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In this study, an alkyl chain\u2010functionalized series of nitronyl nitroxide (NN) radicals designed and synthesized by varying their amphiphilic character. Subsequently, their thiol\u2010based reactivity and microenvironment accessibility, along with antioxidant profile, were investigated. Radical behavior was monitored in aqueous media and sodium dodecyl sulfate (SDS) micelles. Accessibility properties and micellar partitioning of all radicals were evaluated in a concentration\u2010dependent manner, using electron paramagnetic resonance (EPR). Glutathione (GSH) reactivity and quantitative EPR kinetic analysis revealed that the reduction rate constants systematically decrease with increasing alkyl chain length, leading to the formation of diamagnetic hydroxylamine species. In the presence of SDS, the reactivity of NN derivatives with GSH was dramatically suppressed, confirming the protection of the nitroxide center from thiol reduction. The NN\u2010functionalized derivatives displayed a dual antioxidant mechanism, based on electron transfer and hydrogen atom transfer (HAT). The limited superoxide scavenging and pro\u2010oxidant effects indicated radical\u2010specific selectivity under single\u2010electron transfer (SET) conditions. Notably, all derivatives exhibited pronounced inhibition of lipid peroxidation, confirming their effectiveness in chain\u2010breaking antioxidant activity and rendering them competitive agents in targeted therapeutics and stress\u2010based pathologies.<\/jats:p>","DOI":"10.1002\/cbic.70561","type":"journal-article","created":{"date-parts":[[2026,10,20]],"date-time":"2026-10-20T18:25:58Z","timestamp":1792520758000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Alkyl Chain\u2010Functionalized Nitronyl Nitroxide Radicals: Structure\u2010Microenvironment Effects on Thiol Kinetics and Dual Antioxidant Behavior"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-3069-3550","authenticated-orcid":false,"given":"Lavinia\u2010Mihaela","family":"Ciutu","sequence":"first","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0004-1138-2187","authenticated-orcid":false,"given":"Alexandru\u2010Gabriel","family":"Bucur","sequence":"additional","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8850-6932","authenticated-orcid":false,"given":"Alexandru Vincentiu Florian","family":"Neculae","sequence":"additional","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-7934-831X","authenticated-orcid":false,"given":"Georgiana\u2010Alexandra","family":"Sanda","sequence":"additional","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1387-3647","authenticated-orcid":false,"given":"Anca\u2010Roxana","family":"Petrovici","sequence":"additional","affiliation":[{"name":"Centre of Advanced Research in Bionanoconjugates and Biopolymers Department \u201cPetru Poni\u201d Institute of Macromolecular Chemistry  Iasi Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2216-3842","authenticated-orcid":false,"given":"Petre","family":"Ionita","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry, Biochemistry and Catalysis Faculty of Chemistry University of Bucharest  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Adrian","family":"Fifere","sequence":"additional","affiliation":[{"name":"Centre of Advanced Research in Bionanoconjugates and Biopolymers Department \u201cPetru Poni\u201d Institute of Macromolecular Chemistry  Iasi Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ioana\u2010Andreea","family":"Turin\u2010Moleavin","sequence":"additional","affiliation":[{"name":"Centre of Advanced Research in Bionanoconjugates and Biopolymers Department \u201cPetru Poni\u201d Institute of Macromolecular Chemistry  Iasi Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Athanasios","family":"Salifoglou","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Laboratory of Inorganic Chemistry and Advanced Materials Aristotle University of Thessaloniki  Thessaloniki Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3777-9815","authenticated-orcid":false,"given":"Sevasti","family":"Matsia","sequence":"additional","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9235-9093","authenticated-orcid":false,"given":"Gabriela","family":"Ionita","sequence":"additional","affiliation":[{"name":"\u201cIlie Murgulescu\u201d Institute of Physical Chemistry, Romanian Academy  Bucharest Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,20]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/s005990050063"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bioorg.2024.107678"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules30102159"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules27072042"},{"key":"e_1_2_9_6_1","doi-asserted-by":"crossref","DOI":"10.1007\/978-1-4613-0743-3","volume-title":"Spin Labeling: Theory and Applications","author":"Berliner L. 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