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Triplet Fullerenes as Prospective Spin Labels for Nanoscale Distance Measurements by Pulsed Dipolar EPR Spectroscopy
Author(s) -
Krumkacheva Olesya A.,
Timofeev Ivan O.,
Politanskaya Larisa V.,
Polienko Yuliya F.,
Tretyakov Evgeny V.,
Rogozhnikova Olga Yu.,
Trukhin Dmitry V.,
Tormyshev Victor M.,
Chubarov Alexey S.,
Bagryanskaya Elena G.,
Fedin Matvey V.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904152
Subject(s) - fullerene , electron paramagnetic resonance , biomolecule , nitroxide mediated radical polymerization , supramolecular chemistry , chemical physics , chemistry , site directed spin labeling , relaxation (psychology) , pulsed epr , spectroscopy , materials science , nanotechnology , nuclear magnetic resonance , molecule , polymer , organic chemistry , physics , spin echo , quantum mechanics , medicine , psychology , social psychology , radical polymerization , radiology , magnetic resonance imaging , copolymer
Precise nanoscale distance measurements by pulsed electron paramagnetic resonance (EPR) spectroscopy play a crucial role in structural studies of biomolecules. The properties of the spin labels used in this approach determine the sensitivity limits, attainable distances, and proximity to biological conditions. Herein, we propose and validate the use of photoexcited fullerenes as spin labels for pulsed dipolar (PD) EPR distance measurements. Hyperpolarization and the narrower spectrum of fullerenes compared to other triplets (e.g., porphyrins) boost the sensitivity, and superior relaxation properties allow PD EPR measurements up to a near‐room temperature. This approach is demonstrated using fullerene–nitroxide and fullerene–triarylmethyl pairs, as well as a supramolecular complex of fullerene with nitroxide‐labeled protein. Photoexcited triplet fullerenes can be considered as new spin labels with outstanding spectroscopic properties for future structural studies of biomolecules.