title: Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T.
abstract: Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
authors.forename: Jun
authors.initials: J
authors.lastname: Hu
authors.forename: Eduard Y
authors.initials: EY
authors.lastname: Chekmenev
authors.forename: Zhehong
authors.initials: Z
authors.lastname: Gan
authors.forename: Peter L
authors.initials: PL
authors.lastname: Gor'kov
authors.forename: Saikat
authors.initials: S
authors.lastname: Saha
authors.forename: William W
authors.initials: WW
authors.lastname: Brey
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Cross
mesh_terms: D000595:Amino Acid Sequence; D016880:Anisotropy; D001665:Binding Sites; D006096:Gramicidin / Q000737:chemistry*; D006801:Humans; D007477:Ions; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008969:Molecular Sequence Data; D010103:Oxygen Isotopes / Q000737:chemistry*; D011522:Protons; D012995:Solubility
chemical_list: D007477:Ions; D010103:Oxygen Isotopes; D011522:Protons; D006096:Gramicidin