Inversion of Hyperpolarized 13 C NMR Signals through Cross-Correlated Cross-Relaxation in Dissolution DNP Experiments

• Published in: The journal of physical chemistry. B 2022-06, Vol.126 (24), p.4599-4610
• Main Authors: Negroni, Mattia, Guarin, David, Che, Kateryna, Epasto, Ludovica M, Turhan, Ertan, Selimović, Albina, Kozak, Fanny, Cousin, Samuel, Abergel, Daniel, Bodenhausen, Geoffrey, Kurzbach, Dennis
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Magnetic Resonance Imaging; Magnetic Resonance Spectroscopy - methods; or physical chemistry; Protons; Solubility; Theoretical and
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.2c03375

Dissolution dynamic nuclear polarization (DDNP) is a versatile tool to boost signal amplitudes in solution-state nuclear magnetic resonance (NMR) spectroscopy. For DDNP, nuclei are spin-hyperpolarized " " in a dedicated DNP device and then transferred to an NMR spectrometer for detection. Dramatic signal enhancements can be achieved, enabling shorter acquisition times, real-time monitoring of fast reactions, and reduced sample concentrations. Here, we show how the sample transfer in DDNP experiments can affect NMR spectra through cross-correlated cross-relaxation (CCR), especially in the case of low-field passages. Such processes can selectively invert signals of C spins in proton-carrying moieties. For their investigations, we use schemes for simultaneous or "parallel" detection of hyperpolarized H and C nuclei. We find that H → C CCR can invert signals of C spins if the proton polarization is close to 100%. We deduce that low-field passage in a DDNP experiment, a common occurrence due to the introduction of so-called "ultra-shielded" magnets, accelerates these effects due to field-dependent paramagnetic relaxation enhancements that can influence CCR. The reported effects are demonstrated for various molecules, laboratory layouts, and DDNP systems. As coupled C- H spin systems are ubiquitous, we expect similar effects to be observed in various DDNP experiments. This might be exploited for selective spectroscopic labeling of hydrocarbons.