Solid-State CI NMR Spectroscopy of Hydrochloride Salts of Amino Acids Implicated in Chloride Ion Transport Channel Selectivity: Opportunities at 900 MHz.

The results of a detailed systematic chlorine solid-state NMR study of several hydrochloride salts of amino acids implicated in chloride ion transport channel selectivity are reported. Cl and Cl NMR spectra have been obtained for stationary and/or magic-angle spinning powdered samples of the followi...

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Publicado en:Journal of the American Chemical Society Vol. 128; no. 6; pp. 2121 - 2135
Autores principales: Bryce, David L., Sward, Gregory D., Adiga, Samyuktha
Formato: Artículo
Publicado: American Chemical Society 2/15/2006
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Acceso en línea:Ver este registro en EBSCOhost
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        10.1021/ja057253i
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        atl: Solid-State CI NMR Spectroscopy of Hydrochloride Salts of Amino Acids Implicated in Chloride Ion Transport Channel Selectivity: Opportunities at 900 MHz.
      aug:
        au:
          Bryce, David L.
          Sward, Gregory D.
          Adiga, Samyuktha
        affil: Department of Chemistry, University of Ottawa, Ottawa, Ontario KIN 6N5, Canada.
      su:
        Nuclear magnetic resonance spectroscopy
        Amino acids
        Halogens
        Ion channels
        Spectrum analysis
        Optical diffraction
        Electronic structure
      sug:
        subj:
          Nuclear magnetic resonance spectroscopy
          Amino acids
          Halogens
          Ion channels
          Spectrum analysis
          Optical diffraction
          Electronic structure
      ab: The results of a detailed systematic chlorine solid-state NMR study of several hydrochloride salts of amino acids implicated in chloride ion transport channel selectivity are reported. Cl and Cl NMR spectra have been obtained for stationary and/or magic-angle spinning powdered samples of the following compounds on 500 and/or 900 MHz spectrometers: DL-arginine HCI monohydrate, L-lysine HCI, L-serine HCI, L-glutamic acid HCI, L-proline HCI, L-isoleucine HCI, L-valine HCI, L-phenylalanine HCI, and glycine HCI. Spectral analyses provide information on the anisotropic properties and relative orientations of the chlorine electric field gradient and chemical shift (CS) tensors, which are intimately related to the local molecular and electronic structure. Data obtained at 900 MHz provide unique examples of the effects of CS anisotropy on the NMR spectrum of a quadrupolar nucleus. The range of chlorine quadrupolar coupling constants (C) measured, -6.42 to 2.03 MHz, demonstrates the sensitivity of this parameter to the chloride ion environment and suggests the applicability of chlorine solid-state NMR as a novel experimental tool for defining chloride binding environments in larger ion channel systems. Salts of hydrophobic amino acids are observed to tend to exhibit larger values of C than salts of hydrophilic amino acids. A simple model for rationalizing the observed trend in C is proposed. For salts for which neutron diffraction structures are available, we identify a quantum chemical method which reproduces experimental values of C with a root-mean-square deviation of 0.1 MHz and a correlation coefficient of 0.9998. On the basis of this, chlorine NMR tensors are predicted for the Cl binding site in CIC channels.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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