Abstract
The new process of abies ethanol lignin sulfation by a low-toxic mixture of sulfamic acid and urea in 1,4-dioxane medium was optimized, and the structure of sulfated ethanol lignin was studied. The process of lignin sulfation is described by a first-order equation in the temperature range 70–100 °C. The value of the rate constants is weakly dependent on the ratios of lignin and sulfating complex (sulfamic acid–urea mixture). The activation energy of the sulfation process decreases from 11.5 to 7.5 kJ/mol with an increase in the content of the sulfating complex (SC). The optimal conditions for sulfation of abies ethanol lignin with a high yield of water-soluble sulfated lignin [(100% of mass) with sulfur content of 7.9%] were found: temperature 95–100 °C, L/SC ratio 1:2.3–1:2.9, time 2 h. The composition and structure of water-soluble sulfated ethanol lignin were determined by elemental analysis, FTIR spectroscopy, two-dimensional NMR spectroscopy and gel permeation chromatography. It was shown that only alcoholic OH groups of ethanol lignin react with sulfamic acid. Sulfated ethanol lignin has a higher molecular weight and a lower degree of polydispersity compared to the initial ethanol lignin.
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References
Agrawal A, Kaushik N, Biswas S (2014) Derivatives and applications of lignin—an insight. SciTech J 01(07):30–36
Al-Horani RA, Desai UR (2010) Chemical sulfation of small molecules—advances and challenges. Tetrahedron 66(16):2907–2918
Bajpai P (2010) Recent developments in cleaner production. In: Bajpai P (ed) Environmentally friendly production of pulp and paper. Wiley, Hoboken, NJ, pp 264–340
Calvo-Flores FG, Dobado JA, Isac-García J, Martín-Martínez FJ (2015) Lignin and lignans as renewable raw materials: chemistry, technology and applications. Wiley, Chichester, UK
Chen G, Zhang B, Zhao J, Chen H (2013) Improved process for the production of cellulose sulfate using sulfuric acid/ethanol solution. Carbohydr Polym 95:332–337
Fulmer GR, Miller AJM, Sherden NH, Gottlieb HE, Nudelman A, Stoltz BM, Bercaw JE, Goldberg KI (2010) NMR chemical shifts of trace impurities: common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist. Organometallics 29:2176–2179
Gilca IA, Ghitescu RE, Puitel AC, Popa VI (2014) Preparation of lignin nanoparticles by chemical modification. Iran Polym J 23(5):355–363
Heitner C, Dimmel D, Schmidt J (eds) (2010) Lignin and lignans: advances in chemistry. CRC Press, Boca Raton
Henry BL, Desai UR (2014) Sulfated low molecular weight lignins, allosteric inhibitors of coagulation proteinases via the heparin binding site, significantly alter the active site of thrombin and factor xa compared to heparin. Thromb Res 134(5):1123–1129
Kalabin GA, Kanitskaya LV, Kushnarev DF (2000) Quantitative NMR spectroscopy of natural organic raw materials and products of their processing. Khimiya Publishing House, Moscow
Kangas H, Hakala TK, Tamminen T, Määttänen M, Rovio S, Liitiä T, Poppius-Levlin K (2015) Optimisation of acetic acid lignofibre organosolv process. BioResources 10(2):2699–2718
Karger J, Grinberg F, Heitjans P (2005) Diffusion fundamentals. Leipzig University, Leipzig
Kuznetsov BN, Malyar YN, Kuznetsova SA, Grishechko LI, Kazachenko AS, Levdansky AV, Pestunov AV, Boyandin AN, Celzard A (2016) An isolation, study and application of organosolv lignins (review). J Sib Fed Univ Chem 4(9):454–482
Kuznetsov BN, Vasilyeva NYu, Kazachenko AS, Skvortsova GP, Levdansky VA, Lutoshkin MA (2018a) Development of the method of abies wood ethanol lignin sulfation using sulfamic acid. J Sib Fed Univ Chem 1(11):122–130
Kuznetsov B, Levdansky V, Kuznetsova S, Garyntseva N, Sudakova I, Levdansky A (2018b) Integration of peroxide delignification and sulfamic acid sulfation methods for obtaining cellulose sulfates from aspen wood. Eur J Wood Prod 76(3):999–1007
Levdansky AV, Kuznetsov BN, Djakovitch L, Pinel C (2014) Sulfation of microcrystalline cellulose with sulfamic acid in N, N-dimethylformamide and diglyme. J Sib Fed Univ Chem 2(7):162–169
Lindner A, Wegener G (1988) Characterization of lignins from organosolv pulping according to the organocell process PART 1. Elemental analysis, nonlignin portions and functional groups. J Wood Chem Technol 8(3):323–340
Prinsen P, Narani A, Hartog AF, Wever R, Rothenberg G (2017) Dissolving lignin in water through enzymatic sulfation with aryl sulfotransferase. ChemSusChem 10:1–8. https://doi.org/10.1002/cssc.201700376
Qin Z, Ji L, Yin X, Zhu L, Qin J (2014) Synthesis and characterization of bacterial cellulose sulfates using a SO3/pyridine complex in DMAc/LiCl. Carbohydr Polym 101:947–953
Raghuraman A, Tiwari V, Thakkar JN, Gunnarsson GT, Shukla D, Hindle M, Desai UR (2005) Structural characterization of a serendipitously discovered bioactive macromolecule, lignin sulfate. Biomacromolecules 6:2822–2832
Raghuraman A, Tiwari V, Zhao Q, Shukla D, Debnath AK, Desai UR (2007) Viral inhibition studies on sulfated lignin, a chemically modified biopolymer and a potential mimic of heparan sulfate. Biomacromolecules 8:1759–1763
Roeges NPG (1995) A guide to the complete interpretation of infrared spectra of organic structures. Wiley, Chichester
Schutyser W, Renders T, Van den Bosch S, Koelewijn SF, Beckham GT, Sels BF (2018) Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading. Chem Soc Rev 47(3):852–908
Sudakova IG, Garyntseva NV, Yatsenkova OV, Kuznetsov BN (2013) Optimization of aspen wood delignification by H2O2 with sulfuric acid catalyst. J Sib Fed Univ Chem 6:76–84
Thakkar JN (2006) Discovery of lignin sulfate as a potent inhibitor of HSV entry cells. Theses and Dissertations Graduate School, Virginia Commonwealth University
Torre MJ, Moral A, Hernández MD, Cabeza E, Tijero A (2013) Organosolv lignin for biofuel. Ind Crops Prod 45:58–63
Vasilyeva NYu, Levdansky VA, Skvortsova GP, Kazachenko AS, Kuznetsov BN (2018) Method of sulfating organosolv lignin. Patent 2641758 RU. Publ. Date 22.01.2018
Vinardell MP, Mitjans M (2017) Lignins and their derivatives with beneficial effects on human health. Int J Mol Sci 18(1219):2–15
Zeng J, Helms GL, Gao X, Chen S (2013) Quantification of wheat straw lignin structure by comprehensive NMR analysis. J Agric Food Chem 61:10848–10857
Zouohua S, Balbit F, de Santi A, Saravankumar E, Katalin B (2018) Bright side of lignin depolymerization: towards new platform chemicals. Chem Rev 118:614–678
Acknowledgements
The reported study was supported by the Russian Science Foundation (Grant No. 16-13-10326). The devices of the Krasnoyarsk Regional Centre for Collective Use of the SB RAS were used in the work. The authors are grateful to I.V. Korolkova for obtaining infrared spectra.
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Kuznetsov, B.N., Vasilyeva, N.Y., Kazachenko, A.S. et al. Optimization of the process of abies ethanol lignin sulfation by sulfamic acid–urea mixture in 1,4-dioxane medium. Wood Sci Technol 54, 365–381 (2020). https://doi.org/10.1007/s00226-020-01157-6
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DOI: https://doi.org/10.1007/s00226-020-01157-6