响应面优化脂肪酶催化Baeyer-Villiger反应制备ε-己内酯

兰州理工大学学报 ›› 2022, Vol. 48 ›› Issue (6): 67-73.

响应面优化脂肪酶催化Baeyer-Villiger反应制备ε-己内酯

许慧, 薛晓, 李楷原, 刘翠, 邓雅姗, 张媛媛^*

青岛科技大学化工学院, 山东青岛 266042

收稿日期:2021-09-21 出版日期:2022-12-28 发布日期:2023-03-21
通讯作者: 张媛媛(1980-),女,山东青岛人,教授.Email:yyzlw_618@163.com
基金资助:
国家自然科学基金(21546004,21576145)

Optimization of Baeyer-Villiger reaction mediated by lipase for preparation of ε-caprolactone using response surface methodology

XU Hui, XUE Xiao, LI Kai-yuan, LIU Cui, DENG Ya-shan, ZHANG Yuan-yuan

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Received:2021-09-21 Online:2022-12-28 Published:2023-03-21

摘要/Abstract

摘要： 固定化T.laibaccii脂肪酶介导化学-酶Baeyer-Villiger氧化法制备ε-己内酯.运用响应面法进行了实验设计,获得了最优反应条件:环己酮初始浓度为1.22 mol/L,环己酮与过氧化氢脲的物质的量比为1∶1.3,反应温度为56.5 ℃,产率达到98.06%,浓度高达1.2 mol/L.在环己酮、乙酸乙酯反应体系中有三个反应,其中第三个反应是过氧化氢脲通过固定化脂肪酶的作用与中间产物乙酸反应,乙酸原位生成过氧乙酸.建立了二次多项式模型,其R²值为0.998 8,可以准确地预测ε-己内酯产率.该模型考虑了环己酮的初始浓度、环己酮与过氧化氢脲的物质的量比和反应温度对ε-己内酯产率的影响,环己酮与过氧化氢脲的物质的量比对ε-己内酯的产率有非常显著的影响(p<0.000 6).

关键词: 化学-酶Baeyer-Villiger氧化, 固定化脂肪酶, 己内酯, 最优化, 响应面法

Abstract: Immobilized T. laibaccii lipase-mediated chemical-enzyme Baeyer-Villiger oxidation method can prepare ε-caprolactone. The experimental design was carried out by response surface method, and the optimal reaction conditions were obtained, which the concentration of cyclohexanone was 1.22 mol/L, the molar ratio of cyclohexanone to urea hydrogen peroxide was 1∶1.3, the reaction temperature was 56.5 ℃, the yield reached 98.06%, and the concentration was as high as 1.2 mol/L. There are three reactions in the reaction system of cyclohexanone and ethyl acetate, which the third reaction is that urea hydrogen peroxide reacts with the intermediate acetic acid under the action of immobilized lipase, and acetic acid generates peracetic acid in situ. The quadratic polynomial model was established with the R² value of 0.998 8, which can accurately predict the yield of ε-caprolactone. In this model, the effect of initial concentration of cyclohexone, the ratio of cyclohexone to urea hydrogen peroxide and reaction temperature on ε-caprolactone yield are considered. The molar ratio of cyclohexone to urea hydrogen peroxide has a very significant effect on the yield of ε-caprolactone (p<0.000 6).

Key words: chemo-enzymatic Baeyer-Villiger reaction, immobilized lipase, caprolactone, optimization, response surface methodology

中图分类号:

TQ317

许慧, 薛晓, 李楷原, 刘翠, 邓雅姗, 张媛媛. 响应面优化脂肪酶催化Baeyer-Villiger反应制备ε-己内酯[J]. 兰州理工大学学报, 2022, 48(6): 67-73.

XU Hui, XUE Xiao, LI Kai-yuan, LIU Cui, DENG Ya-shan, ZHANG Yuan-yuan. Optimization of Baeyer-Villiger reaction mediated by lipase for preparation of ε-caprolactone using response surface methodology[J]. Journal of Lanzhou University of Technology, 2022, 48(6): 67-73.

参考文献

[1] GONZALEZ-MARTINEZ D,RODRIGUEZ-MATA M,MENDEZ-SANCHEZ D,et al.Lactonization reactions through hydrolase-catalyzed peracid formation.Use of lipases for chemoenzymatic Baeyer-Villiger oxidations of cyclobutanones [J].J Mol Catal B Enzym,2015,114:31-36.
[2] MICHLIN R A,SGARBOSSA P,SCARSO A,et al.The Baeyer-Villiger oxidation of ketones:A paradigm for the role of soft Lewis acidity in homogeneous catalysis [J].Coord Chem Rev,2010,254(5/6):646-660.
[3] MATHPATI A C,BADGUJAR K C,BHANAGE B M.Kinetic modeling and docking study of immobilized lipase catalyzed synthesis of furfuryl acetate [J].Enzyme Microb Technol,2016,84:1-10.
[4] CHAVEZ G,HATTI-KAUL R,SHELDON R A,et al.Baeyer-Villiger oxidation with peracid generated in situ by CaLB-CLEA catalyzed perhydrolysis [J].J Mol Catal B Enzym,2013,89:67-72.
[5] DROZDZ A,ERFURT K,BIELAS R,et al.Chemo-enzymatic Baeyer-Villiger oxidation in the presence of Candida antarctica lipase B and ionic liquids [J].New J Chem,2015,39(2):1315-1321.
[6] DROZDZ A,CHROBOK A.Chemo-enzymatic Baeyer-Villiger oxidation of 4-methylcyclohexanone via kinetic resolution of racemic carboxylic acids:Direct access to enantioenriched lactone [J].Chem Commun,2016,52(6):1230-1233.
[7] SHUAI W,DAS R K,NAGHDI M,et al.A review on the important aspects of lipase immobilization on nanomaterials [J].Biotechnol Appl Biochem,2017,64(4):496-508.
[8] SHELDON R A,WOODLEY J M.Role of biocatalysis in sustainable chemistry [J].Chem Rev,2017,118(2):801-838.
[9] BARBOSA O,ORTIZ C,BERENGUER-MURCIAL A,et al.Glutaraldehyde in bio-catalysts design:A useful crosslinker and a versatile tool in enzyme immobilization [J].RSC Adv,2014,4(4):1583-1600.
[10] WANG P,HYEON T,PARK H G,et al.Crosslinked enzyme aggregates in hierarchically-ordered mesoporous silica:A simple and effective method for enzyme stabilization [J].Biotechnol Bioeng,2007,96(2):210-218.
[11] KIM M,KIM J,LEE J,et al.One-dimensional crosslinked enzyme aggregates in SBA-15:Superior catalytic behavior to conventional enzyme immobilization [J].Microporous Mesoporous Mater,2008,111(1/2/3):18-23.
[12] RESHMI R,SUGUNAN S.Improved biochemical characteristics of crosslinked β-glucosidase on nanoporous silica foams [J].J Mol Catal B Enzym,2013,85:111-118.
[13] ZHANG Y Y,LIU J H.Purification and in situ immobilization of lipase from of a mutant of Trichosporon laibacchii using aqueous two-phase systems [J].J Chromatogr B Anal Technol Biomed Life Sci,2010,878(11/12):909-912.
[14] LIU J H,ZHANG Y Y.Optimisation of lipase production by a mutant of Candida antarctica DSM-3855 using response surface methodology [J].Int J Food Sci Technol,2011,46(4):695-701.
[15] SELVARAJ R,MOORTHY I G,KUMAR R V,et al.Microwave mediated production of FAME from waste cooking oil: Modelling and optimization of process parameters by RSM and ANN approach [J].Fuel,2019,237:40-49.
[16] AMIRI S,SHAKERI A,SOHRABI M R,et al.Optimization of ultrasonic assisted extraction of fatty acids from Aesculus hippocastanum fruit by response surface methodology [J].Food Chem,2019,271:762-766.
[17] KIM Y,NICELL J A.Laccase-catalysed oxidation of aqueous triclosan [J].J Chem Technol Biotechnol Int Res Process Environ Clean Technol,2006,81(8):1344-1352.
[18] WAGHMARE G V,CHATTERJI A,Rathod V K.Kinetics of enzymatic synthesis of cinnamyl butyrate by immobilized lipase [J].Appl Biochem Biotechnol,2017,183(3):792-806.
[19] DHAKE K P,TAMBADE P J,QURESHI Z S,et al. HPMC-PVA Film immobilized rhizopus oryzae lipase as a biocatalyst for transesterification reaction [J].ACS Catal,2011,1(4):316-322.
[20] DE MIRANDA A S,MIRANDA L S M,DE SOUZA R O M A.Lipases: Valuable catalysts for dynamic kinetic resolutions [J].Biotechnol Adv,2015,33(5):372-393.
[21] SHELDON R A.Enzyme immobilization: The quest for optimum performance [J].Adv Synth Catal,2007,349(8/9):1289-1307.
[22] TORNVALL U,HEDSTROM M,SCHILLEN K,et al.Structural,functional and chemical changes in Pseudozyma antarctica lipase B on exposure to hydrogen peroxide [J].Biochimie,2010,92(12):1867-1875.
[23] ORELLANA-COCA C,CAMOCHO S,ADLERCREUTZ D,et al.Chemo-enzymatic epoxidation of linoleic acid:Parameters influencing the reaction [J].Eur J Lipid Sci Technol,2005,107(12):864-870.
[24] KATRITZKY A R,AKHMEDOV N G,DENISKOe O V.¹H and¹³C NMR spectroscopic study of oxidation of D,L-cystine and 3,3′-dithiobis(propionic acid) with hydrogen peroxide in aqueous solution [J].Magn Reson Chem,2003,41(1):37-41.