Structural Analysis of Lignins from Different Sources

Five lignin samples were fractionated with Acetone/Water mixtures and the obtained fractions were subjected to extensive structural characterization, including Fourier Transform Infrared (FT-IR), Gel permeation Chromatography (GPC) and Phosphorus-31 NMR spectroscopy (31P-NMR). The results showed that for all studied lignins the solubility increases with the increment of the acetone concentration. Wheat straw lignin has the highest solubility in 90/10 (v/v) Acetone/Water mixture, 400 mg lignin being dissolved in 1 mL mixture. The weight average molecular weight of the obtained fractions increased with the increment of acetone concentration and thus with solubility. 31P-NMR analysis based on lignin modification by reactive phospholane into phosphitylated compounds was used to differentiate and quantify the different types of OH groups (aromatic, aliphatic, and carboxylic) found in the fractions obtained with 70/30 (v/v) Acetone/Water mixture.




References:
[1] K. V. Sarkanen, C. H. Ludwig, Lignins: Occurrence, Formation,
Structure and Reactions, Wiley-Interscience, New-York, 1971.
[2] A.T Martinez, M. Speranza, F.J. Ruiz-Duenas, P. Ferreira, S. Camarero,
F. Guillen, M.J. Martinez, A. Gutierrez, J.C. del Rio, "Biodegradation
of lignocellulosics: microbial, chemical, and enzymatic aspects of the
fungal attack of lignin", Int Microbiol, vol. 8, pp. 195-204, 2005.
[3] M. Dashtban, H. Schraft, T. A. Syed, W. Qin, "Fungal biodegradation
and enzymatic modificationof lignin", Int J Biochem Mol Biol, vol. 1(1)
pp. 36-50, 2010.
[4] E. A. Capanema, M. YU. Balakshin, J. F. Kadla, "Quantitative
Characterization of a Hardwood Milled Wood Lignin by Nuclear
Magnetic Resonance Spectroscopy", J. Agric. Food Chem. vol. 53, pp.
9639- 9649, 2005.
[5] J.R. Obst, " Guaiacyl and Syringyl Lignin Composition in Hardwood
Cell Components", Holzforschung, vol. 36, pp. 143-152, 1982
[6] J.R. Rostrup-Nielsen, "Chemistry: making fuels from biomass", Science
vol. 308, pp. 1421-1422, 2005.
[7] D. Yang, X. Qiu, M. Zhou, H. Lou, "Properties of sodium lignosulfonate
as dispersant of coal water slurry", Energy Convers. Manage., vol. 48
pp. 2433-2438, 2007.
[8] C. Pouteau, P. Dole, B. Cathala, L. Averous, N. Boquillon, "Antioxidant
properties of lignin in polypropylene", Polymer Degradation and
Stability, vol. 81, pp. 9-18, 2003.
[9] A. Granata, D. S. Argyropoulos, "2-Chloro-4,4,5,5-tetramethyl-1,3,2-
dioxaphospholane, a reagent for the accurate determination of the
uncondensed and condensed phenolic moieties in lignins", J. Agric.
Food Chem., vol. 43, pp. 1538-1544, 1995.
[10] Y. Ni, Q. Hu, "Alcell lignin solubility in ethanol-water mixtures" J.
Appl. Polym. Sci., vol. 57, pp. 1441-1446, 1995.
[11] O., Faix, Fourier transformed infrared spectroscopy, In: S.Y., Lin, C.W.
Dence, (Eds.), Methods in Lignin Chemistry, Springer-Verlag, Berlin-
Heidelberg, pp. 458-464, 1992.
[12] C. G. Boeriu, D. Bravo, R.J.A. Gosselink, J.E.G. van Dam
"Characterisation of structure-dependent functional properties of lignin
with infrared spectroscopy", Industrial Crops and Products, vol. 20, pp.
205-218, 2004.
[13] Y. Pu ,S. Cao, A. J. Ragauskas, "Application of quantitative 31P-NMR in
biomass lignin and biofuel precursors characterization", Energy Environ.
Sci., vol. 4, pp. 3154 - 3166, 2011.
[14] F. Abdelkafi, H. Ammar, B. Rousseau, M. Tessier, R. El Gharbi, A.
Fradet, "Structural analysis of alfa grass (Stipa tenacissima L.) lignin
obtained by acetic acid/formic acid delignification", Biomacromolecules,
vol. 12, pp. 3895−3902, 2011.