Investigating magnetically aligned phospholipid bilayers with various lanthanide ions for X-band spin-label EPR studies

This paper reports the EPR spectroscopic characterization of a model membrane system that magnetically aligns with a variety of different lanthanide ions in the applied magnetic field (< 1 T) of an X-band EPR spectrometer. The ability to align phospholipid bilayer systems is valuable because the anisotropic spectra provide a more detailed and complete description of the structural and motional properties of the membrane-associated spin label when compared to randomly dispersed EPR spectra. The nitroxide spin probe 3β-doxyl-5α-cholestane (cholestane or CLS) was inserted into the bilayer discs to demonstrate the effects of macroscopic bilayer alignment through the measurement of orientational dependent hyperfine splittings. The effects of different lanthanide ions with varying degrees of magnetic susceptibility anisotropy and relaxation properties were examined. For X-band EPR studies, the minimal amounts of the Tm3+, Yb3+, and Dy3+ lanthanide ions needed to align the phospholipid bilayers were determined. Power saturation EPR experiments indicate that for the sample compositions described here, the spin-lattice relaxation rate of the CLS spin label was increased by varying amounts in the presence of different lanthanide (Gd3+, Dy3+, Er3+, Yb3+, and Tm3+) ions, and in the presence of molecular oxygen. The addition of Gd3+ caused a significant increase in the spin-lattice relaxation rate of CLS when compared to the other lanthanide ions tested. (C) 2003 Elsevier Science B.V. All rights reserved.