Home Quantitative structural characterization of the lignins from the stem and pith of bamboo (Phyllostachys pubescens)
Article
Licensed
Unlicensed Requires Authentication

Quantitative structural characterization of the lignins from the stem and pith of bamboo (Phyllostachys pubescens)

  • Jia-Long Wen , Shao-Long Sun , Bai-Liang Xue and Run-Cang Sun EMAIL logo
Published/Copyright: February 15, 2013
Become an author with De Gruyter Brill
Submit Manuscript Author Information
Holzforschung
From the journal Holzforschung Volume 67 Issue 6

Abstract

Milled wood lignins (MWL) were isolated from the stem (MWLS) and pith (MWLP) of bamboo (Phyllostachys pubescens). The nonacetylated and acetylated bamboo MWLs were investigated by Fourier transform infrared, quantitative 13C-nuclear magnetic resonance (NMR), 2D heteronuclear single quantum coherence (HSQC) NMR, and 31P-NMR spectroscopy. The MWL consists of p-hydroxyphenyl (1–2%), guaiacyl (21–31%), and syringyl (67–78%) units associated with p-coumarates and ferulates. A modified quantitative 13C-NMR and 2D-HSQC analysis has demonstrated that the predominant intermonomeric linkages are of the type β-O-4 (45–49 per 100 C9 units, i.e., per C900) along with small amounts of other structural units such as resinols (3.6–7.4 per C900), tetrahydrofuran (2.0–2.3 per C900), phenylcoumaran (2.8–4.5 per C900), spirodienones (1.3–2.3 per C900), and α,β-diaryl ethers (2.8–2.9 per C900). MWLP contained more p-coumarates than MWLS. The various degrees of γ-acylation (17–27%) were positively associated with S/G ratios in the lignins; however, γ-acylation was inversely correlated to the ratio between β-β and β-O-4 side chains in these lignin fractions. Moreover, a flavonoid compound (tricin) was also detected in the MWLS but not in MWLP. The two MWLs are very similar in terms of molecular weights and the contents of OHphen and OHaliph.

Keywords: acylation; bamboo lignin; β-O-4 linkage; quantitative NMR; tricin
Corresponding author: Run-Cang Sun, Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China, Phone: +86-10-62336903, Fax: +86-10-62336903

This work was supported by the Fundamental Research Funds for the Central Universities (BLYJ201313), the National Natural Science Foundation of China (31110103902), and the Major State Basic Research Projects of China (973-2010CB732204). In addition, we wish to express our heartfelt thanks to Prof. Faix. O (Editor-in-Chief of Holzforschung) for his insightful comments and massive revisions.

References

Adler, E. (1977) Lignin chemistry: past, present and future. Wood Sci. Technol. 11:169–218.Search in Google Scholar

Bjorkman, A. (1956) Studies on finely divided wood. Part I. Extraction of lignin with neutral solvents. Svensk Papperstidn. 59:477–485.Search in Google Scholar

Capanema, E.A., Balakshin, M.Y., Kadla, J.F. (2005) Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy. J. Agric. Food Chem. 53:9639–9649.10.1021/jf0515330Search in Google Scholar PubMed

Chang, C.L., Wang, G.J., Zhang, L.J., Tsai, W.J., Chen, R.Y., Wu, Y.C., Kuo, Y.H. (2010) Cardiovascular protective flavonolignans and flavonoids from Calamus quiquesetinervius. Phytochemistry 71:271–279.10.1016/j.phytochem.2009.09.025Search in Google Scholar PubMed

Choi, J.W., Faix, O. (2011) NMR study on residual lignins isolated from chemical pulps of beech wood by enzymatic hydrolysis. J. Ind. Eng. Chem. 17:25–28.Search in Google Scholar

Crestini, C., Argyropoulos, D.S. (1997) Structural analysis of wheat straw lignin by quantitative 31P and 2D NMR spectroscopy. The occurrence of ester bonds and α-O-4 substructures. J. Agric. Food Chem. 45:1212–1219.10.1021/jf960568kSearch in Google Scholar

Faix, O. (1991a) Classification of lignin from different botanical origins by FT-IR spectroscopy. Holzforschung (Suppl.) 45:21–27.10.1515/hfsg.1991.45.s1.21Search in Google Scholar

Faix, O. (1991b) Condensation indices of lignins determined by FTIR-spectroscopy. Holz Roh- Werkst. 49:356.10.1007/BF02662706Search in Google Scholar

Faix, O. (1992) Fourier transform infrared spectroscopy. In: Methods in Lignin Chemistry. Eds. Lin, S.Y., Dence, C.W. Springer-Verlag, Berlin. pp. 83–109.Search in Google Scholar

Faix, O., Argyropoulos, D.S., Robert, D., Neirinck, V. (1994) Determination of hydroxyl groups in lignins evaluation of 1H-, 13C-, and 31P-NMR FT-IR and wet chemical methods. Holzforschung 48:387–394.10.1515/hfsg.1994.48.5.387Search in Google Scholar

Fengel, D., Shao, X. (1984) A chemical and ultrastructural study of the bamboo species Phyllostachys makinoi Hay. Wood Sci. Technol. 18:103–112.Search in Google Scholar

Fengel, D., Shao, X. (1985) Studies on the lignin of the bamboo species Phyllostachys makinoi Hay. Wood Sci. Technol. 19:131–137.Search in Google Scholar

Fujii, Y., Azuma, J., Marchessault, R.H., Morin, F.G., Aibara, S., Okamura, K. (1993) Chemical composition change of bamboo accompanying its growth. Holzforschung 47:109–115.10.1515/hfsg.1993.47.2.109Search in Google Scholar

Fujii, Y., Azuma, J., Okamura, K. (1996) Changes in chemical composition within an internode of elongating bamboo. Holzforschung 50:525–530.10.1515/hfsg.1996.50.6.525Search in Google Scholar

Higuchi, T., Tanahashi, M., Nakatsubo, F. (1972) Acidolysis of bamboo lignin III. Estimation of arylglycerol-β-aryl ether groups in lignins. Wood Res. 54:9–18.Search in Google Scholar

Holtman, K.M., Chang, H.M., Jameel, H., Kadla, J.F. (2006) Quantitative C-13 NMR characterization of milled wood lignins isolated by different milling techniques. J. Wood Chem. Technol. 26:21–34.Search in Google Scholar

Jahan, M.S., Mun, S.P. (2009) Isolation and characterization of lignin from Tropical and Temperate Hardwood S.P. Bangladesh J. Sci. Ind. Res. 44:271–280.Search in Google Scholar

Jiao, J., Zhang, Y., Liu, C., Liu, J., Wu, X., Zhang, Y. (2007) Separation and purification of tricin from an antioxidant product derived from bamboo leaves. J. Agric. Food Chem. 55:10086–10092.10.1021/jf0716533Search in Google Scholar PubMed

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.Search in Google Scholar

Kim, J.S., Lee, K.H., Cho, C.H., Koch, G., Kim, Y.S. (2008) Micromorphological characteristics and lignin distribution in bamboo (Phyllostachys pubescens) degraded by the white rot fungus Lentinus edodes. Holzforschung 62:481–487.10.1515/HF.2008.080Search in Google Scholar

Kishimoto, T., Uraki, Y., Ubukata, M. (2008) Synthesis of β-O-4-type artificial lignin polymers and their analysis by NMR spectroscopy. Org. Biomol. Chem. 6:2982–2987.Search in Google Scholar

Kupče, E., Freeman, R. (2007) Compensated adiabatic inversion pulses: broadband INEPT and HSQC. J. Magn. Reson. 187:258–265.10.1016/j.jmr.2007.05.009Search in Google Scholar PubMed

Lai, Y.Z., Sarkanen, K.V. (1971) Isolation and structural studies. In: Lignin-Occurrence, Formation, Structure and Reactions. Eds. Sarkanen, K.V., Ludwig, C. Wiley Interscience, New York. pp. 165–240.Search in Google Scholar

Lu, F., Ralph, J. (1997) Derivatization followed by reductive cleavage (DFRC method), a new method for lignin analysis: protocol for analysis of DFRC monomers. J. Agric. Food Chem. 45: 2590–2592.10.1021/jf970258hSearch in Google Scholar

Lu, F., Ralph, J. (2005) Novel β-β structures in lignins incorporating acylated monolignols. Appita 233–237.Search in Google Scholar

Lu, F., Ralph, J. (2008) Novel tetrahydrofuran structures derived from β-β-coupling reactions involving sinapyl acetates in kenaf lignins. Org. Biomol. Chem. 6:3681–3694.Search in Google Scholar

Malanit, P., Barbu, M.C., Frühwald, A. (2011) Physical and mechanical properties of oriented strand lumber made from an Asian bamboo (Dendrocalamus asper Backer). Eur. J. Wood Prod. 69:27–36.10.1007/s00107-009-0394-1Search in Google Scholar

Mansfield, S.D., Kim, H., Lu, F., Ralph, J. (2012) Whole plant cell wall characterization using solution-state 2D NMR. Nat. Protocols 7:1579–1589.10.1038/nprot.2012.064Search in Google Scholar PubMed

Martínez, A.T., Rencoret, J., Marques, G., Gutiérrez, A., Ibarra, D., Jiménez-Barbero, J., Del Río, J.C. (2008) Monolignol acylation and lignin structure in some nonwoody plants: a 2D NMR study. Phytochemistry 69:2831–2843.10.1016/j.phytochem.2008.09.005Search in Google Scholar PubMed

Mousavioun, P., Doherty, W.O.S. (2010) Chemical and thermal properties of fractionated bagasse soda lignin. Ind. Crop. Prod. 31:52–58.Search in Google Scholar

Nakamura, Y., Higuchi, T. (1976) Ester linkage of p-coumaric acid in bamboo lignin. Holzforschung 30:187–191.10.1515/hfsg.1976.30.6.187Search in Google Scholar

Nakatsubo, F., Tanahashi, M., Higuchi, T. (1972) Acidolysis of bamboo lignin II. Isolation and identification of acidolysis products. Wood Res. 53:9–18.Search in Google Scholar

Nimz, H.H., Robert, D., Faix, O., Nemr, M. (1981) Carbon-13 NMR spectra of lignins, 8: structural differences between lignins of hardwood, softwoods, grasses and compression wood. Holzforschung 35:16–26.10.1515/hfsg.1981.35.1.16Search in Google Scholar

Pan, X., Kadla, J.F., Ehara, K., Gilkes, N., Saddler, J.N. (2006) Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity. J. Agric. Food Chem. 54:5806–5813.10.1021/jf0605392Search in Google Scholar PubMed

Qu, C., Kishimoto, T., Ogita, S., Hamada, M., Nakajima, N. (2012) Dissolution and acetylation of ball-milled birch (Betula platyphylla) and bamboo (Phyllostachys nigra) in the ionic liquid [Bmim]Cl for HSQC NMR analysis. Holzforschung 66:607–614.10.1515/hf.2011.186Search in Google Scholar

Ralph, J., Hatfield, R.D., Quideau, S., Helm, R.F., Grabber, J.H., Jung, H.J.G. (1994) Pathway of p-coumaric acid incorporation into maize lignin as revealed by NMR. J. Am. Chem. Soc. 116: 9448–9456.Search in Google Scholar

Ralph, J., Hatfield, R.D., Piquemal, J., Yahiaoui, N., Pean, M., Lapierre, C., Boudet, A.M. (1998) NMR characterization of altered lignins extracted from tobacco plants down-regulated for lignification enzymes cinnamyl-alcohol dehydrogenase and cinnamyl-CoA reductase. Proc. Natl. Acad. Sci. USA 95:12803–12808.10.1073/pnas.95.22.12803Search in Google Scholar PubMed PubMed Central

Ralph, J., Marita, J., Ralph, S.A., Hatfield, R.D., Lu, F., Ede, R.M., Peng, J., Quideau, S., Helm, R.F., Grabber, J.H., Kim, H., Jimenez-Monteon, G., Zhang, Y., Jung, H.J.G., Landucci, L.L., MacKay, J.J., Sederoff, R.R., Chapple, C., Boudet, A.M. (1999) Solution-state NMR of lignins. In: Advances in Lignocellulosics Characterization. Ed. Argyropoulos, D.S. Tappi Press, Atlanta. pp. 55–108.Search in Google Scholar

Ralph, J., Bunzel, M., Marita, J.M., Hatfield, R.D., Lu, F.C., Kim, H., Schatz, P.F., Grabber, J.H., Steinhart, H. (2004a) Peroxidase-dependent cross-linking reactions of p-hydroxycinnamates in plant cell walls. Phytochem. Rev. 3:79–96.10.1023/B:PHYT.0000047811.13837.fbSearch in Google Scholar

Ralph, S.A., Ralph, J., Landucci, L. (2004b) NMR database of lignin and cell wall model compounds. U.S. Forest Products Laboratory, Madison, WI. Available at http://www.ars.usda.gov/Services/docs.htm?docid=10491. Accessed on 2 February 2013.Search in Google Scholar

Río, J.C. del, Prinsen, P., Rencoret, J., Nieto, L., Jiménez-Barbero, J., Ralph, J., Martínez, A.T., Gutiérrez, A. (2012a) Structural characterization of the lignin in the cortex and pith of elephant grass (Pennisetum purpureum) stems. J. Agric. Food Chem. 60:3619–3634.10.1021/jf300099gSearch in Google Scholar PubMed

Río, J.C. del, Rencoret, J., Prinsen, P., Martínez, A.T., Ralph, J., Gutiérrez, A. (2012b) Structural characterization of wheat straw lignin as revealed by analytical pyrolysis, 2D-NMR, and reductive cleavage methods. J. Agric. Food Chem. 60:5922–5935.10.1021/jf301002nSearch in Google Scholar PubMed

Robinson, A.R., Mansfield, S.D. (2009) Rapid analysis of poplar lignin monomer composition by a streamlined thioacidolysis procedure and near-infrared reflectance-based prediction modeling. Plant J. 58:06–714.10.1111/j.1365-313X.2009.03808.xSearch in Google Scholar PubMed

Seca, A.M., Cavaleiro, J.A., Domingues, F.M., Silvestre, A.J., Evtuguin, D., Neto, C.P. (2000) Structural characterization of the lignin from the nodes and internodes of Arundo donax reed. J. Agric. Food Chem. 48:817–824.10.1021/jf9910988Search in Google Scholar PubMed

Shao, S., Wen, G., Jin, Z. (2008) Changes in chemical characteristics of bamboo (Phyllostachys pubescens) components during steam explosion. Wood Sci. Technol. 42:439–451.Search in Google Scholar

Shao, S., Jin, Z., Wen, G., Liyama, K. (2009) Thermo characteristics of steam-exploded bamboo (Phyllostachys pubescens) lignin. Wood Sci. Technol. 43:643–652.Search in Google Scholar

Shimada, M., Fukuzuka, T., Higuchi, T. (1971) Ester linkages of p-coumaric acid in bamboo and grass lignins. Tappi 54:72–78.Search in Google Scholar

Shimizu, S., Yokoyama, T., Akiyama, T., Matsumoto, Y. (2012) Reactivity of lignin with different composition of aromatic syringyl/guaiacyl structures and erythro/threo side chain structures in β-O-4 type during alkaline delignification: as a basis for the different degradability of hardwood and softwood lignin. J. Agric. Food Chem. 60:6471–6476.10.1021/jf301329vSearch in Google Scholar PubMed

Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., Crocker, D. (2008) Determination of structural carbohydrates and lignin in biomass. Technical Report, NREL/TP-510-42618.Search in Google Scholar

Stewart, J.J., Akiyama, T., Chapple, C., Ralph, J., Mansfield, S.D. (2009) The effects on lignin structure of overexpression of ferulate 5-hydroxylase in hybrid poplar. Plant Physiol. 150:621–635.10.1104/pp.109.137059Search in Google Scholar PubMed PubMed Central

Tanahashi, M., Nakatsubo, F., Higuchi, T. (1975) Structural elucidation of bamboo lignin by acidolysis and ozonolysis I. Wood Res. 58:9–18.Search in Google Scholar

Vishtal, A., Kraslawski, A. (2011) Challenges in industrial applications of technical lignins. BioResources 6:3547–3568.10.15376/biores.6.3.3547-3568Search in Google Scholar

Wen, J.L., Sun, Z.J., Sun, Y.C., Sun, S.N., Xu, F., Sun, R.C. (2010) Structural characterization of alkali-extractable lignin fractions from bamboo. J. Biobased Mater. Bio. 4:408–425.Search in Google Scholar

Wen, J.L., Xue, B.L., Xu, F., Sun, R.C. (2012) Unveiling the structural heterogeneity of bamboo lignin by in situ HSQC NMR technique. Bioenerg. Res. 5:886–903.Search in Google Scholar

Wen, J.L., Xue, B.L., Xu, F., Sun, R.C. (2013) Unmasking the structural features and property of lignin from bamboo. Ind. Crops Prod. 42:332–343.10.1016/j.indcrop.2012.05.041Search in Google Scholar

Wenzig, E., Kunert, O., Ferreira, D., Schmid, M., Schühly, W., Bauer, R., Hiermann, A. (2005) Flavonolignans from Avena sativa. J. Nat. Prod. 68:289–292.Search in Google Scholar

Yamamura, M., Hattori, T., Suzuki, S., Shibata, D., Umezawa, T. (2010) Microscale alkaline nitrobenzene oxidation method for high-throughput determination of lignin aromatic components. Plant Biotechnol. 27:305–310.10.5511/plantbiotechnology.27.305Search in Google Scholar

Yuan, T.Q., Sun, S.N., Xu, F., Sun, R.C. (2011a) Characterization of lignin structures and lignin-carbohydrate complex (LCC) linkages by quantitative C-13 and 2D HSQC NMR spectroscopy. J. Agric. Food Chem. 59:10604–10614.10.1021/jf2031549Search in Google Scholar PubMed

Yuan, T.Q., Sun, S.N., Xu, F., Sun, R.C. (2011b) Structural characterization of lignin from Triploid of Populus tomentosa Carr. J. Agric. Food Chem. 59:6605–6615.10.1021/jf2003865Search in Google Scholar PubMed

Zhang, A.P., Lu, F.C., Sun, R.C., Ralph, J. (2010a) Isolation of cellulolytic enzyme lignin from wood preswollen/dissolved in dimethyl sulfoxide/N-methylimidazole. J. Agric. Food Chem. 58:3446–3450.10.1021/jf903998dSearch in Google Scholar PubMed

Zhang, A.P., Lu, F.C., Liu, C.F., Sun R.C. (2010b) Isolation and characterization of lignins from Eucalyptus tereticornis (12ABL). J. Agric. Food Chem. 58:11287–11293.10.1021/jf103354xSearch in Google Scholar PubMed

Received: 2012-10-3
Accepted: 2013-1-15
Published Online: 2013-02-15
Published in Print: 2013-08-01

©2013 by Walter de Gruyter Berlin Boston

Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Review
  4. Novel cellulose-based composites based on nanofibrillated plant and bacterial cellulose: recent advances at the University of Aveiro – a review
  5. Original Articles
  6. Quantitative structural characterization of the lignins from the stem and pith of bamboo (Phyllostachys pubescens)
  7. Fractionation and characterization of lignin-carbohydrate complexes (LCCs) of Eucalyptus globulus in residues left after MWL isolation. Part II: Analyses of xylan-lignin fraction (X-L)
  8. Alkali consumption of aliphatic carboxylic acids during alkaline pulping of wood and nonwood feedstocks
  9. Improvement of kraft pulp bleaching by treatments with laccase, urea, and refining
  10. Development and evaluation of new curing agents derived from glycerol for formaldehyde-free soy-based adhesives in wood composites
  11. Formation of highly hydrophobic wood surfaces using silica nanoparticles modified with long-chain alkylsilane
  12. The fracture behavior of birch and spruce in the radial-tangential crack propagation direction at the scale of the growth ring
  13. Flatwise Young’s modulus and flatwise shear modulus of plywood measured by flexural vibration test
  14. A numerical and experimental study regarding the influence of some process parameters on the damage state in wood chips
  15. Treatment of wood with silica sols against attack by wood-decaying fungi and blue stain
  16. Mimicking of the strength loss in the Vasa: model experiments with iron-impregnated recent oak
  17. Improved heat insulation system (Mirrorpanel) for construction of wood buildings
  18. Meetings
  19. Meetings
https://doi.org/10.1515/hf-2012-0162
Keywords for this article
acylation; bamboo lignin; β-O-4 linkage; quantitative NMR; tricin

Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Review
  4. Novel cellulose-based composites based on nanofibrillated plant and bacterial cellulose: recent advances at the University of Aveiro – a review
  5. Original Articles
  6. Quantitative structural characterization of the lignins from the stem and pith of bamboo (Phyllostachys pubescens)
  7. Fractionation and characterization of lignin-carbohydrate complexes (LCCs) of Eucalyptus globulus in residues left after MWL isolation. Part II: Analyses of xylan-lignin fraction (X-L)
  8. Alkali consumption of aliphatic carboxylic acids during alkaline pulping of wood and nonwood feedstocks
  9. Improvement of kraft pulp bleaching by treatments with laccase, urea, and refining
  10. Development and evaluation of new curing agents derived from glycerol for formaldehyde-free soy-based adhesives in wood composites
  11. Formation of highly hydrophobic wood surfaces using silica nanoparticles modified with long-chain alkylsilane
  12. The fracture behavior of birch and spruce in the radial-tangential crack propagation direction at the scale of the growth ring
  13. Flatwise Young’s modulus and flatwise shear modulus of plywood measured by flexural vibration test
  14. A numerical and experimental study regarding the influence of some process parameters on the damage state in wood chips
  15. Treatment of wood with silica sols against attack by wood-decaying fungi and blue stain
  16. Mimicking of the strength loss in the Vasa: model experiments with iron-impregnated recent oak
  17. Improved heat insulation system (Mirrorpanel) for construction of wood buildings
  18. Meetings
  19. Meetings
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 8.10.2025 from https://www.degruyterbrill.com/document/doi/10.1515/hf-2012-0162/html?lang=en
Scroll to top button