水热协同低共熔溶剂预处理促进木质纤维拆解与利用OA
Hydrothermal-assisted Deep Eutectic Solvent Pretreatment for Efficient Poplar Disassembly and Utilization
以杨木片(PL)为研究对象,分别进行双螺杆挤压(E)、水热(P)、低共熔溶剂(DES)单一预处理以及多步协同预处理(E-DES/P-DES/P-E-DES),其中,DES体系由氯化胆碱、对甲基苯磺酸、1,4-丁二醇组成,通过扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、核磁共振(NMR)等手段,探究了不同预处理体系对木质纤维组分拆解及底物和木质素理化结构的影响,并进一步评价了底物纤维素的酶水解性能和回收木质素的抗氧化性能.研究结果表明:多步协同预处理大幅度促进了木质纤维的高效拆解与利用,其中,水热耦合挤压协同DES(PL-P-E-DES)预处理物料的半纤维素、木质素脱除率分别达88.54%和83.46%,葡萄糖、木糖得率分别为99.69%和78.66%,低聚木糖得率达45.71%.SEM分析结果显示:多步协同预处理后的底物纤维呈现明显卷曲及孔洞结构,碎片化程度严重,有利于纤维素酶的作用.XRD分析表明:所有预处理都没有破坏纤维素天然Ⅰ型晶型结构,随着半纤维素与木质素的脱除,结晶度有所提升,其中PL-P-E-DES的结晶度(CrI)达70.38%.FT-IR分析显示:多步协同预处理底物的半纤维素及木质素的相关特征峰信号明显减弱.凝胶渗透色谱(GPC)结果显示:PL-DES木质素(PL-DES-L)的重均相对分子质量(Mw)最小为1 587.NMR结果显示:经多步协同预处理后,尽管木质素中紫丁香基(S)和愈创木基(G)单元的缩聚信号有所增加,但其酚羟基含量进一步提升,其中PL-P-E-DES预处理后回收得到的木质素(PL-P-E-DES-L)总酚羟基达2.81 mmol/g,而PL-E-DES-L对DPPH自由基的半数抑制质量浓度(IC50值)最低,仅为56.16 mg/L,略高于阳性对照Vc(35.36 mg/L).因此,采用多步协同预处理不仅大幅度提升了木质纤维的拆解效率,同时可促进纤维素、半纤维素和木质素分别向单糖、低聚糖和抗氧化产品的转化应用.
Taking poplar(PL)as the research object,the twin-screw extrusion(E),hydrothermal(P),deep eutectic solvent(DES)pretreatment,and multi-step synergistic pretreatment(E-DES/P-DES/P-E-DES)were conducted,respectively.The DES system was composed of choline chloride/p-toluenesulfonic acid/1,4-butanediol.The effects of different pretreatment systems on the fractionation of PL,the changes in the physicochemical structure characteristics of pretreated substrates/lignin,the enzymatic hydrolysis performance of cellulose,and the antioxidant performance of recycled lignin were investigated by scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),and nuclear magnetic resonance(NMR).The results showed that the multi-step synergistic pretreatment significantly promoted the efficient fractionation and utilization of PL.The removal of hemicellulose and lignin of PL-P-E-DES residues reached 88.54%and 83.46%,as well as the yields of glucose and xylose(99.69%and 78.66%),and the yield of xylooligosaccharides(45.71%),respectively.The SEM images showed that the PL-P-E-DES residues presented obvious curling and pore structures that was much severe than others.The XRD analysis indicated that the natural type Ⅰ crystalline of cellulose remained in all systems,and the crystallinity(CrI)of PL-P-E-DES residues reached 70.38%.The FT-IR results showed that the signals of hemicellulose and lignin of PL-P-E-DES residues were significantly weakened.The gel permeation chromatography(GPC)results showed that the weight-average molecular weight(Mw)of PL-DES lignin(PL-DES-L)was 1 587.The NMR results showed that the condensation signals of the syringyl(S)and the guaiacyl(G)units in lignin increased,while the content of phenolic hydroxyl groups increased simultaneously.The total phenolic hydroxyl content of the lignin recovered after PL-P-E-DES reached 2.81 mnmol/g.The lowest IC50 value of PL-E-DES-L against DPPH radicals was only 56.16 mg/L,slightly higher than the positive control vitamin C(Vc,35.36 mg/L).Therefore,the multi-step synergistic pretreatment not only improved the fractionation efficiency of PL but also promoted the conversion and application of cellulose,hemicellulose,and lignin to monosaccharides,oligosaccharides,and antioxidant products,respectively.
费宇彬;张少杰;詹云妮;周雪莲;黄晨;张军华
森林食物资源挖掘与利用全国重点实验室||南京林业大学,江苏南京 210037森林食物资源挖掘与利用全国重点实验室||南京林业大学,江苏南京 210037森林食物资源挖掘与利用全国重点实验室||中国林业科学研究院 林产化学工业研究所,江苏南京 210042||江苏省生物质能源与材料重点实验室||国家林业和草原局林产化学工程重点实验室,江苏南京 210042||林产化学与材料国际创新高地||江苏省林业资源高效加工利用协同创新中心,江苏南京 210042森林食物资源挖掘与利用全国重点实验室||中国林业科学研究院 林产化学工业研究所,江苏南京 210042||江苏省生物质能源与材料重点实验室||国家林业和草原局林产化学工程重点实验室,江苏南京 210042||林产化学与材料国际创新高地||江苏省林业资源高效加工利用协同创新中心,江苏南京 210042森林食物资源挖掘与利用全国重点实验室||中国林业科学研究院 林产化学工业研究所,江苏南京 210042||江苏省生物质能源与材料重点实验室||国家林业和草原局林产化学工程重点实验室,江苏南京 210042||林产化学与材料国际创新高地||江苏省林业资源高效加工利用协同创新中心,江苏南京 210042森林食物资源挖掘与利用全国重点实验室||南京林业大学,江苏南京 210037
化学化工
杨木低共熔溶剂酶水解木质素抗氧化活性
poplar wooddeep eutectic solventsenzymatic hydrolysisligninantioxidant activity
《林产化学与工业》 2026 (3)
71-81,11
江苏省自然科学基金资助项目(BK20230405)国家自然科学基金资助项目(32301546)中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2024QF021)
评论