Chelation and stabilization of berkelium in oxidation state +IV

Deblonde, Gauthier J.‐P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiří; Jong, Wibe A. de; Strong, Roland K.; Abergel, Rebecca J.

doi:10.1038/nchem.2759

Cited by 76 publications

(118 citation statements)

References 60 publications

(59 reference statements)

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“…248 Cm, t½ = 340,000 yr) that can be produced and purified on the multi-gram scale, (ii) in aqueous solution it is exclusively found in the +III oxidation state and, (iii) trivalent Cm(III) can readily be sensitised by organic ligands in aqueous media. 40,[42][43][44][45][46][47][48][49][50][51] The three metal ions probed in this study, Eu(III), Tb(III), and Cm(III), are very similar in size, as indicated by their respective ionic radii (Fig. 1, r = 0.03 Å), and, from a coordination chemistry perspective, can almost exclusively be differentiated by the nature of their valence electrons.…”

Section: Introductionmentioning

confidence: 98%

Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand

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TitleInvestigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand In order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(III), terbium(III) and curium(III) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(III) and Eu(III) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(III) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. In contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(III), Tb(III,) and Cm(III) complexes.

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Section: Introductionmentioning

confidence: 98%

Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand

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“…249 Bk β-decays into 249 Cf with a half-life of 330 days, and because of this short half-life relatively little is known about its properties. For example, only in the last two years were single crystal structures of Bk(III) compounds reported and the +IV valence state stabilized in solution [2,3]. Notably, we could not find electron energy loss spectra (EELS), even though both EELS and transmission electron microscopy (TEM) in general have proven useful for analyzing radioactive materials [4].…”

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confidence: 84%

Electron Energy Loss Spectroscopy of Actinides at the Nanogram Scale

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Actinide atoms have seven valence 5f-orbitals, leading to complicated electronic structures and fascinating properties for both free metal ions and their compounds [1]. Yet, comparatively little is known about most of them, mostly because they are without exception radioactive and handling them poses an inherent health risk. Due to contamination and radiation safety issues, it is often necessary to extensively prepare experiments, perform dry runs using non-radioactive surrogates, and to use dedicated instruments and facilities. Most actinides are synthetic elements and their preparation is timeconsuming, difficult and therefore expensive, with microgram prices reaching thousands of dollars.

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“…Octadentate HOPO-based molecules usually exhibit a high selectivity toward tetravalent metals ions at the expense of the trivalent ions. 12,15 The difference in stability constants between the Th(IV) and Eu(III) complexes is extremely high (Δlog β 110 = 19.9) and highlights the suitability of L 1 for 227 Th complexation. Since single crystals of the Th(IV) complex could not be obtained, structural information on the Th system was gained via extended X-ray absorbance fine structure (EXAFS) spectroscopy.…”

Section: Based On Previous Reports On the Chelation Of Tetravalent Mementioning

confidence: 99%

Solution Thermodynamics and Kinetics of Metal Complexation with a Hydroxypyridinone Chelator Designed for Thorium-227 Targeted Alpha Therapy

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The solution chemistry of a chelator developed for 227 Th targeted alpha therapy was probed. The compound of interest is an octadentate ligand comprising four N-methyl-3-hydroxy-pyridine-2-one metal-binding units, two tertiary amine groups, and one carboxylate arm appended for bioconjugation. The seven pK a values of the ligand and the stability constants of complexes formed with Th(IV), Hf(IV), Zr(IV), Gd(III), Eu(III), Al(III), and Fe(III) were determined. The ligand exhibits extreme thermodynamic selectivity towards tetravalent metal ions, with a ca. 20 orders of magnitude difference between the formation constant of the Th(IV) species formed at physiological pH, namely [ThL]-, and that of its Eu(III) analogue. Likewise, log β 110 values of 41.7 ± 0.3 and 26.9 ± 0.3 (T = 25°C) were measured for [ThL]-and [Fe III L] 2-, respectively, highlighting the high affinity and selectivity of the ligand for Th ions over potentially competing endogenous metals. Single-crystal structural analysis of the Fe(III) complex revealed a dinuclear 2:2 metal:chelator complex crystallizing in the P-1 space group. The formation of this dimeric species is likely favored by several intramolecular hydrogen bonds and the protonation state of the chelator in acidic media. L III edge EXAFS data on the Th(IV) complexes of both the ligand and a monoclonal antibody conjugate revealed the expected mononuclear 1:1 metal:chelator coordination environment. This was also confirmed by high resolution mass spectrometry. Finally, kinetic experiments demonstrated that labeling the bioconjugated ligand with Th(IV) could be achieved and Page 2 of 40 completed after1 hour at room temperature, reinforcing the high suitability of this chelator for 227 Th targeted alpha therapy.

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Chelation and stabilization of berkelium in oxidation state +IV

Cited by 76 publications

References 60 publications

Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand

Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand

Electron Energy Loss Spectroscopy of Actinides at the Nanogram Scale

Solution Thermodynamics and Kinetics of Metal Complexation with a Hydroxypyridinone Chelator Designed for Thorium-227 Targeted Alpha Therapy

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