodextrin (2-HE-β-CD), (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) and (4-sulfobutylether)-β-cyclodextrin (SBE-β-CD) were used as hydrophilic selectors, respectively. Process variables affecting extraction efficiency were investigated, namely influence of the type of organic solvents and β-CD derivatives, concentrations of selectors and terbutaline enantiomers, pH, and temperature. Experimental results show that the efficiency of extraction depends, often strongly, on process variables. All five β-CD derivatives studied preferentially extract the more biologically active (R)-terbutaline from the organic phase; HP-β-CD has the strongest recognition ability. The maximum enantioselectivity (α) of 1.42 was achieved under optimal conditions: pH 7.0 and temperature of 5°C. Utilization of the extraction method for separation of terbutaline enantiomers is expected to be cheap and easy to scale up to commercial scale.     

Purification and mechanical nanosizing of Eu-doped GaN

Eu:GaN powder synthesized using a high temperature ammonothermal process is known to be dark in appearance due to presence of Eu-containing absorbing particles. Improvement of the visual quality of the Eu:GaN powder is achieved by rinsing in dilute acids. Acid-rinsed Eu:GaN has photoluminescence (PL) enhanced by a factor of 3 when compared to as-prepared Eu:GaN. Such visually clear powders are used for making Eu:GaN nanoparticles of sizes 30–50 nm using a soft ball-milling technique. The particle size was determined using X-ray diffraction, scanning electron microscopy and a dynamic light scattering system. Longer durations of a “soft” ball-milling technique results in particle size reduction. These nanopowders show significant photoluminescence intensity with no yellow luminescence, and have a reduced PL intensity with increasing ball-milling time. Eu:GaN nanopowder embedded in a KBr matrix shows at least a 10× improvement in transmittance when compared to as-prepared powders. The improvement of transmittance depends on both the concentration and particle size. This improved transmittance suggests that such a transparent matrix could be used as a laser gain medium.     

Determination of Capillary Pressure Function from Resistivity Data

A model has been derived theoretically to correlate capillary pressure and resistivity index based on the fractal scaling theory. The model is simple and predicts a power law relationship between capillary pressure and resistivity index (P _c = p _e · I ^β) in a specific range of low water saturation. To verify the model, gas-water capillary pressure and resistivity were measured simultaneously at a room temperature in 14 core samples from two formations in an oil reservoir. The permeability of the core samples ranged from 0.028 to over 3000 md. The porosity ranged from less than 8 to over 30. Capillary pressure curves were measured using a semi-permeable porous-plate technique. The model was tested against the experimental data obtained in this study. The results demonstrated that the model could match the experimental data in a specific range of low water saturation. The experimental results also support the fractal scaling theory in a low water saturation range. The new model developed in this study may be deployed to determine capillary pressure from resistivity data both in laboratories and reservoirs, especially in the case in which permeability is low or it is difficult to measure capillary pressure.     

Separation of phenylsuccinic acid enantiomers using biphasic chiral recognition high‐speed countercurrent chromatography

High‐speed countercurrent chromatography (HSCCC) combined with biphasic chiral recognition was successfully applied to the resolution of phenylsuccinic acid enantiomers. d ‐Isobutyl tartrate and hydroxypropyl‐β‐cyclodextrin were employed as lipophilic and hydrophilic selectors dissolved in the organic stationary phase and aqueous mobile phase, respectively. The two‐phase solvent system was made up of n‐hexane/methyl tert‐butyl ether/water (0.5:1.5:2, v/v/v). Impacts of the type and concentration of chiral selectors, the pH value of the aqueous phase solution as well as the temperature on the separation efficiency were investigated. By means of preparative HSCCC, pure enantiomer was obtained by separating 810 mg of racemate with a purity >99.5% and a recovery rate between 82 and 85%. The experimental results indicate that biphasic recognition HSCCC provide a promising means for efficient separation of racemates.     

三种烷基化和硅烷化β-环糊精作为气相色谱固定相的研究

合成了三种新的烷基化和硅烷化β－环糊精衍生物手性固定相，以甲基苯基硅油为稀释剂，采用快速超动态法，成功地将其涂渍到弹性石英毛细管柱上，经测试，柱效高，柱性能稳定，柱寿命较长，通过对酯类，烯烃类，酮类等对映体色谱分离，显示三种固定相具有较强的手性拆分能力，随着烷基链的增长，对α－蒎烯，β－蒎烯，α－紫萝酮等拆分能力逐渐增强，而对α－苯乙醇，1，20丙二醇，乳酸乙酯等对映体的拆分能力逐渐减弱。