title: Hybrid polarizing solids for pure hyperpolarized liquids through dissolution dynamic nuclear polarization.
abstract: Hyperpolarization of substrates for magnetic resonance spectroscopy (MRS) and imaging (MRI) by dissolution dynamic nuclear polarization (D-DNP) usually involves saturating the ESR transitions of polarizing agents (PAs; e.g., persistent radicals embedded in frozen glassy matrices). This approach has shown enormous potential to achieve greatly enhanced nuclear spin polarization, but the presence of PAs and/or glassing agents in the sample after dissolution can raise concerns for in vivo MRI applications, such as perturbing molecular interactions, and may induce the erosion of hyperpolarization in spectroscopy and MRI. We show that D-DNP can be performed efficiently with hybrid polarizing solids (HYPSOs) with 2,2,6,6-tetramethyl-piperidine-1-oxyl radicals incorporated in a mesostructured silica material and homogeneously distributed along its pore channels. The powder is wetted with a solution containing molecules of interest (for example, metabolites for MRS or MRI) to fill the pore channels (incipient wetness impregnation), and DNP is performed at low temperatures in a very efficient manner. This approach allows high polarization without the need for glass-forming agents and is applicable to a broad range of substrates, including peptides and metabolites. During dissolution, HYPSO is physically retained by simple filtration in the cryostat of the DNP polarizer, and a pure hyperpolarized solution is collected within a few seconds. The resulting solution contains the pure substrate, is free from any paramagnetic or other pollutants, and is ready for in vivo infusion.
authors.affiliation: Centre de Résonance Magnétique Nucléaire (RMN) à Très Hauts Champs, Institut des Sciences Analytiques [Centre National de la Recherche Scientifique (CNRS)/Ecole Normale Supérieure (ENS) Lyon/Université Claude Bernard Lyon 1 (UCBL)], Université de Lyon, 69100 Villeurbanne, France;
authors.forename: David
authors.initials: D
authors.lastname: Gajan
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland;
authors.forename: Aurélien
authors.initials: A
authors.lastname: Bornet
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland;
authors.forename: Basile
authors.initials: B
authors.lastname: Vuichoud
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland;
authors.forename: Jonas
authors.initials: J
authors.lastname: Milani
authors.affiliation: Bruker Italia S.r.l., IT-20158 Milan, Italy;
authors.forename: Roberto
authors.initials: R
authors.lastname: Melzi
authors.affiliation: Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Chimie, Catalyse, Polymères et Procédés (LC2P2), Unité Mixte de Recherche (UMR) 5265 Centre National de la Recherche Scientifique (CNRS)-Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon)-Université Claude Bernard Lyon 1 (UCBL), Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon), 69100 Villeurbanne, France;
authors.forename: Henri A
authors.initials: HA
authors.lastname: van Kalkeren
authors.affiliation: Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Chimie, Catalyse, Polymères et Procédés (LC2P2), Unité Mixte de Recherche (UMR) 5265 Centre National de la Recherche Scientifique (CNRS)-Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon)-Université Claude Bernard Lyon 1 (UCBL), Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon), 69100 Villeurbanne, France;
authors.forename: Laurent
authors.initials: L
authors.lastname: Veyre
authors.affiliation: Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Chimie, Catalyse, Polymères et Procédés (LC2P2), Unité Mixte de Recherche (UMR) 5265 Centre National de la Recherche Scientifique (CNRS)-Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon)-Université Claude Bernard Lyon 1 (UCBL), Ecole Supérieure de Chimie Physique Electronique de Lyon (CPE Lyon), 69100 Villeurbanne, France;
authors.forename: Chloé
authors.initials: C
authors.lastname: Thieuleux
authors.affiliation: Department of Chemistry and Applied Biosciences, Eidgenössiche Technische Hochschule (ETH), 8093 Zurich, Switzerland;
authors.forename: Matthew P
authors.initials: MP
authors.lastname: Conley
authors.affiliation: Department of Chemistry and Applied Biosciences, Eidgenössiche Technische Hochschule (ETH), 8093 Zurich, Switzerland;
authors.forename: Wolfram R
authors.initials: WR
authors.lastname: Grüning
authors.affiliation: Department of Chemistry and Applied Biosciences, Eidgenössiche Technische Hochschule (ETH), 8093 Zurich, Switzerland;
authors.forename: Martin
authors.initials: M
authors.lastname: Schwarzwälder
authors.affiliation: Centre de Résonance Magnétique Nucléaire (RMN) à Très Hauts Champs, Institut des Sciences Analytiques [Centre National de la Recherche Scientifique (CNRS)/Ecole Normale Supérieure (ENS) Lyon/Université Claude Bernard Lyon 1 (UCBL)], Université de Lyon, 69100 Villeurbanne, France;
authors.forename: Anne
authors.initials: A
authors.lastname: Lesage
authors.affiliation: Department of Chemistry and Applied Biosciences, Eidgenössiche Technische Hochschule (ETH), 8093 Zurich, Switzerland;
authors.forename: Christophe
authors.initials: C
authors.lastname: Copéret
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland; Département de Chimie, Ecole Normale Supérieure (ENS)-Paris Sciences et Lettres (PSL) Research University, F-75005 Paris, France; Laboratoire de Biomolécules (LBM), Université Pierre et Marie Curie (UPMC) Université Paris 06, Sorbonnes Universités, F-75005 Paris, France; and Laboratoire de Biomolécules (LBM), Unité Mixte de Recherche (UMR) 7203 Centre National de la Recherche Scientifique (CNRS), F-75005 Paris, France.
authors.forename: Geoffrey
authors.initials: G
authors.lastname: Bodenhausen
authors.affiliation: Centre de Résonance Magnétique Nucléaire (RMN) à Très Hauts Champs, Institut des Sciences Analytiques [Centre National de la Recherche Scientifique (CNRS)/Ecole Normale Supérieure (ENS) Lyon/Université Claude Bernard Lyon 1 (UCBL)], Université de Lyon, 69100 Villeurbanne, France; Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland; lyndon.emsley@ens-lyon.fr.
authors.forename: Lyndon
authors.initials: L
authors.lastname: Emsley
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland;
authors.forename: Sami
authors.initials: S
authors.lastname: Jannin
mesh_terms: D000085:Acetates / Q000737:chemistry; D066241:Carbon-13 Magnetic Resonance Spectroscopy; D004151:Dipeptides / Q000737:chemistry; D005650:Fumarates / Q000737:chemistry; D008279:Magnetic Resonance Imaging; D066244:Proton Magnetic Resonance Spectroscopy; D011773:Pyruvates / Q000737:chemistry; D012995:Solubility; D013696:Temperature
chemical_list: D000085:Acetates; D004151:Dipeptides; D005650:Fumarates; D011773:Pyruvates; C028872:alanylglycine
keywords: D-DNP; NMR signal enhancement; mesostructured hybrid silica; molecular imaging; porous materials