title: Complexation of oxoanions and cationic metals by the biscatecholate siderophore azotochelin.
abstract: Azotochelin is a biscatecholate siderophore produced by the nitrogen-fixing soil bacterium Azotobacter vinelandii. The complexation properties of azotochelin with a series of oxoanions [Mo(VI), W(VI) and V(V)] and divalent cations [Cu(II), Zn(II), Co(II) and Mn(II)] were investigated by potentiometry, UV-vis and X-ray spectroscopy. Azotochelin forms a strong 1:1 complex with molybdate (log K=7.6+/-0.4) and with tungstate and vanadate; the stability of the complexes increases in the order Mo<V<W (log KappMo=7.3+/-0.4; log KappV=8.8+/-0.4 and log KappW=9.0+/-0.4 at pH 6.6). The Mo atom in the 1:1 Mo-azotochelin complex is bound to two oxo groups in a cis position and to the two catecholate groups of azotochelin, resulting in a slightly distorted octahedral configuration. Below pH 5, azotochelin appears to form polynuclear complexes with Mo in addition to the 1:1 complex. Azotochelin also forms strong complexes with divalent metals. Of the metals studied, Cu(II) binds most strongly to azotochelin (log betaCuLH2-=-12.9+/-0.1), followed by Zn(II) log betaZnL3-=-24.1+/-0.14, log betaZnLH2-=-17.83+/-0.09), Mn(II) (log betaMnL3-=-29, log betaMnLH2-=-18.6+/-0.8, log betaMnLH2-=-11.5+/-0.7) and Co(II) (log betaCoLH2-=-23.0+/-0.3, log betaCoLH2-=-13.5+/-0.2). Since very few organic ligands are known to bind strongly to oxoanions (and particularly molybdate) at circumneutral pH, the unusual properties of azotochelin may be used for the separation and concentration of oxoanions in the laboratory and in the field. In addition, azotochelin may prove useful for the investigation of the biogeochemistry of Mo, W and V in aquatic and terrestrial systems.
authors.affiliation: UMR 7517 (CNRS-ULP), EOST, 1 Rue Blessig, 67084, Strasbourg Cedex, France.
authors.forename: Jean-Philippe
authors.initials: JP
authors.lastname: Bellenger
authors.forename: Françoise
authors.initials: F
authors.lastname: Arnaud-Neu
authors.forename: Zouhair
authors.initials: Z
authors.lastname: Asfari
authors.forename: Satish C B
authors.initials: SC
authors.lastname: Myneni
authors.forename: Edward I
authors.initials: EI
authors.lastname: Stiefel
authors.forename: Anne M L
authors.initials: AM
authors.lastname: Kraepiel
mesh_terms: D000838:Anions; D016948:Azotobacter vinelandii / Q000737:chemistry / Q000378:metabolism; D002413:Cations, Divalent; D006863:Hydrogen-Ion Concentration; D008239:Lysine / Q000031:analogs & derivatives* / Q000737:chemistry; D019216:Metals, Heavy / Q000737:chemistry*; D015394:Molecular Structure; D017262:Siderophores / Q000737:chemistry*
chemical_list: D000838:Anions; D002413:Cations, Divalent; D019216:Metals, Heavy; D017262:Siderophores; C041892:azotochelin; D008239:Lysine