TY - JOUR
T1 - Fivefold Helical Cellulose Trapped in a Sulfuric Acid Framework
AU - Li, Wei
AU - Ogawa, Yu
AU - Perez, Javier
AU - Mazeau, Karim
AU - Morfin, Isabelle
AU - Nishiyama, Yoshiharu
N1 - Publisher Copyright:
© 2021 American Chemical Society
PY - 2022/1/5
Y1 - 2022/1/5
N2 - A sulfuric acid aqueous solution effectively dissolves cellulose at a concentration of 64 wt % when it is precooled 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 fivefold 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 drives the sulfuric acid to recruit cellulose hydroxyl groups to form a stable tetrahydrate-like hydration state. 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.
AB - A sulfuric acid aqueous solution effectively dissolves cellulose at a concentration of 64 wt % when it is precooled 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 fivefold 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 drives the sulfuric acid to recruit cellulose hydroxyl groups to form a stable tetrahydrate-like hydration state. 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.
UR - http://www.scopus.com/inward/record.url?scp=85119116007&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.1c00664
DO - 10.1021/acs.cgd.1c00664
M3 - Article
AN - SCOPUS:85119116007
SN - 1528-7483
VL - 22
SP - 20
EP - 25
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 1
ER -