Extending the scope of enantiomer separation by capillary supercritical fluid chromatography on immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex)

Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others. Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, R_s, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated.     

偏最小二乘法分光光度同时测定复方扑热息痛片中各组分含量

本文介绍了偏最小二乘法(PLS)用于多组分分光光度分析的基本原理和算法.研究了复方扑热患痛片中扑热息痛、阿司匹林和咖啡因的PLS测定方法,各组分的平均回收率分别为99.88±0.33％、99.99±0.14％和99.92±1.24％(置信度95％).     

Pr0.15TbxDy0.85-xFe2 内禀磁致伸缩的测量

对稀土金属间Laves相赝二元化合物进行X射线衍射分析。其(440)峰出现劈裂，由(440)峰劈裂的程度可以确定内禀磁致伸缩的大小。本文采用X射线衍射的方法对Pr0．15TbxDy0．85-xFe2系列粉末样品的(440)峰步进扫描，并对扫描结果进行拟合，对拟合得到的两组双线峰之间的间距计算得到内禀磁致伸缩λ111,拟合曲线与实验点符合很好，结果表明Pr0．15TbxDy0．85-xFe2的内禀磁致伸缩随Tb含量的增加而增加，并且用0．15的Pr替代Dy后，在x=0．3时，Pr0．15TbxDy0．85-xFe2的内禀磁致伸缩λ111比Tb0.27Dy0.73Fe2的内禀磁致伸缩λ1ll大。     

XPS,AFM, ATR and TPD evidence for terraced,dihydrogen terminated, 1×1 (100) silicon

Heating (100) silicon at high temperature (say, higher than 850 °C) in H₂, cooling to 670–700 °C in the same ambient, and quenching to room temperature in N₂ results in environmentally robust, terraced 1 × 1 (100) SiH₂. Evidence for this conclusion is based on angle‐resolved x‐ray photoelectron spectroscopy, atomic force microscopy, infrared absorption spectroscopy in the attenuated total reflection mode, thermal programmed desorption, and reflection high‐energy electron diffraction. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of ansa -zirconocenes based on 2-(phenylethynyl)-1 H -indene. The crystal and molecular structure of the complex [μ-CH2CH2(η5-2-PhC≡CInd)2]ZrCl2 (Ind is inden-1-yl)

Alkynyl-substituted indene was first used as a ligand for the synthesis of transition metal complexes. ansa-Zirconocenes containing ethylene and dimethylsilylene bridges were synthesized starting from 2-(phenylethynyl)-1H-indene. The structure of the former compound was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 68–73, January, 2007.     

Synthesis,molecular and crystal structures,and characteristic features of electronic structures of salicylamide-based B,Si-containing chelates

The reaction of 4-(2-hydroxybenzoyl)-2,2,6,6-tetramethyl-2,6-disilamorpholine with BF₃Et₂O afforded (O-B)-chelate 4-[2-(difluoroboroxy)benzoyl]-2,2,6,6-tetramethyl-2,6-disilamorpholine. Treatment of the latter with BF₃Et₂O or SOCl₂ gave rise to products of the disilamorpholine ring opening, viz., (O-B) chelate 2-(difluoroboroxy)-N,N-bis(dimethylfluorosilylmethyl)benzamide or 2-(difluoroboroxy)-N, N-bis(dimethylchlorosilylmethyl)benzamide, respectively. The structures of the compounds synthesized were confirmed by X-ray diffraction analysis and ¹H, ¹³C, and ²⁹Si NMR spectroscopy. High-precision X-ray diffraction study and quantum-chemical calculations demonstrated that the coordination OSi bond is absent in the two last-mentioned compounds.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1846–1853, September, 2004.     

Enzymatic synthesis of neopentylpolyol esters in organic media

Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane, which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters were determined in order to define optimal conditions.     

Crystallization of chiral compounds. 1. Spectroscopic,thermochemical, and crystallographic investigation of homochiral and racemic glycidyl p-toluenesulfonate

Crystalline specimens of homochiral and racemic glycidyl p-toluenesulfonate were studied by IR spectroscopy, differential scanning calorimetry, and X-ray diffraction analysis. The melting phase diagram of glycidyl p-toluenesulfonate was constructed. The stacking effect in the crystals of the racemic sulfonate is responsible for a more dense molecular packing, with the result that a heterochiral type of crystallization becomes more favorable.     

X-ray investigation of the role of the mixed emulsifier in the structure formation in o/w creams

The aim of this research work was to clarify the role of the mixed emulsifier in the structure formation and water binding mode in the case of o/w creams prepared with different surfactants. The swelling behavior of mixed emulsifiers was examined by means of direct investigation methods such as transmission electron microscopy (TEM) and X-ray diffraction. The detailed structure image of the creams was created with the help of the latter. The influence of the structure of the hydrophilic gel phase, and the structural changes during storage were studied with rheological methods. On the basis of the results, it can be stated that the investigated creams had different structures from those mentioned in the literature: surfactant did not create a mixed bilayer with the structure to furnish fatty amphiphile; instead, micelles were formed. These results correlated well with the results of the rheological tests.