LiCl急冷过程中结构变化研究的一种几何学方法

计算了900 K、698 K、498 K和298 K温度下共4800个Voronoi多面体并对它们进行了统计分析. 计算表明: 在玻璃态转变温度区间, Voronoi多面体的统计分布有明显的变化。在以阳离子为中心的Voronoi多面体中, 在298 K时,四面体、五面体和六面体占总数的80%以上。     

A new C21-steroidal glycoside from Cynanchum stauntonii

A new C21-steroidal glycoside with two known compounds were isolated from the root of Cynanchum Stauntonii.Based on thespectral analysis,including MS,1H NMR,13C NMR,DEPT,1H-1H COSY,13C-1H COSY,HMQC and HMBC,their chemicalstructures were determinated as glaucogenin-C 3-O-a-L-cymaropyranosyl-(1→4)-b-D-digitoxopyranosyl-(1→4)-β-D-canaropyranoside(1),stigmasterol(2)and ursolic acid(3).     

氨基酚异构体的离子对反相液相色谱分析的研究

本文研究了离子对反相液相色谱分析氨基酚异构体的可能性、影响因素和色谱条件，发现以含４×１０－８ｍｏｌ／Ｌ四丁基碘化铵、０．１８４ｍｏｌ／Ｌ醋酸钠的甲醇水溶液（２３：７７）作为流动相，ＯＤＳ为固定相时可以实现氨基酚异构体的良好分离。     

内-α-取代-α-甲基双环[2,2,1]庚烷-2-基甲醇的合成及其结构与香气的关系

合成了18种内-α-取代-α-甲基双环[2,2,1]庚烷-2-基甲醇(Ⅰ)。测定了所有化合物的折光率(或熔点)、质谱、红外光谱、~1H核磁共振谱、气相色谱的保留时间和薄层色谱的比移值。评定了它们的香气,并与相应的内-α-取代-α-甲基双环[2,2,1]-5-庚烯-2-基甲醇(Ⅱ)系列化合物的香气进行了比较,初步探讨了结构与香气的关系。     

Liquid–solid disk extraction followed by supercritical fluid elution and gas chromatography of phenols from water

A method combining the techniques of liquid – solid disk extraction (LSDE) and supercritical fluid elution (SFE) has been developed for the phenols regulated by the Clean Water Act. LSDE uses a disk or membrane made of polytetrafluoroethylene (PTFE) fibrils impregnated with small particles, e.g. styrene divinylbenzene (SDB) resin, to extract phenols from water. After disk extraction the retained analytes are eluted from the disk using SFE. SFE is used as an alternative to liquid solvent elution with an organic solvent. Analytes are separated, identified, and quantified using gas chromatography – ion trap detector mass spectrometry (GC-ITDMS). The method is capable of sub parts per billion detection limits, and precision of 5–28% RSD. Evaluation of various disks or membranes, such as C₁₈-silica disks, SDB disks, and ion exchange membranes, has also been performed for the extraction of phenols from water. The results obtained from the in-situ aqueous acetylation of phenols and extraction of their acetates are quantitative. The utilization of LSDE and SFE techniques has proven to be a more effective approach than liquid – liquid extraction in minimizing air pollution and solvent waste.     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.     

Development and application of a new general method for the asymmetric synthesis of syn- and anti-1,3-amino alcohols

A general method is described for asymmetric synthesis of both syn- and anti-1,3-amino alcohols. The first application of metalloenamines derived from N-sulfinyl imines is reported for the highly diastereoselective addition to aldehydes. The reduction of the product beta-hydroxy N-sulfinyl imines 2 with catecholborane and LiBHEt(3) provides syn- and anti-1,3-amino alcohols with very high diastereomeric ratios. This method was found to be effective for a variety of substrates incorporating either aromatic or various aliphatic substituents. The convergent and efficient asymmetric syntheses of the two natural products, (-)-8-epihalosaline and (-)-halosaline, were also accomplished.     

Physical/chemical separations in the break-up of highly charged droplets from electrosprays

Highly-charged droplets, as formed by an electrospray process, are known to undergo asymmetric fission to form smaller droplets. We have observed a chemical and physical separation phenomenon that occurs in the droplet break-up process and is related to a compound's surface activity in solution. Two experimental approaches demonstrated that the smaller satellite droplets and the progeny droplets generated by the spray formation and asymmetric fission processes to be surfactant-enriched. These smaller droplets were also effectively separated from the larger primary and residual droplets because of their smaller inertia and high surface charge density, and a region attributed to the initially formed smaller satellite droplets was found to be strikingly confined in a narrow periphery region of the electrospray. The phenomenon may have utility for chemical separations and have significant implications for the sensitivity and selectivity of electrospray ionization-mass spectrometry.