Optically Enhanced Solid-State 1 H NMR Spectroscopy.

Autor: De Biasi F; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Hope MA; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Avalos CE; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Karthikeyan G; Institute of Radical Chemistry, Aix-Marseille University, CNRS, ICR, 13013 Marseille, France., Casano G; Institute of Radical Chemistry, Aix-Marseille University, CNRS, ICR, 13013 Marseille, France., Mishra A; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Badoni S; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Stevanato G; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Kubicki DJ; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Milani J; Institut de Physique, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Ansermet JP; Institut de Physique, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland., Rossini AJ; U.S. Department of Energy, Ames Laboratory, Ames, Iowa 50011, United States.; Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States., Lelli M; Magnetic Resonance Center (CERM) and Department of Chemistry 'Ugo Schiff', University of Florence, 50019 Sesto Fiorentino, Italy.; Consorzio Interuniversitario Risonanze Magnetiche delle Metalloproteine Paramagnetiche (CIRMMP), 50019 Sesto Fiorentino, Italy., Ouari O; Institute of Radical Chemistry, Aix-Marseille University, CNRS, ICR, 13013 Marseille, France., Emsley L; Institut des Sciences et Ingenierie Chimiques, École Polytechnique Fedérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 Jul 12; Vol. 145 (27), pp. 14874-14883. Date of Electronic Publication: 2023 Jun 27.
DOI: 10.1021/jacs.3c03937
Abstrakt: Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor-acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for 13 C and 15 N nuclei. However, the low gyromagnetic ratio and natural abundance of these nuclei trap the local hyperpolarization in the vicinity of the chromophore and limit the utility for bulk hyperpolarization. Here, we report the first example of optically enhanced solid-state 1 H NMR spectroscopy in the high-field regime. This is achieved via photo-CIDNP of a donor-chromophore-acceptor molecule in a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusion among the abundant strongly coupled 1 H nuclei relays polarization through the whole sample, yielding a 16-fold bulk 1 H signal enhancement under continuous laser irradiation at 450 nm. These findings enable a new strategy for hyperpolarized NMR beyond the current limits of conventional microwave-driven DNP.
Databáze: MEDLINE
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