Lipozyme TL IM催化油酸酯化反应制备1,3-甘油二酯

doi:10.7503/cjcu20141106

摘要/Abstract

摘要：

探究了固定化脂肪酶Lipozyme TL IM催化单甘酯与油酸进行酯化反应制备1,3-甘油二酯的可能性, 考察了溶剂、水活度、反应温度、底物摩尔比以及溶剂用量对甘油二酯产率及脂肪酶1,3-位置选择性的影响. 在优化的实验条件(45 ℃, 1.5 g Lipozyme TL IM, 油酸与单甘酯摩尔比1.5∶1, 6.0 g三氯甲烷, 水活度为0.33)下, 反应6 h时, 甘油二酯产率可达80%, 其中1,3-甘油二酯产率高达92%以上. Lipozyme TL IM循环使用5次后, 甘油二酯产率及脂肪酶选择性无明显下降.

关键词: Lipozyme TL IM, 油酸, 单甘酯, 1, 3-甘油二酯, 位置选择性

Abstract:

The potential of using lipase Lipozyme TL IM-mediated esterification of oleic acid with monoglyceride for 1,3-dioleoylglycerol(DO) preparation was explored and the effects of solvent, water activity, temperature, molar ratio of oleic acid to monostearin(MO) and the solvent quantity on the DO yield and 1,3-positional selectivity of the lipase were investigated systematically. Under the optimum conditions(45 ℃, 1.5 g of Lipozyme TL IM, molar ratio of oleic acid to MO is 1.5∶1, 6.0 g chloroform, and water activity is 0.33), a total DO yield of 80% could be achieved with the content of 1,3-DO over 92%. Lipozyme TL IM showed rather good operational stability in the system and there was no obvious reduction in lipase’s activity and selectivity even after being continually used for 5 batches.

Key words: Lipozyme TL IM, Oleic acid, Monoglyceride, 1, 3-DAG, Positional selectivity

中图分类号:

TrendMD:

王子田, 苏剑晓, 杜伟, 戴玲妹, 刘德华. Lipozyme TL IM催化油酸酯化反应制备1,3-甘油二酯. 高等学校化学学报, 2015, 36(8): 1535.

WANG Zitian, SU Jianxiao, DU Wei, DAI Lingmei, LIU Dehua. Lipozyme TL IM-catalyzed Esterification of Oleic Acid for 1,3-Diacylglycerol Preparation^†. Chem. J. Chinese Universities, 2015, 36(8): 1535.

图/表 7

Table 1 Gradient elution programa

Time/min	V(Dichloromethane)∶V(Acetonitrile-acetic acid)^b
0	0∶100
4	0∶100
12	10∶90
25	10∶90
30	30∶70
35	30∶70
45	80∶20
55	80∶20
60	0∶100
65	0∶100

Fig.1 Effects of solvents on DO yield(A) and positional selectivity(B) during esterificationn(OA)∶n(MO)=1.5∶1, water activity=0.53, 45 ℃, 15%(mass ratio) enzyme to OA, 200 r/min,3 g molecular sieve. a. Acetone; b.t-butanol; c. chloroform; d. n-hexane.

Fig.2 Effects of water activity on DO yield(A) and positional selectivity(B) during esterificationn(OA)∶n(MO)=1.5∶1, 20%(mass fraction) chloroform, 45 ℃, 15%(mass ratio) enzyme to OA, 200 r/min, 3 g molecular sieve. Water activity: a. 0.11; b. 0.33; c. 0.53; d. 0.75; e. 0.97.

Fig.3 Effects of temperature on DO yield(A) and positional selectivity(B) during esterificationn(OA)∶n(MO)=1.5∶1, 20%(mass fraction) chloroform, water activity: 0.33, 15%(mass ratio) enzyme to OA, 200 r/min, 3 g molecular sieve. Temperature/℃: a. 45; b. 55; c. 60.

Fig.4 Effects of molar ratio of oleic acid to monoglycerid on DO yield(A) and positional selectivity(B) during esterification20%(mass fraction) Chloroform, water activity: 0.33, 45 ℃, 15% enzyme, 200 r/min, 3 g molecular sieve.n(OA)∶n(MO): a. 1∶1; b. 1.2∶1; c. 1.5∶1; d. 2∶1.

Fig.5 Effects of solvent quantity on DO yield(A) and positional selectivity(B) during esterificationn(OA)∶n(MO)=1.5∶1, chloroform, water activity: 0.33, 45 ℃, 15% enzyme, 200 r/min, 3 g molecular sieve. Mass fraction of solvent: a. 20%; b. 40%; c. 60%; d. 80%.

Fig.6 Operational yield(A) and selectivity(B) of Lipozyme TL IM during the esterification Reaction conditions: n(OA)∶n(MO)=1.5∶1, 60% chloroform, water activity: 0.33, 45 ℃, 15% enzyme, 200 r/min, 3 g molecular sieve.

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