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  • B. Martinez, C. Livache, E. Meriggio, X. Z. Xu, H. Cruguel, E. Lacaze, A. Proust, S. Ithurria, M. G. Silly, G. Cabailh, F. Volatron, et E. Lhuillier, « Polyoxometalate as Control Agent for the Doping in HgSe Self-Doped Nanocrystals », The Journal of Physical Chemistry C, vol. 122, nᵒ 46, p. 26680-26685, nov. 2018.
    Résumé : Intraband and plasmonic transitions have appeared over the last years as an interesting tool to achieve optical absorption in the mid-infrared. Tuning the doping magnitude has become a major challenge not only to tune the optical spectrum but also properties such as the dark current or the time response. Here, we investigate the case of self-doped HgSe colloidal quantum dots (CQDs). At present, tuning of the doping relies on band bending induced by a dipole design at the nanoparticle surface. With such a surface gating approach, it is difficult to conciliate both massive tuning of the Fermi level and the preservation of transport properties of the CQD arrays. Here, we propose a strategy to graft functionalized polyoxometalates (POMs) at the CQD surface and obtain simultaneously a massive tuning of the carrier density (≈5 electrons per nanoparticle) and conduction properties. We bring a consistent demonstration of the HgSe CQD doping decrease by a charge transfer to the POM. This method is highly promising for large tuning of carrier density in degenerately doped semiconductor nanoparticles.
    Mots-clés : E-POM.

  • F. Medici, G. Gontard, E. Derat, G. Lemière, et L. Fensterbank, « Synthesis of Stable Pentacoordinate Silicon(IV)–NHC Adducts: An Entry to Anionic N-Heterocyclic Carbene Ligands », Organometallics, vol. 37, nᵒ 4, p. 517-520, févr. 2018.
    Résumé : This work features the previously undescribed interactions of Martin’s spirosilane with different types of N-heterocyclic carbenes (NHCs). The level of interaction proved to be strongly dependent on the size of the Lewis base and could vary from the formation of isolable classical Lewis adducts to abnormal Lewis adducts, as evidenced by X-ray diffraction structure analyses and NMR studies. It has been found that abnormal adducts could be used as precursors for the synthesis of anionic NHCs bearing a weakly coordinating siliconate component. Complexation of these new types of carbenes with gold(I) and copper(I) has been efficiently accomplished. DFT calculations performed on the siliconate-based anionic NHC ligands revealed a high-lying HOMO and therefore a strong σ-donor character.
    Mots-clés : MACO, POLE 1.

  • G. Mellot, P. Beaunier, J. - M. Guigner, L. Bouteiller, J. Rieger, et F. Stoffelbach, « Beyond Simple AB Diblock Copolymers: Application of Bifunctional and Trifunctional RAFT Agents to PISA in Water », Macromolecular Rapid Communications, p. 1800315, 2018.
    Résumé : The influence of the macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent architecture on the morphology of the self-assemblies obtained by aqueous RAFT dispersion polymerization in polymerization-induced self-assembly (PISA) is studied by comparing amphiphilic AB diblock, (AB)2 triblock, and triarm star-shaped (AB)3 copolymers, constituted of N,N-dimethylacrylamide (DMAc = A) and diacetone acrylamide (DAAm = B). Symmetrical triarm (AB)3 copolymers could be synthesized for the first time in a PISA process. Spheres and higher order morphologies, such as worms or vesicles, could be obtained for all types of architectures and the parameters that determine their formation have been studied. In particular, we found that the total DPn of the PDMAc and the PDAAm segments, i.e., the same overall molar mass, at the same Mn(PDMAc)/Mn(PDAAm) ratio, rather than the individual length of the arms determined the morphologies for the linear (AB)2 and star shaped (AB)3 copolymers obtained by using the bi- and trifunctional macro-RAFT agents.
    Mots-clés : aqueous RAFT dispersion polymerizations, architectures, morphologies, PISA, POLE 4, POLYMERES, triarm star copolymers.

  • G. Mellot, J. - M. Guigner, L. Bouteiller, F. Stoffelbach, et J. Rieger, « Templated-PISA: Driving Polymerization-Induced Self-Assembly towards the Fibre Morphology », Angewandte Chemie International Edition, nᵒ ja, 2018.
    Résumé : Dispersions of block-copolymer fibres in water have many potential applications and can be obtained by polymerization-induced self-assembly (PISA), but only in very restricted experimental conditions. In order to enlarge this experimental window, we introduced a supramolecular moiety, a hydrogen-bonded bis-urea sticker, in the macromolecular reversible addition-fragmentation chain transfer agent to drive the morphology of the nano-objects produced by RAFT-mediated PISA towards the fibre morphology. This novel concept is tested in the synthesis of a series of poly(N,N-dimethylacrylamide)-b-poly(2-methoxyethyl acrylate) (PDMAc-b-PMEA) diblock copolymers prepared by dispersion polymerization in water. The results prove that the introduction of the templating bis-urea stickers into PISA greatly promotes the formation of fibres in a large experimental window.
    Mots-clés : block copolymers, hydrogen bonds, Nanoparticles, POLYMERES, self-assembly, supramolecular chemistry.
    Pièce jointe Full Text PDF 1.6 Mo (source)

  • G. Mellot, J. - M. Guigner, J. Jestin, L. Bouteiller, F. Stoffelbach, et J. Rieger, « Bisurea-Functionalized RAFT Agent: A Straightforward and Versatile Tool toward the Preparation of Supramolecular Cylindrical Nanostructures in Water », Macromolecules, déc. 2018.
    Résumé : We report a versatile and simple approach to produce cylindrical micelles by the direct dissolution of polymers in water. The developed strategy relies on a RAFT agent functionalized by a bisurea sticker that allowed to synthesize a series of α-bisurea-functionalized poly(N,N-dimethylacrylamide) (PDMAc), poly(acrylic acid) (PAA), polyacrylamide (PAM), and poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) with number-average degrees of polymerization (DPn) varying from about 10 to 50. Their spontaneous self-assembly in water was studied by electron microscopy (cryo-TEM), neutron scattering (SANS), and calorimetry (ITC) analyses which showed that long cylindrical micelles are spontaneously formed in water. The crucial role of the bisurea sticker end-groups was established by comparison with the corresponding bisurea-free model polymers that only formed spherical micelles. Finally, we have shown that it is possible to trigger reversibly the assembly/disassembly of the nanofibers by pH changes.
    Mots-clés : POLE 4, POLYMERES.

  • M. Ménand, M. Sollogoub, B. Boitrel, et S. Le Gac, « Cyclodextrin-Sandwiched Hexaphyrin Hybrids: Side-to-Side Cavity Coupling Switched by a Temperature- and Redox-Responsive Central Device », Chemistry - A European Journal, vol. 24, nᵒ 22, p. 5804-5812, avr. 2018.

  • F. Mercier-Bion, J. Li, H. Lotz, L. Tortech, D. Neff, et P. Dillmann, « Electrical properties of iron corrosion layers formed in anoxic environments at the nanometer scale », Corrosion Science, vol. 137, p. 98-110, juin 2018.
    Résumé : The electrical properties of the corrosion layers on archaeological iron artefacts were determined by Conductive Atomic Force Microscopy. Different corrosion products were studied: FeII carbonates, magnetite entrapped in the carbonate, and iron sulfides. The results indicate that the ferrous carbonate matrix is insulating, and that magnetite and iron sulfides have a conductive character, although these phases are not systematically connected to the metal. This suggests that electrons produced by the anodic dissolution of metal would be conducted to the external part of the corrosion product layer through a three-dimensional network of connected magnetite strips passing through the ferrous carbonate matrix.
    Mots-clés : Archaeological artefact, C-AFM, E-POM, Electrical properties, FESEM, Iron corrosion, POLE 2, μRaman.

  • V. Mouriès-Mansuy e

    t L. Fensterbank, « Gold-Catalyzed Migration of Propargyl Acetate as an Entry into the Total Synthesis of Natural Products », Israel Journal of Chemistry, vol. 58, nᵒ 5, p. 586-595, avr. 2018.
    Résumé : Abstract Gold catalysis has emerged over the last two decades as a protocole of choice for the efficient and selective activation of a variety of organic functional groups. This has served to the total synthesis of natural products at several occasions. In this context, the gold-catalyzed migration (1,2- or 1,3-) of propargyl acetates has been particularly used. This review highlights these different synthetic developments which are presented according to the involved mechanisms.
    Mots-clés : acetate migration, gold catalysis, MACO, organogold intermediate, POLE 1, propargyl acetate, total synthesis.
    Pièce jointe Full Text PDF 4.6 Mo (source)

  • F. Najlaoui, P. Pigeon, S. Aroui, M. Pezet, L. Sancey, N. Marrakchi, A. Rhouma, G. Jaouen, M. Waard, B. Busser, et S. Gibaud, « Anticancer properties of lipid and poly(ε-caprolactone) nanocapsules loaded with ferrocenyl-tamoxifen derivatives », Journal of Pharmacy and Pharmacology, vol. 70, nᵒ 11, p. 1474-1484, 2018.
    Résumé : Abstract Objective We synthesized new tamoxifen derivatives as anticancer drug candidates and elaborated on convection-enhanced delivery (CED) as a strategy for delivery. Methods To overcome the issue of their poor solubility, these ferrocenyl-tamoxifen derivatives were esterified and encapsulated into different nanocarriers, that is lipid (LNC) and polymeric nanocapsules (PNL-NC). We describe the chemistry, the encapsulation and the physicochemical characterization of these formulations. Key findings Starting compounds [phthalimido-ferrocidiphenol and succinimido-ferrocidiphenol], esterified prodrugs and their nanocapsules formulations were characterized. These drug candidates displayed a strong in vitro activity against breast and glioblastoma cancer cells. The ester prodrugs were toxic for glioblastoma cells (IC50 = 9.2 ? 10?2 ?m and 6.7 ? 10?2 ?m, respectively). The IC50 values for breast cancer cells were higher for these compounds. The encapsulation of the esterified compounds in LNCs (≈50 nm) or PCL-NCs (≈300 nm) did not prevent their efficacy on glioblastoma cells. These anticancer effects were due to both blockade in the S-phase of the cell cycle and apoptosis. Moreover, the tamoxifen derivatives-loaded nanocapsules induced no toxicity for healthy astrocytes and showed no haemolytic properties. Loaded Lipid Nanocapsules (LNCs) presented interesting profiles for the optimal delivery of active compounds. Conclusions Phthalimido- and Succinimido-esters represent an innovative approach to treat cancers with cerebral localizations such as glioblastoma or brain metastases from breast cancers.
    Mots-clés : breast cancer, CHEMBIO, ferrocenyl-tamoxifen derivatives, glioblastoma, Lipid nanocapsules, POLE 3, polymer nanocapsules.
    Note Note
    <p>doi: 10.1111/jphp.12998</p>

  • R. K. Nandi, A. Perez‐Luna, D. Gori, R. Beaud, R. Guillot, C. Kouklovsky, V. Gandon, et G. Vincent, « Triflic Acid as an Efficient Brønsted Acid Promoter for the Umpolung of N‐Ac Indoles in Hydroarylation Reactions », Advanced Synthesis & Catalysis, vol. 360, nᵒ 1, p. 161-172, janv. 2018.

  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, et J. M. García Fernández, « Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins », The Journal of Organic Chemistry, vol. 83, nᵒ 10, p. 5588-5597, mai 2018.

  • E. Nikoloudakis, K. Karikis, M. Laurans, C. Kokotidou, A. Solé-Daura, J. J. Carbó, A. Charisiadis, G. Charalambidis, G. Izzet, A. Mitraki, A. M. Douvas, J. M. Poblet, A. Proust, et A. G. Coutsolelos, « Self-assembly study of nanometric spheres from polyoxometalate-phenylalanine hybrids, an experimental and theoretical approach », Dalton Transactions, vol. 47, nᵒ 18, p. 6304-6313, mai 2018.
    Résumé : Herein, we report on the study of supramolecular assemblies based on polyoxometalates (POMs) upon their modification with amino acids. Two POM-amino acid hybrids were synthesized by coupling a functionalized Keggin type polyoxoanion [PW11O39{Sn(C6H4)CC(C6H4)COOH}]4− with carboxyl-protected (methyl-ester) phenylalanine or diphenylalanine peptides. Surprisingly, all compounds, including the initial POM, formed supramolecular nanospheres in different solvent mixtures, which were examined by scanning electron microscopy (SEM). Molecular dynamics (MD) simulations for the POM-amino acid species revealed that the hydrophobic forces are mainly responsible for the initial aggregation into incipient micelle type structures, in which the organic arms are buried inside the aggregate while POM polar heads are more exposed to the solvent with tetrabutyl-ammonium counter cations acting as linkers.
    Mots-clés : E-POM.
    Pièce jointe Full Text PDF 6.6 Mo (source)

  • Y. Ning, J. Cui, Y. Lu, X. Wang, C. Xiao, S. Wu, J. Li, et Y. Zhang, « De novo design and synthesis of a novel colorimetric fluorescent probe based on naphthalenone scaffold for selective detection of hypochlorite and its application in living cells », Sensors and Actuators B: Chemical, vol. 269, p. 322-330, 2018.

  • Y. Ning, X. Wang, K. Sheng, L. Yang, W. Han, C. Xiao, J. Li, Y. Zhang, et S. Wu, « A novel colorimetric and fluorescence turn-on pH sensor with a notably large Stokes shift for its application », New Journal of Chemistry, vol. 42, nᵒ 17, p. 14510-14516, 2018.

  • D. R. Nunes, M. Raynal, B. Isare, P. - A. Albouy, et L. Bouteiller, « Organogel formation rationalized by Hansen solubility parameters: improved methodology », Soft Matter, vol. 14, nᵒ 23, p. 4805-4809, juin 2018.
    Résumé : An organogel is obtained when a low molar mass compound forms a network of anisotropic fibres in a liquid that is therefore transformed into a macroscopic solid. Various approaches have been proposed to correlate organogel formation and Hansen solubility parameters. These approaches are well adapted to specific experimental datasets but lack universality. A general method to determine the gelation domain from the solubility data of low molecular weight gelators is here reported.
    Mots-clés : POLE 4, POLYMERES.
    Pièce jointe Full Text PDF 2.2 Mo (source)

  • Ortiz Mayreli, Debela Ahmed M., Méthivier Christophe, Thorimbert Serge, Hasenknopf Bernold, et O'Sullivan Ciara K., « Stable Carboxylate-Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyltin Compound », Chemistry – A European Journal, vol. 24, nᵒ 43, p. 11177-11184, 2018.
    Résumé : Abstract Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol?gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. Herein, it is demonstrated that a ca

    rboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques were used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long-term stability studies over a period of one year, demonstrating thermostability up to 90?°C and storage stability for at least 12?months at 4?°C protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications, including molecular techniques, such as solid-phase amplification and solid-phase melting curve analysis, that require elevated temperature stability, as well as biosensors, which require long-term storage stability.
    Mots-clés : biosensors, CHEMBIO, electrochemistry, GOBS, gold, POLE 3, surface chemistry, tin.
    Note Note
    <p>doi: 10.1002/chem.201801854</p>

  • S. Ouedraogo, B. Chouchene, C. Desmarets, T. Gries, L. Balan, R. Fournet, G. Medjahdi, K. Bayo, et R. Schneider, « Copper octacarboxyphthalocyanine as sensitizer of graphitic carbon nitride for efficient dye degradation under visible light irradiation », Applied Catalysis A- General, vol. 563, p. 127-136, août 2018.
    Résumé : In this paper, copper octacarboxyphthalocyanine (CuPc) was demonstrated to be an efficient photosensitizer of graphitic carbon nitride (g-CN) for the degradation of dyes like Orange II or Methylene Blue under visible light irradiation. UV–vis absorption, photoluminescence and photocurrent measurements demonstrate that CuPc not only allows to extend the absorption to wavelengths up to 1000 nm but also enhances the charge-transfer efficiency. The high photocatalytic efficiency of CuPc/g-CN nanohybrids originates from the strong association between the carboxylic acid groups of CuPc with g-CN which favor the transfer of photo-excited electrons from CuPc to g-CN. The CuPc/g-CN catalyst is stable, can be reused up to five times without significant loss of activity and is therefore of high potential for photocatalytic applications like wastewater treatment or hydrogen production under visible or near-infrared irradiation.
    Mots-clés : ARC, Copper octacarboxyphthalocyanine, Graphitic carbon nitride, Nanohybrids, Photocatalysis, POLE 1.

  • K. Passador, S. Thorimbert, et C. Botuha, « Heteroaromatic Rings of the Future’: Exploration of Unconquered Chemical Space », Synthesis, vol. 51, nᵒ 02, p. 384-398, nov. 2018.
    Résumé : William Pitt and co-workers have created a virtual exploratory heterocyclic library ‘VEHICLe’ containing over 200 unconquered bicyclic heteroaromatic rings, synthetically feasible with potential medicinal interest. Since the publication of the 22 ‘heteroaromatic rings of the future’ by Pitt in 2009, 15 of them have been successfully synthesized as bicyclic or polycyclic forms and evaluated for applications in both biology and material science. This short review presents the critical synthesis associated with innovative synthetic methodologies of the synthetically conquered ring scaffolds from the list of 22 with a spotlight on the scientific contribution of this fascinating article for the expansion of the chemical diversity.
    Mots-clés : CHEMBIO, POLE 3.

  • M. Piot, B. Abécassis, D. Brouri, C. Troufflard, A. Proust, et G. Izzet, « Control of the hierarchical self-assembly of polyoxometalate-based metallomacrocycles by redox trigger and solvent composition », Proceedings of the National Academy of Sciences, vol. 115, nᵒ 36, p. 8895-8900, sept. 2018.
    Résumé : Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe the formation of hierarchical nanostructures using preformed metallomacrocycles by coordination-driven self-assembly of a covalent organic–inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage of the presence of charged subunits (POM, metal linker, and counterions) within the metallomacrocycles, which drive their aggregation through intermolecular electrostatic interactions. We show that the solvent composition and the charge of the metal linker are key parameters that steer the supramolecular organization. Different types of hierarchical self-assemblies, zero-dimensional (0D) dense nanoparticles, and 1D worm-like nanoobjects, can be selectively formed owing to different aggregation modes of the metallomacrocycles. Finally, we report that the worm-like structures drastically enhance the solubility in water of a pyrene derivative and can act as molecular carriers.
    Mots-clés : E-POM, hierarchical self-assembly, molecular carrier, organic–inorganic hybrids, polyoxometalates, SAXS.
    Pièce jointe Full Text PDF 1.1 Mo (source)

  • R. Plamont, J. Tami, J. - R. Jimenez, A. Benchohra, O. Khaled, G. Gontard, Y. Li, et R. Lescouëzec, « A soluble cyanide-bridged {Fe <sub>4</sub> Ni <sub>4</sub> } box encapsulating a Cs <sup>+</sup> ion: synthesis, structure and electronic properties », Journal of Coordination Chemistry, vol. 71, nᵒ 5, p. 601-614, mars 2018.

  • C. Przybylski, J. M. Benito, V. Bonnet, C. O. Mellet, et J. M. García Fernández, « Revealing cooperative binding of polycationic cyclodextrins with DNA oligomers by capillary electrophoresis coupled to mass spectrometry », Analytica Chimica Acta, vol. 1002, p. 70-81, 2018.

  • E. Rathahao-Paris, S. Alves, N. Boussaid, N. Picard-Hagen, V. Gayrard, P. - L. Toutain, J. - C. Tabet, D. N. Rutledge, et A. Paris, « Evaluation and validation of an analytical approach for high-throughput metabolomic fingerprinting using direct introduction–high-resolution mass spectrometry: Applicability to classification of urine of scrapie-infected ewes », European Journal of Mass Spectrometry, p. 146906671880645, oct. 2018.

  • M. Raynal et L. Bouteiller, « Polymères supramoléculaires et catalyse asymétrique - L'Actualité Chimique », L'Actualité Chimique, nᵒ 430-431, p. 37-41, 2018.
    Résumé : Dans le but de développer des catalyseurs asymétriques innovants, des sites catalytiques ont été connectés à des polymères supramoléculaires adoptant une configuration hélicoïdale. Les avantages de cette nouvelle classe de catalyseurs sont que leur composition peut être aisément modulée, qu’une quantité minimale de monomères chiraux est utilisée sans diminuer la sélectivité (amplification de chiralité) et que leur sélectivité est contrôlée en temps réel. Toutes ces propriétés, démontrées pour des réactions métallo-catalysées (Rh, Cu), ne sont pas accessibles avec des catalyseurs conventionnels basés sur des liaisons covalentes. L’utilisation de ces catalyseurs supramoléculaires pour la préparation de petites molécules d’intérêt ou de polymères, non accessibles via les méthodes catalytiques conventionnelles, est envisageable.
    Mots-clés : POLE 4, POLYMERES.

  • Y. Ren, K. Cheaib, J. Jacquet, H. Vezin, L. Fensterbank, M. Orio, S. Blanchard, et M. Desage‐El Murr, « Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis », Chemistry – A European Journal, vol. 24, nᵒ 20, p. 5086-5090, avr. 2018.
    Résumé : Small-molecule catalysts as mimics of biological systems illustrate the chemists’ attempts at emulating the tantalizing abilit

    ies displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.
    Mots-clés : aziridination, copper catalysis, E-POM, MACO, multistate reactivity, POLE 1, POLE 2, redox-active ligands, spin catalysis.
    Pièce jointe Full Text PDF 963.4 ko (source)

  • J. - C. Ribierre, T. Tanaka, L. Zhao, Y. Yokota, S. Matsumoto, D. Hashizume, K. Takaishi, T. Muto, B. Heinrich, S. Méry, F. Mathevet, T. Matsushima, M. Uchiyama, C. Adachi, et T. Aoyama, « Simultaneous Edge-on to Face-on Reorientation and 1D Alignment of Small π-Conjugated Molecules Using Room-Temperature Mechanical Rubbing », Advanced Functional Materials, vol. 28, nᵒ 19, p. 1707038, mai 2018.
    Résumé : In this study, room-temperature mechanical rubbing is used to control the 3D orientation of small π-conjugated molecular systems in solution-processed polycrystalline thin films without using any alignment substrate. High absorption dichroic ratio and significant anisotropy in charge carrier mobilities (up to 130) measured in transistor configuration are obtained in rubbed organic films based on the ambipolar quinoidal quaterthiophene (QQT(CN)4). Moreover, a solvent vapor annealing treatment of the rubbed film is found to improve the optical and charge transport anisotropy due to an increased crystallinity. X-ray diffraction and atomic force microscopy measurements demonstrate that rubbing does not only lead to an excellent 1D orientation of the QQT(CN)4 molecules over large areas but also modifies the orientation of the crystals, moving molecules from an edge-on to a face-on configuration. The reasons why a mechanical alignment technique can be used at room temperature for such a polycrystalline film are rationalized, by the plastic characteristics of the QQT(CN)4 layer and the role of the flexible alkyl side chains in the molecular packing. This nearly complete conversion from edge-on to face-on orientation by mechanical treatment in polycrystalline small-molecule-based thin films opens perspectives in terms of fundamental research and practical applications in organic optoelectronics.
    Mots-clés : ambipolar organic field-effect transistors, crystalline domain orientation, mechanical rubbing, molecular alignments, POLE 4, POLYMERES, small π-conjugated molecules.

  • S. Roland, J. Meijide Suarez, et M. Sollogoub, « Confinement of Metal-N-Heterocyclic Carbene Complexes to control reactivity in catalytic reactions », Chemistry - A European Journal, avr. 2018.

  • F. Roudesly, L. F. Veiros, J. Oble, et G. Poli, « Pd-Catalyzed Direct C–H Alkenylation and Allylation of Azine N-Oxides », Organic Letters, vol. 20, nᵒ 8, p. 2346-2350, avr. 2018.
    Résumé : A Pd-catalyzed direct C2-alkenylation of azine N-oxides with allyl acetate is disclosed. The products are formed through an allylation/isomerization cascade process. The use of a tri-tert-butylphosphonium salt as the ligand precursor and KF is mandatory for optimal yields. When cinnamyl acetate is used, the same catalytic system promotes C2-cinnamylation of the azine N-oxide without subsequent isomerization. A mechanism is proposed on the basis of experimental studies and DFT calculations.
    Mots-clés : POLE 1, ROCS.

  • H. Sesolis, G. Gontard, A. Jutand, M. P. Gullo, E. Bandini, A. Barbieri, et H. Amouri, « A Convenient Approach to Luminescent Cyclometalated Platinum(II) Complexes with Organometallic π-Bonded Benzenedithiolate », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 34, p. 3804-3812, 2018.
    Résumé : A family of neutral cyclometalated platinum(II) complexes [(C^N)Pt(η-S^S)] with π-bonded benzenedithiolate (η-S^S) = Cp*Ru(C6H4S2) and various cyclometalated ligands, (C^N) = 2-phenylpyridine (ppy), (2); 2,4-difluorophenylpyridine (F2ppy) (3), benzo[h]quinoline (bzq) (4); dibenzo[f,h]quinoline (dbzq) (5) were prepared and fully characterized. For comparison purposes the related bipyridine platinum(II) complex [(bpy)Pt(η-S^S)][OTf] (6) was also prepared. The electrochemistry behavior of these complexes was investigated and shows the enhanced stability of these compounds toward oxidation due to the presence of Cp*Ru moiety which is now π-bonded to the benzenedithiolato group. Moreover, several complexes were identified by single-crystal X-ray molecular structures. To the best of our knowledge, these are the first structures to be reported for cyclometalated platinum complexes with a π-bonded benzenedithiolate (bdt) ligand. All of the complexes are luminescent in fluid solution at room temperature and in glassy solution at 77 K; their emission properties can be tuned through ligand variation.
    Mots-clés : ARC, Cyclometalated complexes, Luminescence, Photophysics, Platinum, POLE 1, Structure elucidation.

  • F. Siopa, V. - A. R. Cladera, C. A. M. Afonso, J. Oble, et G. Poli, « Ruthenium-Catalyzed C-H Arylation and Alkenylation of Furfural Imines with Boronates », European Journal of Organic Chemistry, vol. 2018, nᵒ 44, p. 6101-6106, 2018.
    Résumé : A Ru0-catalyzed direct C-H arylation and alkenylation of furfural imines with aryl- or alkenyl-boronates, in the presence of benzylideneacetone as a sacrificial hydride acceptor, is disclosed. This reaction provides access, after hydrolysis, to C3-arylated or vinylated furfural derivatives, and thus valorizes these relevant building-blocks obtained from lignocellulosic biomass. This approach, involving C-H activation by a Ru0/RuII, cycle offers several advantages, notably simple, mild and neutral reaction conditions.
    Mots-clés : Boronate derivatives, C-H activation, Furfurals, Imines, POLE 1, ROCS, Ruthenium.

  • P. Stiernet, M. Dréan, C. Jérôme, P. Midoux, P. Guégan, J. Rieger, et A. Debuigne, « Tailor-Made Poly(vinylamine)s via Thermal or Photochemical Organometallic Mediated Radical Polymerization », in Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies, vol. 1284, American Chemical Society, 2018, p. 349-363.
    Résumé : Poly(vinylamine) is a highly valuable class of polymer used in several applications. Although free radical polymerization has been extensively exploited for its synthesis, the preparation of poly(vinylamine) with low dispersity and controlled molar mass is barely developed. Recently, a great step was made in this direction via organometallic-mediated radical polymerization (OMRP) of N-vinylacetamides followed by hydrolysis of the pendent amide groups. This chapter summarizes, completes and put in perspective the main accomplishments in the OMRP of acyclic N-vinylamides for the controlled synthesis of both primary and secondary poly(vinylamine)s. Thermal and photochemical initiating systems are compared and the controlled thermally initiated radical polymerization of N-vinylacetamide is reported for the first time. The optimal hydrolysis conditions for producing the poly(vinylamine) derivatives as well as their potential as vectors for gene transfection are also presented.
    Mots-clés : POLE 4, POLYMERES.

  • Y. Tang, Z. - Y. Zhu, Y. Liu, H. Sun, Q. - Y. Song, et Y. Zhang, « The chemical structure and anti-aging bioactivity of an acid polysaccharide obtained from <i>rose</i> buds », Food & Function, vol. 9, nᵒ 4, p. 2300-2312, 2018.

  • A. Tomer, B. T. Kusema, J. - F. Paul, C. Przybylski, E. Monflier, M. Pera-Titus, et A. Ponchel, « Cyclodextrin-assisted low-metal Ni-Pd/Al2O3 bimetallic catalysts for the direct amination of aliphatic alcohols », Journal of Catalysis, vol. 368, p. 172-189, 2018.

  • K. Tõnsuaadu, M. Gruselle, F. Kriisa, A. Trikkel, P. Gredin, et D. Villemin, « Dependence of the interaction mechanisms between l-serine and O-phospho-l-serine with calcium hydroxyapatite and copper modified hydroxyapatite in relation with the acidity of aqueous medium », JBIC Journal of Biological Inorganic Chemistry, vol. 23, nᵒ 6, p. 929-937, août 2018.
    Résumé : Motivated by the role of copper ions in biological processes the aim of this study was to elucidate the impact of copper ions bound to hydroxyapatite on l-serine (l-Ser) and O-phospho-l-serine (O-Ph-l-Ser) adsorption at different acidity of aqueous solutions. The adsorption phenomenon was studied by FTIR, UV, and AA spectroscopy, XRD and thermal analysis methods together with the evolved gases analysis taking into consideration the ionic state of the amino acids as well as the apatite surface state, which are tightly correlated with the solution pH. In acidic solution, the main process involves apatite dissolution releasing calcium and copper ions. At pH > 5 the complexation of amino acids with Ca2+ or Cu2+ ions is more important leading also to the release of cations. The ability of copper ions to form water soluble complexes with l-Ser and O-Ph-l-Ser leads to an important loss of these ions, while calcium release is very low at this pH. Therefore, the use of copper ions substituting calcium in the apatite structure to enhance the ability of amino acids adsorption on the apatite surface seems problematic even at pH > 5.
    Mots-clés : Adsorption, ARC, Calcium hydroxyapatite, Copper modified hydroxyapatite, l-Serine, O-Phospho-l-serine, POLE 1.

  • A. T. Tran, A. Sadet, P. Calligari, P. Lopes, J. Ouazzani, M. Sollogoub, E. Miclet, et D. Abergel, « Targeting the Pentose Phosphate Pathway: Characterization of a New 6PGL Inhibitor », Biophysical Journal, 2018.

  • Y. Wang, P. M. Dansette, P. Pigeon, S. Top, M. J. McGlinchey, D. Mansuy, et G. Jaouen, « A new generation of ferrociphenols leads to a great diversity of reactive metabolites, and exhibits remarkable antiproliferative properties », Chemical Science, vol. 9, p. 70-78, 2018.

  • Y. Wang, F. Heinemann, S. Top, A. Dazzi, C. Policar, L. Henry, F. Lambert, G. Jaouen, M. Salmain, et A. Vessieres, « Ferrocifens labelled with an infrared rhenium tricarbonyl tag: synthesis, antiproliferative activity, quantification and nano IR mapping in cancer cells », Dalton Transactions, vol. 47, p. 9824-9833, 2018.
    Résumé : Antiproliferative activities of several members of the ferrocifen family, both in vitro and in vivo, are well documented although their precise location in cancer cells has not yet been elucidated. However, two different infrared imaging techniques have been used to map the non-cytotoxic cyrhetrenyl analogue of ferrociphenol in a single cell. This observation prompted us to tag two ferrocifens with a cyrhetrenyl unit [CpRe(CO)3; Cp = η5-cyclopentadienyl] by grafting it, via an ester bond, either to one of the phenols (4, 5) or to the hydroxypropyl chain (6). Complexes 4–6 retained a high cytotoxicity on breast cancer cells (MDA-MB-231) with IC50 values in the range 0.32–2.5 μM. Transmission IR spectroscopy was used to quantify the amount of cyrhetrenyl tag present in cells incubated with 5 or 6. The results show that after a 1-hour incubation of cells at 37 °C, complexes 5 and 6 are mainly present within cells while only a limited percentage, quantified by ICP-OES, remained in the incubation medium. AFM-IR spectroscopy, a technique coupling infrared irradiation with near-field AFM detection, was used to map the cyrhetrenyl unit in a single MDA-MB-231 cell, incubated at 37 °C for 1 hour with 10 μM of 6. The results show that signal distribution of the characteristic band of the Re(CO)3 entity at 1950 cm−1 matched those of amide and phosphate, thus indicating a location of the complex mainly in the cell nucl
    Mots-clés : CHEMBIO, POLE 3.

  • J. Wengler, S. Ognier, M. Zhang, E. Levernier, C. Guyon, C. Ollivier, L. Fensterbank, et M. Tatoulian, « Microfluidic chips for plasma flow chemistry: application to controlled oxidative processes », Reaction Chemistry & Engineering, oct. 2018.
    Résumé : The present paper reports the integration of nonthermal plasma into a biphasic gas–liquid microfluidic chip. It evaluates the potential of plasma activation to become a synthetic tool in organic chemistry, operating under mild conditions (room temperature, atmospheric pressure) and without a catalyst. Few preceding works on plasma chemistry involved a liquid phase and none of them was able to handle the high reactivity of plasma to achieve both high conversion rates and selective reactions. We fabricated a glass-polymer microfluidic chip comprising a one metre long serpentine channel, in which a parallel gas–liquid flow was stabilized thanks to a specific step-like cross-sectional shape. Transparent ITO electrodes, deposited on both sides of the chip and linked to an AC high voltage source, produced a dielectric barrier discharge along the channel. We assessed the behaviour of the flow through optical observations and characterized the discharge through electrical measurements and real time intensified-CCD monitoring. We report the successful treatment of liquid cyclohexane with oxygen plasma inside our chip. The GC analysis of the outflowing liquid revealed only a partial oxidation of cyclohexane into a mixture of cyclohexanol and cyclohexanone (industrially known as “KA oil”), and cyclohexyl hydroperoxide, with a total selectivity above 70% and conversion up to 30%. This indicates that alkanes can be activated and functionalized by means of plasma discharges, in a controlled way. In that respect, we claim to have successfully overcome some of the barriers to industrially relevant plasma chemistry. We believe that the combined use of plasma and microfluidic technologies is essential to the development of this new field of research.
    Mots-clés : MACO, POLE 1.

  • K. Wu, J. Y. Park, R. Al-Saadon, H. Nam, Y. Lee, S. Top, G. Jaouen, M. - H. Baik, et W. E. Geiger, « Oxidation of Cymantrene Analogues of Ferrocifen: Electrochemical, Spectroscopic, and Computational Studies of the Parent Complex 1,1′-Diphenyl-2-cymantrenylbutene », Organometallics, vol. 37, nᵒ 12, p. 1910-1918, 2018.
    Résumé : The oxidative electrochemical behavior of 1,1′-diphenyl-2-cymantrenylbutene (1), a cymantrene analogue of the breast cancer drug ferrocifen, was shown to involve the sequential electron-transfer series 1/1+/12+ in dichloromethane/0.05 M [NBu4][B(C6F5)4] (E1/2 values 0.78 and 1.18 V vs ferrocene). By a combination of spectroscopic and computational techniques, it was shown that the cymantrene functionality plays an important role in dissipating the positive charges in the oxidized compounds and is therefore an active participant in the redox events. The redox-active orbital goes from roughly equal degrees of organometallic and π-organic (diphenylolefin) makeup in 1 to increasingly organic based fractions in 1+ and 12+. Structural changes mimicking those of oxidized tetrakis(aryl)ethylenes accompany the one-electron oxidations. There is sufficient unpaired electron density on the manganese center in 1+ to allow for oxidatively induced ligand exchange of one or more of the carbonyl ligands with donor ligands, including phosphites and pyridine. The complex Mn(CO)2P(OPh)3(η5-C5H4(Et)C═C(C6H5)2) was prepared by the “electrochemical switch” method, wherein [Mn(CO)2P(OPh)3(η5-C5H4(Et)C═C(C6H5)2)]+, produced by the oxidation of 1 in the presence of P(OPh)3, was reduced back to the neutral CO-substituted complex.
    Mots-clés : CHEMBIO, POLE 3.
    Note Note
    <p>doi: 10.1021/acs.organomet.8b00186</p>

  • Y. Yang, J. Wang, Y. Zhang, J. Li, et W. Sun, « Black Sesame Seeds Ethanol Extract Ameliorates Hepatic Lipid Accumulation, Oxidative Stress, and Insulin Resistance in Fructose-Induced Nonalcoholic Fatty Liver Disease », Journal of Agricultural and Food Chemistry, vol. 66, nᵒ 40, p. 10458-10469, oct. 2018.

  • Y. Yang, Z. Wang, L. Zhang, B. Yin, L. Lv, J. He, Z. Chen, X. Wen, B. Qiao, W. Sun, M. Fang, et Y. Zhang, « Protective effect of gentiopicroside from Gentiana macrophylla Pall. in ethanol-induced gastric mucosal injury in mice », Phytotherapy Research, vol. 32, nᵒ 2, p. 259-266, 2018.

  • Y. Yang, Y. Zhang, C. Wei, J. Li, et W. Sun, « Silver ion chromatography for peak resolution enhancement: Application to the preparative separation of two sesquiterpenes using online heart-cutting LC-LC technique », Talanta, vol. 187, p. 252-258, 2018.

  • N. V. Yerra, P. Pallerla, S. Pandeti, J. - C. Tabet, et J. R. Thota, « Characterization of degradation products of macitentan under various stress conditions using liquid chromatography/mass spectrometry », Rapid Communications in Mass Spectrometry, vol. 32, nᵒ 13, p. 1075-1084, juill. 2018.

  • T. Zhang, L. Mazaud, L. - M. Chamoreau, C. Paris, A. Proust, et G. Guillemot, « Unveiling the Active Surface Sites in Heterogeneous Titanium-Based Silicalite Epoxidation Catalysts: Input of Silanol-Functionalized Polyoxotungstates as Soluble Analogues », ACS Catalysis, vol. 8, nᵒ 3, p. 2330-2342, mars 2018.
    Résumé : We report on a site-isolated model for Ti(IV) by reacting [Ti(iPrO)4] with the silanol-functionalized polyoxotungstates [XW9O34–x(tBuSiOH)3]3– (X = P, x = 0, 1; X = Sb, x = 1, 2) in tetrahydrofuran. The resulting titanium(IV) complexes [XW9O34–x(tBuSiO)3Ti(OiPr)]3– (X = P, 3; X = Sb, 4) were obtained in monomeric forms both in solution and in the solid state, as proved by diffusion NMR experiments and by X-ray crystallographic analysis. Anions 3 and 4 represent relevant soluble models for heterogeneous titanium silicalite epoxidation catalysts. The POM scaffolds feature slight conformational differences that influence the chemical behavior of 3 and 4 as demonstrated by their reaction with H2O. In the case of 3, the hydrolysis reaction of the isopropoxide ligand is only little shifted toward the formation of a monomeric [PW9O34(tBuSiO)3Ti(OH)]3– (5) species [log K = −1.96], whereas 4 reacted readily with H2O to form a μ-oxo bridged dimer {[SbW9O33(tBuSiO)3Ti]2O}6– (6). The more confined was the coordination site, the more hydrophobic was the metal complex. By studying the reaction of 3 and 4 with hydrogen peroxide using NMR and Raman spectroscopies, we concluded that the reaction leads to the formation of a titanium-hydroperoxide Ti-(η1-OOH) moiety, which is directly involved in the epoxidation of the allylic alcohol 3-methyl-2-buten-1-ol. The combined use of both spectroscopies also led to understanding that a shift of the acid–base equilibrium toward the formation of Ti(η2-O2) and H3O+ correlates with the partial hydrolysis of the phosphotungstate scaffold in 3. In that case, the release of protons also catalyzed the oxirane opening of the in situ formed epoxide, leading to an increased selectivity for 1,2,3-butane-triol. In the case of the more stable [SbW9O33(tBuSiO)3Ti(OiPr)]3– (4), the evolution to Ti(η2-O2) peroxide was not detected by Raman spectroscopy, and we performed reaction progress kinetic analysis by NMR monitoring the 3-methyl-2-buten-1-ol epoxidation to assess the efficiency and integrity of 4 as precatalyst.
    Mots-clés : E-POM, POLE 2.

  • T. Zhang, A. Solé-Daura, S. Hostachy, S. Blanchard, C. Paris, Y. Li, J. J. Carbó, J. M. Poblet, A. Proust, et G. Guillemot, « Modeling the Oxygen Vacancy at a Molecular Vanadium(III) Silica-Supported Catalyst », Journal of the American Chemical Society, vol. 140, nᵒ 44, p. 14903-14914, nov. 2018.
    Résumé : Here we report on the use of a silanol-decorated polyoxotungstate, [SbW9O33(tBuSiOH)3]3– (1), as a molecular support to describe the coordination of a vanadium atom at a single-site on silica surfaces. By reacting [V(Mes)3·thf] (Mes = 2,4,6-trimethylphenyl) with 1 in tetrahydrofuran, the vanadium(III) derivative [SbW9O33(tBuSiO)3V(thf)]3– (2) was obtained. Compound 2 displays the paramagnetic behavior expected for a d2-VIII high spin complex (SQUID measurements) with a triplet electronic ground state (ca. 30 kcal·mol–1 more stable than the singlet, from DFT calculations). Compound 2 proves to be a reliable model for reduced isolated-vanadium atom dispersed on silica surfaces [(≡Si—O)3VIII(OH2)], an intermediate that is often proposed in a Mars–van Krevelen type mechanism for partial oxidation of light alcohols. Oxidation of 2 under air produced the oxo-derivative [SbW9O33(tBuSiO)3VO]3– (3). In compound 2, the d2-electrons are localized in degenerated d(V) orbitals, whereas in the electronically analogous bireduced-[SbW9O33(tBuSiO)3VO]5–, 3·(2e), one electron is localized on d(V) orbital and the second one is delocalized on the polyoxotungstic framework, leading to a unique case of a bireduced heteropolyanion derivative with completely decoupled d1-V(IV) and d1-W(V). Our body of experimental results (EPR, magnetic measurements, spectroelectrochemical studies, Raman spectroscopy) and theoretical studies highlights (i) the role of the apical ligand coordination, i.e., thf (σ-donor) vs oxo (π-donor), in destabilizing or stabilizing the d(V) orbitals relative to the d(W) orbitals, and (ii) a geometrical distortion of the O3VO entity that causes a splitting of the degenerated orbitals and the stabilization of one d(V) orbital in the bireduced compound 3·(2e).
    Mots-clés : E-POM, ERMMES, POLE 2.

  • C. Zheng, H. Qu, W. Liao, T. Bavaro, M. Terreni, M. Sollogoub, K. Ding, et Y. Zhang, « Chemoenzymatically synthesized GM3 analogues as potential therapeutic agents to recover nervous functionality after injury by inducing neurite outgrowth », European Journal of Medicinal Chemistry, vol. 146, p. 613-620, 2018.

  • X. Zhu, S. Xiao, D. Zhou, M. Sollogoub, et Y. Zhang, « Design, synthesis and biological evaluation of water-soluble per- O -methylated cyclodextrin-C 60 conjugates as anti-influenza virus agents », European Journal of Medicinal Chemistry, vol. 146, p. 194-205, 2018.

  • Z. - Y. Zhu, L. - C. Pan, Y. Tang, et Y. Zhang, « Structural analysis and antioxidant activity of the glycoside from Imperial Chrysanthemum », Bioorganic & Medicinal Chemistry Letters, vol. 28, nᵒ 9, p. 1581-1590, 2018.


  • F. Abbassi, M. Mbarek, D. Kreher, et K. Alimi, « Synthesis and characterization of a copolymer involving PVK and MEH-PPV for organic electronic devices », Journal of Physics and Chemistry of Solids, vol. 103, p. 142-146, avr. 2017.
    Résumé : A statistic copolymer denoted (PVK)x-(MEH-PPV)y containing poly(N-vinylcarbazole) (PVK) as well as poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) building blocks was prepared by chemical oxidative way. Correlations structure-properties of the synthesized copolymer were investigated by using different experimental analyses (IR, XRD, ATG, optical absorption, PL and PLRT) combined with theoretical calculations (DFT). The new copolymer exhibits interesting properties compared to PVK and MEH-PPV homopolymers taken separately. The resulting copolymer has improved thermal stability and it exhibits original optical properties compared to the PVK and MEH-PPV ones as well as its reveled charge transfer process and the continuous donor acceptor existence. All these experimental and theoretical analysis argue the originality of this new material which could then be exploited in optoelectronics.
    Mots-clés : A. Polymers, B. Chemical synthesis, C. Ab initio calculations, C. Optical properties, POLE 4, POLYMERES.
  • R. Albigès, P. Klein, S. Roi, F. Stoffelbach, C. Creton, L. Bouteiller, et J. Rieger, « Water-based acrylic coatings reinforced by PISA-derived fibers », Polymer Chemistry, avr. 2017.
    Résumé : Polymerization-induced self-assembly (PISA) is an efficient approach to synthesize self-assembled core–shell nanofibers in water, made of amphiphilic block copolymers. We demonstrate here for the first time that such anisotropic and high Tg nanofibers can be used as reinforcing fillers for water-based acrylic materials. This strategy opens the way for strong all-organic aqueous coatings.
    Mots-clés : POLE 4, POLYMERES.
    Pièce jointe Full Text PDF 407.3 ko (source)

  • Q. Arnoux, A. Boucly, V. Barth, R. Benbalagh, A. Cossaro, L. Floreano, M. Silly, F. Sirotti, E. Derat, S. Carniato, F. Bournel, J. - J. Gallet, D. Fichou, L. Tortech, et F. Rochet, « Energy-Level Alignment of a Hole-Transport Organic Layer and ITO: Toward Applications for Organic Electronic Devices », ACS Applied Materials & Interfaces, vol. 9, nᵒ 36, p. 30992-31004, sept. 2017.
    Résumé : 2,2′,6,6′-Tetraphenyl-4,4′-dipyranylidene (DIPO-Ph4) was grown by vacuum deposition on an indium tin oxide (ITO) substrate. The films were characterized by atomic force microscopy as well as synchrotron radiation UV and X-ray photoelectron spectroscopy to gain an insight into the material growth and to better understand the electronic properties of the ITO/DIPO-Ph4 interface. To interpret our spectroscopic data, we consider the formation of cationic DIPO-Ph4 at the ITO interface owing to a charge transfer from the organic layer to the substrate. Ionization energy DFT calculations of the neutral and cationic species substantiate this hypothesis. Finally, we present the energetic diagram of the ITO/DIPO-Ph4 system, and we discuss the application of this interface in various technologically relevant systems, as a hole-injector in OLEDs or as a hole-collector interfacial layer adjacent to the prototypical OPV layer P3HT:PCBM.
    Mots-clés : E-POM, POLE 1, POLE 2.
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