Zero to ultralow magnetic field NMR of [1−13C]pyruvate and [2−13C]pyruvate enabled by SQUID sensors and hyperpolarization

Abstract

Accurately characterizing magnetic resonance of molecules at zero to ultralow magnetic field (nTs-µTs) is challenging, due to vanishingly small sensitivity, which depends on the thermal equilibrium polarization of the nuclear spins and instrumentation. We overcome the former limitation with the parahydrogen-based hyperpolarization method SABRE-SHEATH (signal amplification by reversible exchange in shield enables alignment transfer to heteronuclei). This method allows for the continuous transfer of spin order from parahydrogen to a substrate via chemical exchange, reaching polarization levels of some percent (level equivalent to C13 polarization at 20 kT). We address the latter with our application of a superconducting quantum interference device (SQUID)-based detector setup that allows for broadband detection (dc-MHz) with exquisite sensitivity over its entire range. Here, we present the results of our comprehensive characterization of [1−13C]pyruvate and [2−13C]pyruvate, hyperpolarized via SABRE-SHEATH, from zero field to 100 µT. To this end, we show low-noise, high-resolution spectra for both molecules, detecting how the NMR spectrum changes from the J-coupling dominated zero-field spectrum to the strongly coupled spectrum, and then finally to the conventional high-field, otherwise known Zeeman-dominated spectrum. We also analytically derive the evolution of product operators in arbitrary magnetic fields, which aid in the understanding of the differences between spin evolution and spin-coupling regimes. We predict and confirm that the absence of spin precession at zero field can result in observable oscillation of magnetization along one axis with a frequency of the J-coupling constant, no observable spin evolution, or observing spin evolution that corresponds to “forbidden” transitions at high field. The zero-field spectra with their near-dc signals reveal different relaxation rates for the different spin states of hyperpolarized C13 pyruvates, demonstrating the utility of SQUID detectors and hyperpolarization for the characterization of magnetic resonance phenomena.

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