Hiller, M;
Tkach, I;
Wiechers, H;
Eltzner, B;
Huckemann, S;
Pokern, Y;
Bennati, M;
(2021)
Distribution of H-beta Hyperfine Couplings in a Tyrosyl Radical Revealed by 263 GHz ENDOR Spectroscopy.
Applied Magnetic Resonance
10.1007/s00723-021-01411-5.
(In press).
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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.
| Type: | Article |
|---|---|
| Title: | Distribution of H-beta Hyperfine Couplings in a Tyrosyl Radical Revealed by 263 GHz ENDOR Spectroscopy |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1007/s00723-021-01411-5 |
| Publisher version: | http://dx.doi.org/10.1007/s00723-021-01411-5 |
| Language: | English |
| Additional information: | Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. |
| Keywords: | HIGH-FIELD EPR, COLI RIBONUCLEOTIDE REDUCTASE, ELECTRON-SPIN-RESONANCE, AMINO-ACID RADICALS, PHOTOSYSTEM-II, BOND NETWORK, SOLID-STATE, DISPERSION, CRYSTALS |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Statistical Science |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10134425 |
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