TY - JOUR
T1 - DMSO/IL solvent systems for cellulose dissolution: Binary or ternary mixtures?
AU - Paiva, Tiago G.
AU - Zanatta, Marcileia
AU - Cabrita, Eurico J.
AU - Bernardes, Carlos E. S.
AU - Corvo, Marta C.
N1 - Funding Information:
info:eu-repo/grantAgreement/FCT/OE/SFRH%2FBD%2F133447%2F2017/PT#
info:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC%2FQUI-QFI%2F31508%2F2017/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50025%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
The NMR spectrometers at NOVA are part of Rede Nacional de RMN (PTNMR), supported by FCT, Portugal ( ROTEIRO/0031/2013 – PINFRA/22161/2016 ) co- ), co-financed by FEDER, European funds, through COMPETE 2020, POCI, PORL and FCT through PIDDAC ( POCI-01-0145-FEDER-007688;
info:eu-repo/grantAgreement/FCT/OE/SFRH%2FBD%2F133447%2F2017/PT#
info:eu-repo/grantAgreement/FCT/9444 - RNIIIE/PINFRA%2F22161%2F2016/PT#
info:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC%2FQUI-QFI%2F31508%2F2017/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50025%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2022/1/1
Y1 - 2022/1/1
N2 - The mechanism of cellulose dissolution in ionic liquid (IL)/dimethyl sulfoxide (DMSO) solvent systems has attracted much attention due to the possible replacement of synthetic materials. However, the solvent behaviour is not completely understood. This work has found an explanation for the solvent behaviour in cellulose dissolution, considering the almost unavoidable presence of the water. Ternary [C4mim]Cl/DMSO/H2O mixtures were studied with Nuclear Magnetic Resonance experiments and molecular dynamics simulations to explore IL/molecular solvents interactions and disclose the water interactions in these complex media. Titration of binary and ternary solvent systems with water and DMSO disclosed a relation between water's proton chemical shift and the molar fraction of the mixture components, creating an unprecedent theory to predict the cellulose solvation ability. A “working range” for IL/DMSO/H2O ratio was observed, tested in cellulose dissolution, and rationalized using cellobiose interaction. Within this solvent ratio, the interactions between components are maximized, being switched on, while out of the range, the interactions are no longer detected.
AB - The mechanism of cellulose dissolution in ionic liquid (IL)/dimethyl sulfoxide (DMSO) solvent systems has attracted much attention due to the possible replacement of synthetic materials. However, the solvent behaviour is not completely understood. This work has found an explanation for the solvent behaviour in cellulose dissolution, considering the almost unavoidable presence of the water. Ternary [C4mim]Cl/DMSO/H2O mixtures were studied with Nuclear Magnetic Resonance experiments and molecular dynamics simulations to explore IL/molecular solvents interactions and disclose the water interactions in these complex media. Titration of binary and ternary solvent systems with water and DMSO disclosed a relation between water's proton chemical shift and the molar fraction of the mixture components, creating an unprecedent theory to predict the cellulose solvation ability. A “working range” for IL/DMSO/H2O ratio was observed, tested in cellulose dissolution, and rationalized using cellobiose interaction. Within this solvent ratio, the interactions between components are maximized, being switched on, while out of the range, the interactions are no longer detected.
KW - Intermolecular interaction
KW - Molecular dynamics simulation
KW - NMR
KW - Solvation behaviour
KW - Water effect
UR - http://www.scopus.com/inward/record.url?scp=85117402611&partnerID=8YFLogxK
U2 - 10.1016/j.molliq.2021.117810
DO - 10.1016/j.molliq.2021.117810
M3 - Article
AN - SCOPUS:85117402611
SN - 0167-7322
VL - 345
JO - Journal of Molecular Liquids
JF - Journal of Molecular Liquids
M1 - 117810
ER -