392. 13C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions

Andreas B. Schmidt, Isaiah Adelabu, Christopher Nelson, Shiraz Nantogma, Valerij G. Kiselev, Maxim Zaitsev, Abubakar Abdurraheem, Henri de Maissin, Matthew S. Rosen, Sören Lehmkuhl, Stephan Appelt, Thomas Theis and Eduard Y. Chekmenev; Journal of the American Chemical Society (2023); DOI: 10.1021/jacs.3c00776

Conventional nuclear magnetic resonance (NMR) enables detection of chemicals and their transformations by exciting nuclear spin ensembles with a radio-frequency pulse followed by detection of the precessing spins at their characteristic frequencies. The detected frequencies report on chemical reactions in real time and the signal amplitudes scale with concentrations of products and reactants. Here, we employ Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), a quantum phenomenon producing coherent emission of 13C signals, to detect chemical transformations. The 13C signals are emitted by the negatively hyperpolarized biomolecules without external radio frequency pulses and without any background signal from other, nonhyperpolarized spins in the ensemble. Here, we studied the hydrolysis of hyperpolarized ethyl-[1-13C]acetate to hyperpolarized [1-13C]acetate, which was analyzed as a model system by conventional NMR and 13C RASER. The chemical transformation of 13C RASER-active species leads to complete and abrupt disappearance of reactant signals and delayed, abrupt reappearance of a frequency-shifted RASER signal without destroying 13C polarization. The experimentally observed “quantum” RASER threshold is supported by simulations.