title: A slowly relaxing rigid biradical for efficient dynamic nuclear polarization surface-enhanced NMR spectroscopy: expeditious characterization of functional group manipulation in hybrid materials.
abstract: A new nitroxide-based biradical having a long electron spin-lattice relaxation time (T(1e)) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (ε) of over 100 at a magnetic field of 9.4 T and sample temperatures of ~100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (Σ(†)) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T(1e), which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12,700, making the acquisition of (13)C and (15)N one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic-silica material.
authors.affiliation: Centre de RMN à Très Hauts Champs, Université de Lyon (CNRS/ENS Lyon/UCB Lyon 1), 69100 Villeurbanne, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Zagdoun
authors.forename: Gilles
authors.initials: G
authors.lastname: Casano
authors.forename: Olivier
authors.initials: O
authors.lastname: Ouari
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Lapadula
authors.forename: Aaron J
authors.initials: AJ
authors.lastname: Rossini
authors.forename: Moreno
authors.initials: M
authors.lastname: Lelli
authors.forename: Mathieu
authors.initials: M
authors.lastname: Baffert
authors.forename: David
authors.initials: D
authors.lastname: Gajan
authors.forename: Laurent
authors.initials: L
authors.lastname: Veyre
authors.forename: Werner E
authors.initials: WE
authors.lastname: Maas
authors.forename: Melanie
authors.initials: M
authors.lastname: Rosay
authors.forename: Ralph T
authors.initials: RT
authors.lastname: Weber
authors.forename: Chloé
authors.initials: C
authors.lastname: Thieuleux
authors.forename: Christophe
authors.initials: C
authors.lastname: Coperet
authors.forename: Anne
authors.initials: A
authors.lastname: Lesage
authors.forename: Paul
authors.initials: P
authors.lastname: Tordo
authors.forename: Lyndon
authors.initials: L
authors.lastname: Emsley
mesh_terms: D018360:Crystallography, X-Ray; D003497:Cyclic N-Oxides / Q000737:chemistry*; D003510:Cyclohexanes / Q000737:chemistry*; D005609:Free Radicals / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D013696:Temperature
chemical_list: D003497:Cyclic N-Oxides; D003510:Cyclohexanes; D005609:Free Radicals; C003959:TEMPO