Synthesis and Characterization of Uranyl Compounds with Iminodiacetate and Oxydiacetate Displaying Variable Denticity

Jiang, Jun; Sarsfield, Mark J.; Renshaw, Joanna C.; Livens, Francis R.; Collison, David; Charnock, John; Helliwell, Madeleine; Eccles, Harry

doi:10.1021/ic020121v

Cited by 72 publications

(71 citation statements)

References 22 publications

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“…Moreover, titrations conducted with competing ligands allowed us to control the metal speciation and to avoid precipitation of hydroxo uranyl species. Iminodiacetic acid (IDA) was chosen as a competing ligand as it shows a quite simple speciation with uranyl and reliable equilibrium constants are reported . The conditional stability constants of the uranyl complexes formed with IDA were calculated and inserted in the fitting procedure according to models described in the Experimental Section.…”

Section: Resultsmentioning

confidence: 99%

Cyclic Phosphopeptides to Rationalize the Role of Phosphoamino Acids in Uranyl Binding to Biological Targets

Starck

Laporte

Oros

et al. 2017

Chemistry A European J

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The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo.

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Section: Resultsmentioning

confidence: 99%

Cyclic Phosphopeptides to Rationalize the Role of Phosphoamino Acids in Uranyl Binding to Biological Targets

Starck

Laporte

Oros

et al. 2017

Chemistry A European J

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“…The conditional stability constants of uranyl with the competing agent (IDA) were taken into account in the procedure. These constants were calculated at pH 7.4 from published global constants:

true UO_{2}^{2 +} + IDA^{2 -} \vec{\leftarrow} UO_{2} IDA; \log β_{11}^{pH 7.4} = 7.8

true UO_{2}^{2 +} + 2 IDA^{2 -} \vec{\leftarrow} UO_{2} (IDA)_{2}^{2 -}; \log β_{12}^{pH 7.4} = 12.2

true 2 UO_{2}^{2 +} + 2 IDA^{2 -} + 2 OH^{-} \vec{\leftarrow} (UO_{2})_{2} (IDA)_{2} (OH)_{2}^{2 -}; \log β_{22}^{pH 7.4} = 21.4

…”

Section: Methodsmentioning

confidence: 99%

Phosphate‐Rich Biomimetic Peptides Shed Light on High‐Affinity Hyperphosphorylated Uranyl Binding Sites in Phosphoproteins

Laporte

Lebrun

Vidaud

et al. 2019

Chemistry A European J

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Some phosphoproteins such as osteopontin (OPN) have been identified as high‐affinity uranyl targets. However, the binding sites required for interaction with uranyl and therefore involved in its toxicity have not been identified in the whole protein. The biomimetic approach proposed here aimed to decipher the nature of these sites and should help to understand the role of the multiple phosphorylations in UO22+ binding. Two hyperphosphorylated cyclic peptides, pS168 and pS1368 containing up to four phosphoserine (pSer) residues over the ten amino acids present in the sequences, were synthesized with all reactions performed in the solid phase, including post‐phosphorylation. These β‐sheet‐structured peptides present four coordinating residues from four amino acid side chains pointing to the metal ion, either three pSer and one glutamate in pS168 or four pSer in pS1368. Significantly, increasing the number of pSer residues up to four in the cyclodecapeptide scaffolds produced molecules with an affinity constant for UO22+ that is as large as that reported for osteopontin at physiological pH. The phosphate‐rich pS1368 can thus be considered a relevant model of UO22+ coordination in this intrinsically disordered protein, which wraps around the metal ion to gather four phosphate groups in the UO22+ coordination sphere. These model hyperphosphorylated peptides are highly selective for UO22+ with respect to endogenous Ca2+, which makes them good starting structures for selective UO22+ complexation.

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“…Thermodynamic [6] and structural [4,6] data on the complexation of U(VI) with ODA have revealed that the ether-oxygen of ODA could be in a bonding mode (R U-O ~ 2.5 -2.6 Å), non-bonding mode (R U-O ~ 3.12 Å), or dynamic mode between bidentate and tridentate configurations (R U-O ~ 2.90 Å) in solution. Whether the ether-oxygen participates in bonding with metal ions, particularly the dioxo-actinyl ions where steric hindrance may exist, has always been an interesting subject of study.…”

Section: Coordination Modesmentioning

confidence: 99%

“…Whether the ether-oxygen participates in bonding with metal ions, particularly the dioxo-actinyl ions where steric hindrance may exist, has always been an interesting subject of study. The M-O distances in these complexes are compared with those in a tridentate UO 2 (ODA) 2 2complex [4] in Figure 6. For the complexes of actinyl ions with DMOGA or TMOGA, we haven't identified the structures in solution.…”

Section: Coordination Modesmentioning

confidence: 99%

“…Thermodynamic [6] and structural [4,6] data on the complexation of U(VI) with ODA have revealed that the ether-oxygen of ODA could be in a bonding mode (R U-O ~ 2.5 -2.6 Å), non-bonding mode (R U-O ~ 3.12 Å), or dynamic mode between bidentate and tridentate configurations (R U-O ~ 2.90 Å) in solution. [4]. However, solid-state crystal structures of NpO 2 (TMOGA) 2 ClO 4 (cr) [11] and UO 2 (TMOGA) 2 (ClO 4 ) 2 (cr) [12] have been obtained, showing the ether-oxygen in TMOGA participates in bonding with Np(V) and U(VI).…”

Section: Coordination Modesmentioning

confidence: 99%

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Complexation of Actinides with Amide Derivatives of Oxydiacetic Acid

Rao

Tian

2005

MRS Proc.

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Complexation of Np(V), U(VI) and Nd(III) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) was studied in comparison with the complexation with oxydiacetic acid (ODA). Stability constants and enthalpy of complexation were determined by potentiometry, spectrophotometry and calorimetry. Thermodynamic parameters, in conjunction with structural information of solid compounds, indicate that DMOGA and TMOGA form tridentate complexes with the ether-oxygen participating in bonding with actinide/lanthanide ions. The trends in the stability constants, enthalpy and entropy of complexation are discussed in terms of the difference in the hydration of the amide groups and carboxylate groups and the difference in the charge density of the metal ions.

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Synthesis and Characterization of Uranyl Compounds with Iminodiacetate and Oxydiacetate Displaying Variable Denticity

Cited by 72 publications

References 22 publications

Cyclic Phosphopeptides to Rationalize the Role of Phosphoamino Acids in Uranyl Binding to Biological Targets

Cyclic Phosphopeptides to Rationalize the Role of Phosphoamino Acids in Uranyl Binding to Biological Targets

Phosphate‐Rich Biomimetic Peptides Shed Light on High‐Affinity Hyperphosphorylated Uranyl Binding Sites in Phosphoproteins

Complexation of Actinides with Amide Derivatives of Oxydiacetic Acid

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