title: Simultaneous biosynthesis of putrebactin, avaroferrin and bisucaberin by Shewanella putrefaciens and characterisation of complexes with iron(III), molybdenum(VI) or chromium(V).
abstract: Cultures of Shewanella putrefaciens grown in medium containing 10mM 1,4-diamino-2-butanone (DBO) as an inhibitor of ornithine decarboxylase and 10mM 1,5-diaminopentane (cadaverine) showed the simultaneous biosynthesis of the macrocyclic dihydroxamic acids: putrebactin (pbH2), avaroferrin (avH2) and bisucaberin (bsH2). The level of DBO did not completely repress the production of endogenous 1,4-diaminobutane (putrescine) as the native diamine substrate of pbH2. The relative concentration of pbH2:avH2:bsH2was 1:2:1, which correlated with the substrate selection of putrescine:cadaverine in a ratio of 1:1. The macrocycles were characterised using LC-MS as free ligands and as 1:1 complexes with Fe(III) of the form [Fe(pb)]+, [Fe(av)]+or [Fe(bs)]+, with labile ancillary ligands in six-coordinate complexes displaced during ESI-MS acquisition; or with Mo(VI) of the form [Mo(O)2(pb)], [Mo(O)2(av)] or [Mo(O)2(bs)]. Chromium(V) complexes of the form [CrO(pb)]+were detected from solutions of Cr(VI) and pbH2in DMF using X-band EPR spectroscopy. Supplementation of S. putrefaciens medium with DBO and 1,3-diaminopropane, 1,6-diaminohexane or 1,4-diamino-2(Z)-butene (Z-DBE) resulted only in the biosynthesis of pbH2. The work has identified a native system for the simultaneous biosynthesis of a suite of three macrocyclic dihydroxamic acid siderophores and highlights both the utility of precursor-directed biosynthesis for expanding the structural diversity of siderophores, and the breadth of their coordination chemistry.
authors.affiliation: School of Medical Sciences (Pharmacology) and Bosch Institute, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Cho Zin
authors.initials: CZ
authors.lastname: Soe
authors.affiliation: School of Medical Sciences (Pharmacology) and Bosch Institute, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Telfer
authors.affiliation: School of Chemistry, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Aviva
authors.initials: A
authors.lastname: Levina
authors.affiliation: School of Chemistry, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Peter A
authors.initials: PA
authors.lastname: Lay
authors.affiliation: School of Medical Sciences (Pharmacology) and Bosch Institute, The University of Sydney, New South Wales 2006, Australia. Electronic address: rachel.codd@sydney.edu.au.
authors.forename: Rachel
authors.initials: R
authors.lastname: Codd
mesh_terms: D001426:Bacterial Proteins / Q000037:antagonists & inhibitors / Q000235:genetics / Q000378:metabolism; D002103:Cadaverine / Q000378:metabolism; D002857:Chromium / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry; D003959:Diamines / Q000494:pharmacology; D004578:Electron Spin Resonance Spectroscopy; D015870:Gene Expression; D006877:Hydroxamic Acids / Q000037:antagonists & inhibitors; D007501:Iron / Q000737:chemistry*; D008982:Molybdenum / Q000737:chemistry*; D009955:Ornithine Decarboxylase / Q000235:genetics / Q000378:metabolism; D065108:Ornithine Decarboxylase Inhibitors / Q000494:pharmacology; D010456:Peptides, Cyclic / Q000037:antagonists & inhibitors / Q000096:biosynthesis*; D011700:Putrescine / Q000031:analogs & derivatives* / Q000037:antagonists & inhibitors / Q000096:biosynthesis / Q000494:pharmacology; D020614:Shewanella putrefaciens / Q000187:drug effects / Q000235:genetics / Q000378:metabolism*; D013386:Succinates / Q000037:antagonists & inhibitors
chemical_list: D001426:Bacterial Proteins; D056831:Coordination Complexes; D003959:Diamines; D006877:Hydroxamic Acids; D065108:Ornithine Decarboxylase Inhibitors; D010456:Peptides, Cyclic; D013386:Succinates; C000599724:avaroferrin; C531912:putrebactin; D002857:Chromium; C054842:bisucaberin; C014458:1,4-diaminobutanone; C021006:diaminobutene; D008982:Molybdenum; D007501:Iron; D009955:Ornithine Decarboxylase; D002103:Cadaverine; D011700:Putrescine; C007297:1,6-diaminohexane
keywords: Chromium(V); Hydroxamic acid; Iron(III); Macrocyclic siderophore; Molybdenum(VI); Precursor-directed biosynthesis