This is a very neat analysis of the underlying lineshape of an NMR signal to extract the degree of polarization obtained in a dissolution-DNP experiment. It is similar to a technique used when working with polarized targets. Here the asymmetry of the dueterium Pake pattern is used to determine the degree of polarization (https://doi.org/10.1016/0029-554X(81)90443-2).
Koptyug, Igor V., Quentin Stern, Sami Jannin, and Stuart J. Elliott. “Frozen Water NMR Lineshape Analysis Enables Absolute Polarization Quantification.” Physical Chemistry Chemical Physics 24, no. 10 (March 9, 2022): 5956–64.
https://doi.org/10.1039/D1CP05127J.
Typical magnetic resonance experiments are routinely limited by weak signal responses. In some cases, the low intrinsic sensitivity can be alleviated by the implementation of hyperpolarization technologies. Dissolution-dynamic nuclear polarization offers a means of hyperpolarizing small molecules. Hyperpolarized water is employed in several dynamic nuclear polarization studies, and hence accurate and rapid quantification of the 1H polarization level is of utmost importance. The solid-state nuclear magnetic resonance spectrum of water acquired under dissolution-dynamic nuclear polarization conditions has revealed lineshapes which become asymmetric at high levels of 1H polarization, which is an interesting fundamental problem in itself, but also complicates data interpretation and can prevent correct estimations of polarization levels achieved. In previous studies, attempts to simulate the 1H spectral lineshape of water as a function of the 1H polarization led to significant disagreement with the experimental results. Here we propose and demonstrate that such simulations, and therefore polarization quantification, can be implemented accurately, in particular by taking into account the detector dead time during 1H signal acquisition that can lead to severe spectral distortions. Based on these findings, we employed an echo-based radiofrequency pulse sequence to achieve distortion-free 1H spectra of hyperpolarized water, and adequate simulations of these echo-based spectra were implemented to extract the absolute 1H polarization level from the hyperpolarized water signal only, thus alleviating the need for lengthy and insensitive measurements of thermal equilibrium signals.