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  • P. a Evenou, J. Rossignol, G. Pembouong, A. Gothland, D. Colesnic, R. Barbeyron, S. Rudiuk, A. - G. Marcelin, M. Ménand, D. Baigl, V. Calvez, L. Bouteiller, and M. Sollogoub, “Bridging beta-Cyclodextrin prevents self-inclusion and allows formation of supramolecular polymers: self-assembly and cooperative interaction with nucleic acids”, Angewandte Chemie International Edition, Apr. 2018.

  • S. a Roland, J. Meijide Suarez, and M. Sollogoub, “Confinement of Metal-N-Heterocyclic Carbene Complexes to control reactivity in catalytic reactions”, Chemistry - A European Journal, Apr. 2018.

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

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

  • M. Barbazanges and L. Fensterbank, “The Invention of New Methodologies: An Opportunity for Dating Natural Products”, Synlett, Aug. 2018.
    Abstract: 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
    Tags: asymmetric synthesis, bis(sulfoxides), gold catalysis, Key words radical chemistry, MACO, natural products, POLE 1, total synthesis.
    Attachment Full Text PDF 450.4 kb (source)

  • M. Ben Haddada, M. Salmain, and 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, Mar. 2018.

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

  • B. Bertrand, K. Passador, C. Goze, F. Denat, E. Bodio, and M. Salmain, “Metal-based BODIPY derivatives as multimodal tools for life sciences”, Coordination Chemistry Reviews, vol. 358, p. 108-124, Mar. 2018.
    Abstract: 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.
    Tags: Bimodal imaging, BODIPY, CHEMBIO, Fluorescence, Metal-based drugs, Photodynamic therapy, POLE 3, Theranostics.

  • P. Biais, P. Beaunier, F. Stoffelbach, and J. Rieger, “Loop-stabilized BAB triblock copolymer morphologies by PISA in water”, Polymer Chemistry, vol. 9, no. 35, p. 4483-4491, Sep. 2018.
    Abstract: 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) macroRAFT 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.
    Tags: POLE 4, POLYMERES.
    Attachment Full Text PDF 1.8 Mb (source)

  • V. N. Bochatay, F. Chemla, F. Ferreira, O. Jackowski, and 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.

  • N. Bridonneau, P. Quatremare, H. J. von Bardeleben, J. - L. Cantin, S. Pillet, E. - E. Bendeif, and 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, Jan. 2018.
    Abstract: 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.
    Tags: Copper, E-POM, Electron transfer, Magentic properties, Molybdenum, Photomagnetism, POLE 2, Spin transition.
    Attachment Full Text PDF 1.7 Mb (source)

  • N. Chahin, L. A. Uribe, A. M. Debela, S. Thorimbert, B. Hasenknopf, M. Ortiz, I. Katakis, and 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, Oct. 2018.
    Abstract: 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 interrogated. 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.
    Tags: CHEMBIO, Electrochemical primer extension reaction (éPEX), Multiplexed electrochemical detection, POLE 3, Polyoxometalate-labelled ddNTPs, SNP detection.

  • L. Chang, N. Klipfel, L. Dechoux, and 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.
    Abstract: 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.
    Tags: CHEMBIO, POLE 3.

  • T. F. C. Cruz, C. A. Figueira, J. C. Waerenborgh, L. C. J. Pereira, Y. Li, R. Lescouëzec, and 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, and 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, Jan. 2018.
    Abstract: 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.
    Tags: Artificial metalloenzymes, Asymmetric catalysis, CHEMBIO, 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, and 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, Aug. 2018.

  • S. De, S. Tewary, D. Garnier, Y. Li, G. Gontard, L. Lisnard, A. Flambard, F. Breher, M. - L. Boillot, G. Rajaraman, and 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, Jan. 2018.
    Abstract: 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.
    Tags: Density functional calculations, ERMMES, Iron, Paramagnetic NMR spectroscopy, POLE 2, Spin crossover, β-Diimine ligand.
    Attachment Full Text PDF 3.1 Mb (source)

  • S. Dhifaoui, C. Mchiri, P. Quatremare, V. Marvaud, A. Bujacz, and 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, Feb. 2018.
    Abstract: 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.

    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, and 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, May 2018.
    Abstract: 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.
    Tags: E-POM, Iron(III) porphyrins, Magnetic properties, Mössbauer, POLE 2, UV-visible, X-ray molecular structure.

  • B. Doistau, L. Benda, B. Hasenknopf, V. Marvaud, and G. Vives, “Switching Magnetic Properties by a Mechanical Motion”, Magnetochemistry, vol. 4, no. 1, p. 5, Jan. 2018.

  • S. Douix, H. Dossmann, E. Nicol, D. Duflot, and A. Giuliani, “Spectroscopy and Photodissociation of the Perfluorooctanoate Anion”, Chemistry - A European Journal, Sep. 2018.

  • M. Dréan, A. Debuigne, C. Jérôme, C. Goncalves, P. Midoux, J. Rieger, and P. Guégan, “Poly(N-methylvinylamine)-Based Copolymers for Improved Gene Transfection”, Macromolecular Bioscience, vol. 18, no. 4, p. 1700353, Apr. 2018.
    Abstract: 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.
    Tags: gene delivery, nanoparticles, POLE 4, POLYMERES, polyvinylamine.
    Attachment Full Text PDF 3.2 Mb (source)

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

  • L. Fensterbank, J. - P. Goddard, and C. Ollivier, “Visible-Light-Mediated Free Radical Synthesis”, in Visible Light Photocatalysis in Organic Chemistry, Wiley-Blackwell, 2018, p. 25-71.
    Abstract: 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).
    Tags: 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, and B. Bujoli, “Phosphonate-Mediated Immobilization of Rhodium/Bipyridine Hydrogenation Catalysts”, Chemistry – A European Journal, vol. 24, no. 10, p. 2457-2465, Feb. 2018.
    Abstract: 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.
    Tags: hydrogenation, immobilization, MACO, N ligands, POLE 1, rhodium, supported catalysts.
    Attachment Full Text PDF 1.1 Mb (source)

  • G. Gaiffe, M. C. Bridoux, C. Costanza, and 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, and 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, May 2018.

  • D. P. Goronzy, M. Ebrahimi, F. Rosei, Arramel, Y. Fang, S. De Feyter, S. L. Tait, C. Wang, P. H. Beton, A. T. S. Wee, P. S. Weiss, and D. F. Perepichka, “Supramolecular Assemblies on Surfaces: Nanopatterning, Functionality, and Reactivity”, ACS Nano, vol. 12, no. 8, p. 7445-7481, Aug. 2018.
    Abstract: Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces.

  • A. Gosset, Z. Xu, F. Maurel, L. - M. Chamoreau, S. Nowak, G. Vives, C. Perruchot, V. Heitz, and 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, and 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, and 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.

  • J. - R. Jiménez, A. Sugahara, M. Okubo, A. Yamada, L. - M. Chamoreau, L. Lisnard, and R. Lescouëzec, “A [FeIII(Tp)(CN)3]− scorpionate-based complex as a building block for designing ion storage hosts (Tp: hydrotrispyrazolylborate)”, Chemical Communications, Apr. 2018.
    Abstract: 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.
    Tags: ERMMES, POLE 2.
    Attachment Full Text PDF 1.7 Mb (source)

  • Y. Journaux, J. Ferrando-Soria, E. Pardo, R. Ruiz-Garcia, M. Julve, F. Lloret, J. Cano, Y. Li, L. Lisnard, P. Yu, H. Stumpf, and 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, Jan. 2018.
    Abstract: 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.
    Tags: Bridging ligands, Coordination Polymer, ERMMES, Heterometallic complexes, Ligand design, Magnetic properties, Metal-Organic Frameworks, Metallacycles, N, O ligands, POLE 2.
    Attachment Full Text PDF 8.5 Mb (source)

  • R. Karim, E. Lepeltier, L. Esnault, P. Pigeon, L. Lemaire, C. Lépinoux-Chambaud, N. Clere, G. Jaouen, J. Eyer, G. Piel, and C. Passirani, “Enhanced and preferential internalization of lipid nanocapsules into human glioblastoma cells: effect of a surface-functionalizing NFL peptide”, Nanoscale, vol. 10, no. 28, p. 13485-13501, 2018.
    Abstract: Increasing intracellular drug concentration using nanocarriers can be a potential strategy to improve efficacy against glioblastoma (GBM). Here, the fluorescent-labelled NFL-TBS·40-63 peptide (fluoNFL) concentration on a lipid nanocapsule (LNC) was studied to enhance nanovector internalization into human GBM cells. LNC surface-functionalization with various fluoNFL concentrations was performed by adsorption. LNC size and surface charge altered gradually with increasing peptide concentration, but their complement protein consumption remained low. Desorption of fluoNFL from the LNC surface was found to be slow. Furthermore, it was observed that the rate and extent of LNC internalization in the U87MG human glioblastoma cells were dependent on the surface-functionalizing fluoNFL concentration. In addition, we showed that the uptake of fluoNFL-functionalized LNCs was preferential towards U87MG cells compared to healthy human astrocytes. The fluoNFL-functionalized LNC internalization into the U87MG cells was energy-dependent and occurred possibly by macropinocytosis and clathrin-mediated and caveolin-mediated endocytosis. A new ferrocifen-type molecule (FcTriOH), as a potent anticancer candidate, was then encapsulated in the LNCs and the functionalization improved its in vitro efficacy compared to other tested formulations against U87MG cells. In the preliminary study, on subcutaneous human GBM tumor model in nude mice, a significant reduction of relative tumor volume was observed at one week after the second intravenous injection with FcTriOH-loaded LNCs. These results showed that enhancing NFL peptide concentration on the LNC surface is a promising approach for increased and preferential nanocarrier internalization into human GBM cells, and the FcTriOH-loaded LNCs are a promising therapy approach for GBM. ER
    Tags: CHEMBIO, POLE3.

  • Y. Liu, Z. Mao, A. Pradal, P. - Q. Huang, J. Oble, and G. Poli, “Palladium-Catalyzed [3 + 2]-C–C/N–C Bond-Forming Annulation”, Organic Letters, vol. 20, no. 13, p. 4057-4061, Jul. 2018.
    Abstract: The synthesis of bi- and tricyclic structures incorporating pyrrolidone rings is disclosed, starting from resonance-stabilized acetamides and cyclic α,β-unsaturated-γ-oxycarbonyl derivatives. This process involves an intermolecular Tsuji–Trost allylation/intramolecular nitrogen 1,4-addition sequence. Crucial for the success of this bis-nucleophile/bis-electrophile [3 + 2] annulation is its well-defined step chronology in combination with the total chemoselectivity of the former step. When the newly formed annulation product carries a properly located o-haloaryl moiety at the nitrogen substituent, a further intramolecular keto α-arylation can join the cascade, thereby forming two new cycles and three new bonds in the same synthetic operation.

  • O. Makrygenni, E. Secret, A. Michel, D. Brouri, V. Dupuis, A. Proust, J. - M. Siaugue, and R. Villanneau, “Heteropolytungstate-decorated core-shell magnetic nanoparticles: A covalent strategy for polyoxometalate-based hybrid nanomaterials”, Journal of Colloid and Interface Science, vol. 514, p. 49-58, Mar. 2018.
    Abstract: Amino-functionalized core–shell magnetic nanoparticles have been covalently grafted with Polyoxometalates (POMs). These multifunctional nanocomposites have been obtained through the coupling of heteropolytungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core–shell nanoparticles. The physical properties of the resulting materials have been studied by a large set of techniques. The very good nanostructuration of the POMs at the surface of the obtained nanoparticles have thus been directly observed by high-resolution transmission electronic microscopy (HR-TEM). Furthermore, the hyperthermia properties of these nanocomposites have been also considered as a function of the size of the magnetic core. Finally, the stability of these suspensions in organic media makes them particularly interesting in the frame of their processing or their potential use as nanocatalysts.
    Tags: Core-shell nanoparticles, E-POM, HR-TEM, Hybrid materials, POLE 2, Polyoxometalates.

  • H. Mamad-Hemouch, L. Bacri, C. Huin, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, and J. Pelta, “Versatile cyclodextrin nanotube synthesis with functional anchors for efficiency ion channel formation: design, characterization and ion conductance”, Nanoscale, 2018.

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

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

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

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

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

  • Ortiz Mayreli, Debela Ahmed M., Méthivier Christophe, Thorimbert Serge, Hasenknopf Bernold, and O'Sullivan Ciara K., “Stable Carboxylate-Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyltin Compound”, Chemistry – A European Journal, 2018.
    Abstract: Abstract Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol?gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. Herein, it is demonstrated that a carboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques were used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long-term stability studies over a period of one year, demonstrating thermostability up to 90?°C and storage stability for at least 12?months at 4?°C protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications, including molecular techniques, such as solid-phase amplification and solid-phase melting curve analysis, that require elevated temperature stability, as well as biosensors, which require long-term storage stability.
    Tags: biosensors, CHEMBIO, electrochemistry, gold, POLE 3, surface chemistry, tin.
    Note Note
    <p>doi: 10.1002/chem.201801854</p>

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

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

  • Y. Ren, K. Cheaib, J. Jacquet, H. Vezin, L. Fensterbank, M. Orio, S. Blanchard, and M. Desage‐El Murr, “Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis”, Chemistry – A European Journal, vol. 24, no. 20, p. 5086-5090, Apr. 2018.
    Abstract: Small-molecule catalysts as mimics of biological systems illustrate the chemists’ attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.
    Tags: aziridination, copper catalysis, E-POM, MACO, multistate reactivity, POLE 1, POLE 2, redox-active ligands, spin catalysis.
    Attachment Full Text PDF 963.4 kb (source)

  • D. Rosa Nunes, M. Raynal, B. Isare, P. - A. Albouy, and L. Bouteiller, “Organogel formation rationalized by Hansen solubility parameters: improved methodology”, Soft Matter, vol. 14, no. 23, p. 4805-4809, 2018.

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

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

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