Tren-based analogues of bacillibactin: structure and stability.
Synthetic analogues were designed to highlight the effect of the glycine moiety of bacillibactin on the overall stability of the ferric complex as compared to synthetic analogues of enterobactin. Insertion of a variety of amino acids to catecholamide analogues based on a Tren (tris(2-aminoethyl)amine) backbone increased the overall acidity of the ligands, causing an enhancement of the stability of the resulting ferric complex as compared to TRENCAM. Solution thermodynamic behavior of these siderophores and their synthetic analogues was investigated through potentiometric and spectrophotometric titrations. X-ray crystallography, circular dichroism, and molecular modeling were used to determine the chirality and geometry of the ferric complexes of bacillibactin and its analogues. In contrast to the Tren scaffold, addition of a glycine to the catechol chelating arms causes an inversion of the trilactone backbone, resulting in opposite chiralities of the two siderophores and a destabilization of the ferric complex of bacillibactin compared to ferric enterobactin.
Dertz
Emily A
EA
Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
Xu
Jide
J
Raymond
Kenneth N
KN
D002942:Circular Dichroism; D004952:Esters / Q000737:chemistry*; D005029:Ethylenediamines / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry*; D005998:Glycine / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D007783:Lactones / Q000138:chemical synthesis / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009842:Oligopeptides / Q000737:chemistry*; D011199:Potentiometry; D017262:Siderophores / Q000138:chemical synthesis / Q000737:chemistry; D016339:Spectrometry, Mass, Fast Atom Bombardment; D013329:Structure-Activity Relationship; D013816:Thermodynamics
D004952:Esters; D005029:Ethylenediamines; D005290:Ferric Compounds; D007783:Lactones; D008024:Ligands; D009842:Oligopeptides; D017262:Siderophores; C430721:bacillibactin; C099539:tris(2-aminoethyl)amine; D005998:Glycine