Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution

Carter, Korey P.; Smith, Kurt F.; Tratnjek, Toni; Deblonde, Gauthier J.‐P.; Moreau, Liane M.; Rees, Julian A.; Booth, C. H.; Abergel, Rebecca J.

doi:10.1021/acs.inorgchem.0c03088

Cited by 11 publications

(16 citation statements)

References 55 publications

(135 reference statements)

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“…While research continues by others on developing treatments for internal radionuclide exposure [ 34 , 35 , 36 , 37 ], the results of this preliminary investigation showed that nutraceutical compounds could function as chelators for some metals considered internal radionuclide contamination hazards. Clearly, further research is required.…”

Section: Discussionmentioning

confidence: 98%

Nutraceuticals as Potential Radionuclide Decorporation Agents

Vergara

Kalinich

2021

Nutrients

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Exposure of individuals to radioactive material as a result of ingestion of contaminated food and water is an increasing public health concern. Unfortunately, there are limited treatment modalities for dealing with these types of potentially toxic exposures. Recent research suggests that many plant-based nutraceuticals may possess metal-binding properties. This preliminary study investigated the ability of genistein, curcumin, quercetin, and lentinan to bind metals considered internal contamination risks, namely cesium, uranium, cobalt, and strontium, in a variety of matrices. The efficacy of these nutraceuticals in protecting cultured cells from metal-induced toxicity was also explored. Results showed that none of the compounds bound cesium or strontium. However, genistein, curcumin, and quercetin could bind uranium. Curcumin and quercetin also bound cobalt and could also protect cultured cells from metal-induced cytotoxicity. Lentinan did not bind any of the metals tested. Metal binding was also pH dependent, with no binding observed at lower pH values. This project showed that nutraceuticals could function as chelators for metals considered internal radionuclide contamination hazards. Further investigations are required in order to determine whether these compounds will become a new nontoxic arsenal of pharmaceutical compounds with which to treat radionuclide contamination.

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Section: Discussionmentioning

confidence: 98%

Nutraceuticals as Potential Radionuclide Decorporation Agents

Vergara

Kalinich

2021

Nutrients

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“…Since the significant mobility of uranyl (UO 2 2+ ) in environment can originate health risks derived from radiological contamination, complexation of U 4+ and U 6+ by L27 was recently analyzed by UV-spectrophotometry, XANES and EXAFS. It was found that L27 , as well as other spermine-derived analogues (e.g., L28 ), can stabilize U 4+, in aqueous media (inert complex towards oxidation/hydrolysis in acidic aqueous media) which is particularly relevant since tetravalent actinides are quite susceptible to hydrolysis even under very acidic conditions [ 74 ]. This study allows the further understanding of the conditions under which the uranium species are stable in solution, therefore contributing to preview the chemical behavior of radionuclides in diverse systems (chemical, biological or environmental).…”

Section: Poly-hydroxypyridinonesmentioning

confidence: 99%

Hydroxypyridinone-Based Metal Chelators towards Ecotoxicity: Remediation and Biological Mechanisms

et al. 2022

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Hydroxypyridinones (HPs) are recognized as excellent chemical tools for engineering a diversity of metal chelating agents, with high affinity for hard metal ions, exhibiting a broad range of activities and applications, namely in medical, biological and environmental contexts. They are easily made and functionalizable towards the tuning of their pharmacokinetic properties or the improving of their metal complex thermodynamic stabilities. In this review, an analysis of the recently published works on hydroxypyridinone-based ligands, that have been mostly addressed for environmental applications, namely for remediation of hard metal ion ecotoxicity in living beings and other biological matrices is carried out. In particular, herein the most recent developments in the design of new chelating systems, from bidentate mono-HP to polydentate multi-HP derivatives, with a structural diversity of soluble or solid-supported backbones are outlined. Along with the ligand design, an analysis of the relationship between their structures and activities is presented and discussed, namely associated with the metal affinity and the thermodynamic stability of the corresponding metal complexes.

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“…The exaggerated stability and mobile nature of uranyl(VI) UO 2 2+ ion makes it the most important uranium species that contaminates groundwater. − To reduce the mobility of UO 2 2+ , it is usually reduced to insoluble uranium(IV) species. , Recently, octadentate hydroxypyridinone, catecholamide chelating ligands, and uranium generated tetravalent uranium that is practically inert toward oxidation or hydrolysis in acidic and aqueous solutions . Adsorption of uranium species in different oxidation states of the metal ion was studied experimentally using mass spectrometry and theoretical calculations.…”

Section: Introductionmentioning

confidence: 99%

Relativistic DFT Probe for Reaction Energies and Electronic/Bonding Properties of Polypyrrolic Hetero-Bimetallic Actinide Complexes: Effects of Uranylendo-Oxo Functionalization

Zheng

Bacha

et al. 2021

Inorg. Chem.

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A series of hetero-bimetallic actinide complexes of the Schiff-base polypyrrolic macrocycle (L), featuring cation− cation interactions (CCIs), were systematically investigated using relativistic density functional theory (DFT). The tetrahydrofuran (THF) solvated complex [(THF)(OU VI OU IV )(THF)(L)] 2+ has high reaction free energy (Δ r G), and its replacement with electrondonating iodine promotes the reaction thermodynamics to obtain uranyl iodide [(I)(OU VI OU IV )(I)(L)] 2+ (U VI −U IV ). Retaining this coordination geometry, calculations have been extended to other An(IV) (An = Th, Pa, Np, Pu), i.e., for the substitution of U(IV) to obtain U VI −An IV . As a consequence, the reaction free energy is appreciably lowered, suggesting the thermodynamic feasibility for the experimental synthesis of these bimetallic complexes. Among all U VI −An IV , the electron-spin density and high-lying occupied orbitals of U VI −Pa IV show a large extent of electron transfer from electron-rich Pa(IV) to electron-deficient U(VI), leading to a more stable U V −Pa V oxidation state. Additionally, the shortest bond distance and the comparatively negative E int of the Pa−O endo bond suggest more positive and negative charges (Q) of Pa and endooxo atoms, respectively. As a result of the enhanced Pa−O endo bond and strong CCI in U VI −Pa IV along with the corresponding lowest reaction free energy among all of the optimized complexes, uranyl species is a better candidate for the experimental synthesis in the ultimate context of environmental remediation.

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Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution

Cited by 11 publications

References 55 publications

Nutraceuticals as Potential Radionuclide Decorporation Agents

Nutraceuticals as Potential Radionuclide Decorporation Agents

Hydroxypyridinone-Based Metal Chelators towards Ecotoxicity: Remediation and Biological Mechanisms

Relativistic DFT Probe for Reaction Energies and Electronic/Bonding Properties of Polypyrrolic Hetero-Bimetallic Actinide Complexes: Effects of Uranylendo-Oxo Functionalization

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