title: The location of phenolic antioxidants and radicals at interfaces determines their activity.
abstract: To characterize parameters influencing the antioxidant activity at interfaces a novel ESR approach was developed, which facilitates the investigation of the reaction stoichiometry of antioxidants towards stable radicals. To relate the activity of antioxidants towards the location of radicals at interfaces NMR experiments were conducted. Micellar solutions of SDS, Brij and CTAB were used to model interfaces of different chemical nature. The hydrophilic Fremy's radical was found to be solubilized exclusively in the aqueous phase of SDS micellar solution but partitioned partly into the hydrophilic headgroup area of Brij micelles. In contrast the hydrophobic galvinoxyl was exclusively located in the micellar phase with the increasing depth of intercalation in the order SDS < Brij < CTAB. Gallates revealed a higher stoichiometric factor towards galvinoxyl in CTAB systems, which is accounted to a concentration effect of antioxidant and radical being both solubilized in the palisade layer. In contrast, in SDS solutions hardly any reaction between galvinoxyl and gallates was found. SDS acted as a physical barrier between radical (palisade layer) and antioxidant (stern layer). The influence of the hydrophobic properties of the antioxidant was clearly seen in Brij micelles. Elongation of the alkyl chain in gallate molecule resulted in increasing stoichiometric factors in the presence of galvinoxyl being located in the deeper region of the bulky headgroup area. The reverse trend was found in the presence of Fremy's radical being located in the hydrated area of the micelles.
authors.affiliation: Institute of Human Nutrition and Food Science, University of Kiel, Heinrich-Hecht-Platz 10, 24118 Kiel, Germany. info@foodtech.uni-kiel.de
authors.forename: Anja
authors.initials: A
authors.lastname: Heins
authors.forename: Donald B
authors.initials: DB
authors.lastname: McPhail
authors.forename: Tobias
authors.initials: T
authors.lastname: Sokolowski
authors.forename: Heiko
authors.initials: H
authors.lastname: Stöckmann
authors.forename: Karin
authors.initials: K
authors.lastname: Schwarz
mesh_terms: D000975:Antioxidants / Q000737:chemistry* / Q000494:pharmacology*; D002592:Cetomacrogol / Q000737:chemistry; D002593:Cetrimonium Compounds / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D016166:Free Radical Scavengers / Q000494:pharmacology; D005609:Free Radicals / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008823:Micelles; D015394:Molecular Structure; D010084:Oxidation-Reduction / Q000187:drug effects; D010636:Phenols / Q000737:chemistry* / Q000494:pharmacology*; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry; D012995:Solubility; D013329:Structure-Activity Relationship; D013499:Surface Properties; D013501:Surface-Active Agents
chemical_list: D000975:Antioxidants; D002593:Cetrimonium Compounds; D016166:Free Radical Scavengers; D005609:Free Radicals; D008823:Micelles; D010636:Phenols; D013501:Surface-Active Agents; D012967:Sodium Dodecyl Sulfate; D002592:Cetomacrogol