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  • L. Ben Haj Hassen, S. Dhifaoui, Y. Rousselin, V. Marvaud, C. Stern, C. E. Schulz, et H. Nasri, « New insights on the electronic, magnetic, electric and molecular structure of a bis-(4-cyanopyridine) iron(III) complex with the meso-tetrakis(4-methoxyphenyl)porphyrin », Inorganica Chimica Acta, vol. 486, p. 675-683, févr. 2019.
    Résumé : We have successfully synthesized and characterized a new low-spin iron(III) bis(4-cyanopyridine) complex with a meso-porphyrin substituted in the para positions of the phenyls by the methoxy group, namely the bis(4-cyanopyridine)[(meso-tetrakis(4-metoxyphenylporphyrinato)]iron(III) trifluoromethanesulfonate chlorobenzene monosolvate complex with the formula [FeIII(TMPP)(4-CNpy)2]SO3CF3.C6H5Cl (I). This species was characterized through ultraviolet–visible, Fourier-transform infrared and Mössbauer spectroscopy as well as by SQUID magnetometry, cyclic voltammetry, and X-ray crystallography. These characterizations indicated that our synthetic heme model is a low-spin (S = 1/2) coordination compound and especially shows that the structural, electronic and the magnetic properties of complex (I) are closely dominated by the presence of the methoxy σ-donor group at the para positions of the meso-porphyrin.
    Mots-clés : Cyclic voltammetry, E-POM, Iron(III) porphyrin, Magnetic properties, X-ray Molecular structure.


  • L. Bacri, H. Mamad-Hemouch, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, et J. Pelta, « Biomimetic ion channels formation by emulsion based on chemically modified cyclodextrin nanotubes », Faraday Discussions, 2018.

  • M. Barbazanges et L. Fensterbank, « The Invention of New Methodologies: An Opportunity for Dating Natural Products », Synlett, août 2018.
    Résumé : This Account surveys almost two decades of methodological developments and their straightforward applications to the total synthesis of simple natural products. The main directions covered include radical chemistry and cascades, electrophilic catalysis based on coinage metals, and asymmetric synthesis based on bis(sulfoxides) auxiliaries. 1 Introduction 2 Radical Cascades 2.1 N-Cyanamides 2.2 Homolytic Substitution at Sulfur Atom to Give Sultines 3 Electrophilic Catalysis Based on Platinum(II) and Gold(I) Complexes 4 From Alkylydene Bis(sulfoxides) to Chiral Carboxylic Acids 5 Conclusion and Perspectives
    Mots-clés : asymmetric synthesis, bis(sulfoxides), gold catalysis, Key words radical chemistry, MACO, natural products, POLE 1, total synthesis.
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  • P. Barbier Saint Hilaire, U. M. Hohenester, B. Colsch, J. - C. Tabet, C. Junot, et F. Fenaille, « Evaluation of the High-Field Orbitrap Fusion for Compound Annotation in Metabolomics », Analytical Chemistry, vol. 90, nᵒ 5, p. 3030-3035, mars 2018.

  • P. Bayat, D. Gatineau, D. Lesage, V. Robert, A. Martinez, et R. B. Cole, « Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling », Journal of The American Society for Mass Spectrometry, nov. 2018.

  • P. Bayat, D. Lesage, et R. B. Cole, « Low-energy collision-induced dissociation (low-energy CID), collision-induced dissociation (CID), and higher energy collision dissociation (HCD) mass spectrometry for structural elucidation of saccharides and clarification of their dissolution mechanism i », Journal of Mass Spectrometry, vol. 53, nᵒ 8, p. 705-716, 2018.

  • M. Ben Haddada, M. Salmain, et S. Boujday, « Gold colloid-nanostructured surfaces for enhanced piezoelectric immunosensing of staphylococcal enterotoxin A », Sensors and Actuators B: Chemical, vol. 255, nᵒ 2, p. 1604-1613, 2018.

  • L. Benda, B. Doistau, B. Hasenknopf, et G. Vives, « Synthesis and Guest Recognition of Switchable Pt-Salphen Based Molecular Tweezers », Molecules, vol. 23, nᵒ 5, p. 990, avr. 2018.

  • B. Bertrand, K. Passador, C. Goze, F. Denat, E. Bodio, et M. Salmain, « Metal-based BODIPY derivatives as multimodal tools for life sciences », Coordination Chemistry Reviews, vol. 358, p. 108-124, 2018.
    Résumé : Nowadays, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene – better known as BODIPY – is at the forefront of fluorophores for life sciences. Indeed, its high brightness, its tunable excitation and emission wavelengths along with its high chemical and photochemical stability draw more and more the interest of researchers. In the last decade, chemists have taken advantage of the versatility of the synthesis of BODIPY to design sophisticated objects. This review focuses on the different recent studies dealing with the conception of metal-based-BODIPY derivatives for medical purposes. More precisely, emphasis is put on the use of BODIPY derivatives for the elaboration of BODIPY-based theranostics, multimodal imaging probes, and photodynamic therapy sensitizers.
    Mots-clés : Bimodal imaging, BODIPY, CHEMBIO, Fluorescence, Metal-based drugs, Photodynamic therapy, POLE 3, Theranostics.

  • P. Biais, P. Beaunier, F. Stoffelbach, et J. Rieger, « Loop-stabilized BAB triblock copolymer morphologies by PISA in water », Polymer Chemistry, vol. 9, nᵒ 35, p. 4483-4491, sept. 2018.
    Résumé : A straightforward strategy to synthesize loop-stabilized particles in water via PISA is developed. These particular structures can in theory be obtained through the synthesis of amphiphilic BAB triblock copolymers, starting from a hydrophilic middle block A, which is chain extended in an aqueous PISA process with two hydrophobic external blocks B. For this purpose, symmetrical bifunctional poly(N,N-dimethylacrylamide) ma

    croRAFT agents with a central benzoic acid group and an alkyl chain as the Z group are used in the aqueous dispersion polymerization of diacetone acrylamide. For the first time, stable BAB flower-like particles are formed via PISA in pure water. It is shown that the colloidal stability and the resulting particle morphology (spheres, worms, vesicles) strongly depend on the degree of ionization of the central charge in the stabilizer loop, and thus on the pH at which PISA is performed. Moreover, the influence of the length of the alkyl Z group (dodecyl and butyl alkyl chains) on the colloidal stability is studied.
    Mots-clés : POLE 4, POLYMERES.
    Pièce jointe Full Text PDF 1.8 Mo (source)

  • F. A. Black, A. Jacquart, G. Toupalas, S. Alves, A. Proust, I. P. Clark, E. A. Gibson, et G. Izzet, « Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates », Chemical Science, vol. 9, nᵒ 25, p. 5578-5584, 2018.
    Mots-clés : CSOB, E-POM, POLE 2, POLE 3.

  • V. N. Bochatay, F. Chemla, F. Ferreira, O. Jackowski, et A. Pérez-Luna, « β‐Amino Propargylic Fluorides through Stereoselective Electrophilic Fluorodesilylation of 4‐Amino‐1‐allenylsilanes - Bochatay - 2018 - European Journal of Organic Chemistry - Wiley Online Library », European Journal of Organic Chemistry, p. 3862, 2018.

  • B. Brahim, J. - C. Tabet, et S. Alves, « Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of “three-body” noncovalent fragment ions », European Journal of Mass Spectrometry, vol. 24, nᵒ 1, p. 168-177, 2018.

  • N. Bridonneau, P. Quatremare, H. J. von Bardeleben, J. - L. Cantin, S. Pillet, E. - E. Bendeif, et V. Marvaud, « Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum-Copper” Molecular Compounds », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 3-4, p. 370-377, janv. 2018.
    Résumé : For the first time, direct evidence of a photoinduced intramolecular electron transfer has been found in the “molybdenum-copper“ family of cyanide complexes that corresponds to a [MoIV–CuII]→[MoV–CuI] transition. The design and synthesis of a diluted molecular system, [Mo(Zn(1–x)Cux)2-tren] (x = 0, ε, 1, 5 and 10 %, , with ε corresponding to ppm ratio), viewed as new model compounds, have allowed good characterization of the metastable states involved in the process and provided evidence for two different mechanisms. By using squid magnetometry, EPR spectroscopy and X-ray diffraction, the results of this study have confirmed not only the photoinduced electron transfer, but also supports the light-induced excited spin state trapping effect centred on the molybdenum, thought to be due to the presence of a high-spin state (S = 1). This article provides a better understanding of the photomagnetic behaviour in Mo-Cu complexes and reveals the importance of orbital overlap to differentiate the two effects.
    Mots-clés : Copper, E-POM, Electron transfer, Magentic properties, Molybdenum, Photomagnetism, POLE 2, Spin transition.
    Pièce jointe Full Text PDF 1.7 Mo (source)

  • R. Brisse, D. Guianvarc'h, C. Mansuy, S. Sagan, D. Kreher, L. Sosa-Vargas, L. Hamitouche, V. Humblot, I. Arfaoui, V. Labet, C. Paris, C. Petit, et A. - J. Attias, « Probing the in-air growth of large area of 3D functional structures into a 2D supramolecular nanoporous network », Chemical Communications, vol. 54, nᵒ 72, p. 10068-10071, 2018.

  • T. Buchecker, P. Schmid, S. Renaudineau, O. Diat, A. Proust, A. Pfitzner, et P. Bauduin, « Polyoxometalates in the Hofmeister series », Chemical Communications, vol. 54, nᵒ 15, p. 1833-1836, févr. 2018.
    Résumé : We propose a simple experimental procedure based on the cloud point measurement of a non-ionic surfactant as a tool for (i) estimating the super-chaotropic behaviour of polyoxometalates (POMs) and for (ii) establishing a classification of POMs according to their affinity towards polar surfaces.
    Mots-clés : E-POM.

  • X. Callies, E. Ressouche, C. Fonteneau, G. Ducouret, S. Pensec, L. Bouteiller, et C. Creton, « Effect of the Strength of Stickers on Rheology and Adhesion of Supramolecular Center-Functionalized Polyisobutenes », Langmuir, vol. 34, nᵒ 42, p. 12625-12634, oct. 2018.
    Résumé : In order to systematically investigate the effect of the strength of the supramolecular interactions on the debonding properties of associative polymers, a series of model systems have been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(isobutylene) chains (Mn ≈ 3 kg/mol) center-functionalized by a single bis-urea sticker, are able to self-assemble by four hydrogen bonds. Three types of stickers are used in the present study: a bis-urea with a methylene diphenyl (MDI) spacer, a bis-urea with a tolyl (TOL) spacer, and a bis-urea with a xylyl (XYL) spacer. In order to investigate the influence of stickers in depth, both the nanostructure of the materials and the linear rheology were investigated by small-angle X-ray scattering (SAXS) and oscillatory shear, respectively. For two types of stickers (TOL and XYL), the association of polymers via hydrogen bonds induces the formation of bundles of rodlike aggregates at room temperature and the behavior of a soft elastic material was observed. For bis-urea MDI, no structure is detected by SAXS and a Newtonian behavior is observed at room temperature. In probe-tack experiments, all these materials show a cohesive mode of failure, a signature of flowing materials as previously observed for tri-urea center-functionalized poly(butylacrylate) (PnBA3U). However, XYL center-functionalized polyisobutene shows much higher debonding energies than PnBA3U, revealing the importance of the strength of noncovalent bonds in the scission/recombination dynamics. On the basis of the analysis of the debonding images, this effect is discussed via the mechanical behavior at large deformation.
    Mots-clés : POLE 4, POLYMERES.

  • N. Chahin, L. A. Uribe, A. M. Debela, S. Thorimbert, B. Hasenknopf, M. Ortiz, I. Katakis, et C. K. O'Sullivan, « Electrochemical primer extension based on polyoxometalate electroactive labels for multiplexed detection of single nucleotide polymorphisms », Biosensors and Bioelectronics, vol. 117, p. 201-206, 2018.
    Résumé : Polyoxymetalates (POMs) ([SiW11O39{Sn(CH2)2CO)}]4- and [P2W17O61{Sn(CH2)2CO)}]6-) were used to modify dideoxynucleotides (ddNTPs) through amide bond formation, and applied to the multiplexed detection of single nucleotide polymorphisms (SNPs) in an electrochemical primer extension reaction. Each gold electrode of an array was functionalised with a short single stranded thiolated DNA probe, specifically designed to extend with the POM-ddNTP at the SNP site to be interroga

    ted. The system was applied to the simultaneous detection of 4 SNPs within a single stranded 103-mer model target generated using asymmetric PCR, highlighting the potential of POM-ddNTPs for targeted, multiplexed SNP detection. The four DNA bases were successfully labelled with both ([SiW11O39{Sn(CH2)2CO)}]4- and [P2W17O61{Sn(CH2)2CO)}]6-), and [SiW11O39{Sn(CH2)2CO)}]4- demonstrated to be the more suitable due to its single oxidation peak, which provides an unequivocal signal. The POM-ddNTP enzymatically incorporated to the DNA anchored to the surface was visualised by AFM using gold coated mica. The developed assay has been demonstrated to be highly reproducible, simple to carry out and with very low non-specific background signals. Future work will focus on applying the developed platform to the detection of SNPs associated with rifampicin resistance in real samples from patients suffering from tuberculosis.
    Mots-clés : CHEMBIO, Electrochemical primer extension reaction (éPEX), Multiplexed electrochemical detection, POLE 3, Polyoxometalate-labelled ddNTPs, SNP detection.

  • L. Chang, N. Klipfel, L. Dechoux, et S. Thorimbert, « A solvent-free, base-catalyzed domino reaction towards trifluoromethylated benzenes from bio-based methyl coumalate », Green Chemistry, vol. 20, nᵒ 7, p. 1491-1498, 2018.
    Résumé : A novel, efficient, and environmentally compatible method for CF3-substituted benzene production is reported. It sources a bio-based feedstock, employs tBuOK as a catalyst, and is solvent-free. This regioselective approach provides various trifluoromethyl benzenes in good to excellent yields, without any extra oxidant or special care. CO2 and water are the only byproducts of this process, and the reaction conditions can scale up to gram quantities. The transformation involves an unprecedented tBuOK-catalyzed domino process, and features Michael addition/6[small pi]-electrocyclic ring opening/[1,5]-H shift/carba-6[small pi]-electrocyclic ring closure/decarboxylative aromatization reactions.
    Mots-clés : CHEMBIO, POLE 3.

  • T. F. C. Cruz, C. A. Figueira, J. C. Waerenborgh, L. C. J. Pereira, Y. Li, R. Lescouëzec, et P. T. Gomes, « Synthesis, characterization and magnetism of homoleptic bis(5-aryl-2-iminopyrrolyl) complexes of iron(II) and cobalt(II) », Polyhedron, vol. 152, p. 179-187, 2018.

  • de Jesús Cázares-Marinero José, Przybylski Cédric, et Salmain Michèle, « Proteins as Macromolecular Ligands for Metal-Catalysed Asymmetric Transfer Hydrogenation of Ketones in Aqueous Medium », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 12, p. 1383-1393, 2018.
    Résumé : Biohybrid catalysts resulting from the dative anchoring of half-sandwich organometallic complexes [M(arene)(H2O)x(Cl)y]n+ (M = RuII, arene = ?6-benzene, p-cymene or mesitylene; M = IrIII, RhIII, arene = ?5-Cp*; x = 1?3, y = 0?2, n = 0?2) to bovine beta-lactoglobulin (?LG) or hen egg white lysozyme showed unprecedented behaviour. These constructs were shown to catalyse the asymmetric transfer hydrogenation of aryl ketones in water with sodium formate as hydrogen donor at a much faster rate than the complexes alone. Full conversion of the benchmark substrate 2,2,2-trifluoroacetophenone was reached with an ee of 86?% for the most selective biohybrid. Surprisingly, even the crude biohybrid gave a good ee despite the presence of non-protein-bound metal species in the reaction medium. Other aryl ketones were reduced in the same way, and the highest ee was obtained for ortho-substituted acetophenone derivatives. Furthermore, treatment of ?LG with dimethyl pyrocarbonate resulted in a noticeable decrease of the activity and selectivity of the biohybrid, indicating that the sole accessible histidine residue (His146) was probably involved in the coordination and activation of Ru(benzene). This work underscores that protein scaffolds are efficient chiral ligands for asymmetric catalysis. The use of sodium formate instead of dihydrogen makes this approach safe, inexpensive and environmentally friendly.
    Mots-clés : Artificial metalloenzymes, Asymmetric catalysis, CHEMBIO, CSOB, Hydrogenation, Mass spectrometry, POLE 3, Ruthenium.
    Note Note
    <p>doi: 10.1002/ejic.201701359</p>

  • S. De, L. - M. Chamoreau, H. El Said, Y. Li, A. Flambard, M. - L. Boillot, S. Tewary, G. Rajaraman, et R. Lescouëzec, « Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone) », Frontiers in Chemistry, vol. 6, août 2018.

  • S. De, S. Tewary, D. Garnier, Y. Li, G. Gontard, L. Lisnard, A. Flambard, F. Breher, M. - L. Boillot, G. Rajaraman, et R. Lescouëzec, « Solution and Solid-State Study of the Spin-Crossover [FeII(R-bik)3](BF4)2 Complexes (R = Me, Et, Vinyl) », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 3-4, p. 414-428, janv. 2018.
    Résumé : The magnetic properties of three spin-crossover complexes, [FeII(R-bik)3](BF4)2·nH2O (1–3), based on bis(imidazolyl)ketone ligands, were investigated in solution and the solid state. Their properties were compared with those of the ketone-free analogue, [FeII(bim)3](OTf)2 (4). The alkyl and vinyl R groups have weak influence on the transition temperature, T1/2, in solution, while stronger differences are observed in the solid state, because different intermolecular interactions occur in 1–3. The spin-state equilibria in solution were followed by SQUID magnetometry and the Evans NMR spectroscopy method. Interestingly, the equilibria can also be simply and efficiently probed by following the temperature dependence of an adequately chosen 1H chemical shift. Overall, these experiments give coherent results, with T1/2 located between 320 and 335 K, a narrow range, in comparison with the solid state. DFT calculations have allowed the rationalization of the magnetic differences. The molecular-orbital and spin-density calculations reveal that the presence of the C=O group between the imidazolyl units in the ligands of 1–3 leads to an extended aromatic system, an effective π-acceptor effect, stabilizing the LS state and reducing the LS–HS gap, in comparison with 4.
    Mots-clés : Density functional calculations, ERMMES, Iron, Paramagnetic NMR spectroscopy, POLE 2, Spin crossover.
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  • S. Dhifaoui, C. Mchiri, P. Quatremare, V. Marvaud, A. Bujacz, et H. Nasri, « Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin », Journal of Molecular Structure, vol. 1153, p. 353-359, févr. 2018.
    Résumé : In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV–visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C–H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.
    Mots-clés : E-POM, Iron(III) porphyrins, Magnetic data, POLE 2, UV–Visible, X-ray molecular structure.

  • S. Dhifaoui, S. Nasri, G. Gontard, A. C. Ghosh, Y. Garcia, C. Bonifàcio, S. Najmudin, V. Marvaud, et H. Nasri, « Synthesis, Mössbauer, cyclic voltammetry, magnetic properties and molecular structures of the low-spin iron(III) bis(pyrazine) complexes with the para-fluoro and para-chloro substituted meso-tetraphenylporphyrin », Inorganica Chimica Acta, vol. 477, p. 114-121, mai 2018.
    Résumé : Two new bis(pyrazine) iron(III) meso-porphyrin complexes are reported here: the bis(pyrazine)[5,10,15,20-tetra(para-fluoro-phenyl)porphyrinato]iron(III) triflate; [Fe(TFPP)(pyz)2]SO3CF3 (1) and the bis(pyrazine)[5,10,15,20-tetra(para-chlorophenyl)porphyrinato]iron(III) triflate; [Fe(TClPP)(pyz)2]SO3CF3 (2). The X-ray molecular structures of 1–2 show that the planes of the two pyrazine axial ligands are perpendicular and that the porphyrin macrocycles of these derivatives are very distorted, leading to a short average equatorial iron-pyrrole N atoms distance appropriate for low-spin ferric porphyrinates. The Mössbauer data of 1–2 feature relatively low values of the quadrupole splitting (ΔEQ ∼ 1.20 mm.s−1) appropriate for low-spin Fe(III) metalloporphyrin with perpendicular orientation of N-donor planar ligands. The temperature dependence of the magnetic susceptibility and the magnetization curves have shown that the results for complexes 1–2 confirm the low-spin state of our two-ferric species, while the cyclic voltammetry data show that the half potential [Fe(III)/Fe(II)] values are shifted anodically compared to the β-pyrrole substituted porphyrin octaethylporphyrin with parallel bis(N-donor) planar axial ligands.
    Mots-clés : E-POM, Iron(III) porphyrins, Magnetic properties, Mössbauer, POLE 2, UV-visible, X-ray molecular structure.

  • F. Ding, Y. Gao, X. He, et Y. Zhang, « Theranostic Applications of Antibody-Based Systems in Human Diseases », Journal of Biomedical Nanotechnology, vol. 14, nᵒ 3, p. 405-429, mars 2018.

  • F. Ding et Y. Zhang, « Biomedical Applications of Glycoconjugates », Mini-Reviews in Medicinal Chemistry, vol. 18, nᵒ 18, p. 1508-1523, oct. 2018.

  • B. Doistau, L. Benda, B. Hasenknopf, V. Marvaud, et G. Vives, « Switching Magnetic Properties by a Mechanical Motion », Magnetochemistry, vol. 4, nᵒ 1, p. 5, janv. 2018.
    Mots-clés : E-POM, GOBS, POLE 2, POLE 3.

  • S. Douix, H. Dossmann, E. Nicol, D. Duflot, et A. Giuliani, « Spectroscopy and Photodissociation of the Perfluorooctanoate Anion », Chemistry - A European Journal, sept. 2018.

  • M. Dréan, A. Debuigne, C. Jérôme, C. Goncalves, P. Midoux, J. Rieger, et P. Guégan, « Poly(N-methylvinylamine)-Based Copolymers for Improved Gene Transfection », Macromolecular Bioscience, vol. 18, nᵒ 4, p. 1700353, avr. 2018.
    Résumé : Poly(N-methylvinylamines) with secondary amines can form complexes with plasmid DNA (pDNA) and provide transfection efficiency in HeLa cells in the same order as linear polyethyleneimine but with higher cell viability. Chemical modifications of poly(N-methylvinylamine) backbones are performed to further improve transfection efficiency while maintaining low degree of cytotoxicity. In a first type of polymer, primary amino groups are incorporated via a copolymerization strategy. In a second one, primary amino and imidazole groups are incorporated also via a copolymerization strategy. In a third one, secondary amino groups are substituted with methylguanidine functions through a postpolymerization reaction. Thus, novel polymers of various molecular masses are synthesized, characterized, and their interaction with pDNA studied. Then, their transfection efficiency and cytotoxicity are tested in HeLa cells. Two polymethylvinylamine-based copolymers, one containing 20% of imidazole moieties and another one composed of 12% of guanidinyl units allow remarkable transfection efficiency of HeLa, pulmonary (16HBE), skeletal muscle (C2C12), and dendritic (DC2.4) cells. Overall, this work thus identifies new promising DNA carriers and chemical modifications that improve the transfection efficiency while maintaining low degree of cytotoxicity.
    Mots-clés : gene delivery, nanoparticles, POLE 4, POLYMERES, polyvinylamine.
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  • B. Ebeling, K. Belal, F. Stoffelbach, P. Woisel, M. Lansalot, et F. D'Agosto, « Polymer Nanospheres with Hydrophobic Surface Groups as Supramolecular Building Blocks Produced by Aqueous PISA », Macromolecular Rapid Communications, p. 1800455, 2018.
    Résumé : A robust and straightforward synthesis of waterborne polymer nanospheres bearing the supramolecular association unit dialkoxynapthalene at their surface is presented using polymerization-induced self-assembly (PISA). A RAFT agent bearing this unit is first employed to produce poly(acrylic acid) chains, which are then chain-extended with styrene (S) to spontaneously form the nano-objects via RAFT aqueous emulsion polymerization. The particular challenge posed by the dialkoxynapthalene hydrophobicity can be overcome by the use of PISA and the deprotonation of the poly(acrylic acid). At pH = 7, very homogeneous latexes are obtained. The particle diameters can be tuned from 36 to 105 nm (with a narrow particle size distribution) by varying the molar mass of the PS block. The surface accessibility of the dialkoxynapthalene moieties is demonstrated by complexation with the complementary host cyclobis(paraquat-p-phenylene) (CBPQT4+ · Cl−), highlighting the potential of the nanospheres to act as building blocks for responsive supramolecular structures.
    Mots-clés : emulsion polymerization, POLE 4, polymer nanoparticles, POLYMERES, polymerization-induced self-assembly, RAFT polymerization, supramolecular assembly.

  • J. Elloumi-Mseddi, S. Mnif, N. Akacha, B. Hakim, P. Pigeon, G. Jaouen, S. Top, et S. Aifa, « Selective cytotoxicity of arene tricarbonylchromium towards tumour cell lines », Journal of Organometallic Chemistry, vol. 862, p. 7-12, 2018.
    Mots-clés : 50% inhibitory concentration, CHEMBIO, Cytotoxicity, Inorganic chromium (VI), Organometallics, POLE 3, Tricarbonylchromium, Tumour cell lines.

  • Z. Eskandani, T. Le Gall, T. Montier, P. Lehn, F. Montel, L. Auvray, C. Huin, et P. Guégan, « Polynucleotide transport through lipid membrane in the presence of starburst cyclodextrin-based poly(ethylene glycol)s », The European Physical Journal E, vol. 41, nᵒ 11, p. 132, nov. 2018.
    Résumé : .Symmetrical cyclodextrin-based 14-arm star polymers with poly(ethylene glycol) PEG branches were synthesized and characterized. Interactions of the star polymers with lipid bilayers were studied by the “black lipid membrane” technique in order to demonstrate the formation of monomolecular artificial channels. The conditions for the insertion are mainly based on dimensions and amphiphilic properties of the star polymers, in particular the molar mass of the water-soluble polymer branches. Translocation of single-strand DNA (ssDNA) through those synthetic nanopores was investigated, and the close dimension between the cross-section of ssDNA and the cyclodextrin cavity led to an energy barrier that slowed down the translocation process.Graphical abstract Open image in new window
    Mots-clés : POLE 4, POLYMERES, Polymers: From Adsorption to Translocation - Topical Issue in Memoriam Loïc Auvray (1956-2016).

  • P. Evenou, J. Rossignol, G. Pembouong, A. Gothland, D. Colesnic, R. Barbeyron, S. Rudiuk, A. - G. Marcelin, M. Ménand, D. Baigl, V. Calvez, L. Bouteiller, et M. Sollogoub, « Bridging β-Cyclodextrin Prevents Self-Inclusion, Promotes Supramolecular Polymerization, and Promotes Cooperative Interaction with Nucleic Acids », Angewandte Chemie International Edition, vol. 57, nᵒ 26, p. 7753-7758, juin 2018.
    Résumé : A bridge to assemble: Cyclodextrins bridged with an ammonium linker bearing a hydrophobic substituent can efficiently form supramolecular polymers and avoid the competing self-inclusion and head-to-head processes. Furthermore, the self-assembling cyclodextrin derivative interacts in a highly cooperative manner with DNA, as demonstrated by compaction experiments. It also interacts cooperatively with siRNA and allows its transfection.
    Mots-clés : cyclodextrin, GOBS, inclusion complexes, nucleic acids, POLE 3, POLE 4, POLYMERES, supramolecular polymers.
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  • L. Fensterbank, S. Gao, et A. Zakarian, « Themed collection: Synthetic approaches to natural products via catalytic processes », Organic Chemistry Frontiers, vol. 5, nᵒ 4, p. 529-530, févr. 2018.
    Résumé : A graphical abstract is available for this content
    Mots-clés : MACO, POLE 1.
    Pièce jointe Full Text PDF 481 ko (source)

  • L. Fensterbank, J. - P. Goddard, et C. Ollivier, « Visible-Light-Mediated Free Radical Synthesis », in Visible Light Photocatalysis in Organic Chemistry, Wiley-Blackwell, 2018, p. 25-71.
    Résumé : This chapter concentrates on the photocatalytic generation of radical intermediates that have already been encountered in the past and generated through other pathways. It particularly emphasizes how photocatalysis can really improve the reaction conditions and outcomes. Different oxygenated moieties can be introduced by photocatalysis in place of an initial C—H bond. The development of visible-light photoredox catalysis for radical synthesis has demonstrated high efficiency, selectivity, versatility, and functional group tolerance in various transformations, becoming of great interest in cascade processes intramolecular radical steps. One of the most developed cascade sequence is tandem intermolecular radical addition/homolytic aromatic substitution, which first comprises radical addition onto activated double bond followed by cyclization onto arene and rearomatization by subsequent oxidation of the radical adduct. Radical multicomponent processes have emerged as a convenient and flexible strategy to elaborate complex molecular building blocks. Among them, visible-light photoredox catalysis proved to be efficient for promoting radical/cationic multicomponent reactions (MCRS).
    Mots-clés : cationic multicomponent reaction, C—C bond formation, C—X bond formation, MACO, photocatalytic cycle, POLE 1, radical cascade applications, radical intermediates, radical multicomponent reaction, visible-light-mediated free radical synthesis.

  • F. Forato, A. Belhboub, J. Monot, M. Petit, R. Benoit, V. Sarou‐Kanian, F. Fayon, D. Jacquemin, C. Queffelec, et B. Bujoli, « Phosphonate-Mediated Immobilization of Rhodium/Bipyridine Hydrogenation Catalysts », Chemistry – A European Journal, vol. 24, nᵒ 10, p. 2457-2465, févr. 2018.
    Résumé : RhL2 complexes of phosphonate-derivatized 2,2′-bipyridine (bpy) ligands L were immobilized on titanium oxide particles generated in situ. Depending on the structure of the bipy ligand—number of tethers (1 or 2) to which the phosphonate end groups are attached and their location on the 2,2′-bipyridine backbone (4,4′-, 5,5′-, or 6,6′-positions)—the resulting supported catalysts showed comparable chemoselectivity but different kinetics for the hydrogenation of 6-methyl-5-hepten-2-one under hydrogen pressure. Characterization of the six supported catalysts suggested that the intrinsic geometry of each of the phosphonate-derivatized 2,2′-bipyridines leads to supported catalysts with different microstructures and different arrangements of the RhL2 species at the surface of the solid, which thereby affect their reactivity.
    Mots-clés : hydrogenation, immobilization, MACO, N ligands, POLE 1, rhodium, supported catalysts.
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  • G. Gaiffe, M. C. Bridoux, C. Costanza, et R. B. Cole, « A systematic tandem mass spectrometric study of anion attachment for improved detection and acidity evaluation of nitrogen-rich energetic compounds », Journal of Mass Spectrometry, vol. 53, nᵒ 1, p. 21-29, 2018.

  • G. Gaiffe, R. B. Cole, S. Lacpatia, et M. C. Bridoux, « Characterization of Fluorinated Polymers by Atmospheric-Solid-Analysis-Probe High-Resolution Mass Spectrometry (ASAP/HRMS) Combined with Kendrick-Mass-Defect Analysis », Analytical Chemistry, vol. 90, nᵒ 10, p. 6035-6042, mai 2018.

  • D. Gatineau, D. Lesage, H. Clavier, H. Dossmann, C. H. Chan, A. Milet, A. Memboeuf, R. B. Cole, et Y. Gimbert, « Bond dissociation energies of carbonyl gold complexes: a new descriptor of ligand effects in gold( <span style="font-variant:small-caps;">i</span> ) complexes? », Dalton Transactions, vol. 47, nᵒ 43, p. 15497-15505, 2018.

  • M. Girardi, D. Platzer, S. Griveau, F. Bedioui, S. Alves, A. Proust, et S. Blanchard, « Assessing the Electrocatalytic Properties of the {Cp*Rh <sup>III</sup> } <sup>2+</sup> -Polyoxometalate Derivative [H <sub>2</sub> PW <sub>11</sub> O <sub>39</sub> {Rh <sup>III</sup> Cp*(OH <sub>2</sub> )}] <sup>3-</sup> towards CO <sub>2</sub> Reduction: Assessing the Electrocatalytic Properties of the {Cp*Rh <sup>III</sup> } <sup>2+</sup> -Polyoxometalate Derivative [H <sub>2</sub> PW <sub>11</sub> O <sub>39</sub> {Rh <sup>III</sup> Cp*(OH <sub>2</sub> )}] <sup>3-</sup> towards CO <sub>2</sub> Reduction », European Journal of Inorganic Chemistry, juill. 2018.
    Mots-clés : CSOB, E-POM, POLE 2, POLE 3.

  • A. Gosset, Z. Xu, F. Maurel, L. - M. Chamoreau, S. Nowak, G. Vives, C. Perruchot, V. Heitz, et H. - P. Jacquot de Rouville, « A chemically-responsive bis-acridinium receptor », New Journal of Chemistry, vol. 42, nᵒ 6, p. 4728-4734, 2018.

  • B. Habchi, S. Alves, D. Jouan-Rimbaud Bouveresse, B. Appenzeller, A. Paris, D. N. Rutledge, et E. Rathahao-Paris, « Potential of dynamically harmonized Fourier transform ion cyclotron resonance cell for high-throughput metabolomics fingerprinting: control of data quality », Analytical and Bioanalytical Chemistry, vol. 410, nᵒ 2, p. 483-490, 2018.

  • B. Habchi, A. Kassouf, Y. Padellec, E. Rathahao-Paris, S. Alves, D. N. Rutledge, J. Maalouly, et V. Ducruet, « An untargeted evaluation of food contact materials by flow injection analysis-mass spectrometry (FIA-MS) combined with independent components analysis (ICA) », Analytica Chimica Acta, 2018.

  • S. Han, E. Nicol, F. Niepceron, O. Colombani, S. Pensec, et L. Bouteiller, « Oligo-Urea with No Alkylene Unit Self-Assembles into Rod-Like Objects in Water », Macromolecular Rapid Communications, p. 1800698, 2018.
    Résumé : Long and rigid objects formed by self-assembly in water are useful as templates or for their rheological or biological properties. They are usually obtained by combining hydrogen bonding and strong hydrophobic interactions brought by an alkyl or alkylene chain. A simple access to well-defined rod-like assemblies in water is reported based on a penta-urea sticker directly connected to poly(ethylene oxide) side chains. These assemblies are characterized by an average length of several hundreds of nanometers and a monodisperse radius (4.5 nm) resulting from a reduced lateral aggregation of the stickers.
    Mots-clés : hydrogen bonds, light scattering, POLE 4, POLYMERES, rod-like nanoparticles, self-assembly.

  • S. Hupin, H. Lavanant, S. Renaudineau, A. Proust, G. Izzet, M. Groessl, et C. Afonso, « A calibration framework for the determination of accurate collision cross sections of polyanions using polyoxometalate standards », Rapid Communications in Mass Spectrometry, vol. 32, nᵒ 19, p. 1703-1710, 2018.
    Résumé : Rationale Polyoxometalates (POMs) are remarkable oxo-clusters forming compact highly charged anions. We measured their collision cross sections (CCS) in N2 with drift tube ion mobility spectrometry (DTIMS). These values were then used to calibrate a traveling wave ion mobility spectrometry (TWIMS) device and the accuracy of the calibration was tested. Methods Six POM standards were analyzed by DTIM-MS (Tofwerk, Thun, Switzerland) at different voltages to determine absolute DTCCS (N2) values. Five POM compounds (Lindqvist TBA2Mo6O19; decatungstate TBA4W10O32; Keggin TBA3PMo12O40; TBA3PW12O40 and Dawson TBA6P2W18O62) were used for the calibration of the TWIM-MS instrument (Synapt G2 HDMS, Waters, Manchester, UK) and a sixth Dawson POM, TBA9P2Nb3W15O62, was used to compare the accuracy of the calibrations with POM or with polyalanine and dextran reference ions. Results We determined 45 DTCCS (N2) values at 30°C or 60°C. Fourteen DTCCS (N2) values at 30°C were used to perform calibration of the TWIMS instrument. Better correlations were observed than when DTCCS values in helium from the literature were used. The accuracy tests on six ions of Dawson POM TBA9P2Nb3W15O62 led to relative errors below 3.1% while relative errors of 3.6% to 10.1% were observed when calibration was performed with polyalanine and dextran reference ions. Conclusions Our novel calibration strategy for determination of CCS values of multiply negatively charged ions on TWIM-MS devices based on DTCCS (N2) of standard POM structures covered a wider range of CCS and improved the accuracy to 2.1% relative error on average compared with 6.9% using polyalanine and dextran calibration.
    Mots-clés : E-POM.
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  • A. Jagtap, N. Goubet, C. Livache, A. Chu, B. Martinez, C. Gréboval, J. Qu, E. Dandeu, L. Becerra, N. Witkowski, S. Ithurria, F. Mathevet, M. G. Silly, B. Dubertret, et E. Lhuillier, « Short Wave Infrared Devices Based on HgTe Nanocrystals with Air Stable Performances », The Journal of Physical Chemistry C, vol. 122, nᵒ 26, p. 14979-14985, juill. 2018.
    Résumé : Colloidal quantum dots (CQDs) are candidates of interest for the design of low cost IR detector, especially in the short wave infrared (SWIR; 0.8–3 μm), where the vicinity of the visible range makes the high cost of available technologies even more striking. HgTe nanocrystals are among the most promising candidates to address SWIR since their spectrum can be tuned all over this range while demonstrating photoconductive properties. However, several main issues have been swept under the rug, which prevents further development of active materials and devices. Here we address two central questions, which are (i) the stability of the device under ambient air condition and (ii) the reduction of dark current. Encapsulation of HgTe CQDs is difficult because of their extreme sensitivity to annealing, we nevertheless demonstrate an efficient encapsulation method based on a combination of O2 and H2O repellant layers leading to stability over >100 days. Finally, we demonstrate that the dark current reduction can be obtained by switching from a photoconductive geometry to a photovoltaic (PV) device, which is fabricated using solution and low temperature based approach. We demonstrate fast photoresponse (>10 kHz) and detectivity enhancement by 1 order of magnitude in the PV configuration at room temperature. These results pave the way for narrow bandgap CQD based cost-effective optoelectronic devices in developing next generation SWIR photonic systems.
    Mots-clés : POLE 4, POLYMERES.

  • J. - R. Jiménez, A. Sugahara, M. Okubo, A. Yamada, L. - M. Chamoreau, L. Lisnard, et R. Lescouëzec, « A [FeIII(Tp)(CN)3]− scorpionate-based complex as a building block for designing ion storage hosts (Tp: hydrotrispyrazolylborate) », Chemical Communications, avr. 2018.
    Résumé : Using a scorpionate-based complex, [FeIII(Tp)(CN)3]−, as a building block, a new cyanide-based molecular material [{FeIII(Tp)(CN)3}2NiII(H2O)2]·4H2O (1), which can be viewed as a lower dimensional model of Prussian blue analogues, was investigated as a lithium-ion storage host.
    Mots-clés : ERMMES, POLE 2.
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  • Y. Journaux, J. Ferrando-Soria, E. Pardo, R. Ruiz-Garcia, M. Julve, F. Lloret, J. Cano, Y. Li, L. Lisnard, P. Yu, H. Stumpf, et C. L. M. Pereira, « Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 3-4, p. 228–247, janv. 2018.
    Résumé : The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex-as-ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the strategies we have later used to obtain the desired target compounds. The use of complexes as building-blocks, associated to a control of the metal ions chirality and stoichiometry, allowed us to obtain coordination polymers with predictable dimensionality. For the synthesis of single-chain magnets (SCMs) we show that the ligand chemical flexibility makes the isolation of the chains in the solid and the occurence of slow magnetic relaxation possible. For 1D and 2D molecule-based magnets (MBMs), the magnetic ordering strongly depends on the interchain or interplane interactions, which are difficult to control. Again the flexibility of the oxamate ligands allowed their strengthening in the solid sate, yielding MBMs with critical temperatures up to 30 K. We will also present our results on 3D coordination polymers, particularly on the porous magnets displaying large octagonal channels. This family of porous MBMs possess outstanding chemical properties, such as post-synthetic transformation in the solid state. Finally, we will also show that oxamate ligands allows the design of multifunctional materials, as in the case of the first chiral SCM. Overall, the results presented in this review show the impressive potential the oxamate ligands have for the design of coordination polymers.
    Mots-clés : Bridging ligands, Coordination Polymer, ERMMES, Heterometallic complexes, Ligand design, Magnetic properties, Metal-Organic Frameworks, Metallacycles, N, O ligands, POLE 2.
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