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Fivefold Helical Cellulose Trapped in a Sulfuric Acid Framework

Abstract : Sulfuric acid aqueous solution effectively dissolves cellulose at a concentration of 64 wt% when it is pre-cooled at-20 ˚C. Although this low-temperature acid solution has a high potential as an aqueous cellulose solvent, the molecular detail of its swelling and dissolution mechanism is not known. In this study, we followed the swelling behavior of cellulose in sulfuric acid using X-ray diffraction and found a crystalline complex of cellulose and sulfuric acid at-20 ˚C. In this structure, the sulfuric acid molecules are organized in a similar manner to those in its tetrahydrate crystal. Cellulose molecules adopt a rare five-fold helical conformation, and their hydroxyl groups participate in the hydration of sulfuric acid. This complexation is acid-concentration dependent and occurs only above 62 wt%, indicating that the deficiency of the number of water molecules around sulfuric acid to form tetrahydrate drives the sulfuric acid to recruit cellulose hydroxyl groups. It swells and opens the cellulose structure without completely destroying the crystalline order as can be confirmed by the partial reversibility to regenerate cellulose I.
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https://hal.archives-ouvertes.fr/hal-03431820
Contributor : Yu Ogawa Connect in order to contact the contributor
Submitted on : Tuesday, November 16, 2021 - 10:41:45 PM
Last modification on : Monday, January 10, 2022 - 10:16:08 AM

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Wei Li, Yu Ogawa, Javier Perez, Karim Mazeau, Isabelle Morfin, et al.. Fivefold Helical Cellulose Trapped in a Sulfuric Acid Framework. Crystal Growth & Design, American Chemical Society, 2021, ⟨10.1021/acs.cgd.1c00664⟩. ⟨hal-03431820⟩

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