ESR parameters for cupric bleomycin in the mobilized state.
The configuration of the copper complex of the glycopeptide bleomycin, CuBlm, is presumed to be pyramidal square planar from a previous X-ray structural determination of a fragment of cupric bleomycin. This study presents evidence for a difference in the ESR parameters for cupric bleomycin in the liquid as opposed to the solid state. A decrease in Aiso for CuBlm in the liquid state can be directly surmised from the low frequency S-band spectrum for which three of the four cupric hyperfine lines are partially resolved. Computer simulated spectra infer that the absolute value of All increases about 100 MHz and the value of Al may change sign for CuBlm in the liquid state. Simulations using a rotational correlation time of about 250 psec. indicate that CuBLM may not be spherical in the liquid phase. The fastest component for anisotropic motion could dominate and account for the well resolved cupric hyperfine structure. Furthermore, it is argued from an analysis of the cupric hyperfine coupling constants that the CuBlm structure opens up at room temperature and that the cupric ion is displaced from the square plane.
D001761:Bleomycin / Q000031:analogs & derivatives; D004578:Electron Spin Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D012996:Solutions; D013696:Temperature
D012996:Solutions; C023502:copper bleomycin; D001761:Bleomycin