Gas-phase structures of Pb(2+)-cationized phenylalanine and glutamic acid determined by infrared multiple photon dissociation spectroscopy and computational chemistry.

Infrared multiple photon dissociation (IRMPD) spectroscopy in the 3200-3800 cm(-1) region was used to determine the gas-phase structures of bare and monohydrated [Pb(Phe-H)](+) and [Pb(Glu-H)](+). These experiments were supported by infrared spectra calculated at the B3LYP/6-31+G(d,p) level of theory as well as 298 K enthalpies and Gibbs energies determined using the MP2(full)/6-311++G(2d,2p)//B3LYP/6-31+G(d,p) method. The gas-phase structure of [Pb(Phe-H)](+) has Pb(2+) bound in a tridentate fashion between Phe's amine nitrogen, one oxygen of the deprotonated carboxyl group, and the aromatic ring. The IRMPD spectrum of [Pb(Glu-H)](+) can be assigned to a structure where the side chain carboxyl group is deprotonated. The structure of [Pb(Phe-H)H(2)O](+) is simply the hydrated analogue of [Pb(Phe-H)](+) where water attaches to Pb(2+) in the same hemisphere as the ligated amino acid. The spectrum of [Pb(Glu-H)H(2)O](+) could not be assigned a unique structure. The IRMPD spectrum shows features attributed to symmetric and antisymmetric O-H stretching of water and a broad band characteristic of a hydrogen bonded O-H stretching vibration. These features can only be explained by the presence of at least two isomers and agree with the computational results that predict the four lowest energy structures to be within 6 kJ mol(-1) of one another.