Anisotropic motion effects in CW non-linear EPR spectra: relaxation enhancement of lipid spin labels.


Continuous-wave (CW) EPR measurements of enhancements in spin-lattice (T(1)-) relaxation rate find wide application for determining spin-label locations in biological systems. Often, especially in membranes, the spin-label rotational motion is anisotropic and subject to an orientational potential. We investigate here the effects of anisotropic diffusion and ordering on non-linear CW-EPR methods for determining T(1) of nitroxyl spin labels. Spectral simulations are performed for progressive saturation of the conventional in-phase, first-harmonic EPR signal, and for the first-harmonic absorption EPR signals detected 90 degrees -out-of-phase with respect to the Zeeman field modulation. Motional models used are either rapid rotational diffusion, or strong-jump diffusion of unrestricted frequency, within a cone of fixed maximum amplitude. Calculations of the T(1)-sensitive parameters are made for both classes of CW-experiment by using motional parameters (i.e., order parameters and correlation times), intrinsic homogeneous and inhomogeneous linewidth parameters, and spin-Hamiltonian hyperfine- and g-tensors, that are established from simulation of the linear CW-EPR spectra. Experimental examples are given for spin-labelled lipids in membranes.

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@article{Livshits2003AnisotropicME, title={Anisotropic motion effects in CW non-linear EPR spectra: relaxation enhancement of lipid spin labels.}, author={Vsevolod A. Livshits and Boris G. Dzikovski and Derek Marsh}, journal={Journal of magnetic resonance}, year={2003}, volume={162 2}, pages={429-42} }