2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy
Journal article, 2020

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] .

Nitroxyl radical

Cellulose dissolution

Quantitative HSQC



Ionic liquid


Tetyana Koso

University of Helsinki

Daniel Rico del Cerro

University of Helsinki

Sami Heikkinen

University of Helsinki

Tiina Nypelö

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Wallenberg Wood Science Center (WWSC)

Jean Buffiere

Aalto University

Jesus E. Perea-Buceta

University of Helsinki

Antje Potthast

University of Natural Resources and Life Sciences

Thomas Rosenau

University of Natural Resources and Life Sciences

Harri Heikkinen

Finnish Institute for Verification of the Chemical Weapons Convention (VERIFIN)

Hannu Maaheimo

Technical Research Centre of Finland (VTT)

Akira Isogai

University of Tokyo

Ilkka Kilpelainen

University of Helsinki

Alistair W. T. King

University of Helsinki


0969-0239 (ISSN)

Vol. 27 14 7929-7953

Subject Categories

Analytical Chemistry

Polymer Technologies

Other Chemistry Topics



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