Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeFe Dimer and Associated Catalytic Chemistry.
Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (HO) to dioxygen (O) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous micro...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 30; pp. 9704 - 9716 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
8/5/2015
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=108979689&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 108979689 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/5/2015 vid: 137 iid: 30 pid: 997 pub: American Chemical Society artinfo: ui: 108979689 10.1021/jacs.5b05229 ppf: 9704 ppct: 12 formats: tig: atl: Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeFe Dimer and Associated Catalytic Chemistry. aug: au: Tang, Liang L. Gunderson, William A. Weitz, Andrew C. Hendrich, Michael P. Ryabov, Alexander D. Collins, Terrence J. affil: Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States su: Reversed micelles Oxygen Photochemistry Micelles Refrigerants sug: subj: Reversed micelles Oxygen Photochemistry Micelles Refrigerants ab: Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (HO) to dioxygen (O) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous microreactors of reverse micelles where water is present in much lower abundance than in bulk water. n-Octane serves as a proximate reservoir supplying O to result in partial oxidation of Fe to Fe-containing species, mostly the FeFe (major) and FeFe (minor) dimers which coexist with the Fe TAML monomeric species. The speciation depends on the pH and the degree of hydration w, viz., the amount of water in the reverse micelles. The previously unknown FeFe dimer has been characterized by UV-vis, EPR, and Mössbauer spectroscopies. Reactive electron donors such as NADH, pinacyanol chloride, and hydroquinone undergo the TAML-catalyzed oxidation by O. The oxidation of NADH, studied in most detail, is much faster at the lowest degree of hydration w (in "drier micelles") and is accelerated by light through NADH photochemistry. Dyes that are more resistant to oxidation than pinacyanol chloride (Orange II, Safranine O) are not oxidized in the reverse micellar media. Despite the limitation of low reactivity, the new systems highlight an encouraging step in replacing TAML peroxidase-like chemistry with more attractive dioxygen-activation chemistry. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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