安艳霞;洪元芳;董艳梅;张剑;李梦琴;

• 1:河南农业大学食品科学技术学院农业部大宗粮食加工重点实验室

摘要(Abstract)：

在传统溶剂提取木质素的基础上,重点综述了新型深度共熔溶剂提取木质素的研究进展,探讨深度共熔溶剂的官能团、氢键受体、溶剂参数等与木质素提取率之间的构效关系,分析了不同类型深度共熔溶剂提取木质素过程中发生的化学反应,最后针对深度共熔溶剂黏度高、电导率差、酶相容性低等问题以及绿色、高效的木质素提取技术面临的机遇和挑战进行了展望,为进一步深入探究深度共熔溶剂对木质素的高效提取及应用提供理论支持与技术指导。

关键词(KeyWords)： 深度共熔溶剂;木质素提取;构效关系;官能团;氢键受体;溶剂参数;化学反应

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金项目(21706052);; 河南农业大学创新基金项目(KJCX2017C05)

作者(Authors): 安艳霞;洪元芳;董艳梅;张剑;李梦琴;

DOI: 10.16445/j.cnki.1000-2340.20210816.001

参考文献(References)：

• [1] SUN Z,FRIDRICH B,DE S A,et al.Bright side of lignin depolymerization:toward new platform chemicals[J].Chemical Reviews,2018,118(2):614-678.
• [2] 宋丽丽，张永良，张志平，等.白腐菌液体发酵降解烟梗木质素的研究[J].轻工学报，2019,34(1):36-42.
• [3] WANG H,PU Y,RAGAUSKAS A,et al.From lignin to valuable products-strategies,challenges,and prospects[J].Bioresource Technology,2019,271:449-461.
• [4] 王旭，侯华伟，司玲玉，等.漆酶对纤维素酶催化作用的影响[J].河南农业大学学报，2018,52(2):244-248.
• [5] LAURICHESSE S,AVEROUS L.Chemical modification of lignins:towards biobased polymers[J].Progress in Polymer Science,2014,39(7):1266-1290.
• [6] KUMAR A K,SHARMA S.Recent updates on different methods of pretreatment of lignocellulosic feedstocks:a review[J].Bioresources and Bioprocessing,2017,4(1):7.
• [7] XUE Z,ZHAO X,SUN R C,et al.Biomass-derived gamma-valerolactone-based solvent systems for highly efficient dissolution of various lignins:dissolution behavior and mechanism study[J].Acs Sustainable Chemistry & Engineering,2016,4(7):3864-3870.
• [8] SATHITSUKSANOH N,HOLTMAN K M,YELLE D J,et al.Lignin fate and characterization during ionic liquid biomass pretreatment for renewable chemicals and fuels production[J].Green Chemistry,2014,16:1236-1247.
• [9] MA C,LAAKSONEN A,LIU C,et al.The peculiar effect of water on ionic liquids and deep eutectic solvents[J].Chemical Society Reviews,2018,47:8685-8720.
• [10] ABBOTT A P,CAPPER G,DAVIES D L,et al.Novel solvent properties of choline chloride/urea mixtures[J].Chemical Communications,2003(1):70-71.
• [11] ALVAREZ-VASCO C,MA R S,QUINTERO M,et al.Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES):a source of lignin for valorization[J].Green Chemistry,2016,18:5133-5141.
• [12] 李真真，杨国龙，刘伟.酸性低共熔溶剂催化葵花籽油甲酯化反应研究[J].河南工业大学学报(自然科学版),2020,41(6):41-46.
• [13] 司马国宝，王帅，崔莹，等.低共熔溶剂对木质纤维素分离及木质素提取的研究进展[J].现代化工，2019,39(9):26-30.
• [14] CHEN Z,BAI X,LUSI A,et al.One-pot selective conversion of lignocellulosic biomass into furfural and co-products using aqueous choline chloride/methyl isobutyl ketone biphasic solvent system[J].Bioresource Techno-logy,2019,289:121708.
• [15] FRANCISCO M,VAN D B A,KROON M C.New natural and renewable low transition temperature mixtures (LTTMs):Screening as solvents for lignocellulosic biomass processing[J].Green Chemistry,2012,14(8):2153-2157
• [16] LIU Y,CHEN W,XIA Q,et al.Efficient cleavage of lignin-carbohydrate complexes and ultrafast extraction of lignin oligomers from wood biomass by microwave-assisted treatment with deep eutectic solvent[J].Chem Sus Chem,2017,10(8):1692-1700.
• [17] JESSOP P G,JESSOP D A,FU D,et al.Solvatochromic parameters for solvents of interest in green chemistry[J].Green Chemistry,2012,14(5):1245-1259.
• [18] CHEN Z,WAN C X.Ultrafast fractionation of lignocellulosic biomass by microwave-assisted deep eutectic solvent pretreatment[J].Bioresource Technology,2018,250:532-537.
• [19] LIU X,LI T,WU S,et al.Structural characterization and comparison of enzymatic and deep eutectic solvents isolated lignin from various green processes:toward lignin valorization[J].Bioresource Technology,2020,310:123460.
• [20] HOU X D,LIN K P,LI A L,et al.Effect of constituents molar ratios of deep eutectic solvents on rice straw fractionation efficiency and the micro-mechanism investigation[J].Industrial Crops and Products,2018,120:322-329.
• [21] KOHLI K,KATUWAL S,BISWAS A,et al.Effective delignification of lignocellulosic biomass by microwave assisted deep eutectic solvents[J].Bioresource Technology,2020,303:122897.
• [22] CHEN Z,RAGAUSKAS A,WAN C X.Lignin extraction and upgrading using deep eutectic solvents[J].Industrial Crops and Products,2020,147:112241.
• [23] TAN Y T,NGOH G C,CHUA A S M.Effect of functional groups in acid constituent of deep eutectic solvent for extraction of reactive lignin[J].Bioresource Technology,2019,281:359-366.
• [24] CHEN Y,MU T.Application of deep eutectic solvents in biomass pretreatment and conversion[J].Green Energy & Environment,2019,4(2):95-115.
• [25] 张成武.低共熔溶剂预处理木质纤维素的研究[D].天津：天津大学，2016.
• [26] TANG X,ZUO M,LI Z,et al.Green processing of lignocellulosic biomass and its derivatives in deep eutectic solvents[J].Chem Sus Chem,2017,10(13):2696-2706.
• [27] SMITH E L,ABBOTT A P,Ryder K S.Deep eutectic solvents(DESs)and their applications[J].Chemical Reviews,2014,114(21):11060-11082.
• [28] LOOW Y L,NEW E K,YANG G H,et al.Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion[J].Cellulose,2017,24(9):3591-3618.
• [29] FLORINDO C,OLIVEIRA F S,REBELO L P N,et al.Insights into the synthesis and properties of deep eutectic solvents based on cholinium chloride and carboxylic acids[J].Acs Sustainable Chemistry & Engineering,2014,2:2416-2425.
• [30] FRANCISCO M,VAN DEN BRUINHORST A,KROON M C.Low-transition-temperature mixtures (LTTMs):a new generation of designer solvents[J].Angewandte Chemie-International Edition,2013,52(11):3074-3085.
• [31] DEL MONTE F,CARRIAZO D,SERRANO M.C,et al.Deep eutectic solvents in polymerizations:a greener alternative to conventional syntheses[J].Chem Sus Chem,2014,7(4):999-1009.
• [32] ABBOTT A P,CAPPER G,DAVIES D L,et al.Novel solvent properties of choline chloride/urea mixtures[J].Chemical Communications,2003(1):70-71.
• [33] ESPINO M,DE LOS A F M,GOMEZ F J V,et al.Natural designer solvents for greening analytical chemistry[J].Trac-Trends in Analytical Chemistry,2016,76:126-136.
• [34] ZHANG Q H,BENOIT M,VIGIER K D,et al.Green and inexpensive choline-derived solvents for cellulose decrystallization[J].Chemistry-A European Journal,2012,18(4):1043-1046.
• [35] REN N Q,ZHAO L,CHEN C,et al.A review on bioconversion of lignocellulosic biomass to H2:key challenges and new insights[J].Bioresour Technol,2016,215:92-99.
• [36] ABO-HAMAD A,HAYYAN M,ALSAADI M.A,et al.Potential applications of deep eutectic solvents in nanotechnology[J].Chemical Engineering Journal,2015,273:551-567.
• [37] ZHANG Y,JI X,LU X.Choline-based deep eutectic solvents for CO2 separation:Review and thermodynamic analysis[J].Renewable & Sustainable Energy Reviews,2018,97:436-455.
• [38] CHEN Y,CHEN W,FU L,et al.Surface tension of 50 deep eutectic solvents:effect of hydrogen-bonding donors,hydrogen-bonding acceptors,other solvents,and temperature[J].Industrial & Engineering Chemistry Research,2019,58:12741-12750.
• [39] GARCIA G,APARICIO S,ULLAH R,et al.Deep eutectic solvents:physicochemical properties and gas separation applications[J].Energy & Fuels,2015,29:2616-2644.
• [40] HAKKINEN R,ABBOTT A.Solvation of carbohydrates in five choline chloride-based deep eutectic solvents and the implication for cellulose solubility[J].Green Chemistry,2019,21:4673-4682.
• [41] CHEN Z F,GREAVES T L,WARR G G,et al.Mixing cations with different alkyl chain lengths markedly depresses the melting point in deep eutectic solvents formed from alkylammonium bromide salts and urea[J].Chemical Communications,2017,53(15):2375-2377.
• [42] ABBOTT A P,MCKENZIE K J.Application of ionic li-quids to the electrodeposition of metals[J].Physical Chemistry Chemical Physics,2006,8(37):4265-4279.
• [43] CARVALHO M M,RUOTOLO L A M,FERNANDEZ F R.Synthesis of aluminophosphate by the ionothermal method using factorial design[J].Microporous and Mesoporous Materials,2013,165:163-167.
• [44] RAMESH S,SHANTI R,MORRIS E.Characterization of conducting cellulose acetate based polymer electrolytes doped with “green” ionic mixture[J].Carbohydrate Polymers,2013,91(1):14-21.
• [45] GUO W,HOU Y,WU W,et al.Separation of phenol from model oils with quaternary ammonium salts via forming deep eutectic solvents[J].Green Chemistry,2013,15(1):226-229.
• [46] CUI Q,PENG X,YAO X H,et al.Deep eutectic solvent-based microwave-assisted extraction of genistin,genistein and apigenin from pigeon pea roots[J].Separation and Purification Technology,2015,150:63-72.
• [47] CVJETKO B M,JURINJAK T A,VINKOVIC M,et al.Cholinium-based deep eutectic solvents and ionic liquids for lipase-catalyzed synthesis of butyl acetate[J].Journal of Molecular Catalysis B-Enzymatic,2015,122:188-198.
• [48] ZHAO H,ZHANG C,CRITTLE T D.Choline-based deep eutectic solvents for enzymatic preparation of biodiesel from soybean oil[J].Journal of Molecular Catalysis B-Enzymatic,2013,85:243-247.
• [49] ZHAO H,BAKER G A,HOLMES S.Protease activation in glycerol-based deep eutectic solvents[J].Journal of Mole-cular Catalysis B-Enzymatic,2011,72(3/4):163-167.
• [50] LI N,WANG Y,XU K,et al.Development of green betaine-based deep eutectic solvent aqueous two-phase system for the extraction of protein[J].Talanta,2016,152:23-32.
• [51] GARCIA A,RODDRIGUEZ-JUAN E,RODRIGUEZ-GUTIERREZ G,et al.Extraction of phenolic compounds from virgin olive oil by deep eutectic solvents (DESs)[J].Food Chemistry,2016,197:554-561.
• [52] CHEN Z,BAI X L,LUSI A,et al.One-pot selective conversion of lignocellulosic biomass into furfural and co-products using aqueous choline chloride/methyl isobutyl ketone biphasic solvent system[J].Bioresource Techno-logy,2019 (289) :121708.
• [53] MBOUS Y P,HAYYAN M,HAYYAN A,et al.Applications of deep eutectic solvents in biotechnology and bioengineering-promises and challenges[J].Biotechnology Advances,2017,35(2):105-134.
• [54] SOARES B,SILVESTRE A J D,RODRUGUES PINTO P C,et al.Hydrotropy and cosolvency in lignin solubilization with deep eutectic solvents[J].Acs Sustainable Chemistry & Engineering,2019,7:12485-12493.
• [55] LIU Y Z,CHEN W S,XIA Q Q,et al.Efficient cleavage of lignin-carbohydrate complexes and ultrafast extraction of lignin oligomers from wood biomass by microwave-assisted treatment with deep eutectic solvent[J].Chem Sus Chem,2017,10(8):1692-1700.
• [56] ZHANG C W,XIA S Q,MAP S.Facile pretreatment of lignocellulosic biomass using deep eutectic solvents[J].Bioresource Technology,2016,219:1-5.
• [57] LI T F,LYU G J,LIU Y,et al.Deep eutectic solvents(DESs)for the isolation of willow lignin(Salix matsudana cv.Zhuliu)[J].International Journal of Molecular Sciences,2017,18(11):2266 .
• [58] HOU X D,LI A L,LIN K P,et al.Insight into the structure-function relationships of deep eutectic solvents during rice straw pretreatment[J].Bioresource Technology,2018,249:261-267.
• [59] CHEN Y,ZHANG L,YU J,et al.High-purity lignin isolated from poplar wood meal through dissolving treatment with deep eutectic solvents[J].Royal Society Open Science,2019,6(1):181757.
• [60] TAN Y T,CHUA A SM,NGOH G C.Deep eutectic solvent for lignocellulosic biomass fractionation and the subsequent conversion to bio-based products:a review[J].Bioresource Technology,2020,297:122522.
• [61] D’AGOSTINO C,HARRIS R C,ABBOTT A P,et al.Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by H-1 pulsed field gradient NMR spectroscopy[J].Physical Chemistry Chemical Physics,2011,13(48):21383-21391.
• [62] GUO Z W,LING Z,WANG C,et al.Integration of facile deep eutectic solvents pretreatment for enhanced enzymatic hydrolysis and lignin valorization from industrial xylose residue[J].Bioresource Technology,2018,265:334-339.
• [63] FLORINDO C,MARGARIDA O M,BRANCO L C,et al.Carbohydrates-based deep eutectic solvents:thermophysical properties and rice straw dissolution[J].Journal of Molecular Liquids,2017,247:441-447.
• [64] PROCENTESE A,JOHNSON E,ORR V,et al.Deep eutectic solvent pretreatment and subsequent saccharification of corncob[J].Bioresource Technology,2015,192:31-36.
• [65] ZHAO Z,CHEN X,ALI M F,et al.Pretreatment of wheat straw using basic ethanolamine-based deep eutectic solvents for improving enzymatic hydrolysis[J].Bioresource Technology,2018,263:325-333.
• [66] TELES A R R,CAPELA E.V,CARMO R.S,et al.Solvatochromic parameters of deep eutectic solvents formed by ammonium-based salts and carboxylic acids[J].Fluid Phase Equilibria,2017,448:15-21.
• [67] KIM K H,DUTTA T,SUN J,et al.Biomass pretreatment using deep eutectic solvents from lignin derived phenols[J].Green Chemistry,2018,20:809-815.
• [68] CHEN L,YU Q,WANG Q,et al.A novel deep eutectic solvent from lignin-derived acids for improving the enzymatic digestibility of herbal residues from cellulose[J].Cellulose,2019,26(3):1947-1959.
• [69] KIM K H,EUDES A,JEONG K,et al.Integration of renewable deep eutectic solvents with engineered biomass to achieve a closed-loop biorefinery[J].Proceedings of the National Academy of Sciences of the United States of America,2019,116(28):13816-13824.
• [70] MALAEKE H,HOUSAIDOKHT M.R,MONHEMI H,et al.Deep eutectic solvent as an efficient molecular liquid for lignin solubilization and wood delignification[J].Journal of Molecular Liquids,2018,263:193-199.
• [71] YU Q,ZHANG A P,WANG W,et al.Deep eutectic solvents from hemicellulose-derived acids for the cellulosic ethanol refining of Akebia' herbal residues[J].Bioresource Technology,2018,247:705-710.
• [72] 李奥林.深度共熔溶剂介导的水稻秸秆关键组分分离及相关机理研究[D].广州：广东工业大学，2019.
• [73] LOOW Y L,NEW E K,YANG G H,et al.Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion[J].Cellulose,2017,24(9):3591-3618.
• [74] LOPES A M D,GOMES J R B,COUNHO J A P,et al.Novel insights into biomass delignification with acidic deep eutectic solvents:a mechanistic study of beta-O-4 ether bond cleavage and the role of the halide counterion in the catalytic performance[J].Green Chemistry,2020,22(8):2474-2487.
• [75] KUMAR A K,PARIKH B S,PRAVAKAR M.Natural deep eutectic solvent mediated pretreatment of rice straw:bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue[J].Environmental Science and Pollution Research,2016,23(10):9265-9275.
• [76] LIU Q,ZHAO X,YU D,et al.Novel deep eutectic solvents with different functional groups towards highly efficient dissolution of lignin[J].Green Chemistry,2019,21:5291-5297.
• [77] GUO Z,ZHANG Q,YOU T,et al.Short-time deep eutectic solvent pretreatment for enhanced enzymatic saccharification and lignin valorization[J].Green Chemistry,2019,21:3099-3108.
• [78] XIA Q Q,LIU Y Z,MENG J,et al.Multiple hydrogen bond coordination in three-constituent deep eutectic solvents enhances lignin fractionation from biomass[J].Green Chemistry,2018,20:2711-2721.
• [79] CHEN Z,JACOBY W A,WAN C.Ternary deep eutectic solvents for effective biomass deconstruction at high solids and low enzyme loadings[J].Bioresource Technology,2019,279:281-286.
• [80] YIIN C L,QUITAIN A T,YUSUP S,et al.Characterization of natural low transition temperature mixtures (LTTMs):green solvents for biomass delignification[J].Bioresource Technology,2016,199:258-264.
• [81] DAIY T,VAN SPRONSEN J,WITKAMP G J,et al.Na-tural deep eutectic solvents as new potential media for green technology[J].Analytica Chimica Acta,2013,766:61-68.
• [82] DAI Y,WITKAMP G J,VERPOORTE R,et al.Tailoring properties of natural deep eutectic solvents with water to facilitate their applications[J].Food Chemistry,2015,187:14-19.
• [83] LOU R,MA R,LIN K T,et al.Facile extraction of wheat straw by deep eutectic solvent(DES)to produce lignin nanoparticles[J].Acs Sustainable Chemistry & Engineering,2019,7:10248-10256.
• [84] KANDANELLI R,THULLURI C,MANGALA R,et al.A novel ternary combination of deep eutectic solvent-alcohol (DES-OL) system for synergistic and efficient delignification of biomass[J].Bioresource Technology,2018,265:573-576.
• [85] HO M C,WU TY,CHEE S W Q,et al.An application of low concentration alkaline hydrogen peroxide at non-severe pretreatment conditions together with deep eutectic solvent to improve delignification of oil palm fronds[J].Cellulose,2019,26(16):8557-8573.
• [86] HONG S,SHEN X J,PANG B,et al.In-depth interpretation of the structural changes of lignin and formation of diketones during acidic deep eutectic solvent pretreatment[J].Green Chemistry,2020,22:1851-1858.
• [87] LIU Q,MOU H,CHEN W,et al.Highly efficient dissolution of lignin by eutectic molecular liquids[J].Industrial & Engineering Chemistry Research,2019,58:23438-23444.
• [88] LI W Q,AMOS K,LI M,et al.Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks[J].Biotechnology for Biofuels,2018,11:304.
• [89] WANG S Z,LI H L,XIAO L P,et al.Unraveling the structural transformation of wood lignin during deep eutectic solvent treatment[J].Frontiers in Energy Research,2020,8:48.
• [90] HONG S,SHEN X J,XUE Z,et al.Structure-function relationships of deep eutectic solvents for lignin extraction and chemical transformation[J].Green Chemistry,2020,22:7219-7232.
• [91] IMAI T,YOKOYAMA T,MATSUMOTO Y.Revisiting the mechanism of beta-O-4 bond cleavage during acidolysis of lignin IV:dependence of acidolysis reaction on the type of acid[J].Journal of Wood Science,2011,57(3):219-225.
• [92] SUN Y C,XU J K,XU F,et al.Dissolution,regeneration and characterisation of formic acid and alcell lignin in ionic liquid-based systems[J].Rsc Advances,2014,4:2743-2755.
• [93] SCHUTYSER W,RENDERS T,VAN D B S,et al.Chemicals from lignin:an interplay of lignocellulose fractionation,depolymerisation,and upgrading[J].Chemical Society Reviews,2018,47(3):852-908.
• [94] RAHIMI A,ULBRICH A,COON J J,et al.Formic-acid-induced depolymerization of oxidized lignin to aromatics[J].Nature,2014,515(7526):249-252.
• [95] SHEN X J,WEN J L,MEI Q Q,et al.Facile fractionation of lignocelluloses by biomass-derived deep eutectic solvent(DES)pretreatment for cellulose enzymatic hydrolysis and lignin valorization[J].Green Chemistry,2019,21:275-283.
• [96] HILTUNEN J,KUUTTI L,ROVIO S,et al.Using a low melting solvent mixture to extract value from wood biomass[J].Scientific Reports,2016,6:32420.
• [97] PAN M Z,ZHAO G M,DING C X,et al.Physicochemical transformation of rice straw after pretreatment with a deep eutectic solvent of choline chloride/urea[J].Carbohydrate Polymers,2017,176:307-314.
• [98] AN Y X,LI N,WU H,et al.Changes in the structure and the thermal properties of Kraft lignin during its dissolution in cholinium ionic liquids[J].Acs Sustainable Chemistry & Engineering,2015,3:2951-2958.
• [99] DUTTA T,ISERN N G,SUN J,et al.Survey of lignin-structure changes and depolymerization during ionic liquid pretreatment[J].Acs Sustainable Chemistry & Engineering,2017,5:10116-10127.
• [100] CHEN Z,REZNICEK W D,WAN C.Deep eutectic solvent pretreatment enabling full utilization of switchgrass[J].Bioresource Technology,2018,263:40-48.
• [101] CHEN Z,BAI X,LUSI A,et al.High-solid lignocellulose processing enabled by natural deep eutectic solvent for lignin extraction and industrially relevant production of renewable chemicals[J].Acs Sustainable Chemistry & Engineering,2018,6(9):12205-12216.
• [102] WANG S,SU S,XIAO L P,et al.Catechyl lignin extra-cted from castor seed coats using deep eutectic solvents:characterization and depolymerization[J].Acs Sustai-nable Chemistry & Engineering,2020,8:7031-7038.