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利用压力对致密二氧化碳中脂肪酶催化蜡酯合成的影响。

Exploiting the pressure effect on lipase-catalyzed wax ester synthesis in dense carbon dioxide.

作者信息

Knez Zeljko, Laudani Chiara Giulia, Habulin Maja, Reverchon Ernesto

机构信息

University of Maribor, Faculty of Chemistry and Chemical Engineering, Laboratory for Separation Processes, Smetanova ul. 17, SI-2000 Maribor, Slovenia.

出版信息

Biotechnol Bioeng. 2007 Aug 15;97(6):1366-75. doi: 10.1002/bit.21331.

DOI:10.1002/bit.21331
PMID:17221889
Abstract

The present work focuses on the thermodynamic interpretation of the lauryl oleate biosynthesis in high-pressure carbon dioxide. Lipase-catalyzed lauryl oleate production by oleic acid esterification with 1-dodecanol over immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) was successfully performed in a sapphire window batch stirred tank reactor (BSTR) using dense CO(2) as reaction medium. The experiments were planned to elucidate the pressure effect on the reaction performance. With increasing the pressure up to 10 MPa, the catalytic efficiency of the studied enzyme improved rising up to a maximum and decreased at higher pressure values. Kinetic observations, exhibiting that dense CO(2) expanded reaction mixture in subcritical conditions led to higher performance than when diluted in a single supercritical phase, were elucidated by phase-equilibrium arguments. The experimental results were justified with emphasis on thermodynamic interpretation of the studied system. Particularly, the different reaction performances obtained were related to the position of the operating point with respect to the location of liquid-vapor phase boundaries of the reactant fatty acid/alcohol/CO(2) ternary system. The outlook for exploitation of CO(2) expanded phase at lower pressure compared to supercritical phase, with heterogeneous system in which the solid catalyst particles are exposed to dense CO(2) expanded reaction mixture, in developing new biotransformation schemes is promising.

摘要

本研究聚焦于高压二氧化碳中月桂醇油酸酯生物合成的热力学解释。在以密相二氧化碳为反应介质的蓝宝石窗口间歇搅拌釜式反应器(BSTR)中,成功进行了米黑根毛霉固定化脂肪酶(Lipozyme RM IM)催化油酸与1 - 十二醇酯化生成月桂醇油酸酯的反应。实验旨在阐明压力对反应性能的影响。随着压力升高至10 MPa,所研究酶的催化效率先升高至最大值,然后在更高压力值时降低。动力学观察表明,在亚临界条件下密相二氧化碳使反应混合物膨胀,其性能高于在单一超临界相中稀释时的性能,这通过相平衡理论得以阐释。实验结果通过对所研究体系的热力学解释得到了验证。特别地,所获得的不同反应性能与操作点相对于反应物脂肪酸/醇/二氧化碳三元体系液 - 气相边界位置有关。与超临界相相比,在较低压力下利用二氧化碳膨胀相,以及在非均相体系中使固体催化剂颗粒暴露于密相二氧化碳膨胀反应混合物中,在开发新的生物转化方案方面具有广阔前景。

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High yield of wax ester synthesized from cetyl alcohol and octanoic acid by lipozyme RMIM and Novozym 435.
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Int J Mol Sci. 2012;13(9):11694-11704. doi: 10.3390/ijms130911694. Epub 2012 Sep 17.