Fingerprint patterns from laser-induced azido photochemistry of spin-labeled photoaffinity ATP analogs in matrix-assisted laser desorption/ionizationmass spectrometry

The photochemical reaction of azide derivatives induced by ultraviolet (UV) laser in matrix-assisted laser desorption/ionization mass spectrometry (MA LDI) is reported. A novel synthesized class of azide aromatic derivatives, spin-labeled photoaffinity non-nucleoside adenosine triphosphate (ATP) anal ogs which are useful probes in study of muscle contraction mechanism, is us ed in this investigation. In the negative ion MALDI spectra of these ATP an alogs, "fingerprint" peaks corresponding to [M - 10 - 1](-), [M - 12 - 1](- ), [M - 16 - 1](-), [M - 26 - 1](-), [M - 28 - 1](-), [M - 41 - 1](-), and [M - 42 - 1](-) were observed with relative intensities depending on the MA LDI matrix. Only the [M - 16 - 1] is present in the similar mass spectra of the analog in which the azido group is replaced by a hydrogen. A model is suggested for the photochemical reactions of azide derivatives under UV las er irradiation. The photoreaction fingerprint information is diagnostically useful in characterization of azido compounds, especially for spin-labeled photoaffinity non-nucleoside ATP analogs. (C) 1999 American Society for Ma ss Spectrometry.