多糖存在下异丁香酚的脱氢聚合及LCC的形成

doi:10.3969/j.issn.0253-2417.2016.02.007

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (2): 45-50.doi: 10.3969/j.issn.0253-2417.2016.02.007

多糖存在下异丁香酚的脱氢聚合及LCC的形成

叶哲孜¹, 谢益民^1,2, 吴晨曦¹, 王鹏^1,2, 乐喜¹

1. 湖北工业大学制浆造纸工程学院, 湖北武汉 430068;
2. 湖北工业大学绿色轻工材料湖北省重点实验室, 湖北武汉 430068

收稿日期:2015-10-28 出版日期:2016-04-25 发布日期:2016-04-26
通讯作者: 谢益民,教授,博士生导师,研究领域为木质素化学与制浆造纸技术;E-mail:ppymxie@163.com。 E-mail:ppymxie@163.com
作者简介:叶哲孜(1992—),男,浙江温州人,硕士生,主要从事植物纤维资源化学方面的研究
基金资助:
国家自然科学基金资助项目(31370574,31300494);湖北省教育厅科学研究计划资助项目(Q20131402)

Dehydrogenation Polymerization of Isoeugenol and Formation of Lignin-carbohydrate Complexes with Presence of Polysaccharide

YE Zhe-zi¹, XIE Yi-min^1,2, WU Chen-xi¹, WANG Peng^1,2, LE Xi¹

1. School of Pulp & Paper Engineering, Hubei University of Technology, Wuhan 430068, China;
2. Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan 430068, China

Received:2015-10-28 Online:2016-04-25 Published:2016-04-26

摘要/Abstract

摘要： 以异丁香酚为木质素生物合成的前驱物,采用混合法合成了木质素脱氢聚合物(DHP)和木质素-碳水化合物复合体(LCC),同时采用红外光谱、¹³C NMR 波谱分析聚合产物的结构,探讨了漆酶催化脱氢聚合过程中形成的DHP与多糖(阿拉伯半乳聚糖)的聚合反应机理。结果表明:在漆酶的催化作用下,异丁香酚与阿拉伯半乳聚糖发生聚合形成了DHP与LCC, ¹³C NMR 波谱结果证实DHP中以β-O-4,β-β,β-5和β-1等结构为主,而LCC的 ¹³C NMR 谱图中既有来自木质素的芳香族碳原子的信息,也有来自阿拉伯半乳聚糖的共振信号。

关键词: 木质素, 聚合, 木质素脱氢聚合物, 木质素-碳水化合物复合体, 阿拉伯半乳聚糖

Abstract: Dehydrogenation polymer (DHP) and lignin-carbohydrate complexes (LCC) were prepared using isoeugenol as precursor of lignin biosynthesis by mixing method. The chemical structure of the polymers was analyzed with Fourier transform infrared spectroscopy (FT-IR) and ¹³C NMR spectroscopy. The dehydrogenation polymerization reaction between DHP and polysaccharide (arabinogalactan) using the laccase as catalyst was investigated. The results showed that isoeugenol could be polymerized with arabinogalactan to form DHP and LCC catalyzed by laccase. The analysis of the ¹³C NMR spectra also indicated that the DHP was mainly composed of β-O-4, β-β, β-5 and β-1 subunits. The information from the aromatic carbons of lignin and resonance signals of the arabinogalactan could be found in the ¹³C NMR spectrum of the LCC.

Key words: lignin, polymerization, dehydrogenation polymer, LCC, arabinogalactan

中图分类号:

TQ35

叶哲孜, 谢益民, 吴晨曦, 王鹏, 乐喜. 多糖存在下异丁香酚的脱氢聚合及LCC的形成[J]. 林产化学与工业, 2016, 36(2): 45-50.

YE Zhe-zi, XIE Yi-min, WU Chen-xi, WANG Peng, LE Xi. Dehydrogenation Polymerization of Isoeugenol and Formation of Lignin-carbohydrate Complexes with Presence of Polysaccharide[J]. Chemistry and Industry of Forest Products, 2016, 36(2): 45-50.

参考文献

[1] TIMELL T E.Recent progress in the chemistry of wood hemicelluloses[J].Wood Science and Technology,1967,1(1):45-70.
[2] 杨淑蕙.植物纤维化学[M].3版.北京:中国轻工业出版社,2001. YANG Shu-hui.Lignocellulosic Chemistry[M].3rd ed.Beijing:China Light Industry Press,2001.
[3] ALEKHINA M,ERSHOVA O,EBERT A,et al.Softwood kraft lignin for value-added applications:Fractionation and structural characterization[J].Industrial Crops and Products,2015,66:220-228.
[4] DU Xue-yu,LI Jie-bing,GELLERSTEDT G,et al.Understanding pulp delignification by Laccase-Mediator systems through isolation and characterization of lignin-carbohydrate complexes[J].Biomacromolecules,2013,14(9):3073-3080.
[5] LAWOKO M,HENRIKSSON G,GELLERSTEDT G.Structural differences between the lignin-carbohydrate complexes present in wood and in chemical pulps[J].Biomacromolecules,2005,6(6):3467-3473.
[6] DU Xue-yu,GELLERSTEDT G,LI Jie-bing.Universal fractionation of lignin-carbohydrate complexes (LCCs) from lignocellulosic biomass:An example using spruce wood[J].Plant Journal,2013,74(2):328-338.
[7] MIN Dou-yong,LI Quan-zi,CHIANG V,et al.The influence of lignin-carbohydrate complexes on the cellulase-mediated saccharification.I:Transgenic black cottonwood (western balsam poplar,California poplar) P.trichocarpa including the xylan down-regulated and the lignin down-regulated lines[J].Fuel,2014,119:207-213.
[8] BOLKER H I.A lignin carbohydrate bond as revealed by infra-red spectroscopy[J].Nature,1963,197(486):489-490.
[9] LAM T T,IIYAMA K,STONE B A.Lignin and hydroxycinnamic acids in walls of brown midrib mutants of sorghum,pearl millet and maize stems[J].Journal of the Science of Food and Agriculture,1996,71(2):174-178.
[10] FREUDENBERG K.Lignin:Its constitution and formation from p-hydroxycinnamyl alcohols:Lignin is duplicated by dehydrogenation of these alcohols;intermediates explain formation and structure[J].Science,1965,148(3670):595-600.
[11] FREUDENBERG K,REZNIK H,FUCHS W,et al.Untersuchung über die entstehung des lignins und des holzes[J].Naturwissenschaften,1955,42(2):29-35.
[12] TERASHIMA N,ATALLA R H,RALPH S A,et al.New preparations of lignin polymer models under conditions that approximate cell wall lignification.I.Synthesis of novel lignin polymer models and their structural characterization by ¹³C NMR [J].Holzforschung-International Journal of the Biology,Chemistry,Physics and Technology of Wood,1995,49(6):521-527.
[13] 顾瑞军,谢益民.木素-碳水化合物复合体的形成机理及化学结构的研究(I)——综纤维素存在下DHP的合成[J].造纸科学与技术,2001,20(5):1-6. GU Rui-jun,XIE Yi-min.Studies on lignin and carbohydrate complex of monolignols (I)——Synthesized DHP from holocellulose and coniferins[J].Paper Science & Technology,2001,20(5):1-6.
[14] 孙雪,谢益民,杨海涛,等.半乳糖醛酸-木质素复合体结构的研究[J].林产化学与工业,2012,32(5):24-28. SUN Xue,XIE Yi-min,YANG Hai-tao,et al.Study on the structure of galacturonic acid-dehydrogenation polymer complexs[J].Chemistry and Industry of Forest Products,2012,32(5):24-28.
[15] KELLY G S.Larch arabinogalactan:Clinical relevance of a novel immune-enhancing polysaccharide[J].Alternative Medicine Review :A Journal of Clinical Therapeutic,1999,4(2):96-103.
[16] LOPINA S T,WU G,MERRILL E W,et al.Hepatocyte culture on carbohydrate-modified star polyethylene oxide hydrogels[J].Biomaterials,1996,17(6):559-569.
[17] 李金玲.LCC支架材料的制备及其在人体正常肝细胞L-02培养中的应用[D].武汉:湖北工业大学硕士学位论文,2014. LI Jin-ling.Preparation of lignin-carbohydrate complexes based scaffold and application in culturing human hepatocytes[D].Wuhan:Mastre Degree Thesis of Hubei University of Technology,2014.
[18] 顾瑞军.木素和木素-碳水化合物复合体的化学结构及形成机理[D].广州:华南理工大学硕士学位论文,2002. GU Rui-jun.Study on lignin and lignin-carbohydrate complexes from monolignol[D].Guangzhou:Mastre Degree Thesis of South China University of Technology,2002.
[19] XIE Yi-min,YASUDA S,WU Hong,et al.Analysis of the structure of lignin-carbohydrate complexes by the specific ¹³C tracer method[J].Journal of Wood Science,2000,46(2):130-136.

多糖存在下异丁香酚的脱氢聚合及LCC的形成

Dehydrogenation Polymerization of Isoeugenol and Formation of Lignin-carbohydrate Complexes with Presence of Polysaccharide

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

[1]	张清桐, 运晓静, 颜德鹏, 李明富, 王双飞, 闵斗勇. 太阳光催化木质素制备银纳米颗粒[J]. 林产化学与工业, 2019, 39(4): 35-41.
[2]	孙永昌, 张冰清, 刘力鸣, 刘肖南, 史正军. 木质素基炭材料的制备及其对Cr(VI)的吸附机制研究[J]. 林产化学与工业, 2019, 39(4): 120-128.
[3]	陈超, 王傲, 孙康, 卢辛成, 许伟, 蒋剑春. 生物质原料的Ni催化石墨化研究[J]. 林产化学与工业, 2019, 39(3): 94-100.
[4]	程增会, 张代晖, 王基夫, 王春鹏, 储富祥, 许凤. 分散聚合法制备单分散松香基聚合物微球[J]. 林产化学与工业, 2019, 39(2): 39-45.
[5]	赵存异, 应文俊, 史正军, 杨海艳, 郑志锋, 杨静. 羟丙基化碱木质素的制备及其对纤维素酶水解的影响[J]. 林产化学与工业, 2019, 39(2): 109-114.
[6]	许利娜, 杨小华, 丁海阳, 李梅, 夏建陵. 氧化改性木质素磺酸钠-石墨烯复合量子点的制备及性能[J]. 林产化学与工业, 2019, 39(1): 29-34.
[7]	李继辉, 孙康, 宋曜光, 王傲, 蒋剑春. 木质素基炭纳米片的制备及其电化学性能[J]. 林产化学与工业, 2019, 39(1): 67-74.
[8]	王广彬, 陈家宝, 谷利敏, 王春鹏, 许玉芝. 木质素基RAFT链转移剂的合成及其聚合特性研究[J]. 林产化学与工业, 2018, 38(6): 75-80.
[9]	周方浪, 郑志锋, 杨静, 杨海艳, 邓佳, 史正军. 木质素基酚醛树脂泡沫的制备及性能研究[J]. 林产化学与工业, 2018, 38(6): 103-109.
[10]	贾转, 万广聪, 李明富, 罗斌, 王双飞, 闵斗勇. 蔗渣硫酸盐木质素的分级分离与表征[J]. 林产化学与工业, 2018, 38(5): 107-114.
[11]	杨晓慧, 尚倩倩, 贾普友, 周永红. 酸性熔盐水合物解聚木质素及其改性酚醛泡沫的性能研究[J]. 林产化学与工业, 2018, 38(5): 115-121.
[12]	冯年捷, 汪继明, 谢益民, 杨鑫, 刘达岸. 杨木预水解液中木质素质量浓度的P因子调控作用[J]. 林产化学与工业, 2018, 38(4): 35-40.
[13]	叶结旺, 蒋剑春, 金贞福, 章卫钢, 张晓春. 超临界甲醇中复合金属氧化物催化木质素的解聚[J]. 林产化学与工业, 2018, 38(4): 52-60.
[14]	张海芸, 贺亮, 李琴, 杨波, 杨光. 超声波法辅助定向降解阿拉伯半乳聚糖的研究[J]. 林产化学与工业, 2018, 38(4): 61-68.
[15]	杨昇, 王钧, 李改云, 范东斌. 镁离子催化合成木质素-酚醛树脂的结构与固化特性[J]. 林产化学与工业, 2018, 38(4): 74-78.