Abstract
Milled wood lignins from alkaline pretreated wood with very low sugar content and a wide range of syringyl-to-guaiacyl (S/G) ratio between 1.2 and 3.0 were isolated from 12 industrially valuable hardwood (HW) species. The lignin preparations were investigated by means of a comprehensive 13C nuclear magnetic resonance (NMR) methodology to address the possibilities and limitations of this approach for HW native lignins and to estimate the structural variations within HW lignins. Good correlations were found for different independent methods for the quantification of major lignin moieties. The results were reliable at the C6 level and not only for relative comparison. The correlation was good between methoxyl group determinations by wet chemistry and those by 13C NMR spectroscopy. The limitations of the 13C NMR method were also pointed out. The differences in the S/G ratios can be large, but other structural deviations are less significant. Strong correlations between the S/G ratios and the amounts of other structural peculiarities could not be found by the 13C NMR approach. However, with increasing S/G ratios, the β-O-4 content showed increasing tendencies and the degree of condensation showed decreasing tendencies.
References
Adler, E. (1977) Lignin chemistry: past, present and future. Wood Sci. Technol. 11:169–218.Search in Google Scholar
Akiyama, T., Goto, H., Nawawi, D.S., Syafii, W., Matsumoto, Y., Meshitsuka, G. (2005) Erythro/threo ratio of β-O-4 structures as an important structural characteristic of lignin. Part IV. Variation in erythro/threo ratio in softwood and hardwood lignins and its relation to syringyl/guaiacyl ratio. Holzforschung 59:276–281.10.1515/HF.2005.045Search in Google Scholar
Balakshin, M.Y., Capanema, E.A. (2014) Towards optimum methodology to assess molecular structure of native and technical lignins. In: Proc. 13th EWLP, Seville, Spain. pp. 63–66.Search in Google Scholar
Balakshin, M.Y., Capanema, E.A. (2015) On the quantification of lignin hydroxyl groups with 31P and 13C NMR spectroscopy. J. Wood Chem. Technol. In press.10.1080/02773813.2014.928328Search in Google Scholar
Balakshin, M.Y., Capanema, E.A., Goldfarb, B., Frampton, J., Kadla, J. (2005) NMR studies on Fraser fir Abies fraseri (Pursh) Poir. lignins. Holzforschung 59:488–496.10.1515/HF.2005.081Search in Google Scholar
Balakshin, M.Y., Capanema, E.A., Chang, H-m. (2008) Recent advances in isolation and analysis of lignins and lignin-carbohydrate complexes. In: Characterization of Lignocellulosics. Ed. Hu, T. Blackwell, Oxford, UK. pp. 148–166.10.1002/9781444305425.ch9Search in Google Scholar
Balakshin, M.Y., Berlin, A., Dellicolli, H.T., Grunert, C.A.N.J., Maximanko Gutman, V., Ortiz, D., Pye, E.K. (2010) Derivatives of native lignin. US8431635 B2.Search in Google Scholar
Balakshin, M., Capanema, E.A., Chang, H.-m., Jameel, H. (2013) Comprehensive evaluation of traditional and modified methods for isolation of lignin and LCC preparations. In: Proc. 17th ISWPC, Vancouver, Canada.Search in Google Scholar
Balakshin, M.Y., Capanema, E.A., Berlin, A. (2014) Isolation and analysis of lignin-carbohydrate complexes (LCC) preparations with traditional and advanced methods. A review. In: Studies in Natural Products Chemistry, v. 42. Elsevier, Amsterdam. pp. 83–115.Search in Google Scholar
Berlin, A., Balakshin M. (2014) Industrial lignins: analysis, properties and applications. In: Bioenergy Research: Advances and Applications. Eds. Gupta, V.K., Kubicek, C.P., Saddler, J., Xu, F., Tuohy, M. Elsevier, Amsterdam. pp. 315–336.Search in Google Scholar
Björkman, 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. (2004) A comprehensive approach for quantitative lignin characterization by NMR spectroscopy. J. Agric. Food Chem. 52:1850–1860.10.1021/jf035282bSearch in Google Scholar
Capanema, E.A., Balakshin, M.Y., Kadla, J.F. (2005a) Quantitative characterization of a hardwood milled wood lignin by NMR spectroscopy. J. Agric. Food Chem. 53:9639–9649.10.1021/jf0515330Search in Google Scholar
Capanema, E.A., Balakshin, M.Y., Chang, H-m., Jameel, H. (2005b) Isolation and characterization of residual lignins from hardwood pulps: method improvements. In: Proc. 13th Int. Symp. Wood Fibre Pulping Chem., Auckland, New Zealand, v. II. pp. 57–64.Search in Google Scholar
Capanema, E.A., Balakshin, M.Y., Kadla, J.F., Chang, H.-m. (2007a) On isolation of milled wood lignin from eucalyptus wood. O Papel 2007:74–79.Search in Google Scholar
Capanema, E.A., Balakshin, M.Y., Katahira, R., Chang, H-m., Jameel, H. (2007b) Structural variations in hardwood lignins. In: Proc. 14th Int. Symp. Wood Fibre Pulping Chem. CD-ROM. Durban, South Africa, June 25–28, 2007.Search in Google Scholar
Chen, C.-L. (1991) Lignin: occurrence in wood tissues, isolation, reactions and structure. In: Wood Structure and Composition. Eds. Lewis, M., Goldstein, I.S. Marcel Dekker, Inc., New York. pp. 183–261.Search in Google Scholar
Chen, C.-L. (1992) Determination of methoxyl groups. In: Methods in Lignin Chemistry. Eds. Lin, S.Y., Dence, C.W. Springer-Verlag, Berlin/Heidelberg. pp. 465–472.10.1007/978-3-642-74065-7_32Search in Google Scholar
Chen, C.-L. (1998) Characterization of milled wood lignins and dehydrogenative polymerisates from monolignols by carbon-13 NMR spectroscopy. In: ACS Symposium Series 697, Lignin and Lignan Biosynthesis. Eds. Lewis, N., Sarkanen, S. American Chemical Society, Washington, DC. pp. 255–275.10.1021/bk-1998-0697.ch018Search in Google Scholar
Chen, C.-L., Robert, D. (1988) Characterization of lignin by 1H and 13C NMR spectroscopy. In: Methods in Enzymology. Vol. 161B. Eds. Wood, W.A., Kellogg, S.T. Academic Press, Inc., New York. pp. 137–174.10.1016/0076-6879(88)61017-2Search in Google Scholar
del Río, J.C., Rencoret, J., Prinsen, P., Martinez, A.T., Ralph, J., Gutiérrez, A. (2012) 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
Duarte, A.P., Robert, D., Lachenal, D. (2000) Eucalyptus globulus kraft residual lignins. Part 1. Effect of extraction methods upon lignin structure. Holzforschung 54:365–372.10.1515/HF.2000.063Search in Google Scholar
Faix, O. (1991) Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 45:21–27.10.1515/hfsg.1991.45.s1.21Search in Google Scholar
Goto, H., Koda, K., Tong, G., Matsumoto, Y., Meshitsuka, G. (2006) Interference of carbohydrates in the determination of methoxyl content of lignin in woody samples. J. Wood Chem. Technol. 26:81–93.Search in Google Scholar
Kringstad, K.P., Mörck, R. (1983) 13C-NMR spectra of kraft lignins. Holzforschung 37:237–244.10.1515/hfsg.1983.37.5.237Search in Google Scholar
Landucci, L.L., Ralph, S.A., Hammel, K.E. (1998) 13C NMR characterization of guaiacyl, guaiacyl/syringyl and syringyl dehydrogenation polymers. Holzforschung 52:160–170.10.1515/hfsg.1998.52.2.160Search in Google Scholar
Mörck, R., Kringstad, K.P. (1985) 13C-NMR spectra of kraft lignins. II. Kraft lignin acetates. Holzforschung 39:109–119.10.1515/hfsg.1985.39.2.109Search 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 hardwoods, softwoods, grasses and compression wood. Holzforschung 35:16–26.10.1515/hfsg.1981.35.1.16Search in Google Scholar
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, S.A., Ralph, J., Landucci, L.L. (2004a) NMR database of lignin and cell wall model compounds. Available at: http://ars.usda.gov/SP2UserFiles/Place/36553000/software/NMR/NMR_DataBase_Intro_&_Index.pdf.Search in Google Scholar
Ralph, J., Lundquist, K., Brunow, G., Lu, F., Kim, H., Schatz, P.F., Marita, J.M., Hatfield, R., Ralph, S.A., Christensen, J.H., Boerjan, W. (2004b) Lignins: natural polymers from oxidative coupling of 4-hydroxyphenylpropanoids. Phytochem. Rev. 3:29–60.10.1023/B:PHYT.0000047809.65444.a4Search in Google Scholar
Robert, D.R., Brunow, G. (1984) Quantitative estimation of hydroxyl groups in milled wood lignin from spruce and in a dehydrogenation polymer from coniferyl alcohol using 13C NMR spectroscopy. Holzforschung 38:85–90.10.1515/hfsg.1984.38.2.85Search in Google Scholar
Robert, D., Gagnaire, D. (1981) Quantitative analysis of lignins by 13C NMR. In: Proc. International Symposium on Wood and Pulping Chemistry Ekman Days, Stockholm, Sweden, June 9–12, Vol. I. pp. 86–88.Search in Google Scholar
Sakakibara, A. (1991) Chemistry of lignin. In: Wood and Cellulose Chemistry. Eds. Hon, D.N.-S., Shiraishi, N. Marcel Dekker, Inc., New York. pp. 113–175.Search in Google Scholar
Sarkanen, K.V., Hergert, H.L. (1971) Classification and distribution. Chapter 3, 43-94. In: Lignins – Occurrence, Formation, Structure and Reactions. Eds. Sarkanen, K.V., Ludwig, C.H. Wiley-Interscience, New York. p. 916.Search in Google Scholar
Sarkanen, K.V., Ludwig, G.H. (1971) Lignins. Occurrence, Formation, Structure and Reactions. Wiley-Interscience, New York, 1971.Search in Google Scholar
Santos, R.B., Capanema, E.A., Balakshin, M.Y., Chang, H.-m., Jameel, H. (2012) Lignin structural variations in hardwood species. J. Agric. Food Chem. 60:4923–4930.10.1021/jf301276aSearch in Google Scholar PubMed
Xia, Z., Akim, L., Argyropoulos, D.S. (2001) Quantitative 13C NMR of lignins with internal standards. J. Agric. Food Chem. 49:3573–3578.10.1021/jf010333vSearch in Google Scholar PubMed
Zhang, L., Gellerstedt, G. (2007) Quantitative 2D HSQC NMR determination of polymer structures by selecting suitable internal standard reference. Magn. Res. Chem. 45:37–45.Search in Google Scholar
©2016 by De Gruyter