First-principles electronic structure study of rhizoferrin and its Fe(III) complexes

    Authors

    A. Dubey;O. Heinonen

    Comments

    Authors: contact us about adding a copy of your work at STARS@ucf.edu

    Abbreviated Journal Title

    Biometals

    Keywords

    Rhizoferrin; Siderophore; Iron transport; MOLECULAR-ORBITAL METHODS; DRUG-DELIVERY AGENTS; GAUSSIAN-TYPE BASIS; COUPLING-CONSTANTS; SIDEROPHORE RHIZOFERRIN; DIRECTED FERMENTATION; ORGANIC-MOLECULES; IRON; ANALOGS; DEPENDENCE; Biochemistry & Molecular Biology

    Abstract

    We have determined the structure and coordination chemistry of rhizoferrin (Rf), which is a particular type of siderophore, and its Fe(III) complexes using density functional theory calculations. Our results show that the Fe(III) ion binds in an octahedral coordination, with a low-spin (S = 1/2) charge-neutral chiral complex having the largest binding energy of the investigated complexes. We have also calculated nuclear magnetic resonance parameters, such as chemical shifts for H-1 and C-13, and indirect nuclear spin-spin couplings for H-1-H-1 and C-13-H-1 in free Rf and in a low-spin neutral Rf metal complex, as well as nuclear quadrupole interaction parameters, such as asymmetry parameter and nuclear quadrupole coupling constants for N-14. Our calculated values for the chemical shifts for free Rf are in excellent agreement with experimental data while the calculated NMR parameters for Fe(III) complexes are predictions for future experimental work.

    Journal Title

    Biometals

    Volume

    26

    Issue/Number

    6

    Publication Date

    1-1-2013

    Document Type

    Article

    Language

    English

    First Page

    1003

    Last Page

    1012

    WOS Identifier

    WOS:000326926800013

    ISSN

    0966-0844

    Share

    COinS