2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy

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Journal Title
Journal ISSN
Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2020-09-01
Major/Subject
Mcode
Degree programme
Language
en
Pages
25
7929-7953
Series
Cellulose, Volume 27, issue 14
Abstract
The limited access to fast and facile general analytical methods for cellulosic and/or biocomposite materials currently stands as one of the main barriers for the progress of these disciplines. To that end, a diverse set of narrow analytical techniques are typically employed that often are time-consuming, costly, and/or not necessarily available on a daily basis for practitioners. Herein, we rigorously demonstrate a general quantitative NMR spectroscopic method for structural determination of crystalline cellulose samples. Our method relies on the use of a readily accessible ionic liquid electrolyte, tetrabutylphosphonium acetate ([P-4444][OAc]):DMSO-d(6), for the direct dissolution of biopolymeric samples. We utilize a series of model compounds and apply now classical (nitroxyl-radical and periodate) oxidation reactions to cellulose samples, to allow for accurate resonance assignment, using 2D NMR. Quantitative heteronuclear single quantum correlation (HSQC) was applied in the analysis of key samples to assess its applicability as a high-resolution technique for following cellulose surface modification. Quantitation using HSQC was possible, but only after applying T(2)correction to integral values. The comprehensive signal assignment of the diverse set of cellulosic species in this study constitutes a blueprint for the direct quantitative structural elucidation of crystalline lignocellulosic, in general, readily available solution-state NMR spectroscopy. [GRAPHICS] .
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Keywords
Cellulose dissolution, Ionic liquid, Nitroxyl radical, Periodate, Quantitative HSQC, TEMPO
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Citation
Koso, T, Rico del Cerro, D, Heikkinen, S, Nypelö, T, Buffiere, J, Perea-Buceta, J E, Potthast, A, Rosenau, T, Heikkinen, H, Maaheimo, H, Isogai, A, Kilpeläinen, I & King, A W T 2020, ' 2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy ', Cellulose, vol. 27, no. 14, pp. 7929-7953 . https://doi.org/10.1007/s10570-020-03317-0