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Probing cellulose–solvent interactions with self-diffusion NMR : Onium hydroxide concentration and co-solvent effects

Medronho, B. LU ; Pereira, A. ; Duarte, H. ; Gentile, L. LU ; Rosa da Costa, A. M. ; Romano, A. and Olsson, U. LU (2023) In Carbohydrate Polymers 303.
Abstract

The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that “bind” to each anhydroglucose unit) and Pb (i.e., fraction of “bound” molecules of DMSO, TBAH or H2O to cellulose) parameters. The α values suggest that TBA+ ions can bind to cellulose within 0.5 TBA+ to 2.3 TBA+/AGU. On the other hand, the Pb... (More)

The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that “bind” to each anhydroglucose unit) and Pb (i.e., fraction of “bound” molecules of DMSO, TBAH or H2O to cellulose) parameters. The α values suggest that TBA+ ions can bind to cellulose within 0.5 TBA+ to 2.3 TBA+/AGU. On the other hand, the Pb parameter increases when raising cellulose concentration for TBA+, DMSO and water in all solvent systems. Data suggests that TBAH interacts with the ionized OH groups from cellulose forming a sheath of bulky TBA+ counterions which consequently leads to steric hindrance between cellulose chains.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Cellulose dissolution, Dimethylsulfoxide, Nuclear magnetic resonance, Self-diffusion, Tetrabutylammonium hydroxide
in
Carbohydrate Polymers
volume
303
article number
120440
publisher
Elsevier
external identifiers
  • pmid:36657835
  • scopus:85143870653
ISSN
0144-8617
DOI
10.1016/j.carbpol.2022.120440
language
English
LU publication?
yes
additional info
Funding Information: This work was supported by funding from the Portuguese Foundation for Science and Technology (FCT) through the projects UIDB/05183/2020 , PTDC/ASP-SIL/30619/2017 and the researcher grant CEECIND/01014/2018 . Publisher Copyright: © 2022 The Authors
id
8ffae8a5-7d45-452f-b6db-3d4988760047
date added to LUP
2024-01-12 10:38:15
date last changed
2024-04-13 04:08:46
@article{8ffae8a5-7d45-452f-b6db-3d4988760047,
  abstract     = {{<p>The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that “bind” to each anhydroglucose unit) and P<sub>b</sub> (i.e., fraction of “bound” molecules of DMSO, TBAH or H<sub>2</sub>O to cellulose) parameters. The α values suggest that TBA<sup>+</sup> ions can bind to cellulose within 0.5 TBA<sup>+</sup> to 2.3 TBA<sup>+</sup>/AGU. On the other hand, the P<sub>b</sub> parameter increases when raising cellulose concentration for TBA<sup>+</sup>, DMSO and water in all solvent systems. Data suggests that TBAH interacts with the ionized OH groups from cellulose forming a sheath of bulky TBA<sup>+</sup> counterions which consequently leads to steric hindrance between cellulose chains.</p>}},
  author       = {{Medronho, B. and Pereira, A. and Duarte, H. and Gentile, L. and Rosa da Costa, A. M. and Romano, A. and Olsson, U.}},
  issn         = {{0144-8617}},
  keywords     = {{Cellulose dissolution; Dimethylsulfoxide; Nuclear magnetic resonance; Self-diffusion; Tetrabutylammonium hydroxide}},
  language     = {{eng}},
  month        = {{03}},
  publisher    = {{Elsevier}},
  series       = {{Carbohydrate Polymers}},
  title        = {{Probing cellulose–solvent interactions with self-diffusion NMR : Onium hydroxide concentration and co-solvent effects}},
  url          = {{http://dx.doi.org/10.1016/j.carbpol.2022.120440}},
  doi          = {{10.1016/j.carbpol.2022.120440}},
  volume       = {{303}},
  year         = {{2023}},
}