Application of W-band 19F electron nuclear double resonance (ENDOR) spectroscopy to distance measurement using a trityl spin probe and a fluorine label

Application of W-band 19F electron nuclear double resonance (ENDOR) spectroscopy to distance measurement using a trityl spin probe and a fluorine label Full article

Journal

Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084

Output data

Year: 2022, Volume: 24, Number: 10, Pages: 5982-6001 Pages count : 20 DOI: 10.1039/d1cp05445g

Authors

Asanbaeva N.B. ¹ , Sukhanov A.A. ^2,3 , Diveikina A.A. ¹ , Rogozhnikova O.Y. ¹ , Trukhin D.V. ¹ , Tormyshev V.M. ¹ , Chubarov A.S. ⁴ , Maryasov A.G. ¹ , Genaev A.M. ¹ , Shernyukov A.V. ¹ , Salnikov G.E. ¹ , Lomzov A.A. ⁴ , Pyshnyi D.V. ⁴ , Bagryanskaya E.G. ¹

Affiliations

1	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS
2	Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS
3	Kazan State Medical University
4	Institute of Chemical Biology and Fundamental Medicine SB RAS

Funding (1)

Российский Научный Фонд

21-14-00219

Recently, Marina Bennati and coworkers (M. Bennati et al., Angew. Chem., Int. Ed., 2020, 59, 373–379., M. Bennati et al., J. Magn. Reson., 2021, 333, 107091) proposed to use electron nuclear double resonance (ENDOR) spectroscopy in the W-band for a pair of labels, nitroxide and 19F, for measurements of short (0.5–1.0 nm) distances in biomolecules. In our paper, we investigated the suitability of high-field ENDOR spectroscopy in the W-band for pairs of triarylmethyl and fluorine labels using five newly synthesized model compounds. It is shown that the application of strong magnetic fields allows distinguishing nuclear frequencies of 19F and protons with sufficient resolution. On the one hand, in contrast to nitroxides, for triarylmethyl radicals, it is not necessary to obtain spectra in different orientations owing to low g-factor anisotropic and long electron spin relaxation times of triarylmethyls. On the other hand, the size of the triarylmethyl radical is substantially larger than that of nitroxide and comparable with measured distances. We theoretically analyzed the suitability of the dipole–dipole approach for triarylmethyl to be used in a 19F ENDOR experiment and determined limitations of this approach. Finally, for comparison, we performed paramagnetic relaxation enhancement (PRE) NMR on the same compounds. In addition, we applied this approach to study the process of a thiol exchange between molecules of triarylmethyl-labeled and 19F-labeled human serum albumin (HSA).

Asanbaeva N.B. , Sukhanov A.A. , Diveikina A.A. , Rogozhnikova O.Y. , Trukhin D.V. , Tormyshev V.M. , Chubarov A.S. , Maryasov A.G. , Genaev A.M. , Shernyukov A.V. , Salnikov G.E. , Lomzov A.A. , Pyshnyi D.V. , Bagryanskaya E.G.
Application of W-band 19F electron nuclear double resonance (ENDOR) spectroscopy to distance measurement using a trityl spin probe and a fluorine label
Physical Chemistry Chemical Physics. 2022. V.24. N10. P.5982-6001. DOI: 10.1039/d1cp05445g WOS РИНЦ

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