Abstract
We used to consider native cellulose to be composed of microfibrils continuously crystalline along the chain direction with constant lateral dimension. To sulfate the surface of cellulose microfibrils, we activated cotton fibers by pre-swelling in water or DMF followed by immersion in an excess amount of sulfamic acid in dimethylformamide (DMF) in heterogeneous conditions. The degree of sulfation was followed by elemental analysis and conductometric titration, while the structural changes associated with the sulfation and the homogenization were investigated by infrared spectroscopy, solid-state NMR, and X-ray diffraction. The initial sulfation of the cellulose surface was well described as a first order reaction with a kinetic constant of 2\(\times\)10\(^{-3}\)s\(^{-1}\) at 80 °C using 3.6% sulfamic, indicating that about half of the available hydroxy groups were sulfated within the first 5 min. A water pre-swelling step, followed by solvent exchange with DMF, increased the amount of available hydroxy groups by up to a factor of two. At long reaction times, there was a gradual increase in the degree of sulfation beyond the initially available surface by up to 20% during the two hours reaction investigated. FTIR and solid-state NMR spectra both suggest the reaction of surface primary hydroxy groups with sulfamic acid. While the apparent lateral crystallite size of cotton is unaffected by sulfation treatment, X-ray diffraction suggested that homogenization resulted in cellulose nanofibers (CNFs) with a crystallite width below 3 nm, much smaller than the initial cellulose microfibrils (6–7 nm). This apparent crystallite splitting during homogenization suggests that cotton microfibrils have an intertwined polycrystalline structure, rather than being monocrystalline along the whole length.
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Data and materials availability
All original data are available at https://github.com/yoshi-CERMAV/cellulose-2023 together with the python code for the data treatment. The corresponding Jupyter notebook is “https://github.com/yoshi-CERMAV/cellulose-2023/cellulose2023.ipynb”.
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Acknowledgments
The authors are grateful for the financial support for this work by the Guangdong Basic and Applied Basic Research Foundation (2022A1515010565, 2023B1515040013) and State Key Laboratory of Pulp & Paper Engineering Grant (2023PY05, 202306). P.C. acknowledges financial support from the Beijing Natural Science Foundation (2232064) and the National Natural Science Foundation (52373097). We also thank Dr. Weiying Li from SCUT/State Key Laboratory of Pulp and Paper Engineering for the elemental analysis. We thank Dr. Thomas Parton from the University of Cambridge for fruitful discussions and advice on the manuscript.
Funding
China Guangdong Basic and Applied Basic Research Foundation (Q.H.: 2022A1515010565, 2023B1515040013), China State Key Laboratory of Pulp & Paper Engineering Grant (Q.H.: 2023PY05, 202306), Beijing Natural Science Foundation (P.C.: 2232064), National Natural Science Foundation (P.C.: 52373097).
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Y. N., Q. H., and P. C designed the experiments. X.W. prepared the samples, carried out the kinetics study, and turbidimetry, Y. O. carried out the solid-state NMR measurement, Y. N. carried out X-ray and FTIR measurements, analyzed the data, and wrote the manuscript. All authors reviewed the manuscript.
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This article is part of a collection of articles in honor of Dr. Henri Chanzy on the occasion of his 90th birthday. The article was not finished in time to be bound with the rest of the papers in the Special Issue #13, September, 2023.
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Wang, X., Chen, P., Ogawa, Y. et al. Structural changes during heterogeneous sulfation and following homogenization of cotton cellulose. Cellulose 31, 2729–2742 (2024). https://doi.org/10.1007/s10570-024-05787-y
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DOI: https://doi.org/10.1007/s10570-024-05787-y