Abstract
To clarify the formation of pseudo-lignin during pretreatment is vital to high-value utilization of lignocellulose. In this study, hydrothermally treated bamboo and α-cellulose were employed to investigate the generation of pseudo-lignin during deep eutectic solvent (DES) treatment. It is found that pseudo-lignin not only contains some characteristic substructures of natural lignin, but also has the structural characteristics of phenol-type oxygenated and furan-type compounds. It is proposed that chloride anion probably stimulates the deconstruction of crystalline cellulose to form pseudo-lignin. Besides, it’s suggested that the change in lignin content can be reflected from the viewpoint of acid-soluble lignin to minimize the interference from pseudo-lignin, and there may exist a competition between 5-chloromethylfurfural production and pseudo-lignin formation. This study provides a feasible route to produce pseudo-lignin from α-cellulose via DES and contributes to a better understanding of pseudo-lignin formation.
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References
Aarum I, Devle H, Ekeberg D, Horn SJ, Stenstrom Y (2018) Characterization of pseudo-lignin from steam exploded birch. ACS Omega 3:4924–4931. https://doi.org/10.1021/acsomega.8b00381
Aarum I, Solli A, Gunnarsson H, Kalyani D, Devle H, Ekeberg D, Stenstrøm Y (2019) Comparison of pyrolyzed lignin before and after milled wood lignin purification of Norway spruce with increasing steam explosion. Wood Sci Technol 53:601–618. https://doi.org/10.1007/s00226-019-01088-x
Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK, Tambyrajah V (2001) Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains. Chem Commun 19:2010–2011. https://doi.org/10.1039/b106357j
Abdellah MH, Pérez-Manríquez L, Puspasari T, Scholes CA, Kentish SE, Peinemann K-V (2018) Effective interfacially polymerized polyester solvent resistant nanofiltration membrane from bioderived materials. Adv Sustainable Syst 2:1800043. https://doi.org/10.1002/adsu.201800043
Abranches DO, Martins MAR, Silva LP, Schaeffer N, Pinho SP, Coutinho JAP (2019) Phenolic hydrogen bond donors in the formation of non-ionic deep eutectic solvents: the quest for type V DES. Chem Commun 55:10253–10256. https://doi.org/10.1039/c9cc04846d
Bazant P, Kuritka I, Munster L, Kalina L (2015) Microwave solvothermal decoration of the cellulose surface by nanostructured hybrid Ag/ZnO particles: a joint XPS, XRD and SEM study. Cellulose 22:1275–1293. https://doi.org/10.1007/s10570-015-0561-y
Cao Q, Wu Q, Dai L, Shen X, Si C (2021) A well-defined lignin-based filler for tuning the mechanical properties of polymethyl methacrylate. Green Chem 23:2329–2335. https://doi.org/10.1039/d1gc00249j
Chen Z, Jacoby WA, Wan C (2019) Ternary deep eutectic solvents for effective biomass deconstruction at high solids and low enzyme loadings. Bioresour Technol 279:281–286. https://doi.org/10.1016/j.biortech.2019.01.126
Chen Z, Ragauskas A, Wan C (2020) Lignin extraction and upgrading using deep eutectic solvents. Ind Crops Prod 147:112241. https://doi.org/10.1016/j.indcrop.2020.112241
Chen B, Li Z, Feng Y, Hao W, Sun Y, Tang X, Zeng X, Lin L (2021a) Green process for 5-(chloromethyl)furfural production from biomass in three-constituent deep eutectic solvent. Chemsuschem 14:847–851. https://doi.org/10.1002/cssc.202002631
Chen B, Peng Z, Li C, Feng Y, Sun Y, Tang X, Zeng X, Lin L (2021b) Catalytic conversion of biomass to furanic derivatives with deep eutectic solvents. Chemsuschem 14:1496–1506. https://doi.org/10.1002/cssc.202100001
Cheng B, Wang X, Lin Q, Zhang X, Meng L, Sun RC, **n F, Ren J (2018) New understandings of the relationship and initial formation mechanism for pseudo-lignin, humins, and acid-induced hydrothermal carbon. J Agric Food Chem 66:11981–11989. https://doi.org/10.1021/acs.jafc.8b04754
da Costa SL, Chundawat SP, Balan V, Dale BE (2009) “Cradle-to-grave” assessment of existing lignocellulose pretreatment technologies. Curr Opin Biotechnol 20:339–347. https://doi.org/10.1016/j.copbio.2009.05.003
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Hansen BB, Spittle S, Chen B, Poe D, Zhang Y, Klein JM, Horton A, Adhikari L, Zelovich T, Doherty BW, Gurkan B, Maginn EJ, Ragauskas A, Dadmun M, Zawodzinski TA, Baker GA, Tuckerman ME, Savinell RF, Sangoro JR (2021) Deep eutectic solvents: a review of fundamentals and applications. Chem Rev 121:1232–1285. https://doi.org/10.1021/acs.chemrev.0c00385
Hao N, Lu K, Ben H, Adhikari S, Lacerda TB, Ragauskas AJ (2017) Effect of autohydrolysis pretreatment conditions on sugarcane bagasse structures and product distribution resulting from pyrolysis. Energ Technol 6:640–648. https://doi.org/10.1002/ente.201700490
He J, Huang C, Lai C, Huang C, Li X, Yong Q (2018) Elucidation of structure-inhibition relationship of monosaccharides derived pseudo-lignin in enzymatic hydrolysis. Ind Crops Prod 113:368–375. https://doi.org/10.1016/j.indcrop.2018.01.046
He J, Huang C, Lai C, Huang C, Li M, Pu Y, Ragauskas AJ, Yong Q (2020a) The effect of lignin degradation products on the generation of pseudo-lignin during dilute acid pretreatment. Ind Crops Prod 146:112205. https://doi.org/10.1016/j.indcrop.2020.112205
He J, Huang C, Lai C, ** Y, Ragauskas A, Yong Q (2020b) Investigation of the effect of lignin/pseudo-lignin on enzymatic hydrolysis by quartz crystal microbalance. Ind Crops Prod 157:112927. https://doi.org/10.1016/j.indcrop.2020.112927
Hong S, Shen X-J, Xue Z, Sun Z, Yuan T-Q (2020a) Structure–function relationships of deep eutectic solvents for lignin extraction and chemical transformation. Green Chem 22:7219–7232. https://doi.org/10.1039/d0gc02439b
Hong S, Shen X, Pang B, Xue Z, Cao X, Wen J, Sun Z, Lam SS, Yuan T, Sun R (2020b) In-depth interpretation of the structural changes of lignin and formation of diketones during acidic deep eutectic solvent pretreatment. Green Chem 22:1851–1858. https://doi.org/10.1039/d0gc00006j
Hu F, Ragauskas A (2014) Suppression of pseudo-lignin formation under dilute acid pretreatment conditions. RSC Adv 4:4317–4323. https://doi.org/10.1039/c3ra42841a
Hu F, Jung S, Ragauskas A (2012a) Impact of pseudolignin versus dilute acid-pretreated lignin on enzymatic hydrolysis of cellulose. ACS Sustain Chem Eng 1:62–65. https://doi.org/10.1021/sc300032j
Hu F, Jung S, Ragauskas A (2012b) Pseudo-lignin formation and its impact on enzymatic hydrolysis. Bioresour Technol 117:7–12. https://doi.org/10.1016/j.biortech.2012.04.037
Jiang Z, Budarin VL, Fan J, Remón J, Li T, Hu C, Clark JH (2018) Sodium chloride-assisted depolymerization of xylo-oligomers to xylose. ACS Sustain Chem Eng 6:4098–4104. https://doi.org/10.1021/acssuschemeng.7b04463
Komesu A, Martins Martinez PF, Lunelli BH, Oliveira J, Wolf Maciel MR, Maciel Filho R (2017) Study of lactic acid thermal behavior using thermoanalytical techniques. J Chem 2017:1–7. https://doi.org/10.1155/2017/4149592
Kumalaputri AJ, Randolph C, Otten E, Heeres HJ, Deuss PJ (2018) Lewis acid catalyzed conversion of 5-hydroxymethylfurfural to 1,2,4-benzenetriol, an overlooked biobased compound. ACS Sustain Chem Eng 6:3419–3425. https://doi.org/10.1021/acssuschemeng.7b03648
Kumar R, Hu F, Sannigrahi P, Jung S, Ragauskas AJ, Wyman CE (2013) Carbohydrate derived-pseudo-lignin can retard cellulose biological conversion. Biotechnol Bioeng 110:737–753. https://doi.org/10.1002/bit.24744
Lee CBTL, Wu TY, Cheng CK, Siow LF, Chew IML (2021) Nonsevere furfural production using ultrasonicated oil palm fronds and aqueous choline chloride-oxalic acid. Ind Crops Prod 166:113397. https://doi.org/10.1016/j.indcrop.2021.113397
Lin WQ, **ng S, ** YC, Lu XM, Huang CX, Yong Q (2020) Insight into understanding the performance of deep eutectic solvent pretreatment on improving enzymatic digestibility of bamboo residues. Bioresour Technol 306:123163. https://doi.org/10.1016/j.biortech.2020.123163
Liu Q, Yuan T, Fu Q, Bai Y, Peng F, Yao C (2019) Choline chloride-lactic acid deep eutectic solvent for delignification and nanocellulose production of moso bamboo. Cellulose 26:9447–9462. https://doi.org/10.1007/s10570-019-02726-0
Liu B, Li T, Wang W, Sagis LMC, Yuan Q, Lei X, Cohen Stuart MA, Li D, Bao C, Bai J, Yu Z, Ren F, Li Y (2020) Corncob cellulose nanosphere as an eco-friendly detergent. Nat Sustain 3:448–458. https://doi.org/10.1038/s41893-020-0501-1
Luo X, Liu J, Wang H, Huang L, Chen L (2014) Comparison of hot-water extraction and steam treatment for production of high purity-grade dissolving pulp from green bamboo. Cellulose 21:1445–1457. https://doi.org/10.1007/s10570-014-0234-2
Ma X, Yang X, Zheng X, Chen L, Huang L, Cao S, Akinosho H (2015) Toward a further understanding of hydrothermally pretreated holocellulose and isolated pseudo lignin. Cellulose 22:1687–1696. https://doi.org/10.1007/s10570-015-0607-1
Mansfield SD, Kim H, Lu F, Ralph J (2012) Whole plant cell wall characterization using solution-state 2D NMR. Nat Protoc 7:1579–1589. https://doi.org/10.1038/nprot.2012.064
Pagán-Torres YJ, Wang T, Gallo JMR, Shanks BH, Dumesic JA (2012) Production of 5-hydroxymethylfurfural from glucose using a combination of lewis and brønsted acid catalysts in water in a biphasic reactor with an alkylphenol solvent. ACS Catal 2:930–934. https://doi.org/10.1021/cs300192z
Sannigrahi P, Kim DH, Jung S, Ragauskas A (2011) Pseudo-lignin and pretreatment chemistry. Energy Environ Sci 4:1306–1310. https://doi.org/10.1039/c0ee00378f
Schmatz AA, Salazar-Bryam AM, Contiero J, Sant’Anna C, Brienzo M, (2020) Pseudo-lignin content decreased with hemicellulose and lignin removal, improving cellulose accessibility, and enzymatic digestibility. Bioenerg Res 14:106–121. https://doi.org/10.1007/s12155-020-10187-8
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794
Shinde SD, Meng X, Kumar R, Ragauskas AJ (2018) Recent advances in understanding the pseudo-lignin formation in a lignocellulosic biorefinery. Green Chem 20:2192–2205. https://doi.org/10.1039/c8gc00353j
Sirviö JA, Visanko M (2017) Anionic wood nanofibers produced from unbleached mechanical pulp by highly efficient chemical modification. J Mater Chem A 5:21828–21835. https://doi.org/10.1039/c7ta05668k
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2012) Determination of structural carbohydrates and lignin in biomass. Lab Anal Proced (LAP). 1617(1):1–16
Smink D, Juan A, Schuur B, Kersten SRA (2019) Understanding the role of choline chloride in deep eutectic solvents used for biomass delignification. Ind Eng Chem Res 58:16348–16357. https://doi.org/10.1021/acs.iecr.9b03588
Smith EL, Abbott AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114:11060–11082. https://doi.org/10.1021/cr300162p
Tu R, Sun Y, Wu Y, Fan X, Wang J, Shen X, He Z, Jiang E, Xu X (2019) Effect of surfactant on hydrothermal carbonization of coconut shell. Bioresour Technol 284:214–221. https://doi.org/10.1016/j.biortech.2019.03.120
Vivekanand V, Olsen EF, Eijsink VG, Horn SJ (2013) Effect of different steam explosion conditions on methane potential and enzymatic saccharification of birch. Bioresour Technol 127:343–349. https://doi.org/10.1016/j.biortech.2012.09.118
Wan G, Zhang Q, Li M, Jia Z, Guo C, Luo B, Wang S, Min D (2019) How pseudo-lignin is generated during dilute sulfuric acid pretreatment. J Agric Food Chem 67:10116–10125. https://doi.org/10.1021/acs.jafc.9b02851
Wang R, Wang K, Zhou M, Xu J, Jiang J (2021) Efficient fractionation of moso bamboo by synergistic hydrothermal-deep eutectic solvents pretreatment. Bioresour Technol 328:124873. https://doi.org/10.1016/j.biortech.2021.124873
**a Q, Liu Y, Meng J, Cheng W, Chen W, Liu S, Liu Y, Li J, Yu H (2018) Multiple hydrogen bond coordination in three-constituent deep eutectic solvent enhances lignin fractionation from biomass. Green Chem 20:2711–2721. https://doi.org/10.1039/C8GC00900G
Xu G, Wang L, Liu J, Wu J (2013) FTIR and XPS analysis of the changes in bamboo chemical structure decayed by white-rot and brown-rot fungi. Appl Surf Sci 280:799–805. https://doi.org/10.1016/j.apsusc.2013.05.065
Zhang L, Yu H (2013) Conversion of xylan and xylose into furfural in biorenewable deep eutectic solvent with trivalent metal chloride added. BioResources 8:6014–6025
Zhang L-X, Yu H, Yu H-B, Chen Z, Yang L (2014) Conversion of xylose and xylan into furfural in biorenewable choline chloride–oxalic acid deep eutectic solvent with the addition of metal chloride. Chin Chem Lett 25:1132–1136. https://doi.org/10.1016/j.cclet.2014.03.029
Zhang H, Wang X, Chen Y, Chen Q, Li S, Shi Y, Cao S, Ma X (2021) Insights into the effect of hydrolysis medium on the holocellulose decomposition, furfural, and pseudo-lignin formation. Biofuels Bioprod Bioref 15:1046–1053. https://doi.org/10.1002/bbb.2215
Zhuang J, Wang X, Xu J, Wang Z, Qin M (2016) Formation and deposition of pseudo-lignin on liquid-hot-water-treated wood during cooling process. Wood Sci Technol 51:165–174. https://doi.org/10.1007/s00226-016-0872-7
Zuo M, Li Z, Jiang Y, Tang X, Zeng X, Sun Y, Lin L (2016) Green catalytic conversion of bio-based sugars to 5-chloromethyl furfural in deep eutectic solvent, catalyzed by metal chlorides. RSC Adv 6:27004–27007. https://doi.org/10.1039/c6ra00267f
Acknowledgements
This work was supported by the guiding project of Science and Technology Plan of Fujian Province (Grant No. 2020N0011). We also greatly appreciate the analysis support provided by Instrumental Analysis Center of Huaqiao University.
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This work was supported by the guiding project of Science and Technology Plan of Fujian Province (Grant No. 2020N0011).
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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Longjun Chang. The first draft of the manuscript was written by Longjun Chang and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
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Chang, L., Sun, Y. & Gan, L. Insights into cellulose deconstruction and pseudo-lignin formation during deep eutectic solvent treatment. Cellulose 30, 141–152 (2023). https://doi.org/10.1007/s10570-022-04917-8
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DOI: https://doi.org/10.1007/s10570-022-04917-8