Methylation-triggered fractionation of lignocellulosic biomass to afford cellulose-, hemicellulose-, and lignin-based functional polymers via click chemistry
Methylation-triggered fractionation of lignocellulosic biomass to afford cellulose-, hemicellulose-, and lignin-based functional polymers via click chemistry
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DOI：
10.1039/d0gc00451k
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发表时间：
2020-05
期刊：
影响因子：
9.8
通讯作者：
Kentaro Miki;Hiroshi Kamitakahara;A. Yoshinaga;Y. Tobimatsu;T. Takano
中科院分区：
文献类型：
--
作者：
Kentaro Miki;Hiroshi Kamitakahara;A. Yoshinaga;Y. Tobimatsu;T. Takano
本文报道了木质纤维素生物质生物精炼的新概念，其中木质纤维素的衍生化和分馏同时完成。将落叶松锯末在二甲亚砜/四丁基氟化铵中甲基化，然后进行分级分离，得到三种不同的聚合物衍生物级分：甲基化纤维素、木质素和半纤维素。甲基化半纤维素级分的水溶液是两亲性的并且具有与工业生产的甲基纤维素相似的表面活性。叠氮基官能化的甲基化纤维素和木质素级分通过Huisgen 1,3-偶极环加成与过乙酰基炔丙基β-纤维二糖反应，然后去除乙酰基，分别产生甲基纤维素-嵌段-纤维二糖和甲基化木质素-接枝-纤维二糖。二嵌段甲基纤维素类似物甲基纤维素-嵌段-纤维二糖的水溶液在接近人体温度下形成热可逆超分子水凝胶。甲基化半纤维素表现出两亲特性并充当表面活性剂。甲基化木质素接枝纤维二糖形成的纳米颗粒。木质纤维素生物质中的三种主要成分——纤维素、半纤维素和木质素——被成功转化为三种不同的功能材料。
This paper reports a new concept for the biorefinery of lignocellulosic biomass where the derivatisation and fractionation of lignocellulose are accomplished at the same time. Methylation of sawdust of Larix kaempferi (Lamb.) Carriere in dimethyl sulfoxide/tetrabutylammonium fluoride followed by fractionation provided three different polymeric derivative fractions: methylated cellulose, lignin, and hemicellulose. An aqueous solution of the methylated hemicellulose fraction was amphiphilic and possessed surface activity similar to that of industrially-produced methylcellulose. The azido-functionalised methylated cellulose and lignin fractions reacted with peracetyl propargyl β-cellobioside via Huisgen 1,3-dipolar cycloaddition followed by the removal of acetyl groups to yield a methylcellulose-block-cellobiose and methylated lignin-graft-cellobiose, respectively. An aqueous solution of diblock methylcellulose analogue, methylcellulose-block-cellobiose, formed thermoreversible supramolecular hydrogels near human body temperature. Methylated hemicellulose exhibited amphiphilic properties and acted as a surfactant. Methylated lignin-graft-cellobiose formed nanoparticles. Three major components in lignocellulosic biomass, cellulose, hemicellulose, and lignin, were successfully converted into three different functional materials.