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1.
Comparison of lipase-catalysed esterification in supercritical carbon dioxide and in n-hexane 总被引:2,自引:0,他引:2
A. Marty W. Chulalaksananukul J. S. Condoret R. M. Willemot G. Durand 《Biotechnology letters》1990,12(1):11-16
Summary Oleic acid esterification by ethanol has been performed by an immobilized lipase fromMucor miehei in supercritical carbon dioxide and in n-hexane as solvents. In both media, determination of apparent kinetic constants has been achieved and influence of water content has been shown to be different due to various rates of water solubilities. Stability of the lipase has been proved to be correct and similar in both solvents. Inhibition by ethanol excess has been found but is greater in n-hexane. That can explain the higher initial velocities obtained in supercritical carbon dioxide for the highest ethanol concentrations. 相似文献
2.
Summary Subtilisin Carlsberg was found to catalyze transesterification between N-acetyl-L-phenylalanine chloroethyl ester and ethanol in supercritical carbon dioxide. The effects of different temperatures and carbon dioxide/ethanol ratios on the reaction rate were investigated. A comparative study showed that enzymatic transesterification is faster in supercritical carbon dioxide than in anhydrous organic solvents. 相似文献
3.
Lozano P Delgado D Gómez D Rubio M Iborra JL 《Journal of biochemical and biophysical methods》2000,43(1-3):367-378
A supercritical carbon dioxide extraction method to obtain selectively volatile compounds of saffron without sample destruction has been developed. The influence of both pressure and temperature was studied, 20 MPa and 100 degrees C being the best conditions to extract the total safranal content. A decrease in supercritical fluid density was shown to be a critical parameter for enhancing the extraction power of carbon dioxide. For all the assay conditions, the extracts mainly contained safranal and HTCC, as demonstrated by gas chromatography and high-performance liquid chromatography analyses. Both chromatographic methods were suitable for safranal quantification and showed excellent agreement. Supercritical extracts from five different saffron types were studied by high-performance liquid chromatography and their safranal contents were determined. 相似文献
4.
NVT ensemble molecular dynamics (MD) simulation has been applied to calculate the self-diffusion coefficients of carbon dioxide and the tracer diffusion coefficients of naphthalene in supercritical carbon dioxide. The simulation was carried out in the pressure range from 8 to 40 MPa. The elementary physical model proposed by Harris and Yung was adopted for carbon dioxide and some approximation models were used for naphthalene. The systems of MD simulation for carbon dioxide consist of 256 particles. One naphthalene molecule was added for carbon dioxide+naphthalene system. The system can be assumed to be an infinite dilution condition for carbon dioxide+naphthalene system and the mutual diffusion coefficients are equal to the tracer diffusion coefficients of naphthalene. The self-diffusion coefficients of carbon dioxide and the tracer diffusion coefficients of naphthalene in supercritical carbon dioxide can be calculated by mean square displacement. The calculated results of diffusion coefficients showed good agreement with the experimental data without adjustable parameters. 相似文献
5.
Investigations of enzymatic reactions in supercritical CO(2) are often hindered by the high pressure involved in these processes, making reaction monitoring extremely difficult. This paper describes the implementation of a fiber optic based oxygen sensor into a high pressure reactor for supercritical carbon dioxide. The sensor is pressure resistant, working in supercritical carbon dioxide and reusable after depressurisation. The sensor signal is found to be affected by pressure changes, but stable at constant pressure. Oxygen concentration in supercritical CO(2) is monitored using the disproportionation of hydrogen peroxide as a simple oxygen producing reaction. 相似文献
6.
Biocatalytic transesterification of methylmethacrylate is possible in many different solvents. The reaction rate is readily controlled by variation in solvent physical properties. The reaction proceeds better in hydrophobic solvents, and activity can be restored in hydrophilic solvents by the addition of water. We have now demonstrated that supercritical carbon dioxide is not a good solvent for the reaction between 2-ethlhexanol and methylmethacrylate. It apperars that the supercritical carbon dioxide may either alter the pH of the microaqueous environment associated with the protein or reversibly form covalent complexes with free amine groups on the surface of the enzyme. Although supercritical carbon dioxide is a poor solvent for acrylate transesterification, many other supercritical fluids (ethane, ethylene, sulfur hexafluoride, and fluoroform) are better than most conventional solvents. In supercritical ethane it is possible to control the activity of the enzyme by changing pressure, and the enzyme appears to follow Michaelis-Menten Kinetics. We find that sulfur hexafluoride, the first anhydrous inorganic solvent in which biocatalytic activity has been reported, is a better solvent than any conventional or supercritical organic fluid tested. 相似文献
7.
Biocatalytic synthesis of acrylates in organic solvents and supercritical fluids: III. Does carbon dioxide covalently modify enzymes? 总被引:3,自引:0,他引:3
We have previously demonstrated that the activity of the lipase (Candida cylindracea) catalyzed transesterification reaction between methylmethacrylate and 2-ethylhexanol in supercritical carbon dioxide is comparatively low. In this article, we have investigated the same reaction in supercritical carbon dioxide with a special emphasis on determining the extent of any interaction between the enzyme and carbon dioxide. Transesterification reaction rates in hexane and supercritical carbon dioxide are compared at different temperatures. In supercritical carbon dioxide, temperature was found to have no significant effect on reaction rate in the range of 40 degrees to 55 degrees C. Above 55 degrees C, however, the reaction rate increased significantly as a function of temperature. It appears that carbon dioxide forms reversible complexes with the free amine groups on the surface of the enzyme. Direct evidence of modification was obtained using mass spectroscopy to detect the extent of modification of a pure protein. The kinetics of the reaction have been studied in hexane, and they obey a ping-pong bi-bi mechanism with inhibition by 2-ethylhexanol. The effect of bubbling carbon dioxide and/or fluoroform on the reaction rate in hexane at different temperatures suggests that the enzyme undergoes shear inactivation in hexane. (c) 1995 John Wiley & Sons, Inc. 相似文献
8.
Polymers with a low molecular weight derived from soybean oil have been prepared in a supercritical carbon dioxide medium by cationic polymerization. Boron trifluoride diethyl etherate was used as an initiator. Influences of polymerization temperature, amount of initiator, and carbon dioxide pressure on the molecular weight were investigated. It is shown that the higher polymerization temperature favors polymers with relatively higher molecular weights. Larger amounts of initiator also provide polymers with higher molecular weights. Higher pressure favors polymers with relatively higher molecular weights. The applications of these soy-based materials will be in the lubrication and hydraulic fluid areas. 相似文献
9.
Solvent-modified carbon dioxide extractions of the roots of Harpagophytum procumbens have been investigated with respect to extraction efficiency and content of harpagoside, and compared with a conventional extract. The effects of pressure, temperature, type and concentration of the modifier have been examined. Two extraction steps were necessary in order to achievehigh anti-inflammatory harpagoside-enriched extracts. The first extraction step was carried out in the supercritical state using carbon dioxide modified with n-propanol to remove undesired lipophilic substances. The main extraction was performed either in the supercritical or in the subcritical state with carbon dioxide modified with ethanol. The supercritical fluid extraction resulted in extracts containing up to 30% harpagoside. The subcritical extracts showed a harpagoside content of ca. 20%, but the extraction yield was nearly three times greater compared with supercritical conditions. The total harpagoside recovery resulting from the sum of the extract and the crude drug residue was greater than 99% in all experiments. The conventional extract and two carbon dioxide extracts were tested for in-vitro inhibition of 5-lipoxygenase or cyclooxygenase-2 biosynthesis. Both carbon dioxide extracts showed total inhibition on 5-lipoxygenase biosynthesis at a concentration of 51.8 mg/L. In contrast, the conventional extract failed to show any inhibition of 5-lipoxygenase biosynthesis. 相似文献
10.
Production of micronic particles of biocompatible polymer using supercritical carbon dioxide 总被引:6,自引:0,他引:6
Three micronization techniques, based on the use of supercritical carbon dioxide, were investigated to produce microspheres of a natural biocompatible polysaccharide. Particles smaller than 20 mum were obtained by means of the rapid expansion of a supercritical solution method (RESS), both with and without cosolvents. The mean diameter of the particles was reduced to about 0.5 mum when a solution of the polymer in an organic solvent was expanded by using carbon dioxide as a supercritical antisolvent (SAS). The SAS process was operated both in a continuous and in a batch mode. The former leads to aggregated structures and fibers, and the latter to the formation of micronic spherical particles. It was found that the experimental temperature did not substantially affect the shape and dimension of the particles. A stronger dependence is shown with respect to the solute concentration in the starting solution. The proposed method is attractive as the basis of a new process for the preparation of drug delivery systems. (c) 1997 John Wiley & Sons, Inc. 相似文献
11.
Paul D. Siders 《Molecular simulation》2016,42(9):693-701
The stationary phase in supercritical fluid chromatography includes alkylsilanes, bearing typically 18-carbon alkane chains, bonded to silica. The silanes are in contact with supercritical carbon dioxide. Interaction of the stationary phase with analytes from the mobile phase depends on conformation of the silanes, whether they form a collapsed layer between the silica and the carbon dioxide or are extended into the carbon dioxide. Although equilibrium conformation of alkylsilanes can be determined by equilibrium Monte Carlo (MC) simulation, that is hampered by slow relaxation of the chains. An alternative is to pull alkylsilanes from collapsed to extended conformations, then calculate free energy change from the Jarzynski equality. This work compares conformational results from equilibrium MC simulation to free energies from nonequilibrium pulling simulations. Because both equilibrium and nonequilibrium simulations are faster for shorter silanes, this work also compares results from 8-carbon and 18-carbon silanes. Free energies from nonequilibrium pulling predict that alkylsilanes tend to bend over and form a layer between silica and carbon dioxide. Results from equilibrium simulations are qualitatively consistent with results from nonequilibrium pulling. Longer-chain silanes have greater tendency to extend slightly into the carbon dioxide. 相似文献
12.
Heinz-Dieter Brannolte Helmut K. Mangold Egon Stahl 《Chemistry and physics of lipids》1983,33(3):297-299
The rate of extraction of triacylglycerols with supercritical carbon dioxide can be greatly enhanced by raising the pressure of the fluid to 600 bar, or higher, and its temperature to 60°C, or higher. Both the amount of carbon dioxide and the time required for complete extraction are reduced at such high pressures and temperatures. 相似文献
13.
Paprika powder, naturally contaminated with aflatoxins, was extracted by supercritical carbon dioxide at standard conditions (300 bar and 50 degrees C). A lipophilic top phase and an aqueous base phase were obtained. These and the extraction residue were analysed by HPLC for aflatoxins. The main quantity of aflatoxins, about 60% of aflatoxin B1 and about 70% of aflatoxin B2 related to the original paprika powder, was found to be located in the extraction residue. This confirms the results of previous studies with other spices and demonstrates that the use for flavouring purposes of supercritical carbon dioxide extracts, rather than natural spice, offers potential application in reducing aflatoxin levels in spiced foods. 相似文献
14.
A method for the extraction of the alkaloids colchicine, 3-demethylcolchicine and colchicoside from seeds of Colchicum autumnale by supercritical carbon dioxide has been established. Several parameters such as pressure, temperature, percentage of modifier and extraction time have been examined. Two extraction steps with constant carbon dioxide density (0.90 g/mL) and flux (1.5 mL/min) were required to extract the alkaloids in 110 min using 3% methanol as modifier. The quantitative determination of the alkaloids was performed by HPLC; the percentages of recovery were higher than 98% for the three alkaloids. This extraction procedure was compared with a conventional method involving maceration and sonication, and the same levels of alkaloids were obtained in each case. The supercritical carbon dioxide method is, however, very efficient, more rapid and more environmentally friendly than conventional methods. 相似文献
16.
The highest yield (14.4 g/kg) of naringin, the major flavonoid from the peel of Citrus paradisi L., that could be achieved by supercritical fluid extraction was obtained using supercritical carbon dioxide modified with 15% ethanol and fresh (rather than dried) peels at 95 bar and 58.6 degrees C. This yield is higher than that attained by the conventional technique of maceration, and close to those obtained by reflux and Soxhlet methods. Furthermore, supercritical fluid extraction consumes less solvent and provides a shorter extraction time than conventional extraction methods. 相似文献
17.
The enantioselective esterification of racemic ibuprofen with n-propanol by immobilized Mucor miehel lipase in supercritical carbon dioxide was studied. The enantiomeric excess of the product (eep) was 70 % at 15...20 % conversion. The enantioselectivity was faintly affected by temperature and the concentration of ibuprofen and lipase. The optimum temperature was 45 °C. The initial reaction rate increased with pressure, but enantioselectivity was not affected by pressure changes. The reaction rates in supercritical carbon dioxide at optimized conditions and in n-hexane were similar. 相似文献
18.
《Biocatalysis and Biotransformation》2013,31(1-4):115-121
From the comparation of esterification between oleic acid and oleyl alcohol, catalyzed by the Mucor miehei immobilized lipase in a batch stirred tank reactor, in a solvent free system and system where the solvent was supercritical carbon dioxide it is obvious that reaction rates are higher at supercritical conditions than in the solvent free system. To obtain the data on the solubility of substrates and product (oleyl oleate) in supercritical carbon dioxide, fluid phase equilibria measurements in the static equilibrium cell have been done. The results showed that the temperature change between 30 d`C and 50 d`C doesn't affect the solubility of the substances in SC CO2 very much, but with higher pressure (between 100 and 300 bar) the solubilities of oleic acid, oleyl alcohol and oleyl oleate slightly increase. From the data it is obvious that oleic acid and oleyl alcohol have better solubility in supercritical CO2 than oleyl oleate and therefore the separation of both substrates from oleyl oleate with supercritical CO2 is possible-Key words: esterification, supercritical fluids, lipase. 相似文献
19.
应用超临界CO2流体萃取技术研究中药百里香挥发性化学成分 总被引:10,自引:2,他引:10
采用分析型超临界(CO2)流体萃取技术(SFE-CO2)与传统水蒸气蒸馏法(SD),提取中药百里香挥发油,并通过气相色谱/质谱联用技术测定了提取物的化学成分。从中分别鉴定出61个50个化合物,主要包括:百里酚、石竹烯、桉油精、伞花醇、芳樟醇、豆甾醇等成分。 相似文献