Infrared multiple photon dissociation action spectroscopy of protonated uracil and thiouracils: Effects of thioketo-substitution on gas-phase conformation

• Published in: International journal of mass spectrometry Vol. 297; no. 1; pp. 139 - 151
• Main Authors: Nei, Y.-w., Akinyemi, T.E., Steill, J.D., Oomens, J., Rodgers, M.T.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.11.2010
• Subjects: Free electron laser; Infrared multiple photon dissociation; Proton; Thiouracil; Uracil; Proton; Free electron laser; Thiouracil; Uracil; Infrared multiple photon dissociation
• ISSN: 1387-3806; 1873-2798
• DOI: 10.1016/j.ijms.2010.08.005

The gas-phase structures of protonated complexes of uracil and five thiouracils are examined via IRMPD action spectroscopy and theoretical calculations. Present results indicate that protonation stabilizes minor tautomers of these nucleobases. [Display omitted] ▶ Protonation preferentially stabilizes minor tautomers of uracil and thiouracils. ▶ IRMPD spectroscopy efficiently differentiates hydroxyl rotamers of uracil and the thiouracils. ▶ IRMPD spectroscopy cannot differentiate sulfhydryl rotamers of the thiouracils. The gas-phase structures of protonated complexes of uracil and five thiouracils including 2-thiouracil (2SU), 5-methyl-2-thiouracil (5Me2SU), 6-methyl-2-thiouracil (6Me2SU), 4-thiouracil (4SU), and 2,4-dithiouracil (24dSU) are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra of all six protonated complexes exhibit both similar and distinct spectral features over the range of ∼1000–1900 cm −1, such that the complexes are easily differentiated by their IRMPD action spectra. Absence of the carbonyl stretch at ∼1825 cm −1 in the IRMPD spectra for the H +(U), H +(2SU), H +(5Me2SU), and H +(6Me2SU) complexes suggests that the binding of a proton preferentially stabilizes alternative tautomers of the nucleobases in these complexes such that no free carbonyl stretch is observed. In contrast, the intense band at ∼1825 cm −1 in the IRMPD action spectrum of H +(4SU) indicates that a free carbonyl group is still present in this complex. Measured IRMPD action spectra are compared to linear IR spectra calculated at the B3LYP/6-31G(d) level of theory to identify the structures accessed in the experimental studies. On the basis of these comparisons and energetics derived from the calculations, protonation results in preferential stabilization of a minor tautomer of the nucleobase in the H +(U), H +(2SU), H +(5Me2SU), H +(6Me2SU), and H +(24dSU) complexes, where both keto (thioketo) groups are converted to hydroxy (sulfhydryl) groups by proton binding and proton transfer from the neighboring N3H group. In contrast, the proton preferentially binds at the 4-thioketo position to the canonical keto–thioketo tautomer in the H +(4SU) complex. Additional band(s) are present in the IRMPD action spectra of the H +(U) and H +(4SU) complexes that suggest that a small population of excited low-energy conformers are also accessed in those systems.