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  • Q. Arnoux, B. Watts, S. Swaraj, F. Rochet, et L. Tortech, « X-ray microscopic investigation of molecular orientation in a hole carrier thin film for organic solar cells », Nano Research, p. 1-12, nov. 2017.
    Résumé : As dipyranylidenes are excellent hole carriers, applications in organic solar cells or organic light emitting diode are envisaged. In the present study, we investigate the morphology of 2,2′,6,6′-tetraphenyl-4,4′-dipyranylidene (DIPO-Ph4) deposited under vacuum on a silicon nitride (Si3N4) substrate, a paradigmatic system for the study of molecular crystal/inorganic substrate interfaces. Samples with various coating ratios and different thermal treatments were prepared. The films were characterized by atomic force microscopy and scanning transmission X-ray microscopy to gain insight into material growth. The results show a change in orientation at a molecular level depending upon the evaporation conditions. We are now able to tailor an organic layer with a specific molecular orientation and a specific electronic behavior.Open image in new window
    Mots-clés : E-POM, POLE 2.
    Pièce jointe Full Text PDF 2.2 Mo (source)

  • T. Auvray, M. - P. Santoni, B. Hasenknopf, et G. S. Hanan, « Covalent hybrids based on Re(I) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: synthesis, characterization and electronic properties », Dalton Transactions, vol. 46, nᵒ 30, p. 10029-10036, 2017.

  • S. P. Babailov, E. V. Peresypkina, Y. Journaux, et K. E. Vostrikova, « Nickel(II) complex of a biradical: Structure, magnetic properties, high NMR temperature sensitivity and moderately fast molecular dynamics », Sensors and Actuators B: Chemical, vol. 239, p. 405-412, 2017.

  • P. Barbier Saint Hilaire, A. Warnet, Y. Gimbert, U. M. Hohenester, G. Giorgi, M. - F. Olivier, F. Fenaille, B. Colsch, C. Junot, et J. - C. Tabet, « Mechanistic study of competitive releases of H2O, NH3 and CO2 from deprotonated aspartic and glutamic acids: Role of conformation », Journal of Chromatography B, vol. 1047, p. 64-74, mars 2017.
    Résumé : The aims of this study were to highlight the impact of minor structural differences (e.g. an aminoacid side chain enlargement by one methylene group), on ion dissociation under collision-induced dissociation conditions, and to determine the underlying chemical mechanisms. Therefore, we compared fragmentations of deprotonated aspartic and glutamic acids generated in negative electrospray ionization. Energy-resolved mass spectrometry breakdown curves were recorded and MS3 experiments performed on an Orbitrap Fusion for high-resolution and high-mass accuracy measurements. Activated fragmentations were performed using both the resonant and non-resonant excitation modes (i.e., CID and HCD, respectively) in order to get complementary information on the competitive and consecutive dissociative pathways. These experiments showed a specific loss of ammonia from the activated aspartate but not from the activated glutamate. We mainly focused on this specific observed loss from aspartate. Two different mechanisms based on intramolecular reactions (similar to those occurring in organic chemistry) were proposed, such as intramolecular elimination (i.e. Ei-like) and nucleophilic substitution (i.e. SNi-like) reactions, respectively, yielding anions as fumarate and α lactone from a particular conformation with the lowest steric hindrance (i.e. with antiperiplanar carboxyl groups). The detected deaminated aspartate anion can then release CO2 as observed in the MS3 experimental spectra. However, quantum calculations did not indicate the formation of such a deaminated aspartate product ion without loss of carbon dioxide. Actually, calculations displayed the double neutral (NH3+CO2) loss as a concomitant pathway (from a particular conformation) with relative high activation energy instead of a consecutive process. This disagreement is apparent since the concomitant pathway may be changed into consecutive dissociations according to the collision energy i.e., at higher collision energy and at lower excitation conditions, respectively. The latter takes place by stabilization of the deaminated aspartate solvated with two residual molecules of water (present in the collision cell). This desolvated anion formed is an α lactone substituted by a methylene carboxylate group. The vibrational excitation acquired by [(D−H)−NH3]−during its isolation is enough to allow its prompt decarboxylation with a barrier lower than 8.4 kJ/mol. In addition, study of glutamic acid-like diastereomers constituted by a cyclopropane, hindering any side chain rotation, confirms the impact of the three-dimensional geometry on fragmentation pathways. A significant specific loss of water is only observed for one of these diastereomers. Other experiments, such as stable isotope labeling, need to be performed to elucidate all the observed losses from activated aspartate and glutamate anions. These first mechanistic interpretations enhance understanding of this dissociative pathway and underline the necessity of studying fragmentation of a large number of various compounds to implement properly new algorithms for de novo elucidation of unknown metabolites.
    Mots-clés : CSOB, Electrospray high-resolution mass spectrometry, POLE 3, Regioselective dissociation, Unexpected cleavage of aspartate anion.

  • R. Beaud, R. K. Nandi, A. Perez-Luna, R. Guillot, D. Gori, C. Kouklovsky, N. - E. Ghermani, V. Gandon, et G. Vincent, « Revealing the electrophilicity of N-Ac indoles with FeCl3: a mechanistic study », Chemical Communications, vol. 53, nᵒ 43, p. 5834-5837, mai 2017.
    Résumé : Herein, we report a mechanistic exploration of the unusual FeCl3-mediated hydroarylation of N-Ac indoles. Electron density topology analysis of a crystal, in situ IR monitoring, Hammett and Taft studies as well as DFT computations allowed us to determine that activation of acetyl with FeCl3 and of the C2C3 bond with a proton is involved.
    Mots-clés : POLE 1, ROCS.

  • M. Beaupérin, D. Polat, F. Roudesly, S. Top, A. Vessières, J. Oble, G. Jaouen, et G. Poli, « Approach to ferrocenyl-podophyllotoxin analogs and their evaluation as anti-tumor agents », Journal of Organometallic Chemistry, vol. 839, p. 83-90, juin 2017.
    Résumé : Podophyllotoxin is a natural product endowed of a high antimitotic activity and a high affinity for tubulin. Its action results in the cessation of cell division, inducing cell death. However, its high toxicity restrains its use as drug. To overcome this drawback, several chemical modifications of the native podophyllotoxin have been made. However, to date, no reports have so far been directed toward incorporation of a metallocene moiety. The search for new organometallic drugs is a central field in drug discovery, including the domain of cancer therapy. In particular, metallocenyl moieties are known to increase or decrease, depending on the degree of conjugation in the organometallic motif, the selectivity of drugs toward cancer cells. The conjugate organometallic compound reduces the damage of healthy tissues, yet permitting the selective desired antimitotic and cytotoxic effects of the active principle. We report here the synthesis of ferrocene-containing podophyllotoxin analogs and preliminary antiproliferative tests.
    Mots-clés : Antitumor agent, Bioorganometallic chemistry, CHEMBIO, Ferrocene, Multi-step synthesis, Palladium, Podophyllotoxin, POLE 1, POLE 3, ROCS.

  • M. Ben Haddada, D. Hu, M. Salmain, L. Zhang, C. Peng, Y. Wang, B. Liedberg, et S. Boujday, « Gold nanoparticle-based localized surface plasmon immunosensor for staphylococcal enterotoxin A (SEA) detection », Analytical and bioanalytical chemistry, vol. 409, nᵒ 26, p. 6227-6234, 2017.
    Mots-clés : CHEMBIO, POLE 3.
    Note Note

  • J. Blass, J. Brunke, F. Emmerich, C. Przybylski, V. M. Garamus, A. Feoktystov, R. Bennewitz, G. Wenz, et M. Albrecht, « Interactions between shape-persistent macromolecules as probed by AFM », Beilstein Journal of Organic Chemistry, vol. 13, p. 938-951, mai 2017.

  • V. N. Bochatay, L. Debien, F. Chemla, F. Ferreira, O. Jackowski, et A. Perez-Luna, « Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines », Comptes Rendus Chimie, vol. 20, nᵒ 6, p. 609-616, juin 2017.
    Résumé : Lithium alkynyl(disilyl)zincates obtained from metalated ethynyloxiranes, as well as from N-tert-butanesulfinyl(ethynyl)aziridines or N-tert-butanesulfonyl(ethynyl)aziridines, undergo 1,2-migration of the organosilyl group with ring opening of the oxirane or aziridine ring by SNi displacement. A developed protocol that involves nBuLi for the metalation step offers a straightforward approach to the corresponding δ-oxy- and δ-amino α-silyl allenylzinc intermediates. The reagents derived from the epoxides are amenable to subsequent in situ condensation with aldehydes or ketones to provide 1,3-diols but not those derived from aziridines that only react sluggishly in similar condensations.
    Mots-clés : alkynes, carbenoids, POLE 1, rearrangement, ROCS, silicon, Zinc.

  • P. - E. Bodet, I. Salard, C. Przybylski, F. Gonnet, C. Gomila, J. Ausseil, et R. Daniel, « Efficient recovery of glycosaminoglycan oligosaccharides from polyacrylamide gel electrophoresis combined with mass spectrometry analysis », Analytical and Bioanalytical Chemistry, vol. 409, nᵒ 5, p. 1257-1269, 2017.

  • T. Borelli, S. Brenna, G. Broggini, J. Oble, et G. Poli, « (Diacyloxyiodo)benzenes-Driven Palladium-Catalyzed Cyclizations of Unsaturated N-Sulfonylamides: Opportunities of Path Selection », Advanced Synthesis & Catalysis, vol. 359, nᵒ 4, p. 623-628, 2017.
    Résumé : A study of the palladium(II)-catalyzed cyclization of unsaturated N-sulfonylamides was undertaken, using (diacyloxyiodo)benzenes as terminal oxidizing agents. Different reactivities were observed as a function of the nature of the unsaturation (terminal vs. internal), or of the hypervalent iodine compound used (diacetoxyiodobenzene vs. bistrifluoroacetoxyiodobenzene). Proper parameter selection allows the direction of the cyclization to be chosen towards either a global aminoacetoxylation, an allylic amination via aminopalladation, or an allylic amination via allylic C–H activation.
    Mots-clés : allylic compounds, amination, C–H activation, homogeneous catalysis, Palladium, POLE 1, ROCS.

  • G. Bouhalleb, O. Mhasni, G. Poli, et F. Rezgui, « Direct palladium-catalyzed allylic alkylations of alcohols with enamines: Synthesis of homoallyl ketones », Tetrahedron Letters, vol. 58, p. 2525-2529, 2017.
    Résumé : An efficient, direct nucleophilic allylic substitution of α-, β- and γ-substituted alcohols with enamines, using the Pd(OAc)2/PPh3 catalyst system and ZnBr2 as a promoter in CH2Cl2 at reflux, is reported. The reaction course was dependent on the steric hindrance at the α- or γ-positions with respect to the functionalized α-carbon, selectively affording in moderate to good yields, α- or γ-homoallyl ketones, the so-called “linear” and “branched” products, respectively.
    Mots-clés : Allylic alcohol, Allylic substitution, Enamine, Homoallyl ketone, Palladium, POLE 1, ROCS.

  • L. Chang, K. Plevová, S. Thorimbert, et L. Dechoux, « Preparation of Substituted 2H-Pyrans via a Cascade Reaction from Methyl Coumalate and Activated Methylene Nucleophiles », The Journal of Organic Chemistry, vol. 82, nᵒ 10, p. 5499-5505, 2017.
    Résumé : The reaction of methyl coumalate with a wide range of methylene active compounds, such as keto-esters or keto-sulfones and cyclic or acyclic diketones, afforded more than 30 2,3,5,6-tetrasubstituted 2H-pyrans. The reaction proceeds via a cascade reaction involving a Michael addition-6π-electrocyclic ring opening-proton transfer and 6π electrocyclization, in which a variety of functional groups were tolerated.
    Mots-clés : CHEMBIO, POLE 3.

  • M. Chenal, C. Véchambre, J. - M. Chenal, L. Chazeau, V. Humblot, L. Bouteiller, C. Creton, et J. Rieger, « Mechanical properties of nanostructured films with an ultralow volume fraction of hard phase », Polymer, vol. 109, p. 187-196, janv. 2017.
    Résumé : We demonstrate in this paper how polymerization induced self-assembly (PISA) using RAFT can be used to synthesize very asymmetric but monodisperse poly(acrylic acid)-b-poly(n-butyl acrylate) block copolymers, PAA-b-PBA, with a short PAA block and a long PBA block. In the course of the surfactant-free emulsion polymerization, core-shell particles form in water, with the short hydrophilic block located at the water-particle interface, and the long hydrophobic block constituting the particle core. Drying at room temperature creates films possessing an out of equilibrium structure, where the glassy PAA block generates a percolating network of shells. When deformed in uniaxial elongation, these films combine a high stiffness in small strains (considering the low volume fraction of PAA, of only 3 wt%), a yield stress and a significant extensibility before failure. The modulus, yield stress and extensibility can be tuned by modifying the composition of the latex serum with cations or positively charged low molar mass polymers, or by changing the copolymer composition. Of particular interest was the synthesis by PISA of particles of triblock copolymer PAA-b-PBA-b-PS. The out of equilibrium structure obtained had a very interesting combination of high stiffness, extensibility and high fracture toughness.
    Mots-clés : Core-shell latexes, Film, Mechanical properties, Nanostructure, POLE 4, POLYMERES, RAFT polymerization.

  • A. Conte-Daban, V. Borghesani, S. Sayen, E. Guillon, Y. Journaux, G. Gontard, L. Lisnard, et C. Hureau, « Link between Affinity and Cu(II) Binding Sites to Amyloid-β Peptides Evaluated by a New Water-Soluble UV–Visible Ratiometric Dye with a Moderate Cu(II) Affinity », Analytical Chemistry, vol. 89, nᵒ 3, p. 2155-2162, févr. 2017.
    Résumé : Being able to easily determine the Cu(II) affinity for biomolecules of moderate affinity is important. Such biomolecules include amyloidogenic peptides, such as the well-known amyloid-β peptide involved in Alzheimer’s disease. Here, we report the synthesis of a new water-soluble ratiometric Cu(II) dye with a moderate affinity (109 M–1 at pH 7.1) and the characterizations of the Cu(II) corresponding complex by X-ray crystallography, EPR, and XAS spectroscopic methods. UV–vis competition was performed on the Aβ peptide as well as on a wide series of modified peptides, leading to an affinity value of 1.6 × 109 M–1 at pH 7.1 for the Aβ peptide and to a coordination model for the Cu(II) site within the Aβ peptide that agrees with the one mostly accepted currently.
    Mots-clés : ERMMES, POLE 2.

  • M. W. Cooke, M. - P. Santoni, F. Loiseau, B. Hasenknopf, et G. S. Hanan, « Energy transfer in rhodium–ruthenium dimer-of-dimer assemblies », Inorganica Chimica Acta, vol. 454, p. 208-215, 2017.

  • M. Courté, M. Alaaeddine, V. Barth, L. Tortech, et D. Fichou, « Structural and electronic properties of 2,2′,6,6′-tetraphenyl-dipyranylidene and its use as a hole-collecting interfacial layer in organic solar cells », Dyes and Pigments, vol. 141, p. 487-492, juin 2017.
    Résumé : The accumulation of positive charges at the anodic interface considerably limits the efficiency of photovoltaic solar cells based on polymer/fullerene bulk heterojunctions (BHJs). Interfacial layers (IFLs) such as PEDOT:PSS improve charge injection but have no effect on the unbalanced electron/hole transport across the BHJ. We report here the use of 2,2′,6,6′-tetraphenyl-dipyranylidene (DIPO-Ph4), a planar quinoïd compound, as an efficient anodic IFL in organic solar cells based on BHJs made of poly(3-hexylthiophene)/[6,6]-phenyl-C61-butyric-acid-methyl-ester (P3HT:PCBM). When deposited under vacuum onto a glass substrate, DIPO-Ph4 thin films are constituted of densely packed and vertically aligned crystalline needles. Current-sensing atomic force microscopy (CS-AFM) reveals a considerable increase of the hole-carrying pathways in DIPO-Ph4 thin films as compare to PEDOT:PSS, thus revealing their hole transporting/electron blocking properties. Inserting a 10 nm thick IFL of DIPO-Ph4 in combination with a 5 nm thick PEDOT:PSS between the ITO electrode and the P3HT:PCBM film leads to photocurrent densities up to 11.5 mA/cm2 under AM 1.5G and conversion efficiencies up to 4.6%, that is substantially higher than PEDOT:PSS-only devices.
    Mots-clés : Atomic force microscopy, Bulk heterojunction, E-POM, Hole collection, Interfacial layers, NASCO, Organic solar cells, POLE 1, POLE 2.

  • M. Courté, S. G. Surya, R. Thamankar, C. Shen, V. R. Rao, S. G. Mhailsalkar, et D. Fichou, « A non-volatile resistive memory effect in 2,2′,6,6′-tetraphenyl-dipyranylidene thin films as observed in field-effect transistors and by conductive atomic force microscopy », RSC Advances, vol. 7, nᵒ 6, p. 3336-3342, janv. 2017.
    Résumé : The charge transport properties of 2,2′,6,6′-tetraphenyldipyranylidene (DIPO-Ph4), a large planar quinoïd π-conjugated heterocycle, are investigated in field-effect transistor (FET) configuration and by conductive atomic force microscopy (c-AFM). The FET properties show a clear p-type behavior with a hole mobility up to 2 × 10−2 cm2 V−1 s−1 and on/off ratio of 104. The transfer characteristics Id/Vg present a clear hysteresis typical of a resistive memory effect. This memory effect is again observed by means of c-AFM in lateral mode using a nearby gold top-contact as the counter-electrode. The c-AFM current response recorded for variable distances d = 0.5–9.0 μm between the AFM tip and the top electrode shows a resistive switching behavior in the low-voltage 0.0–3.0 V region. Repeated “write-read-erase-read” cycles performed at low frequency reveal a non-volatile memory effect in the form of high-resistance and low-resistance states with a stable on/off ratio of 102 during cycling operation.
    Mots-clés : NASCO, POLE 2.
    Pièce jointe Full Text PDF 1009.9 ko (source)

  • E. Darii, S. Alves, Y. Gimbert, A. Perret, et J. - C. Tabet, « Meaning and consequence of the coexistence of competitive hydrogen bond/salt forms on the dissociation orientation of non-covalent complexes », Journal of Chromatography B, vol. 1047, p. 45-58, mars 2017.
    Résumé : Non-covalent complexes (NCC) between hexose monophosphates (HexP) and arginine (R) were analyzed using ESI MS and MS/MS in negative mode under different (hard, HC and soft, SC) desolvation conditions. High resolution mass spectrometry (HRMS) revealed the presence of different ionic species, namely, homo- and heteromultimers of R and HexP. Deprotonated heterodimers and corresponding sodiated species were enhanced under HC likely due to a decrease in available charge number associated with the reduction of H+/Na+ exchange. The quantum calculations showed that the formation of covalent systems is very little exothermic, therefore, such systems are disfavored. Desolvation dependent CID spectra of deprotonated [(HexP+R)‒H]− complexes demonstrated that they can exist within the hydrogen bond (HB) and salt bridge (SB) forms, yielding either NCC separation or covalent bond cleavages, respectively. Although HB forms are the main species, they cannot survive under HC; therefore, the minor SB forms became detectable. Energy-resolved mass spectrometry (ERMS) experiments revealed diagnostic fragment ions from both SB and HB forms, providing evidence that these isomeric forms are inconvertible. SB formation should result from the ionic interactions of highly acidic group of HexP with strongly basic guanidine group of arginine and thus requires an arginine zwitterion (ZW) form. This was confirmed by quantum calculations. Ion-ion interactions are significantly affected by the presence of sodium cation as demonstrated by the fragmentation patterns of sodiated complex species. Regarding CID data, only SB between protonated amino group of R and deprotonated phosphate group of HexP could be suggested, but the primary amine is not enough basic then, the SB must be fleeting. Nevertheless, the observation of the covalent bond cleavages suggests the presence of structures with a free negative charge able to induce fragmentations. Indeed, according to quantum calculations, solvated salt (SS) systems involving Na+/COO− salt solvated by neutral phosphate and negative charge on sugar ring are preferentially formed.
    Mots-clés : CSOB, POLE 3.

  • M. Desage‐El Murr, L. Fensterbank, et C. Ollivier, « Iron and Single Electron Transfer: All is in the Ligand », Israel Journal of Chemistry, vol. 57, nᵒ 12, p. 1160-1169, déc. 2017.
    Résumé : This account describes some advances we have made in the field of iron catalysis. Two types of reactivity have been uncovered. Based on the use of an iron(II) precatalyst in the presence of NaBH4, the first one consists in a SET which can be useful for the reductive dehalogenation of iodide and bromide derivatives. Switching to the non-innocent bis-iminopyridine ligands promotes a previously undescribed Csp2−H activation reaction leading to biaryl derivatives. First clues into the intricate nature of the mechanism were obtained and suggested that the redox-active bis-iminopyridine ligand acts as an electron reservoir. The resulting buildup of electron density triggers the C−H bond breaking. All these findings are discussed in light of the existing literature and perspectives are given.
    Mots-clés : C−H Activation, C−X Activation, Iron Hydride, MACO, Redox Ligand, Single Electron Transfer.
    Pièce jointe Full Text PDF 3.8 Mo (source)

  • B. Doistau, L. Benda, J. - L. Cantin, L. - M. Chamoreau, E. Ruiz, V. Marvaud, B. Hasenknopf, et G. Vives, « Six states switching of redox-active molecular tweezers by three orthogonal stimuli », Journal of the American Chemical Society, juin 2017.
    Résumé : A six level molecular switch based on terpyridine(Ni-salphen)2 tweezers and addressable by three orthogonal stimuli (metal coordination, redox reaction and guest binding) is reported. By a metal coordination stimulus, the tweezers can be mechanically switched from an open “W”-shaped conformation to a closed “U”-shaped form. Theses two states can each be reversibly oxidized by the redox stimulus and bind to a pyrazine guest resulting in four additional states. All six states are stable and accessible by the right combination of stimuli and were studied by NMR, XRD, EPR spectroscopy and DFT calculations. The combination of the supramolecular concepts of mechanical motion and guest binding with the redox non-innocent and valence tautomerism properties of Ni-salphen complexes added two new dimensions to a mechanical switch.
    Mots-clés : E-POM, GOBS, POLE 2, POLE 3.

  • M. Dréan, A. Debuigne, C. Goncalves, C. Jérôme, P. Midoux, J. Rieger, et P. Guégan, « Use of Primary and Secondary Polyvinylamines for Efficient Gene Transfection », Biomacromolecules, vol. 18, nᵒ 2, p. 440-451, févr. 2017.
    Résumé : Gene transfection with polymeric carrier remains a challenge; particularly, high transfection levels combined with low toxicity are hard to achieve. We herein revisit polyvinylamines, an old and neglected family of cationic polymers. They can be readily obtained by controlled hydrolysis of polyvinylamides prepared through (controlled) radical polymerization. A series of tailor-made and well-defined polyvinylamines bearing primary amino groups, and poly(N-methylvinylamine) bearing secondary amines, were evaluated for the transfection of cells with pDNA as a function of their molar mass, molar mass distribution, and degree of deacetylation. Unexpected high transfection levels, in combination with low cytotoxicity were recorded for both series. Surprisingly, a great impact of the molar mass was observed for the primary amine polyvinylamine series, whereas the results were mostly independent of molar mass or dispersity for the polymer bearing secondary amine. It was further established that a certain percentage of acetamide groups increased the transfection level, while maintaining low cytotoxicity. These results highlight for the first time the real potential of polyvinylamines as gene carriers, and make these polymers very attractive for further development in gene therapy.
    Mots-clés : POLE 4, POLYMERES.

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    T. Driant, F. Nachon, C. Ollivier, P. - Y. Renard, et E. Derat, « On the Influence of the Protonation States of Active Site Residues on AChE Reactivation: A QM/MM Approach », ChemBioChem, vol. 18, nᵒ 7, p. 666-675, 2017.
    Résumé : Acetylcholinesterase (AChE), an enzyme of the serine hydrolase superfamily, is a mediator of signal transmission at cholinergic synapses by catalyzing acetylcholine cleavage into acetate and choline. This enzyme is vulnerable to covalent inhibition by organophosphate compounds (like VX). Covalent inhibition of AChE does not revert spontaneously. Known reactivator compounds have limited action in restoring catalytic activity. QM/MM simulations of VX-inhibited AChE reactivation by pralidoxime (2-PAM), a classical reactivator, were performed. These afforded a broad view of the effect of protonation states of active-site residues, and provide evidence for the role of Glu202, which needs to be protonated for reactivation to occur. In situ deprotonation of 2-PAM for both protonation states of Glu202 showed that His447 is able to deprotonate 2-PAM with the assistance of Glu202. Because the active site of serine hydrolases is highly conserved, this work provides new insights on the interplay between the catalytic triad residues and this glutamate, newly identified as protonatable.
    Mots-clés : acetylcholinesterase, Computational chemistry, MACO, organophosphate, POLE 1, protonation, QM/MM, reactivation.

  • L. Ferrand, Y. Lyu, A. Rivera-Hernández, B. J. Fallon, M. Amatore, C. Aubert, et M. Petit, « Hydroboration and Diboration of Internal Alkynes Catalyzed by a Well-Defined Low-Valent Cobalt Catalyst », Synthesis, avr. 2017.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : MACO, POLE 1.

  • L. Ferrand, Y. Tang, C. Aubert, L. Fensterbank, V. Mouriès-Mansuy, M. Petit, et M. Amatore, « Niobium-Catalyzed Intramolecular Addition of O–H and N–H Bonds to Alkenes: A Tool for Hydrofunctionalization », Organic Letters, vol. 19, nᵒ 8, p. 2062-2065, 2017.
    Résumé : A convenient, versatile, and easy to handle intramolecular hydrofunctionalization of alkenes (C–O and C–N bonds formation) is reported using a novel niobium-based catalytic system. This atom economic and eco-friendly methodology provides an additional synthetic tool for the straightforward formation of valuable building blocks enabling molecular complexity. Various pyran, furan, pyrrolidine, piperidine, lactone, and lactam derivatives as well as spirocyclic compounds are produced in high yields and selectivities.
    Mots-clés : MACO, POLE 1.

  • A. Flambard, A. Sugahara, S. De, M. Okubo, A. Yamada, et R. Lescouëzec, « Probing the local structure of Prussian blue electrodes by 113Cd NMR spectroscopy », Dalton Transactions, vol. 46, nᵒ 19, p. 6159-6162, mai 2017.
    Résumé : We demonstrate that 113Cd NMR is a potent technique to monitor the local electronic and structural states of the Prussian blue electrode during Li+ intercalation, providing an atomic-scale insight into the reaction mechanism.
    Mots-clés : ERMMES, POLE 2.
    Pièce jointe Full Text PDF 354.8 ko (source)

  • C. Fopp, K. Isaac, E. Romain, F. Chemla, F. Ferreira, O. Jackowski, M. Oestreich, et A. Perez-Luna, « Stereodivergent Synthesis of β-Heteroatom-Substituted Vinyl­silanes by Sequential Silylzincation–Copper(I)-Mediated Electrophilic­ Substitution », Synthesis, vol. 49, nᵒ 04, p. 724-735, 2017.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : POLE 1, ROCS.

  • J. W. Fredy, J. Scelle, G. Ramniceanu, B. - T. Doan, C. S. Bonnet, É. Tóth, M. Ménand, M. Sollogoub, G. Vives, et B. Hasenknopf, « Mechanostereoselective One-Pot Synthesis of Functionalized Head-to-Head Cyclodextrin [3]Rotaxanes and Their Application as Magnetic Resonance Imaging Contrast Agents », Organic Letters, vol. 19, nᵒ 5, p. 1136-1139, mars 2017.
    Mots-clés : GOBS, POLE 3.
    Note Note
    <p>doi: 10.1021/acs.orglett.7b00153</p>

  • M. Fumagalli, K. Belal, H. Guo, F. Stoffelbach, G. Cooke, A. Marcellan, P. Woisel, et D. Hourdet, « Supramolecular polymer hydrogels induced by host–guest interactions with di-[cyclobis(paraquat-p-phenylene)] cross-linkers: from molecular complexation to viscoelastic properties », Soft Matter, vol. 13, nᵒ 31, p. 5269-5282, août 2017.
    Résumé : Supramolecular polymer networks have been designed on the basis of a π-electron donor/acceptor complex: naphthalene (N)/cyclobis(paraquat-p-phenylene) (CBPQT4+ = B). For this purpose, a copolymer of N,N-dimethylacrylamide P(DMA-N1), lightly decorated with 1 mol% of naphthalene pendant groups, has been studied in semi-dilute un-entangled solution in the presence of di-CBPQT4+ (BB) crosslinker type molecules. While calorimetric experiments demonstrate the quantitative binding between N and B groups up to 60 °C, the introduction of BB crosslinkers into the polymer solution gives rise to gel formation above the overlap concentration. From a comprehensive investigation of viscoelastic properties, performed at different concentrations, host/guest stoichiometric ratios and temperatures, the supramolecular hydrogels are shown to follow a Maxwellian behavior with a strong correlation of the plateau modulus and the relaxation time with the effective amount of interchain cross-linkers and their dissociation dynamics, respectively. The calculation of the dissociation rate constant of the supramolecular complex, by extrapolation of the relaxation time of the network back to the beginning of the gel regime, is discussed in the framework of theoretical and experimental works on associating polymers.
    Mots-clés : POLE 4, POLYMERES.
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  • G. A. Garcia, H. Dossmann, L. Nahon, S. Daly, et I. Powis, « Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions », ChemPhysChem, vol. 18, nᵒ 5, p. 500-512, mars 2017.
    Résumé : Electron–ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly-oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally-resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward–backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck–Condon simulations of the photoelectron spectra. A previously proposed quasi-diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation. It provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes, which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate and which are then only weakly excited in the Franck–Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes.
    Mots-clés : circular dichroism, CSOB, photoelectron circular dichroism, photoelectron spectroscopy, photoionization, Photophysics, POLE 3.

  • D. Gatineau, A. Memboeuf, A. Milet, R. B. Cole, H. Dossmann, Y. Gimbert, et D. Lesage, « Experimental bond dissociation energies of benzylpyridinium thermometer ions determined by threshold-CID and RRKM modeling », International Journal of Mass Spectrometry, 2017.

  • M. N. Godoi, F. de Azambuja, P. D. G. Martinez, N. H. Morgon, V. G. Santos, T. Regiani, D. Lesage, H. Dossmann, R. B. Cole, M. N. Eberlin, et C. R. D. Correia, « Revisiting the Intermolecular Fujiwara Hydroarylation of Alkynes », European Journal of Organic Chemistry, vol. 2017, nᵒ 13, p. 1794-1803, avr. 2017.

  • C. Gonçalves, J. - P. Gomez, W. Même, B. Rasolonjatovo, D. Gosset, S. Nedellec, P. Hulin, C. Huin, T. Le Gall, T. Montier, P. Lehn, C. Pichon, P. Guégan, H. Cheradame, et P. Midoux, « Curcumin/poly(2-methyl-2-oxazoline-b-tetrahydrofuran-b-2-methyl-2-oxazoline) formulation: An improved penetration and biological effect of curcumin in F508del-CFTR cell lines », European Journal of Pharmaceutics and Biopharmaceutics, vol. 117, p. 168-181, août 2017.
    Résumé : Neutral amphiphilic triblock ABA copolymers are of great interest to solubilize hydrophobic drugs. We reported that a triblock ABA copolymer consisting of methyl-2-oxazoline (MeOx) and tetrahydrofuran (THF) (MeOx6-THF19-MeOx6) (TBCP2) can solubilize curcumin (Cur) a very hydrophobic molecule exhibiting multiple therapeutic effects but whose insolubility and low stability in water is a major drawback for clinical applications. Here, we provide evidences by flow cytometry and confocal microscopy that Cur penetration in normal and ΔF508-CFTR human airway epithelial cell lines is facilitated by TBCP2. When used on ΔF508-CFTR cell lines, the Cur/TBCP2 formulation promotes the restoration of the expression of the CFTR protein in the plasma membrane. Furthermore, patch-clamp and MQAE fluorescence experiments show that this effect is associated with a correction of a Cl− selective current at the membrane surface of F508del-CFTR cells. The results show the great potential of the neutral amphiphilic triblock copolymer MeOx6-THF19-MeOx6 as carrier for curcumin in a Cystic Fibrosis context. We anticipate that other MeOxn-THFm-MeOxn copolymers could have similar behaviours for other highly insoluble therapeutic drugs or cosmetic active ingredients.
    Mots-clés : Amphiphilic polymer, CFTR, Curcumin, Cystic fibrosis, POLE 4, POLYMERES, Triblock copolymer.

  • M. Gormen, P. Pigeon, Y. Wang, A. Vessières, S. Top, F. Martial, C. Gros, M. J. McGlinchey, et G. Jaouen, « Side-Chain Effects on the 1-(Bis-aryl-methylidene)-[3]ferrocenophane Skeleton: Antiproliferative Activity against TNBC Cancer Cells and Comparison with the Acyclic Ferrocifen Series », European Journal of Inorganic Chemistry, vol. 2017, nᵒ 2, p. 454-465, janv. 2017.
    Résumé : As part of our ongoing study of the toxicity of compounds derived from 1,1-bis(4-hydroxyphenyl)-2-ferrocenylbut-1-ene, we have recently shown that closely analogous [3]ferrocenophane complexes have an in vitro toxicity level substantially higher than that of their ferrocene counterparts, particularly in the case of mono- and diphenol complexes. In this study we have examined whether the presence of a dimethylamino chain, analogous to the chain in hydroxytamoxifen, is capable of producing in the ferrocenophane series the same antiestrogenic effect observed for OH-Tam and Fc-OH-Tam. To this end, we have synthesized and characterized new complexes bearing various side-chains [O(CH2)3NMe2, O(CH2)3piperidine, O(CH2)3pyrrolidine, NHCO(CH2)2NMe2] and studied the biochemical properties of those complexes possessing appropriate solubility. The results revealed that the new complexes of [3]ferrocenophane have very strong antiproliferative effects; one of the compounds bearing an NHCO(CH2)2NMe2 chain has an IC50 value of 0.05 ± 0.02 µm for MDA-MB-231 breast cancer cells. All the complexes showed affinity for the estradiol receptor. At the low (nanomolar range) concentrations at which the estrogenic/antiestrogenic effect is expressed in these molecules, the presence of an amino-substituted side-chain does not induce in the [3]ferrocenophane series the antiestrogenic effect observed with OH-Tam and Fc-OH-Tam. However, this effect has been found for the complex with a slightly longer chain [O(CH2)4NMe2].
    Mots-clés : Antitumor agents, Bioorganometallic chemistry, CHEMBIO, Ferrocene, POLE 3, substituent effects, Toxicity.

  • S. Guélen, M. Blazejak, L. - M. Chamoreau, A. Huguet, S. Derenne, F. Volatron, V. Mouriès-Mansuy, et L. Fensterbank, « Photochemical studies on bis-sulfide and -sulfone tethered polyenic derivatives », Organic & Biomolecular Chemistry, vol. 15, nᵒ 19, p. 4180-4190, mai 2017.
    Résumé : This study focusses on the [2 + 2]-photocycloaddition of a symmetric polyenic system tethered by an aryl bis-sulfide or sulfone platform. Using direct irradiation or photosensitization, no expected ladderane product was isolated. In most cases, only tricyclic products including a single cyclobutane moiety were formed. Irradiation of bis-acrylic precursors in water with encapsulation by a host (cyclodextrin or cucurbituril) provided a stereoselective access to valuable cyclobutyl adducts.
    Mots-clés : MACO, POLE 1.
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  • B. Habchi, S. Alves, D. J. - R. Bouveresse, B. Moslah, A. Paris, Y. Lécluse, P. Gauduchon, P. Lebailly, D. N. Rutledge, et E. Rathahao-Paris, « An innovative chemometric method for processing direct introduction high resolution mass spectrometry metabolomic data: independent component–discriminant analysis (IC–DA) », Metabolomics, vol. 13, nᵒ 4, p. 45, avr. 2017.
    Résumé : IntroductionTo perform large scale metabolomic analyses, high throughput approaches are required. The direct introduction mass spectrometry (DIMS) approach appears to be very attractive to achieve this goal. However, processing DIMS data is still very challenging due to the large number of samples and the intrinsic complexity of the mass spectra.ObjectivesThe objective of this study is to develop a computational procedure, based on an innovative chemometric method, i.e. Independent component–discriminant analysis (IC–DA), for processing DIMS data.MethodMetabolomic fingerprints were obtained by direct introduction high resolution mass spectrometry (DI-HRMS) analysis of urine samples of subjects that had been professionally exposed to pesticides. Spectral data were processed using the developed IC–DA procedure. Results obtained from this method were compared to those obtained by the conventional Partial least squares–discriminant analysis (PLS–DA). For both the IC–DA and PLS–DA methods, a validation was performed based on a permutation test.ResultIC–DA results enabled a good detection of discriminant variables and a clear discrimination of control samples and exposure classes whereas a less striking discrimination was obtained with PLS–DA. Putative annotation of these variables was performed using metabolomic databases. Targeted correlation analysis was used for the detection of ions associated with the most discriminant variables, consolidating their identity assignment.ConclusionThis study demonstrated the efficiency of IC–DA to discriminate the different exposure groups. As well the improvement of high throughput metabolomic studies was provided by combining DI–HRMS with this new chemometric tool.
    Mots-clés : CSOB, POLE 3.

  • X. Han, L. - L. Si, Y. - Y. Shi, Z. - B. Fan, S. - X. Wang, Z. - Y. Tian, M. Li, J. - Q. Sun, P. - X. Jiao, F. - X. Ran, Y. - M. Zhang, D. - M. Zhou, et S. - L. Xiao, « Synthesis and In Vitro Anti-Influenza Virus Evaluation of Novel Sialic Acid (C-5 and C-9)-Pentacyclic Triterpene Derivatives », Molecules, vol. 22, nᵒ 7, p. 1018, juin 2017.

  • L. Hassouna, N. Illy, et P. Guégan, « Phosphazene/triisobutylaluminum-promoted anionic ring-opening polymerization of 1,2-epoxybutane initiated by secondary carbamates », Polymer Chemistry, vol. 8, nᵒ 27, p. 4005-4013, juill. 2017.
    Résumé : Attempts to use a carbamate-phosphazene base as the initiating system for the polymerization of 1,2-epoxybutane was unsuccessful. As a matter of fact, carbamate deprotonation by phosphazene bases led to their fast decomposition generating alkoxide anions which initiate the polymerization rather than carbamate anions. Conversely, in the presence of triisobutylaluminum – a Lewis acid – the in situ generation of an anionic initiator X− obtained by the deprotonation of the tBuP4 phosphazene base was tested as a possible way to initiate the polymerization of 1,2-epoxybutane. Particular attention was given to the detection of eventual transfer or side-reactions according to the carbamate:triisobutylaluminum:phosphazene base ratio, to the solvent dielectric constant and to the number of PN– units in the phosphazene base. The reaction was performed with a stoichiometric ratio (1:1:1) of carbamate:triisobutylaluminum:tBuP2, which gave the best results. Under these conditions, the initiation of the polymerization by the carbamate anion was quantitative; no transfer reactions have been observed and the polymerization proceeded in a controlled manner to afford amide end-capped poly(butylene oxide) with a narrow molar mass distribution and expected molar masses.
    Mots-clés : POLE 4, POLYMERES.
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  • G. Izzet, F. Volatron, et A. Proust, « Tailor–made Covalent Organic-Inorganic Polyoxometalate Hybrids: Versatile Platforms for the Elaboration of Functional Molecular Architectures », The Chemical Record, vol. 17, nᵒ 2, p. 250-266, 2017.
    Résumé : Post-functionalization of organically modified polyoxometalates (POMs) is a powerful synthetic tool to devise functional building blocks for the rational elaboration of POM-based molecular materials. In this personal account we focus on iodoaryl-terminated POM platforms, describe reliable routes to the synthesis of covalent organic-inorganic POM-based hybrids and their integration into advanced molecular architectures or multi-scale assemblies as well as their immobilization onto surfaces. Valorisation of the remarkable redox properties of POMs in the fields of artificial synthesis and molecular electronic is especially considered.
    Mots-clés : artificial photosynthesis, E-POM, modified electrodes, organic-inorganic hybrids, palladium cross-coupling, POLE 2, Polyoxometalates.

  • J. Jacquet, K. Cheaib, Y. Ren, H. Vezin, M. Orio, S. Blanchard, L. Fensterbank, et M. Desage‐El Murr, « Circumventing Intrinsic Metal Reactivity: Radical Generation with Redox-Active Ligands », Chemistry – A European Journal, vol. 23, nᵒ 60, p. 15030-15034, oct. 2017.
    Résumé : Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni0 to NiIV. Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox-active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand-based oxidation performing electron transfer to an electrophilic CF3+ source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox-active ligands.
    Mots-clés : CF3. radicals, E-POM, MACO, nickel, POLE 2, redox-active ligand, single electron transfer.
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  • J. - R. Jiménez, M. Tricoire, D. Garnier, L. - M. Chamoreau, J. von Bardeleben, Y. Journaux, Y. Li, et R. Lescouëzec, « A new {Fe4Co4} soluble switchable nanomagnet encapsulating Cs+: enhancing the stability and redox flexibility and tuning the photomagnetic effect. », Dalton Transactions, vol. 46, nᵒ 44, p. 15549–15557, nov. 2017.
    Résumé : We report a new cyanide-bridged Cs⊂{Fe4Co4} box, a soluble model of photomagnetic Prussian blue analogues (PBAs). The Cs+ ion has a high affinity for the box and can replace the K+ ion in the preformed K-cube. This exchange is kinetically impeded at room temperature but is accelerated by heating and using the 18-crown-6 ether. The inserted Cs+ ion confers a high robustness to the cube, which withstands boiling, as shown by variable-temperature NMR studies. The stability of this model complex in solution allows the probing of the electronic interaction between the alkali ion and the cyanide cage by using various techniques. These interactions are known to play a role in the photomagnetic behaviour of PBAs. Firstly, the 133Cs NMR spectroscopy proves that there is an electronic communication between the encapsulated alkali ion and the cyanide cage. The measured up-field signal, observed at ca. −200 ppm at 300 K, reveals that a certain amount of spin density is transferred through the bonds from the paramagnetic Co(II) ion to the encapsulated cation. Secondly, cyclovoltammetric studies show that the nature of the inserted ions affects the redox properties of the cage and influences the electronic communication between the metal ions. However, the differences in the electrochemical properties of the K-cube and the Cs-cube remain moderate. As the switching properties are influenced by the redox potential of the Fe and Co centers, similar photomagnetic behaviour is observed, with both of them being highly photomagnetic. This result contrasts strikingly with previous studies on the 3D polymeric PBAs, where the PBAs with a high amount of Cs+ show poor photomagnetic behaviour. In that case, cooperative behaviour likely influences the switching properties. Finally, EPR spectroscopy shows that the K-cube is more anisotropic than the Cs-cube. This difference is reflected in the changes occurring in the slow magnetic relaxation (single molecule magnet behaviour) observed in the two cubes.
    Mots-clés : ERMMES, POLE 2.

  • E. Ketata, A. Neifar, W. Mihoubi, P. Pigeon, H. Gouzi, J. - M. Mallet, S. Top, G. K. Gupta, G. Jaouen, A. Gargouri, et M. El Arbi, « The inhibition of tyrosinase by some aryl butenes: A desired activity or a side effect to avoid », Journal of organometallic chemistry, vol. 848, p. 133-141, 2017.

  • L. Le Falher, A. Mumtaz, A. Nina Diogo, S. Thorimbert, et C. Botuha, « Chemoselective Access to π-Conjugated Heterocycles by Stille and Sonogashira Reactions on 2-Substituted 4H-Pyrido[e][1,3]oxazin-4-ones », European Journal of Organic Chemistry, vol. 2017, nᵒ 4, p. 827-832, janv. 2017.
    Résumé : Site-selective PdII-catalyzed cross-coupling reactions of 2-substituted-4H-pyrido[e][1,3]oxazin-4-ones were developed. C4- and C5-alkynylated pyridooxazinones were thus obtained through Sonogashira coupling, whereas the efficient incorporation of (hetero)aryl and ethenyl substituents at the C5 position was achieved by Stille coupling. Finally, an example of one-pot sequential multiple Sonogashira reactions with different alkynes was realized. The strategy developed herein provides rapid access to polyfunctionalized precursors with extended π-conjugation for further application as fluorescent materials.
    Mots-clés : CHEMBIO, cross-coupling, Fluorescent probes, heterocycles, homogeneous catalysis, Palladium, POLE 3.

  • K. J. Lee, Y. Xiao, J. H. Woo, E. Kim, D. Kreher, A. - J. Attias, F. Mathevet, J. - C. Ribierre, J. W. Wu, et P. André, « Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues », Nature Materials, vol. advance online publication, juin 2017.
    Résumé : Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7—that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal–dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.
    Mots-clés : Metamaterials, POLE 4, POLYMERES, Structural properties, Ultrafast photonics.

  • C. Lévêque, V. Corcé, L. Chenneberg, C. Ollivier, et L. Fensterbank, « Photoredox/Nickel Dual Catalysis for the C(sp3)–C(sp3) Cross-Coupling of Alkylsilicates with Alkyl Halides », European Journal of Organic Chemistry, vol. 2017, nᵒ 15, p. 2118-2121, 2017.
    Résumé : Alkylsilicates were engaged under photoredox/nickel dual catalysis conditions with alkyl halides for the first time. The C(sp3)–C(sp3) cross-coupling products were obtained in moderate yields and were accompanied by the homocoupling products of the alkyl halide derivatives. These promising findings are strongly suggestive of the high synthetic potential of the dual catalytic approac

    h for the forging of alkyl carbon–carbon bonds.
    Mots-clés : cross-coupling, C–C coupling, MACO, Nickel, photoredox catalysis, POLE 1, radical reactions.

  • F. Liu, Z. - Y. Zhu, X. Sun, H. Gao, et Y. - M. Zhang, « The preparation of three selenium-containing Cordyceps militaris polysaccharides: Characterization and anti-tumor activities », International Journal of Biological Macromolecules, vol. 99, p. 196-204, 2017.

  • J. Malinge, B. Géraudie, P. Savel, V. Nataf, A. Prignon, C. Provost, Y. Zhang, P. Ou, K. Kerrou, J. - N. Talbot, J. - M. Siaugue, M. Sollogoub, et C. Ménager, « Liposomes for PET and MR Imaging and for Dual Targeting (Magnetic Field/Glucose Moiety): Synthesis, Properties, and in Vivo Studies », Molecular Pharmaceutics, vol. 14, nᵒ 2, p. 406-414, févr. 2017.
    Résumé : We describe the potentiality of a new liposomal formulation enabling positron emission tomography (PET) and magnetic resonance MR imaging. The bimodality is achieved by coupling a 68Ga-based radiotracer on the bilayer of magnetic liposomes. In order to enhance the targeting properties obtained under a permanent magnetic field, a sugar moiety was added in the lipid formulation. Two new phospholipids were synthesized, one with a specific chelator of 68Ga (DSPE-PEG-NODAGA) and one with a glucose moiety (DSPE-PEG-glucose). The liposomes were produced according to a fast and safe process, with a high radiolabeling yield. MR and PET imaging were performed on mice bearing human glioblastoma tumors (U87MG) after iv injection. The accumulation of the liposomes in solid tumor is evidenced by MR imaging and the amount is evaluated in vivo and ex vivo according to PET imaging. An efficient magnetic targeting is achieved with these new magnetic liposomes.
    Mots-clés : GOBS, POLE 3.

  • Z. Mao, E. Martini, G. Prestat, J. Oble, P. - Q. Huang, et G. Poli, « Analogues of the 2-carboxyl-6-hydroxyoctahydroindole (CHOI) unit from diverging Pd-catalyzed allylations: Selectivity as a function of the double bond position », Tetrahedron Letters, vol. 58, nᵒ 44, p. 4174-4178, nov. 2017.
    Résumé : Pd-catalyzed allylations of cyclic bis-allylic substrates, carried out either as two separate steps or in a pseudo-domino fashion, can generate 2-carboxyl-hexahydroindoles bearing an unsaturation in different positions. Sequential homologation, and epoxidation or syn-dihydroxylation steps were investigated to access analogues of the bicyclic 2-carboxyl-6-hydroxyoctahydroindole motif of aeruginosins, a family of peptides displaying serine protease inhibitor activity.
    Mots-clés : Allylic substitution, CHOI core, Domino reaction, Palladium catalysis, POLE 1, ROCS.

  • M. Mon, J. Ferrando-Soria, M. Verdaguer, C. Train, C. Paillard, B. Dkhil, C. Versace, R. Bruno, D. Armentano, et E. Pardo, « Postsynthetic Approach for the Rational Design of Chiral Ferroelectric Metal-Organic Frameworks », Journal of the American Chemical Society, vol. 139, nᵒ 24, p. 8098-8101, juin 2017.
    Résumé : Ferroelectrics (FEs) are materials of paramount importance with a wide diversity of applications. Herein, we propose a postsynthetic methodology for the smart implementation of ferroelectricity in chiral metal organic frameworks (MOFs): following a single crystal to single-crystal cation metathesis, the Ca2+ counterions of a preformed chiral MOF of formula Ca-6(II){C-24(II)[(S,S)-hismox](12) (OHO2)}center dot 212H(2)O ( 1), where hismox is a chiral ligand derived from the natural amino acid L-histidine, are replaced by CH3NH3+. The resulting compound, (CH3NH3)(12){Cu-24(II)[(S,S)-hiSMOX](12)(OH2)(3)}center dot 178H(2)O (2), retains the polar space group of 1 and is ferroelectric below 260 K. These results open a new synthetic avenue to enlarge the limited number of FE MOFs.
    Mots-clés : behavior, crystals, HorsPole, multiferroics, polarization.

  • J. Moussa, A. Loch, L. - M. Chamoreau, A. Degli Esposti, E. Bandini, A. Barbieri, et H. Amouri, « Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands », Inorganic Chemistry, vol. 56, nᵒ 4, p. 2050-2059, févr. 2017.
    Résumé : A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)]n+ (n = 0, 1) with π-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt–πCp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.
    Mots-clés : ARC, POLE 1.
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