联苯型木素模型化合物的漆酶催化合成及其结构表征  

Catalytic Synthesis of Biphenyl Type Lignin Model Compound Catalyzed by Laccace and its Structural Characterization

作　　者：马明玉[1] 谢益民[1,2] 王鹏[2] 季万镇[1] 

机构地区：[1]山东轻工业学院制浆造纸科学与技术教育部重点实验室,山东济南250353 [2]湖北工业大学制浆造纸工程研究所,湖北武汉430068

出　　处：《高校化学工程学报》2012年第3期465-469,共5页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(31070521;30871996);国家'十一五'水污染控制与治理重大专项资助项目(2008ZX07010-008-001)

摘　　要：联苯型(5-5’)木素模型化合物能较好地代表缩合型木素结构单元,对于从分子水平上研究制浆及漂白过程中木素结构的变化具有重要的意义,本研究对该化合物的漆酶法合成进行了探索。首先在漆酶的作用下以香草醛为底物合成了脱氢香草醛,得率为78.3%;再用硼氢化钠将其还原为脱氢香草醇,即为目标产物,得率69.5%。研究了漆酶法合成中漆酶用量、温度、pH值对得率的影响。合成的最佳条件为:漆酶用量16.12 IU g 1,温度40℃,pH值4.5,时间5 h。采用红外光谱、核磁共振波谱分别对两步产物进行了结构表征。实验证明,与传统的辣根过氧化物酶法相比,漆酶法合成标题化合物具有条件温和、专一性强、得率高、易于控制等优点。As a representative substructural unit of condensed lignin, biphenyl type lignin model compound （5-5＇） is an important compound in the study of the lignin structural changes in pulp and bleaching proccesses at molecular level. In this study, its synthetic route with laccace as catalyst was investigated. Firstly, the vanillin was polymerized to form the dehydrodivanillin with laccase as catalyst, and the yield is 78.3%. Then, the carbonyls were reduced to the hydroxyls by NaBH4, and the title compound,, dehydrodi-vanillyl alcohol, was obtained with the yield of 69.5%. The effects of laccase dosage, temperature, and pH on the yield of the dehydrodivanillin were investigated. The optimal conditions were obtained as following： laccase dosage is 16.12 IU per gram of vanillin, reaction temperature is 40~C, pH is 4.5 and reaction time is 5 h. The structures of the obtained compounds were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The results show that, compared with traditional method in which the horseradish peroxidase is used, the proposed new procedure of using laccase is mild, highly specific, high yielding and easy to control. Therefore this method is very suitable for preparation ofbiphenyl type lignin model compound.

关 键 词：木素模型物 联苯结构 漆酶 香草醛 

分 类 号：O636.2[理学—高分子化学] TQ351.013[理学—化学]