7-azatryptophan and nitroxyl

Aal and 7-Atrp, quasi-isosteric with Trp, have been inserted together with a TOAC residue in two 3(10)-helical, model hexapeptides. The interaction of photoexcited AA1 and 7-Atrp with the nitroxide group of TOAC was investigated by time resolved EPR. Both peptides showed nitroxide spin polarized signals revealing that an intramolecular interaction takes places between the excited chromophore and the free radical moiety. The observation of a spin polarized signal in emission for AA1 is accounted for by the formation of triplet azulene by radical promoted enhanced inter system crossing (EISC).

Topics: Alanine; Electron Spin Resonance Spectroscopy; Free Radicals; In Vitro Techniques; Molecular Structure; Nitrogen Oxides; Oligopeptides; Spin Labels; Tryptophan