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Photochemically Induced Dynamic Nuclear Polarization of Heteronuclear Singlet Order. 2021

Kirill F Sheberstov, and Liubov Chuchkova, and Yinan Hu, and Ivan V Zhukov, and Alexey S Kiryutin, and Artur V Eshtukov, and Dmitry A Cheshkov, and Danila A Barskiy, and John W Blanchard, and Dmitry Budker, and Konstantin L Ivanov, and Alexandra V Yurkovskaya
Institut für Physik, Johannes Gutenberg Universität-Mainz, 55128 Mainz, Germany.

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is a method to hyperpolarize nuclear spins using light. In most cases, CIDNP experiments are performed in high magnetic fields and the sample is irradiated by light inside a nuclear magnetic resonance (NMR) spectrometer. Here we demonstrate photo-CIDNP hyperpolarization generated in the Earth's magnetic field and under zero- to ultralow-field (ZULF) conditions. Irradiating a sample containing tetraphenylporphyrin and para-benzoquinone for several seconds with light-emitting diodes produces strong hyperpolarization of 1H and 13C nuclear spins, enhancing the NMR signals more than 200 times. The hyperpolarized spin states at the Earth's field and in ZULF are different. In the latter case, the state corresponds to the singlet order between scalar-coupled 1H-13C nuclear spins. This state has a longer lifetime than the state hyperpolarized at Earth's field. The method is simple and cost-efficient and should be applicable to many molecular systems known to exhibit photo-CIDNP, including amino acids and nucleotides.

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