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  Distribution of Hβ hyperfine couplings in a tyrosyl radical revealed by 263 GHz ENDOR spectroscopy

Hiller, M., Tkach, I., Wiechers, H., Eltzner, B., Huckemann, S., Pokern, Y., et al. (2021). Distribution of Hβ hyperfine couplings in a tyrosyl radical revealed by 263 GHz ENDOR spectroscopy. Applied Magnetic Resonance, In Press. doi:10.1007/s00723-021-01411-5.

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Hiller, M.1, Author              
Tkach, I.2, Author              
Wiechers, H., Author
Eltzner, B., Author
Huckemann, S., Author
Pokern, Y., Author
Bennati, M.1, Author              
Affiliations:
1Research Group of Electron Paramagnetic Resonance, MPI for Biophysical Chemistry, Max Planck Society, ou_578606              
2Research Group of Electron Paramagnetic Resonance, MPI for biophysical chemistry, Max Planck Society, ou_578606              

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 Abstract: 1H ENDOR spectra of tyrosyl radicals (Y∙) have been the subject of numerous EPR spectroscopic studies due to their importance in biology. Nevertheless, assignment of all internal 1H hyperfine couplings has been challenging because of substantial spectral overlap. Recently, using 263 GHz ENDOR in conjunction with statistical analysis, we could identify the signature of the Hβ2 coupling in the essential Y122 radical of Escherichia coli ribonucleotide reductase, and modeled it with a distribution of radical conformations. Here, we demonstrate that this analysis can be extended to the full-width 1H ENDOR spectra that contain the larger Hβ1 coupling. The Hβ2 and Hβ1 couplings are related to each other through the ring dihedral and report on the amino acid conformation. The 263 GHz ENDOR data, acquired in batches instead of averaging, and data processing by a new “drift model” allow reconstructing the ENDOR spectra with statistically meaningful confidence intervals and separating them from baseline distortions. Spectral simulations using a distribution of ring dihedral angles confirm the presence of a conformational distribution, consistent with the previous analysis of the Hβ2 coupling. The analysis was corroborated by 94 GHz 2H ENDOR of deuterated Y∙122. These studies provide a starting point to investigate low populated states of tyrosyl radicals in greater detail.

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Language(s): eng - English
 Dates: 2021-08-26
 Publication Status: Published online
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 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00723-021-01411-5
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Title: Applied Magnetic Resonance
Source Genre: Journal
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