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Licensed Unlicensed Requires Authentication Published by De Gruyter February 27, 2013

Molecular weight distributions of acetylated lignocellulosic biomasses recovered from an ionic liquid system

Chen Qu, Takao Kishimoto, Masahiro Hamada and Noriyuki Nakajima
From the journal Holzforschung

Abstract

Recently, a method was presented for the dissolution and nuclear magnetic resonance analysis of cell wall components in lignocellulosic biomass, which involves cell wall ball-milling, dissolution in ionic liquids (ILs), in situ acetylation, and the recovery of acetylated materials. However, the dissolution in ILs and the relatively long ball-milling times may partially degrade the plant cell wall components. In the present study, the molecular weight (MW) distributions of acetylated biomasses from fir (Abies sachalinensis), birch (Betula platyphylla), and bamboo (Phyllostachys nigra) recovered from IL systems were examined by size exclusion chromatography. The effects of IL types, cosolvents, dissolution temperatures and times, and ball-milling times were evaluated. The MW of acetylated fir woods recovered from 1-allyl-3-methylimidazolium chloride at 30–80°C or from 1-butyl-3-methylimidazolium chloride at 100°C for 2 h were similar to those materials that were recovered from the N-methylimidazole/dimethyl sulfoxide system. In contrast, a significant decrease in MW was observed with 1-ethyl-3-methylimidazolium acetate ([Emim]OAc) even at 30°C. The degradation of cell wall components in [Emim]OAc was reduced to some extent in the presence of N,N-dimethylacetamide or pyridine. The MW decreased gradually with increased ball-milling time.


Corresponding author: Takao Kishimoto, Faculty of Engineering, Department of Biotechnology, Toyama Prefectural University, Imizu 939-0398, Japan, e-mail:

References

Bentivoglio, G., Röder, T., Fasching, M., Buchberger, M., Schottenberger, H., Sixta, H. (2006) Cellulose processing with chloride-based ionic liquids. Lenzinger Berichte. 86:154–161.Search in Google Scholar

Fort, D.A., Remsing, R.C., Swatloski, R.P., Moyna, P., Moyna, G., Rogers, R. D. (2007) Can ionic liquids dissolve wood? Processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride. Green Chem. 9:63–69.Search in Google Scholar

Fujimoto, A., Matsumoto, Y., Chang, H.-M., Meshitsuka, G. (2005) Quantitative evaluation of milling effects on lignin structure during the isolation process of milled wood lignin. J. Wood Sci. 51:89–91.Search in Google Scholar

Fukaya, Y., Hayashi, K., Wada, M., Ohno, H. (2008) Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions. Green Chem. 10:44–46.Search in Google Scholar

George, A., Tran, K., Morgan, T.J., Benke, P.I., Berrueco, C., Lorente, E., Wu, B.C., Keasling, J.D., Simmons, B.A., Holmes, B.M. (2011) The effect of ionic liquid cation and anion combinations on the macromolecular structures of lignins. Green Chem. 13:3375–3385.Search in Google Scholar

Honglu, X., Tiejun, S. (2006) Wood liquefaction by ionic liquids. Holzforschung 60:509–512.Search in Google Scholar

Jia, S., Cox, B.J., Guo, X., Zhang, Z.C., Ekerdt, J.G. (2010) Decomposition of a phenolic lignin model compound over organic N-bases in an ionic liquid. Holzforschung 64:577–580.Search in Google Scholar

Kilpelainen, I., Xie, H., King, A., Granstrom, M., Heikkinen, S., Argyropoulos, D.S. (2007) Dissolution of wood in ionic liquid. J. Agric. Food Chem. 55:9142–9146.Search in Google Scholar

Kubo, S., Hashida, K., Yamada, T., Hishiyama, S., Magara, K., Kishino, M., Ohno, H., Hosoya, S. (2008) A characteristic reaction of lignin in ionic liquids; glycelol type enol-ether as the primary decomposition product of β-O-4 model compound. J. Wood Chem. Technol. 28:84–96.Search in Google Scholar

Liebner, F., Patel, I., Ebner, G., Becker, E., Horix, M., Potthast, A., Rosenau, T. (2010) Thermal aging of 1-alkyl-3-methylimidazolium ionic liquids and its effect on dissolved cellulose. Holzforschung 64:161–166.Search in Google Scholar

Lu, F., Ralph, J. (2003) Non-degradative dissolution and acetylation of ball-milled plant cell walls: high-resolution solution-state NMR. Plant J. 35:535–544.Search in Google Scholar

Lu, F., Ralph, J. (2011) Solution-state NMR of lignocellulosic biomass. J. Biobased Mater. Bioenergy 5:169–180.Search in Google Scholar

Nakamura, A., Miyafuji, H., Saka, S., Mori, M., Takahashi, H. (2010) Liquefaction behavior of Western red cedar and Japanese beech in the ionic liquid 1-ethyl-3-methylimidazolium chloride. Holzforschung 64:289–294.Search in Google Scholar

Qu, C., Kishimoto, T., Kishino, M., Hamada, M., Nakajima N. (2011) Heteronuclear single-quantum coherence nuclear magnetic resonance (HSQC NMR) characterization of acetylated fir (Abies sachallnensis MAST) wood regenerated from ionic liquid. J. Agric. Food Chem. 59:5382–5389.Search in Google Scholar

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.Search in Google Scholar

Qu, C., Kishimoto, T., Ogita, S., Hamada, M., Nakajima N. (2013) Dissolution and acetylation of ball-milled lignocellulosic biomass in ionic liquids at room temperature: application to NMR analysis of cell-wall components. Holzforschung 67:25–32.Search in Google Scholar

Schrems, M., Brandt, A., Welton, T., Liebner, F., Rosenau, T., Potthast, A. (2011) Ionic liquids as media for biomass processing: opportunities and restrictions. Holzforschung 65:527–533.Search in Google Scholar

Stasiewicz, M., Fojutowski, A., Kropacz, A., Pernak, J. (2008) 1-Alkoxymethyl-X- dimethylaminopyridinium-base ionic liquids in wood preservation. Holzforschung 62:309–317.Search in Google Scholar

Sun, N., Rahman, M., Qin, Y., Maxim, M.L., Rodriguez, H., Rogers, R.D. (2009) Complete dissolution and partial delignification of wood in the ionic liquid 1-ethyl-3-methyl- imidazolium acetate. Green Chem. 11:646–655.Search in Google Scholar

Viell, J., Marquardt, W. (2011) Disintegration and dissolution kinetics of wood chips in ionic liquids. Holzforschung 65:519–525.Search in Google Scholar

Yelle, D.J., Ralph, J., Frihart, C.R. (2008) Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy. Magn. Reson. Chem. 46:508–517.Search in Google Scholar

Zoia, L., King, A.W.T., Argyropoulos, D.S. (2011) Molecular weight distributions and linkages in lignocellulosic materials derivatized from ionic liquid media. J. Agric. Food Chem. 53:829–838.Search in Google Scholar

Received: 2012-11-1
Accepted: 2013-1-21
Published Online: 2013-02-27
Published in Print: 2013-10-01

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