Time- and site-resolved kinetic NMR for real-time monitoring of off-equilibrium reactions by 2D spectrotemporal correlations. Academic Article uri icon


  • Nuclear magnetic resonance (NMR) spectroscopy provides detailed information about dynamic processes through line-shape changes, which are traditionally limited to equilibrium conditions. However, a wealth of information is available by studying chemical reactions under off-equilibrium conditions-e.g., in states that arise upon mixing reactants that subsequently undergo chemical changes-and in monitoring the reactants and products in real time. Herein, we propose and demonstrate a time-resolved kinetic NMR experiment that combines rapid mixing techniques, continuous flow, and single-scan spectroscopic imaging methods, leading in unison to a 2D spectrotemporal NMR correlation that provides high-quality kinetic information of off-equilibrium chemical reactions. These kinetic 2D NMR spectra possess a high-resolution spectral dimension revealing the individual chemical sites, correlated with a time-independent, steady-state spatial axis that delivers information concerning temporal changes along the reaction coordinate. A comprehensive description of the kinetic, spectroscopic, and experimental features associated with these spectrotemporal NMR analyses is presented. Experimental demonstrations are carried out using an enzymatically catalyzed reaction leading to site- and time-resolved kinetic NMR data, that are in excellent agreement with control experiments and literature values.

published proceedings

  • Nat Commun

altmetric score

  • 6.8

author list (cited authors)

  • Jaroszewicz, M. J., Liu, M., Kim, J., Zhang, G., Kim, Y., Hilty, C., & Frydman, L.

citation count

  • 4

complete list of authors

  • Jaroszewicz, Michael J||Liu, Mengxiao||Kim, Jihyun||Zhang, Guannan||Kim, Yaewon||Hilty, Christian||Frydman, Lucio

publication date

  • January 2022