甘蔗渣木质素的结构及其对纤维素酶解的影响

doi:10.12034/j.issn.1009-606X.216376

过程工程学报 ›› 2017, Vol. 17 ›› Issue (5): 1002-1010.DOI: 10.12034/j.issn.1009-606X.216376

甘蔗渣木质素的结构及其对纤维素酶解的影响

崔兴凯¹，陈可¹，赵雪冰^1,2*，刘德华^1,2

1. 清华大学化学工程系，北京 100084；2. 东莞深圳清华大学研究院创新中心，广东东莞 523808

收稿日期:2016-12-16 修回日期:2017-02-26 出版日期:2017-10-20 发布日期:2017-10-10
通讯作者: 赵雪冰 zhaoxb@mail.tsinghua.edu.cn
基金资助:
东莞市社会科技发展项目;国家自然科学基金

Structures of Several Lignins Isolated from Sugarcane Bagasse and Their Effects on Enzymatic Hydrolysis of Cellulose

Xingkai CUI¹, Ke CHEN¹, Xuebing ZHAO^1,2*, Dehua LIU^1,2

1. Department of Chemical Engineering, Tsinghua University, Beijing 100084, China;
2. Tsinghua Innovation Center in Dongguan, Dongguan, Guangdong 523808, China

Received:2016-12-16 Revised:2017-02-26 Online:2017-10-20 Published:2017-10-10

摘要/Abstract

摘要： 对甘蔗渣有机酸预处理、碱处理和氧化预处理过程中得到的5种木质素[乙酸木质素(AAL)、Acetosolv木质素(AsL)、Milox木质素(ML)、过氧乙酸木质素(PAAL)和碱木质素(AL)]进行了结构表征，通过元素、官能团和化学组分分析、分子量测定及光谱特性分析，验证了甘蔗渣木质素为典型的H?S?G型木质素，除PAAL外其余4种木质素具有类似的结构特性，而PAAL由于过氧乙酸的氧化作用使木质素结构显著变化，从而具有较低的分子量、较高的酸溶木质素和羰基含量. 将5种木质素添加至纤维素酶催化水解体系中，纤维素转化率均有不同程度降低，PAAL的抑制作用最强. 结合添加木质素单体模型化合物的实验表明，酚羟基是木质素抑制纤维素酶作用的关键官能团，对羟苯基中酚羟基的抑制作用比愈创木基和紫丁香基更强. 木质素对纤维素酶解的抑制作用不只是通过无效吸附纤维素酶实现，小分子的酚类降解产物也会降低纤维素的酶解转化效率.

关键词: 分离木质素, 结构特性, 表征, 纤维素酶解, 抑制作用, 酚羟基

Abstract: Five types of lignin by-products were isolated from sugarcane bagasse by organic acid, alkaline and oxidative pretreatments, respectively, namely acetic acid lignin (AAL), acetosolve lignin (AsL), milox lignin (ML), peracetic acid lignin (PAAL) and alkaline lignin (AL). Structure characterizations were performed by analysis of elements, functional groups, chemical components, molecular weights and spectra. The results confirmed that sugarcane bagasse lignin was a typical H?G?S lignin. Except PAAL lignin, other four isolated lignins showed similar structures. PAAL lignin had lower molecular weight, higher carbonyl and acid-soluble lignin contents. Inhibition of cellulose conversion were observed when addition of these five lignins individually into the system of enzymatic hydrolysis of cellulose, and PAAL showed the highest inhibitive action. Further experiments by addition of lignin model compounds in to the system indicated that phenolic hydroxyl group (Ph-OH) was a key functional group mediating the inhibition of cellulose conversion by lignin, and the inhibitive effect of Ph-OH in p-hydroxyphenyl (H) was stronger than those in guaiacyl and syringyl structures. The finding of this work demonstrated that the inhibitive action of lignin to enzymatic hydrolysis of cellulose was not only attributed to non-productive adsorption of enzymes, but also to the inhibition of small-molecule phenol compounds yielded by deplymerization of lignin during the pretreatment.

Key words: Isolated lignin, Structural features, Characterization, Enzymatic hydrolysis of cellulose, Inhibitive action, Phenolic hydroxyl group

崔兴凯陈可赵雪冰刘德华. 甘蔗渣木质素的结构及其对纤维素酶解的影响[J]. 过程工程学报, 2017, 17(5): 1002-1010.

Xingkai CUI Ke CHEN Xuebing ZHAO Dehua LIU. Structures of Several Lignins Isolated from Sugarcane Bagasse and Their Effects on Enzymatic Hydrolysis of Cellulose[J]. Chin. J. Process Eng., 2017, 17(5): 1002-1010.

参考文献

[1]Calvo‐Flores F G, Dobado J A.Lignin as Renewable Raw Material[J].ChemSusChem, 2010, 3(11):1227-1235 [2]Galkin M V, Samec J S M.Lignin Valorization through Catalytic Lignocellulose Fractionation: A Fundamental Platform for the Future Biorefinery[J].ChemSusChem, 2016, 9(36):1544-1558 [3]Zhao X B, Zhang L H, Liu D H.Biomass recalcitrancePart I: the Chemical Compositions and Physical Structures Affecting the Enzymatic Hydrolysis of Lignocellulose[J].Biofuels, Bioproducts and Biorefining, 2012, 6(4):465-482 [4]Zhao X B, Zhang L H, Liu D H.Biomass recalcitrancePart II: Fundamentals of Different Pre-Treatments to Increase the Enzymatic Digestibility of Lignocellulose[J].Biofuels, Bioproducts and Biorefining, 2012, 6(5):561-579 [5]Ding S Y, Liu Y S, Zeng Y, et al.How does Plant Cell Wall Nanoscale Architecture Correlate with Enzymatic Digestibility?[J].Science, 2012, 338(6110):1055-1060 [6]Zeng Y, Zhao S, Yang S, et al.Lignin Plays a Negative Role in the Biochemical Process for Producing Lignocellulosic Biofuels[J].Current Opinion in Biotechnology, 2014, 27(6):38-45 [7]周妍, 赵雪冰, 刘德华.非离子型表面活性剂对木质纤维素酶催化水解的影响及机理[J].化学进展, 2015, 27(11):1555-1565 [8]Pan X.Role of Functional Groups in Lignin Inhibition of Enzymatic Hydrolysis of Cellulose to Glucose[J].Journal of Biobased Materials and Bioenergy, 2008, 2(1):25-32 [9] Nakagame S, Chandra R P, Saddler J N, et al.The Influence of Lignin on the Enzymatic Hydrolysis of Pretreated Biomass Substrates[J]. Sustainable Production of Fuels, Chemicals, and Fibers from Forest Biomass, 2011, 1067(1): 145-167. [10]Fritz C, Ferrer A, Salas C, et al.Interactions between Cellulolytic Enzymes with Native,Autohydrolysis,and Technical Lignins and the Effect of a Polysorbate Amphiphile in Reducing Nonproductive Binding[J].Biomacromolecules, 2015, 16(12):3878-3888 [11]周海峰, 杨东杰, 伍晓蕾, 等.漆酶改性木质素磺酸钠的结构表征及吸附特征[J].高等学校化学学报, 2013, 34(1):218-224 [12]Pan X J, Sano Y.Atmospheric Acetic Acid Pulping of Rice Straw IV: Physico-Chemical Characterization of Acetic Acid Lignins from Rice Straw and WoodsPart 1. Physical Characteristics[J].Holzforschung, 1999, 53(5):511-518 [13]Kumar R, Wyman C E.Access of Cellulase to Cellulose and Lignin for poplar Solids Produced by Leading Pretreatment Technologies[J].Biotechnology Progress, 2009, 25(3):807-819 [14]Sewalt V J H, Glasser W G, Beauchemin K A.Lignin Impact on Fiber Degradation3. Reversal of Inhibition of Enzymatic Hydrolysis by Chemical Modification of Lignin And By Additives[J].Journal of Agricultural and Food Chemistry, 1997, 45(5):1823-1828 [15] Sluiter A, Hames B, Ruiz R, et al.Determination of Structural Carbohydrates and Lignin in Biomass[J]. Laboratory Analytical Procedure, 2008, 1(1):1617-1617. [16]Zhao X B, Liu D H.Chemical and Thermal Characteristics of Lignins Isolated from Siam Weed Stem by Acetic Acid and Formic Acid Delignification[J].Industrial Crops and Products, 2010, 32(3):284-291 [17]Zhang T, Zhou Y, Liu D, et al.Qualitative Analysis of Products Formed During the Acid Catalyzed Liquefaction of Bagasse in Ethylene Glycol[J].Bioresource Technology, 2007, 98(7):1454-1459 [18] 石淑兰，何福望.制浆造纸分析与检测[M]. 北京：化学工业出版社, 2004: 74-77. Shi S L, He F W. Analysis and Detection of Pulping and Papermaking[M]. Beijing: Chinese Light Industry Press, 2003: 74-77 [19] 刘贵生.木素官能团分析[M]. 哈尔滨: 东北林业大学出版社, 1996: 140-146 Liu G S. Functional Group Analysis of Lignin[M]. Haerbing: Northeast Forestry University Press, 1996: 140-146 [20]Pan X J, Sano Y.Atmospheric Acetic Acid Pulping of Rice Straw IV: Physico-Chemical Characterization of Acetic Acid Lignins from Rice Straw and WoodsPart 2. Chemical Structures[J].Holzforschung, 1999, 53(6):590-596 [21]Zhang Y H P.Reviving the Carbohydrate Economy via Multi-Product Lignocellulose Biorefineries[J].Journal of Industrial Microbiology & Biotechnology, 2008, 35(5):367-375 [22]Jahan M S, Mun S P.Characteristics of Dioxane Lignins Isolated at Different Ages of Nalita Wood (Trema Orientalis)[J].Journal of Wood Chemistry and Technology, 2007, 27(2):83-98 [23]Gierer J.The Chemistry of Delignification-A General Concept-Part II[J].Holzforschung-International Journal of the Biology, Chemistry, Physics and Technology of Wood, 1982, 36(2):55-64 [24]Shukry N, Fadel S M, Agblevor F A, et al.Some Physical Properties of Acetosolv Lignins from Bagasse[J].Journal of applied polymer science, 2008, 109(1):434-444 [25] 蒋挺大, 木质素[M].第一版，北京：化学工业出版社, 2001:16-19 Jiang T. D., Lignin[M]. Second Edition, Beijing: Chemical Industry Press, 2001: 16-19 [26]Qin L, Li W C, Liu L, et al.Inhibition of Lignin-Derived Phenolic Compounds to Cellulase[J].Biotechnology for biofuels, 2016, 9(1):1-10 [27]Kim Y, Ximenes E, Mosier N S, et al.Soluble InhibitorsDeactivators of Cellulase Enzymes from Lignocellulosic Biomass[J].Enzyme and Microbial Technology, 2011, 48(4):408-415 [28]Lou H, Zhu J Y, Lan T Q, et al.pH‐Induced Lignin Surface Modification to Reduce Nonspecific Cellulase Binding and Enhance Enzymatic Saccharification of Lignocelluloses[J].ChemSusChem, 2013, 6(5):919-927

甘蔗渣木质素的结构及其对纤维素酶解的影响

Structures of Several Lignins Isolated from Sugarcane Bagasse and Their Effects on Enzymatic Hydrolysis of Cellulose

PDF

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

[1]	谢冰琪周才金黄小婷马向东张吉松. 微分散法连续制备微气泡的研究进展[J]. 过程工程学报, 2021, 21(8): 865-876.
[2]	施帅何廷树李慧. Ca²⁺和Mg²⁺对辉钼矿可浮性的影响对比[J]. 过程工程学报, 2021, 21(2): 153-159.
[3]	薛岗丁磊高阳钟梅英. 表面印迹耦合溶胶-凝胶法制备4-硝基酚印迹材料及性能表征[J]. 过程工程学报, 2020, 20(4): 440-448.
[4]	杨兴卫杨茂立安海杨兴卫张少朋梁志松. 玉米芯炭质燃料的理化性能及热解过程分析[J]. 过程工程学报, 2018, 18(4): 851-857.
[5]	马培勇武晋州张贤文邢献军郭晓薇. K2CO3-锯末干混合制备成型活性炭[J]. 过程工程学报, 2018, 18(1): 159-164.
[6]	宋翠葛佳李秀男李强陈超王鹏马光辉. 一种可进行梯度调节的流动相控制系统在生物大分子表征中的应用[J]. 过程工程学报, 2018, 18(1): 171-176.
[7]	赵凯孙苒荻朱高远张红玲张炳烛徐红彬张懿. 硼砂与尿素在N2气氛下合成六方氮化硼的工艺[J]. 过程工程学报, 2016, 16(5): 870-875.
[8]	郑昭韩云龙殷传慧李朋飞张浩. 铁矿石尾矿渣制备催化剂催化氧化甲醛[J]. 过程工程学报, 2015, 15(5): 871-875.
[9]	吴锦绣李梅柳召刚胡艳宏王觅堂. 水溶性壳聚糖稀土配合物的合成、表征及其抑菌性研究[J]. , 2012, 12(6): 1038-1042.
[10]	王超胡建杭王华刘慧利. 预煅烧处理对铜渣特性及生物质气化催化活性的影响[J]. , 2011, 11(5): 806-811.
[11]	孙晓英赵雪冰杜伟刘德华. 微量硫酸催化环氧大豆油的合成[J]. , 2010, 10(4): 714-719.
[12]	周君曹妍李会泉张懿. 新型含氟季铵盐(C4H9)4NAlF4的合成、表征及电化学性质[J]. , 2010, 10(2): 390-394.
[13]	谭义秋黄祖强农克良. 高取代度木薯羧甲基淀粉的合成及表征[J]. , 2010, 10(1): 173-178.
[14]	吴新民刘磊宋永吉. 分子筛负载型加氢脱硫催化剂的制备及其性能[J]. , 2009, 9(1): 165-170.
[15]	姚忠孙蓓蓓李霜何冰芳. 高强度耐有机溶剂蛋白酶的纯化及性质[J]. , 2008, 8(6): 1195-1199.