Abstract
Thioacidolysis is widely used for lignin structural characterization by cleaving β-aryl ethers to release syringyl (S), guaiacyl (G), and p-hydroxyphenyl (H) monomers followed by GC analysis. However, the traditional thioacidolysis method requires tedious extraction steps with chlorinated solvent underlying harmful to health, limiting its efficiency and application. Herein, an improved thioacidolysis method with high sensitivity for the quantitation of lignin-derived monomers was developed. The improved protocol used a quick, streamlined procedure to recover the monomeric products using ethyl acetate as extracting solvent and MS detector in multi-reaction monitoring mode to enhance its ability to detect extremely low concentration (0.1 ppb with signal-to-noise higher than 2) of monomeric products. Additionally, a fast GC program was established to speed up the GC quantitation. Several representative lignocellulose samples, including gymnosperm, angiosperm, and poaceae, were used to test this tailored method. The results demonstrated that the ratios of lignin monomer compositions determined by this method were consistent with that of traditional procedure despite the slightly higher monomer yields measured. More importantly, this method uses non-chlorinated solvent for microscale extraction and requires no evaporation step for workup, which is a green and efficient way for the quantification of lignin monomer compositions.
Funding source: National Natural Science Foundation of China
Award Identifier / Grant number: 31770621
Award Identifier / Grant number: 31870560
Funding source: The DOE Great Lakes Bioenergy Research Center
Award Identifier / Grant number: DOE BER Office of Science DE-SC0018409
Acknowledgments
The authors are very grateful to Dr. Wenzhang Ma of Herbarium (KUN), Kunming Institute of Botany, Chinese Academy of Sciences for kindly providing the Polytrichum and Pogonatum proliferum samples.
-
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
-
Research funding: The work was supported by the National Natural Science Foundation of China (31870560 and 31770621) and the DOE Great Lakes Bioenergy Research Center (DOE BER Office of Science, DE-SC0018409).
-
Conflict of interest statement: The authors declare that they have no conflicts of interest regarding this article.
References
Bateman, R.M., Crane, P.R., Dimichele, W.A., Kenrick, P.R., Rowe, N.P., Speck, T., and Stein, W.E. (1998). Early evolution of land plants: phylogeny, physiology, and ecology of the primary terrestrial radiation. Annu. Rev. Ecol. Evol. Syst. 29: 263–292, https://doi.org/10.1146/annurev.ecolsys.29.1.263.Search in Google Scholar
Boerjan, W., Ralph, J., and Baucher, M. (2003). Lignin biosynthesis. Annu. Rev. Plant Biol. 54: 519–546, https://doi.org/10.1146/annurev.arplant.54.031902.134938.Search in Google Scholar
Chen, F., Zhuo, C., Xiao, X., Pendergast, T.H., and Devos, K.M. (2021). A rapid thioacidolysis method for biomass lignin composition and tricin analysis. Biotechnol. Biofuels 14: 18. https://doi.org/10.1186/s13068-020-01865-y.Search in Google Scholar
Cove, D., Bezanilla, M., Harries, P., and Quatrano, R. (2006). Mosses as model systems for the study of metabolism and development. Annu. Rev. Plant Biol. 57: 497–520, https://doi.org/10.1146/annurev.arplant.57.032905.105338.Search in Google Scholar
Dien, B.S., Miller, D.J., Hector, R.E., Dixon, R.A., Chen, F., McCaslin, M., Reisen, P., Sarath, G., and Cotta, M.A. (2011). Enhancing alfalfa conversion efficiencies for sugar recovery and ethanol production by altering lignin composition. Bioresour. Technol. 102: 6479–6486, https://doi.org/10.1016/j.biortech.2011.03.022.Search in Google Scholar
Erickson, M. and Miksche, G.E. (1974). On the occurrence of lignin or polyphenols in some mosses and liverworts. Phytochemistry 13: 2295–2299, https://doi.org/10.1016/0031-9422(74)85042-9.Search in Google Scholar
Espiñeira, J.M., Novo Uzal, E., Gómez Ros, L.V., Carrión, J.S., Merino, F., Ros Barceló, A., and Pomar, F. (2011). Distribution of lignin monomers and the evolution of lignification among lower plants. Plant Biol. 13: 59-68.10.1111/j.1438-8677.2010.00345.xSearch in Google Scholar PubMed
Friedman, W.E. and Cook, M.E. (2000). The origin and early evolution of tracheids in vascular plants: integration of palaeobotanical and neobotanical data. Philos. Trans. R. Soc. Lond. B Biol. Sci. 355(1398): 857–868, https://doi.org/10.1098/rstb.2000.0620.Search in Google Scholar PubMed PubMed Central
Geiger, H., Seeger, T., Zinsmeister, H.D., and Frahm, J.P. (1997). The occurrence of flavonoids in arthrodontous mosses – an account of the present knowledge. J. Hattori Bot. Lab. 83: 273–308.Search in Google Scholar
Hambardzumyan, A., Foulon, L., Chabbert, B., and Aguié-Béghin, V. (2012). Natural organic UV-absorbent coatings based on cellulose and lignin: designed effects on spectroscopic properties. Biomacromolecules 13: 4081–4088, https://doi.org/10.1021/bm301373b.Search in Google Scholar PubMed
Harman-Ware, A.E., Foster, C., Happs, R.M., Doeppke, C., Meunier, K., Gehan, J., Yue, F., Lu, F., and Davis, M.F. (2016). A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers. Biotechnol. J. 11: 1268–1273, https://doi.org/10.1002/biot.201600266.Search in Google Scholar PubMed PubMed Central
Himmel, M.E., Ding, S.Y., Johnson, D.K., Adney, W.S., Nimlos, M.R., Brady, J.W., and Foust, T.D. (2007). Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 315: 804–807, https://doi.org/10.1126/science.1137016.Search in Google Scholar PubMed
Huntley, S.K., Ellis, D., Gilbert, M., Chapple, C., and Mansfield, S.D. (2003). Significant increases in pulping efficiency in C4H-F5H-transformed poplars: improved chemical savings and reduced environmental toxins. J. Agric. Food Chem. 51: 6178–6183, https://doi.org/10.1021/jf034320o.Search in Google Scholar PubMed
Jin, Z., Matsumoto, Y., Tange, T., Akiyama, T., Higuchi, M., Ishii, T., and Iiyama, K. (2005). Proof of the presence of guaiacyl-syringyl lignin in Selaginella tamariscina. J. Wood Sci. 51: 424–426, https://doi.org/10.1007/s10086-005-0725-8.Search in Google Scholar
Jin, Z., Matsumoto, Y., Tange, T., and Iiyama, K. (2007a). Structural characteristics of lignin in primitive pteridophytes: Selaginella species. J. Wood Sci. 53: 412–418, https://doi.org/10.1007/s10086-006-0872-6.Search in Google Scholar
Jin, Z., Shao, S., Katsumata, K.S., and Iiyama, K. (2007b). Lignin characteristics of peculiar vascular plants. J. Wood Sci. 53: 520–523, https://doi.org/10.1007/s10086-007-0891-y.Search in Google Scholar
Kenrick, P. and Crane, P.R. (1997). The origin and early evolution of plants on land. Nature 389: 33–39, https://doi.org/10.1038/37918.Search in Google Scholar
Lan, W., Rencoret, J., Lu, F., Karlen, S., Smith, B., Harris, P., Del Río, J., and Ralph, J. (2016). Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny. Plant J. 88: 1046–1057, https://doi.org/10.1111/tpj.13315.Search in Google Scholar PubMed
Lapierre, C., Monties, B., and Rolando, C. (1986). Thioacidolysis of poplar lignins: identification of monomeric syringyl products and characterization of guaiacyl-syringyl lignin fractions. Holzforschung 40: 113–118, https://doi.org/10.1515/hfsg.1986.40.2.113.Search in Google Scholar
Lepifre, S., Froment, M., Cazaux, F., Houot, S., Lourdin, D., Coqueret, X., Lapierre, C., and Baumberger, S. (2004). Lignin incorporation combined with electron-beam irradiation improves the surface water resistance of starch films. Biomacromolecules 5: 1678, https://doi.org/10.1021/bm040005e.Search in Google Scholar PubMed
Li, Y., Shuai, L., Kim, H., Motagamwala, A., Mobley, J., Yue, F., Tobimatsu, Y., Havkin-Frenkel, D., Chen, F., and Dixon, R. (2018). An “ideal lignin” facilitates full biomass utilization. Sci. Adv. 4: eaau 2968, https://doi.org/10.1126/sciadv.aau2968.Search in Google Scholar PubMed PubMed Central
López-Blanco, R., Moreno-González, D., Nortes-Méndez, R., García-Reyes, J.F., Molina-Díaz, A. and Gilbert-López, B. (2018). Experimental and theoretical determination of pesticide processing factors to model their behavior during virgin olive oil production. Food Chem. 239: 9–16.10.1016/j.foodchem.2017.06.086Search in Google Scholar PubMed
Magaton, A.D., Colodette, J.L., Gouvea, A.D.G., Gomide, J.L., Muguet, M.C.D., and Pedrazzi, C. (2009). Eucalyptus wood quality and its impact on Kraft pulp production and use. Tappi J. 8: 32–39.Search in Google Scholar
Ragauskas, A.J., Williams, C.K., Davison, B.H., Britovsek, G., Cairney, J., and Eckert, C.A. (2006). The path forward for biofuels and biomaterials. Science 311: 484–489, https://doi.org/10.1126/science.1114736.Search in Google Scholar PubMed
Ralph, J., Lapierre, C., and Boerjan, W. (2019). Lignin structure and its engineering. Curr. Opin. Biotechnol. 56: 240–249, https://doi.org/10.1016/j.copbio.2019.02.019.Search in Google Scholar PubMed
Ralph, J., Lundquist, K., Brunow, G., Lu, F., Kim, H., Schatz, P.F., Marita, J.M., Hatfield, R.D., Ralph, S.A., Christensen, J.H., et al.. (2004). Lignins: natural polymers from oxidative coupling of 4-hydroxyphenyl-propanoids. Phytochemistry Rev. 3: 29–60, https://doi.org/10.1023/b:phyt.0000047809.65444.a4.10.1023/B:PHYT.0000047809.65444.a4Search in Google Scholar
Regner, M., Bartuce, A., Padmakshan, D., Ralph, J., and Karlen, S.D. (2018). Reductive cleavage method for quantitation of monolignols and low-abundance monolignol conjugates. ChemSusChem. 11: 1600–1605, https://doi.org/10.1002/cssc.201800617.Search in Google Scholar PubMed PubMed Central
Rencoret, J., Gutiérrez, A., Marques, G., Del Río, J.C., Tobimatsu, Y., Lam, P.Y., Pérez-Boada, M., Ruiz-Dueñas, F.J., Barrasa, J.M., and Martínez, A.T. (2021). New insights on structures forming the lignin-like fractions of ancestral plants. Front. Plant Sci. 12: 740923. https://doi.org/10.3389/fpls.2021.740923.Search in Google Scholar PubMed PubMed Central
Rensing, S.A. (2018). Great moments in evolution: the conquest of land by plants. Curr. Opin. Plant Biol. 42: 49–54, https://doi.org/10.1016/j.pbi.2018.02.006.Search in Google Scholar PubMed
Robinson, A.R. and Mansfield, S.D. (2009). Rapid analysis of poplar lignin monomer composition by a streamlined thioacidolysis procedure and near-infrared reflectance-based prediction modeling. Plant J. 58: 706–714, https://doi.org/10.1111/j.1365-313x.2009.03808.x.Search in Google Scholar
Rolando, C., Monties, B., and Lapierre, C. (1992). Thioacidolysis. In: Lin, S.Y. and Dence, C.W. (Eds.). Methods in lignin chemistry. Springer, Berlin, Heidelberg, pp. 334–349. https://doi.org/10.1007/978-3-642-74065-7_23.Search in Google Scholar
Saeman, J.F., Bubl, J.L. and Harris, E. (1944). Quantitative saccharification of wood and cellulose. Ind. Eng. Chem. Anal. Ed. 17: 35–37.10.1021/i560137a008Search in Google Scholar
Saeman, J.F., Harris, E.E., and Kline, A.A. (1945). Analysis of wood sugars. Ind. Eng. Chem. Anal. Ed. 17: 95–99, https://doi.org/10.1021/i560138a006.Search in Google Scholar
Shen, X. and Sun, R. (2021). Recent advances in lignocellulose prior-fractionation for biomaterials, biochemicals, and bioenergy. Carbohydr. Polym. 261: 117884. https://doi.org/10.1016/j.carbpol.2021.117884.Search in Google Scholar PubMed
Siegel, S.M. (1969). Evidence for the presence of lignin in moss gametophytes. Am. J. Bot. 56: 175–179, https://doi.org/10.1002/j.1537-2197.1969.tb07520.x.Search in Google Scholar
Stewart, J.J., Akiyama, T., Chapple, C., Ralph, J., and Mansfield, S.D. (2009). The effects on lignin structure of over expression of ferulate 5-hydroxylase in hybrid poplar. Plant Physiol. 150: 621–635, https://doi.org/10.1104/pp.109.137059.Search in Google Scholar PubMed PubMed Central
Yamamura, M., Hattori, T., Suzuki, S., Shibata, D., and Umezawa, T. (2012). Microscale thioacidolysis method for the rapid analysis of β-O-4 substructures in lignin. Plant Biotechnol. 29: 419–423, https://doi.org/10.5511/plantbiotechnology.12.0627a.Search in Google Scholar
Yong, W., Guo, T., Fang, P., Liu, J., Dong, Y., and Zhang, F. (2017). Direct determination of multi-pesticides in wine by ambient mass spectrometry. Int. J. Mass Spectrom. 417: 53–57, https://doi.org/10.1016/j.ijms.2017.03.005.Search in Google Scholar
Yue, F., Lu, F., Sun, R., and Ralph, J. (2012). Syntheses of lignin-derived thioacidolysis monomers and their uses as quantitation standards. J. Agric. Food Chem. 60: 922–928, https://doi.org/10.1021/jf204481x.Search in Google Scholar PubMed
Zhao, Q. (2016). Lignification: flexibility, biosynthesis and regulation. Trends Plant Sci. 21: 713–721, https://doi.org/10.1016/j.tplants.2016.04.006.Search in Google Scholar PubMed
Ziebell, A., Gracom, K., Katahira, R., Chen, F., Pu, Y., Ragauskas, A., Dixon, R.A., and Davis, M. (2010). Increase in 4-coumaryl alcohol units during lignification in alfalfa (medicago sativa) alters the extractability and molecular weight of lignin. J. Biol. Chem. 285: 38961–38968, https://doi.org/10.1074/jbc.m110.137315.Search in Google Scholar
Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/hf-2021-0224).
© 2022 Walter de Gruyter GmbH, Berlin/Boston
