Abstract
Main conclusion
Six types of lignin–carbohydrate complex (LCC) fractions were isolated from Eucalyptus. The acidic dioxane treatment applied significantly improved the yield of LCCs. The extraction conditions had a limited impact on the LCC structures and linkages.
Characterization of the lignin–carbohydrate complex (LCC) structures and linkages promises to offer insight on plant cell wall chemistry. In this case, Eucalyptus LCCs were extracted by aqueous dioxane, and then precipitated sequentially by 70% ethanol, 100% ethanol, and acidic water (pH = 2). The composition and structure of the six LCC fractions obtained by selective precipitation were investigated by sugar analysis, molecular weight determination, and 2D HSQC NMR. It was found that the acidic (0.05-M HCl) dioxane treatment significantly improved the yield of LCCs (66.4% based on Klason lignin), which was higher than the neutral aqueous dioxane extraction, and the extraction condition showed limited impact on the LCC structures and linkages. In the fractionation process, the low-molecular-weight LCCs containing a high content of carbohydrates (60.3–63.2%) were first precipitated by 70% ethanol from the extractable solution. The phenyl glycoside (PhGlc) bonds (13.0–17.0 per 100Ar) and highly acetylated xylans were observed in the fractions recovered by the precipitation with 100% ethanol. On the other hand, such xylan-rich LCCs exhibited the highest frequency of β-O-4 linkages. The benzyl ether (BE) bonds were only detected in the fractions obtained by acidic water precipitation.
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References
Balakshin M (2008) Recent advances in the tsolation and analysis of lignins and lignin-carbohydrate complex. In: Hu TQ (ed) Characterization of lignocellulosic materials. Wiley, Oxford
Balakshin M, Capanema E, Gracz H, Chang HM, Jameel H (2011) Quantification of lignin-carbohydrate linkages with high-resolution NMR spectroscopy. Planta 233:1097–1110
Balakshin M, Capanema E, Berlin A (2014) Isolation and analysis of lignin-carbohydrate complexes preparations with traditional and advanced methods: a review. Stud Nat Prod Chem 42:83–115
Balan V, Sousa LdC, Chundawat SP, Marshall D, Sharma LN, Chambliss CK, Dale BE (2009) Enzymatic digestibility and pretreatment degradation products of AFEX-treated hardwoods (Populus nigra). Biotechnol Prog 25:365–375
Bian J, Peng F, Peng P, Xu F, Sun RC (2010) Isolation and fractionation of hemicelluloses by graded ethanol precipitation from Caragana korshinskii. Carbohyd Res 345:802–809
Bjorkman A (1957) Lignin and lignin-carbohydrate complexes. Ind Eng Chem 49:1395–1398
Björkman A (1954) Isolation of lignin from finely divided wood with neutral solvents. Nature 174:1057–1058
Boerjan W, Ralph J, Baucher M (2003) Lignin biosynthesis. Annu Rev Plant Biol 54:519–546
Chen L, Fu S (2013) Enhanced cellulase hydrolysis of eucalyptus waste fibers from pulp mill by tween80-assisted ferric chloride pretreatment. J Agric Food Chem 61:3293–3300
Du X, Gellerstedt G, Li J (2013) Universal fractionation of lignin-carbohydrate complexes (LCCs) from lignocellulosic biomass: an example using spruce wood. Plant J 74:328–338
Du X, Perez-Boada M, Fernandez C, Rencoret J, del Rio JC, Jimenez-Barbero J, Li J, Gutierrez A, Martinez AT (2014) Analysis of lignin-carbohydrate and lignin-lignin linkages after hydrolase treatment of xylan-lignin, glucomannan-lignin and glucan-lignin complexes from spruce wood. Planta 239:1079–1090
Fengel D, Wegener G (1983) Wood: chemistry, ultrastructure, reactions. Walter de Gruyter, Berlin
Gírio FM, Fonseca C, Carvalheiro F, Duarte LC, Marques S, Bogel-Łukasik R (2010) Hemicelluloses for fuel ethanol: a review. Bioresour Technol 101:4775–4800
Giummarella N, Lawoko M (2016) Structural basis for the formation and regulation of lignin-xylan bonds in Birch. ACS Sustain Chem Eng 4:5319–5326
Goldstein IS (1981) Organic chemicals from biomass, vol 310. CRC Press, Boca Raton
Isikgor FH, Becer CR (2015) Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers. Polym Chem 6:4497–4559
Jääskeläinen A, Sun Y, Argyropoulos D, Tamminen T, Hortling B (2003) The effect of isolation method on the chemical structure of residual lignin. Wood Sci Technol 37:91–102
Kim H, Ralph J (2010) Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d 6/pyridine-d 5. Org Biomol Chem 8:576–591
Lawoko M, Henriksson G, Gellerstedt G (2005) Structural differences between the lignin-carbohydrate complexes present in wood and in chemical pulps. Biomacromol 6:3467–3473
Li J, Martin-Sampedro R, Pedrazzi C, Gellerstedt G (2011) Fractionation and characterization of lignin-carbohydrate complexes (LCCs) from eucalyptus fibers. Holzforschung 65:43–50
Li X, Ye D, Liang H, Zhu H, Qin L, Zhu Y, Wen Y (2015) Effects of successive rotation regimes on carbon stocks in eucalyptus plantations in subtropical China measured over a full rotation. PLoS One 10:e0132858
Mansfield SD, Kim H, Lu F, Ralph J (2012) Whole plant cell wall characterization using solution-state 2D NMR. Nat Protoc 7:1579–1589
Miyagawa Y, Takemoto O, Takano T, Kamitakahara H, Nakatsubo F (2012) Fractionation and characterization of lignin carbohydrate complexes (LCCs) of Eucalyptus globulus in residues left after MWL isolation. Part I: analyses of hemicellulose-lignin fraction (HC-L). Holzforschung 66:459–465
Miyagawa Y, Mizukami T, Kamitakahara H, Takano T (2014) Synthesis and fundamental HSQC NMR data of monolignol β-glycosides, dihydromonolignol β-glycosides and p-hydroxybenzaldehyde derivative β-glycosides for the analysis of phenyl glycoside type lignin-carbohydrate complexes (LCCs). Holzforschung 68:747–760
Peng F, Ren JL, Xu F, Bian J, Peng P, Sun RC (2009) Comparative study of hemicelluloses obtained by graded ethanol precipitation from sugarcane bagasse. J Agric Food Chem 57:6305–6317
Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis MF, Davison BH, Dixon RA, Gilna P, Keller M, Langan P, Naskar AK, Saddler JN, Tschaplinski TJ, Tuskan GA, Wyman CE (2014) Lignin valorization: improving lignin processing in the biorefinery. Science 344:1246843
Romaní A, Garrote G, Parajó JC (2012) Bioethanol production from autohydrolyzed Eucalyptus globulus by simultaneous saccharification and fermentation operating at high solids loading. Fuel 94:305–312
Sakagami H, Kushida T, Oizumi T, Nakashima H, Makino T (2010) Distribution of lignin-carbohydrate complex in plant kingdom and its functionality as alternative medicine. Pharmacol Therapeut 128:91–105
Salanti A, Zoia L, Tolppa EL, Orlandi M (2012) Chromatographic detection of lignin-carbohydrate complexes in annual plants by derivatization in ionic liquid. Biomacromol 13:445–454
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2008) Determination of structural carbohydrates and lignin in biomass. Laboratory analytical procedure. Technical Report NREL/TP-510-42618; 1617
Sun R, Fang J, Tomkinson J, Geng Z, Liu J (2001) Fractional isolation, physico-chemical characterization and homogeneous esterification of hemicelluloses from fast-growing poplar wood. Carbohyd Polym 44:29–39
Sun XF, Sun RC, Fowler P, Baird MS (2005) Extraction and characterization of original lignin and hemicelluloses from wheat straw. J Agric Food Chem 53:860–870
Traynard P, Ayroud A, Eymery A (1953) Existence dune liaison lignine-hydrates de carbone dans la bois. Assoc Tech Ind Papetière Bull 2:45–52
Wang Z, Akiyama T, Yokoyama T, Matsumoto Y (2013) Fractionation and characterization of wood cell wall components of Fagus crenata blume using LiCl/DMSO solvent system. J Wood Chem Technol 33:188–196
Wen JL, Sun SL, Xue BL, Sun RC (2013a) Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology. Materials 6:359–391
Wen JL, Xue BL, Xu F, Sun RC, Pinkert A (2013b) Unmasking the structural features and property of lignin from bamboo. Ind Crops Prod 42:332–343
Wu S, Argyropoulos D (2003) An improved method for isolating lignin in high yield and purity. J Pulp Pap Sci 29:235–240
Yang S, Yuan TQ, Sun RC (2015) Structural elucidation of whole lignin in cell walls of triploid of Populus tomentosa Carr. ACS Sustain Chem Eng 4:1006–1015
Yuan TQ, Sun SN, Xu F, Sun RC (2011) Characterization of lignin structures and lignin-carbohydrate complex (LCC) linkages by quantitative 13C and 2D HSQC NMR spectroscopy. J Agric Food Chem 59:10604–10614
Yue FX, Lan W, Hu SG, Chen KL, Lu FC (2016) Structural modifications of sugarcane bagasse lignins during wet-storage and soda-oxygen pulping. ACS Sustain Chem Eng 4:5311–5318
Yue FX, Lu FC, Regner M, Sun RC, Ralph J (2017) Lignin-derived thioacidolysis dimers: reevaluation, new Products, authentication, and quantification. Chemsuschem 10:830–835
Zhao BC, Chen BY, Yang S, Yuan TQ, Charlton A, Sun RC (2016) Structural variation of lignin and lignin-carbohydrate complex in Eucalyptus grandis × E. urophylla during its growth process. ACS Sustain Chem Eng 5:1113–1122
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This work was financially supported by the National Natural Science Foundation of China (31430092 and 31400296) and the Fundamental Research Funds for the Central Universities (2015ZCQ-CL-02).
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Zhao, BC., Xu, JD., Chen, BY. et al. Selective precipitation and characterization of lignin–carbohydrate complexes (LCCs) from Eucalyptus. Planta 247, 1077–1087 (2018). https://doi.org/10.1007/s00425-018-2842-9
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DOI: https://doi.org/10.1007/s00425-018-2842-9