Advances in the investigation of dioxouranium(VI) complexes of interest for natural fluids

Alberto Pettignano, Antonio Gianguzza, Francesco Crea, Silvia Berto, Pier Giuseppe Daniele, Silvio Sammartano

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64 Citazioni (Scopus)

Abstract

The interactions of dioxouranium(VI) cation with different organic and inorganic ligands of environmental and biological interest were carefully examined with the aim to draw a chemical speciation picture of this ion in natural aquatic ecosystems and in biological fluids. Since UO22+ ion shows a significant tendency to hydrolyze, particular attention was paid in considering the hydrolysis species formation both in the presence and in absence of ligands. The results reported in the literature show that formation ofthe hydrolytic species assumes a great importance in the complexation models for all the UO22+ - ligand systems considered. In particular, the following ligands have been taken into account: (i) hydroxyl, chloride, fluoride, sulfate, carbonate and phosphate, as inorganic ligands, and (ii) carboxylates (with particular reference to oxalate and citrate), amines, amino acids, poly(amino carboxylates) (complexones),nucleotides, phosphonates, mercapto compounds and sulfonates, as organic ligands. In order to elucidate the speciation of uranyl in the presence of dissolved natural organic matter, the interactions with humic and fulvic acids were also considered. The strength of interaction in all the systemsconsidered was expressed in terms of stability constants of complex species and, if available, of the relative thermodynamic stability parameters. When possible, if data reported in the literature were sufficientlyhomogeneous, trends of stability were found for the different ligands of the same class and for ligands of different classes. Moreover, relationships were derived for poly-functional ligands, such aspoly-carboxylate, poly-amine and poly(amino carboxylate) ones, useful to predict the stability constants as a function of the number of binding sites per molecule, considering also, as in the case of amino acids, the contribution of the single functional groups to the whole stability of uranyl species formed. In addition,using the stability data collected for the uranyl-ligand systems considered, the sequestering capacity of some classes of ligands towards uranyl was calculated in terms of pL0.5, i.e., the ligand concentration useful to bind at least 50% of the cation. A comparison of pL0.5 of the most important classes of ligandsconsidered was made to point out the different effectiveness in the UO22+ sequestration by the differentligands which can be present in multi-component solutions as natural waters and biological fluids. Finally, some considerations are reported about the different experimental techniques employed to study the complex formation in solution.
Lingua originaleEnglish
pagine (da-a)63-81
Numero di pagine19
RivistaCoordination Chemistry Reviews
Volume256
Stato di pubblicazionePublished - 2012

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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