Abstract
A combination of high-resolution mass spectrometry based on an orbital ion trap and 2D NMR spectroscopy was first applied to the characterization of the structure of poorly studied lignins of herbaceous plants using dioxane lignin from sedge (Cárex) as an example. Macromolecules of the Cárex lignin are found to be constructed from guaiacyl, syringyl, and p-hydroxyphenyl structural units in a ratio of 57:22:21 bound mainly by ether β-O-4 bonds. The key role of p-hydroxycinnamic acids in the formation of the lignin structure and ester bonds with polysaccharides was shown. A possible structural formula of the macromolecule fragment of the Cárex lignin was proposed on the basis of an analysis of the 2D NMR spectra (HSQC).
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J. Ralph, K. Lundquist, G. Brunow, F. Lu, H. Kim, P. F. Schatz, J. M. Marita, R. D. Hatfield, S. A. Ralph, J. H. Christensen, W. Boerjan, Phytochemistry Rev., 2004, 3, 29–60.
C. Heitner, D. R. Dimmel, J. A. Schmidt, Lignin and Lignans: Advances in Chemistry, Boca Raton, CRC Press, 2010, 683.
A. Abe, K. Dusek, S. Kobayashi, Advances in Polymer Science, Springer-Verlag, 2010, 212.
G. N. Kononov, Khimiya drevesiny i ee osnovnykh komponentov [Chemistry of Wood and Its Major Components], MGU, Moscow, 1999, 247 pp. (in Russian).
V. Tarabanko, D. Petukhov, Chem. Sustain. Dev., 2003, 11, 655–667.
C. W. Dence, S. Y. Lin, The Determination of Lignin, Springer-Verlag, 1992, 33–61.
J. C. del Río, J. Rencoret, P. Prinsen, A. T. Martínez, J. Ralph, A. Gutiérrez, J. Agric. Food Chem., 2012, 60, 5922–5935.
L. Zhang, G. Gellerstedt, Magn. Reson. Chem., 2007, 45, 37–45.
S. Constant, H. L. J. Wienk, A. E. Frissen, R. Boelens, D. S. van Es, R. J. H. Grisel, B. M. Weckhuysen, W. J. J. Huijgen, R. J. A. Gosselink, P. C. A. Bruijnincx, Green Chem., 2016, 18, 2651–2665.
A. P. Karmanov, L. S. Kocheva, V. Yu. Belyaev, Khimiya Rastitelnogo syrya [Chemistry of Plant Raw Materials], 2009, 4, 15–19 (in Russian).
V. A. Beliy, A. A. Pechnikova, L. S. Kocheva, A. A. Moskalev, A. P. Karmanov, Adv. Gerontol., 2010, 23, 221–227.
W. Lan, F. Lu, M. Regner, Y. Zhu, J. Rencoret, S. A. Ralph, U. I. Zakai, K. Morreel, W. Boerjan, J. Plant Physiol., 2015, 167, 1284–1295.
J. C. del Río, J. Rencoret, A. Gutierrez, L. Nieto, J. Jimenez-Barbero, A. T. Martinez, J. Agric. Food Chem., 2011, 59, 11088–11099.
A. U. Buranov, G. Mazza, Industrial Crops and Products, 2008, 28, 237–259.
R. Sun, J. M. Lawther, W. B. Banks, Industrial Crops and Products, 1997, 6, 1–8.
T. B. Lam, K. Kadoya, K. Iiyama, Phytochemistry, 2001, 57, 987–992.
D. S. Kosyakov, N. V. Ul’yanovskii, E. A. Anikeenko, N. S. Gorbova, Rapid Commun. Mass Spectrom., 2016, 30, 2099–2108.
D. S. Kosyakov, E. V. Ipatova, S. M. Krutov, N. V. Ul’yanovskii, I. I. Pikovskoi, J. Anal. Chem., 2017, 72, 1396–1403.
I. I. Pikovskoi, D. S. Kosyakov, N. V. Ul’yanovskii, J. Anal. Chem., 2019, 74, 1404–1412.
N. N. Bambalov, Eurasian Soil Sci., 2007, 40, 1175–1180.
J. Schellekens, P. Buurman, T. Kuyper, Soil Biology and Biochemistry, 2012, 53, 32–42.
J. Z. Mao, L. M. Zhang, F. Xu, Cellulose Chem. Technol., 2012, 46, 193–205.
J. M. Pepper, P. E. T. Baylis, E. Adler, Can. J. Chem., 1959, 37, 1241–1248.
S. Y. Lin, C. W. Dence, Methods in Lignin Chemistry, Springer-Verlag, 1992, 578.
S. Baumberger, A. Abaecherli, M. Fasching, G. Gellerstedt, R. Gosselink, B. Hortling, J. Li, B. Saake, E. Jong, Holzforschung, 2007, 61, 459–468.
D. Van Krevelen, Fuel, 1950, 29, 269–228.
A. P. Karmanov, Yu. B. Monakov, Russ. Chem. Rev., 2003, 72, 715–734.
J. Ralph, R. D. Hatfield, S. Quideau, J. Am. Chem. Soc., 1994, 116, 9448–9456.
C. Crestini, D. S. Argyropoulos, J. Agric. Food Chem., 1997, 45, 1212–1219.
E. A. Capanema, M. Y. Balakshin, C. L. Chen, J. S. Gratzl, H. Gracz, Holzforschung, 2001, 55, 302–308.
A. T. Martínez, J. Rencoret, G. Marques, A. Gutierrez, D. Ibarra, J. Jimenez-Barbero, J. C. del Río, Phytochemistry, 2008, 69, 2831–2843.
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The equipment of the Core Facility Center “Arktika” at the M. V. Lomonosov Northern (Arctic) Federal University was used in the work.
This work was financially supported by the Russian Science Foundation (Project No. 18-73-10138), as well as by the Russian Foundation for Basic Research (Project No. 19-33-90043-asp, work of post-graduate student I. I. Pikovskoi).
Russian Chemical Bulletin, International Edition, Vol. 69, No. 10, pp. 2004–2012, October, 2020
Published in Russian in Izyestiya AkademiiNauk. Seriya Khimicheskaya, No. 10, pp. 2004–2012, October, 2020.
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Pikovskoi, I.I., Kosyakov, D.S., Faleva, A.V. et al. Study of the sedge (Cárex) lignin by high-resolution mass spectrometry and NMR spectroscopy. Russ Chem Bull 69, 2004–2012 (2020). https://doi.org/10.1007/s11172-020-2992-3
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DOI: https://doi.org/10.1007/s11172-020-2992-3