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Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution

Publication ,  Journal Article
Batinić-Haberle, I; Spasojević, I; Crumbliss, AL
Published in: Inorganic Chemistry
July 1, 1994

The association constant for the Fe(III) complex of the linear trihydroxamic acid siderophore ferrioxamine B (FeHDFB+; HDFB2- = H3N-[(CH2)5-N(O)C(O)-(CH2)2C(O)NH-)]2(CH2)5-N(O)C(O)-CH3) binding to sodium dodecyl sulfate (SDS) micelles was determined by ultrafiltration and kinetic methods. Both methods are in agreement and yield an average value of the association constant Km = 98 M-1. Association constants for the Al(III) analogue of ferrioxamine B, AlHDFB+, and of the metal-free ligand deferriferrioxamine B, H4DFB+, were also determined by ultrafiltration and found to be Km = 90 and 362 M-1, respectively. Ion-exchange constants (Kex) are calculated from Km values [Kex(FeHDFB+/Na+) = Kex(AlHDFB+/Na+) = 13; Kex(H4DFB+/Na+) = 46] and are discussed in relation to Kex for alky lammonium cations. Kinetic and thermodynamic parameters for the hydrolysis of ferrioxamine B in SDS solutions (0.01-0.15 M) at 25 °C have been obtained by stopped-flow and spectrophotometric titration methods at I = 0.1 M (NaClO4/HClO4, NaNO3/HNO3) over a p[H+]tot range from 4.80 to 2.05. Good agreement is found between equilibrium constants determined by spectral and kinetic methods. Comparison with the parameters previously reported for the hydrolysis of FeHDFB+ in aqueous acidic solution suggests that FeHDFB+ resides in the Stem layer of the micelle, and consequently in a region of increased H+ concentration. Once a correction is made for the higher [H+] in the Stern layer, kinetic and thermodynamic parameters obtained in the presence of SDS micelles agree well with those reported for the reaction in aqueous medium. This agreement also gives additional support to the Km and Kex values obtained by ultrafiltration and kinetics. Results reported here show that there is no micellar stabilization of the siderophore complex. © 1994, American Chemical Society. All rights reserved.

Duke Scholars

Published In

Inorganic Chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

July 1, 1994

Volume

33

Issue

14

Start / End Page

3151 / 3158

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry
 

Citation

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Batinić-Haberle, I., Spasojević, I., & Crumbliss, A. L. (1994). Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution. Inorganic Chemistry, 33(14), 3151–3158. https://doi.org/10.1021/ic00092a022
Batinić-Haberle, I., I. Spasojević, and A. L. Crumbliss. “Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution.” Inorganic Chemistry 33, no. 14 (July 1, 1994): 3151–58. https://doi.org/10.1021/ic00092a022.
Batinić-Haberle I, Spasojević I, Crumbliss AL. Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution. Inorganic Chemistry. 1994 Jul 1;33(14):3151–8.
Batinić-Haberle, I., et al. “Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution.” Inorganic Chemistry, vol. 33, no. 14, July 1994, pp. 3151–58. Scopus, doi:10.1021/ic00092a022.
Batinić-Haberle I, Spasojević I, Crumbliss AL. Hydrolysis of Ferrioxamine B in Aqueous Micellar Solution. Inorganic Chemistry. 1994 Jul 1;33(14):3151–3158.
Journal cover image

Published In

Inorganic Chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

July 1, 1994

Volume

33

Issue

14

Start / End Page

3151 / 3158

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry