title: Utilizing reversible copper(II) peptide coordination in a sequence-selective luminescent receptor.
abstract: Although vast information about the coordination ability of amino acids and peptides to metal ions is available, little use of this has been made in the rational design of selective peptide receptors. We have combined a copper(II) nitrilotriacetato (NTA) complex with an ammonium-ion-sensitive and luminescent benzocrown ether. This compound revealed micromolar affinities and selectivities for glycine- and histidine-containing sequences, which closely resembles those of copper(II) ion peptide binding: the two free coordination sites of the copper(II) NTA complex bind to imidazole and amido nitrogen atoms, replicating the initial coordination steps of non-complexed copper(II) ions. The benzocrown ether recognizes the N-terminal amino moiety intramolecularly, and the significantly increased emission intensity signals the binding event, because only if prior coordination of the peptide has taken place is the intramolecular ammonium ion-benzocrown ether interaction of sufficient strength in water to trigger an emission signal. Intermolecular ammonium ion-benzocrown ether binding is not observed. Isothermal titration calorimetry confirmed the binding constants derived from emission titrations. Thus, as deduced from peptide coordination studies, the combination of a truncated copper(II) coordination sphere and a luminescent benzocrown ether allows for the more rational design of sequence-selective peptide receptors.
authors.affiliation: Institut für Organische Chemie, Universität Regensburg, 93040 Regensburg, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Stadlbauer
authors.forename: Alexander
authors.initials: A
authors.lastname: Riechers
authors.forename: Andreas
authors.initials: A
authors.lastname: Späth
authors.forename: Burkhard
authors.initials: B
authors.lastname: König
mesh_terms: D000595:Amino Acid Sequence; D003300:Copper / Q000737:chemistry*; D043844:Crown Ethers / Q000737:chemistry; D010455:Peptides / Q000138:chemical synthesis / Q000737:chemistry*; D013050:Spectrometry, Fluorescence
chemical_list: D043844:Crown Ethers; D010455:Peptides; D003300:Copper