Rate constants for saturation-recovery EPR and ELDOR of 14N-Spin labels

Marsh, Derek

doi:10.1016/j.jmr.2023.107414

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

Rate constants for saturation-recovery EPR and ELDOR of ¹⁴N-Spin labels

MPS-Authors

/persons/resource/persons15495

Marsh, Derek
Department of NMR Based Structural Biology, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Marsh, D. (2023). Rate constants for saturation-recovery EPR and ELDOR of ¹⁴N-Spin labels. Journal of Magnetic Resonance, 350: 107414. doi:10.1016/j.jmr.2023.107414.

Cite as: https://hdl.handle.net/21.11116/0000-000C-F569-A

Abstract

Saturation-recovery (SR)-EPR can determine electron spin–lattice relaxation rates in liquids over a wide range of effective viscosity, making it especially useful for biophysical and biomedical applications. Here, I develop exact solutions for the SR-EPR and SR-ELDOR rate constants of ¹⁴N-nitroxyl spin labels as a function of rotational correlation time and spectrometer operating frequency. Explicit mechanisms for electron spin–lattice relaxation are: rotational modulation of the N-hyperfine and electron-Zeeman anisotropies (specifically including cross terms), spin-rotation interaction, and residual frequency-independent vibrational contributions from Raman processes and local modes. Cross relaxation from mutual electron and nuclear spin flips, and direct nitrogen nuclear spin–lattice relaxation, also must be included. Both the latter are further contributions from rotational modulation of the electron-nuclear dipolar interaction (END). All the conventional liquid-state mechanisms are defined fully by the spin-Hamiltonian parameters; only the vibrational contributions contain fitting parameters. This analysis gives a firm basis for interpreting SR (and inversion recovery) results in terms of additional, less standard mechanisms.