波谱学杂志 >

2021 , Vol. 38 >Issue 2: 277 - 290

DOI: https://doi.org/10.11938/cjmr20202850

综述评论

核磁共振技术在生物质转化中的应用

  • 陈晓丽 ,
  • 吕微 ,
  • 苏秋成 ,
  • 付娟 ,
  • 莫家媚 ,
  • 刘琪英
展开
  • 1. 中国科学院广州能源研究所, 广东 广州 510640
    2. 中国科学院可再生能源重点实验室, 广东 广州 510640
    3. 广东省新能源和可再生能源研究开发与应用重点实验室, 广东 广州 510640

收稿日期: 2020-09-02

  网络出版日期: 2020-11-04

基金资助

国家重点研发计划资助项目(2019YFC1905303);国家自然科学基金资助项目(51976220)

收起

Conversion of Lignocellulose Studied by Nuclear Magnetic Resonance

  • Xiao-li CHEN ,
  • Wei LV ,
  • Qiu-cheng SU ,
  • Juan FU ,
  • Jia-mei MO ,
  • Qi-ying LIU
Expand
  • 1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
    2. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China
    3. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Received date: 2020-09-02

  Online published: 2020-11-04

Fold

摘要

生物质结构的精确分析研究有利于其各个组分的转化利用，而核磁共振（NMR）技术是生物质解聚及结构演变分析中重要的表征技术.本文主要介绍了1H NMR、13C NMR、31P NMR和2D HSQC四种NMR技术在生物质结构、产物定性和定量分析、反应路径和催化解聚机理探究中的应用，然后讨论了NMR技术应用于生物质研究中存在的主要问题，并进行了展望.

关键词： 生物质; 1H NMR; 13C NMR; 31P NMR; 2D HSQC

本文引用格式

陈晓丽 , 吕微 , 苏秋成 , 付娟 , 莫家媚 , 刘琪英 . 核磁共振技术在生物质转化中的应用[J]. 波谱学杂志, 2021 , 38(2) : 277 -290 . DOI: 10.11938/cjmr20202850

Abstract

Nuclear magnetic resonance (NMR) is an important characterization method for the depolymerization of lignocellulosic biomass and its structure evolution analysis. The accurate NMR analysis facilitates the selective transformation of different biomass components. In this review, the principles of NMR are presented. Four types of NMR experimental methods, including 1H NMR, 13C NMR, 31P NMR and 2D HSQC, and their applications in the structure elucidation, qualitative and quantitative analysis of products, reaction path and catalytic depolymerization mechanism of lignocellulose are mainly introduced. Finally, the main problems and perspectives of NMR method in valorization of lignocellulosic biomass are discussed.

Key words： lignocellulose; 1H NMR; 13C NMR; 31P NMR; 2D HSQC

参考文献

1 RAGAUSKAS A J , BECKHAM G T , BIDDY M J , et al. Lignin valorization: Improving lignin processing in the biorefinery[J]. Science, 2014, 344 (6185): 1246843.
2 LI C Z , ZHAO X C , WANG A Q , et al. Catalytic transformation of lignin for the production of chemicals and fuels[J]. Chem Rev, 2015, 115 (21): 11559- 11624.
3 LU Y , WEI X Y , ZONG Z M , et al. Structural investigation and application of lignins[J]. Progress in Chemistry, 2013, 25, 839- 858.
3 路瑶, 魏贤勇, 宗志敏, 等. 木质素的结构研究与应用[J]. 化学进展, 2013, 25, 839- 858.
4 SHU R Y , XU Y , ZHANG Q , et al. Progress in catalytic depolymerization of lignin[J]. Journal of Chemical Industry and Engineering, 2016, 67 (11): 4524- 4532.
4 舒日洋, 徐莹, 张琦, 等. 木质素催化解聚的研究进展[J]. 化工学报, 2016, 67 (11): 4524- 4532.
5 CHEN Q , WANG Y , ZHAI H M . Pyrolysis characteristics of coconut shell based on TG-FTIR and Py-GC-MS analysis[J]. Chemistry and Industry of Forest Products, 2020, 40 (1): 45- 52.
5 陈强, 王艳, 翟华敏. 基于TG-FTIR和Py-GC-MS分析的椰壳热解特性研究[J]. 林产化学与工业, 2020, 40 (1): 45- 52.
6 GUO J B , TAO Z Y , LUO X G . Analysis of bamboo lignin with FTIR and XPS[J]. Acta Chim Sinica, 2005, 63 (16): 1536- 1540.
6 郭京波, 陶宗娅, 罗学刚. 竹木质素的红外光谱与X射线光电子能谱分析[J]. 化学学报, 2005, 63 (16): 1536- 1540.
7 AMUL B , MUTHU S , RAJA M , et al. Molecular structure, spectroscopic (FT-IR, FT-Raman, NMR, UV-VIS), chemical reactivity and biological examinations of ketorolac[J]. J Mol Struct, 2020, 1210, 128040.
8 WU X F , SU X J , CHEN L , et al. Research progress in analyzing methods of lignin structure[J]. Renewable Energy Resources, 2015, 33 (2): 267- 274.
8 武小芬, 苏小军, 陈亮, 等. 木质素结构分析方法研究进展[J]. 可再生能源, 2015, 33 (2): 267- 274.
9 WEI D , LI T , ZOU X H , et al. Progress in application of nuclear magnetic resonance in plant research[J]. Journal of Fujian Forestry Science and Technology, 2018, 45 (04): 116- 121.
9 韦丹, 李涛, 邹显花, 等. 核磁共振技术在植物研究中的应用进展[J]. 福建林业科技, 2018, 45 (04): 116- 121.
10 张汉辉, 郑威, 陈义平. 波谱学原理及应用[M]. 北京: 化学工业出版社, 2016.
11 HUANG Y , DUAN Y J , QIU S , et al. Lignin-first biorefinery: A reusable catalyst for lignin depolymerization and application of lignin oil to jet fuel aromatics and polyurethane feedstock[J]. Sustain Energ Fuels, 2018, 2 (3): 637- 647.
12 CHENG H N , NEISS T G . Solution NMR spectroscopy of food polysaccharides[J]. Polym Rev, 2012, 52 (2): 81- 114.
13 LV W , LIAO Y H , ZHU Y T , et al. The effect of Ru/C and MgCl2 on the cleavage of interand intra-molecular linkages during cornstalk hydrolysis residue valorization[J]. Cellulose, 2020, 27 (2): 799- 823.
14 ZHANG X Q , CHEN M J , WANG H H , et al. Characterization of xylan-graft-polycaprolactone copolymers prepared in ionic liquid[J]. Ind Eng Chem Res, 2015, 54, 6282- 6290.
15 TAN J , LIU Q Y , CHEN L G , et al. Efficient production of ethyl levulinate from cassava over Al2 (SO4)3catalyst in ethanol-water system[J]. J Energy Chem, 2017, 26, 115- 130.
16 ZHU C H , WANG H Y , CAI C L , et al. Tandem conversion of fructose to 2, 5-dimethylfuran with the aid of ionic liquids[J]. ACS Sustainable Chem Eng, 2019, 7 (19): 16026- 16040.
17 DU X N , WANG W , LEI W . The prospect application and development of stable isotope labeling reagent[J]. Chemical Reagent, 2015, 37 (9): 769- 775.
17 杜晓宁, 王伟, 雷雯. 稳定性同位素标记试剂的研发及应用展望[J]. 化学试剂, 2015, 37 (9): 769- 775.
18 CHOUDHARY V , PINAR A B , LOBO R F , et al. Comparison of homogeneous and heterogeneous catalysts for glucose-to-fructose isomerization in aqueous media[J]. Chemsuschem, 2013, 6 (12): 2369- 2376.
19 SHIN S J , CHO N S . Conversion factors for carbohydrate analysis by hydrolysis and 1H-NMR spectroscopy[J]. Cellulose, 2008, 15 (2): 255- 260.
20 ZHENG Q K , DONG Q S . Structural analysis of lignins from three different sourses[J]. Journal of Wei Fang University, 2011, 11 (6): 58- 61.
20 郑秋闿, 董庆顺. 三种不同来源木质素的结构分析[J]. 潍坊学院学报, 2011, 11 (6): 58- 61.
21 YIN T P , LUO Z H , CAI L , et al. Research progress and NMR spectral features of natural C19-diterpenoid alkaloids[J]. Chinese J Magn Reson, 2019, 36 (1): 113- 126.
21 尹田鹏, 罗智慧, 蔡乐, 等. 天然C19-二萜生物碱的研究进展及其核磁共振波谱特征[J]. 波谱学杂志, 2019, 36 (1): 113- 126.
22 XU F , ZHAO H , ZHAO G J , et al. Chemical characteristic of organosolv lignins from wheat straw[J]. Transactions of China Pulp and Paper, 2007, 22 (4): 23- 27.
22 许凤, 赵红, 赵广杰, 等. 有机溶剂法麦草木质素的化学特性研究[J]. 中国造纸学报, 2007, 22 (4): 23- 27.
23 ZHANG T , BAI F D , LI Z , et al. Extraction methods of lignin from fermentation residue[J]. Chemical Research and Application, 2018, 30 (6): 901- 906.
23 张通, 白富栋, 李政, 等. 酶解秸秆残渣中木质素提取方法的研究[J]. 化学研究与应用, 2018, 30 (6): 901- 906.
24 LIU Q Y , WANG H Y , XIN H , et al. Selective cellulose hydrogenolysis to ethanol using Ni@C combined with phosphoric acid catalysts[J]. ChemSusChem, 2019, 12 (17): 3977- 3987.
25 HALLERAKER H V , GHOREISHI S , BARTH T . Investigating reaction pathways for formic acid and lignin at HTL conditions using 13C-labeled formic acid and 13C NMR[J]. Results in Chemistry, 2020, 2, 100019.
26 XIE Y M , JIANG C , LIU Y C . Study on formation mechanism of lignin dehydrogenation polymer-glucose complex[J]. China Pulp and Paper, 2020, 39 (4): 27- 33.
26 谢益民, 蒋晨, 刘雁超. 木素脱氢聚合物-葡萄糖复合体形成机理的研究[J]. 中国造纸, 2020, 39 (4): 27- 33.
27 YOSHIHIROSANO , TAKAOKISHIMOTO . Delignification mechanism during high-boiling solvent pulping.Ⅴ. Reaction of nonphenolic β-O-4 model compounds in the presence and absence of glucose[J]. J Wood Chem Technol, 2003, 23 (3-4): 279- 292.
28 WEN J L , SUN S L , XUE B L , et al. Quantitative structures and thermal properties of birch lignins after ionic liquid pretreatment[J]. J Agr Food Chem, 2013, 61 (3): 635- 645.
29 LIU C F , SUN R C , YE J . Application of CP/MAS 13C-NMR spectroscopy in the study of lignocellulosic materials[J]. Transactions of China Pulp and Paper, 2005, 20 (2): 184- 188.
29 刘传富, 孙润仓, 叶君. 固体核磁CP/MAS 13C-NMR在植物纤维原料研究中的应用[J]. 中国造纸学报, 2005, 20 (2): 184- 188.
30 LIANG L X , DENG F , HOU G J , et al. Quantitative cross polarization magic-angle spinning NMR spectroscopy in solids[J]. Chinese J Magn Reson, 2020, 37 (1): 1- 15.
30 梁力鑫, 邓风, 侯广进, 等. 固体核磁共振魔角旋转条件下的定量交叉极化技术(英文)[J]. 波谱学杂志, 2020, 37 (1): 1- 15.
31 CHEN L , ZHANG Q , MENG X S , et al. CP/MAS 13C NMR and SEM characterization of corn stover lignin degradation[J]. Chemistry and Bioengineering, 2013, 30 (6): 75- 78.
31 陈琳, 张全, 孟雪松, 等. 玉米秸秆木质素降解过程的CP/MAS 13CNMR和SEM表征[J]. 化学与生物工程, 2013, 30 (6): 75- 78.
32 EVSTIGNYEV E I , MAZUR A S , KALUGINA A V , et al. Solid-state 13C CP/MAS NMR for Alkyl-O-Aryl bond determination in lignin preparations[J]. J Wood Chem Technol, 2018, 38 (2): 137- 148.
33 CHENG H N , BISWAS A . Chemical modification of cotton-based natural materials: Products from carboxymethylation[J]. Carbohyd Polym, 2011, 84 (3): 1004- 1010.
34 YU Q , ZHU Y P , BIAN S X , et al. Structural characteristics of corncob and eucalyptus contributed to sugar release during hydrothermal pretreatment and enzymatic hydrolysis[J]. Cellulose, 2017, 24, 4899- 4909.
35 CADE-MENUN , BARBARA J . Improved peak identification in 31P-NMR spectra of environmental samples with a standardized method and peak library[J]. Geoderma, 2015, 257-258, 102- 114.
36 MENG X Z , CRESTINI C , BEN H X , et al. Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy[J]. Nat Protoc, 2019, 14, 2627- 2647.
37 WEN J L , YUAN T Q , SUN S L , et al. Understanding the chemical transformations of lignin during ionic liquid pretreatment[J]. Green Chem, 2013, 16 (1): 181- 190.
38 ARGYROPOULOS D S , Li H Y , GASPAR A R , et al. Quantitative 31P NMR detection of oxygen-centered and carbon-centered radical species[J]. Bioorg Med Chem, 2006, 14 (12): 4017- 4028.
39 CHEN T Y , WANG B , WU Y Y , et al. Structural variations of lignin macromolecule from different growth years of triploid of Populus tomentosa Carr.[J]. Int J Biol Macromol, 2017, 101, 747- 757.
40 LAGERQUIST L , RAHKILA J , EKLUND P . Utilization of 31P PULCON for quantitative hydroxyl group determination in lignin by NMR spectroscopy[J]. ACS Sustainable Chem Eng, 2019, 7 (9): 9002- 9006.
41 XIAO H H , LV J , MOK D , et al. NMR applications for botanical mixtures: The use of HSQC data to determine lignan content in sambucus williamsii[J]. J Nat Prod, 2019, 82 (7): 1733- 1740.
42 ZHAO C K , HUANG J T , YANG L J , et al. Revealing structural differences between alkaline and kraft lignins by HSQC NMR[J]. Ind Eng Chem Res, 2019, 58, 5707- 5714.
43 WEN J L , CHEN T Y , SUN R C . Research progress on separation and structural analysis of lignin in lignocellulosic biomass[J]. Journal of Forestry Engineering, 2017, 2 (5): 76- 84.
43 文甲龙, 陈天影, 孙润仓. 生物质木质素分离和结构研究方法进展[J]. 林业工程学报, 2017, 2 (5): 76- 84.
44 LIU J , ZHU Y T , LV W , et al. Characterization of structural changes in lignin from biomass oxidation during formic acid production[J]. Advances in New and Renewable Energy, 2019, 7 (3): 207- 215.
44 刘竞, 朱妤婷, 吕微, 等. 氧化生物质制备甲酸过程中木质素结构变化的表征[J]. 新能源进展, 2019, 7 (3): 207- 215.
45 LI B Y , ZHAN H Y , LIANG C , et al. Analysis of lignin structure in bambusa chungii SCMP by 2D NMR[J]. Paper Science & Technology, 2010, 29 (5): 62- 66.
45 李兵云, 詹怀宇, 梁辰, 等. 粉丹竹SCMP木素结构的2D NMR分析[J]. 造纸科学与技术, 2010, 29 (5): 62- 66.
46 LV W , SI Z , TIAN Z P , et al. Synergistic effect of EtOAc/H2O biphasic solvent and Ru/C catalyst for cornstalk hydrolysis residue depolymerization[J]. ACS Sustainable Chem Eng, 2017, 5 (4): 2981- 2993.
47 WEN J L , SUN S L , XUE B L , et al. Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology[J]. Materials, 2013, 6 (1): 359- 391.
48 DELRIO J C , RENCORET J , MARQUES G , et al. Structural characterization of the lignin from jute (corchorus capsularis) fibers[J]. J Agr Food Chem, 2009, 57 (21): 10271- 10281.
49 YANG S , YUAN T Q , SUN R C . Structural elucidation of whole lignin in cell walls of triploid of populus tomentosa carr[J]. ACS Sustainable Chem Eng, 2015, 4 (3): 1006- 1015.
50 LIN Y , KING J Y , KARLEN S D , et al. Using 2D NMR spectroscopy to assess effects of UV radiation on cell wall chemistry during litter decomposition[J]. Biogeochemistry, 2015, 125 (3): 427- 436.
51 MORI T , TSUBOI Y , ISHIDA N , et al. Multidimensional high-resolution magic angle spinning and solution-state NMR characterization of 13C-labeled plant metabolites and lignocellulose[J]. Sci Rep, 2015, 5 (1): 11848.
Options
文章导航

/

〈 〉

网站设计版权所有 © 2017 《波谱学杂志》编辑部
地址：湖北省武汉市武昌区小洪山西30号 中科院精密测量科学与技术创新研究院波谱楼 《波谱学杂志》编辑部
邮编：430071　电话/传真：(086)027－87198791   E-mail: magres@wipm.ac.cn
本系统由北京玛格泰克科技发展有限公司设计开发