Combining the Best of Two Chelating Titans: A Hydroxypyridinone‐Decorated Macrocyclic Ligand for Efficient and Concomitant Complexation and Sensitized Luminescence of f‐Elements

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

doi:10.1002/cplu.202100083

Cited by 8 publications

(13 citation statements)

References 87 publications

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“…These linkers were incorporated for synthetic reasons: the syntheses of the analogous ligands without the linker were very poor yielding. Notably, similar tripodal TACN-based and tetrapodal cyclen-based HOPO complexes were previously reported by Raymond 26 and Law, 27,28 respectively, for imaging applications, although neither their kinetic inertness nor their affinity for anions were investigated.…”

Section: ■ Introductionmentioning

confidence: 75%

Kinetically Inert Macrocyclic Europium(III) Receptors for Phosphate

2023

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The significant role that phosphate plays in environmental water pollution and biomedical conditions such as hyperphosphatemia highlights the need to develop robust receptors that can sequester the anion effectively and selectively from complex aqueous media. Toward that goal, four macrocyclic tris-bidentate 1,2-hydroxypyridonate (HOPO) europium(III) complexes containing either a cyclen, cyclam, TACN, or TACD ligand cap were synthesized and evaluated as phosphate receptors. The solubility of EuIII-TACD-HOPO in water was insufficient for luminescent studies. Whereas EuIII-cyclen-HOPO is eight coordinate with two inner-sphere water molecules, both EuIII-cyclam-HOPO and EuIII-TACN-HOPO are nine coordinate with three inner-sphere water molecules, suggesting that the two coordination states are very close in energy. As observed previously with linear analogues of tripodal HOPO complexes, there is no relationship between the number of inner-sphere water molecules and the affinity of the complex for phosphate. Whereas all three complexes do bind phosphate, EuIII-cyclen-HOPO has the highest affinity for phosphate with the anion displacing both of its inner-sphere water molecules. On the other hand, only one or two of the three inner-sphere water molecules of EuIII-TACN-HOPO and EuIII-cyclam-HOPO are displaced by phosphate, respectively. All three complexes are highly selective for phosphate over other anions, including arsenate. All three complexes are highly stable. EuIII-cyclen-HOPO and, to a lesser extent, EuIII-TACN-HOPO are more kinetically inert than the linear EuIII-Ser-HOPO. EuIII-cyclam-HOPO, on the other hand, is not. This study highlights the significant effect that minor changes in the ligand cap can have on both the ligand exchange rate and affinity for phosphate of tripodal 1,2-dihydroxypyridinonate complexes.

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Section: ■ Introductionmentioning

confidence: 75%

Kinetically Inert Macrocyclic Europium(III) Receptors for Phosphate

2023

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“…For example penicillamine, recommended to treat Wilson's disease, leading to copper overload, has been evaluated for decorporation of polonium or cobalt. Preclinical studies were undertaken on rodents (58).…”

Section: Discussionmentioning

confidence: 99%

Treatment of radiological contamination: a review

Bodin¹,

Ménétrier²

2021

J. Radiol. Prot.

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After nuclear accidents, people can be contaminated internally via ingestion, inhalation and via intact skin or wounds. The assessment of absorbed, committed doses after internal exposure is based on activity measurement by in vivo or in vitro bioassay. Estimation of dose following internal contamination is dependent on understanding the nature and form of the radionuclide. Direct counting methods that directly measure γ-rays coming from within the body or bioassay methods that measure the amount of radioactive materials in urine or feces are used to estimate the intake, which is required for calculating internal exposure doses. The interpretation of these data in terms of intake and the lifetime committed dose requires knowledge or making assumptions about a number of parameters (time, type of exposure, route of the exposure, physical, biological and chemical characteristics) and their biokinetics inside the body. Radioactive materials incorporated into the body emit radiation within the body. Accumulation in some specific organs may occur depending on the types of radioactive materials. Decorporation therapy is that acceleration of the natural rate of elimination of the contaminant will reduce the amount of radioactivity retained in the body. This article presents an overview of treatment of radiological contamination after internal contamination.

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“…An octadentate 3,4-HP derivative compound (THPN, L31 ) demonstrated to have very high chelating capacities in aqueous solution towards zirconium and iron (pZr = 42.8 and pFe = 38) and to be a stronger Zr(IV) chelator than DFO (pZr = 32.2) although slightly weaker than L27 (pZr = 44.0) [ 89 ]. Another innovative water-soluble rigid chelator for f -elements, a hydroxypyridinone(1,2-HP)-decorated macrocycle DOTHOPO ( L29 ), showed rapid kinetics for the formation of stable complexes with lanthanides (Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , pM = 19.9–20.8) and a late actinide (Cm 3+ , pCm = 21.9), and it can be used as a luminescence antenna for each metal ion [ 90 ]. In fact, this rigid cyclen backbone diminishes the movement of the pendant arms, therefore providing a closely packed coordination core for the octadentate Eu 3+ metal ion of L33 .…”

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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Combining the Best of Two Chelating Titans: A Hydroxypyridinone‐Decorated Macrocyclic Ligand for Efficient and Concomitant Complexation and Sensitized Luminescence of f‐Elements

Cited by 8 publications

References 87 publications

Kinetically Inert Macrocyclic Europium(III) Receptors for Phosphate

Kinetically Inert Macrocyclic Europium(III) Receptors for Phosphate

Treatment of radiological contamination: a review

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

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