Format

Send to

Choose Destination
Rapid Commun Mass Spectrom. 2013 Aug 30;27(16):1867-72. doi: 10.1002/rcm.6640.

Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

Author information

1
Department of Chemistry, Wichita State University, Wichita, KS, USA.

Abstract

RATIONALE:

Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores.

METHODS:

The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations.

RESULTS:

The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group.

CONCLUSIONS:

IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group.

PMID:
23857932
DOI:
10.1002/rcm.6640
[Indexed for MEDLINE]

Supplemental Content

Loading ...
Support Center