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Effect of a Bromo Substituent on the Glutathione Peroxidase Activity of a Pyridoxine-like Diselenide
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
Department of Chemistry, Howard University, USA..
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Applied Materials Sciences.
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2015 (English)In: The Journal of Organic Chemistry, Vol. 50, no 15, 7385-7395 p.Article in journal (Refereed) Published
Abstract [en]

In search for better mimics of the glutathioneperoxidase enzymes, pyridoxine-like diselenides 6 and 11,carrying a 6-bromo substituent, were prepared. Reaction of2,6-dibromo-3-pyridinol 5 with sodium diselenide provided 6via aromatic nucleophilic substitution of the 2-bromosubstituent. LiAlH4 caused reduction of all four ester groupsand returned 11 after acidic workup. The X-ray structure of 6showed that the dipyridyl diselenide moiety was kept in analmost planar, transoid conformation. According to NBOanalysis,this was due to weak intramolecular Se···O (1.1 kcal/mol) and Se···N-interactions (2.5 kcal/mol). That the 6-bromo substituent increased the positive charge on seleniumwas confirmed by NPA-analysis and seen in calculated andobserved 77Se NMR-shifts. Diselenide 6 showed a more than 3-fold higher reactivity than the corresponding des-bromocompound 3a and ebselen when evaluated in the coupled reductase assay. Experiments followed for longer time (2 h) confirmedthat diselenide 6 is a better GPx-catalyst than 11. On the basis of 77Se-NMR experiments, a catalytic mechanism for diselenide 6was proposed involving selenol, selenosulfide and seleninic acid intermediates. At low concentration (10 μM) where it showedonly minimal toxicity, it could scavenge ROS produced by MNC- and PMNC-cells more efficiently than Trolox.

Place, publisher, year, edition, pages
2015. Vol. 50, no 15, 7385-7395 p.
National Category
Chemical Sciences Engineering and Technology
Research subject
Chemistry with specialization in Organic Chemistry; Engineering Science with specialization in Materials Science
Identifiers
URN: urn:nbn:se:uu:diva-259460DOI: 10.1021/acs.joc.5b00797ISI: 000359393500007OAI: oai:DiVA.org:uu-259460DiVA: diva2:844254
Funder
Swedish Research CouncilCarl Tryggers foundation , CTS 13:120 13:346
Available from: 2015-08-04 Created: 2015-08-04 Last updated: 2015-09-22Bibliographically approved

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Singh, Vijay PPoon, Jia-feiLu, XiMestres, GemmaKarlsson Ott, MarjamEngman, Lars

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