title: Formation and structure of the potassium complex of valinomycin in solution studied by Raman optical activity spectroscopy.
abstract: The formation and structure of the potassium complex with valinomycin in solution were studied by means of Raman and Raman optical activity (ROA) spectroscopy. The complexation caused significant spectral changes, particularly in the region 1200-1400 cm(-1). The experimental spectra were interpreted using first principles computations. A complete computational conformational search combined with the spectral analysis revealed the arrangement of the isopropyl side chains in the complex. From a total of 6579 unique conformers two predominant ones were confirmed in the solution by ROA. A third one was predicted theoretically, but its population in the experiment could be estimated only roughly. The most populated conformer does not exhibit C(3) symmetry, and is different from that present in the crystal and the NMR-derived structure. Molecular dynamics techniques were used to estimate the molecular flexibility and its effect on the spectra. Density functional computations and Cartesian coordinate transfer (CCT) techniques provided the ROA and Raman spectral shapes and intensities well comparable with the experiment. The polar solvent (methanol) environment modeled with a polarizable continuum model (PCM) leads to rather minor changes in the conformer populations and vibrational properties as compared to vacuum computations, due to the hydrophobic character of the complex. Additional computational experiments suggest that the vibrational interactions determining the ROA spectra are quite local, which contributes to the good spatial resolution of the method. A reduction of the noise in the experimental spectra as well as increased precision of the simulations is desirable for the further exploration of the potential of the ROA spectroscopy for biomolecular studies in the future.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences, 166 10 Prague, Czech Republic. aporoa@gmail.com
authors.forename: Shigeki
authors.initials: S
authors.lastname: Yamamoto
authors.forename: Michal
authors.initials: M
authors.lastname: Straka
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Watarai
authors.forename: Petr
authors.initials: P
authors.lastname: Bour
mesh_terms: D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D009942:Organometallic Compounds / Q000737:chemistry*; D011188:Potassium / Q000737:chemistry*; D012996:Solutions; D013059:Spectrum Analysis, Raman; D014634:Valinomycin / Q000737:chemistry*; D014732:Vibration
chemical_list: D009942:Organometallic Compounds; D012996:Solutions; D014634:Valinomycin; D011188:Potassium