超临界二氧化碳流体在酶催化反应中的应用

酶催化反应已发展到了利用超临界二氧化碳流体为介质来进行。文章评述了在超临界二氧化碳中影响酶活性和稳定性的重要因素，介绍了SCCO2介质中酶催化反应的最新进展。     

超临界流体技术在催化反应和金属有机反应中的应用

本文详细地介绍了超临界流体技术在催化反应和金属有机反应中近10年来国内外发展的最新成果及动向,表明将超临界流体技术应用于催化反应中,将提高催化剂活性,选择性及寿命,并可提高反应速率,改变反应历程,特别是在开展控制化学及环境友好的绿化学反应方面的研究具有很大的潜在优势。     

酶催化反应研究进展

简要评述了近年来酶催化反应的进展,以及近年来5种不同反应体系(有机溶剂体系、反胶束体系、低共熔体系、超临界流体体系和气相体系)中酶催化反应的进展,并对不同体系中酶促反应的主要影响因素、酶催化底物的拓宽和模拟酶研究及酶催化的手性合成等作了简要概述。参考文献52篇。     

超临界二氧化碳介质中的有机反应*

本文主要介绍了超临界近5年来超临界二氧化碳中的有机反应研究的最新进展,包括加氢反应、氧化反应、羰基化反应、碳碳键形成反应、酯化反应和酶催化反应的研究现状;同时,还介绍了超临界二氧化碳作为反应底物用于合成碳酸酯和氨基甲酸酯的研究进展;并对未来的发展进行了展望。     

ZrO2催化合成气制异丁烯

制得了纯净的单斜和四方晶形ＺｒＯ２，给出了制取单一晶形的条件：ＰＨ值保持在９．５左右能够生成单斜晶形成ＺｒＯ２；四方晶形ＺｒＯ２的生成需要ＰＨ≥１１．５，催化反应结果表明，晶形对慢丁烯的选择性有着重要的影响，单斜晶形ＺｒＯ有利于异丁烯的生成；四方晶形ＺｒＯ２使异丁烯的生成量显著降低，不同方法制备的ＺｒＯ２催化性能有所没，超临界流体干燥法制得的ＺｒＯ２催化剂的舔生科物选择性均高于其它方法，文中对此反     

超临界流体在有机合成中的应用

超临界化学反应是一种新型的反应体系，本文对超临界流体在有机合成反应中应用的最新进展进行了综述。     

超临界流体技术研究进展

本文综述了超临界流体技术在萃取、材料制备、化学反应及相转移催化等方面的应用, 介绍了有代表性的超临界萃取和反应装置。对今后工作提出了一些建议。     

超（近）临界流体中的催化加氢反应

就近年来超临界流体, 特别是超临界二氧化碳中几个重要的均相、非均相加氢反应的研究进展进行综述。     

超临界流体干燥方法在丁烷选择性氧化制顺酐

分别用超临界流体干燥方法和传统方法制备了用于丁烷选择性氧化制顺酐的VPO催化剂. 用超临界流体干燥方法制备的催化剂VPOⅡ的比表面积高达38.8 m2/g,而用传统方法制备的催化剂VPOⅠ的比表面积只有10.7 m2/g. XRD分析表明,除催化剂VPOⅡ中的VOPO4相含量比催化剂VPOⅠ稍多外,这两种催化剂的主要结构均为(VO)2P2O7相. 在有氧和无氧条件下进行的丁烷氧化制顺酐的催化反应结果表明,用超临界流体干燥方法制备的催化剂不仅具有较高的顺酐收率,而且含有更多的可在无氧条件下参与选择性氧化反应的晶格氧(催化剂VPOⅡ的可利用选择性晶格氧量比催化剂VPOⅠ增加了1.5倍). 用超临界流体干燥方法可以改善催化剂性能的原因可能与催化剂具有较大的比表面积和较多的V5+有关.     

超临界流体干燥方法在丁烷选择性氧化制顺酐VPO催化剂制备中的应用

分别用超临界流体干燥方法和传统方法制备了用于丁烷选择性氧化顺酐的VPO催化剂。用超临界流体干燥方法制备的催化剂VPOⅡ的比表面积高达38．8m^2/g,而用传统方法制备的催化剂VPOⅠ的比表面积只有10.7m^2/g。XRD分析表明,除催化剂VPOⅡ中的VOPO4相含量比催化剂VPOⅠ稍多外,这两种催化剂的主要结构均为（VO）2P2O7相。在有氧和无氧条件下进行的丁烷氧化制顺酐的催化反应结果表明,用超临界流体干燥方法制备的催化剂不仅具有较高的顺酐收率,而且含有更多的可在无氧条件下参与选择性氧化反应的晶格氧（催化剂VPOⅡ的可利用选择性晶格氧量比催化剂VPOⅠ增加了1．5倍）。用超临界流体干燥方法可以改善催化剂性能的原因可能与催化剂具有较大的比表面积和较多的V^5 有关。     

超临界流体技术在萃取中的应用简介

超临界流体萃取技术具有许多传统技术所没有的快速、高效、高选择性、低能耗等优点,特别是超临界流体的特性是它可以代替高毒有机溶剂做反应介质,符合绿色化学的要求。本文综述了超临界流体的特性,介绍了超临界流体萃取的原理,归纳了超临界流体萃取的应用现状,并介绍了超临界流体的其他领域应用概况。     

Gradient separation of pharmaceuticals employing supercritical CO2 and modifiers

Sub- and Supercritical Fluid Chromatography (SFC) were used to separate seven purine and pyrimidine-based drugs. A two-pump system was used, where one pump delivered the carbon dioxide, and the other pump delivered modifier. The modifiers used in this work were methanol, and methanol containing 0.001 M tetrabutylammonium hydroxide. Two of the compounds studied were hydrochloride salts. These compounds were analyzed by a Supercritical Fluid Extraction (SFE)/SFC method.     

渣油加氢转化催化剂初期结焦规律的研究

以孤岛减压渣油及其超临界流体萃取分馏所得的窄馏分为原料,采用齐鲁石化公司胜利炼油厂VRDS装置的主催化剂,在高压釜反应器内考察了渣油加氢转化催化剂的初期结焦规律。结果表明,焦炭的生成是一个动态过程,其产率和性质与反应体系的温度、时间、氢气初始压力及原料的性质密切相关;结焦催化剂的孔壁焦炭沉积和堵孔现象严重,导致其比表面积大大减小,孔分布向小孔范围迁移。     

Book Reviews

Ultraviolet Spectroscopy and UV Lasers, Edited by P. Misra and M. A. Dubinskii Supercritical Fluid Technology in materials Science and Engineering (Syntheses, Properties and Applications), Edited by Ya-Ping Sun This revised version was published online in August 2006 with corrections to the Cover Date.     

Identification and Isotopic Analysis of Safranal from Supercritical Fluid Extraction and Alcoholic Extracts of Saffron

Abstract

Saffron is one of the most expensive spices. Consequently, it is not so difficult to understand that fraudulent saffron exists. Thus, it was interesting to study the most important flavouring component, in terms of aroma, volatile compound of saffron - safranal - by ¹³C isotopic analysis. Five saffron samples from different countries have been analysed. Safranal has been extracted by methanol or by Supercritical Fluid Extraction (SFE). The results indicate that there is a significant difference between the synthetic safranal and the natural one. On the contrary, it is difficult to conclude on the difference between the various geographical origins, as the isotopic variations are small. Moreover, it has been found that Supercritical Fluid Extraction allowed the selective extraction of volatile compounds from saffron under optimised conditions. It is a cleaner and faster method of extraction compared to the extraction using organic solvent. Nevertheless, an isotopic fractionation occurs in relation to the extraction yield of safranal.     

太湖水体中有机污染物的分析

利用超临界流体萃取与热脱附两种样品预自理方法的优势互补,与气相色谱分析相结合对太湖水体中不同沸点有机污染物进行了分析,发现太湖水中除了烃类污染物外还存在大量含氮有机污染物。其分布表明入湖河道中排放的工业污染物的流入是导致太湖水富营养化的一个重要因素。     

Control of flow rate in supercritical fluid chromatography

Summary Supercritical Fluid Chromatograph was constructed using two pumps and two restrictors. With this system in conjunction with the fused silica column packed with relatively large particles (40 μm), the flow rate was controlled both for isobaric and pressure programmed operations. Application of this system to the determination of molecular weight distribution of polystyrene oligomers was presented.     

Supercritical Fluid Chromatography of polyphenolic compounds in grape seed extract

Summary Supercritical Fluid Chromatography with a packed column on a mixture of eight polyphenols has been optimized. Carbon dioxide which was modified with methanol which contained less than 1% (w/w) citric acid as a secondary additive served as the mobile phase. Two tandem diol columns were used sequentially. The optimized method was applied to a supercritical fluid grape seed extract. Various components in the extract could be identified by retention time and ultraviolet spectral comparison with our synthetic mixture of polyphenols.     

Supercritical fluid chromatography (SFC) of linear and cyclic components in technical silicone oils

Since technical silicone oils are widely used, high performance analysis and exact quality control are necessary. The quantity of low molecular cyclic components is of special importance for the properties of the oils. Supercritical Fluid Chromatography (SFC) provides a facility for determining such cyclic components. Accurate assignment of linear and cyclic polydimethylsiloxanes is possible by coupling SFC with mass spectrometry (MS) or by using standard materials.     

Application of direct on-line coupling of HPLC and SFC with 1HNMR spectroscopy for the investigation of monomeric acrylates

The separation of monomeric acrylates was performed with High Performance Liquid Chromatography (HPLC) and Supercritical Fluid Chromatography (SFC). A direct on-line structural assignment of all compounds by continuous-flow ¹HNMR spectroscopy is possible with both separation techniques. The direct SFC-NMR coupling offers the advantage that the recorded continuous-flow ¹HNMR spectrum is not obscured by solvent signals.