Skip to main content
Log in

Selective precipitation and characterization of lignin–carbohydrate complexes (LCCs) from Eucalyptus

  • Original Article
  • Published:
Planta Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

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

    Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Bjorkman A (1957) Lignin and lignin-carbohydrate complexes. Ind Eng Chem 49:1395–1398

    Article  CAS  Google Scholar 

  • Björkman A (1954) Isolation of lignin from finely divided wood with neutral solvents. Nature 174:1057–1058

    Article  Google Scholar 

  • Boerjan W, Ralph J, Baucher M (2003) Lignin biosynthesis. Annu Rev Plant Biol 54:519–546

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • Fengel D, Wegener G (1983) Wood: chemistry, ultrastructure, reactions. Walter de Gruyter, Berlin

    Book  Google Scholar 

  • 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

    Article  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Goldstein IS (1981) Organic chemicals from biomass, vol 310. CRC Press, Boca Raton

    Google Scholar 

  • Isikgor FH, Becer CR (2015) Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers. Polym Chem 6:4497–4559

    Article  CAS  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    Article  PubMed  PubMed Central  Google Scholar 

  • Mansfield SD, Kim H, Lu F, Ralph J (2012) Whole plant cell wall characterization using solution-state 2D NMR. Nat Protoc 7:1579–1589

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  PubMed  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Wu S, Argyropoulos D (2003) An improved method for isolating lignin in high yield and purity. J Pulp Pap Sci 29:235–240

    CAS  Google Scholar 

  • 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

    Article  Google Scholar 

  • 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

    Article  CAS  PubMed  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • 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

    Article  Google Scholar 

Download references

Acknowledgements

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).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Tong-Qi Yuan or Run-Cang Sun.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 95 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00425-018-2842-9

Keywords

Navigation