TY - JOUR
T1 - On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide
T2 - a frustrated solvent
AU - Idström, Alexander
AU - Gentile, Luigi
AU - Gubitosi, Marta
AU - Olsson, Carina
AU - Stenqvist, Björn
AU - Lund, Mikael
AU - Bergquist, Karl Erik
AU - Olsson, Ulf
AU - Köhnke, Tobias
AU - Bialik, Erik
PY - 2017/9
Y1 - 2017/9
N2 - We have found that the dissolution of cellulose in the binary mixed solvent tetrabutylammonium acetate/dimethyl sulfoxide follows a previously overlooked near-stoichiometric relationship such that one dissolved acetate ion is able to dissolve an amount of cellulose corresponding to about one glucose residue. The structure and dynamics of the resulting cellulose solutions were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance techniques as well as molecular dynamics simulation. This yielded a detailed picture of the dissolution mechanism in which acetate ions form hydrogen bonds to cellulose and causes a diffuse solvation sheath of bulky tetrabutylammonium counterions to form. In turn, this leads to a steric repulsion that helps to keep the cellulose chains apart. Structural similarities to previously investigated cellulose solutions in aqueous tetrabutylammonium hydroxide were revealed by SAXS measurement. To what extent this corresponds to similarities in dissolution mechanism is discussed.
AB - We have found that the dissolution of cellulose in the binary mixed solvent tetrabutylammonium acetate/dimethyl sulfoxide follows a previously overlooked near-stoichiometric relationship such that one dissolved acetate ion is able to dissolve an amount of cellulose corresponding to about one glucose residue. The structure and dynamics of the resulting cellulose solutions were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance techniques as well as molecular dynamics simulation. This yielded a detailed picture of the dissolution mechanism in which acetate ions form hydrogen bonds to cellulose and causes a diffuse solvation sheath of bulky tetrabutylammonium counterions to form. In turn, this leads to a steric repulsion that helps to keep the cellulose chains apart. Structural similarities to previously investigated cellulose solutions in aqueous tetrabutylammonium hydroxide were revealed by SAXS measurement. To what extent this corresponds to similarities in dissolution mechanism is discussed.
KW - Cellulose dissolution
KW - Ionic liquids
KW - Molecular dynamics simulations
KW - Nuclear magnetic resonance
KW - Small angle X-ray scattering
U2 - 10.1007/s10570-017-1370-2
DO - 10.1007/s10570-017-1370-2
M3 - Article
AN - SCOPUS:85021162537
SN - 0969-0239
VL - 24
SP - 3645
EP - 3657
JO - Cellulose
JF - Cellulose
IS - 9
ER -