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28 results on '"ERC Advanced Grant No. 320860"'

1. Cubic three-dimensional hybrid silica solids for nuclear hyperpolarization

Author: Aurélien Bornet, Laurent Veyre, David Baudouin, Christophe Copéret, Matthieu Cavaillès, David Gajan, Lyndon Emsley, Anne Lesage, Geoffrey Bodenhausen, Wei-Chih Liao, Chloé Thieuleux, Basile Vuichoud, Sami Jannin, H. A. van Kalkeren, Martin Schwarzwälder, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Structure et Dynamique des Biomolécules (LBM-E3), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), This work was supported by the CNRS, the SATT Lyon (Pulsalys), the European Research Council (ERC) Advanced Grant No. 320860, the Swiss National Science Foundation (SNSF), the Ecole Polytechnique Federale de Lausanne (EPFL), ETH Zurich, and the Swiss Commission for Technology & Innovation (CTI)., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, 010405 organic chemistry, Radical, technology, industry, and agriculture, General Chemistry, 010402 general chemistry, behavioral disciplines and activities, 01 natural sciences, humanities, Porous network, 0104 chemical sciences, Chemistry, Nuclear magnetic resonance, Chemical engineering, [CHIM]Chemical Sciences, Hyperpolarization (physics), Mesoporous material, Dissolution
Abstract: Hyperpolarization of metabolites by dissolution dynamic nuclear polarization (D-DNP) for MRI applications often requires fast and efficient removal of the radicals (polarizing agents). Ordered mesoporous SBA-15 silica materials containing homogeneously dispersed radicals, referred to as HYperPolarizing SOlids (HYPSOs), enable high polarization – P(1H) = 50% at 1.2 K – and straightforward separation of the polarizing HYPSO material from the hyperpolarized solution by filtration. However, the one-dimensional tubular pores of SBA-15 type materials are not ideal for nuclear spin diffusion, which may limit efficient polarization. Here, we develop a generation of hyperpolarizing solids based on a SBA-16 structure with a network of pores interconnected in three dimensions, which allows a significant increase of polarization, i.e. P(1H) = 63% at 1.2 K. This result illustrates how one can improve materials by combining a control of the incorporation of radicals with a better design of the porous network structures., Chemical Science, 7 (11), ISSN:2041-6520, ISSN:2041-6539
Published: 2016
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2. Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR

Author: Lyndon Emsley, David Gajan, Arthur C. Pinon, Cory M. Widdifield, Aaron J. Rossini, Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by ERC Advanced Grant No. 320860. C.M.W. would like to acknowledge NSERC for a postdoctoral fellowship., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: Phase transition, Magnetic Resonance Spectroscopy, Chemistry, Vasodilator Agents, Pharmaceutical Science, Nuclear magnetic resonance spectroscopy, polymorphs, theophylline, Article, Grinding, dynamic nuclear polarization, Crystallography, Models, Chemical, Solid-state nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Drug Discovery, medicine, solid-state NMR, Molecular Medicine, Physical chemistry, Sample preparation, Theophylline, Polarization (electrochemistry), Inert gas, medicine.drug
Abstract: We are grateful to Prof. P. Tordo, Dr. O. Ouari and Dr. G. Casano (Aix-Marseille Universite, France) for providing the biradicals used in the DNP NMR experiments.; International audience; We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as H-1-C-13 and H-1-N-15 HETCOR or C-13-C-13 INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs.
Published: 2015
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3. Hyperpolarized long-lived nuclear spin states in monodeuterated methyl groups

Author: Elliott, Stuart J., Meier, Benno, Vuichoud, Basile, Stevanato, Gabriele, Brown, Lynda J., Alonso-Valdesueiro, Javier, Emsley, Lyndon, Jannin, Sami, Levitt, Malcolm H., School of Chemistry [Southampton, UK], University of Southampton, ISA - Hyperpolarized Magnetic Resonance, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), This research was supported by the Engineering and Physical Sciences Research Council (UK), grant codes EP/N002482/1, EP/P009980 and EP/L505067/1, the European Research Council under the European Unions Horizon 2020 research and innovation programme (ERC Grant Agreement n 714519/HP4all), ERC advanced grant no. 320860, the Swiss National Science Foundation, and Bruker BioSpin., European Project: 714519,HP4all, European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Nuclear Theory, Physics::Medical Physics, Physics::Chemical Physics, Nuclear Experiment, ComputingMilieux_MISCELLANEOUS, Physics::Geophysics
Abstract: Dissolution-dynamic nuclear polarization is implemented to hyperpolarize long-lived nuclear spin states in monodeuterated methyl groups., Monodeuterated methyl groups may support a long-lived nuclear spin state, with a relaxation time exceeding the conventional spin–lattice relaxation time T1. Dissolution-DNP (dynamic nuclear polarization) may be used to hyperpolarize such a long-lived spin state. This is demonstrated for the CH2D groups of a piperidine derivative. The polarized sample is manipulated in the ambient magnetic field of the laboratory, without destruction of the hyperpolarized singlet order. Strongly enhanced CH2D signals are observed more than one minute after dissolution, even in the presence of paramagnetic radicals, by which time the NMR signal from the hyperpolarized proton magnetization has completely disappeared.
Published: 2018
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4. Hammett Parameter in Microporous Solids as Macroligands for Heterogenized Photocatalysts

Author: Anne Lesage, Luis Cardenas, Elsje Alessandra Quadrelli, Florian M. Wisser, Pierrick Berruyer, David Farrusseng, Jérôme Canivet, Yorck Mohr, IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Etudes & analyse de surfaces, XPS, LEIS (XPS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors are very grateful to N. Cristin and P. Mascunan for ICP-OES analysis, to L. Burel for electron microscopy, to Prof. Dr. G. Kickelbick (Saarland University) for providing access to CHN-analysis and to Dr. O. Ouari and Prof. Dr. P. Tordo (both from Aix -Marseille University) for providing polarizing agent TEKPOL. F.M.W. gratefully acknowledges financial support from the Deutsche Forschungsgemeinschaft (DFG, Postdoctoral Research Fellowship, grant number WI 4721/1-1). The authors acknowledge financial support from ERC Advanced Grant No. 320860., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: conjugated microporous polymers, 02 engineering and technology, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, Catalysis, Conjugated microporous polymer, Electronic effect, Electrochemical reduction of carbon dioxide, chemistry.chemical_classification, carbon dioxide reduction, microporous materials, General Chemistry, Polymer, Microporous material, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Hammett constant, 0104 chemical sciences, chemistry, Chemical engineering, Photocatalysis, 0210 nano-technology, photocatalysis, rhodium complex
Abstract: XPS+ING+FWI:LCS:YMO:DFA:JEC; International audience; Here we present a series of heterogeneous catalysts based on metal–organic frameworks and microporous polymers used as macroligands for heterogenized organometallic complexes. We show that both homogeneous and heterogenized catalysts follow the same linear correlation between the electronic effect of the ligand, described by the Hammett parameter, and the catalytic activity. This correlation highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure of the porous support. The rational design of heterogenized catalysts can thus be guided by molecular chemistry rules. The conception of highly efficient heterogeneous catalyst based on porous polymer support and driven by the Hammett parameter of bipyridine-chelating macroligand is demonstrated here for the Rh-catalyzed photoreduction of carbon dioxide with turnover frequencies up to 28 h–1, among the highest reported for heterogeneous photocatalytic formate production.
Published: 2018
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5. Frozen Acrylamide Gels as Dynamic Nuclear Polarization Matrices

Author: David Gajan, Lyndon Emsley, Jean-Marie Basset, Jasmine Viger-Gravel, Pierrick Berruyer, Anne Lesage, Olivier Ouari, Paul Tordo, Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), KAUST Catalysis Center (KCC), King Abdullah University of Sciences & Technologie, Institut de Chimie Radicalaire (ICR), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), This work was supported by ERC Advanced Grant No. 320860., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Analytical chemistry, Nanoparticle, quantum dots, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Spectral line, dynamic nuclear polarization, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Polarization (electrochemistry), Aqueous solution, 010405 organic chemistry, Chemistry, technology, industry, and agriculture, polyacrylamide gel, General Medicine, General Chemistry, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, 0104 chemical sciences, NMR spectra database, acrylamide gels, Quantum dot, Acrylamide, nanoparticles, 0210 nano-technology
Abstract: We thank Dr. B.J. Walder for help in processing the PASS data, Dr. C. Chamignon for assistance with quantitative liquid-state NMR, and Dr. D. Cala for her insight and advice in gel synthesis.; International audience; Aqueous acrylamide gels can be used to provide dynamic nuclear polarization (DNP) NMR signal enhancements of around 200 at 9.4 T and 100 K. The enhancements are shown to increase with crosslinker concentration and low concentrations of the AMUPol biradical. This DNP matrix can be used in situations where conventional incipient wetness methods fail, such as to obtain DNP surface enhanced NMR spectra from inorganic nanoparticles. In particular, we obtain Cd-113 spectra from CdTe-COOH NPs in minutes. The spectra clearly indicate a highly disordered cadmium-rich surface.
Published: 2017
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6. Measuring Nano- to Microstructures from Relayed Dynamic Nuclear Polarization NMR

Author: Tran N. Pham, Anne Lesage, Mingxue Tang, Staffan Schantz, Judith Schlagnitweit, Etienne Socie, Lyndon Emsley, Arthur C. Pinon, Aaron J. Rossini, Pierrick Berruyer, Moreno Lelli, Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Karolinska Institutet [Stockholm], Dept Chem, Iowa State University (ISU), Center for Magnetic Resonance, Università degli Studi di Firenze = University of Florence (UniFI), GSK Med Res Ctr, GlaxoSmithKline SA, AstraZeneca, This work was supported by ERC Advanced Grant No. 320860., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)
Subjects: chemistry.chemical_classification, Chemistry, Doping, Analytical chemistry, 02 engineering and technology, Polymer, Mesoporous silica, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, Polarization (waves), Electronic, Optical and Magnetic Materials, Energy (all), Physical and Theoretical Chemistry, Surfaces, Coatings and Films, 01 natural sciences, Molecular physics, Histidine Hydrochloride Monohydrate, 0104 chemical sciences, Complex materials, General Energy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Nano, 0210 nano-technology
Abstract: We are grateful to Matthew Conley and Christophe Coperet from ETH Zurich for providing the mesoporous silica materials. We are grateful to Prof. P. Tordo, Dr. O. Ouari, and Dr. G. Casano (Aix-Marseille Universite, France) for providing the biradicals used in the DNP NMR experiments.; International audience; We show how dynamic nuclear polarization (DNP) NMR can be used in combination with models for polarization dynamics to determine the domain sizes in complex materials. By selectively doping a source component with radicals and leaving the target undoped, we Can measure experimental polarization buildup curves which can be compared with simulations based on heterogeneous distributions of polarization-within the sample. The variation of the integrated DNP enhancement as a function of the polarization time is found to be characteristic of the geometry. We demonstrate the method experimentally on four different systems where we successfully determine domain sizes between 200 and 20 000 nm, specifically in powdered histidine hydrochloride monohydrate) pore lengths of mesoporous silica materials, and two domain sizes in two component polymer film coatings. Additionally, we find that even in the apparently homogeneous frozen solutions used as polarization sources in most DNP experiments, polarization is relayed from protons near the radicals to the bulk of the solution by spin diffusion, which explains the experimentally observed buildup times in these samples.
Published: 2017
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7. Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T

Author: Brownbill, Nick J, Gajan, David, Lesage, Anne, Emsley, Lyndon, Blanc, Frédéric, Dept Chem, University of Liverpool, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Polytechnique Fédérale de Lausanne (EPFL), Department of Chemistry and Stephenson Institute for Renewable Energy, Financial support from the EPSRC for a DTA studentship for N. J. B. and grant EP/M00869X/1 to F. B., ERC Advanced Grant No. 320860 for L. E. and EQUIPEX contract ANR-10-EQPX-47-01 for A. L. and L. E. is acknowledged., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM]Chemical Sciences
Abstract: We thank Dr Sachin R. Chaudhari (CRMN Lyon), Kenneth K. Inglis (University of Liverpool), and Dr O. Ouari and Prof. P. Tordo (Aix-Marseille Universite, CNRS) for valuable technical assistance, sample preparation, and radicals, respectively. F. B. thanks the TGIR-RMN-THC Fr3050 CNRS for access to the 18.8 T DNP NMR facility at the CRMN. The experimental data are provided as a supporting dataset from the University of Liverpool Data Catalogue portal at https://datacat.liverpool.ac.uk/245/.; International audience; We report (17)O dynamic nuclear polarisation (DNP) enhanced solid-state NMR experiments at 18.8 T. Several formulations were investigated on the Mg(OH)2 compound. A signal enhancement factor of 17 could be obtained when the solid particles were incorporated into a glassy o-terphenyl matrix doped with BDPA using the Overhauser polarisation transfer scheme whilst the cross effect mechanism enabled by TEKPol yielded a slightly lower enhancement but more time efficient data acquisition.
Published: 2017
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8. Solvent suppression in DNP enhanced solid state NMR

Author: Anne Lesage, Jayasubba Reddy Yarava, Lyndon Emsley, Aaron J. Rossini, Sachin Rama Chaudhari, Ecole Polytechnique Fédérale de Lausanne (EPFL), Department of Chemistry [Ames], Iowa State University (ISU), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Financial support from ERC Advanced Grant No. 320860 and Swiss National Science Foundation Grant No. 200021_160112., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nuclear and High Energy Physics, 010405 organic chemistry, Chemistry, Paramagnetic relaxation enhancement (PRE), Biophysics, Analytical chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Biochemistry, Solid-state NMR, Relaxation filters, Solvent suppression, 0104 chemical sciences, Solvent, NMR spectra database, Paramagnetism, Solid-state nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, DNP, Hyperpolarization (physics)
Abstract: We thank Prof. P. Tordo, Dr. O. Ouari and Dr. G. Casano (Aix-Marseille Universite) for supplying TEKPol and AMUPol, and Prof. Christophe Coperet (ETH Zurich) for supplying the silica based materials.; International audience; We show how DNP enhanced solid-state NMR spectra can be dramatically simplified by suppression of solvent signals. This is achieved by (i) exploiting the paramagnetic relaxation enhancement of solvent signals relative to materials substrates, or (ii) by using short cross-polarization contact times to transfer hyperpolarization to only directly bonded carbon-13 nuclei in frozen solutions. The methods are evaluated for organic microcrystals, surfaces and frozen solutions. We show how this allows for the acquisition of high-resolution DNP enhanced proton-proton correlation experiments to measure inter-nuclear proximities in an organic solid
Published: 2017
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9. Amplifying Dynamic Nuclear Polarization of Frozen Solutions by Incorporating Dielectric Particles

Author: Lyndon Emsley, Olivier Ouari, Paul Tordo, Anne Lesage, Frank Engelke, Aaron J. Rossini, Alexandre Zagdoun, Dominik J. Kubicki, Armin Purea, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Bruker BioSpin GmbH, D-76287 Rheinstetten, Germany, affiliation inconnue, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Polytechnique Fédérale de Lausanne (EPFL), This work was supported by ERC Advanced Grant No. 320860., European Project, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diffraction, C-13, Analytical chemistry, EFFICIENT, Nanoparticle, Dielectric, 010402 general chemistry, 01 natural sciences, Biochemistry, Molecular physics, Article, Catalysis, Colloid and Surface Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, TEMPERATURES, NANOPARTICLES, Spectroscopy, SPECTROSCOPY, 010405 organic chemistry, Chemistry, Scattering, General Chemistry, Polarization (waves), SOLID-STATE NMR, 0104 chemical sciences, SIGNAL ENHANCEMENT, Dielectric loss, POLYMERS, Microwave
Abstract: We thank Claire Sauvee and Dr. Gilles Casano (Universite Aix-Marseille) for synthesizing the biradicals used here. We thank Bruker France and Drs. Alain Belguise and Fabien Aussenac for providing initial access to the DNP spectrometer.; International audience; There is currently great interest in understanding the limits on NMR signal enhancements provided by dynamic nuclear polarization (DNP), and in particular if the theoretical maximum enhancements can be achieved. We show that over a 2-fold improvement in cross-effect DNP enhancements can be achieved in MAS experiments on frozen solutions by simply incorporating solid particles into the sample. At 9.4 T and similar to 105 K, enhancements up to epsilon(H) = 515 are obtained in this way, corresponding to 78% of the theoretical maximum. We also underline that degassing of the sample is important to achieve highest enhancements. We link the amplification effect to the dielectric properties of the solid material, which probably gives rise to scattering, diffraction, and amplification of the microwave field in the sample. This is substantiated by simulations of microwave propagation. A reduction in sample heating at a given microwave power also likely occurs due to reduced dielectric loss. Simulations indicate that the microwave field (and thus the DNP enhancement) is inhomogeneous in the sample, and we deduce that in these experiments between 5 and 10% of the solution actually yields the theoretical maximum signal enhancement of 658. The effect is demonstrated for a variety of particles added to both aqueous and organic biradical solutions.
Published: 2014
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10. Hydrophobic radicals embedded in neutral surfactants for dynamic nuclear polarization of aqueous environments at 9.4 Tesla

Author: Lyndon Emsley, Anne Lesage, Aaron J. Rossini, Paul Tordo, Moreno Lelli, Olivier Ouari, Gilles Casano, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ERC Advanced Grant No. 320860., Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Aqueous solution, Radical, Metals and Alloys, Analytical chemistry, General Chemistry, Photochemistry, Polyvinyl alcohol, Micelle, Catalysis, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Pulmonary surfactant, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Amphiphile, Materials Chemistry, Ceramics and Composites, Polarization (electrochemistry)
Abstract: We thank Brad Chmelka for discussions and suggestions.; International audience; We show how large DNP enhancements of NMR signals can be obtained from several hydrophobic radicals that are solubilised in aqueous environments by a variety of biologically compatible neutral amphiphiles. In particular we show that the bi-radical TEKPOL can be incorporated into micelles formed by the surfactant polysorbate 80 (Tween-80), where we obtain large DNP enhancements (similar to 60) at 9.4 T and similar to 100 K.
Published: 2014
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11. Silica-surface reorganization during organotin grafting evidenced by Sn-119 DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges

Author: Christophe Copéret, Anne Lesage, Maxence Valla, Gilles Casano, Paul Tordo, Matthew P. Conley, Lyndon Emsley, Aaron J. Rossini, Olivier Ouari, Aleix Comas-Vives, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ERC Advanced Grant No. 320860, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Physics and Astronomy, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, DOUBLE-RESONANCE NMR, Cascade reaction, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Polymer chemistry, Organic chemistry, ROTATIONAL-ECHO, Reactivity (chemistry), Physical and Theoretical Chemistry, ENHANCED NMR-SPECTROSCOPY, Geminal, 010405 organic chemistry, CATALYSIS, DEHYDROXYLATED SILICA, Nuclear magnetic resonance spectroscopy, Grafting, 0104 chemical sciences, SOLID-STATE NMR, ORGANOMETALLIC CHEMISTRY, chemistry, TIN, Siloxane, COMPLEXES, DYNAMIC NUCLEAR-POLARIZATION, Vicinal
Abstract: Dr Fabien Aussenac (Bruker France) for assistance with the DNP NMR experiments the Swiss National Science Foundation (Ambizione project PZ00P2_148059) for support.; International audience; Grafting reactive molecular complexes on dehydroxylated amorphous silica is a strategy to develop "single-site" heterogeneous catalysts. In general, only the reactivity of isolated silanols is invoked for silica dehydroxylated at 700 degrees C ([SiO2-700]), though ca. 10% of the surface silanols are in fact geminal Q(2)-silanols. Here we report the reaction of allyltributylstannane with (SiO2-700] and find that the geminal Q(2)-silanols react to form products that would formally arise from vicinal Q(3)-silanols that are not present on (SiO2-700], indicating that a surface rearrangement occurs. The reorganization of the silica surface is unique to silica dehydroxylated at 700 degrees C or above. The findings were identified using Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) combined with DFT calculations.
Published: 2014
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12. Dendritic polarizing agents for DNP SENS

Author: Christophe Copéret, David Gajan, Anne Lesage, Wei-Chih Liao, Roman Schowner, Margherita Pucino, Florian Bernada, Olivier Ouari, Gunnar Jeschke, Ta-Chung Ong, Lyndon Emsley, Martin Schwarzwälder, Claire Sauvée, Michael R. Buchmeiser, Paul Tordo, Maxim Yulikov, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Inst Polymerchem, University of Stuttgart, Ecole Polytechnique Fédérale de Lausanne (EPFL), We acknowledge financial support from the SNF for the 600 MHz DNP spectrometer (206021_150710) and for WCL (200020_149704), and ERC Advanced Grant No. 320860, the University of Aix-Marseille and the CNRS. MRB acknowledges financial support by the Deutsche Forschungsgemeinschaft (DFG, BU 2174/19-1). The EU COST action TD1103 Eurohyperpol is gratefully acknowledged for stimulating interactions and travel funds., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)
Subjects: Chemical substance, 010405 organic chemistry, Chemistry, Nanotechnology, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Photochemistry, Metathesis, 01 natural sciences, 0104 chemical sciences, Catalysis, Unpaired electron, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Dendrimer, Polarization (electrochemistry), Science, technology and society
Abstract: Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an effective method to significantly improve solid-state NMR investigation of solid surfaces. The presence of unpaired electrons (polarizing agents) is crucial for DNP, but it has drawbacks such as leading to faster nuclear spin relaxation, or even reaction with the substrate under investigation. The latter can be a particular problem for heterogeneous catalysts. Here, we present a series of carbosilane-based dendritic polarizing agents, in which the bulky dendrimer can reduce the interaction between the solid surface and the free radical. We thereby preserve long nuclear T′2 of the surface species, and even successfully enhance a reactive heterogeneous metathesis catalyst., Chemical Science, 8 (1), ISSN:2041-6520, ISSN:2041-6539
Published: 2017
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13. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

Author: Lyndon Emsley, Andrei Gurinov, David Gajan, Edy Abou-Hamad, Bilel Hamzaoui, Anissa Bendjeriou-Sedjerari, Eva Pump, Jean-Marie Basset, Anne Lesage, Dalaver H. Anjum, Jasmine Viger-Gravel, Manoja K. Samantaray, KAUST Catalysis Center (KCC), King Abdullah University of Sciences & Technologie, Ecole Polytechnique Fédérale de Lausanne (EPFL), Imaging & Characterizat Lab, King Abdullah University of Science and Technology (KAUST), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860, European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Pore size, Nitroxide mediated radical polymerization, 010405 organic chemistry, Chemistry, Radical, fungi, technology, industry, and agriculture, Analytical chemistry, food and beverages, hemic and immune systems, chemical and pharmacologic phenomena, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, NMR spectra database, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Polarization (electrochemistry), Porous medium
Abstract: Reactive surface species immobilized inside porous materials with suitably small windows can be studied by DNP SENS., Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [( 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 Si–O–)W(Me)5] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.
Published: 2017
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14. Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks

Author: Alexandre Legrand, Lyndon Emsley, David Farrusseng, Pierrick Berruyer, Jérôme Canivet, Caroline Mellot-Draznieks, Xavier Rozanska, Tanya K. Todorova, Linh Ngoc Ho, Christel Gervais, Anne Lesage, Laboratoire de Chimie des Processus Biologiques (LCPB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SARL Mat Design, Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), We acknowledge financial support from the French National Research Agency (ANR project: HOPFAME ANR-13-BS07-0002-01), the Fondation de l'Orangerie and the ERC Advanced Grant No. 320860. The calculations were performed by using the HPC resources from GENCI (CINES/TGCC/IDRIS) through Grants 2016-097343 and -097535., ANR-13-BS07-0002,HOPFAME,Matériaux poreux hybrides comme métalloenzymes artificielles(2013), European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Magnetic Resonance Spectroscopy, Proline, Glycine, Molecular Conformation, Peptide, 02 engineering and technology, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Catalysis, Molecular dynamics, NMR spectroscopy, Computational chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, metal-organic frameworks, chemistry.chemical_classification, Hydrogen bond, Chemical shift, Organic Chemistry, fungi, Hydrogen Bonding, General Chemistry, Nuclear magnetic resonance spectroscopy, Dipeptides, 021001 nanoscience & nanotechnology, molecular dynamics, 0104 chemical sciences, Characterization (materials science), chemistry, density functional calculations, peptides, Metal-organic framework, Density functional theory, 0210 nano-technology
Abstract: We thank Prof. Paul Tordo and Dr. Olivier Ouari for providing TEKPoL2.; International audience; We use density functional theory, newly parameterized molecular dynamics simulations, and last generation (15) N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalized MOF. Focusing on two grafts typified by MIL-68-proline (-Pro) and MIL-68-glycine-proline (-Gly-Pro), we identified the most likely peptide conformations adopted in the functionalized hybrid frameworks. We found that hydrogen bond interactions between the graft and the surface hydroxyl groups of the MOF are essential in determining the peptides conformation(s). DNP SENS methodology shows unprecedented signal enhancements when applied to these peptide-functionalized MOFs. The calculated chemical shifts of selected MIL-68-NH-Pro and MIL-68-NH-Gly-Pro conformations are in a good agreement with the experimentally obtained (15) N NMR signals. The study shows that the conformations of peptides when grafted in a MOF host are unlikely to be freely distributed, and conformational selection is directed by strong host-guest interactions.
Published: 2016
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15. Correlating synthetic methods, morphology, atomic-level structure, and catalytic activity of Sn-beta catalysts

Author: Ive Hermans, Christophe Copéret, Anne Lesage, Maxence Valla, Lyndon Emsley, Connor Firth, Francisco Núñez-Zarur, Patrick Wolf, Aleix Comas-Vives, Aaron J. Rossini, Hana Kallas, Dept Biol & Chem, University of Wisconsin-Madison, Dept Chem, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Instituto de Quimica, Universidad de Antioquia, Ecole Polytechnique Fédérale de Lausanne (EPFL), Dept Chem, Ames, Iowa State University (ISU), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SNF Grants No. 200021_143600 and 200021_146661, Ambizione project PZ00P2_148059, EQUIPEX contract ANR-10-EQPX-47-01, and ERC Advanced Grant No. 320860, ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), and European Project
Subjects: BAEYER-VILLIGER OXIDATIONS, 010402 general chemistry, 01 natural sciences, Catalysis, EFFECTIVE CORE POTENTIALS, Sn-beta zeolites, DENSITY-FUNCTIONAL THEORY, Hydrolysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Sn-119 solid-state NMR, Organic chemistry, Zeolite, LEWIS-ACID SITES, ENHANCED NMR-SPECTROSCOPY, Ion exchange, 010405 organic chemistry, Chemistry, ab initio calculations, stannosilicates, Aqueous two-phase system, General Chemistry, Nuclear magnetic resonance spectroscopy, [CHIM.CATA]Chemical Sciences/Catalysis, GLUCOSE ISOMERIZATION, DNP SENS, ORDER REGULAR APPROXIMATION, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, MEERWEIN-PONNDORF-VERLEY, ANGLE-SPINNING NMR, Density functional theory, DYNAMIC NUCLEAR-POLARIZATION, Isomerization
Abstract: Dr. Frank Krumeich is gratefully thanked for the SEM-EDX measurements. We also thank Dr. Ta-Chung Ong and Wei-Chih Liao for their help with some of the DNP-NMR experiments.; International audience; Sn-beta zeolites prepared using different recipes feature very different catalytic activities for aqueous phase glucose isomerization, suggesting the presence of different active sites. A systematic study of the morphology and atomic-level structure of the materials using DNP NMR spectroscopy in combination with first-principles calculations allows for the discrimination between potential sites and leads to a proposal of specific structural features that are important for high activity. The results indicate that the materials showing the highest activity possess a highly hydrophobic, defect-free zeolite framework. Those materials show so-called closed and associated partially hydrolyzed Sn(IV) sites in the T6 and T5/T7 lattice positions. On the other hand, postsynthetically synthesized Sn-beta samples prepared in two steps via dealumination and subsequent solid-state ion exchange from Al-beta show significantly lower activity, which is associated with a hydrophilic framework and/or a lower accessibility and different lattice position of the Sn sites in the zeolite crystal. Further, we provide a method to distinguish between different Sn sites on the basis of NMR cartography using chemical shift and chemical shift anisotropy as readily measurable parameters. This cartography allows identifying not only the nature of the active sites (closed, defect-open, and hydrolyzed-open) but also their position within the BEA framework.
Published: 2016
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16. Monolayer doping of silicon through grafting a tailored molecular phosphorus precursor onto cxide-passivated silicon surfaces

Author: Laurent Veyre, Hervé Fontaine, Lyndon Emsley, Martin Schwarzwälder, François Martin, Laurent Mathey, Aaron J. Rossini, Virginie Enyedi, Tsung-Han Lin, Thibault Alphazan, Marc Veillerot, Raphael Wischert, Chloé Thieuleux, Christophe Copéret, Anne Lesage, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dept Chem & Appl Biosci, Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), transversal CEA project Zero POVA, CNRS and ERC Advanced Grant No. 320860, European Project, Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Silicon, Annealing (metallurgy), General Chemical Engineering, Inorganic chemistry, Oxide, chemistry.chemical_element, 02 engineering and technology, NANOWIRES, 010402 general chemistry, 01 natural sciences, SIO2 SURFACES, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Monolayer, Materials Chemistry, ICP-MS, Wafer, POLYHEDRAL OLIGOSILSESQUIOXANES, SEMICONDUCTOR NANOCRYSTALS, ENHANCED NMR-SPECTROSCOPY, Dopant, Doping, ORGANIC FUNCTIONALIZATION, technology, industry, and agriculture, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, LAYER DEPOSITION, Silsesquioxane, 0104 chemical sciences, ORGANOMETALLIC CHEMISTRY, chemistry, DYNAMIC NUCLEAR-POLARIZATION, 0210 nano-technology
Abstract: The authors thank S. Deleonibus (DRT/LETI), M. Sanquer (DSM/INAC), and L. Vandroux (DRT/LETI) for their continuous support, as well as V. Loup, P. Besson, M. Danielou, S. Kerdiles, A. Andre, L. Andreutti, and J.P. Barnes from CEA/LETI/Minatec; and K. Szeto from C2P2-LCOMS. ETH Zurich, CPE Lyon and UCBL are also acknowledged for their scientific support and the access to the process and characterization facilities.; International audience; Monolayer doping (MLD) of silicon substrates at the nanoscale is a powerful method to provide controlled doses of dopants and defect-free materials. However, this approach requires the deposition of a thick SiO2 cap layer to limit dopant evaporation during annealing. Here, we describe the controlled surface doping of thin oxide-passivated silicon wafers through a two-step process involving the grafting of a molecular phosphorus precursor containing a polyhedral oligomeric silsesquioxane (POSS) scaffold with silica-like architecture and thermal annealing. We show that the POSS scaffold favors the controlled formation of dopant-containing surface species with up to similar to 8 x 10(13) P atoms cm(-2) and efficiently avoids phosphorus evaporation during annealing for temperatures up to 800 degrees C. Silicon doping is demonstrated, in particular, by grafting the POSS phosphorus triester on SiO2/Si wafers with optimized surface preparation (thin SiO2 layer of 0.7 nm) and annealing temperature (1000 degrees C), which provides phosphorus doses of similar to 7 x 10(12) P atoms cm(-2) in the silicon substrates together with a decrease of their sheet resistance. A detailed study of the surface chemistry on SiO2 nanoparticles used as a high-surface-area model yields the grafting mechanism and the structure of the surface species. We show that the POSS scaffold is conserved upon grafting, that its size controls the final P-surface density, and that it behaves as a self-protecting ligand against phosphorus volatilization during the annealing step. We thus demonstrate that the use of custom-made dopant precursors with self-capping properties is a promising approach to tune medium to low doping doses in technologically relevant semiconductors.
Published: 2016
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17. The structure and binding mode of citrate in the stabilization of gold nanoparticles

Author: Lyndon Emsley, Hind Al-Johani, Luigi Cavallo, Abdesslem Jedidi, Michael J. Kelly, Jean-Marie Basset, David Gajan, Andrei Gurinov, Samy Ould-Chikh, Mohamed N. Hedhili, Jasmine Viger-Gravel, Shiv Shankar Sangaru, Edy Abou-Hamad, Cory M. Widdifield, Dalaver H. Anjum, Mohamad El Eter, KAUST Catalysis Center (KCC), King Abdullah University of Sciences & Technologie, Chem Dept, University of Tabuk, Dept Chem, King Abdulaziz University, Department of Chemistry, Durham University, Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Imaging & Characterizat Lab, King Abdullah University of Science and Technology (KAUST), This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: MECHANISM, ADSORPTION, Denticity, SURFACE, Trace Amounts, General Chemical Engineering, 02 engineering and technology, METAL NANOPARTICLES, 010402 general chemistry, 01 natural sciences, ANIONS, law.invention, Ion, chemistry.chemical_compound, Oxidation state, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Carboxylate, AU(111), Chemistry, THIN-FILM ELECTRODES, AU NANOPARTICLES, SINGLE-CRYSTAL, MICROSCOPY, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, Colloidal gold, Electron microscope, 0210 nano-technology
Abstract: For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.; International audience; Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by C-13 and Na-23 solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1 kappa O-1) mode is favoured at high citrate: gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Au delta+ are observed. Na-23 NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e(-) L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.
Published: 2016
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18. High-resolution NMR of hydrogen in organic solids by DNP enhanced natural abundance deuterium spectroscopy

Author: Anne Lesage, Lyndon Emsley, Aaron J. Rossini, Judith Schlagnitweit, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Polytechnique Fédérale de Lausanne (EPFL), Prof. P. Tordo, Dr. O. Ouari and Dr. G. Casano (Aix-Marseille Universite) are thanked for supplying TEKPol. Financial support was from EQUIPEX contract ANR-10-EQPX-47-01, ERC Advanced Grant No. 320860 and the Ecole Polytechnique Federale de Lausanne. JS acknowledges support from a Schrodinger Fellowship J 3377-N28 from the Austrian Science Fund., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), and European Project
Subjects: Nuclear and High Energy Physics, Magnetic Resonance Spectroscopy, LINE-SHAPES, Analytical chemistry, Biophysics, 010402 general chemistry, 01 natural sciences, Biochemistry, Homonuclear molecule, Electromagnetic Fields, NMR spectroscopy, Theophylline, DYNAMIC-NUCLEAR-POLARIZATION, MAGNETIC-RESONANCE, Hydrocarbons, Chlorinated, Magic angle spinning, NANOPARTICLES, BIRADICALS, Histidine, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Spectroscopy, SN-BETA ZEOLITE, Ethane, Glycylglycine, 010405 organic chemistry, Chemistry, Chemical shift, Hyper-polarization, Temperature, Nuclear magnetic resonance spectroscopy, Condensed Matter Physics, Deuterium, Tetrachloroethane, 0104 chemical sciences, NMR spectra database, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, STATE NMR, MAS NMR, Indicators and Reagents, CHEMICAL-SHIFTS, BACTERIOPHAGE, Hydrogen
Abstract: We demonstrate that high field (9.4T) dynamic nuclear polarization (DNP) at cryogenic (similar to 100 K) sample temperatures enables the rapid acquisition of natural abundance H-1-H-2 cross-polarization magic angle spinning (CPMAS) solid-state NMR spectra of organic solids. Spectra were obtained by impregnating substrates with a solution of the stable DNP polarizing agent TEKPol in tetrachloroethane. Tetrachloroethane is a non-solvent for the solids, and the unmodified substrates are then polarized through spin diffusion. High quality natural abundance H-2 CPMAS spectra of histidine hydrochloride monohydrate, glycylglycine and theophylline were acquired in less than 2 h, providing direct access to hydrogen chemical shifts and quadrupolar couplings. The spectral resolution of the H-2 solid-state NMR spectra is comparable to that of H-1 spectra obtained with state of the art homonuclear decoupling techniques. (C) 2015 The Authors. Published by Elsevier Inc.
Published: 2015
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19. Nanostructure of materials determined by relayed paramagnetic relaxation enhancement

Author: Schlagnitweit, Judith, Tang, Mingxue, Baias, Maria, Richardson, Sara, Schantz, Staffan, Emsley, Lyndon, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), AstraZeneca, Ecole Polytechnique Fédérale de Lausanne (EPFL), J.S. acknowledges a Schrodinger Fellowship (J3377-N28) from the Austrian Science Fund (FWF). Financial support is acknowledged from ERC Advanced grant no. 320860. We would like to thank Alexandre Zagdoun, Andrew J. Pell, and Cory Widdifield (all CRMN Lyon) for useful discussions as well as Mariagrazia Marucci and Johan Hjartstam (both AZ) for providing the samples. We also want to thank Mariagrazia Marucci, Christian von Corswant, J. Kohlbrecher, and Ulf Olsson for sharing data from the SANS measurements prior to publication., and European Project
Subjects: Magnetic Resonance Spectroscopy, SPECTROSCOPY, Communication, INSERTION, SPIN-DIFFUSION, FILMS, Nanostructures, SOLID-STATE NMR, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, MORPHOLOGY, [CHIM]Chemical Sciences, PERMEABILITY, NUCLEAR-MAGNETIC-RESONANCE, POLYMERS, Cellulose, FORMULATIONS
Abstract: International audience; Particle and domain sizes strongly influence the properties of materials. Here we present an NMR approach based on paramagnetic relaxation enhancement (PRE) relayed by spin diffusion (SD), which allows us to determine lengths in the nm pm range. We demonstrate the method on multicomponent organic polymer mixtures by selectively doping one component with a paramagnetic center in order to measure the domain size in a second component. Using this approach we determine domain sizes in ethyl cellulose/hydroxypropyl cellulose film coatings in pharmaceutical controlled release formulations. Here we measure particle sizes ranging from around 50 to 200 nm.
Published: 2015
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20. Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations

Author: Céline Chizallet, Maxime Caillot, Aaron J. Rossini, Pascal Raybaud, Maxence Valla, Lyndon Emsley, Christophe Copéret, Jeroen A. van Bokhoven, Anne Lesage, Mathieu Digne, Alexandra Chaumonnot, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Ecole Polytechnique Fédérale de Lausanne (EPFL), IFP Energies nouvelles (IFPEN), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), M.V. thanks the SNF foundation for financial support (Grant No. 200021_142600). This work was funded in part by the ERC Advanced Grant No. 320860 and SNF equipment grant (206021_150710)., and European Project
Subjects: AMORPHOUS SILICA, inorganic chemicals, Silicon, Industrial catalysts, chemistry.chemical_element, Biochemistry, complex mixtures, Catalysis, Article, BRONSTED ACID SITES, Colloid and Surface Chemistry, Aluminosilicate, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, MAGNETIC-RESONANCE, M-XYLENE ISOMERIZATION, GAMMA-ALUMINA, Organic chemistry, Polarization (electrochemistry), AL-27 NMR, SN-BETA ZEOLITE, INTEGER QUADRUPOLAR NUCLEI, technology, industry, and agriculture, General Chemistry, Nuclear magnetic resonance spectroscopy, equipment and supplies, Amorphous solid, SOLID-STATE NMR, RESOLUTION SI-29 NMR, Solid-state nuclear magnetic resonance, chemistry, Chemical engineering, Density functional theory
Abstract: Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively., Journal of the American Chemical Society, 137 (33), ISSN:0002-7863, ISSN:1520-5126
Published: 2015
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21. Solid-State Dynamic Nuclear Polarization at 9.4 and 18.8 T from 100 K to Room Temperature

Author: David Gajan, Moreno Lelli, Aaron J. Rossini, Olivier Ouari, Gilles Casano, Anne Lesage, Lyndon Emsley, Paul Tordo, Sachin Rama Chaudhari, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Polytechnique Fédérale de Lausanne (EPFL), Financial support is acknowledged from ERC Advanced Grant No. 320860 and EQUIPEX contract ANR-10-EQPX-47-01., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Catalysis, Chemistry, Surface Chemistry, ENHANCED NMR-SPECTROSCOPY, SPIN-LATTICE-RELAXATION, HIGH-FREQUENCY DNP POLARIZING AGENT, O-TERPHENYL, Cross effect, Communication, Spin–lattice relaxation, Solid-state, Analytical chemistry, General Chemistry, Polarization (waves), Biochemistry, 3. Good health, Solvent, Molecular dynamics, Colloid and Surface Chemistry, Nuclear magnetic resonance, [CHIM]Chemical Sciences, Glass transition
Abstract: We thank Lenaic Leroux for technical help.; International audience; Efficient dynamic nuclear polarization (DNP) in solids, which enables very high sensitivity NMR experiments, is currently limited to temperatures of around 100 K and below. Here we show how by choosing an adequate solvent, 1H cross effect DNP enhancements of over 80 can be obtained at 240 K. To achieve this we use the biradical TEKPol dissolved in a glassy phase of ortho-terphenyl (OTP). We study the solvent DNP enhancement of both TEKPol and BDPA in OTP in the range from 100 to 300 K at 9.4 and 18.8 T. Surprisingly, we find that the DNP enhancement decreases only relatively slowly for temperatures below the glass transition of OTP (Tg = 243 K), and 1H enhancements around 15–20 at ambient temperature can be observed. We use this to monitor molecular dynamic transitions in the pharmaceutically relevant solids Ambroxol and Ibuprofen.
Published: 2015
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22. NMR signatures of the active sites in Sn-beta zeolite

Author: Francisco Núñez-Zarur, Lyndon Emsley, Bernard Malaman, Ive Hermans, Maxence Valla, Aleix Comas-Vives, Patrick Wolf, Christophe Copéret, Anne Lesage, Aaron J. Rossini, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Dept Chem, University of Wisconsin-Madison, Dept Biol & Chem, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), We acknowledge SNF Grants No. 200021_143600 and 200021_146661, Ambizione project PZ00P2_148059, EQUIPEX contract ANR-10-EQPX-47-01, and ERC Advanced Grant No. 320860 for funding., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project, Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: Magic angle, BAEYER-VILLIGER OXIDATIONS, Inorganic chemistry, Mossbauer spectroscopy, AROMATIC-ALDEHYDES, chemistry.chemical_element, zeolites, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, WATER-TOLERANT, 01 natural sciences, Catalysis, DENSITY-FUNCTIONAL THEORY, MAGIC-ANGLE, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, active sites, Mössbauer spectroscopy, LEWIS-ACID CATALYST, Zeolite, Polarization (electrochemistry), solid-state NMR spectroscopy, 010405 organic chemistry, General Chemistry, GLUCOSE ISOMERIZATION, DNP SENS, 0104 chemical sciences, Lewis acid catalysis, Crystallography, MEERWEIN-PONNDORF-VERLEY, chemistry, Octahedron, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, DYNAMIC NUCLEAR-POLARIZATION, LACTIC-ACID: active sites, Tin
Abstract: International audience; Dynamic nuclear polarization surface enhanced NMR (DNP-SENS), Mossbauer spectroscopy, and computational chemistry were combined to obtain structural information on the active-site speciation in Sn-beta zeolite. This approach unambiguously shows the presence of framework Sn-IV-active sites in an octahedral environment, which probably correspond to so-called open and closed sites, respectively (namely, tin bound to three or four siloxy groups of the zeolite framework).
Published: 2014
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23. Dynamic nuclear polarisation enhanced (14)N overtone MAS NMR spectroscopy

Author: Luke A. O'Dell, Aaron J. Rossini, Lyndon Emsley, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Inst Frontier Mat, Deakin University [Burwood], financial support from EQUIPEX Contract ANR-10-EQPX-47-01 and ERC Advanced Grant No. 320860. The Australian Research Council is also acknowledged for funding Deakin University's Magnetic Resonance Facility through LIEF grant LE11010014., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project, Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: AMPLITUDE CROSS-POLARIZATION, HIGH-FREQUENCY, SAMPLE, 010405 organic chemistry, Chemistry, Chemical shift, Overtone, Dynamic nuclear polarisation, Analytical chemistry, SOLIDS, General Physics and Astronomy, EFFICIENT, Natural abundance, Pulse sequence, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, NMR spectra database, SPINNING NMR, Heteronuclear molecule, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Magic angle spinning, SPECTRA, Physical and Theoretical Chemistry
Abstract: Dr David Gajan is thanked for assistance in setting up the DNP experiments, and Dr Andreas Brinkmann (National Research Council, Canada) is acknowledged for writing the SpinDynamica code to simulate overtone MAS spectra (SpinDynamica is available at spindynamica. soton. ac. uk). We thank Prof. Paul Tordo, Dr Olivier Ouari, Dr Gilles Casano and Claire Sauve ' e (Aix-Marseille University) for providing the TEKPol and AMUPol biradicals.; International audience; Dynamic nuclear polarisation (DNP) has been used to obtain magic angle spinning (14)N(OT) (nitrogen-14 overtone) solid-state NMR spectra from several model amino acids, with both direct and indirect observation of the (14)N(OT) signal. The crystalline solids were impregnated with biradical solutions of organic liquids that do not dissolve the crystalline phase. The bulk phase was then polarized via(1)H spin diffusion from the highly-polarized surface (1)H nuclei, resulting in (1)H DNP signal enhancements of around two orders of magnitude. Cross polarisation from (1)H nuclei directly to the (14)N overtone transition is demonstrated under magic angle spinning, using a standard pulse sequence with a relatively short contact time (on the order of 100 μs). This method can be used to acquire (14)N overtone MAS powder patterns that match closely with simulated line shapes, allowing isotropic chemical shifts and quadrupolar parameters to be measured. DNP enhancement also allows the rapid acquisition of 2D (14)N(OT) heteronuclear correlation spectra from natural abundance powder samples. (1)H-(14)N(OT) HETCOR and (13)C-(14)N(OT) HMQC pulse sequences were used to observe all single-bond H-N and C-N correlations in histidine hydrochloride monohydrate, with the spectra obtained in a matter of hours. Due to the high natural abundance of the (14)N isotope (99.6%) and the advantages of observing the overtone transition, these methods provide an attractive route to the observation of C-N correlations from samples at natural isotopic abundance and enable the high resolution measurement of (14)N chemical shifts and quadrupolar interaction parameters.
Published: 2014
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24. Unraveling the core-shell structure of ligand-capped Sn/SnOx nanoparticles by surface-enhanced nuclear magnetic resonance, Mössbauer, and X-ray absorption spectroscopies

Author: Maksym V. Kovalenko, Maxence Valla, Dominik Kriegner, Kostiantyn V. Kravchyk, Anne Lesage, Lyndon Emsley, Christophe Copéret, Bernard Malaman, Maarten Nachtegaal, Antoine de Kergommeaux, Peter Reiss, Julian Stangl, Marc Walter, Aaron J. Rossini, Loredana Protesescu, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Swiss Federal Laboratories for Materials Science and Technology [Dübendorf] (EMPA), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Semiconductor and Solid State Physics, Johannes Kepler Universität Linz (JKU), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), EQUIPEX contract ANR-10-EQPX-47-01, ERC Advanced Grant No. 320860, ERC Starting Grant No. 306733, EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574), SNF fellowship (200021_143600), Austrian Academy of Sciences (DOC fellowship)., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), AII - Amsterdam institute for Infection and Immunity, APH - Amsterdam Public Health, Global Health, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Nanosciences et Cryogénie (INAC), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: Materials science, POLARIZATION, XAS, Analytical chemistry, General Physics and Astronomy, chemistry.chemical_element, Nanoparticle, Li-ion batteries, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, OXIDATION, 01 natural sciences, Nanomaterials, dynamic nuclear polarization, Nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, General Materials Science, SEMICONDUCTOR NANOCRYSTALS, SNO2, X-ray absorption spectroscopy, HIGH-FREQUENCY, Extended X-ray absorption fine structure, colloidal, General Engineering, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, TRANSFORMATION, 0104 chemical sciences, EXAFS, Solid-state nuclear magnetic resonance, chemistry, TIN, NMR-SPECTROSCOPY, core/shell structure, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], solid-state NMR, MONODISPERSE, nanoparticles, Absorption (chemistry), 0210 nano-technology, Tin, Dynamic nuclear polarization, Solid-state NMR, Nanoparticles, Colloidal, Core/shell structure
Abstract: A particularly difficult challenge in the chemistry of nanomaterials is the detailed structural and chemical analysis of multicomponent nano-objects. This is especially true for the determination of spatially resolved information. In this study, we demonstrate that dynamic nuclear polarization surface-enhanced solid-state NMR spectroscopy (DNP-SENS), which provides selective and enhanced NMR signal collection from the (near) surface regions of a sample, can be used to resolve the core–shell structure of a nanoparticle. Li-ion anode materials, monodisperse 10–20 nm large tin nanoparticles covered with a ∼3 nm thick layer of native oxides, were used in this case study. DNP-SENS selectively enhanced the weak 119Sn NMR signal of the amorphous surface SnO2 layer. Mössbauer and X-ray absorption spectroscopies identified a subsurface SnO phase and quantified the atomic fractions of both oxides. Finally, temperature-dependent X-ray diffraction measurements were used to probe the metallic β-Sn core and indicated that even after 8 months of storage at 255 K there are no signs of conversion of the metallic β-Sn core into a brittle semiconducting α-phase, a phase transition which normally occurs in bulk tin at 286 K (13 °C). Taken together, these results indicate that Sn/SnOx nanoparticles have core/shell1/shell2 structure of Sn/SnO/SnO2 phases. The study suggests that DNP-SENS experiments can be carried on many types of uniform colloidal nanomaterials containing NMR-active nuclei, in the presence of either hydrophilic (ion-capped surfaces) or hydrophobic (capping ligands with long hydrocarbon chains) surface functionalities., ACS Nano, 8 (3), ISSN:1936-0851, ISSN:1936-086X
Published: 2014
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25. Large molecular weight nitroxide biradicals providing efficient dynamic nuclear polarization at temperatures up to 200 K

Author: Gilles Casano, Alexandre Zagdoun, Lyndon Emsley, Fabien Aussenac, Martin Schwarzwälder, Olivier Ouari, Gunnar Jeschke, Paul Tordo, Christophe Copéret, Maxim Yulikov, Anne Lesage, Aaron J. Rossini, ISA - Centre de RMN à très hauts champs, Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory of Inorganic Chemistry, Bruker BioSpin SA, EU Marie-Curie IIF Fellowship (PIIF-GA-2010-274574), SNF for financial support (200021_134775/1), EQUIPEX contract ANR-10-EQPX-47-01, ERC Advanced grant no. 320860, ETH Zurich., European Project, Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nitroxide mediated radical polymerization, Magnetic Resonance Spectroscopy, Free Radicals, Proton, PROTEINS, IMPACT, C-13, Analytical chemistry, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Biochemistry, Catalysis, Colloid and Surface Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Phase (matter), Magic angle spinning, Spectroscopy, Polarization (electrochemistry), SURFACE INTERACTIONS, SPECTROSCOPY, Molecular Structure, 010405 organic chemistry, Chemistry, Relaxation (NMR), ELECTRON-SPIN RELAXATION, Temperature, General Chemistry, 0104 chemical sciences, SOLID-STATE NMR, Molecular Weight, Solid-state nuclear magnetic resonance, Nitrogen Oxides, MEMBRANE, GLASSY SOLVENTS
Abstract: A series of seven functionalized nitroxide biradicals (the bTbK biradical and six derivatives) are investigated as exogenous polarization sources for dynamic nuclear polarization (DNP) solid-state NMR at 9.4 T and with ca. 100 K sample temperatures. The impact of electron relaxation times on the DNP enhancement (ε) is examined, and we observe that longer inversion recovery and phase memory relaxation times provide larger ε. All radicals are tested in both bulk 1,1,2,2-tetrachloroethane solutions and in mesoporous materials, and the difference in ε between the two cases is discussed. The impact of the sample temperature and magic angle spinning frequency on ε is investigated for several radicals each characterized by a range of electron relaxation times. In particular, TEKPol, a bulky derivative of bTbK with a molecular weight of 905 g·mol–1, is presented. Its high-saturation factor makes it a very efficient polarizing agent for DNP, yielding unprecedented proton enhancements of over 200 in both bulk and materials samples at 9.4 T and 100 K. TEKPol also yields encouraging enhancements of 33 at 180 K and 12 at 200 K, suggesting that with the continued improvement of radicals large ε may be obtained at higher temperatures., Journal of the American Chemical Society, 135 (34), ISSN:0002-7863, ISSN:1520-5126
Published: 2013
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26. Three-Dimensional Structure Determination of Surface Sites

Author: Moreno Lelli, Pierrick Berruyer, David Gajan, Lyndon Emsley, Cory M. Widdifield, Daniel L. Silverio, Georges Siddiqi, Matthew P. Conley, Christophe Copéret, Anne Lesage, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Magnet Resonance Ctr CERM, Université de Florence, Department of Chemistry and Applied Biosciences [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Dept Chem, Durham University, Ecole Polytechnique Fédérale de Lausanne (EPFL), and Financial support is acknowledged from the ERC Advanced Grant No. 320860.
Subjects: Surface (mathematics), organometallic, Platinum Metal, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, Catalysis, dynamic nuclear polarization, DYNAMIC NUCLEAR-POLARIZATION, ENHANCED NMR-SPECTROSCOPY, SOLID-STATE NMR, DOUBLE-RESONANCE NMR, ORGANOMETALLIC CATALYSTS, METATHESIS CATALYSTS, ROTATIONAL-ECHO, SILICA, APPROXIMATION, NANOPARTICLES, Colloid and Surface Chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Polarization (electrochemistry), Extended X-ray absorption fine structure, 010405 organic chemistry, Chemistry, atomic-level, General Chemistry, Nuclear magnetic resonance spectroscopy, NMR, 0104 chemical sciences, Crystallography, Chemical physics, three-dimensional structures, DNP, Chemical function, Surface reconstruction
Abstract: Lenaic Leroux is acknowledged for technical assistance at the CRMN. Prof. Paul Tordo and Dr. Olivier Ouari are thanked for providing TEKPo12.; International audience; The spatial arrangement of atoms is directly linked to chemical function. A fundamental challenge in surface chemistry and catalysis relates to the determination of three-dimensional structures with atomic-level precision. Here we determine the three-dimensional structure of an organometallic complex on an amorphous silica surface using solid-state NMR measurements, enabled through a dynamic nuclear polarization surface enhanced NMR spectroscopy approach that induces a 200-fold increase in the NMR sensitivity for the surface species. The result, in combination with EXAFS, is a detailed structure for the surface complex determined with a precision of 0.7 angstrom. We observe a single well-defined conformation that is folded toward the surface in such a way as to include an interaction between the platinum metal center and the surface oxygen atoms.
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27. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates

Author: Lawrence R. Roberts, Lyndon Emsley, Bradley F. Chmelka, Anne Lesage, Benjamin J. Smith, Aaron J. Rossini, Rahul P. Sangodkar, David Gajan, Gary P. Funkhouser, Dept Chem Engn, University of California [Santa Barbara] (UCSB), University of California-University of California, Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Roberts Consulting Grp, Halliburton, Ecole Polytech Fed Lausanne, Inst Sci & Ingn Chim, BCH, CH-1015 Lausanne, Switzerland, This work was supported in part by Halliburton, Inc., and by the U.S. Federal Highway Administration (FHWA) under agreement no. DTFH61-12-H-00003. We thank Dr. M. Caporini and Dr. M. Rosay for helpful discussions concerning the DNP NMR measurements, and Bruker Biospin Corp., Billerica, Massachusetts, USA, for access to the DNP NMR instrumentation. We are grateful to Prof. H. Oschkinat and Dr. W. T. Franks for access to the DNP NMR facilities at the Leibniz-Institute fur Molekulare Pharmakologie (FMP), Berlin, Germany, where initial measurements were conducted. We also thank Prof. P. Tordo and Dr. O. Ouari (Aix-Marseille Universite, France) for providing the biradicals used in the DNP NMR experiments. Characterization measurements were conducted using the Central Facilities of the UCSB Materials Research Laboratory (MRL) that are supported by the MRSEC program of the U.S. National Science Foundation under award no. DMR-1121053. The MRL Central Facilities are a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). DNP NMR measurements were conducted at the Centre de RMN a Tres Hauts Champs at the Ecole Normale Superieure, Lyon, France, with technical support from Lenaic Leroux. Financial support for the DNP NMR studies is acknowledged from EQUIPEX contract ANR-10-EQPX-47-01 and ERC Advanced grant no. 320860. B.F.C. was a Professeur Invite at the ENS-Lyon during portions of 2012 and 2013., ANR-10-EQPX-0047,SENS,RMN de Surface Exalté par Polarisation Dynamique Nucléaire(2010), European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), University of California [Santa Barbara] (UC Santa Barbara), University of California (UC)-University of California (UC), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: IONS, Sucrose, C-13, Cations, Divalent, Surface Properties, Inorganic chemistry, TRICALCIUM SILICATE, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, law.invention, chemistry.chemical_compound, Colloid and Surface Chemistry, Adsorption, DYNAMIC-NUCLEAR-POLARIZATION, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, law, Molecule, Crystallization, Dissolution, Silicates, Water, Hydrogen Bonding, CORRELATION SPECTROSCOPY, General Chemistry, 021001 nanoscience & nanotechnology, Silicate, SOLID-STATE NMR, 0104 chemical sciences, chemistry, Heteronuclear molecule, Solid-state nuclear magnetic resonance, 13. Climate action, CROSS-POLARIZATION, Particle, Calcium, SI-29 MAS NMR, 0210 nano-technology, CRYSTAL-GROWTH, PORTLAND-CEMENT
Abstract: International audience; Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (similar to 0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (similar to 1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D Si-29{H-1}, C-13{H-1}, and P-31{H-1} heteronuclear correlation and 1D Si-29{C-13} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca2+ cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low-surface-area materials, notably for compositions that are industrially relevant.
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28. Predicting the DNP-SENS efficiency in reactive heterogeneous catalysts from hydrophilicity

Author: Anne Lesage, Lyndon Emsley, Andrei Gurinov, Walid Almaksoud, Jean-Marie Basset, Baptiste Scotto, Luigi Cavallo, Anissa Bendjeriou-Sedjerari, Zhen Cao, Edy Abou-Hamad, Jasmine Viger-Gravel, Manoja K. Samantaray, David Gajan, Eva Pump, KAUST Catalysis Center (KCC), King Abdullah University of Sciences & Technologie, Ecole Polytechnique Fédérale de Lausanne (EPFL), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), KAUST Core Lab, King Abdullah University of Science and Technology (KAUST), This work received support from the King Abdullah University of Science and Technology (KAUST) and the European Research Council (ERC Advanced Grant No. 320860)., European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, chemistry.chemical_element, Nanoparticle, Sorption, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Photochemistry, 01 natural sciences, Nitrogen, 0104 chemical sciences, Catalysis, Molecular level, chemistry, [CHIM]Chemical Sciences, Polarization (electrochemistry), Carbon
Abstract: We thank Dr Olivier Ouari and Paul Tordo of the University of Aix-Marseille for providing the TEKPol radical.; International audience; Identification of surfaces at the molecular level has benefited from progress in dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS). However, the technique is limited when using highly sensitive heterogeneous catalysts due to secondary reaction of surface organometallic fragments (SOMFs) with stable radical polarization agents. Here, we observe that in non-porous silica nanoparticles (NPs) (d(particle) = 15 nm) some DNP enhanced NMR or SENS characterizations are possible, depending on the metal-loading of the SOMF and the type of SOMF substituents (methyl, isobutyl, neopentyl). This unexpected observation suggests that aggregation of the nanoparticles occurs in non-polar solvents (such as ortho-dichlorobenzene) leading to (partial) protection of the SOMF inside the interparticle space, thereby preventing reaction with bulky polarization agents. We discover that the DNP SENS efficiency is correlated with the hydrophilicity of the SOMF/support, which depends on the carbon and SOMF concentration. Nitrogen sorption measurements to determine the BET constant (C-BET) were performed. This constant allows us to predict the aggregation of silica nanoparticles and consequently the efficiency of DNP SENS. Under optimal conditions, C-BET > 60, we found signal enhancement factors of up to 30.
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28 results on '"ERC Advanced Grant No. 320860"'

1. Cubic three-dimensional hybrid silica solids for nuclear hyperpolarization

2. Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR

3. Hyperpolarized long-lived nuclear spin states in monodeuterated methyl groups

4. Hammett Parameter in Microporous Solids as Macroligands for Heterogenized Photocatalysts

5. Frozen Acrylamide Gels as Dynamic Nuclear Polarization Matrices

6. Measuring Nano- to Microstructures from Relayed Dynamic Nuclear Polarization NMR

7. Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T

8. Solvent suppression in DNP enhanced solid state NMR

9. Amplifying Dynamic Nuclear Polarization of Frozen Solutions by Incorporating Dielectric Particles

10. Hydrophobic radicals embedded in neutral surfactants for dynamic nuclear polarization of aqueous environments at 9.4 Tesla

11. Silica-surface reorganization during organotin grafting evidenced by Sn-119 DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges

12. Dendritic polarizing agents for DNP SENS

13. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

14. Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks

15. Correlating synthetic methods, morphology, atomic-level structure, and catalytic activity of Sn-beta catalysts

16. Monolayer doping of silicon through grafting a tailored molecular phosphorus precursor onto cxide-passivated silicon surfaces

17. The structure and binding mode of citrate in the stabilization of gold nanoparticles

18. High-resolution NMR of hydrogen in organic solids by DNP enhanced natural abundance deuterium spectroscopy

19. Nanostructure of materials determined by relayed paramagnetic relaxation enhancement

20. Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations

21. Solid-State Dynamic Nuclear Polarization at 9.4 and 18.8 T from 100 K to Room Temperature

22. NMR signatures of the active sites in Sn-beta zeolite

23. Dynamic nuclear polarisation enhanced (14)N overtone MAS NMR spectroscopy

24. Unraveling the core-shell structure of ligand-capped Sn/SnOx nanoparticles by surface-enhanced nuclear magnetic resonance, Mössbauer, and X-ray absorption spectroscopies

25. Large molecular weight nitroxide biradicals providing efficient dynamic nuclear polarization at temperatures up to 200 K

26. Three-Dimensional Structure Determination of Surface Sites

27. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates

28. Predicting the DNP-SENS efficiency in reactive heterogeneous catalysts from hydrophilicity

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28 results on '"ERC Advanced Grant No. 320860"'

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