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.
[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.
[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.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:53295", author = "I. F. Fiţigău and F. Peter and C. G. Boeriu", title = "Structural Analysis of Lignins from Different Sources", abstract = "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.", keywords = "Lignin, fractionation, FT-IR, GPC, 31P-NMR.", volume = "7", number = "4", pages = "172-6", }