Ferrie stability constants of representative marine siderophores: Marinobactins, aquachelins, and petrobactin

Guangping Zhang, Shady Amin, Frithjof C. Küpper, Pamela D. Holt, Carl J. Carrano, Allson Butler

Research output: Contribution to journalArticle

Abstract

The coordination of iron(III) to the marine amphiphilic marinobactin and aquachelin siderophores, as well as to petrobactin, an unusual 3,4-dihydroxybenzoyl siderophore is reported. Potentiometric titrations were performed on the apo siderophore to determine the ligand pK a values, as well as the complex formed with addition of 1 equiv of Fe(III). The log K ML values for Fe(III)-marinobactin-E and Fe(III)-aquachelin-C are 31.80 and 31.4, respectively, consistent with the similar coordination environment in each complex, while log K ML for Fe(lll)-petrobactin is estimated to be about 43. The pK a of the β-hydroxyaspartyl hydroxyl group was determined to be 10.8 by 1H NMR titration. 13C NMR and IR spectroscopy were used to investigate Ga(III) coordination to the marinobactins. The coordination-induced shifts (CIS) in the 13C NMR spectrum of Ga(III)-marinobactin-C compared to apo-marinobactin-C indicates that the hydroxamate groups are coordinated to Ga(III); however, the lack of CISs for the carbons of the β-hydroxyamide group suggests this moiety is not coordinated in the Ga(III) complex. Differences in the IR spectrum of Ga(lll)-marinobactin-C and Fe(III)-marinobactin-C in the 1600-1700 cm -1 region also corroborates Fe(III) is coordinated to the β-hydroxyamide moiety, whereas Ga(III) is not coordinated.

Original languageEnglish (US)
Pages (from-to)11466-11473
Number of pages8
JournalInorganic Chemistry
Volume48
Issue number23
DOIs
StatePublished - Dec 1 2009

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Siderophores
Titration
Nuclear magnetic resonance
titration
nuclear magnetic resonance
Hydroxyl Radical
Commonwealth of Independent States
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Carbon
Iron
Ligands
iron
ligands
petrobactin
carbon
shift
spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Ferrie stability constants of representative marine siderophores : Marinobactins, aquachelins, and petrobactin. / Zhang, Guangping; Amin, Shady; Küpper, Frithjof C.; Holt, Pamela D.; Carrano, Carl J.; Butler, Allson.

In: Inorganic Chemistry, Vol. 48, No. 23, 01.12.2009, p. 11466-11473.

Research output: Contribution to journalArticle

Zhang, Guangping ; Amin, Shady ; Küpper, Frithjof C. ; Holt, Pamela D. ; Carrano, Carl J. ; Butler, Allson. / Ferrie stability constants of representative marine siderophores : Marinobactins, aquachelins, and petrobactin. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 23. pp. 11466-11473.
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AU - Carrano, Carl J.

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AB - The coordination of iron(III) to the marine amphiphilic marinobactin and aquachelin siderophores, as well as to petrobactin, an unusual 3,4-dihydroxybenzoyl siderophore is reported. Potentiometric titrations were performed on the apo siderophore to determine the ligand pK a values, as well as the complex formed with addition of 1 equiv of Fe(III). The log K ML values for Fe(III)-marinobactin-E and Fe(III)-aquachelin-C are 31.80 and 31.4, respectively, consistent with the similar coordination environment in each complex, while log K ML for Fe(lll)-petrobactin is estimated to be about 43. The pK a of the β-hydroxyaspartyl hydroxyl group was determined to be 10.8 by 1H NMR titration. 13C NMR and IR spectroscopy were used to investigate Ga(III) coordination to the marinobactins. The coordination-induced shifts (CIS) in the 13C NMR spectrum of Ga(III)-marinobactin-C compared to apo-marinobactin-C indicates that the hydroxamate groups are coordinated to Ga(III); however, the lack of CISs for the carbons of the β-hydroxyamide group suggests this moiety is not coordinated in the Ga(III) complex. Differences in the IR spectrum of Ga(lll)-marinobactin-C and Fe(III)-marinobactin-C in the 1600-1700 cm -1 region also corroborates Fe(III) is coordinated to the β-hydroxyamide moiety, whereas Ga(III) is not coordinated.

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