Abstract
Inhomogeneous broadening of the ESR lines of nitroxide spin labels due to hyperfine structure is a pest that has complicated the work of spin labelers since shortly after the beginning of the spin-label era (Plachy and Kivelson, 1967; Poggi and Johnson, 1970) continually until the present (for example, Jolicoeur and Friedman, 1971; Kovarskii et al, 1972; Bullock et al, 1975; Ahn, 1976; Freed, 1976; Lim et al, 1976; Jones and Schwartz, 1981; Ottaviani et al, 1983; More et al, 1984; Lee and Shetty, 1985). It is a problem that can and has been solved rigorously for a number of spin labels by combining NMR, ESR, and chemical substitution techniques (Kreilick, 1967; Brière et al, 1967, 1970; Michon and Rassat, 1971; Chiarelli and Rassat, 1973; Lim et al, 1976; Barbarin et al, 1978a, 1978b; Labsky et al, 1980; Windle, 1981; Ottaviani, 1987). These techniques taken together establish the hyperfine patternof a given spin label and ESR simulation fine tunes the hyperfine coupling constants in a given set of experimental conditions. To proceed with rigor, this fine tuning must be done continually because the coupling constants vary with temperature (Kreilick, 1967; Brière et al, 1967,1970; Jolicoeur and Friedman, 1971; Atherton, 1975; Ottaviani, 1987) and solvent (Briere et al, 1970; Freed, 1976; Lim et al, 1976; Eaton et al, 1980; Windle, 1981; Ottaviani, 1987). Also, the effectivespacing of the hyperfine lines varies with spin-label concentration—a variation that depends strongly on temperature (Plachy and Kivelson, 1967). The effective spacing varies with spin-label alignment in an ordered fluid (Polnaszek and Freed, 1975; Bales et al, 1984) and one can imagine that it might vary with other experimental parameters as well. Thus, the problem can be complicated but it can be solved with remarkable precision in some cases, notably with spin labels having particularly simple patterns or ones that give partially resolved ESR spectra. It is a tedious procedure, unavoidable if high precision is required in an experiment involving partially resolved ESR spectra. In most of the spin-label literature, the spectra are unresolved, either intrinsically by nature of the spin label and the experiment, or artificially, because of broadening due to oxygen or some other paramagnetic species. In unresolved spectra the procedures to correct for inhomogeneity become quite simple and remarkably accurate.
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References
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Bales, B.L. (1989). Inhomogeneously Broadened Spin-Label Spectra. In: Berliner, L.J., Reuben, J. (eds) Spin Labeling. Biological Magnetic Resonance, vol 8. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-0743-3_2
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