Linewidth analysis of spin labels in liquids. II. Experimental.
This work demonstrates that homogeneous linewidths can be extracted from continuous wave electron paramagnetic resonance spectra and that they quantitatively agree with the predictions of existing relaxation theory. We suggest that relaxation theory can be used to predict experimental lineshapes provided that the simulations properly include sources of broadening. We have found that the rotational correlation times for spin labels in different percentages of glycerol/water mixtures are best modeled by a power law treatment for the viscosity, similar to that for translational diffusion. The translational diffusion coefficients themselves also have a power law dependence on the viscosity for glycerol/water mixtures. The linewidths were linearly dependent upon both the oxygen and the spin label concentration. The hyperfine splittings of all nuclei were observed to decrease linearly with increasing spin label concentration, completely at odds with existing theory which predicts a quadratic dependence upon concentration. The linear dependence was independent of hyperfine splitting until the magnitude of the hyperfine splitting was less than the homogeneous linewidth.
Robinson
B H
BH
Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
Mailer
C
C
Reese
A W
AW
D003198:Computer Simulation; D003497:Cyclic N-Oxides; D003627:Data Interpretation, Statistical; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D005990:Glycerol; D008433:Mathematics; D008962:Models, Theoretical; D010100:Oxygen; D012984:Software; D013113:Spin Labels; D014783:Viscosity; D014867:Water
D003497:Cyclic N-Oxides; D013113:Spin Labels; D014867:Water; C047253:3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-yloxyl; D005990:Glycerol; D010100:Oxygen; C001803:tempol