Galvinoxyl radicals : Synthesis of new derivatives, determination of low oxygen contents, and stability studies

dc.contributor.authorLampp, Lisa
dc.contributor.authorAzarkh, Mykhailo
dc.contributor.authorDrescher, Malte
dc.contributor.authorImming, Peter
dc.date.accessioned2019-05-29T06:58:23Z
dc.date.available2019-05-29T06:58:23Z
dc.date.issued2019-05eng
dc.description.abstractTwo new derivatives of galvinoxyl (1), a perdeutered (2) and an adamantyl-analog (3) for potential applications as spin probes were synthesized. The synthesis with deuterated educts yielded 2 with 98% D. It exhibited an 18-line EPR spectrum in octanol with narrow peak-to-peak linewidth. The EPR spectrum of 3 was very similar to galvinoxyl, but with differences in the linewidth due to unresolved long-range couplings with adamantyl-protons. Compound 2 showed a higher response to oxygen (4.8 μT/% O2) than 1 (2.8 μT/% O2). The coupling pattern of 2 allowed the determination of oxygen at low levels (0–6%) by a new type of analysis of the EPR pattern. The stability of the radicals strongly depended on the amount of hydrogalvinoxyl, a by-product of the galvinoxyl synthesis, and the solvent type. A molecular mechanism for the stabilization by hydrogalvinoxyl and the influence of solvent type is proposed.eng
dc.description.versionpublishedde
dc.identifier.doi10.1016/j.tet.2019.03.051eng
dc.identifier.urihttps://kops.uni-konstanz.de/handle/123456789/45933
dc.language.isoengeng
dc.subjectGalvinoxyl radicals, EPR, Oximetry, Mechanism of stabilizationeng
dc.subject.ddc540eng
dc.titleGalvinoxyl radicals : Synthesis of new derivatives, determination of low oxygen contents, and stability studieseng
dc.typeJOURNAL_ARTICLEde
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@article{Lampp2019-05Galvi-45933,
  year={2019},
  doi={10.1016/j.tet.2019.03.051},
  title={Galvinoxyl radicals : Synthesis of new derivatives, determination of low oxygen contents, and stability studies},
  number={18},
  volume={75},
  issn={0040-4020},
  journal={Tetrahedron},
  pages={2737--2747},
  author={Lampp, Lisa and Azarkh, Mykhailo and Drescher, Malte and Imming, Peter}
}
kops.citation.iso690LAMPP, Lisa, Mykhailo AZARKH, Malte DRESCHER, Peter IMMING, 2019. Galvinoxyl radicals : Synthesis of new derivatives, determination of low oxygen contents, and stability studies. In: Tetrahedron. 2019, 75(18), pp. 2737-2747. ISSN 0040-4020. eISSN 1464-5416. Available under: doi: 10.1016/j.tet.2019.03.051deu
kops.citation.iso690LAMPP, Lisa, Mykhailo AZARKH, Malte DRESCHER, Peter IMMING, 2019. Galvinoxyl radicals : Synthesis of new derivatives, determination of low oxygen contents, and stability studies. In: Tetrahedron. 2019, 75(18), pp. 2737-2747. ISSN 0040-4020. eISSN 1464-5416. Available under: doi: 10.1016/j.tet.2019.03.051eng
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    <dcterms:abstract xml:lang="eng">Two new derivatives of galvinoxyl (1), a perdeutered (2) and an adamantyl-analog (3) for potential applications as spin probes were synthesized. The synthesis with deuterated educts yielded 2 with 98% D. It exhibited an 18-line EPR spectrum in octanol with narrow peak-to-peak linewidth. The EPR spectrum of 3 was very similar to galvinoxyl, but with differences in the linewidth due to unresolved long-range couplings with adamantyl-protons. Compound 2 showed a higher response to oxygen (4.8 μT/% O&lt;sub&gt;2&lt;/sub&gt;) than 1 (2.8 μT/% O&lt;sub&gt;2&lt;/sub&gt;). The coupling pattern of 2 allowed the determination of oxygen at low levels (0–6%) by a new type of analysis of the EPR pattern. The stability of the radicals strongly depended on the amount of hydrogalvinoxyl, a by-product of the galvinoxyl synthesis, and the solvent type. A molecular mechanism for the stabilization by hydrogalvinoxyl and the influence of solvent type is proposed.</dcterms:abstract>
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