Abstract
Phosphoric acid is widely used for the swelling and hydrolysis of cellulose. The detailed description of molecular interactions between cellulose and phosphoric acid is essential for understanding and controlling these processes. Here, to obtain structural insights into the swelling behavior, we investigated the structural evolution of cellulose swollen in concentrated phosphoric acid solution using X-ray fiber diffraction and solid-state NMR spectroscopy. We observed the formation of a crystalline complex of cellulose and phosphoric acid at − 40 °C, where cellulose molecules adopt a seven-fold helical conformation. This structure is the second known cellulose-acid crystalline complex and the first cellulosic crystal consisting of seven-fold helical chains. Our observation highlights the conformational flexibility of cellulose molecules in the solvated states and the strong influence of cellulose-acid interactions on the packing and conformation of cellulose molecules.
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Acknowledgments
We acknowledge Agence Nationale de la Recherche (ANR Grant Number: ANR-21-CE29-0016-1 and ANR-11-EQPX-0010 under the “Investissements d’Avenir” program) and Glyco@Alps (ANR-15-IDEX-02) for the financial support and the NanoBio-ICMG platform (FR 2607) for granting access to the NMR facility. ESRF is acknowledged for the provision of beamtime (experiment number A02-1-902, D2AM beamline). We acknowledge Benjamin Richter and Yves Watier at the Sample Environment Service of ESRF, who designed the temperature-controlled specimen holder.
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IM and YO designed the experiments. JHL, IM, IJ, YN, and YO performed the experiments. JHL, ADF, YN, and YO analyzed the data. JHL, ADF, and YO prepared the figures and wrote the manuscript. All the authors approved the final version of the manuscript.
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Lim, J.H., Morfin, I., Jeacomine, I. et al. The occurrence of seven-fold helical molecular conformation in cellulose-phosphoric acid complex. Cellulose 30, 8063–8073 (2023). https://doi.org/10.1007/s10570-023-05346-x
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DOI: https://doi.org/10.1007/s10570-023-05346-x