Infrared Spectroscopy of Isolated Nucleotides. 1. The cyclic 3’,5’-Adenosine Monophosphate Anion

The intracellular second messenger deprotonated adenosine 3′,5′-cyclic monophosphate anion (cAMP-H)−, generated as gaseous species by electrospray ionization (ESI) and stored in a Paul ion-trap mass spectrometer, has been investigated by mass-resolved infrared multiple photon dissociation (IRMPD) spectroscopy in the 900–1800 cm−1 fingerprint wavenumber range, exploiting the powerful and continuously tunable radiation from a free electron laser (FEL) at the Centre Laser Infrarouge d’Orsay (CLIO). The IRMPD features are interpreted by comparison with the IR spectra obtained by quantum chemical calculations for different low-lying conformers, allowing an assignment for the observed IRMPD bands. It is to be noted that the calculated IR spectra for the most stable conformers look all rather similar and do not allow an unambiguous structural assignment, based exclusively on the IRMPD spectrum. However, the positions and intensities of the IRMPD features of isolated (cAMP-H)− ions are consistent with a species deprotonated at the phosphate group and compatible with the main equilibrium structures lying within 18 kJ mol−1 from the lowest lying conformation, the anti-chair form with a C3′-endo sugar twist.