Magnetometer-Detected Nuclear Magnetic Resonance of Photochemically Hyperpolarized Molecules.

Photochemically induced dynamic nuclear polarization (photo-CIDNP) enables nuclear spin ordering by irradiating samples with light. Polarized spins are conventionally detected via high-field chemical-shift-resolved NMR (above 0.1 T). In this Letter, we demonstrate in situ low-field photo-CIDNP measurements using a magnetically shielded fast-field-cycling NMR setup detecting Larmor precession via atomic magnetometers. For solutions comprising mM concentrations of the photochemically polarized molecules, hyperpolarized 1H magnetization is detected by pulse-acquired NMR spectroscopy. The observed NMR line widths are about 5 times narrower than normally anticipated in high-field NMR and are systematically affected by light irradiation during the acquisition period, reflecting a reduction of the transverse relaxation time constant, T2*, on the order of 10%. Magnetometer-detected photo-CIDNP spectroscopy enables straightforward observation of spin-chemistry processes in the ambient field range from a few nT to tens of mT. Potential applications of this measuring modality are discussed.

Photochemically Induced Dynamic Nuclear Polarization of Heteronuclear Singlet Order.

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.