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Capture and Stabilization of the Hydroxyl Radical in a Uranyl Peroxide Cluster
Journal article   Open access   Peer reviewed

Capture and Stabilization of the Hydroxyl Radical in a Uranyl Peroxide Cluster

Brett Lottes and Korey P Carter
Chemistry : a European journal, Vol.29(45), e202300749
08/10/2023
DOI: 10.1002/chem.202300749
PMID: 37249248
url
https://doi.org/10.1002/chem.202300749View
Published (Version of record) Open Access

Abstract

Here we describe the synthesis and characterization of a new uranyl peroxide cluster (UPC), U60Ox30*, which captures and stabilizes oxygen-based free radicals for more than one week. These radical species were first detected with a nitroblue tetrazolium colorimetric assay and U60Ox30* was characterized by single crystal X-ray diffraction as well as infrared (IR), Raman, UV-Vis-NIR, and electron paramagnetic resonance (EPR) spectroscopies. Identification of the free radicals present in U60Ox30* was done via room temperature solid and solution state X-band EPR studies using spin trapping methods. The spin trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO) was definitive for identifying the free radicals in U60Ox30*, which are hydroxyl radicals (•OH) that are stable for up to ten days that also persist upon addition of the metalloenzymes catalase and superoxide dismutase. Addition of the spin trapping agent α-(4-pyridyl N-oxide)-N-tert-butylnitrone (POBN) further confirmed the radicals were oxygen based, and deuteration experiments showed that the origin of the free radicals was from the decomposition of H2O2 in water. These results demonstrate that highly oxidizing species such as the •OH radical can be stabilized in UPCs, which alters our understanding of the role of free radicals present in spent nuclear fuel.
Polyoxometalates Free radicals Uranium Electron Paragmagnetic Resonance Spin Trapping Methods UIOWA OA Agreement

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