Vibrational Predissociation Spectroscopy of Cold Protonated Tryptophan with Different Messenger Tags

Vibrational spectra of protonated tryptophan were recorded by predissociation of H-2 messenger tags using cryogenic ion traps. We explore the issue of messenger induced spectral changes by solvating TrpH(+)(H-2), with n = 1-5 to obtain single photon vibrational spectra of TrpH(+) and of its partly deuterated isotopomer in the spectral region of 800-4400 cm(-1). Depending on the number of messenger molecules, the spectra of several conformational isomers associated with multiple H-2 binding locations along with two natural conformations of TrpH(+) were found using the two photon (MSIR2)-I-3 conformational hole burning method. Most probable messenger positions were established by comparison with predictions from DFT calculations on various candidate structures. Mechanical anharmonicity effects associated with the charged amino group were modeled by Born-Oppenheimer ab initio molecular dynamics. The spectra of TrpH(+)(H2O)(m=1,2), recorded by infrared multiphoton dissociation (IRMPD), reveal broad features in the NH stretching region of the NH3+ group, indicating strong hydrogen bonding in acceptor donor configuration with the benzene ring for the first water molecule, while the second water appears to attach to a less strongly perturbing site, yielding unique transitions associated with the free OH stretching fundamentals. We discuss the structural deformations induced by the water molecules and compare our results to recent experiments on similar hydrated cationic systems.