蒜氨酸的热分解及其机理分析-食品科学.PDF

2016-07-14 蒜氨酸的热分解及其机理分析 胡兴鹏，周华*，杜阳敏，欧仕益，晏日安 （暨南大学理工学院食品科学与工程系） 摘 要：研究了蒜氨酸水溶液的热分解动力学过程，拟合得到了动力学参数：活化能为 80.5 kJ/mol，指前 7 因子为 1.27×10 。采用气质联用检测蒜氨酸水溶液在不同反应温度下的热分解产物，发现随着反应温度的 升高，二烯丙基二硫醚的含量由 91.59 %持续降低至 53.62 %，而二烯丙基三硫醚的含量则先增加后减少， 二烯丙基四硫醚的含量始终呈增加趋势，说明高温可促进硫醚类化合物的断裂和重排。采用质谱和 2 ，4 二 硝基苯肼法分析液相产物，证实产物中含有 S-烯丙基-L-半胱氨酸钠盐和丙酮酸。采用 B3LYP 方法，在 3-21+G(d ，p)基组下，优化反应物与产物的结构，对蒜氨酸的分解过渡态进行理论计算，结合蒜氨酸的分 解动力学以及热分解产物分析后初步推断出：蒜氨酸分解过程中会形成一个五元环的过渡中间体，而后发 生 COPE 消除生成次硫酸与丙酮酸，次硫酸进一步反应，形成二烯丙基二硫醚与二烯丙基三硫醚等一系列 产物。 关键词：蒜氨酸；动力学；大蒜；活化能 Thermal Decomposition of Alliin and Mechanism Analysis HU Xingpeng, ZHOU Hua*, DU Yangmin, OU Shiyi, YAN Rian (Department of Food Science and Engineering, Jinan University, Guangzhou 510632, China) Abstract: The kinetic parameters for thermal decomposition of alliin in H2O were determined. The activation energies and pre-exponential factor were separately 80.5 kJ/mol and 1.27×107. By the analysis of thermal decomposition products with GC-MS, it was found that as the temperature rose, the content of diallyl disulfide continued to decrease to 53.62 % from 91.59 %, the content of diallyl trisulfide was first increased and then decreased while the content of diallyl thioether continued to increase. The changing content of sulfur compounds illustrated that high temperature promoted their fracture and rearrangement. Through applying mass spectrometry and 2, 4 dinitrophenylhydrazine method, S-allyl-L-cysteine sodium and pyruvic acid were detected among the liquid products. At the B3LYP/3-21+G(d ，p) leve1, the structure of the reactants and products were optimized, decomposition transition state of alliin was calcula