ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers
The reaction mechanism of ClO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>-mediated TEMP...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/18/6631 |
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| author | Laura Giraldo Isaza Gérard Mortha Nathalie Marlin Florian Molton Carole Duboc |
| author_facet | Laura Giraldo Isaza Gérard Mortha Nathalie Marlin Florian Molton Carole Duboc |
| author_sort | Laura Giraldo Isaza |
| collection | DOAJ |
| description | The reaction mechanism of ClO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>-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<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mo>+</mo></msup></semantics></math></inline-formula>, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mo>−</mo></msup></semantics></math></inline-formula>, 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. |
| first_indexed | 2024-03-10T22:23:54Z |
| format | Article |
| id | doaj.art-258abc7b605d479f8326d6da0411fa2e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T22:23:54Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-258abc7b605d479f8326d6da0411fa2e2023-11-19T12:10:12ZengMDPI AGMolecules1420-30492023-09-012818663110.3390/molecules28186631ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose FibersLaura Giraldo Isaza0Gérard Mortha1Nathalie Marlin2Florian Molton3Carole Duboc4Institute of Engineering, University Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000 Grenoble, FranceInstitute of Engineering, University Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000 Grenoble, FranceInstitute of Engineering, University Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000 Grenoble, FranceDepartment of Molecular Chemistry, University Grenoble Alpes, CNRS, DCM, F-38000 Grenoble, FranceDepartment of Molecular Chemistry, University Grenoble Alpes, CNRS, DCM, F-38000 Grenoble, FranceThe reaction mechanism of ClO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>-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<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mo>+</mo></msup></semantics></math></inline-formula>, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mo>−</mo></msup></semantics></math></inline-formula>, 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.https://www.mdpi.com/1420-3049/28/18/6631TEMPO oxidationchlorine dioxideEPR spectroscopyUV–Vis spectroscopy |
| spellingShingle | Laura Giraldo Isaza Gérard Mortha Nathalie Marlin Florian Molton Carole Duboc ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers Molecules TEMPO oxidation chlorine dioxide EPR spectroscopy UV–Vis spectroscopy |
| title | ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers |
| title_full | ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers |
| title_fullStr | ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers |
| title_full_unstemmed | ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers |
| title_short | ClO<sub>2</sub>-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers |
| title_sort | clo sub 2 sub mediated oxidation of the tempo radical fundamental considerations of the catalytic system for the oxidation of cellulose fibers |
| topic | TEMPO oxidation chlorine dioxide EPR spectroscopy UV–Vis spectroscopy |
| url | https://www.mdpi.com/1420-3049/28/18/6631 |
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