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Off-resonance 13C–2H REDOR NMR for site-resolved studies of molecular motion

Abstract

We introduce a 13C–2H Rotational Echo DOuble Resonance (REDOR) technique that uses the difference between on-resonance and off-resonance 2H irradiation to detect dynamic segments in deuterated molecules. By selectively inverting specific regions of the 2H magic-angle spinning (MAS) sideband manifold to recouple some of the deuterons to nearby carbons, we distinguish dynamic and rigid residues in 1D and 2D 13C spectra. We demonstrate this approach on deuterated GB1, H/D exchanged GB1, and perdeuterated bacterial cellulose. Numerical simulations reproduce the measured mixing-time and 2H carrier-frequency dependence of the REDOR dephasing of bacterial cellulose. Combining numerical simulations with experiments thus allow the extraction of motionally averaged quadrupolar couplings from REDOR dephasing values.

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Data Availability

Data Availability1D and 2D spectral datasets and Bruker pulse programs are available upon request from Mei Hong at meihong@mit.edu.

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Acknowledgements

This work is supported by NIH Grant AG059661 to M.H. The bacterial cellulose work is supported by the Center for Lignocellulose Structure and Formation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0001090. M.D.G. is supported by an NIH Ruth L. Kirschstein Individual National Research Service Award (1F31AI133989).

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Gelenter, M.D., Chen, K.J. & Hong, M. Off-resonance 13C–2H REDOR NMR for site-resolved studies of molecular motion. J Biomol NMR 75, 335–345 (2021). https://doi.org/10.1007/s10858-021-00377-7

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Keywords

  • Protein dynamics
  • Cellulose
  • Quadrupolar coupling
  • Deuterium NMR