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Hellinger, O.

Electron spin resonance of free radicals in X-irradiated cholesterol and 5,6-dihydro-cholesterol.

Elektron-Spin-Resonanz freier Radikale in röntgenbestrahltem Cholesterin und 5,6-Dihydrocholesterin.

Radiat. Environ. Biophys. 6, 63-68 (1969)

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A new interpretation of the electron spin resonance spectrum [2, 5] of X-irradiated pure cholesterol powder was established because in Gordy's former interpretation [5] the difference between the hyperfine splittings of the ESR spectrum from axially and equatorially oriented H atoms in the cyclic part of the cholesterol molecule was neglected. The new interpretation (Cholesteryl-7) was found with regard of data from Onishi and Nitta measured on the cyclohexenyl radical [10], by identifying the triplet splitting (a=26 Oe) in the ESR spectrum of irradiated cholesterol with both axial Hβ1 resp. H′β1 atoms and correlating the doublet splitting (a=15 Oe) with the Hα2 atom and by accepting the hyperfine splittings of the Hα1 atom and of the equatorial Hβ2 atom not exceeding 6 Oe and therefore not being resolved because of the considerable line width of about 10 Oe. The unpaired electron's localisation near the double bond was shown by a control experiment with 5,6-dihydrocholesterol.

Das Elektron-Spin-Resonanz-Spektrum von röntgenbestrahltem, reinem Cholesterinpulver [2, 5] wurde neu interpretiert, da in der vonGordy früher vorgeschlagenen Deutung [5] der Unterschied in der Hyperfeinaufspaltung des ESR-Spektrums durch axial und äquatorial orientierte H-Atome im cyclischen Teil des Cholesterinmoleküls vernachlässigt wurde. Die neue Interpretation, die zu der Radikalstruktur Cholesteryl-7 führte, ergab sich, wenn man unter Berücksichtigung der vonOnishi undNitta am Cyclohexenylradikal gemessenen Daten [10] die Triplettaufspaltung (a=26 Oe) im ESR-Spektrum des bestrahlten Cholesterins den beiden axialen H_β1- bzw. H′_β1-Atomen und die Dublettaufspaltung (a=15 Oe) dem H_α2-Atom zuordnete und annahm, daß die Hyperfeinaufspaltungen des H_α1-Atoms und des äquatorialen H_β2-Atoms wegen der beträchtlichen Linienbreite von ca. 10 Oe nicht aufgelöst waren, also höchstens ca. 6 Oe betrugen. Die Lokalisierung des ungepaarten Elektrons in der Nähe der Doppelbindung wurde durch ein Kontrollexperiment mit 5,6-Dihydrocholesterin nachgewiesen.

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