Mn(II)/Mn(III) and Fe(III) binding capability of two Aspergillus fumigatus siderophores, desferricrocin and N′, N″, N‴- triacetylfusarinine C

E. Farkas, Orsolya Szabó, Péter L. Parajdi-Losonczi, G. Balla, I. Pócsi

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Manganese(II) and manganese(III) complexes of the exocyclic desferricrocin (H3DFCR) and endocyclic triacetylfusarinine C (H3TAF) in solution have been studied by using pH-potentiometry, UV-Vis spectrophotometry, relaxometry and cyclic voltammetry. A comparison between the present results and the corresponding ones for the open-chain analogues, desferrioxamine B (DFB) and desferricoprogen (DFC), shows (i) The dissociation processes of H 3DFCR occur in the expected pH-range (pH 7-10.5), but hydrogen bonding is assumed to be responsible for a quite low proton dissociation constant (pK = 4.18) of H3TAF and also an unusually high one (10.59). (ii) Moderate stability complexes with 1:1 Mn(II) to ligand ratio are formed with all four siderophores. (iii) The coordination of the three hydroxamates of a siderophore takes place in stepwise processes, except the case of desferricrocin, with which, large-extent overlapping of the processes occurs. (iv) Out of the four tris-chelated [ML] type complexes, the complex of DFCR is the most compact, as it is indicated by the relaxivity values. (v) Following the stoichiometric oxidation of the Mn(II)-siderophore complexes at pH ≥ 9, tris-chelated Mn(III) complexes are formed. To make a comparison between the stability of the Mn(III) and the corresponding Fe(III) complexes of DFCR and TAF, the determination of the stability of the Fe(III) complexes under our condition has also been performed, by using UV-Vis spectrophotometry. Comparable stability of the corresponding complexes was found. (vi) Correlation study of the stability constants resulted in estimation of the constant of the Mn(III) monohydroxo complex, for which there was no data in the literature under our conditions.

Original languageEnglish
Pages (from-to)30-37
Number of pages8
JournalJournal of Inorganic Biochemistry
Volume139
DOIs
Publication statusPublished - 2014

Fingerprint

Siderophores
Aspergillus fumigatus
Aspergillus
Spectrophotometry
Manganese
Potentiometry
Deferoxamine
Hydrogen Bonding
Protons
Cyclic voltammetry
Ligands
Hydrogen bonds
desferri-ferricrocin
N,N',N''-triacetylfusarinine C
Oxidation

Keywords

  • Hydroxamate based siderophores
  • Manganese(II)/(III) and iron(III) complexes
  • Manganese(III)-monohydroxo complex
  • Redox behaviour
  • Relaxivity
  • Solution equilibria

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Medicine(all)

Cite this

@article{9362a4f7cc06488b81e45df721f0c4ee,
title = "Mn(II)/Mn(III) and Fe(III) binding capability of two Aspergillus fumigatus siderophores, desferricrocin and N′, N″, N‴- triacetylfusarinine C",
abstract = "Manganese(II) and manganese(III) complexes of the exocyclic desferricrocin (H3DFCR) and endocyclic triacetylfusarinine C (H3TAF) in solution have been studied by using pH-potentiometry, UV-Vis spectrophotometry, relaxometry and cyclic voltammetry. A comparison between the present results and the corresponding ones for the open-chain analogues, desferrioxamine B (DFB) and desferricoprogen (DFC), shows (i) The dissociation processes of H 3DFCR occur in the expected pH-range (pH 7-10.5), but hydrogen bonding is assumed to be responsible for a quite low proton dissociation constant (pK = 4.18) of H3TAF and also an unusually high one (10.59). (ii) Moderate stability complexes with 1:1 Mn(II) to ligand ratio are formed with all four siderophores. (iii) The coordination of the three hydroxamates of a siderophore takes place in stepwise processes, except the case of desferricrocin, with which, large-extent overlapping of the processes occurs. (iv) Out of the four tris-chelated [ML] type complexes, the complex of DFCR is the most compact, as it is indicated by the relaxivity values. (v) Following the stoichiometric oxidation of the Mn(II)-siderophore complexes at pH ≥ 9, tris-chelated Mn(III) complexes are formed. To make a comparison between the stability of the Mn(III) and the corresponding Fe(III) complexes of DFCR and TAF, the determination of the stability of the Fe(III) complexes under our condition has also been performed, by using UV-Vis spectrophotometry. Comparable stability of the corresponding complexes was found. (vi) Correlation study of the stability constants resulted in estimation of the constant of the Mn(III) monohydroxo complex, for which there was no data in the literature under our conditions.",
keywords = "Hydroxamate based siderophores, Manganese(II)/(III) and iron(III) complexes, Manganese(III)-monohydroxo complex, Redox behaviour, Relaxivity, Solution equilibria",
author = "E. Farkas and Orsolya Szab{\'o} and Parajdi-Losonczi, {P{\'e}ter L.} and G. Balla and I. P{\'o}csi",
year = "2014",
doi = "10.1016/j.jinorgbio.2014.06.005",
language = "English",
volume = "139",
pages = "30--37",
journal = "Journal of Inorganic Biochemistry",
issn = "0162-0134",
publisher = "Elsevier Inc.",

}

TY - JOUR

T1 - Mn(II)/Mn(III) and Fe(III) binding capability of two Aspergillus fumigatus siderophores, desferricrocin and N′, N″, N‴- triacetylfusarinine C

AU - Farkas, E.

AU - Szabó, Orsolya

AU - Parajdi-Losonczi, Péter L.

AU - Balla, G.

AU - Pócsi, I.

PY - 2014

Y1 - 2014

N2 - Manganese(II) and manganese(III) complexes of the exocyclic desferricrocin (H3DFCR) and endocyclic triacetylfusarinine C (H3TAF) in solution have been studied by using pH-potentiometry, UV-Vis spectrophotometry, relaxometry and cyclic voltammetry. A comparison between the present results and the corresponding ones for the open-chain analogues, desferrioxamine B (DFB) and desferricoprogen (DFC), shows (i) The dissociation processes of H 3DFCR occur in the expected pH-range (pH 7-10.5), but hydrogen bonding is assumed to be responsible for a quite low proton dissociation constant (pK = 4.18) of H3TAF and also an unusually high one (10.59). (ii) Moderate stability complexes with 1:1 Mn(II) to ligand ratio are formed with all four siderophores. (iii) The coordination of the three hydroxamates of a siderophore takes place in stepwise processes, except the case of desferricrocin, with which, large-extent overlapping of the processes occurs. (iv) Out of the four tris-chelated [ML] type complexes, the complex of DFCR is the most compact, as it is indicated by the relaxivity values. (v) Following the stoichiometric oxidation of the Mn(II)-siderophore complexes at pH ≥ 9, tris-chelated Mn(III) complexes are formed. To make a comparison between the stability of the Mn(III) and the corresponding Fe(III) complexes of DFCR and TAF, the determination of the stability of the Fe(III) complexes under our condition has also been performed, by using UV-Vis spectrophotometry. Comparable stability of the corresponding complexes was found. (vi) Correlation study of the stability constants resulted in estimation of the constant of the Mn(III) monohydroxo complex, for which there was no data in the literature under our conditions.

AB - Manganese(II) and manganese(III) complexes of the exocyclic desferricrocin (H3DFCR) and endocyclic triacetylfusarinine C (H3TAF) in solution have been studied by using pH-potentiometry, UV-Vis spectrophotometry, relaxometry and cyclic voltammetry. A comparison between the present results and the corresponding ones for the open-chain analogues, desferrioxamine B (DFB) and desferricoprogen (DFC), shows (i) The dissociation processes of H 3DFCR occur in the expected pH-range (pH 7-10.5), but hydrogen bonding is assumed to be responsible for a quite low proton dissociation constant (pK = 4.18) of H3TAF and also an unusually high one (10.59). (ii) Moderate stability complexes with 1:1 Mn(II) to ligand ratio are formed with all four siderophores. (iii) The coordination of the three hydroxamates of a siderophore takes place in stepwise processes, except the case of desferricrocin, with which, large-extent overlapping of the processes occurs. (iv) Out of the four tris-chelated [ML] type complexes, the complex of DFCR is the most compact, as it is indicated by the relaxivity values. (v) Following the stoichiometric oxidation of the Mn(II)-siderophore complexes at pH ≥ 9, tris-chelated Mn(III) complexes are formed. To make a comparison between the stability of the Mn(III) and the corresponding Fe(III) complexes of DFCR and TAF, the determination of the stability of the Fe(III) complexes under our condition has also been performed, by using UV-Vis spectrophotometry. Comparable stability of the corresponding complexes was found. (vi) Correlation study of the stability constants resulted in estimation of the constant of the Mn(III) monohydroxo complex, for which there was no data in the literature under our conditions.

KW - Hydroxamate based siderophores

KW - Manganese(II)/(III) and iron(III) complexes

KW - Manganese(III)-monohydroxo complex

KW - Redox behaviour

KW - Relaxivity

KW - Solution equilibria

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U2 - 10.1016/j.jinorgbio.2014.06.005

DO - 10.1016/j.jinorgbio.2014.06.005

M3 - Article

C2 - 24959697

AN - SCOPUS:84903210121

VL - 139

SP - 30

EP - 37

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

SN - 0162-0134

ER -