Ultra-selective ligand-driven separation of strategic actinides

Deblonde, Gauthier J.‐P.; Ricano, Abel; Abergel, Rebecca J.

doi:10.1038/s41467-019-10240-x

Cited by 41 publications

(41 citation statements)

References 47 publications

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“…When another metal that competes with Eu 3+ for 343-HOPO binding is added to the system, the intensity of the emission spectrum of [ Structural chemistry of rare earth complexes with 343-HOPO. While the solution chemistry of 343-HOPO and its use in a variety of applications such as actinide decorporation and separations 37,38 , post-MRI chelation therapy 39 , or 89 Zr PET imaging 40 is increasingly well-characterized, the structural chemistry of this chelator, with trivalent metals in particular, remains largely unexplored. Daumann et al reported the first crystal structure featuring 343-HOPO and Eu 3+ in 2015 41 , and this remained the only published structure featuring 343-HOPO and a trivalent metal until this study.…”

Section: Resultsmentioning

confidence: 99%

Developing scandium and yttrium coordination chemistry to advance theranostic radiopharmaceuticals

et al. 2020

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The octadentate siderophore analog 3,4,3-LI(1,2-HOPO), denoted 343-HOPO hereafter, is known to have high affinity for both trivalent and tetravalent lanthanide and actinide cations. Here we extend its coordination chemistry to the rare-earth cations Sc 3+ and Y 3+ and characterize fundamental metal-chelator binding interactions in solution via UV-Vis spectrophotometry, nuclear magnetic resonance spectroscopy, and spectrofluorimetric metalcompetition titrations, as well as in the solid-state via single crystal X-ray diffraction. Sc 3+ and Y 3+ binding with 343-HOPO is found to be robust, with both high thermodynamic stability and fast room temperature radiolabeling, indicating that 343-HOPO is likely a promising chelator for in vivo applications with both metals. As a proof of concept, we prepared a 86 Y-343-HOPO complex for in vivo PET imaging, and the results presented herein highlight the potential of 343-HOPO chelated trivalent metal cations for therapeutic and theranostic applications.

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Section: Resultsmentioning

confidence: 99%

Developing scandium and yttrium coordination chemistry to advance theranostic radiopharmaceuticals

et al. 2020

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“…27,30,39,40 Extended aging of U IV in aqueous media can also lead to changes in metal-ion speciation; 35,40 however, this was not observed here via UV−vis or investigated via other techniques, which suggests the U IV -343-HOPO complex is very stable, a likely result of the thermodynamic benefits of the chelate effect and the known selectivity of 343-HOPO for tetravalent metal cations. 41 To improve our understanding of U IV and U VI coordination by the 343-ligands, we turned to X-ray absorption spectroscopy.…”

Section: ■ Introductionmentioning

confidence: 99%

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

et al. 2020

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The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV− visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U IV , generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U IV to a lesser extent, as evidenced by the mix of U IV and U VI complexes observed via XAS. CV and SEC measurements confirmed that the U IV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and U VI ions can be reduced, likely proceeding via a two-electron reduction process.

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“…[3] The separation processes of tetravalent ions such as Zr(IV) and Hf(IV) have offered a paradigm shift in the production of strategic elements. [4][5][6] Hafnium and zirconium are hard metals, and their cations are highly oxophilic with a strong Lewis acid character. Thus, the metal-ligand bond is highly ionic, and the geometric arrangement results in the need to minimize electron-electron repulsion.…”

Section: Introductionmentioning

confidence: 99%

“…Hence, PSI-MS transfers ions from the condensed to the gas phase, whereas DFT calculations provide detailed information regarding their stability and structure. Because the separation/extraction processes occur in a nitric medium, [2,6,9] the proposed acidic medium used herein contains high contents of nitrate (NO 3 À ) and fluoride (F À ) to simulate the conditions of alternatives extraction routes. [10][11][12] The identification of these species may suit as a model to understand, at the molecular level, one step of the processes that are of interest to the nuclear industry.…”

Section: Introductionmentioning

confidence: 99%

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Unveiling the Zirconium and Hafnium Speciation in Fluoride‐Nitric Acid Solutions by Paper Spray Ionization Mass Spectrometry Combined with DFT Calculations

et al. 2021

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Paper spray ionization mass spectrometry (PSI-MS) was used to detect a variety of species of hafnium and zirconium present in an aqueous acid solution containing NO 3 À and F À anions. This solution mimetics the acid waters used in separation/extraction processes. Hence, the information provided by PSI-MS is combined with the results achieved from DFT calculations to confirm the nature and stability of each species. In the adopted experimental conditions, Zr(IV) appears coordinated with F À , NO 3 À and H 2 O to generate mainly the dimer [Zr 2 F 3 OH-(NO 3) 2 (H 2 O) 5 ] 2 + , among other complexes, with remarkable thermodynamic stability (À 48.7 kcal mol À 1). On the other hand, Hf(IV) emerges predominantly coordinated with NO 3 À and F À anions. The hafnium monomers [HfF 4 NO 3 ] À and [HfF 3 (NO 3) 2 ] À have thermodynamic stability related to the electron pairing of the valence layer. In the gas phase, the fluoroanions of Zr(IV) demonstrated a high electronic affinity and free energy via DFT (À 156.7 kcal mol À 1) correlating thermodynamic stability to the experimental (À 47 kcal mol À 1), for the formation reaction of [ZrF 5 ] À. Besides, the presence of fluoride and nitrate in the reaction mixture induces the formation of dimers connected in μ 2-F bridges, with coordination 7 and 8 of the central atom. Finally, the results described herein are promising studies of chemical speciation of cationic metals in an aqueous environment, a challenging subject whose importance will grow in the coming years.

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Ultra-selective ligand-driven separation of strategic actinides

Cited by 41 publications

References 47 publications

Developing scandium and yttrium coordination chemistry to advance theranostic radiopharmaceuticals

Developing scandium and yttrium coordination chemistry to advance theranostic radiopharmaceuticals

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

Unveiling the Zirconium and Hafnium Speciation in Fluoride‐Nitric Acid Solutions by Paper Spray Ionization Mass Spectrometry Combined with DFT Calculations

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