Probing cellulose–solvent interactions with self-diffusion NMR : Onium hydroxide concentration and co-solvent effects
(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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- author
- Medronho, B. LU ; Pereira, A. ; Duarte, H. ; Gentile, L. LU ; Rosa da Costa, A. M. ; Romano, A. and Olsson, U. LU
- organization
- publishing date
- 2023-03-01
- 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}}, }