Abstract
The dissolution and regeneration process of cellulose molecules in NMMO aqueous solution was studied by molecular dynamics (MD) simulation. The effect of the concentration of NMMO aqueous solution on the structure of cellulose was discussed. During the simulation process, the aggregation structure of cellulose molecules changed significantly and experienced the dissolution process and regeneration process. During the dissolution of cellulose, the NMMO aqueous solution penetrates into the cellulose bundle from the cellulose O2–H2–O6 direction. NMMO around O6, O3, and O2 plays a vital role in the dissolution of cellulose. NMMO destroys the interchain hydrogen bonds of cellulose, so that cellulose is dissolved in the solvent. During the regeneration process, the concentration of NMMO aqueous solution decreased, and water molecules around the acetal oxygen atom increased, which destroyed the hydrogen bond between NMMO and cellulose, and made the cellulose single chain form aggregates. Although it eventually aggregated into cellulose bunches structure, the hydrogen bond of regenerated cellulose lacked regularity, which affected the stability of the regenerated cellulose structure.
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References
Abascal JLF, Vega C (2005) A general purpose model for the condensed phases of water: TIP4P/2005. J Chem Phys 123:234505. https://doi.org/10.1063/1.2121687
Acharya S, Liyanage S, Parajuli P et al (2021) Utilization of cellulose to its full potential: a review on cellulose dissolution, regeneration, and applications. Polymers 13:4344. https://doi.org/10.3390/polym13244344
Bandura AV, Kubicki JD (2003) Derivation of force field parameters for TiO 2–H 2 O systems from ab initio calculations. J Phys Chem B 107:11072–11081. https://doi.org/10.1021/jp034093t
Bergenstråhle M, Wohlert J, Himmel ME, Brady JW (2010) Simulation studies of the insolubility of cellulose. Carbohydr Res 345:2060–2066. https://doi.org/10.1016/j.carres.2010.06.017
Bering E, Torstensen JØ, Lervik A, de Wijn AS (2022) Computational study of the dissolution of cellulose into single chains: the role of the solvent and agitation. Cellulose 29:1365–1380. https://doi.org/10.1007/s10570-021-04382-9
Bregado JL, Tavares FW, Secchi AR, Segtovich ISV (2021) Molecular dynamics of dissolution of a 36-chain cellulose Iβ microfibril at different temperatures above the critical pressure of water. J Mol Liq 336:116271. https://doi.org/10.1016/j.molliq.2021.116271
Brehm M, Radicke J, Pulst M et al (2020) Dissolving cellulose in 1,2,3-triazolium- and imidazolium-based ionic liquids with aromatic anions. Molecules 25:3539
Carrillo F, Colom X, Suñol JJ, Saurina J (2004) Structural FTIR analysis and thermal characterisation of lyocell and viscose-type fibres. Eur Polym J 40:2229–2234. https://doi.org/10.1016/j.eurpolymj.2004.05.003
Chen J, Guan Y, Wang K et al (2015) Combined effects of raw materials and solvent systems on the preparation and properties of regenerated cellulose fibers. Carbohydr Polym 128:147–153. https://doi.org/10.1016/j.carbpol.2015.04.027
Darden T, York D, Pedersen L (1993) Particle mesh Ewald: an N ⋅log(N) method for Ewald sums in large systems. J Chem Phys 98:10089–10092. https://doi.org/10.1063/1.464397
Dogan H, Hilmioglu ND (2009) Dissolution of cellulose with NMMO by microwave heating. Carbohydr Polym 75:90–94. https://doi.org/10.1016/j.carbpol.2008.06.014
Domin D, Man VH, Van-Oanh N-T et al (2018) Breaking down cellulose fibrils with a mid-infrared laser. Cellulose 25:5553–5568. https://doi.org/10.1007/s10570-018-1973-2
Dumitrică T (2020) Intrinsic twist in Iβ cellulose microfibrils by tight-binding objective boundary calculations. Carbohydr Polym 230:115624. https://doi.org/10.1016/j.carbpol.2019.115624
Eckelt J, Eich T, Röder T et al (2009) Phase diagram of the ternary system NMMO/water/cellulose. Cellulose 16:373–379. https://doi.org/10.1007/s10570-009-9276-2
Eyley S, Schütz C, Thielemans W (2018) Surface chemistry and characterization of cellulose nanocrystals. In: Rosenau T, Potthast A, Hell J (eds) Cellulose science and technology. Wiley, Hoboken, pp 223–252
Fink H-P, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524. https://doi.org/10.1016/S0079-6700(01)00025-9
French AD, Montgomery DW, Prevost NT et al (2021) Comparison of cellooligosaccharide conformations in complexes with proteins with energy maps for cellobiose. Carbohydr Polym 264:118004. https://doi.org/10.1016/j.carbpol.2021.118004
Frisch M, Trucks G, Schlegel HB et al (2002) Gaussian 98, revision A.9. J Am Chem Soc 24:235–247. https://doi.org/10.1145/64140.65025
Funahashi R, Okita Y, Hondo H et al (2017) Different conformations of surface cellulose molecules in native cellulose microfibrils revealed by layer-by-layer peeling. Biomacromol 18:3687–3694. https://doi.org/10.1021/acs.biomac.7b01173
Gomes TCF, Skaf MS (2012) Cellulose-builder: a toolkit for building crystalline structures of cellulose. J Comput Chem 33:1338–1346. https://doi.org/10.1002/jcc.22959
Gupta KM, Jiang J (2015) Cellulose dissolution and regeneration in ionic liquids: a computational perspective. Chem Eng Sci 121:180–189. https://doi.org/10.1016/j.ces.2014.07.025
Heasman P, Mehandzhiyski AY, Ghosh S, Zozoulenko I (2023) A computational study of cellulose regeneration: all-atom molecular dynamics simulations. Carbohydr Polym 311:120768. https://doi.org/10.1016/j.carbpol.2023.120768
Hess B, Bekker H, Berendsen HJC, Fraaije JGEM (1997) LINCS: a linear constraint solver for molecular simulations. J Comput Chem 18:1463–1472. https://doi.org/10.1002/(SICI)1096-987X(199709)18:12%3c1463::AID-JCC4%3e3.0.CO;2-H
Hirosawa K, Fujii K, Hashimoto K, Shibayama M (2017) Solvated structure of cellulose in a phosphonate-based ionic liquid. Macromolecules 50:6509–6517. https://doi.org/10.1021/acs.macromol.7b01138
Humphrey W, Dalke A, Schulten K (1996) VMD: visual molecular dynamics. J Mol Graph 14:33–38. https://doi.org/10.1016/0263-7855(96)00018-5
Jarvis MC (2023) Hydrogen bonding and other non-covalent interactions at the surfaces of cellulose microfibrils. Cellulose 30:667–687. https://doi.org/10.1007/s10570-022-04954-3
Kast KM, Brickmann J, Kast SM, Berry RS (2003) Binary phases of aliphatic N-oxides and water: force field development and molecular dynamics simulation. J Phys Chem A 107:5342–5351. https://doi.org/10.1021/jp027336a
Kirschner KN, Yongye AB, Tschampel SM et al (2008) GLYCAM06: a generalizable biomolecular force field. Carbohydrates: GLYCAM06. J Comput Chem 29:622–655. https://doi.org/10.1002/jcc.20820
Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem-Int Edit 44:3358–3393. https://doi.org/10.1002/anie.200460587
Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromol 2:410–416
Lao TLB, Cordura SLA, Diaz LJL, Vasquez MR (2020) Influence of plasma treatment on the dissolution of cellulose in lithium chloride–dimethylacetamide. Cellulose 27:9801–9811. https://doi.org/10.1007/s10570-020-03454-6
Li Y, Liu X, Zhang S et al (2015) Dissolving process of a cellulose bunch in ionic liquids: a molecular dynamics study. Phys Chem Chem Phys 17:17894–17905. https://doi.org/10.1039/C5CP02009C
Li K, Yang H, Jiang L et al (2020) Glycerin/NaOH aqueous solution as a green solvent system for dissolution of cellulose. Polymers 12:1735
Li Y, Peng J, Liu X et al (2021) Dissolving waste viscose to spin cellulose fibers. Polymer 237:124349. https://doi.org/10.1016/j.polymer.2021.124349
Li C, Fang T, Zhou G et al (2022) Mechanism and conformation changes for the whole regeneration process of cellulose in pyridinium-based ionic liquids. Cellulose 29:5479–5492. https://doi.org/10.1007/s10570-022-04639-x
Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580–592. https://doi.org/10.1002/jcc.22885
Martínez L, Andrade R, Birgin EG, Martínez JM (2009) PACKMOL: a package for building initial configurations for molecular dynamics simulations. J Comput Chem 30:2157–2164. https://doi.org/10.1002/jcc.21224
Matthews JF, Beckham GT, Bergenstråhle-Wohlert M et al (2012) Comparison of cellulose Iβ simulations with three carbohydrate force fields. J Chem Theory Comput 8:735–748. https://doi.org/10.1021/ct2007692
Miyamoto H, Umemura M, Aoyagi T et al (2009) Structural reorganization of molecular sheets derived from cellulose II by molecular dynamics simulations. Carbohydr Res 344:1085–1094. https://doi.org/10.1016/j.carres.2009.03.014
Mostofian B, Smith JC, Cheng X (2014) Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution. Cellulose 21:983–997. https://doi.org/10.1007/s10570-013-0018-0
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082. https://doi.org/10.1021/ja0257319
Pang J, Mehandzhiyski AY, Zozoulenko I (2023) A computational study of cellulose regeneration: coarse-grained molecular dynamics simulations. Carbohydr Polym 313:120853. https://doi.org/10.1016/j.carbpol.2023.120853
Protz R, Lehmann A, Ganster J, Fink H-P (2021) Solubility and spinnability of cellulose-lignin blends in aqueous NMMO. Carbohydr Polym 251:117027. https://doi.org/10.1016/j.carbpol.2020.117027
Qiao Q, Li X, Huang L (2020) Crystalline cellulose under pyrolysis conditions: the structure–property evolution via reactive molecular dynamics simulations. J Chem Eng Data 65:360–372. https://doi.org/10.1021/acs.jced.9b00701
Rabideau BD, Ismail AE (2015) Effect of water content in N-methylmorpholine N-oxide/cellulose solutions on thermodynamics, structure, and hydrogen bonding. J Phys Chem B 119:15014–15022. https://doi.org/10.1021/acs.jpcb.5b07500
Röder T, Morgenstern B (1999) The influence of activation on the solution state of cellulose dissolved in N-methylmorpholine-N-oxide-monohydrate. Polymer 40:4143–4147. https://doi.org/10.1016/S0032-3861(98)00674-0
Rosenau T, Hofinger A, Potthast A, Kosma P (2003) On the conformation of the cellulose solvent N-methylmorpholine-N-oxide (NMMO) in solution. Polymer 44:6153–6158. https://doi.org/10.1016/S0032-3861(03)00663-3
Rosenau T, Potthast A, Hell J (2018) Cellulose science and technology: chemistry, analysis, and applications. Wiley, Hoboken
Rosenau T, Potthast A, Hofinger A et al (2018) Toward a better understanding of cellulose swelling, dissolution, and regeneration on the molecular level. In: Rosenau T, Potthast A, Hell J (eds) Cellulose science and technology. John Wiley & Sons Inc, Hoboken, pp 99–125
Sánchez-Badillo JA, Gallo M, Rutiaga-Quiñones JG, López-Albarrán P (2021) Solvent behavior of an ionic liquid set around a cellulose Iβ crystallite model through molecular dynamics simulations. Cellulose 28:6767–6795. https://doi.org/10.1007/s10570-021-03992-7
Santiago Cintrón M, Johnson GP, French AD (2017) Quantum mechanics models of the methanol dimer: OH⋯ O hydrogen bonds of β-d-glucose moieties from crystallographic data. Carbohydr Res 443:87–94
Sayyed AJ, Deshmukh NA, Pinjari DV (2019) A critical review of manufacturing processes used in regenerated cellulosic fibres: viscose, cellulose acetate, cuprammonium, LiCl/DMAc, ionic liquids, and NMMO based lyocell. Cellulose 26:2913–2940. https://doi.org/10.1007/s10570-019-02318-y
Sayyed AJ, Gupta D, Deshmukh NA et al (2020) Influence of intensified cellulose dissolution process on spinning and properties of lyocell fibres. Chem Eng Process Process Intensif 155:108063. https://doi.org/10.1016/j.cep.2020.108063
Sen S, Martin JD, Argyropoulos DS (2013) Review of Cellulose Non-derivatizing Solvent interactions with emphasis on activity in inorganic molten salt hydrates. ACS Sustain Chem Eng 1:858–870. https://doi.org/10.1021/sc400085a
Silbermann S, Weilach C, Kliba G et al (2017) Improving molar mass analysis of cellulose samples with limited solubility. Carbohydr Polym 178:302–310. https://doi.org/10.1016/j.carbpol.2017.09.031
Sugiyama J, Vuong R, Chanzy H (1991) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175. https://doi.org/10.1021/ma00014a033
Thu TTM, Moreira RA, Weber SAL, Poma AB (2022) Molecular insight into the self-assembly process of cellulose Iβ microfibril. IJMS 23:8505
Van Der Spoel D, Lindahl E, Hess B et al (2005) GROMACS: fast, flexible, and free. J Comput Chem 26:1701–1718. https://doi.org/10.1002/jcc.20291
Wada M, Chanzy H, Nishiyama Y, Langan P (2004) Cellulose IIII crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 37:8548–8555. https://doi.org/10.1021/ma0485585
Wang H, Kataoka H, Tsuchikawa S, Inagaki T (2022) Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: cellulose I to cellulose II, tracing the structural changes under chemical treatment. Cellulose 29:3143–3151. https://doi.org/10.1007/s10570-022-04493-x
Wertz J-L, Bédué O, Mercier JP (2010) Cellulose science and technology. EPFL Press, Lausanne
Wohlert M, Benselfelt T, Wågberg L et al (2022) Cellulose and the role of hydrogen bonds: not in charge of everything. Cellulose 29:1–23. https://doi.org/10.1007/s10570-021-04325-4
Woodcock C, Sarko A (1980) Packing analysis of carbohydrates and polysaccharides. 11. Molecular and crystal structure of native ramie cellulose. Macromolecules 13:1183–1187. https://doi.org/10.1021/ma60077a030
Xue Y, Li W, Yang G et al (2022) Strength enhancement of regenerated cellulose fibers by adjustment of hydrogen bond distribution in ionic liquid. Polymers 14:2030https://doi.org/10.3390/polym14102030
Yuan EC-Y, Huang S-J, Huang H-C et al (2021) Faster magic angle spinning reveals cellulose conformations in woods. Chem Commun 57:4110–4113. https://doi.org/10.1039/D1CC01149A
Zhang J, Xu L, Yu J et al (2016) Understanding cellulose dissolution: effect of the cation and anion structure of ionic liquids on the solubility of cellulose. Sci China Chem 59:1421–1429. https://doi.org/10.1007/s11426-016-0269-5
Zhang H, González-Aguilera L, López D et al (2022) Hydrogen bonding in ternary mixtures of N-methyl morpholine oxide, water and dimethyl sulfoxide for enhanced cellulose dissolution capabilities. J Mol Liq 358:119113
Zhao H, Kwak J, Wang Y et al (2007) Interactions between cellulose and N-methylmorpholine-N-oxide. Carbohydr Polym 67:97–103. https://doi.org/10.1016/j.carbpol.2006.04.019
Zhou Y, Zhang X, Yin D et al (2022) The solution state and dissolution process of cellulose in ionic-liquid-based solvents with different hydrogen-bonding basicity and microstructures. Green Chem 24:3824–3833. https://doi.org/10.1039/D2GC00374K
Acknowledgments
We cordially acknowledge the financial support from the National Natural Science Foundation of China (22178187, 22108139), Natural Science Foundation of Shandong Province (ZR202102180830), and Taishan Scholars Program of Shandong Province (tsqn201909091). State Key Laboratory for Biofibers and Eco-textiles, Grant No. ZDKT202008 and ZDKT202103. Shandong Province Key Technology R&D Program for Middle and Small Enterprises, Grant No. 2021TSGC1189. Shandong Province Key Technology R&D Program, Grant No. 2023CXGC010612. The authors would also like to thank the journal editors and the reviewers who raised valuable points that help to improve the quality of the presentation of this article.
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We cordially acknowledge the financial support from the National Natural Science Foundation of China (22178187, 22108139), Natural Science Foundation of Shandong Province (ZR202102180830), and Taishan Scholars Program of Shandong Province (tsqn201909091). State Key Laboratory for Biofibers and Eco-textiles, Grant No. ZDKT202008 and ZDKT202103.Shandong Province Key Technology R&D Program for Middle and Small Enterprises, Grant No. 2021TSGC1189. Shandong Province Key Technology R&D Program, Grant No. 2023CXGC010612. The authors would also like to thank the journal editors and the reviewers who raised valuable points that help to improve the quality of the presentation of this article.
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Conceptualization: XL, KF; Methodology: XL, KF; Formal analysis: XL, GZ, TF and KF; Investigation: XL, KF; Writing original draft: ZD; Writing review and editing: XL; Supervision: XL; All authors read and approved the final manuscript.
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Deng, Z., Zhou, G., Fang, T. et al. The bidirectional regulation mechanism of NMMO concentration change on cellulose dissolution and regeneration. Cellulose 31, 1205–1222 (2024). https://doi.org/10.1007/s10570-023-05673-z
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DOI: https://doi.org/10.1007/s10570-023-05673-z