title: Highly luminescent and stable hydroxypyridinonate complexes: a step towards new curium decontamination strategies.
abstract: The photophysical properties, solution thermodynamics, and in vivo complex stabilities of Cm(III) complexes formed with multidentate hydroxypyridinonate ligands, 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO), are reported. Both chelators were investigated for their ability to act as antenna chromophores for Cm(III), leading to highly sensitized luminescence emission of the metal upon complexation, with long lifetimes (383 and 196 μs for 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO), respectively) and remarkable quantum yields (45 % and 16 %, respectively) in aqueous solution. The bright emission peaks were used to probe the electronic structure of the 5f complexes and gain insight into ligand field effects; they were also exploited to determine the high (and proton-independent) stabilities of the corresponding Cm(III) complexes (log β110 = 21.8(4) for 3,4,3-LI(1,2-HOPO) and log β120 = 24.5(5) for 5-LIO(Me-3,2-HOPO)). The in vivo complex stability for both ligands was assessed by using (248) Cm as a tracer in a rodent model, which provided a direct comparison with the in vitro thermodynamic results and demonstrated the great potential of 3,4,3-LI(1,2-HOPO) as a therapeutic Cm(III) decontamination agent.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA).
authors.forename: Manuel
authors.initials: M
authors.lastname: Sturzbecher-Hoehne
authors.forename: Birgitta
authors.initials: B
authors.lastname: Kullgren
authors.forename: Erin E
authors.initials: EE
authors.lastname: Jarvis
authors.forename: Dahlia D
authors.initials: DD
authors.lastname: An
authors.forename: Rebecca J
authors.initials: RJ
authors.lastname: Abergel
mesh_terms: D002614:Chelating Agents / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry; D003476:Curium / Q000737:chemistry* / Q000302:isolation & purification; D003666:Decontamination; D049449:Luminescence; D049408:Luminescent Agents / Q000737:chemistry*; D011728:Pyridones / Q000737:chemistry*; D011848:Radioactive Pollutants / Q000737:chemistry* / Q000302:isolation & purification; D013816:Thermodynamics
chemical_list: C580946:1,2-hydroxypyridinone; D002614:Chelating Agents; D056831:Coordination Complexes; D049408:Luminescent Agents; D011728:Pyridones; D011848:Radioactive Pollutants; D003476:Curium
keywords: actinides; curium; energy transfer; luminescence; thermodynamics