Novel Crown Ether Amino Acids as Fluorescent Reporters for Metal Ions

Unnatural amino acids with enhanced properties, such as increased complexing ability and luminescence, are considered to be highly attractive building blocks for bioinspired frameworks, such as probes for biomolecule dynamics, sensitive fluorescent chemosensors, and peptides for molecular imaging, among others. Therefore, a novel series of highly emissive heterocyclic alanines bearing a benzo[d]oxazolyl unit functionalized with different heterocyclic π-spacers and (aza)crown ether moieties was synthesized. The new compounds were completely characterized using the usual spectroscopic techniques and evaluated as fluorimetric chemosensors in acetonitrile and aqueous mixtures in the presence of various alkaline, alkaline-earth, and transition metal ions. The different crown ether binding moieties as well as the electronic nature of the π-bridge allowed for fine tuning of the sensory properties of these unnatural amino acids towards Pd(2+) and Fe(3+), as seen by spectrofluorimetric titrations.