Author: "Danielle Laurencin" / Topic: chemistry - Searchworks@Jio Institute Digital Library Search Results

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1. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author: Gwenaëlle Rousse, François Weill, François Fauth, Montse Casas-Cabanas, Jon Serrano-Sevillano, Marie-Liesse Doublet, Romain Berthelot, Bernard Fraisse, Dany Carlier, Danielle Laurencin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), CIC ENERGIGUNE - Parque Tecnol Alava, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CELLS ALBA, Barcelona 08290, Spain, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ikerbasque - Basque Foundation for Science, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), The BL04-MSPD staff of CELLS-ALBA synchrotron is acknowledged for granting beamtime through InHouse quota (proposal 2020014011)., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Basque Foundation for Science (Ikerbasque)
Subjects: Diffraction, Chemistry, Sodium, Stacking, Honeycomb (geometry), Oxides, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemical physics, Cations, Potassium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Layers, 0210 nano-technology, Stacking fault
Abstract: International audience; The reaction between P2-type honeycomb layered oxides Na2Ni2TeO6 and K2Ni2TeO6 enables the formation of NaKNi2TeO6. The compound is characterized by X-ray diffraction and 23Na solid-state nuclear magnetic resonance spectroscopy, and the structure is discussed through density functional theory calculations. In addition to the honeycomb Ni/Te cationic ordering, NaKNi2TeO6 exhibits a unique example of alternation of sodium and potassium layers instead of a random alkali-mixed occupancy. Stacking fault simulations underline the impact of the successive position of the Ni/Te honeycomb layers and validate the presence of multiple stacking sequences within the powder material, in proportions that evolve with the synthesis conditions. In a broader context, this work contributes to a better understanding of the alkali-mixed layered compounds.
Published: 2021
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2. Looking into the dynamics of molecular crystals of ibuprofen and terephthalic acid using 17 O and 2 H nuclear magnetic resonance analyses

Author: Sébastien Mittelette, Chia-Hsin Chen, Thomas-Xavier Métro, Philippe Gaveau, Danielle Laurencin, Ivan Petit, Christel Gervais, Jessica Špačková, Bruno Alonso, Chuck Mullen, and Ieva Goldberga
Subjects: Oxygen-17, 010405 organic chemistry, Chemistry, Hydrogen bond, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, NMR spectra database, Molecular dynamics, Nuclear magnetic resonance, Deuterium, Solid-state nuclear magnetic resonance, Mechanochemistry, Proton NMR, General Materials Science
Abstract: Oxygen-17 and deuterium are two quadrupolar nuclei that are of interest for studying the structure and dynamics of materials by solid-state nuclear magnetic resonance (NMR). Here, 17 O and 2 H NMR analyses of crystalline ibuprofen and terephthalic acid are reported. First, improved 17 O-labelling protocols of these molecules are described using mechanochemistry. Then, dynamics occurring around the carboxylic groups of ibuprofen are studied considering variable temperature 17 O and 2 H NMR data, as well as computational modelling (including molecular dynamics simulations). More specifically, motions related to the concerted double proton jump and the 180° flip of the H-bonded (-COOH)2 unit in the crystal structure were looked into, and it was found that the merging of the C=O and C-OH 17 O resonances at high temperatures cannot be explained by the sole presence of one of these motions. Lastly, preliminary experiments were performed with a 2 H-17 O diplexer connected to the probe. Such configurations can allow, among others, 2 H and 17 O NMR spectra to be recorded at different temperatures without needing to tune or to change probe configurations. Overall, this work offers a few leads which could be of use in future studies of other materials using 17 O and 2 H NMR.
Published: 2021
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3. A 43 Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives

Author: Yang Li, Christel Gervais, Danielle Laurencin, Dinu Iuga, Melinda J. Duer, and Christian Bonhomme
Subjects: 010405 organic chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Spectral line, 0104 chemical sciences, NMR spectra database, chemistry.chemical_compound, Nuclear magnetic resonance, chemistry, Ab initio quantum chemistry methods, Adipate, Magic angle spinning, General Materials Science, Formate, Octacalcium phosphate, Spectroscopy
Abstract: 43 Ca nuclear magnetic resonance (NMR) spectroscopy has been extensively applied to the detailed study of octacalcium phosphate (OCP), Ca8 (HPO4 )2 (PO4 )4 .5H2 O, and hybrid derivatives involving intercalated metabolic acids (viz., citrate, succinate, formate, and adipate). Such phases are of importance in the development of a better understanding of bone structure. High-resolution 43 Ca magic angle spinning (MAS) experiments, including double-rotation (DOR) 43 Ca NMR, as well as 43 Ca{1 H} rotational echo DOR (REDOR) and 31 P{43 Ca} REAPDOR NMR spectra, were recorded on a 43 Ca-labeled OCP phase at very high magnetic field (20 T), and complemented by ab initio calculations of NMR parameters using the Gauge-Including Projector Augmented Wave-density functional theory (GIPAW-DFT) method. This enabled a partial assignment of the eight inequivalent Ca2+ sites of OCP. Natural-abundance 43 Ca MAS NMR spectra were then recorded for the hybrid organic-inorganic derivatives, revealing changes in the 43 Ca lineshape. In the case of the citrate derivative, these could be interpreted on the basis of computational models of the structure. Overall, this study highlights the advantages of combining high-resolution 43 Ca NMR experiments and computational modeling for studying complex hybrid biomaterials.
Published: 2021
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4. Advances in the synthesis and structure of α-canaphite: a multitool and multiscale study

Author: Florence Porcher, Jérémy Soulié, Cédric Charvillat, Danielle Laurencin, Christèle Combes, Mark E. Smith, Christian Rey, Erik Elkaim, Christel Gervais, Nicholai Daugaard Jensen, Laëtitia Mayen, Pierre Gras, Christian Bonhomme, Maximilien Desbord, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Southampton, Lancaster University, University of Warwick [Coventry], Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), ANR-16-CE19-0013,PyVerres,Développement de nouveaux verres à base de pyrophosphates élaborés par chimie douce pour des applications en régénération osseuse(2016), Commissariat à l'Energie Atomique et aux énergies alternatives - CEA (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), Collège de France (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Synchrotron SOLEIL - SSOLEIL (FRANCE), Sorbonne Université (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), University of Warwick (UNITED KINGDOM), Lancaster University (UNITED KINGDOM), University of Southampton (UNITED KINGDOM), Université de Montpellier (FRANCE), Laboratoire Léon Brillouin - LLB (Gif-sur-Yvette, France), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Université Fédérale Toulouse Midi-Pyrénées, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2), Matériaux, ingénierie et science [Villeurbanne] (MATEIS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Signal, models, algorithms (SIGMA2), Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Université de Rennes (UNIV-RENNES)-INRIA Rennes, Institut National de Recherche en Informatique et en Automatique (Inria), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique et Technologie (LMT), and École normale supérieure - Cachan (ENS Cachan)-Centre National de la Recherche Scientifique (CNRS)
Subjects: α-canaphite, Materials science, Matériaux, Neutron diffraction, 02 engineering and technology, 010402 general chemistry, Calcium pyrophosphates, DFT, 01 natural sciences, Pyrophosphate, Synthesis, chemistry.chemical_compound, symbols.namesake, Canaphite, Synchrotron X-ray and neutron diffraction, [CHIM]Chemical Sciences, Molecule, General Materials Science, ComputingMilieux_MISCELLANEOUS, Tetrahydrate, Hydrogen bond, dehydration, Structure refinement, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, NMR, 0104 chemical sciences, Characterization (materials science), chemistry, Solid-state nuclear magnetic resonance, Tétrahydrate de pyrophosphate, symbols, Physical chemistry, 0210 nano-technology, Raman spectroscopy
Abstract: α-Canaphite (CaNa2P2O7·4H2O) is a layered calcium disodium pyrophosphate tetrahydrate phase of significant geological and potential biological interest. This study overcomes the lack of a reliable protocol to synthesize pure α-canaphite by using a novel simple and reproducible approach of double decomposition in solution at room temperature. The pure α-canaphite is then characterized from the atomic to the macroscopic level using a multitool and multiscale advanced characterization strategy, providing for the first time full resolution of the α-canaphite monoclinic structure, including the hydrogen bonding network. Synchrotron X-ray diffraction and neutron diffraction are combined with multinuclear solid state NMR experimental data and computational modeling via DFT/GIPAW calculations. Among the main characteristics of the α-canaphite structure are some strong hydrogen bonds and one of the four water molecules showing a different coordination scheme. This peculiar water molecule could be the last to leave the collapsed structure on heating, leading eventually to anhydrous α-CaNa2P2O7 and could also be involved in the internal hydrolysis of pyrophosphate ions as it is the closest water molecule to the pyrophosphate ions. Relating such detailed structural data on α-canaphite to its physico-chemical properties is of major interest considering the possible roles of canaphite for biomedical applications. The vibrational spectra of α-canaphite (deuterated or not) are analyzed and Raman spectroscopy appears to be a promising tool for the identification/diagnosis of such microcrystals in vitro, in vivo or ex vivo.
Published: 2020
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5. From operando Raman mechanochemistry to 'NMR crystallography': understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling

Author: Zhehong Gan, Thomas-Xavier Métro, Danielle Laurencin, César Leroy, Ivan Hung, and Christel Gervais
Subjects: Oxygen-17, Materials science, Ion, symbols.namesake, chemistry.chemical_compound, Crystallography, chemistry, Deuterium, Labelling, Mechanochemistry, symbols, Reactivity (chemistry), Raman spectroscopy, Benzene
Abstract: The description of the formation, structure and reactivity of coordination networks and MOFs remains a real challenge in a number of cases. This is notably true for compounds composed of Zn2+ ions and terephthalate ligands (benzene 1,4-dicarboxylate, BDC), because of the difficulties in isolating them as pure phases and/or because of the presence of structural defects. Here, using mechanochemistry in combination with operando Raman spectroscopy, the observation of the formation of various zinc-terephthalate compounds was rendered possible, allowing the distinction and isolation of three intermediates during the ball-milling synthesis of Zn3(OH)4(BDC). An “NMR crystallography” approach was then used, combining solid-state NMR (1H, 13C and 17O) and DFT calculations, in order to refine the poorly described crystallographic structures of these phases. Particularly noteworthy are the high-resolution 17O NMR analyses, which were made possible in a highly efficient and cost-effective way, thanks to the selective 17O-enrichment of either hydroxyl or terephthalate groups by ball-milling. This allowed the presence of defect sites to be identified for the first time in one of the phases, and the nature of the H-bonding network of the hydroxyls to be established in another. Lastly, the possibility of using deuterated precursors (e.g. D2O and d4-BDC) during ball-milling is also introduced, as a means for observing specific transformations during operando Raman spectroscopy studies, that would not have been possible with hydrogenated equivalents. Overall, the synthetic and spectroscopic approaches developed herein are expected to push forward the understanding of the structure and reactivity of other complex coordination networks and MOFs.
Published: 2021
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6. Labeling and probing the silica surface using mechanochemistry and 17O NMR spectroscopy

Author: Philippe Gaveau, Dinu Iuga, Emilie Thomassot, Julien Trébosc, Danielle Laurencin, Mark E. Smith, Nicolas Fabregue, Frederic Mentink-Vigier, Ieva Goldberga, Thomas-Xavier Métro, Kuizhi Chen, Zhehong Gan, Chia-Hsin Chen, Bruno Alonso, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), National High Magnetic Field Laboratory (NHMFL), Florida State University [Tallahassee] (FSU), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Centre de Recherches Pétrographiques et Géochimiques (CRPG), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), University of Warwick [Coventry], University of Southampton, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: Analytical chemistry, Hot Paper, surface chemistry, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Catalysis, Isotopic labeling, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Mechanochemistry, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, Reactivity (chemistry), O-17, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Fumed silica, Full Paper, 17O, Organic Chemistry, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Full Papers, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, solid state NMR spectroscopy, Solid-state nuclear magnetic resonance, chemistry, silica, Siloxane, mechanochemistry, 0210 nano-technology
Abstract: In recent years, there has been increasing interest in developing cost‐efficient, fast, and user‐friendly 17O enrichment protocols to help to understand the structure and reactivity of materials by using 17O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High‐precision 17O compositions were measured at different milling times by using large‐geometry secondary‐ion mass spectrometry (LG‐SIMS). High‐resolution 17O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct 17O polarization and indirect 17O{1H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D 1H−17O D‐HMQC correlations. Finally, the surface‐labeled silica was reacted with titania and using 17O DNP, their common interface was probed and Si−O−Ti bonds identified., A fast, user‐friendly17O enrichment approach by ball milling was developed to selectively enrich the surface of fumed silica. A variety of high‐resolution solid‐state 17O NMR experiments (ultra‐high magnetic field (35.2 T), 17O MQMAS, 2D 17O−1H D‐HMQC, 17O DNP), demonstrate that siloxane and different silanol bonds present at the surface, including H‐bonded and isolated silanols, can be labeled and characterized in detail.
Published: 2021
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7. Cost-efficient and user-friendly

Author: Jessica, Špačková, Charlyn, Fabra, Guillaume, Cazals, Marie, Hubert-Roux, Isabelle, Schmitz-Afonso, Ieva, Goldberga, Dorothée, Berthomieu, Aurélien, Lebrun, Thomas-Xavier, Métro, and Danielle, Laurencin
Subjects: Chemistry, Isotope Labeling, Costs and Cost Analysis, Oxygen Isotopes, Mechanical Phenomena
Abstract: Two mechanochemical procedures for 17O/18O-isotope labeling of fatty acids are reported: a carboxylic acid activation/hydrolysis approach and a saponification approach. The latter route allowed first-time enrichment of important polyunsaturated fatty acids (PUFAs) including docosahexaenoic acid (DHA). Overall, a total of 9 pure labeled products were isolated in high yields (≥80%) and with high enrichment levels (≥37% average labeling of C=O and C-OH carboxylic oxygen atoms), under mild conditions, and in short time (, Two mechanochemical procedures for 17O/18O-isotope labeling of fatty acids are reported: a carboxylic acid activation/hydrolysis approach and a saponification approach.
Published: 2021

8. Cost-efficient and user-friendly 17 O/ 18 O labeling procedures of fatty acids using mechanochemistry

Author: Charlyn Fabra, Aurélien Lebrun, Marie Hubert-Roux, Isabelle Schmitz-Afonso, Dorothée Berthomieu, Jessica Špačková, Danielle Laurencin, Thomas-Xavier Métro, Guillaume Cazals, Ieva Goldberga, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS), Université de Montpellier (UM), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)
Subjects: Carboxylic acid, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Hydrolysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Mechanochemistry, Materials Chemistry, Organic chemistry, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Oxygen atom, Docosahexaenoic acid, Ceramics and Composites, 0210 nano-technology, Saponification, Polyunsaturated fatty acid
Abstract: Two mechanochemical procedures for 17O/18O-isotope labeling of fatty acids are reported: a carboxylic acid activation/hydrolysis approach and a saponification approach. The latter route allowed first-time enrichment of important polyunsaturated fatty acids (PUFAs) including docosahexaenoic acid (DHA). Overall, a total of 9 pure labeled products were isolated in high yields (≥80%) and with high enrichment levels (≥37% average labeling of C=O and C-OH carboxylic oxygen atoms), under mild conditions, and in short time (
Published: 2021
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9. Long-term in vivo performances of polylactide/iron oxide nanoparticles core–shell fibrous nanocomposites as MRI-visible magneto-scaffolds

Author: Florence Bernex, Saad Sene, Danielle Laurencin, Yannick Guari, Laurent Lemaire, Hussein Awada, Benjamin Nottelet, Florence Franconi, Xavier Garric, Audrey Bethry, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Micro et Nanomédecines Translationnelles (MINT), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plate-forme de Recherche en Imagerie et Spectroscopie Multi-modales (PRISM [SFR ICAT - UA]), SFR UA 4208 Interactions Cellulaires et Applications Thérapeutiques (ICAT), Université d'Angers (UA)-Université d'Angers (UA), Institut de Recherche en Cancérologie de Montpellier (IRCM - U1194 Inserm - UM), and CRLCC Val d'Aurelle - Paul Lamarque-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM)
Subjects: Materials science, Biocompatibility, Biomedical Engineering, Nanotechnology, 02 engineering and technology, hybrid biomaterial, histology, 03 medical and health sciences, chemistry.chemical_compound, In vivo, General Materials Science, implantation, poly(lactide) nanofibers, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Magneto, 030304 developmental biology, 0303 health sciences, Lactide, Nanocomposite, iron oxide nanoparticles, 021001 nanoscience & nanotechnology, equipment and supplies, Electrospinning, in vivo, medical resonance imaging (MRI), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Nanofiber, 0210 nano-technology, Iron oxide nanoparticles
Abstract: International audience; There is a growing interest in magnetic nanocomposites in biomaterials science. In particular, nanocomposites that combine poly(lactide) (PLA) nanofibers and superparamagnetic iron oxide nanoparticles (SPIONs), which can be obtained by either electrospinning of a SPION suspension in PLA or by precipitating SPIONs at the surface of PLA, are well documented in the literature. However, these two classical processes yield nanocomposites with altered materials properties, and their long-term in vivo fate and performances have in most cases only been evaluated over short periods of time. Recently, we reported a new strategy to prepare well-defined PLA@SPION nanofibers with a quasi-monolayer of SPIONs anchored at the surface of PLA electrospun fibers. Herein, we report on a 6-month in vivo rat implantation study with the aim of evaluating the long-term magnetic resonance imaging (MRI) properties of this new class of magnetic nanocomposites, as well as their tissue integration and degradation. Using clinically relevant T2-weighted MRI conditions, we show that the PLA@SPION nanocomposites are clearly visible up to 6 months. We also evaluate here by histological analyses the slow degradation of the PLA@SPIONs, as well as their biocompatibility. Overall, these results make these nanocomposites attractive for the development of magnetic biomaterials for biomedical applications.
Published: 2021
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10. Unveiling the Structure and Reactivity of Fatty-Acid Based (Nano)materials Thanks to Efficient and Scalable 17O and 18O-Isotopic Labeling Schemes

Author: Kuizhi Chen, Dorothée Berthomieu, Thomas-Xavier Métro, Zhehong Gan, Danielle Laurencin, Guillaume Cazals, Saad Sene, Sébastien Mittelette, Chia-Hsin Chen, Jessica Špačková, Aurélien Lebrun, Christel Gervais, Emeline Gaillard, Charlyn Fabra, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), National High Magnetic Field Laboratory (NHMFL), Florida State University [Tallahassee] (FSU), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), National Science Foundation Cooperative Agreement No. DMR-1644779, HPC resources from GENCI-IDRIS (Grant 097535), National Science Foundation (DMR-1039938 and DMR-0603042), National Institute of Health P41 GM122698, European Project: 772204,MISOTOP, and Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM)
Subjects: Magnetic Resonance Spectroscopy, Infrared spectroscopy, Context (language use), 02 engineering and technology, Oxygen Isotopes, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, Catalysis, Isotopic labeling, chemistry.chemical_compound, Colloid and Surface Chemistry, Molecule, Reactivity (chemistry), chemistry.chemical_classification, Fatty acid, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Nanostructures, 0104 chemical sciences, Oleic acid, Solid-state nuclear magnetic resonance, chemistry, Isotope Labeling, 0210 nano-technology, Stearic Acids, Oleic Acid
Abstract: International audience; Fatty acids are ubiquitous in biological systems and widely used in materials science, including for the formulation of drugs and the surface-functionalization of nanoparticles. However, important questions regarding the structure and reactivity of these molecules are still to be elucidated, including their mode of binding to certain metal cations or materials surfaces. In this context, we have developed novel, efficient, user-friendly, and cost-effective synthetic protocols based on ball-milling, for the 17O and 18O isotopic labeling of two key fatty acids which are widely used in (nano)materials science, namely stearic and oleic acid. Labeled molecules were analyzed by 1H and 13C solution NMR, IR spectroscopy, and mass spectrometry (ESI-TOF and LC-MS), as well as 17O solid state NMR (for the 17O labeled species). In both cases, the labeling procedures were scaled-up to produce up to gram quantities of 17O- or 18O-enriched molecules in just half-a-day, with very good synthetic yields (all ≥84%) and enrichment levels (up to an average of 46% per carboxylic oxygen). The 17O-labeled oleic acid was then used for the synthesis of a metal soap (Zn-oleate) and the surface-functionalization of ZnO nanoparticles (NPs), which were characterized for the first time by high-resolution 17O NMR (at 14.1 and 35.2 T). This allowed very detailed insight into (i) the coordination mode of the oleate ligand in Zn-oleate to be achieved (including information on Zn···O distances) and (ii) the mode of attachment of oleic-acid at the surface of ZnO (including novel information on its photoreactivity upon UV-irradiation). Overall, this work demonstrates the high interest of these fatty acid-enrichment protocols for understanding the structure and reactivity of a variety of functional (nano)materials systems using high resolution analyses like 17O NMR.
Published: 2020
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11. Direct 17 O-isotopic labeling of oxides using mechanochemistry

Author: Danielle Laurencin, Thomas-Xavier Métro, Emeline Gaillard, Philippe Gaveau, Christian Bonhomme, Bertrand Rebiere, Mark E. Smith, Frederic Mentink-Vigier, Pierre Florian, Kuizhi Chen, Chia-Hsin Chen, Zhehong Gan, Romain Berthelot, Bruno Alonso, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), National High Magnetic Field Laboratory (NHMFL), Florida State University [Tallahassee] (FSU), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Southampton (University of Southampton), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Southampton, Lancaster University, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), ERC, European Project: 772204,MISOTOP, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: enrichment, ball-milling, Oxide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Isotopic labeling, chemistry.chemical_compound, Computational chemistry, Mechanochemistry, Reactivity (chemistry), Physical and Theoretical Chemistry, Polarization (electrochemistry), isotopic labeling, Oxygen-17, 010405 organic chemistry, Chemistry, Analytical technique, [CHIM.MATE]Chemical Sciences/Material chemistry, NMR, 0104 chemical sciences, Solid-state nuclear magnetic resonance, DNP, mechanochemistry
Abstract: While oxygen-17 NMR is increasingly being used for elucidating the structure and reactivity of complex molecular and materials systems, much effort is still required for it to become a routine analytical technique. One of the main difficulties for its development comes from the very low natural abundance of oxygen-17, which implies that isotopic labeling is generally needed prior to NMR analyses. However, 17O-enrichment protocols are often unattractive in terms of cost, safety, and/or practicality, even for compounds as simple as metal oxides. Here, we demonstrate how mechanochemistry can be used in a highly efficient way for the direct 17O-isotopic labeling of a variety of s-, p- and d-block oxides which are of major interest for the preparation of functional ceramics and glasses: Li2O, CaO, Al2O3, SiO2, TiO2, and ZrO2. For each oxide, the enrichment step was performed under ambient conditions in less than 1 hour and at low cost, which makes these synthetic approaches highly appealing in comparison to the existing literature. Using high-resolution 17O solid state NMR and Dynamic Nuclear Polarization, atomic-level insight into the enrichment process is achieved, especially for titania and alumina. Indeed, it was possible to demonstrate that enriched oxygen sites are present not only at the surface, but also within the oxide particles. Moreover, information on the actual reactions occurring during the milling step could be obtained by 17O NMR, both in terms of their kinetics and the nature of the reactive species. Finally, it was demonstrated how high resolution 17O NMR can be used for studying the reactivity at the interfaces between different oxide particles during ball-milling, especially in cases when X-ray diffraction techniques are uninformative. More generally, such investigations will be useful not only for producing 17O-enriched precursors efficiently, but also for understanding better mechanisms of mechanochemical processes themselves.; While oxygen-17 NMR is increasingly being used for elucidating the structure and reactivity of complex molecular and materials systems, much effort is still required for it to become a routine analytical technique. One of the main difficulties for its development comes from the very low natural abundance of oxygen-17, which implies that isotopic labeling is generally needed prior to NMR analyses. However, 17O-enrichment protocols are often unattractive in terms of cost, safety, and/or practicality, even for compounds as simple as metal oxides. Here, we demonstrate how mechanochemistry can be used in a highly efficient way for the direct 17O-isotopic labeling of a variety of s-, p- and d-block oxides which are of major interest for the preparation of functional ceramics and glasses: Li2O, CaO, Al2O3, SiO2, TiO2, and ZrO2. For each oxide, the enrichment step was performed under ambient conditions in less than 1 hour and at low cost, which makes these synthetic approaches highly appealing in comparison to the existing literature. Using high-resolution 17O solid state NMR and Dynamic Nuclear Polarization, atomic-level insight into the enrichment process is achieved, especially for titania and alumina. Indeed, it was possible to demonstrate that enriched oxygen sites are present not only at the surface, but also within the oxide particles. Moreover, information on the actual reactions occurring during the milling step could be obtained by 17O NMR, both in terms of their kinetics and the nature of the reactive species. Finally, it was demonstrated how high resolution 17O NMR can be used for studying the reactivity at the interfaces between different oxide particles during ball-milling, especially in cases when X-ray diffraction techniques are uninformative. More generally, such investigations will be useful not only for producing 17O-enriched precursors efficiently, but also for understanding better mechanisms of mechanochemical processes themselves.
Published: 2020
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12. Recent directions in the solid-state NMR study of synthetic and natural calcium phosphates

Author: Christian Bonhomme, Danielle Laurencin, Christel Gervais, Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Calcium Phosphates, Mineralized tissues, Biological Products, Nuclear and High Energy Physics, Magnetic Resonance Spectroscopy, Radiation, 010405 organic chemistry, Chemistry, chemistry.chemical_element, Biomaterial, High resolution, Nanotechnology, General Chemistry, Calcium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Characterization (materials science), Solid-state nuclear magnetic resonance, [CHIM]Chemical Sciences, Bone regeneration, Instrumentation
Abstract: International audience; Materials containing a calcium phosphate component have been the subject of much interest to NMR spectroscopists, especially in view of understanding the structure and properties of mineralized tissues like bone and teeth, and of developing synthetic biomaterials for bone regeneration. Here, we present a selection of recent developments in their structural characterization using advanced solid state NMR experiments, highlighting the level of insight which can now be accessed.
Published: 2020
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13. Molecular complexes and main-chain organometallic polymers based on Janus bis(carbenes) fused to metalloporphyrins

Author: Jean-François Longevial, Aurélien Lebrun, Danielle Laurencin, Sébastien Richeter, Sébastien Clément, Mamadou Lo, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Ligand, Singlet oxygen, chemistry.chemical_element, Zinc, Polymer, 010402 general chemistry, 01 natural sciences, Porphyrin, Chloride, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, medicine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Janus, Carbene, medicine.drug
Abstract: Janus bis(N-heterocyclic carbenes) composed of a porphyrin core with two N-heterocyclic carbene (NHC) heads fused to opposite pyrroles were used as bridging ligands for the preparation of metal complexes. We first focused our attention on the synthesis of gold(i) chloride complexes [(NHC)AuCl] and investigated the substitution of the chloride ligand by acetylides to obtain the corresponding [(NHC)AuC[triple bond, length as m-dash]CR] complexes. Polyacetylides were then used to obtain molecular multiporphyrinic systems with porphyrins fused to only one NHC ligand, while main-chain organometallic polymers (MCOPs) were obtained when using Janus porphyrin bis(NHCs). Interestingly, MCOPs incorporating zinc(ii) porphyrins proved to be efficient as heterogeneous photocatalysts for the generation of singlet oxygen upon visible light irradiation.
Published: 2020
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14. A soft-chemistry approach to the synthesis of amorphous calcium ortho/pyrophosphate biomaterials of tunable composition

Author: Christian Rey, Christian Bonhomme, Danielle Laurencin, Julien Trébosc, Mark E. Smith, Guillaume Laurent, Laëtitia Mayen, Olivier Marsan, Christèle Combes, Kuizhi Chen, Zhehong Gan, Jérémy Soulié, C. Coelho, Christel Gervais, Nicholai Daugaard Jensen, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [Lancaster], Lancaster University, Institut des matériaux de Paris-Centre (IMPC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, National High Magnetic Field Laboratory (NHMFL), Florida State University [Tallahassee] (FSU), EPSRC and BBSRC (contract reference PR140003), Birmingham Science City Advanced Materials Project 1 and 2, supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF), National Science Foundation Cooperative Agreement No. DMR-1157490 & DMR-1644779, and the State of Florida, French Région Ile de France - SESAME, ANR-16-CE19-0013,PyVerres,Développement de nouveaux verres à base de pyrophosphates élaborés par chimie douce pour des applications en régénération osseuse(2016), Centre National de la Recherche Scientifique - CNRS (FRANCE), Collège de France (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Florida State University - FSU (USA), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Sorbonne Université (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Ecole Centrale de Lille (FRANCE), Lancaster University (UNITED KINGDOM), Université d'Artois (FRANCE), Université de Lille (FRANCE), Université de Montpellier (FRANCE), Unité de Catalyse et de Chimie du Solide - UCCS (Villeneuve d'Ascq, France), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Magnetic Resonance Spectroscopy, Sodium, Matériaux, 0206 medical engineering, Biomedical Engineering, Ionic bonding, chemistry.chemical_element, Biocompatible Materials, Context (language use), 02 engineering and technology, Calcium Pyrophosphate, Spectrum Analysis, Raman, Biochemistry, Pyrophosphate, Article, Soft chemistry, Biomaterials, chemistry.chemical_compound, Amorphous materials, X-Ray Diffraction, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Molecular Biology, Temperature, Phosphorus, General Medicine, Chemistry, Inorganic, 021001 nanoscience & nanotechnology, Phosphate, 020601 biomedical engineering, Amorphous solid, Characterization (materials science), Chemical engineering, chemistry, Thermogravimetry, Mixed calcium ortho/pyrophosphate, 0210 nano-technology, Biotechnology
Abstract: The development of amorphous phosphate-based materials is of major interest in the field of biomaterials science, and especially for bone substitution applications. In this context, we herein report the synthesis of gel-derived hydrated amorphous calcium/sodium ortho/pyrophosphate materials at ambient temperature and in water. For the first time, such materials have been obtained in a large range of tunable orthophosphate/pyrophosphate molar ratios. Multi-scale characterization was carried out thanks to various techniques, including advanced multinuclear solid state NMR. It allowed the quantification of each ionic/molecular species leading to a general formula for these materials: [(Ca2+y Na+z H+3+x-2y-z)(PO43−)1-x(P2O74−)x](H2O)u. Beyond this formula, the analyses suggest that these amorphous solids are formed by the aggregation of colloids and that surface water and sodium could play a role in the cohesion of the whole material. Although the full comprehension of mechanisms of formation and structure is still to be investigated in detail, the straightforward synthesis of these new amorphous materials opens up many perspectives in the field of materials for bone substitution and regeneration. Statement of significance The metastability of amorphous phosphate-based materials with various chain length often improves their (bio)chemical reactivity. However, the control of the ratio of the different phosphate entities has not been yet described especially for small ions (pyrophosphate/orthophosphate) and using soft chemistry, whereas it opens the way for the tuning of enzyme- and/or pH-driven degradation and biological properties. Our study focuses on elaboration of amorphous gel-derived hydrated calcium/sodium ortho/pyrophosphate solids at 70 °C with a large range of orthophosphate/pyrophosphate ratios. Multi-scale characterization was carried out using various techniques such as advanced multinuclear SSNMR (31P, 23Na, 1H, 43Ca). Analyses suggest that these solids are formed by colloids aggregation and that the location of mobile water and sodium could play a role in the material cohesion.
Published: 2020
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15. Gemcitabine Delivery and Photodynamic Therapy in Cancer Cells via Porphyrin-Ethylene-Based Periodic Mesoporous Organosilica Nanoparticles

Author: Jean-Olivier Durand, Sébastien Richeter, Marie Maynadier, Jonas G. Croissant, Laure Lichon, Makhlouf Boufatit, Marcel Garcia, Laurence Raehm, Chiara Mauriello Jimenez, Danielle Laurencin, Dina Aggad, Soraya Dib, Shahad Alsaiari, Magali Gary-Bobo, and Niveen M. Khashab
Subjects: Materials science, Membrane permeability, medicine.medical_treatment, Energy Engineering and Power Technology, Nanotechnology, Photodynamic therapy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Gemcitabine Hydrochloride, Biomaterials, chemistry.chemical_compound, Materials Chemistry, medicine, Photosensitizer, Renewable Energy, Sustainability and the Environment, 021001 nanoscience & nanotechnology, Porphyrin, Gemcitabine, 0104 chemical sciences, Mesoporous organosilica, chemistry, Cancer cell, Cancer research, 0210 nano-technology, medicine.drug
Abstract: Gemcitabine hydrochloride is an FDA-approved chemotherapeutic drug used in the treatment of various cancers. Several drawbacks of gemcitabine including its short in vivo half-life of 8-17 min associated with a rapid excretion by the kidneys and its poor membrane permeability have inspired research on a nanodelivery approach. In this study, we report ethylene-based periodic mesoporous organosilica nanoparticles (PMOs) for photodynamic therapy and the autonomous delivery of gemcitabine in cancer cells. Porphyrins were used as photosensitizers and were localized in the walls of the PMOs while a high loading capacity of gemcitabine was observed in the porous structure. Depending on the nature of the photosensitizer, and its aggregation state, we were able to perform one or two-photon photodynamic therapy. Two-photon excited photodynamic therapy combined with gemcitabine delivery led to a synergy and a very efficient cancer cell killing.
Published: 2017
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16. Synthesis, characterization and modeling of self-assembled porphyrin nanorods

Author: Christel Gervais, Danielle Laurencin, Didier Cot, Sébastien Richeter, Yannick Guari, Sébastien Clément, Matthieu Paillet, Pascal G. Yot, Erik Elkaim, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)
Subjects: NMR crystallography, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, DFT modeling Tel : ++(33)467143971, Spectroscopy, solid state NMR, Tetraphenylborate, Chemistry, NMR cristallography, General Chemistry, self-assembly, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Porphyrin, Synchrotron, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, Nanorod, Self-assembly, 0210 nano-technology, nanorods, DFT modeling, porphyrin, Powder diffraction
Abstract: Porphyrin nanorods were prepared by ion-association between free-base meso 5,10,15,20-tetrakis-(4-[Formula: see text]-methylpyridinium)porphyrin cations and tetraphenylborate anions. The nanorods have variable lengths (up to a few micrometers long) and diameters ([Formula: see text]50–500 nm). Their structure at the molecular level was elucidated by combining multinuclear solid state NMR spectroscopy, synchrotron X-ray powder diffraction and DFT calculations.
Published: 2019
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17. Bis-benzoxaboroles: Design, Synthesis, and Biological Evaluation as Carbonic Anhydrase Inhibitors

Author: Michael Smietana, Jean-Jacques Vasseur, Danielle Laurencin, Adèle Larcher, Claudiu T. Supuran, Jean-Yves Winum, Arie van der Lee, Alessio Nocentini, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), NEUROFARBA Department [Firenze, Italy], Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)
Subjects: Gene isoform, Benzoxaborole, biology, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Imine, carbonic anhydrase, multivalency, 01 natural sciences, Biochemistry, Transmembrane protein, 0104 chemical sciences, 010404 medicinal & biomolecular chemistry, Cytosol, chemistry.chemical_compound, Carbonic anhydrase, Reagent, Amide, Drug Discovery, biology.protein, [CHIM]Chemical Sciences, enzyme inhibition, Biological evaluation
Abstract: International audience; The synthesis, characterization, and biological evaluation of a series of compounds incorporating two or three benzoxaborole moieties is reported. Three different synthetic strategies were used to explore within this series as much chemical space as possible, all starting from the 6-aminobenzoxaborole reagent: amide coupling, imine bond formation, and squarate coupling. Eleven new compounds were isolated in pure form, and single crystals were obtained for two of them. These compounds were then evaluated as carbonic anhydrase inhibitors against the cytosolic hCA I and II and the transmembrane hCA IV, IX, and XII isoforms. While the benzoxaborole scaffold has been recently introduced as a new chemotype for carbonic anhydrase inhibition, these new multivalent derivatives exhibited superior inhibitory activity against the tumor-associated isoform hCA IX. In particular, compared to monovalent 6-aminobenzoxaborole (K-I = 813 nM) and 6-carboxybenzoxaborole (K-I = 400 nM), derivative 2h characterized by a glutamic acid structural core and two benzoxaborole moieties was found to be more potent (K-I = 64 nM) and more selective over human hCA II.
Published: 2019
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18. Controlled Anchoring of Iron Oxide Nanoparticles on Polymeric Nanofibers: Easy Access to Core@Shell Organic-Inorganic Nanocomposites for Magneto-Scaffolds

Author: Benjamin Nottelet, Assala Al Samad, Xavier Dumail, Ryan J. Gilbert, Audrey Bethry, Florence Franconi, Laurent Lemaire, Rebecca D. Pomrenke, Ayman El Jundi, Christopher Johnson, Yannick Guari, Hussein Awada, Danielle Laurencin, Gautier Félix, Joulia Larionova, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Micro et Nanomédecines Translationnelles (MINT), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plate-forme de Recherche en Imagerie et Spectroscopie Multi-modales (PRISM [SFR ICAT - UA]), SFR UA 4208 Interactions Cellulaires et Applications Thérapeutiques (ICAT), Université d'Angers (UA)-Université d'Angers (UA), Department of Pharmaceutics and Biopharmaceutics, and School of Pharmaceutical Sciences, University of Geneva, University of Lausanne
Subjects: chemistry.chemical_classification, Nanocomposite, Materials science, Scanning electron microscope, Nanotechnology, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, law, Transmission electron microscopy, Nanofiber, Monolayer, General Materials Science, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron microscope, 0210 nano-technology, Iron oxide nanoparticles, ComputingMilieux_MISCELLANEOUS
Abstract: Composites combining superparamagnetic iron oxide nanoparticles (SPIONs) and polymers are largely present in modern (bio)materials. However, although SPIONs embedded in polymer matrices are classically reported, the mechanical and degradation properties of the polymer scaffold are impacted by the SPIONs. Therefore, the controlled anchoring of SPIONs onto polymer surfaces is still a major challenge. Herein, we propose an efficient strategy for the direct and uniform anchoring of SPIONs on the surface of functionalized-polylactide (PLA) nanofibers via a simple free ligand exchange procedure to design PLA@SPIONs core@shell nanocomposites. The resulting PLA@SPIONs hybrid biomaterials are characterized by electron microscopy (scanning electron microscopy and transmission electron microscopy) and energy-dispersive X-ray spectroscopy analysis to probe the morphology and detect elements present at the organic-inorganic interface, respectively. A monolayer of SPIONs with a complete and homogeneous coverage is observed on the surface of PLA nanofibers. Magnetization experiments show that magnetic properties of the nanoparticles are well preserved after their grafting on the PLA fibers and that the size of the nanoparticles does not change. The absence of cytotoxicity, combined with a high sensitivity of detection in magnetic resonance imaging both in vitro and in vivo, makes these hybrid nanocomposites attractive for the development of magnetic biomaterials for biomedical applications.
Published: 2019
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19. 87Sr,119Sn,127I Single and {1H/19F}-Double Resonance Solid-State NMR Experiments: Application to Inorganic Materials and Nanobuilding Blocks

Author: Christel Gervais, Lionel Campayo, Christian Bonhomme, Danielle Laurencin, François Ribot, Mark E. Smith, Adrian J. Wright, Guillaume Renaudin, Jean-Marie Nedelec, John V. Hanna, Dinu Iuga, Annabelle R. Baker, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), School of Chemistry University of Birmingham, University of Birmingham [Birmingham], Laboratoire d'études de Matériaux Céramiques pour le Conditionnement (LM2C), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), University of Warwick [Coventry], Lancaster University, Institut de Chimie de Clermont-Ferrand (ICCF), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PICS QMAT, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-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 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), and Solid State NMR Group, University of Warwick
Subjects: GIPAW, wideline NMR, Iodide, Inorganic chemistry, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, WURST, 010402 general chemistry, 01 natural sciences, QD, Vanadate, QC, solid state NMR, chemistry.chemical_classification, Resonance, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Characterization (materials science), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Solid-state nuclear magnetic resonance, 0210 nano-technology, Tin, Hybrid material
Abstract: International audience; 87Sr, 127I and 119Sn wideline NMR spectroscopy was successfully applied to inorganic and hybrid materials: (i) Sr derivatives of medicinal interest (Sr-malonate, Sr-pyrophosphates, mixed Ca,Sr-fluoroapatites); (ii) apatitic structures acting as host matrices for iodine; and (iii) Sn-derived oxo-clusters which can be used as inorganic nanobuilding blocks. The BRAIN (BRoadband Adiabatic INversion) CP (Cross Polarization) approach (by Schurko et al.) was applied to a non integer quadrupolar nucleus (87Sr, I=9/2). The sequence was used in combination with WURST (Wideband Uniform-Rate Smooth-Truncation) QCPMG (Quadrupolar Carr-Purcell Meiboom-Gill) for optimal sensitivity. We showed that 127I WURST QCPMG experiments were sufficiently sensitive to allow rapid characterization of the incorporation of iodide (I−) anions in lead vanadate/phosphate apatites, and that 127I acted as a sensitive probe for the description of local disorder. 1H/19F → 119Sn BRAIN CP was successfully applied to the detailed characterization of tin oxo-clusters, using 1H and 19F as spin baths. We demonstrated that BRAIN CP can be effectively used as a tool of spectral editing leading to the estimation of spatial proximities between 119Sn and 1H/19F nuclei.
Published: 2016
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20. New Layered Polythiophene-Silica Composite Through the Self-Assembly and Polymerization of Thiophene-Based Silylated Molecular Precursors

Author: Danielle Laurencin, Marie-José Zacca, Sébastien Clément, Ahmad Mehdi, Sébastien Richeter, University of Balamand - UOB (LIBAN), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Polymers, Pharmaceutical Science, 02 engineering and technology, Thiophenes, 010402 general chemistry, 01 natural sciences, Article, Analytical Chemistry, Polymerization, lcsh:QD241-441, chemistry.chemical_compound, lcsh:Organic chemistry, Drug Discovery, Thiophene, sol-gel, Lamellar structure, Physical and Theoretical Chemistry, Bifunctional, Sol-gel, chemistry.chemical_classification, Organic Chemistry, hybrid material, lamellar, Polymer, self-assembly, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Silicon Dioxide, polythiophene, 0104 chemical sciences, chemistry, Chemical engineering, Chemistry (miscellaneous), silica, Molecular Medicine, Polythiophene, 0210 nano-technology, Hybrid material, Oxidation-Reduction
Abstract: A new layered hybrid polythiophene-silica material was obtained directly by hydrolysis and polycondensation (sol-gel) of a silylated-thiophene bifunctional precursor, and its subsequent oxidative polymerization by FeCl3. This precursor was judiciously designed to guarantee its self-assembly and the formation of a lamellar polymer-silica structure, exploiting the cooperative effect between the hydrogen bonding interactions, originating from the ureido groups and the &pi, stacking interactions between the thiophene units. The lamellar structure of the polythiophene-silica composite was confirmed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) analyses. The solid-state nuclear magnetic resonance (NMR), UV-Vis, and photoluminescence spectra unambiguously indicate the incorporation of polythiophene into the silica matrix. Our work demonstrates that using a polymerizable silylated-thiophene precursor is an efficient approach towards the formation of nanostructured conjugated polymer-based hybrid materials.
Published: 2018
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21. Porous Porphyrin-Based Organosilica Nanoparticles for NIR Two-Photon Photodynamic Therapy and Gene Delivery in Zebrafish

Author: Nadir Bettache, Jonas G. Croissant, Vincent Chaleix, Michel Wong Chi Man, Mireille Rossel, Xavier Cattoën, Karen Tresfield, Niveen M. Khashab, Danielle Laurencin, Sébastien Richeter, Rachid Sougrat, Sébastien Clément, Jean-Olivier Durand, Chiara Mauriello Jimenez, Dina Aggad, Magali Gary-Bobo, Nicolas Cubedo, Erwan Oliviero, Marcel Garcia, Vincent Sol, Shahad Alsaiari, Marie Maynadier, Laurence Raehm, Manuel A. Roldan-Gutierrez, Clarence Charnay, Dorothée Berthomieu, Dalaver H. Anjum, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Mécanismes moléculaires dans les démences neurodégénératives (MMDN), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut National de la Santé et de la Recherche Médicale (INSERM)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), King Abdullah University of Sciences & Technologie, Optique et Matériaux (OPTIMA ), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), NanoMedSyn, Laboratoire de Chimie des Substances Naturelles (LCSN), Université de Limoges (UNILIM)-Génomique, Environnement, Immunité, Santé, Thérapeutique (GEIST FR CNRS 3503), Dynamique moléculaire des interactions membranaires (DMIM), and Centre National de la Recherche Scientifique (CNRS)-Université Montpellier 2 - Sciences et Techniques (UM2)
Subjects: Materials science, medicine.medical_treatment, Confocal, Nanoparticle, Photodynamic therapy, Nanotechnology, 02 engineering and technology, Gene delivery, 010402 general chemistry, 01 natural sciences, Biomaterials, chemistry.chemical_compound, Two-photon excitation microscopy, Electrochemistry, medicine, Zebrafish, Multiphoton imaging, ComputingMilieux_MISCELLANEOUS, biology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, biology.organism_classification, Porphyrin, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, 0210 nano-technology
Abstract: C.M.J. and D.A. contributed equally to this work. The grant “Chercheur d'Avenir Languedoc-Roussillon” attributed to M.G.-B. and the ANR nanoptPDT are gratefully acknowledged. The authors thank L. Lichon for technical assistance. DFT calculations were performed using HPC resources from the CINES (projects x2016087394 and x2015087394), and from the CALMIP (Grant 2016-[P16042]). The authors thank MRI (Montpellier RIO Imaging platform) for confocal and multiphoton imaging facilities.
Published: 2018
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22. A multinuclear NMR perspective on the complexation between bisboronic acids and bisbenzoxaboroles with cis -diols

Author: Danielle Laurencin, Michael Smietana, Aurélien Lebrun, Adèle Larcher, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: inorganic chemicals, High concentration, 010405 organic chemistry, Chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Computational chemistry, Materials Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: The interaction between boronic acids and cis-diols is an intense area of research, with numerous applications in sensing, separation, drug delivery, and materials science. Several analytical tools have been proposed over the past 20 years to probe these interactions, but most of them are limited by shortcomings such as high concentration requirements and/or the lack of clear evidence of the nature of the species present in solution. These drawbacks are all the more problematic in the case of compounds bearing multiple binding sites. In this work, a multinuclear (1H, 11B, 19F) NMR spectroscopy approach has been used to investigate for the first time the equilibria between bisboronic acids and bisbenzoxaboroles (as well as their monofunctional counterparts) with representative cis-diols, including catechol derivatives. The developed method is shown to provide valuable and straightforward insight into the nature of the species in solution, and the way in which the equilibria can be affected by the complexation media. In particular, the interest of using a 19F-tag on the cis-diol is emphasized.
Published: 2018
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23. Electrochemical Mg alloying properties along the Sb1-xBix solid solution

Author: Danielle Laurencin, Fabrizio Murgia, Marie-Liesse Doublet, Romain Berthelot, Ephrem Terefe Weldekidan, Lorenzo Stievano, Laure Monconduit, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), PEPS CNRS 2014 Alabama and 2015 SurfMag, ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diffraction, Materials science, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 25Mg solid-state NMR, DFT calculations, 01 natural sciences, Bismuth, Ball milling, Antimony, [CHIM]Chemical Sciences, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Operando XRD, 0104 chemical sciences, Mg-battery, chemistry, Electrode, Density functional theory, 0210 nano-technology, Solid solution
Abstract: International audience; Despite strong physical and chemical similarities between antimony and bismuth, a distinct behaviour is observed in the electrochemical magnesiation of their micrometric powders. Bismuth undergoes a complete and highly reversible alloying reaction, whereas antimony displays no electrochemical activity. Taking advantage of the complete SbBi solid solution, monophasic compositions Sb1-xBix were prepared by high-energy mechanochemical synthesis and characterized by X-ray diffraction and solid-state 25Mg nuclear magnetic resonance spectroscopy. The electrochemical magnesiation at low current rate shows a full alloying process of Sb1-xBix-based electrodes leading to monophasic Mg3(Sb1-xBix)2. This chemical association of antimony and bismuth enables a positive effect on the electrochemical magnesiation of the electrode and enables higher specific capacities compared to Bi-based electrodes. However, this synergy only operates in the nominal discharge since an irreversible capacity loss, which scales with the antimony content, is observed in the subsequent charge. Operando XRD reveals a complex segregation process leading to pure bismuth and Mg3Sb2 at the end of charge which is further rationalized by density functional theory calculations as an instability of the Mg3(Sb1-xBix)2 solid solution.
Published: 2018
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24. Drug–Polymer Electrostatic Complexes as New Structuring Agents for the Formation of Drug-Loaded Ordered Mesoporous Silica

Author: Danielle Laurencin, Mélody Mathonnat, Emilie Molina, Jérôme Warnant, Patrick Lacroix-Desmazes, Corine Gérardin, Christine Jérôme, Maël Bathfield, Nathalie Marcotte, Martin In, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Matière Molle, Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and CERM
Subjects: Polymers, Silicon dioxide, Static Electricity, Polyethylene Glycols, chemistry.chemical_compound, Electrochemistry, Copolymer, Organic chemistry, General Materials Science, Spectroscopy, Acrylic acid, chemistry.chemical_classification, Drug Carriers, Ethylene oxide, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, Polymer, Mesoporous silica, Silicon Dioxide, Condensed Matter Physics, [CHIM.POLY]Chemical Sciences/Polymers, Solubility, chemistry, Chemical engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Drug carrier, Hybrid material
Abstract: Using aminoglycoside antibiotics as drug models, it was shown that electrostatic complexes between hydrophilic drugs and oppositely charged double-hydrophilic block copolymers can form ordered mesophases. This phase behavior was evidenced by using poly(acrylic acid)-block-poly(ethylene oxide) block copolymers in the presence of silica precursors, and this allowed preparing drug-loaded mesoporous silica directly from the drug-polymer complexes. The novel synthetic strategy of the hybrid materials is highly efficient, avoiding waste and multistep processes; it also ensures optimal drug loading and provides pH-dependence of the drug release from the materials.
Published: 2015
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25. Insight into the local environment of magnesium and calcium in low-coordination-number organo-complexes using 25 Mg and 43 Ca solid-state NMR: a DFT study

Author: Christian Bonhomme, Christel Gervais, Danielle Laurencin, Cameron Jones, 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), Monash University [Clayton], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-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 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: GIPAW, Coordination number, Metal ions in aqueous solution, chemistry.chemical_element, 02 engineering and technology, Nuclear magnetic resonance crystallography, Crystal structure, 010402 general chemistry, 01 natural sciences, DFT, Inorganic Chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Anisotropy, Magnesium, NMR crystallography, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 43Ca, organo-complexes, computational chemistry, 0104 chemical sciences, 25Mg, Crystallography, Solid-state nuclear magnetic resonance, chemistry, Chemical physics, solid-state NMR, 0210 nano-technology
Abstract: With the increasing number of organocalcium and organomagnesium complexes under development, there is a real need to be able to characterize in detail their local environment in order to fully rationalize their reactivity. For crystalline structures, in cases when diffraction techniques are insufficient, additional local spectroscopies like 25Mg and 43Ca solid-state NMR may provide valuable information to help fully establish the local environment of the metal ions. In this current work, a prospective DFT investigation on crystalline magnesium and calcium complexes involving low-coordination numbers and N-bearing organic ligands was carried out, in which the 25Mg and 43Ca NMR parameters [isotropic chemical shift, chemical shift anisotropy (CSA) and quadrupolar parameters] were calculated for each structure. The analysis of the calculated parameters in relation to the local environment of the metal ions revealed that they are highly sensitive to very small changes in geometry/distances, and hence that they could be used to assist in the refinement of crystal structures. Moreover, such calculations provide a guideline as to how the NMR measurements will need to be performed, revealing that these will be very challenging.
Published: 2017
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26. Unleashing the Potential of 17 O NMR Spectroscopy Using Mechanochemistry

Author: Danielle Laurencin, Christian Bonhomme, Thomas-Xavier Métro, Anthony Martinez, Christel Gervais, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Research groups, Chemistry, 010405 organic chemistry, Nanotechnology, General Chemistry, Nuclear magnetic resonance spectroscopy, General Medicine, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Mechanochemistry, Research community, Mechanosynthesis
Abstract: International audience; 17 O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen-17, 17 O-labelling is generally a prerequisite. This is a real obstacle for most research groups, because of the high cost and/or strong experimental constraints of the most frequently used 17O-labelling schemes. Here, we demonstrate for the first time that mechanosynthesis offers unique opportunities for enriching in 17 O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user-friendly, and low-cost, which makes them highly attractive for a broad research community, and their suitability for 17 O solid state NMR applications is demonstrated.
Published: 2017
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27. Durability testing of an iodate-substituted hydroxyapatite designed for the conditioning of 129I

Author: Sylvie Rossignol, Antoine Coulon, Danielle Laurencin, Lionel Campayo, Agnès Grandjean, Patrick Jollivet, Laboratoire d'études de Matériaux Céramiques pour le Conditionnement (LM2C), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire des Procédés Supercritiques et de Décontamination, Commisariat de l'Energie Atomique, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire d'Etudes du Comportement à Long Terme des matériaux de conditionnement (LCLT), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), Groupe d'Etudes des Matériaux Hétérogènes (GEMH), Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), CEA-Direction de l'Energie Nucléaire (CEA-DEN), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction de l'Energie Nucléaire (CEA-DEN)
Subjects: Nuclear and High Energy Physics, Metal ions in aqueous solution, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Iodine, 01 natural sciences, 7. Clean energy, Apatite, chemistry.chemical_compound, conditioning, 0103 physical sciences, General Materials Science, Dissolution, ComputingMilieux_MISCELLANEOUS, Iodate, 010302 applied physics, Chemistry, iodine, Metallurgy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Phosphate, 6. Clean water, Nuclear Energy and Engineering, 129I, visual_art, apatite, visual_art.visual_art_medium, radioactive waste, Leaching (metallurgy), 0210 nano-technology, Stoichiometry
Abstract: The safe management of iodine coming from spent nuclear fuels by storage in deep geological repositories requires durable materials. For this purpose, we have recently developed an iodate-substituted hydroxyapatite (HA-CaI). In the present article, the chemical durability of this material is assessed as a function of leaching media and apatite stoichiometry. First, the maximum rate for iodine release was determined in unsaturated conditions leading to a congruent dissolution of HA-CaI. In these conditions, the forward rate was equal to 2 × 10 −2 g m −2 d −1 at 50 °C independently of apatite stoichiometry. During this regime, dissolution was controlled by surface reaction and diffusion phenomena. When concentrations of calcium and phosphate ions in solution increased, the system became saturated towards non-substituted hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 and the rate of iodine release consecutively decreased. Consequently, tests were carried out to determine the behaviour of HA-CaI in such experimental conditions (saturated conditions), which were thought to be time-prevalent given the half-life of 129 I (15.7 million years). During this regime, also called residual regime, iodine was released in the solution at a constant rate without being trapped in a secondary phase. The residual rate at 50 °C on the basis of iodine release was of 10 −4 g m −2 d −1 in an initially deionized water, and it fell by one order of magnitude (r = 10 −5 g m −2 d −1 ) in a clay-equilibrated groundwater (hereafter called Callovo-oxfordian (COx) groundwater). This singular behaviour was ascribed to the presence of calcium in COx water. These preliminary results on the chemical durability of HA-CaI suggest that this material is a viable candidate as repository iodine waste form.
Published: 2017
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28. Ultrasmall NHC-coated gold nanoparticles obtained through solvent free thermolysis of organometallic Au(<scp>i</scp>) complexes

Author: Joulia Larionova, Alfonso Ibarra, Julian Crespo, Danielle Laurencin, Miguel Monge, Sébastien Richeter, José M. López-de-Luzuriaga, Yannick Guari, M. Elena Olmos, Tania Lasanta, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Universidad de La Rioja (UR)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Ligand, Inorganic chemistry, Thermal decomposition, 010402 general chemistry, 01 natural sciences, Reductive elimination, 0104 chemical sciences, Nanomaterials, Inorganic Chemistry, chemistry.chemical_compound, Colloidal gold, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reactivity (chemistry), Carbene, ComputingMilieux_MISCELLANEOUS, Alkyl
Abstract: Ultrasmall gold nanoparticles (Au UNPs) represent a unique class of nanomaterials making them very attractive for certain applications. Herein, we developed an organometallic approach to the synthesis of Au UNPs stabilized with the C18H37-NHC ligand by the solvent free thermolysis of [RMIM][Au(C6F5)2] (1) or [Au(C6F5)(RNHC)] (3) (with R = C18H37-), by controlling the reactivity of pentafluorophenyl ligands as deprotonating or reductive elimination agents; Au UNPs can be achieved by solvent free thermolysis. Pentafluorophenyl Au(I) complexes 1 and 3 are synthesized from the corresponding ionic and neutral precursors. The presence of long alkyl chain imidazolium or carbene species in the complexes makes them to behave as isotropic liquids at moderate temperatures. The use of multinuclear NMR allows the description of the mechanism of formation of the UNPs as well as the surface state of the UNPs.
Published: 2014
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29. Improvement of the Oxidative Stability of Nanodiamonds by Surface Phosphorylation

Author: Johan G. Alauzun, Danielle Laurencin, Charlene Presti, P. Hubert Mutin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Phosphoryl chloride, Materials science, General Chemical Engineering, 02 engineering and technology, Oxidative phosphorylation, Thermal treatment, 010402 general chemistry, oxidative stability, 01 natural sciences, Nanodiamonds, chemistry.chemical_compound, Oxidizing agent, Materials Chemistry, Organic chemistry, Thermal stability, Nanodiamond, surface functionalization, phosphorylation, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Phosphate, 0104 chemical sciences, chemistry, Surface modification, 0210 nano-technology, Nuclear chemistry
Abstract: International audience; Surface phosphorylation of nanodiamond was performed by reaction with phosphoryl chloride in dichloromethane. Depending on the reaction conditions, P contents of up to 1.66 mmol/g were reached. Phosphorylation dramatically enhanced the thermal stability of nanodiamond under oxidizing conditions, shifting the oxidation temperature by up to 190 °C and dividing the oxidation rate by a factor of up to 160. The nature of the grafted phosphate species and their evolution during thermal treatment was followed using solid-state NMR.
Published: 2013
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30. Development of a new family of monolithic calcium (pyro)phosphate glasses by soft chemistry

Author: Christian Rey, Jérémy Soulié, Danielle Laurencin, Pierre Gras, Christèle Combes, Olivier Marsan, Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université de Montpellier 1 (FRANCE), Université de Montpellier 2 (FRANCE), Université de Montpellier (FRANCE), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), ANR, ANR-12-BS08-0022,CAPYROSIS,Formation de cristaux de pyrophosphates de calcium et arthrose : études in vitro et in vivo(2012), and Institut National Polytechnique de Toulouse - INPT (FRANCE)
Subjects: Pyrophosphate, Materials science, Differential Thermal Analysis, Static Electricity, Chimie analytique, Biomedical Engineering, Mineralogy, 02 engineering and technology, 010402 general chemistry, Calcium Pyrophosphate, 01 natural sciences, Biochemistry, Science des matériaux, Soft chemistry, law.invention, Biomaterials, chemistry.chemical_compound, law, sol-gel, Crystallization, Molecular Biology, biomaterial, (Pyro) phosphate glasses, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Phosphate, Chemistry, Inorganic, 0104 chemical sciences, Amorphous solid, Solutions, chemistry, Chemical engineering, Ionic strength, Thermogravimetry, Microscopy, Electron, Scanning, Hydroxide, Glass, 0210 nano-technology, Hybrid material, Monolith, Biotechnology
Abstract: The development of bioactive phosphate-based glasses is essential in biomaterials science, and especially for bone substitution applications. In this context, the preparation of amorphous calcium-phosphorus hydroxide/oxide monoliths at low temperature is a key challenge for being able to develop novel hybrid materials for these applications. We herein report for the first time the synthesis and physical chemical characterisation of a novel family of pyrophosphate-based glasses (with the formula: {[(Ca(2+))1-x(H(+)/K(+))2x]2[(P2O7(4-))1-y(PO4(3-))4y/3]} n(H2O)), which were prepared by soft chemistry using low temperatures (T70°C) and water as a solvent. The effect of the initial Ca/Pyrophosphate ratio on the structure and morphology of these pyrophosphate glasses was investigated in detail. Depending on this ratio, a glass (mixed calcium pyro- and orthophosphate) or a glass-ceramic (Ca10K4(P2O7)6·9H2O crystals embedded in the amorphous phase) was obtained. The proportion of the crystalline phase increased with an increase in the Ca/Pyrophosphate ratio in the batch solution. As expected for a glass, the formation of the glassy material was demonstrated not to be thermodynamically but rather kinetically driven, and the washing step was found to be crucial to prevent crystallisation. The stability of the amorphous phase was discussed considering the structural degrees of freedom of pyrophosphate entities, ionic strength of the initial solution and the inhibitory effect of orthophosphate ions. Overall, this new strategy of preparation of monolithic calcium-(pyro)phosphate based glasses using soft chemistry in water is highly promising in view of preparing new functional organic-inorganic hybrids for bone substitution applications.Phosphate-based glasses have gradually emerged as a potential alternative to silicate bioactive glasses in order to induce different biological mechanisms of degradation. The synthesis of such monolithic glasses at low temperature is a key step to allow new inorganic glass compositions to be reached and hybrid materials to be prepared. Although sol-gel and coacervate methods (respectively orthophosphate and metaphosphate precursors) have already been described to prepare such glasses, the use of toxic solvents and/or the final temperature treatment associated to these processes could limit the use of these materials for biomedical applications and/or the further development of hybrids. It is shown here that pyrophosphate precursors are an alternative strategy to obtain monolithic calcium (pyro)phosphate glasses under soft conditions (water solvent, 70°C).
Published: 2016
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31. Back Cover

Author: Frederik Tielens, Miguel Monge, Françoise Remacle, María Rodríguez-Castillo, Gustavo Lugo-Preciado, Yannick Guari, Arie van der Lee, Sébastien Richeter, Danielle Laurencin, Sébastien Clément, José M. López-de-Luzuriaga, and General Chemistry
Subjects: Benzimidazole, 010405 organic chemistry, Chemistry, Organic Chemistry, Nanoparticle, General Chemistry, gold, 010402 general chemistry, 01 natural sciences, DFT, Catalysis, 0104 chemical sciences, carbenes, Surface, chemistry.chemical_compound, Colloidal gold, Polymer chemistry, Cover (algebra), Reactivity (chemistry), nanoparticles
Published: 2016
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32. Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole-2-ylidene Ligands

Author: Miguel Monge, José M. López-de-Luzuriaga, María Rodríguez-Castillo, Danielle Laurencin, Frederik Tielens, Sébastien Richeter, Gustavo Lugo-Preciado, Yannick Guari, Françoise Remacle, Arie van der Lee, Sébastien Clément, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chemistry Department [Liège], Université de Liège, 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)-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), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Departamento de Química, Universidad de La Rioja (UR), Chemistry, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and 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)
Subjects: Benzimidazole, 010405 organic chemistry, Chemistry, Organic Chemistry, Nanoparticle, General Chemistry, 010402 general chemistry, Photochemistry, Grafting, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Adsorption, Computational chemistry, Colloidal gold, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene
Abstract: International audience; The purpose of this work is to shed light on the reactivity of benzimidazol-2-ylidenes with respect to gold nanoparticles (AuNPs), using a combined experimental/computational approach. First, the grafting of benzimidazol-2-ylidenes bearing benzyl groups on the nitrogen atoms is described, and comparisons are made with structurally similar N-heterocyclic carbenes (NHCs) bearing other N-groups. Similar reactivity was observed for all NHCs, with (i) the erosion of the AuNPs under the effect of the NHC and (ii) the formation of bis(NHC) gold complexes. Density Functional Theory (DFT) calculations were performed to investigate the modes of grafting of such ligands, and to determine adsorption energies. Two types of computational models were developed, in order to describe the grafting onto large or small AuNPs, using either periodic or cluster-type DFT calculations. Calculations of NMR parameters were also performed on some these models, and discussed in light of the experimental data.
Published: 2016
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33. Formulation of benzoxaborole drugs in PLLA: from materials preparation to in vitro releasekinetics and cellular assays

Author: Sylvie Bégu, Nicholas J. Schaub, Danielle Laurencin, Joshua S. McLane, Saad Sene, Lee A. Ligon, Ryan J. Gilbert, P. Hubert Mutin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Rensselaer Polytechnic Institute (RPI), ANR, Partner University Fund, and ANR-13-JS08-0004,BOROMAT,Développement d'une nouvelle classe de matériaux hybrides organique-inorganique incorporant des boronates/ benzoxaborolates(2013)
Subjects: Materials science, Kinetics, Biomedical Engineering, Antifungal drug, benzoxaborole, Context (language use), Nanotechnology, formulation, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Molecule, General Materials Science, Materials preparation, General Chemistry, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, In vitro, 0104 chemical sciences, 3. Good health, chemistry, engineering, Hydroxide, Biopolymer, 0210 nano-technology, biomaterials
Abstract: International audience; Benzoxaboroles are a family of organoboron molecules, which have been finding over the past few years an increasing number of biological applications, notably for the design of new drugs. Given that these molecules are still relatively new in the biomedical context, very few investigations regarding their formulation have been reported to date. Here, a complete study on the formulation of benzoxaboroles in a biopolymer, poly-L-lactic acid (PLLA), is reported. The incorporation of two small benzoxaboroles, namely the simplest benzoxaborole molecule (BBzx) and the antifungal drug tavaborole (AN2690), inside PLLA films was investigated. Different variations in the film composition and texture were looked into, by performing a heat-treatment on the PLLA films, or by preparing PLLA–PEO (polyethylene oxide) blends or PLLA–LDH (layered double hydroxide) composites. In each case, the impact of these changes in formulation on the local environment of the benzoxaboroles in the material (as determined by multinuclear solid state NMR), and on the kinetics of release in physiological media were analyzed, showing that a variety of release profiles could be achieved. Finally, cellular assays were carried out looking at the migration of MDA-MB-231 cancer cells. These tests revealed for the first time that benzoxaboroles like AN2690 and BBzx inhibited the migration of these cells. Moreover, the molecules incorporated in the films were found to remain active, and their effect on cancer cells was directly related to the release kinetics from the films. All in all, PLLA-based materials appear as highly versatile and attractive matrices for formulating benzoxaborole-based drugs.
Published: 2016
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34. 87Sr Solid-State NMR as a Structurally Sensitive Tool for the Investigation of Materials: Antiosteoporotic Pharmaceuticals and Bioactive Glasses

Author: Mark E. Smith, Jincheng Du, Ye Xiang, Frédérique Pourpoint, Edouard Jallot, Christian Bonhomme, Jonathan Lao, Nicolas Folliet, Dinu Iuga, Danielle Laurencin, Jean-Marie Nedelec, John V. Hanna, Cristina Coelho Diogo, Christel Gervais, Joséphine Lacroix, Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des matériaux de Paris-Centre (IMPC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique Corpusculaire - Clermont-Ferrand (LPC), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Physics, University of Warwick [Coventry], Solid State NMR Group, University of Warwick, Department of Materials Science and Engineering (Dallas, USA), University of Texas at Dallas [Richardson] (UT Dallas), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), US NSF DMR Biomaterials program award no. 0907593. Montpellier-Warwick partnership grant (JP090313, Institut de Chimie du CNRS (INC)-SIGMA Clermont (SIGMA Clermont)-Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, inorganic chemicals, Magnetic Resonance Spectroscopy, chemistry.chemical_element, Biocompatible Materials, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Strontium Isotopes, Colloid and Surface Chemistry, Tissue engineering, Organic chemistry, Bone growth, Strontium, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Malonates, 0104 chemical sciences, Pharmaceutical Preparations, Solid-state nuclear magnetic resonance, Local environment, Glass, 0210 nano-technology, Strontium malonate
Abstract: International audience; Strontium is an element of fundamental importance in biomedical science. Indeed, it has been demonstrated that Sr(2+) ions can promote bone growth and inhibit bone resorption. Thus, the oral administration of Sr-containing medications has been used clinically to prevent osteoporosis, and Sr-containing biomaterials have been developed for implant and tissue engineering applications. The bioavailability of strontium metal cations in the body and their kinetics of release from materials will depend on their local environment. It is thus crucial to be able to characterize, in detail, strontium environments in disordered phases such as bioactive glasses, to understand their structure and rationalize their properties. In this paper, we demonstrate that (87)Sr NMR spectroscopy can serve as a valuable tool of investigation. First, the implementation of high-sensitivity (87)Sr solid-state NMR experiments is presented using (87)Sr-labeled strontium malonate (with DFS (double field sweep), QCPMG (quadrupolar Carr-Purcell-Meiboom-Gill), and WURST (wideband, uniform rate, and smooth truncation) excitation). Then, it is shown that GIPAW DFT (gauge including projector augmented wave density functional theory) calculations can accurately compute (87)Sr NMR parameters. Last and most importantly, (87)Sr NMR is used for the study of a (Ca,Sr)-silicate bioactive glass of limited Sr content (only 9 wt %). The spectrum is interpreted using structural models of the glass, which are generated through molecular dynamics (MD) simulations and relaxed by DFT, before performing GIPAW calculations of (87)Sr NMR parameters. Finally, changes in the (87)Sr NMR spectrum after immersion of the glass in simulated body fluid (SBF) are reported and discussed.
Published: 2012
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35. Surface modification of calcium carbonate with phosphonic acids

Author: Danielle Laurencin, Gilles Guerrero, Mark E. Smith, P. Hubert Mutin, Wassim El Malti, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Solid State NMR Group, University of Warwick, and University of Warwick [Coventry]
Subjects: Inorganic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Phosphonate, 0104 chemical sciences, Chemical kinetics, chemistry.chemical_compound, Adsorption, chemistry, Physisorption, Solid-state nuclear magnetic resonance, Materials Chemistry, Magic angle spinning, Surface modification, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Tetrahydrofuran
Abstract: The surface of precipitated calcite particles was modified by reaction with phosphonic acids (phenylphosphonic acid and dodecylphosphonic acid) in organic solvents, tetrahydrofuran (THF) and ethanol. The reaction kinetics and adsorption isotherms were determined. Under appropriate conditions, dense phosphonate monolayers were deposited at the surface of the CaCO3 particles. The nature of the grafted species was investigated using 31P and 1H Magic Angle Spinning (MAS) solid state NMR spectroscopy, FTIR spectroscopy and N2 physisorption. These monolayers were found to increase the hydrophobic character of CaCO3 surfaces, especially in the case of dodecylphosphonic acid. The unwanted formation of a bulk crystalline calcium phosphonate phase by dissolution–precipitation was observed only in the reaction of phenylphosphonic acid with CaCO3 in THF, and it could be largely avoided by working at low concentration of the phosphonic acid and/or minimizing reaction times to less than 3 days.
Published: 2012
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36. Photodynamic Therapy: Porous Porphyrin-Based Organosilica Nanoparticles for NIR Two-Photon Photodynamic Therapy and Gene Delivery in Zebrafish (Adv. Funct. Mater. 21/2018)

Author: Marcel Garcia, Nicolas Cubedo, Rachid Sougrat, Vincent Sol, Jean-Olivier Durand, Erwan Oliviero, Magali Gary-Bobo, Vincent Chaleix, Danielle Laurencin, Mireille Rossel, Karen Tresfield, Niveen M. Khashab, Xavier Cattoën, Nadir Bettache, Dorothée Berthomieu, Sébastien Clément, Chiara Mauriello Jimenez, Manuel A. Roldan-Gutierrez, Sébastien Richeter, Dina Aggad, Jonas G. Croissant, Michel Wong Chi Man, Marie Maynadier, Laurence Raehm, Dalaver H. Anjum, Shahad Alsaiari, and Clarence Charnay
Subjects: Materials science, biology, medicine.medical_treatment, Nanoparticle, Photodynamic therapy, 02 engineering and technology, Gene delivery, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, biology.organism_classification, 01 natural sciences, Porphyrin, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Biomaterials, chemistry.chemical_compound, Two-photon excitation microscopy, chemistry, Electrochemistry, Zebrafish embryo, medicine, Biophysics, 0210 nano-technology, Zebrafish
Published: 2018
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37. Two-dimensional 43Ca–1H correlation solid-state NMR spectroscopy

Author: Ray Dupree, Danielle Laurencin, Mark E. Smith, Alan Wong, Solid State NMR Group, University of Warwick, University of Warwick [Coventry], and Bourse Marie Curie Intra-European Fellowship
Subjects: Calcium Isotopes, Nuclear and High Energy Physics, Magnetic Resonance Spectroscopy, dipolar interaction, Carbon-13 NMR satellite, Nuclear magnetic resonance spectroscopy of nucleic acids, 02 engineering and technology, Fluorine-19 NMR, Nuclear magnetic resonance crystallography, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Sensitivity and Specificity, 01 natural sciences, Nuclear magnetic resonance, low-gamma, Magnetization transfer, oxyhydroxyapatite, Instrumentation, 43Ca NMR, Radiation, Chemistry, hydroxyapatite, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, R3-HMQC, 0104 chemical sciences, Durapatite, Solid-state nuclear magnetic resonance, Chemical physics, Residual dipolar coupling, Spin Labels, hetero-nuclear correlation NMR spectroscopy, Protons, 0210 nano-technology, Algorithms, Magnetic dipole–dipole interaction
Abstract: Calcium-43 (nuclear spin, S = 7/2) is an NMR insensitive low-gamma quadrupolar nucleus and up until recently only one-dimensional solid-state Ca-43 NMR spectra have been reported. Through-space correlation experiments are challenging between spin-1/2 and low-gamma quadrupolar nuclei because of the intrinsically weak dipolar interaction and the often-low natural abundance of the quadrupolar nucleus. Rotary-resonance recoupling (R-3) has recently been used to re-introduce hetero-nuclear dipolar interactions for sensitive high-gamma quadrupolar nuclei, but has not yet been applied in the case of low-gamma half-integer quadrupolar nuclei. Here an effective and robust 2D H-1-Ca-43 NMR correlation experiment combining the R-3 dipole-recoupling scheme with 2D HMQC is presented. It is demonstrated that the weak Ca-43-H-1 dipolar coupling in hydroxyapatite and oxy-hydroxyapatite can be readily re-introduced and that this recoupling scheme is more efficient than conventional cross-polarization transfer. Moreover, three Ca-43-H-1 dipolar coupled calcium environments are clearly resolved in the structurally unknown oxy-hydroxyapatite. This local information is not readily available from other techniques such as powder XRD and high resolution electron microscopy. R-3-HMQC is also a desirable experiment because the set-up is simple and it can be applied using conventional multi-resonance probes. (C) 2008 Elsevier Inc. All rights reserved.
Published: 2009
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38. Theoretical Study of the Relative Stabilities of the α/β3-[XW11O39]m− Lacunary Polyoxometalates (X = P, Si)

Author: Danielle Laurencin, Anna Proust, Hélène Gérard, Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), and CIM2 - LCT
Subjects: 010405 organic chemistry, Chemistry, Keggin lacunaire, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Structural difference, 010402 general chemistry, DFT, 01 natural sciences, Relative stability, 0104 chemical sciences, Ion, Inorganic Chemistry, Metal, Crystallography, visual_art, visual_art.visual_art_medium, Beta (velocity), polyoxométallates, Physical and Theoretical Chemistry, Lacunary function
Abstract: A computational study of the relative stability of the monolacunary Keggin polyoxotungstates alpha and beta 3-[XW 11O 39] ( m- ) (X = P, m = 7; X = Si, m = 8) was performed. The influence of the nature of different grafted cations and of the central anion XO 4 ( n- ) on the relative stabilities of the lacunary isomers was analyzed. From these results, an interpretation of the structural difference in the metallic frameworks of alpha-[PW 11O 39{Ru(DMSO) 3(H 2O)}] (5-), alpha-[PW 11O 39{Ru(C 6H 6)(H 2O)}] (5-), and beta 3-[SiW 11O 39{Ru(DMSO) 3(H 2O)}] (6-) is proposed, and conclusions are drawn as to how to favor the formation of beta 3 derivatives in future syntheses.
Published: 2008
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39. Relationship between structure, fluxionality and racemization activity in organometallic derivatives of polyoxometalates

Author: Richard Villanneau, Danielle Laurencin, Anna Proust, Roger A. Sheldon, Anne Brethon, Isabel W. C. E. Arends, Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Biocatalysis and Organic Chemistry - Department of Biotechnology, Delft University of Technology (TU Delft), financement européen COST Action D29, 0016/04, and COST action D29
Subjects: racémisation, oxydes organométalliques, 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, catalyse, Catalysis, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, ruthénium, Organic chemistry, polyoxométallates, Physical and Theoretical Chemistry, Racemization
Abstract: The catalytic activity of several organometallic derivatives of polyoxometalates, especially those of general formula [M 4 O 16 {M′(η 6 -arene)} 4 ] (M = Mo, W; M′ = Ru, Os), was evaluated in the racemization of secondary alcohols. A link between composition, fluxionality and catalytic activity was established.
Published: 2007
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40. Synthesis and reactivity of {Ru(p-cymene)}2+derivatives of [Nb6O19]8−: a rational approach towards fluxional organometallic derivatives of polyoxometalates

Author: René Thouvenot, Anna Proust, Danielle Laurencin, Kamal Boubekeur, Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: p-Cymene, 010405 organic chemistry, Inorganic chemistry, Solid-state, Infrared spectroscopy, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, ruthénium, fluxionalité, Crystal data, Proton NMR, Reactivity (chemistry), polyoxométallates, niobium, Isomerization
Abstract: Three {Ru(p-cym)}(2+) (p-cym = p-cymene) derivatives of [Nb(6)O(19)](8-)-[Nb(6)O(19){Ru(p-cym)}](6-) (Nb(6)Ru(1)), trans-[Nb(6)O(19){Ru(p-cym)}(2)](4-) (t-Nb6Ru2), and [Nb(6)O(19){Ru(p-cym)}(4)] (Nb(6)Ru(4))--have been synthesized in water by reaction between [Ru(p-cym)Cl(2)](2) and the hexaniobate. In the solid state, Nb(6)Ru(1) and Nb(6)Ru(4) have been characterized by IR and EDX spectroscopies, whereas t-Nb(6)Ru(2) has been characterized by IR spectroscopy and single-crystal X-ray diffraction (crystal data for K(4)-trans-[Nb(6)O(19){Ru(p-cym)}(2)].14H(2)O (K(4)-t-Nb(6)Ru(2).14H(2)O). In solution, all compounds were characterized by (1)H NMR and ESI mass spectrometry analyses, and Nb(6)Ru(1) was also analyzed by (17)O NMR. These studies allowed a comparison of the differences in behaviour of the three complexes in water: Nb(6)Ru(1) is particularly stable, Nb(6)Ru(4) decomposes by loss of {Ru(p-cym)}(2+) fragments, and trans-[Nb(6)O(19){Ru(p-cym)}(2)](4-) isomerizes into cis-[Nb(6)O(19){Ru(p-cym)}(2)](4-). A rational mechanism for the isomerisation of t-Nb(6)Ru(2) is proposed on the basis of a kinetic study.
Published: 2007
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41. Biomimetic apatite-based composite materials obtained by spark plasma sintering (SPS): physicochemical and mechanical characterizations

Author: Fabien Brouillet, Christophe Drouet, David Grossin, Danielle Laurencin, Christian Rey, Geoffroy Chevallier, Claude Estournès, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), ANR, ANR-07-BLAN-0373,nanoBiocer,Nouvelle génération de biocéramiques résorbables par consolidation à basse température d'apatites nanocristallines biomimétiques(2007), Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - INPT (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université de Montpellier (FRANCE), and Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Subjects: Ceramics, Magnetic Resonance Spectroscopy, Polymer fiber, Plasma Gases, Composite number, SPS, 02 engineering and technology, 01 natural sciences, Apatite, Nanocomposites, chemistry.chemical_compound, Nanocrystalline apatite, Biomimetic Materials, Apatites, Materials Testing, Spectroscopy, Fourier Transform Infrared, Ceramic, Composite material, chemistry.chemical_classification, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Nanocrystalline material, cellulose, Biomechanical Phenomena, Microcrystalline cellulose, visual_art, visual_art.visual_art_medium, 0210 nano-technology, spark plasma sintering, Materials science, Surface Properties, Matériaux, Biomedical Engineering, Biophysics, Spark plasma sintering, Bioengineering, Composite, 010402 general chemistry, Biomaterials, Humans, composite, Nanocomposite, 0104 chemical sciences, chemistry, apatite, Bone Substitutes, Microscopy, Electron, Scanning, Nanoparticles, Powder Diffraction, Mechanical strength
Abstract: International audience; Nanocrystalline calcium phosphate apatites are biomimetic compounds analogous to bone mineral and are at the origin of the bioactivity of most biomaterials used as bone substitutes. Their unique surface reactivity originates from the presence of a hydrated layer containing labile ions (mostly divalent ones). So the setup of 3D biocompatible apatite-based bioceramics exhibiting a high reactivity requests the development of «low» temperature consolidation processes such as spark plasma sintering (SPS), in order to preserve the characteristics of the hydrated nanocrystals. However, mechanical performances may still need to be improved for such nanocrystalline apatite bioceramics, especially in view of load-bearing applications. The reinforcement by association with biopolymers represents an appealing approach, while preserving the advantageous biological properties of biomimetic apatites. Herein, we report the preparation of composites based on biomimetic apatite associated with various quantities of microcrystalline cellulose (MCC, 1-20 wt%), a natural fibrous polymer. The SPS-consolidated composites were analyzed from both physicochemical (X-ray diffraction, Fourier transform infrared, solid state NMR) and mechanical (Brazilian test) viewpoints. The preservation of the physicochemical characteristics of apatite and cellulose in the final material was observed. Mechanical properties of the composite materials were found to be directly related to the polymer/apatite ratios and a maximum crushing strength was reached for 10 wt% of MCC.
Published: 2015
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42. Intercalation of benzoxaborolate anions in layered double hydroxides: toward hybrid formulations for benzoxaborole drugs

Author: Saad Sene, Arie van der Lee, Christian Bonhomme, Guillaume Renaudin, Danielle Laurencin, Adel Mesbah, Sylvie Bégu, P. Hubert Mutin, Mark E. Smith, Christel Gervais, Jean-Marie Nedelec, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), Institut de Chimie de Clermont-Ferrand (ICCF), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Lancaster University, University of Warwick [Coventry], Institut Européen des membranes (IEM), ANRMarie Curie ERG, ANR-13-JS08-0004,BOROMAT,Développement d'une nouvelle classe de matériaux hybrides organique-inorganique incorporant des boronates/ benzoxaborolates(2013), European Project: 239206,EC:FP7:PEOPLE,FP7-PEOPLE-ERG-2008,CONTRELL(2009), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Sigma CLERMONT (Sigma CLERMONT), Interfaces de Matériaux en Evolution (LIME), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM), Solid State NMR Group, University of Warwick, Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie du CNRS (INC)-SIGMA Clermont (SIGMA Clermont)-Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)
Subjects: General Chemical Engineering, Intercalation (chemistry), Antifungal drug, Layered double hydroxides, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, engineering.material, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Combinatorial chemistry, Characterization (materials science), chemistry.chemical_compound, Solid-state nuclear magnetic resonance, chemistry, Materials Chemistry, engineering, Hydroxide, Organic chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Inorganic matrix, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Benzoxaboroles are a family of cyclic derivatives of boronic acids, whose reactivity makes them interesting candidates for the development of novel drugs. In this study, we describe the preparation of the first hybrid organic-inorganic materials involving benzoxaboroles, as a first step towards their use as new formulations for such drugs. The materials were prepared by intercalation of the simplest benzoxaborole (C7H6BO(OH), BBzx) or of its fluorinated analogue (C7H5FBO(OH), AN2690, a recently developed antifungal drug), both taken under their anionic form (benzoxaborolate), into a biodegradable inorganic matrix (a Mg-Al layered double hydroxide). Extensive characterization was carried out on the materials, notably by powder X-ray diffraction and multinuclear (11B, 27Al, 13C, 19F, 25Mg, 1H) solid state NMR, in order to describe their structure, particularly in the vicinity of the organoboron species. Three crystalline phases involving benzoxaborolate anions in association with Ca2+ or Mg2+ cations were also prepared as part of this work (Mg(C7H6BO(OH)2)2•10H2O, Mg(C7H6BO(OH)2)2•7H2O and Ca3(C7H6BO(OH)2)5(C7H6BO2)•3H2O), in order to assist in the interpretation of the spectroscopic data. A DFT computational model of the interlayer space was proposed, which is consistent with the experimental observations. Several properties of the materials were then determined with a view of using them as part of novel formulations, namely the maximum loading capacity towards benzoxaborol(at)es, the optimal storage conditions, and the release kinetics in simulated physiological media. All in all, this study serves as a benchmark not only for the development of novel formulations for benzoxaborole drugs, but more generally for the preparation of a novel class of organic-inorganic materials involving benzoxaborol(at)es.
Published: 2015
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43. Coordination polymers based on alkylboronate ligands: synthesis, characterization, and computational modelling

Author: Mark E. Smith, Dorothée Berthomieu, Danielle Laurencin, Christel Gervais, Guillaume Renaudin, Marc Reinholdt, Saad Sene, Christian Bonhomme, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), 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), Institut de Chimie de Clermont-Ferrand (ICCF), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solid State NMR Group, University of Warwick, University of Warwick [Coventry], ANR, Marie Curie ERG, ANR-13-JS08-0004,BOROMAT,Développement d'une nouvelle classe de matériaux hybrides organique-inorganique incorporant des boronates/ benzoxaborolates(2013), European Project: 239206,EC:FP7:PEOPLE,FP7-PEOPLE-ERG-2008,CONTRELL(2009), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and 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)
Subjects: chemistry.chemical_classification, Alkaline earth metal, Coordination polymer, Stereochemistry, Infrared spectroscopy, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Synchrotron, Spectral line, law.invention, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Microcrystalline, chemistry, law, Phase (matter)
Abstract: International audience; Boronate ligands (R-B(OH)3-) have recently started to attract attention for the elaboration of coordination polymer networks. Here, three new crystalline structures involving butyl and octylboronate ligands are described: Sr(Bu-B(OH)3)2, Ca(Oct-B(OH)3)2 and Sr(Oct-B(OH)3)2. All were obtained as microcrystalline powders, and their structures were solved using synchrotron powder X-ray diffraction data. IR and multinuclear (13C, 11B, 43Ca, 87Sr and 1H) solid state NMR characterizations were carried out on the materials. Computational models of the novel Sr(Bu-B(OH)3)2 phase and of the previously reported Sr(Ph-B(OH)3)2.H2O structure were then developed. IR O-H stretching modes and NMR parameters were calculated for these models, and discussed in view of the experimental spectra. This work confirms the importance of performing computational studies on boronate phases, to determine the nature of the H-bond network within the materials, and better understand their spectroscopic signatures.
Published: 2015
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44. NMR and EPR characterization of functionalized nanodiamonds

Author: Danielle Laurencin, Olivier Lafon, P. Hubert Mutin, Charlene Presti, Johan G. Alauzun, Aany Sofia Lilly Thankamony, Diego Carnevale, Cédric Lion, Hervé Vezin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Unité de Glycobiologie Structurale et Fonctionnelle UMR 8576 (UGSF), Institut National de la Recherche Agronomique (INRA)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL)-Batochime, Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et de Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Ecole Centrale de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Spectrochimie Infrarouge et Raman - UMR 8516 (LASIR), Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Analytical chemistry, Dangling bond, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Spectral line, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, law.invention, NMR spectra database, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Paramagnetism, Crystallography, General Energy, law, Magic angle spinning, Physical and Theoretical Chemistry, 0210 nano-technology, Electron paramagnetic resonance, Hyperfine structure, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract: We investigated the potential of solid-state NMR using magic angle spinning (MAS) with and without dynamic nuclear polarization (DNP) and electron paramagnetic resonance (EPR) for the characterization of functionalized nanodiamonds (NDs). We showed that conventional 1H, 31P, and 13C solid-state NMR spectra allow differentiating in a straightforward way NDs from commercial sources and custom-made NDs bearing aromatic or aliphatic phosphonate moieties at their surface. Besides, the short nuclear relaxation times prove the close proximity between the endogenous paramagnetic centers of NDs and the grafted organic moieties. EPR spectra confirmed the presence of these paramagnetic centers in functionalized NDs, which are centered on dangling bonds as well as a few N0 defects, corresponding to the substitution of carbon atoms by nitrogen ones. Hyperfine sublevel correlation spectroscopy indicates that the N0 paramagnetic centers are mostly located in the disordered shell of NDs. Preliminary DNP-enhanced NMR experiments at 9.4 T and 100 K under MAS have shown a lack of significant DNP enhancement, which can be attributed to the short relaxation times of the unpaired electrons and the nuclei in NDs. When using exogenous polarizing agents, the endogenous unpaired electrons contribute to a leakage of polarization. Furthermore, low temperatures lead to a broadening of NMR signals. It therefore appears that conventional direct excitation remains the NMR method of choice for the characterization of functionalized NDs.
Published: 2015
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45. The Effect of Surface Modification of Aligned Poly-L-Lactic Acid Electrospun Fibers on Fiber Degradation and Neurite Extension

Author: Clémentine Le Beux, Robert J. Linhardt, Ryan J. Gilbert, Jianjun Miao, Danielle Laurencin, Johan G. Alauzun, Nicholas J. Schaub, Rensselaer Polytechnic Institute (RPI), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Neurite, Plasma Gases, Scanning electron microscope, Polymers, Surface Properties, Polyesters, lcsh:Medicine, Biocompatible Materials, Contact angle, Tissue Culture Techniques, Tissue engineering, Ganglia, Spinal, Cell Adhesion, Ethylamines, Neurites, Polyamines, Animals, Fiber, Lactic Acid, lcsh:Science, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Multidisciplinary, Ethanol, Tissue Engineering, Tissue Scaffolds, Chemistry, lcsh:R, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, Nerve Regeneration, Polyester, Biophysics, Surface modification, lcsh:Q, Chickens, Hydrophobic and Hydrophilic Interactions, Oligopeptides, Research Article
Abstract: The surface of aligned, electrospun poly-L-lactic acid (PLLA) fibers was chemically modified to determine if surface chemistry and hydrophilicity could improve neurite extension from chick dorsal root ganglia. Specifically, diethylenetriamine (DTA, for amine functionalization), 2-(2-aminoethoxy)ethanol (AEO, for alcohol functionalization), or GRGDS (cell adhesion peptide) were covalently attached to the surface of electrospun fibers. Water contact angle measurements revealed that surface modification of electrospun fibers significantly improved fiber hydrophilicity compared to unmodified fibers (p < 0.05). Scanning electron microscopy (SEM) of fibers revealed that surface modification changed fiber topography modestly, with DTA modified fibers displaying the roughest surface structure. Degradation of chemically modified fibers revealed no change in fiber diameter in any group over a period of seven days. Unexpectedly, neurites from chick DRG were longest on fibers without surface modification (1651 ± 488 μm) and fibers containing GRGDS (1560 ± 107 μm). Fibers modified with oxygen plasma (1240 ± 143 μm) or DTA (1118 ± 82 μm) produced shorter neurites than the GRGDS or unmodified fibers, but were not statistically shorter than unmodified and GRGDS modified fibers. Fibers modified with AEO (844 ± 151 μm) were significantly shorter than unmodified and GRGDS modified fibers (p
Published: 2015
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46. French Studies on the Development of Potential Conditioning Matrices for Iodine 129

Author: Lionel Campayo, Sylvie Rossignol, Agnès Grandjean, Frédéric Bernard, Eglantine Courtois-Manara, Jean-Eric Lartigue, François O. Méar, Thomas Lemesle, Sophie Le Gallet, Danielle Laurencin, Antoine Coulon, Lionel Montagne, Fabienne Audubert, Laboratoire d'études de Matériaux Céramiques pour le Conditionnement (LM2C), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire des Technologies d'Elaboration des Combustibles (LTEC), Service Plutonium Uranium et Actinides mineurs (SPUA), Département d'Etudes des Combustibles (DEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Département d'Etudes des Combustibles (DEC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Interdisciplinaire Carnot de Bourgogne (LICB), Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Recherche sur la Réactivité des Solides (LRRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire des Procédés Supercritiques et de Décontamination, Commisariat de l'Energie Atomique, Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), and Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010302 applied physics, Materials science, Silver phosphate, Metallurgy, Spark plasma sintering, Sintering, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Apatite, chemistry.chemical_compound, chemistry, Chemical engineering, Powder metallurgy, Reagent, visual_art, 0103 physical sciences, visual_art.visual_art_medium, Leaching (metallurgy), 0210 nano-technology, Porosity, ComputingMilieux_MISCELLANEOUS
Abstract: Since 1991, in France, studies on the conditioning of iodine were carried out to assess the potential of several specific inorganic host matrices. The apatite family has been mainly studied because of its good chemical durability and its ability to confine iodine over geological time scales. A lead-bearing apatite, Pb10(VO4)4.8(PO4)1.2I2, and a calcium-bearing apatite, Ca10(PO4)6(OH)2-x(IO3)x, were selected on the basis of their incorporation rate (between 7 and 10 wt.%) and a satisfactory resistance to leaching (V0(50 °C, pure water) ∼ 10-2 g.m-2.d-1; Vr(50 °C, pure water) < 10-4 g.m-2.d-1). However, with such materials, the removal of open porosity requires non conventional sintering techniques like spark plasma sintering to decrease the surface exposed to water. This is why, in parallel, other matrices, like silver phosphate glasses, have also been investigated. To improve the chemical durability and thermal properties of these glasses, cross-linking reagents were added to their formulation.
Published: 2015
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47. Innentitelbild: Unleashing the Potential of 17 O NMR Spectroscopy Using Mechanochemistry (Angew. Chem. 24/2017)

Author: Danielle Laurencin, Thomas-Xavier Métro, Christian Bonhomme, Christel Gervais, and Anthony Martinez
Subjects: Crystallography, Chemistry, Mechanochemistry, General Medicine, Nuclear magnetic resonance spectroscopy
Published: 2017
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48. Inside Cover: Unleashing the Potential of 17 O NMR Spectroscopy Using Mechanochemistry (Angew. Chem. Int. Ed. 24/2017)

Author: Anthony Martinez, Thomas-Xavier Métro, Danielle Laurencin, Christel Gervais, and Christian Bonhomme
Subjects: Isotopic labeling, 010405 organic chemistry, Chemistry, Mechanochemistry, Analytical chemistry, Cover (algebra), General Chemistry, 010402 general chemistry, Spectroscopy, 01 natural sciences, Ball mill, Catalysis, 0104 chemical sciences
Published: 2017
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49. Immobilization of iodine into a hydroxyapatite structure prepared by cementation

Author: Danielle Laurencin, Agnès Grandjean, Celine Cau Dit Coumes, Sylvie Rossignol, Antoine Coulon, Lionel Campayo, Laboratoire d'études de Matériaux Céramiques pour le Conditionnement (LM2C), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Service des Procedés de Décontamination et d'Enrobage des Déchets (SPDE), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Renewable Energy, Sustainability and the Environment, Metallurgy, chemistry.chemical_element, Tetracalcium phosphate, ttcp, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Iodine, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Chemical engineering, Cementation (metallurgy), General Materials Science, Cementitious, 0210 nano-technology, Porosity, Sodium iodate, Iodate
Abstract: International audience; In order to manage radioactive iodine-129 coming from nuclear spent fuel, robust host matrices with durable long term behaviour need to be developed. In this work, a new process of synthesis of an iodate-substituted hydroxyapatite by means of a cementation route is described. This material was obtained from a mixture of tetracalcium phosphate (TTCP), tricalcium phosphate (αTCP) and sodium iodate (NaIO3), taken in a molar ratio of 1/2/0.5. The progress of the reaction leading to the setting and hardening of cement paste was monitored by combined measurements of electrical conductivity and heat flux release, together with XRD characterization of materials at definite times of hydration. Sodium iodate acts as a set retarder, by leading to the precipitation of non-cohesive transient phases, which are then destabilized when the massive precipitation of hydroxyapatite occurs. These delays can however be limited by adding hydroxyapatite seeds to the cement paste, which means that it is possible to control the setting time in view of an industrial application. This novel cementitious system leads to a porous material composed of iodine-substituted hydroxyapatite needles covering residual TTCP and αTCP particles. Iodine has entered the hydroxyapatite structure in the form of iodate anions only. An iodine incorporation rate of 6.5 wt% has been obtained by this cementitious system, which is a promising value in view of using these materials for the conditioning of radioactive iodine.
Published: 2014
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50. Synthesis of TiO2-poly(3-hexylthiophene) Hybrid Particles through Surface-Initiated Kumada Catalyst-Transfer Polycondensation

Author: Philippe Dubois, Ahmad Mehdi, Sébastien Richeter, David Moerman, Florian Boon, Danielle Laurencin, Yannick Guari, Sébastien Clément, Roberto Lazzaroni, Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), Laboratoire de Chimie des Matériaux et Polymères (SMPC), Université de Mons-Hainaut, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chimie moléculaire et organisation du solide (CMOS), Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS), and Service de Chimie des Matériaux Nouveaux
Subjects: Organic electronics, chemistry.chemical_classification, Thermogravimetric analysis, Materials science, Condensation polymer, Surfaces and Interfaces, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, Conjugated system, Condensed Matter Physics, 7. Clean energy, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, Polymer chemistry, Dispersion stability, Electrochemistry, General Materials Science, Dispersion (chemistry), Hybrid material, Spectroscopy
Abstract: International audience; TiO2/conjugated polymers are promising materials in solar energy conversion where efficient photo-induced charge transfers are required. Here, a 'grafting-from' approach for the synthesis of TiO2 nanoparticles supported with conjugated polymer brushes is presented. Poly(3-hexylthiophene) (P3HT), a benchmark material for organic electronics, was selectively grown from TiO2 nanoparticles by Surface-Initiated Kumada Catalyst-Transfer Polycondensation (SI-KCTP). The grafting of the polymer onto the surface of the TiO2 nanoparticles by this method was demonstrated by 1H and 13C solid-state NMR, XPS (X-ray photoelectron spectrometry), thermogravimetric analysis (TGA), Transmission Electron Microscopy (TEM) and UV-Visible spectroscopy. Sedimentation tests in THF revealed improved dispersion stability for the TiO2@P3HT hybrid material. Films were produced by solvent casting and the quality of the dispersion of the modified TiO2 nanoparticles was evaluated by Atomic Force Microscopy (AFM). The dispersion of the P3HT-coated TiO2 NPs in the P3HT matrix was found to be homogeneous and the fibrillar structure of the P3HT matrix was maintained which is favourable for charge transport. Fluorescence quenching measurements on these hybrids materials in CHCl3 indicated improved photo-induced electron transfer efficiency. All in all, better physicochemical properties for P3HT/TiO2 hybrid material were reached via surface-initiated "grafted from" approach compared to the "grafting onto" approach
Published: 2014
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