PMID: 11342025May 9, 2001Paper

Redox state dependence of rotamer distributions in tyrosine and neutral tyrosyl radical

Biochimica Et Biophysica Acta
K Warncke, M S Perry

Abstract

Redox state-dependent changes in the relative orientation of the phenol side chain and the peptide group in model tyrosine have been characterized using specific 2H isotopic labelling and X-band electron paramagnetic resonance (EPR) spectroscopy. Tyrosyl radicals were generated by UV photolysis of tyrosine trapped in rigid polycrystalline basic-aqueous medium at T < or = 170 K. Ring-2H(4) and beta-2H(2) substitutions on tyrosine were used to enhance the lineshape contributions from beta-hydrogen or ring-hydrogen hyperfine interactions, respectively. The EPR lineshape at 120 K of the trapped ring-2H(4)-tyrosyl radical is altered dramatically after annealing at 235 K. In contrast, the lineshape of the beta-2H(2)-tyrosyl radical is impervious to annealing. The effect of annealing on the lineshape therefore arises from a change in the isotropic hyperfine coupling between unpaired pi-electron spin density at the ring carbon atom C(1) and the beta-hydrogen nuclei, which is caused by rotational relaxation of the ring and peptide group about the C(1)-C(beta) bond. EPR simulations indicate angular distributions of the peptide group (R-) of 0 degrees < or = theta(R) < or = 30 degrees and 0 degrees < or = theta(R)< or = 18 degrees in the ...Continue Reading

References

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Citations

May 24, 2007·The Journal of Physical Chemistry. B·John McCrackenBridgette A Barry
Mar 23, 2011·Journal of Photochemistry and Photobiology. B, Biology·Bridgette A Barry
Jul 9, 2004·Biophysical Journal·Dimitri A Svistunenko, Chris E Cooper
Feb 21, 2002·Journal of the American Chemical Society·Jenny A CappuccioOlöf Einarsdóttir
Jul 21, 2006·The Journal of Physical Chemistry. B·Ilya R VassilievBridgette A Barry
May 9, 2002·Journal of the American Chemical Society·Idelisa AyalaBridgette A Barry
Jun 15, 2006·The Journal of Physical Chemistry. B·Kevin RangeBridgette A Barry

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