AN UNEXPECTED GAS-PHASE BINDING MOTIF FOR METAL DICATION COMPLEXATION WITH PEPTIDES: IRMPD SPECTROSCOPIC STRUCTURE DETERMINATION

Author Institution: Chemistry Department, Case Western Reserve Univ., Cleveland, OH 44106; Sandia National Laboratory, Livermore, CA; Chemistry Department, Univesity of Florida, Gainesville, FL; FOM Institute for Plasma Physics, Nieuwegein, Netherlands; FOM Institute for Plasma Physics, Nieuwegein, and University of Amsterdam, NetherlandsThe favorable orientation of the amide linkage and the aromatic side chain of N-terminal Phe or Trp leads to several favorable motifs for metal ion binding to dipeptides, having distinct characteristics in the IR spectrum. Infrared multiple photon photodissociation spectroscopy using the FELIX free electron laser has enabled clear resolution of these isomeric forms. The spectral patterns of complexes of small dications (Mg$^{2+}$, Ni$^{2+}$ and Co$^{2+}$) reveal an unexpected new isomeric form, in which the metal ion displaces the amide hydrogen, forming a metal-nitrogen bond with covalent character which is unprecedented in such gas-phase complexes. Spectra of the ions were acquired by irradiating the cell of the Fourier-transform ion cyclotron resonance mass spectrometer with infrared light from the FELIX laser at wavelengths in the approximate range 500 to 1900 cm$^{-1}$