罗旭,钱俊青

• 1:浙江工业大学药学院

摘要(Abstract)：

以蔗糖和乙酸乙烯酯为底物,脂肪酶催化合成蔗糖乙酸酯并分离得到了三氯蔗糖生产的关键中间体蔗糖-6-乙酸酯。今对催化合成蔗糖乙酸酯的反应溶剂进行比较,确定叔丁醇为较好的反应介质,详细考察了各反应参数:酶种类、初始水活度、底物摩尔比、酶用量、反应温度和时间对酯化反应效果的影响,确定了该反应体系的最优工艺条件:蔗糖40mmol?L?1,乙酸乙烯酯/蔗糖(mol/mol)=5,初始水活度aw=0.75,温度60℃,20%(w/w,酶/蔗糖)固定化脂肪酶LipozymeTLIM催化,反应24h后酯化率达84.70%。通过硅胶柱层析分离得到高纯度的其中一种产物,经二维核磁(2D-NMR)结构分析后,确定其为蔗糖-6-乙酸酯,占总酯化产物的质量达48.30%。

关键词(KeyWords)： 蔗糖;乙酸乙烯酯;脂肪酶;叔丁醇;蔗糖-6-乙酸酯

Abstract:

Keywords:

基金项目(Foundation): 国家863科技项目(2006AA10Z311)

作者(Author): 罗旭,钱俊青

参考文献(References)：

• [1]LIANG Cheng(梁诚).Synthesize and application of the high intensity sweet edulcorator sucralose(高效甜味剂三氯蔗糖的应用与合成)[J].China Chlor-Alkali(中国氯碱),2001,9(9):23-24.
• [2]Grice H C,Goldsmith L A.Sucralose?an overview of the toxicity data[J].Food Chemical Toxicol,2000,38(Suppl.2)S1-S6.
• [3]TANG Zhen-xing(唐振兴),SHI Lu-e(石陆娥).Progress of sucralose synthesis(三氯蔗糖合成研究进展)[J].Technology and Development of Chemical Industry(化工技术与开发),2005,34(6):10-15.
• [4]ZHENG Jian-xian(郑建仙),GAO Xian-feng(高宪枫),YUAN Er-dong(袁尔东).Exploration into how to extract sucralose through di-enzymatic-chemico synthesis(双酶-化学联合法制备三氯蔗糖的探索)[J].Beverage and Fast Frozen Food Industry(冷饮与速冻食品工业),2002,8(3):7-9.
• [5]Gargee P J,Oscarson S,Ritzen H.Partially esterified sucrose derivatives:Synthesis of6-O-acetyl-2,3,4-tri-O-3-methylpentanoyl sucrose,anaturally occurring flavor precursor of tobacco[J].Carbohydrates Research,1988,181:89-96.
• [6]Oscarson S,Ritzen H.Synthesis of6-O-acetyl-2,3,4-tri-O-3-methylpentanoyl sucrose and the three regioisomers of6-O-acetyl-2,3,4-tri-O-3-methylpentanoyl sucrose,naturally occurring fatty acid esters of sucrose found in tobacco[J].Carbohydrates Research,1996,284(2):271-277.
• [7]Palocci C,Falconi M,Alcaro S et al.An approach to address Candida Rugosa lipase regioselectivity in the acylation reactions of trytilated glucosides[J].Journal of Biotechnology,2007,128(4):908-918.
• [8]DAI Da-zhang(戴大章),XIA Li-ming(夏黎明).Production of the lipase form penicillium expansum PED-03and its application in the resolution of racemic allethrolone(扩展青霉脂肪酶的生产及其在外消旋烯丙醇酮拆分上的应用)[J].J Chem Eng of Chinese Unive(高校化学工程学报),2008,22(1):166-171.
• [9]HAN Ping-fang(韩萍芳),OUYANG Ping-kai(欧阳平凯).Study of enzymatic synthesis of fructose ester in methyl ethyl ketone(甲乙酮溶剂中酶法合成果糖酯的研究)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2007,21(5):905-910.
• [10]Oosterom M W,van Rantwijk F,Sheldan R A.Regioselective acylation of disaccharides in tert-butyl alcohol catalyzed by Candida Antarctica lipase[J].Biotechnology Bioengineering,1996,49(3):328-333.
• [11]Ferrer M,Cruces M A,Bernabe M et al.Lipase-catalyzed regioselective acylation of sucrose in two-solvent mixtures[J].Biotechnology Bioengineering,1995,65(1):10-5.
• [12]David A M,Evgeny N.V.Reversal of regioselectivity in the enzymatic acylation of secondary hydroxyl groups mediated by organic solvents[J].Enzyme Microbial Technology,1997,20(3):225-228.
• [13]Hyun G P,Ho N C.Enzymatic regioselective synthesis of sucrose acrylate esters[J].Biotechnology Letter,2000,22(1):39-42.
• [14]LIU You-yan(刘幽燕),XU Jian-he(许建和),LIU Hong-lai(刘洪来).Effect of reaction parameters on reactivity and enantioselectivity of lipase-catalyzed esterification(反应条件对脂肪酶酯化活性和对映选择性的影响)[J].J Chem Eng of Chinese Univ(高校化学工程学报),1999,13(4):372-376.
• [15]Laane C,Boeren S,Vos K et al.Rules for optimization of biocatalysts in organic solvents[J].Biotechnology Bioengineering,1987,30(1):81-87.
• [16]Verhaegen M,Leonard P.Enzymatic regioselective6-acylation of sucrose[P].EU Patent:1,905,838,A1,2008-02-04.