Apr 18 – 23, 2010
Casino Conference Centre
UTC timezone

Complexation of curium(III) with pyoverdin-model compounds

Apr 22, 2010, 3:45 AM
15m
Mirror Hall (Casino Conference Centre)

Mirror Hall

Casino Conference Centre

Reitenbergerova 4/95, Marianske Lazne, Czech Republic
Verbal Separation Methods, Speciation Chemistry of Actinide and Trans-actinide Elements 2

Speaker

Dr Henry Moll (Forschungszentrum Dresden-Rossendorf e.V.)

Description

The aerobic groundwater bacterium Pseudomonas fluorescens (CCUG 32456) isolated from the aquifers at the Äspö Hard Rock Laboratory, Sweden secretes siderophores of the pyoverdin-type. Besides iron(III), these unique bioligands are also able to form strong complexes with actinides (e.g., U(VI), Np(V), and Cm(III)) [1-3]. For U(VI) and Np(V) we could show that mainly the catecholate and to less extend the hydroxamate functionalities of the pyoverdin molecule are involved in the actinide coordination [1, 2]. For Cm(III) it is still not clear which functional group of the pyoverdin molecule causes the great stability constants. In general, Cm(III) interactions with pyoverdin-model compounds and especially with chromophore-models are poorly understood. To address this lack, we thus present findings regarding the speciation of Cm(III) with 2,3-­dihydroxynaphthalene in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (0.3 µM) over a wide pH range. TRLFS is a well established direct speciation technique for investigating the complexes formed by actinides in both geochemical and biochemical environments. Four Cm(III)- dihydroxynaphthalene species of the type MxLyHz could be identified from the spectroscopic measurements. The stability constants of these strong Cm(III)- bioligand complexes and their individual spectroscopic properties (excitation and emission spectra, lifetimes) are reported. TRLFS shows that Cm(III)- dihydroxynaphthalene species cause a strong red shift of the characteristic Cm(III) (aq) emission band at 593.8 to 614.4 nm. The findings of our Cm(III) speciation study in comparison with the literature indicate a stronger affinity of Cm(III) to the catechol functionality of the pyoverdin molecules as found for U(VI) and Np(V). [1] H. Moll, M. Glorius, G. Bernhard, A. Johnsson, K. Pedersen, M. Schäfer, H. Budzikiewicz, Geomicrobiol. J. 25, 157-166 (2008). [2] H. Moll, M. Glorius, A. Johnsson, M. Schäfer, H. Budzikiewicz, K. Pedersen, G. Bernhard, Radiochim. Acta, submitted (2009). [3] H. Moll, A. Johnsson, M. Schäfer, K. Pedersen, H. Budzikiewicz, G. Bernhard, BioMetals 21, 219-228 (2008). This work was funded by the BMWi under contract number: 02E9985.

Primary author

Dr Henry Moll (Forschungszentrum Dresden-Rossendorf e.V.)

Co-author

Prof. Gert Bernhard (Forschungszentrum Dresden-Rossendorf e.V.)

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