ClO2-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers

Author:

Giraldo Isaza Laura1,Mortha Gérard1,Marlin Nathalie1ORCID,Molton Florian2ORCID,Duboc Carole2

Affiliation:

1. Institute of Engineering, University Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000 Grenoble, France

2. Department of Molecular Chemistry, University Grenoble Alpes, CNRS, DCM, F-38000 Grenoble, France

Abstract

The reaction mechanism of ClO2-mediated TEMPO oxidation was investigated by EPR spectroscopy and UV–Vis spectroscopy in the context of an alternative TEMPO sequence for cellulose fiber oxidation. Without the presence of a cellulosic substrate, a reversibility between TEMPO and its oxidation product, TEMPO+, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl−, formed as byproducts in the oxidation mechanism, was also evidenced. Trapping HOCl partly inhibits the reaction, whereas adding methylglucoside, a cellulose model compound, inhibits the reversibility of the reaction to TEMPO.

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

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