Hybrids of Gallic AcidSiO2 and {Hyaluronic-Acid Counterpats}@SiO2 against Hydroxyl (●OH) Radicals Studied by EPR : A Comparative Study vs Their Antioxidant Hydrogen Atom Transfer Activity

Hydrogen atom transfer (HAT) and single electron transfer (SET) are two fundamental pathways for antiradical/antioxidant processes; however, a systematic in-tandem operational evaluation of the same system is lacking. Herein, we present a comparative study of the HAT and SET processes applied to a l...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1985. - 40(2024), 50 vom: 17. Dez., Seite 26412-26424
1. Verfasser: Theofanous, Annita (VerfasserIn)
Weitere Verfasser: Deligiannakis, Yiannis, Louloudi, Maria
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2024
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article
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245 1 8 |a Hybrids of Gallic AcidSiO2 and {Hyaluronic-Acid Counterpats}@SiO2 against Hydroxyl (●OH) Radicals Studied by EPR  |b A Comparative Study vs Their Antioxidant Hydrogen Atom Transfer Activity 
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520 |a Hydrogen atom transfer (HAT) and single electron transfer (SET) are two fundamental pathways for antiradical/antioxidant processes; however, a systematic in-tandem operational evaluation of the same system is lacking. Herein, we present a comparative study of the HAT and SET processes applied to a library of well-characterized hybrid materials SiO2GA, SiO2@GLA, SiO2@GLAM, and the doubly hybrid material {GLA@SiO2@GLAM}. Hydroxyl radicals (•OH), produced by a Fenton system, react via the single electron transfer (SET) pathway and hydrogen atom transfer, through oxygen- and carbon-atoms, respectively, while the stable-radical DPPH via the HAT pathway through oxygen-atoms. Electron paramagnetic resonance spectroscopy (EPR), eminently suited for in situ detection and quantification of free radicals, was used as a state-of-the-art tool to monitor •OH using the spin-trapping-EPR method. We found that the SiO2@GA hybrid exhibited the highest SET •OH-scavenging activity i.e., [2.7 mol of •OH per mol of grafted GA]. Then, SiO2@GLA, SiO2@GLAM, and GLA@SiO2@GLAM can scavenge 1.2, 1.3, and 0.57 mol of •OH per mol of anchored organic, respectively. The HAT efficiency for SiO2@GA was [2.0 mol of DPPH per mol of grafted GA], while SiO2@GLA, SiO2@GLAM, and GLA@SiO2@GLAM exhibited a HAT efficiency of 1.1 DPPH moles per mol of anchored organic. The data are analyzed based on the molecular structure of the organics and their -R-OH moieties. Accordingly, based on the present data we suggest that for hydroxyl (•OH) radicals, the mechanisms involved are SET from an oxygen atom and HAT from a carbon atom. In contrast, for DPPH radicals, the HAT mechanism is exclusively operating and involves hydrogen atom abstraction from OH groups 
650 4 |a Journal Article 
700 1 |a Deligiannakis, Yiannis  |e verfasserin  |4 aut 
700 1 |a Louloudi, Maria  |e verfasserin  |4 aut 
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856 4 0 |u http://dx.doi.org/10.1021/acs.langmuir.4c02760  |3 Volltext 
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