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

Tetyana Koso*, Daniel Rico del Cerro, Sami Heikkinen, Tiina Nypelö, Jean Buffiere, Jesus E. Perea-Buceta, Antje Potthast, Thomas Rosenau, Harri Heikkinen, Hannu Maaheimo, Akira Isogai, Ilkka Kilpeläinen, Alistair W.T. King

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

3 Citations (Scopus)
24 Downloads (Pure)

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.

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Original languageEnglish
Pages (from-to)7929-7953
Number of pages25
JournalCellulose
Volume27
Issue number14
Early online date27 Jul 2020
DOIs
Publication statusPublished - 1 Sep 2020
MoE publication typeA1 Journal article-refereed

Keywords

  • Cellulose dissolution
  • Ionic liquid
  • Nitroxyl radical
  • Periodate
  • Quantitative HSQC
  • TEMPO

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