Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion

Franczyk, Thaddeus S.; Czerwinski, Kenneth R.; Raymond, Kenneth N.

doi:10.1021/ja00047a023

Cited by 134 publications

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“…The equatorial coordination plane displays little to no orbital-dictated directionality, with observed coordination geometries ranging from trigonal-through hexagonal-planar, depending on ligand sterics and chelating ability. 12,[17][18][19] While previous uranyl chelation efforts in our laboratory have attempted to employ ligand-directed Lewis acid/base interactions with the terminal oxo atoms, 20,21 recent work has explored the more classical equatorial coordination behavior of the uranyl cation with tetradentate bis (3-hydroxy-N-methyl-pyridin-2-one) (bis-Me-3,2-HOPO) ligands. 22,23 Linearly-linked nLi-Me-3,2-HOPO ligands (where "Li" stands for "linear" and "n" represents the number of methylene units in the linker) bind at four points of a pentagonal-planar coordination geometry about the uranyl cation, with the fifth position occupied by solvent.…”

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confidence: 99%

Influence of Linker Geometry on Uranyl Complexation by Rigidly Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

Szigethy

Raymond²

2010

Inorg. Chem.

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Section: +mentioning

confidence: 99%

Influence of Linker Geometry on Uranyl Complexation by Rigidly Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

Szigethy

Raymond²

2010

Inorg. Chem.

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“…Although some work has been recently done on the synthesis of chelators for the uranyl ion [24] this appears to have little relevance to clinical application. Experi mental data in mice [25] suggests that hexadentate TREN (Me-3,2-HOPO) [N,N',N"-Tris-l,2-didehydro-3-hydroxy-l-methyl-2-oxopyrid-4-yl-(carbonyl)-2,2',2"-triaminotriethyleneamine] is a more effective chelator of uranium compared to Ca DTPA when administered acutely, and suggests that significant reductions in body and kidney uranium may be achieved with treatment.…”

Section: Discussionmentioning

confidence: 99%

Deliberate Overdose of Uranium: Toxicity and Treatment

Pavlakis¹,

Pollock²,

McLean³

et al. 1996

Nephron

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A case is described of deliberate ingestion of 15 g of uranium acetate which resulted in acute renal failure requiring dialytic therapy for 2 weeks, refractory anaemia, rhabdomyolysis, myocarditis, liver dysfunction with a disproportionate coagulopathy and paralytic ileus. Despite significant elevations in plasma uranium levels, treatment with both calcium EDTA and calcium DTPA were ineffective in promoting uranium excretion. Six months later the initial significant renal impairment exists with a persistent incomplete Fanconi syndrome. Future options for management of this unusual cause of acute renal failure are discussed.

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“…In this work, we have undertaken a study to determine if ligands that are known to strongly bind to uranyl ion (the so-called uranophiles) can be used to stabilize Am(V) or Am(VI) in aqueous solution. In the 1990s, Raymond and co-workers proposed that enhanced selectivity for transdioxo cations could be obtained by designing ligands that simultaneously form coordinate bonds to the equatorial region of the metal center and N-H hydrogen bonds to the axial oxygen atoms (Franczyk et al 1992). This has been referred to as stereognostic ligand design and as is conceptually illustrated in Figure 3.2.…”

Section: Stabilization Of Am(v)/am(vi): Backgroundmentioning

confidence: 99%

Sigma Team for Minor Actinide Separation: PNNL FY 2010 Status Report

Lumetta¹,

Sinkov²,

Neiner³

et al. 2010

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SUMMARYWork conducted at Pacific Northwest National Laboratory (PNNL) in FY 2010 addressed two lines of inquiry. The two hypotheses put forth were:1. The extractants from the TRUEX (a) process (CMPO) (b) and from the TALSPEAK (c) process (HDEHP) (d) can be combined into a single process solvent to separate 1) the lanthanides and actinides from acidic high-level waste and 2) the actinides from the lanthanides in a single solvent extraction process. (Note: This combined process will hereafter be referred to as the TRUSPEAK process.) A series of empirical measurements performed (both at PNNL and Argonne National Laboratory) in FY 2009 supported this hypothesis, but also indicated some nuances to the chemistry. Lanthanide/americium separation factors of 12 and higher were obtained with a prototypic TRUSPEAK solvent when extracting the lanthanides from a citrate-buffered DTPA (e) solution. Although the observed separation factors are sufficiently high to design an actinide/lanthanide separation process, a better understanding of the chemistry is expected to lead to improved solvent formulations and improved process performance. Work in FY 2010 focused on understanding the synergistic extraction behavior observed for Nd(III) and Am(III) when extracted into mixtures of CMPO and HDEHP. The interaction between CMPO and HDEHP in dodecane was investigated by 31 P NMR spectroscopy, and an adduct of the type CMPO·HDEHP was found to form. The formation of this adduct will reduce the effective extractant concentrations and must be taken into account when modeling metal ion extraction data in this system. Studies were also initiated to determine the Pitzer parameters for Nd(III) in lactate media.2. Higher oxidation states (e.g., +5 and +6) of Am can be stabilized in solution by complexation with uranophilic ligands, and this chemistry can be exploited to separate Am from Cm. To test this hypothesis, the previously reported stereognostic uranophilic ligands NPB (f) and EETAC (e) were investigated. To assess the potential of these ligands to stabilize pentavalent and hexavalent actinides, stability constants were measured for complexation of these ligands to Nd(III), Np(V), and Pu(VI) in a solvent mixture consisting of 80% methanol/20% water. For comparison, an analogous non-stereognostic ligand, NTA, (f) was also examined. The ligand EETAC showed greater binding affinity for hexavalent Pu versus trivalent Nd by two orders-of-magnitude. Such selectivity was not observed for either NTA or NPB.

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Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion

Cited by 134 publications

References 0 publications

Influence of Linker Geometry on Uranyl Complexation by Rigidly Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

Influence of Linker Geometry on Uranyl Complexation by Rigidly Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

Deliberate Overdose of Uranium: Toxicity and Treatment

Sigma Team for Minor Actinide Separation: PNNL FY 2010 Status Report

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