| Publication type: |
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Article in peer-reviewed journal |
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| Subject: |
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Chemical Sciences/Analytical chemistry
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| Title: |
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A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials |
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| Author(s): |
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Alexandre Zagdoun 1, Gilles Casano 2, Olivier Ouari 2, Giuseppe Lapadula 3, Aaron J. Rossini 1, Moreno Lelli 1, Mathieu Baffert 4, David Gajan 3, Laurent Veyre 4, Werner E. Maas 5, Mélanie Rosay 5, Ralph T Weber 5, Chloé Thieuleux 4, Christophe Coperet 3, Anne Lesage 1, Paul Tordo 2, Lyndon Emsley ( ) 1 |
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| Laboratory: |
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| 1: |
Institut des Sciences Analytiques (ISA) |
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http://isa.univ-lyon1.fr/ |
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Université de Lyon – CNRS : UMR5280 – Université Claude Bernard - Lyon I – École Normale Supérieure - Lyon |
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5 rue de la Doua, 69100 Villeurbanne |
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France |
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| 2: |
Laboratoire Chimie Provence (LCP) |
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http://lc-provence.fr |
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Université de Provence - Aix-Marseille I – CNRS : UMR6264 |
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Université de Provence LCP, Equipe Instrumentation et Reactivité Atmosphérique (case 29) 3, place V Hugo 13331 Marseille Cedex 3 |
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France |
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| 3: |
Laboratory of Inorganic Chemistry |
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Eidgenössische Technische Hochschule Zürich (ETH Zürich) |
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Department of Chemistry, ETH Zürich, CH-8093, Zürich, Switzerland |
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Switzerland |
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| 4: |
Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2) |
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http://www.c2p2-cpe.com/ |
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CNRS : UMR5265 – CPE LYON – Université Claude Bernard - Lyon I |
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43, Bd. du 11 Novembre 1918, Villeurbanne F-69616, |
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France |
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| 5: |
Bruker BioSpin Corporation |
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Bruker BioSpin Corporation |
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Billerica, Massachusetts 01821, United States |
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United States |
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| Research team: |
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Centre de RMN à très hauts champs |
| Abstract: |
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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 (epsilon) of over 100 at a magnetic field of 9.4 T and sample temperatures of similar to 100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (Sigma(dagger)) 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 C-13 and N-15 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. |
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| Fulltext language: |
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English |
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| Journal: |
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| Journal of the American Chemical Society (J Am Chem Soc) |
| Publisher |
American Chemical Society |
| ISSN |
0002-7863 (eISSN : 1520-5126) |
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| Audience: |
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international |
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| Publication date: |
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2012-02-01 |
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| Volume: |
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134 |
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| Issue: |
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4 |
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| Page, identifiant, ...: |
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Volume: 134 Issue: 4 Pages: 2284-2291 DOI: |
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| Keyword(s): |
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SOLID-STATE NMR – HETEROGENEOUS CATALYSTS – MEMBRANE – SILICA – DNP – SOLVENTS |
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| Contract, financing: |
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EU PIIF-GA-2010-274574 ; EQUIPEX ANR-10-EQPX-47-01 ; ETH Zurich |
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| ANR Project: |
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| Project Id |
EQUIPEX ANR-10-EQPX-47-01 |
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| European projet: |
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| Acronyme |
EU PIIF-GA-2010-274574 |
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