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Licensed Unlicensed Requires Authentication Published by De Gruyter October 18, 2013

Multi-step degradation method for β-O-4 linkages in lignins: γ-TTSA method. Part 3. Degradation of milled wood lignin (MWL) from Eucalyptus globulus

  • Daisuke Ando EMAIL logo , Fumiaki Nakatsubo , Toshiyuki Takano , Hiroshi Nishimura , Masato Katahira and Hiroyuki Yano
From the journal Holzforschung

Abstract

Milled wood lignin (MWL) of Eucalyptus globulus has been treated by a selective degradation method for β-O-4 linkages, which lets the lignin carbohydrate complexes (LCC) intact. The method consists of four reaction steps: (1) γ-tosylation, (2) thioetherification, (3) sulfonylation and (4) mild alkali treatment (γ-TTSA method). Each step was followed by spectroscopies for chemical structural analysis; especially, the HSQC-NMR analysis was in focus. It was demonstrated that β-O-4 linkages were selectively and quantitatively cleaved by the γ-TTSA method while the β-β linkages in the MWL remained intact. The method leads to an enrichment of LCCs.


Corresponding author: Daisuke Ando, Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa-oiwakecho Sakyo-ku, Kyoto, 606-8502, Japan, Phone: +81-75-753-6256, Fax: +81-75-753-6300, e-mail:

We thank Dr Kazutsune Tsurumi of Oji Paper Co., Ltd (Tokyo, Japan) for providing the wood sample of E. globulus.

References

Ando, D., Takano, T., Nakatsubo, F. (2012) Multi-steps degradation method for β-O-4 linkage in lignins: γ-TTSA method. Part 1: reaction of non-phenolic dimeric β-O-4 model compounds. Holzforschung 66:331–339.10.1515/hf.2011.068Search in Google Scholar

Ando, D., Nakatsubo, F., Takano, T., Nishimura, H., Katahira, M., Yano, H. (2013) Multistep degradation method for β-O-4 linkage in lignins: γ-TTSA method. Part 2: reaction of lignin model polymer (DHP). Holzforschung 67:249–256.10.1515/hf-2012-0082Search in Google Scholar

Balakshin, M.Y., Capanema, E.A., Chang, H. (2007) MWL fraction with a high concentration of lignin carbohydrate linkages: isolation and 2D NMR spectroscopic analysis. Holzforschung 61:1–7.10.1515/HF.2007.001Search in Google Scholar

Balakshin, M., Capanera, E., Grecz, H., Chang, H., Jameel, H. (2011) Quantification of lignin-carbohydrate linkages with high-resolution NMR spectroscopy. Planta 233:1097–1110.10.1007/s00425-011-1359-2Search in Google Scholar PubMed

Björkman, A. (1956) Studies on finely divided wood. Part 1. Extraction of lignin with neutral solvents. Svensk Papperstidn. 59:477–485.Search in Google Scholar

Björkman, A. (1957) Finely divided wood. III. Extraction of lignin-carbohydrate complexes with neutral solvents. Svensk Papperstidn. 60:243–251.Search in Google Scholar

Brodin, I., Sjöholm, E., Gellerstedt, G. (2009) Kraft lignin as feedstock for chemical products: the effects of membrane filtration. Holzforschung 63:290–297.10.1515/HF.2009.049Search in Google Scholar

Dos Santos M., Marcelo C., Pedrazzi, C., Colodette, J.L. (2011) Xylan deposition onto eucalypt pulp fibers during oxygen delignification. Holzforschung 65:605–612.10.1515/hf.2011.070Search in Google Scholar

Guerra, A., Lucia, L.A., Argyropoulos, D.S. (2008) Isolation and characterization of lignins from Eucalyptus grandis Hill ex Maiden and Eucalyptus globulus Labill. by enzymatic mild acidolysis (EMAL). Holzforschung 62:24–30.10.1515/HF.2008.004Search in Google Scholar

Heikkinen, S., Toikka, M.M., Karhunen, T., Kilpelainen, I.A. (2003) Quantitative 2D HSQC (Q-HSQC) via suppression of J-dependence of polarization transfer in NMR spectroscopy: application to wood lignin. J. Am. Chem. Soc. 125:4362–4367.10.1021/ja029035kSearch in Google Scholar PubMed

Holtman, K.M., Chang, H.M., Jameel, H., Kadla, J.F. (2003) Elucidation of lignin structure through degradative methods: comparison of modified DFRC and thioacidolysis. J. Agric. Food. Chem. 51:3535–3540.Search in Google Scholar

Ibarra, D., Chavez, M.I., Rencoret, J., Del Rio, J.C., Gutierrez, A., Romero, J., Camarero, S., Martinez, M.J., Jumenez-Barbero, J., Martinez, A.T. (2007) Lignin modification during Eucalyptus globulus kraft pulping followed by totally chlorine-free bleaching: A two-dimensional nuclear magnetic resonance, Fourier transform infrared, and pyrolysis-gas chromatography/mass spectrometry study. J. Agric. Food Chem. 55:3477–3490.10.1021/jf063728tSearch 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

Koshijima, T., Watanabe, T. Association between lignin and carbohydrates in wood and other plant tissues. Springer, Berlin, 2003, pp. 91–131.10.1007/978-3-662-05191-7_5Search in Google Scholar

Lapierre, C., Monties, B., Roland, C. (1986) Preparative thioacidolysis of spruce lignin: isolation and identification of main monomeric products. Holzforschung 40:47–50.10.1515/hfsg.1986.40.1.47Search in Google Scholar

Lawoko, M., Henriksson, G., Gellerstedt, G. (2005) Structural differences between the lignin-carbohydrate complexes present in wood and in chemical pulps. Biomacromolecules 6:3467–3473.10.1021/bm058014qSearch in Google Scholar PubMed

Leschinsky, M., Zuckerstätter, G., Weber, H.K., Patt, R., Sixta, H. (2008a) Effect of autohydrolysis of Eucalyptus globulus wood on lignin structure. Part 2: influence of autohydrolysis intensity. Holzforschung 62:653–658.10.1515/HF.2008.133Search in Google Scholar

Leschinsky, M., Zuckerstätter, G., Weber, H.K., Patt, R., Sixta, H. (2008b) Effect of autohydrolysis of Eucalyptus globulus wood on lignin structure. Part 1: comparison of different lignin fractions formed during water prehydrolysis. Holzforschung 62(6):645–652.10.1515/HF.2008.117Search in Google Scholar

Lu, F., Ralph, J. (1997a) 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. (1997b) DFRC method for lignin analysis. 1. New method for beta aryl ether cleavage: lignin model studies. J. Agric. Food Chem. 45:4655–4660.10.1021/jf970539pSearch in Google Scholar

Li, J., Martin-Sampedro, R., Pedrazzi, C., Gellerstedt, G. (2011) Fractionation and characterization of lignin-carbohydrate complexes (LCCs) from eucalyptus fibers. Holzforschung 65:43–50.10.1515/hf.2011.013Search in Google Scholar

Lundquist, K. (1992) Characterization in solution: chemical degradation methods. In: Methods in lignin Chemistry. Eds. Stephen, Y.L., Carlton, W.D. Springer, Berlin. pp. 287–300.Search in Google Scholar

Lundquist, K., Simonsson, R., Tingsvik, K. (1979) On the occurrence of carbohydrates in milled wood lignin. Svensk Papperstidn. 82:272–275.Search in Google Scholar

Mendes, C.V.T., Baptista, C.M.S.G., Rocha, J.M.S., Carvalho, M.G.V.S. (2009) Prehydrolysis of Eucalyptus globulus Labill. hemicelluloses prior to pulping and fermentation of the hydrolysates with the yeast Pichia stipitis 10th EWLP, Stockholm, Sweden, August 25–28, 2008. Holzforschung 63:737–743.10.1515/HF.2009.106Search in Google Scholar

Meshitsuka, G., Lee, Z., Nakano, J.J. (1982) Studies of the nature of lignin-carbohydrate bonding. J. Wood Chem. Technol. 2:251–267.Search in 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 1: analyses of hemicellulose-lignin fraction (HCL). Holzforschung 66:459–465.10.1515/hf.2011.177Search in Google Scholar

Nieminen, K., Sixta, H. (2012) Comparative evaluation of different kinetic models for batch cooking: A review. Holzforschung 66:791–799.10.1515/hf-2011-0122Search in Google Scholar

Patt, R., Kordsachia, O., Fehr, J. (2006) European hardwoods versus Eucalyptus globulus as a raw material for pulping. Water Sci. Technol. 40:39–48.Search in Google Scholar

Rencoret, J., Marques, G., Gutiérrez, A., Ibarra, D., Li, J., Gellerstedt, G., Ignacio Santos, J., Jiménez-Berbero, J., Martínez, Á.T., del Río, J.C. (2008) Structural characterization of milled wood lignins from different eucalypt species. Holzforschung 62:514–526.10.1515/HF.2008.096Search in Google Scholar

Rodríguez-López, J., Romaní, A., González-Muñoz, M.J., Garrote, G., Parajó, J.C. (2012) Extracting value-added products before pulping: Hemicellulosic ethanol from Eucalyptus globulus wood. Holzforschung 66:591–599.10.1515/hf-2011-0204Search in Google Scholar

Roland, C., Monties, B., Lapierre, C. (1992) Characterization in solution: chemical degradation methods. In: Methods in Lignin Chemistry. Eds. Stephen, Y.L., Carlton, W.D. Springer, Berlin. pp. 334–349.Search in Google Scholar

Silverstein, R.M. Spectrometric Identification of Organic Compounds. 2nd Rev. Edn. John Wiley & Sons, New York, 1967.Search in Google Scholar

Vila, C., Francisco, J.L., Santos, V., Parajó, J.C. (2013) Effects of hydrothermal processing on the cellulosic fraction of Eucalyptus globulus wood. Holzforschung 67(1):33–40.10.1515/hf-2012-0046Search in Google Scholar

Watanabe, T. (1995) Important properties of lignin-carbohydrates complexes (LCCs) in environmentally safe paper making. Trends Glycosci. Glycotechnol. 33:57–68.10.4052/tigg.7.57Search in Google Scholar

Received: 2013-1-10
Accepted: 2013-3-1
Published Online: 2013-10-18
Published in Print: 2013-12-01

©2013 by Walter de Gruyter Berlin Boston

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