Absolute ¹H polarization measurement with a spin-correlated component of magnetization by hyperpolarized MAS-DNP...

Sensitivity of magic-angle spinning (MAS) NMR spectroscopy has been dramatically improved by the advent of high-field dynamic nuclear polarization (DNP) technique and its rapid advances over the past decades. In this course, discussions on ways to improve the DNP enhancement factor or the overall sensitivity gain have been numerous, and led to a number of methodological and instrumental breakthroughs. Beyond the sensitivity gain, however, discussions on accurate quantification of the ¹H polarization amplitude achievable in a sample with DNP have been relatively rare. Here, we propose a new method for quantifying the local ¹H hyperpolarization amplitude, which is applicable to un-oriented/powdered solid samples under MAS NMR conditions. The method is based on the ability to observe the high-order spin-correlated term (2I_zS_z) intrinsic to a hyperpolarized IS two-spin state, separately from the lowest-order Zeeman term (S_z) in quasi-equilibrium magnetization. The quantification procedure does not require evaluation of signal amplitudes for a "microwave-off" condition and for an un-doped reference sample, and thus enables quick and accurate quantification unaffected by the effects of the paramagnetic quenching and the MAS-induced depolarization. The method is also shown to elucidate spatial polarization distribution through the 2I_zS_z term prepared domain-selectively. As a potential application, we also demonstrate 2D DQ-SQ spectroscopy utilizing the 2I_zS_z term that is generated in a spatially selective manner without using IS dipolar or J coupling. These salient features may be evolved into a way for characterizing mesoscopic molecular assemblies of medical/biological importance.