<p>For non-invasive imaging of biochemical processes, the ability of NMR to follow biomolecular transformations on different time windows needs to be improved. Long-lived coherences (LLC’s) are molecular-symmetry-adapted nuclear spin coherences that can be sustained for durations up to an order of magnitude longer compared to classical coherences in high-field magnets. 2D-LLC experiments provide contrast for targeted molecules against cell background, as demonstrated herein for glutathione (GSH), a major antioxidant in immune cells and rapidly-proliferating tumors. We tested the oxidative response of immune B-cells to exogenous incubated&#xa0;glutathione and high-dose-rate laser-driven radiation. We found agreement between biochemical methods and 2D-LLC for detecting GSH production induced by incubation. To also address oxidation on FLASH&#xa0;radiation response-relevant timescales, we demonstrate a direct 1D method, WINDOW-LLC. Using this method, we recorded multiple points of GSH oxidation kinetics within 15 seconds after a single excitation step. Thus, LLC’s find potential applications to detect oxido-reduction processes.</p>

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Long-lived coherences for the observation of oxidation kinetics on different timescales by NMR

  • Aude Sadet,
  • Cristina Stavarache,
  • Ioana Fidel,
  • Mihai A. Voda,
  • Andrei Ciumeica,
  • Elena Ionita,
  • Mihai Ciubotaru,
  • Paul R. Vasos

摘要

For non-invasive imaging of biochemical processes, the ability of NMR to follow biomolecular transformations on different time windows needs to be improved. Long-lived coherences (LLC’s) are molecular-symmetry-adapted nuclear spin coherences that can be sustained for durations up to an order of magnitude longer compared to classical coherences in high-field magnets. 2D-LLC experiments provide contrast for targeted molecules against cell background, as demonstrated herein for glutathione (GSH), a major antioxidant in immune cells and rapidly-proliferating tumors. We tested the oxidative response of immune B-cells to exogenous incubated glutathione and high-dose-rate laser-driven radiation. We found agreement between biochemical methods and 2D-LLC for detecting GSH production induced by incubation. To also address oxidation on FLASH radiation response-relevant timescales, we demonstrate a direct 1D method, WINDOW-LLC. Using this method, we recorded multiple points of GSH oxidation kinetics within 15 seconds after a single excitation step. Thus, LLC’s find potential applications to detect oxido-reduction processes.