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  • J. - C. Ribierre, Z. Li, X. Liu, E. Lacaze, B. Heinrich, S. Méry, P. Sleczkowski, Y. Xiao, F. Lafolet, D. Hashizume, T. Aoyama, M. Uchiyama, J. W. Wu, E. Zaborova, F. Fages, A. D’Aléo, F. Mathevet, et C. Adachi, « A solvent-free and vacuum-free melt-processing method to fabricate organic semiconducting layers with large crystal size for organic electronic applications », Journal of Materials Chemistry C, vol. 7, nᵒ 11, p. 3190-3198, mars 2019.
    Résumé : We report on an improved melt-processing method to prepare organic semiconducting layers with large crystal size and enhanced charge carrier mobilities. The organic compound used in this work is a solution-processable oligo(p-phenylene vinylene) derivative substituted at both ends with pyrene moieties. Accurate control of the temperature during the recrystallization of this compound from the melt enables the formation of large single crystal monodomains in thin films. The melt-processed organic layer shows higher mobilities in transistor configuration than in spin-coated films, which can be attributed to the presence of large-size crystalline monodomains as evidenced by X-ray diffraction measurements. We also investigated the photophysical properties of this material in spin-coated and melted films and found an increase of the photoluminescence quantum yield with the size of the crystals in the organic layer. The advantage of this method over the spin coating also allowed observation of amplified spontaneous emission that was only achieved in the melted film due to its improved luminescence efficiency. Overall, this study demonstrates a simple and versatile method, which does not require the use of any solvent and vacuum, to fabricate organic layers with large crystal size, suitable for the realization of organic electronic and light-emitting devices.
    Mots-clés : POLYMERES.

  • D. Rosa Nunes, M. Reche-Tamayo, E. Ressouche, M. Raynal, B. Isare, P. Foury-Leylekian, P. - A. Albouy, P. Brocorens, R. Lazzaroni, et L. Bouteiller, « Organogel Formation Rationalized by Hansen Solubility Parameters: Shift of the Gelation Sphere with the Gelator Structure », Langmuir, vol. 35, nᵒ 24, p. 7970-7977, juin 2019.
    Résumé : To rationalize how the gelation ability of a low molecular weight gelator is influenced by its molecular structure, we performed extensive solubility tests of a group of thiazole-based gelators and made use of Hansen solubility parameter formalism. We observe that the increase of a linear alkyl chain in these gelators promotes an increase of the radius of the gelation sphere as well as a gradual shift of its center to lower values of the polar (δP) and hydrogen bonding (δH) components. The molecular packing within the fibers and the crystal habit were determined by a combination of X-ray diffraction and molecular modeling. We attribute the gradual and linear shift of the gelation sphere to the fact that all of the studied gelators share the same molecular packing, so that an increasing length of the alkyl chain reduces the proportion of polar groups at the surface, resulting in a gradual increase in the contact between apolar parts of the fiber and the solvent.
    Mots-clés : POLYMERES.
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  • M. Rupp, T. Auvray, E. Rousset, G. M. Mercier, V. Marvaud, D. G. Kurth, et G. S. Hanan, « Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex », Inorganic Chemistry, vol. 58, nᵒ 14, p. 9127-9134, juill. 2019.
    Résumé : Since the initial report by Lehn et al. in 1979, ruthenium tris(bipyridine) ([Ru(bpy)3]2+) and its numerous derivatives were applied as photosensitizers (PSs) in a large panel of photocatalytic conditions while the bis(terpyridine) analogues were disregarded because of their low quantum yields and short excited-state lifetimes. In this study, we prepared a new terpyridine ligand, 4′-(4-bromophenyl)-4,4‴:4″,4‴′-dipyridinyl- 2,2′:6′,2″-terpyridine (Bipytpy) and used it to prepare the heteroleptic complex [Ru(Tolyltpy)(Bipytpy)](PF6)2 (1; Tolyltpy = 4′-tolyl-2,2′:6′,2′-terpyridine). Complex 1 exhibits enhanced photophysical properties with a higher quantum yield (7.4 × 10–4) and a longer excited-state lifetime (3.8 ns) compared to those of [Ru(Tolyltpy)2](PF6)2 (3 × 10–5 and 0.74 ns, respectively). These enhanced photophysical characteristics and the potential for PS–catalyst interaction through the peripheral pyridines led us to apply the complex for visible-light-driven hydrogen evolution. The photocatalytic system based on 1 as the PS, triethanolamine as a sacrificial donor, and cobaloxime as a catalyst exhibits sustained activity over more than 10 days under blue-light irradiation (light-emitting diode centered at 450 nm). A maximum turnover number of 764 was obtained after 12 days.
    Mots-clés : E-POM, POLE 2.

  • I. Seffouh, C. Przybylski, A. Seffouh, R. El Masri, R. R. Vivès, F. Gonnet, et R. Daniel, « Mass spectrometry analysis of the human endosulfatase Hsulf-2 », Biochemistry and Biophysics Reports, vol. 18, p. 100617, 2019.
    Résumé : The human 6-O-endosulfatases HSulf-1 and -2 catalyze the region-selective hydrolysis of the 6-O-sulfate group of the glucosamine residues within sulfated domains of heparan sulfate, thereby ensuring a unique and original post-biosynthetic modification of the cell surface proteoglycans. While numerous studies point out the role of HSulf-2 in crucial physiological processes as well as in pathological conditions particularly in cancer, its structural organization in two chains and its functional properties remain poorly understood. In this study, we report the first characterization by mass spectrometry (MS) of HSulf-2. An average molecular weight of 133,115 Da was determined for the whole enzyme by MALDI-TOF MS, i.e. higher than the naked amino acid backbone (98,170 Da), highlighting a significant contribution of post-translational modifications. The HSulf-2 protein sequence was determined by Nano-LC-MS/MS, leading to 63% coverage and indicating at least four N-glycosylation sites at Asn 108, 147, 174 and 217. These results provide a platform for further structural investigations of the HSulf enzymes, aiming at deciphering the role of each chain in the substrate binding and specificities and in the catalytic activities.
    Mots-clés : 6--Endosulfatase, CSOB, Formylglycine, Heparan sulfate, HSulf-2, Mass spectrometry, POLE 3, Sulfatase.

  • C. Sonnendecker, S. Thürmann, C. Przybylski, F. D. Zitzmann, N. Heinke, Y. Krauke, K. Monks, A. A. Robitzki, D. Belder, et W. Zimmermann, « Large‐Ring Cyclodextrins as Chiral Selectors for Enantiomeric Pharmaceuticals », Angewandte Chemie International Edition, 2019.

  • O. Stetsiuk, V. Synytsia, S. R. Petrusenko, V. N. Kokozay, A. El-Ghayoury, J. Cano, F. Lloret, M. Julve, B. Fleury, et N. Avarvari, « Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoIII2MnII2MnIV2 cluster sustained by a multidentate Schiff base ligand », Dalton Transactions, vol. 48, nᵒ 31, p. 11862-11871, 2019.
    Résumé : The successful utilization of the “direct synthesis” approach yielded the unprecedented hexanuclear complex of formula [Co2MnII2MnIV2(L1)4Cl2(μ3-O)2(dmf)4]·2dmf (1) (H3L is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P21/c and it contains a rare mixed-valence CoIII2MnII2MnIV2(μ2-O)8(μ3-O)2 core where all metal ions are linked through the phenolato and alkoxo groups of the L3− ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy. Cryomagnetic studies indicate the coexistence of ferro- (MnIV–MnII, J2 = +1.10(3) cm−1, J3 = +2.19(3) cm−1; MnII–MnII, j = +0.283(3) cm−1) and antiferromagnetic interactions (MnIV–MnIV, J1 = −17.31(4) cm−1), with the six-coordinate CoIII ions being diamagnetic. DFT type calculations were carried out to substantiate these values. The energy diagram for the different spin states using the best-fit parameters shows the occurrence of six low-lying spin states (S = 0–5) which are close in energy but clearly separated from the remaining ones, with the ground spin state being S = 5. Complex 1 is found to be the first example where weak ferromagnetic exchange between MnII ions through the long –O–MnIV–O– pathway takes place.
    Mots-clés : ERMMES, POLE 2.

  • N. Stojiljkovic, F. Leroux, S. Bubanj, M. - A. Popot, A. Paris, J. - C. Tabet, et C. Junot, « Tracking main environmental factors masking a minor steroidal doping effect using metabolomic analysis of horse urine by liquid chromatography–high-resolution mass spectrometry », European Journal of Mass Spectrometry, vol. 25, nᵒ 3, p. 339-353, 2019.

  • J. - C. Tabet, « A 50-year career working and teaching in the fast-moving field of mass spectrometry research », European Journal of Mass Spectrometry, vol. 25, nᵒ 2, p. 195-201, 2019.

  • Y. Tang, Z. - Y. Zhu, L. - C. Pan, H. Sun, Q. - Y. Song, et Y. Zhang, « Structure analysis and anti-fatigue activity of a polysaccharide from Lepidium meyenii Walp », Natural Product Research, vol. 33, nᵒ 17, p. 2480-2489, sept. 2019.

  • Ö. Tezgel, S. Noinville, V. Bennevault, N. Illy, et P. Guégan, « An alternative approach to create N-substituted cyclic dipeptides », Polymer Chemistry, vol. 10, nᵒ 6, p. 776-785, févr. 2019.
    Résumé : N-Modified peptide backbones are promising peptidomimetics which offer several advantages in terms of improved biological activity and stability. They further allow the development of novel functional materials. However, the synthesis of N-substituted peptides is very challenging with the existing methods, particularly the synthesis of peptides with larger N-substituents. In this work, we are introducing a new method to create N-polyether substituted cyclic dipeptides via anionic ring-opening polymerization (AROP). Four different cyclic dipeptides with different hydrophobic functional groups were selected to create N-substituted cyclic dipeptides. Backbone amides –NH– were deprotonated with phosphazene bases to form nucleophilic initiators. Furthermore, the effect of different phosphazene bases (tBuP4 and tBuP2) and of the addition of a Lewis acid (i-Bu3Al) was studied in detail towards creating N-polyether-cyclic dipeptides bearing either hydrophobic poly(butylene oxide) chains, or hydrophilic linear polyglycidol chains, thanks to the polymerization of 1,2-epoxybutane and the polymerization followed by the deprotection of t-butyl glycidyl ether monomers, respectively. Moreover, we have demonstrated the possibility of avoiding the isomerization of cyclic dipeptides during the synthesis of N-substituted analogues depending on the synthetic approach.
    Mots-clés : POLYMERES.
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  • Ö. Tezgel, V. Puchelle, H. Du, N. Illy, et P. Guégan, « Modification of proline-based 2,5-diketopiperazines by anionic ring-opening polymerization », Journal of Polymer Science Part A: Polymer Chemistry, vol. 57, nᵒ 9, p. 1008-1016, 2019.
    Résumé : 2,5-Diketopiperazines (DKPs) are the smallest cyclic dipeptides found in nature with various attractive properties. In this study, we have demonstrated the successful modification of proline-based DKPs using anionic ring-opening polymerization (AROP) as a direct approach. Four different proline-based DKPs with various side chains and increasing steric hindrance were used as initiating species for the polymerization of 1,2-epoxybutane or ethoxyethyl glycidyl ether in the presence of t-BuP4 phosphazene base. The addition of a Lewis acid, tri-isobutyl aluminum, to the reaction mixture strongly decreased the occurrence of side reactions. Impact of the DKP side-chain functionalities on molar mass control and dispersity was successfully evidenced. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1008–1016
    Mots-clés : anionic polymerization, peptides, POLE 4, polyethers, POLYMERES, ring-opening polymerization.
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  • M. Thomas, L. Stuani, E. Darii, C. Lechaplais, E. Pateau, J. - C. Tabet, M. Salanoubat, P. - L. Saaidi, et A. Perret, « De novo structure determination of 3-((3-aminopropyl)amino)-4-hydroxybenzoic acid, a novel and abundant metabolite in Acinetobacter baylyi ADP1 », Metabolomics, vol. 15, nᵒ 3, p. 45, 2019.

  • F. Tonolo, M. Salmain, V. Scalcon, S. TOP, P. Pigeon, A. Folda, B. Caron, M. J. McGlinchey, R. - A. Toillon, A. Bindoli, G. Jaouen, A. Vessieres, et M. P. Rigobello, « Small Structural Differences Between Two Ferrocenyl Diphenols Determine Large Discrepancies of Reactivity and Biological Effects », ChemMedChem, vol. 14, nᵒ 19, p. 1717-1726, sept. 2019.
    Résumé : Ferrocenyl diphenol complexes 1, [1,1-bis(4?-hydroxyphenyl)-2-ferrocenyl-but-1-ene], and Z-2, [1,2-bis(4?-hydroxyphenyl)-1-ferrocenyl-but-1-ene], differing by the relative position of the two phenolic substituents, display dramatically different antiproliferative activities on cancer cells (1 being by far more cytotoxic than 2). In this paper our goal is to decipher the origin of this difference by comparing their reactivity and biological behaviour. In terms of common behaviour we found that 1 and 2 are both very efficient inhibitors of thioredoxin reductase (TrxR) in vitro after oxidation by the HRP/H2O2 system. However, as 1 is only a moderate inhibitor of TrxR in MDA-MB-231 cells, TrxR is probably not a major target responsible for the cytotoxicity of 1. In terms of difference we noted that 1 induces a significant redox imbalance characterized by lipid peroxidation and thiol oxidation and a moderate decrease of the mitochondrial membrane potential in breast cancer cells while 2 has almost no effect. These results underline the importance of the trans configuration in the ferrocenyl /double bond / phenol motif, which is present in 1 but not in Z-2 that exists only in a cis configuration.
    Mots-clés : Bioorganometallic chemistry, cancer, CHEMBIO, iron, lipid peroxidation, POLE 3, Thioredoxin Reductase.
    Note Note
    <p>doi: 10.1002/cmdc.201900430</p>

  • A. Vessieres, « CHAPTER 3 Iron Compounds as Anticancer Agents », in Metal-based Anticancer Agents, The Royal Society of Chemistry, 2019, p. 62-90.
    Résumé : Many ferrocene complexes have been prepared for their oncological potential. Some derive from molecules with known biological effects (taxanes, podophyllotoxine, artemisine, SAHA, etc.) while others are synthetic molecules selected for their cytotoxic effects (N-alkylaminoferrocenes and ferrocenyl alkylpyridinium). Although these complexes have received a great deal of attention, the field of iron metallodrugs is not limited to them. A number of inorganic complexes of iron(ii) and iron(iii) with possible anticancer effects have also been published, although research into their biological effects is often only at an early stage. This chapter also includes iron chelators, molecules that are administered in non-metallic form but whose cytotoxic species are their coordination complexes of iron generated in vivo. The most emblematic molecule of this family is bleomycin, used as an anticancer agent in many chemotherapies. To these can be added the iron chelates originally synthesized to treat iron overload, some of which have been shown to possess interesting anticancer properties. They have been, and continue to be, the subject of many clinical trials, whether alone or in combination. Thus, the area of iron metallodrugs includes molecules with very different structures and reactivity, studied from a number of different perspectives, but focused on increasing the number of molecules at our disposal for combatting cancer.
    Mots-clés : CHEMBIO, POLE 3.

  • A. Vivien, M. Guillaumont, L. Meziane, C. Salzemann, C. Aubert, S. Halbert, H. Gérard, M. Petit, et C. Petit, « Role of Oleylamine Revisited: An Original Disproportionation Route to Monodispersed Cobalt and Nickel Nanocrystals », Chemistry of Materials, vol. 31, nᵒ 3, p. 960-968, févr. 2019.
    Résumé : Herein is highlighted an original disproportionation mechanism for the formation of hexagonal closed packed cobalt nanoparticles starting from low-valent cobalt complexes. By coupling experimental and theoretical studies, we demonstrate that oleylamine promotes the disproportionation of the starting metal complexes and controls the growth of the nanocrystals, in contrast to the role of reducing reagents proposed elsewhere. We also decipher the sensitivity of the synthesis in regard to the nature of the phosphine and of the halogen ligands in the starting cobalt precursors. Understanding of the mechanism allows the development of a less expensive and less toxic synthesis of these nanoparticles by decreasing the amount of oleylamine in alkane solvents. Finally, an extension of this process is presented and allows reaching size- and shape-controlled nanosphere and nanorod nickel nanoparticles.
    Mots-clés : MACO, POLE 1.

  • K. Wang, L. Trichet, C. Rieu, C. Peccate, G. Pembouong, L. Bouteiller, et T. Coradin, « Interactions of Organosilanes with Fibrinogen and Their Influence on Muscle Cell Proliferation in 3D Fibrin Hydrogels », Biomacromolecules, vol. 20, nᵒ 10, p. 3684-3695, oct. 2019.
    Résumé : Silanization of biomacromolecules has emerged as a fruitful approach to prepare hybrid biohydrogels. However, very little is known about interactions between organosilanes and biopolymers in solution. Here we focused on fibrin, a protein of interest in the biomedical field, whose self-assembly process and resultin

    g gel structure are highly sensitive to experimental conditions. Three main silanes were selected to decipher the relative influence of the silanol groups and organic functions. Whereas no protein denaturation was observed, silanes bearing hydrophobic groups had a surfactant-like behavior and could improve the dispersion of fibrinogen molecules, impacting gel formation kinetics and rheological properties. 3D cultures of myoblasts evidenced that organosilanes could promote or impede cell proliferation, suggesting interactions of silanols with fibrin. These results demonstrate that the two sides of the coin of organosilane reactivity are relevant at different stages of fibrin gel formation and must be considered for future development of hybrid biomaterials.
    Mots-clés : POLE 4, POLYMERES.
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  • Y. Wang, P. Pigeon, S. Top, J. García, C. Troufflard, I. Ciofini, M. J. McGlinchey, et G. Jaouen, « Atypical lone pair-π interaction with quinone methides in a series of imido-ferrociphenol anticancer drug candidates », Angewandte Chemie International Edition, vol. 58, nᵒ ja, p. 8421-8425, 2019.
    Résumé : Ferrociphenols, especially those possessing a heterocycle at the terminus of an aliphatic chain, display strong anticancer activity via a novel redox mechanism that generates active metabolites such as quinone methides (QMs). X-ray crystallography and UV-Vis spectroscopy reveal that the specific lone pair (lp)-π interaction between a carbonyl group of the imide and the quinone motif of the QM plays an important role in the exceptional cytotoxic behaviour of their imido-ferrociphenol precursors. This intramolecular lp-π interaction markedly enhanced the stability of the QMs and lowered the pKa values of the corresponding phenolates. As the first example of such a non-covalent interaction that stabilizes QMs remotely, it not only expands the scope of the lp-π interaction in supramolecular chemistry, but also represents a new mode of stabilization of a QM. This unprecedented application of lp-π interactions in imido-ferrociphenol anticancer drug candidates may also have great potential in drug discovery and organocatalyst design.
    Mots-clés : antitumor agents, bioorganometallics, CHEMBIO, ferrocifen, non-covalent interactions, POLE 3, quinones.
    Note Note
    <p>doi: 10.1002/anie.201902456</p>

  • Z. Wen, Y. Zhang, S. Roland, et M. Sollogoub, « Carboboration of Alkynes with Cyclodextrin-Encapsulated N-Heterocyclic Carbene Copper Complexes », European Journal of Organic Chemistry, vol. 2019, nᵒ 15, p. 2682-2687, avr. 2019.

  • Z. Xia, V. Corcé, F. Zhao, C. Przybylski, A. Espagne, L. Jullien, T. L. Saux, Y. Gimbert, H. Dossmann, V. Mouriès-Mansuy, C. Ollivier, et L. Fensterbank, « Photosensitized oxidative addition to gold( i ) enables alkynylative cyclization of o -alkylnylphenols with iodoalkynes », Nature Chemistry, vol. 11, nᵒ 9, p. 797-805, sept. 2019.
    Résumé : Studies into gold-catalysed cross-coupling reactions have expanded over recent decades; however, oxidative addition to gold(i) complexes remains challenging. Now it has been shown that a dual catalytic transformation involving iridium photosensitization to trigger oxidative addition to organogold intermediates enables C(sp2)–C(sp) cross-coupling reactions that are useful for the alkynylation of benzofurans.
    Mots-clés : CHEMBIO, CSOB, MACO, POLE 1, POLE 3.
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  • L. Yang, M. Liu, K. Sheng, X. Li, J. Du, Y. Ning, X. Wang, J. Li, Y. Zhang, et S. Wu, « Design and synthesis of a novel colorimetric fluorescent probe for the selective detection of sulfur dioxide in SH-SY5Y neuroblastoma cells and its applications in traditional Chinese medicines », New Journal of Chemistry, vol. 43, nᵒ 10, p. 4188-4195, 2019.
    Résumé : A fast response time, low limit of detection and high fluorescence quantum yield probe DTCC was designed and synthesized to detect SO 2 derivatives based on coumarin-thiophene dye which was fused with a coumarin moiety and 2-thiophenecarboxaldehyde. , Sulfur fumigation has attracted extensive attention as one of the important post-harvest processing methods for some traditional Chinese medicines (TCMs) in the last decade. However, sulfur fumigation has recently emerged as a controversial topic due to its potential detrimental effects on the safety and efficacy of TCMs as some sulfur-fumigated TCMs contain numerous sulfur dioxide derivatives; moreover, high levels of sulfur dioxide derivatives can cause some diseases and dangerous environmental pollution. In this study, a DTCC probe with a fast response time, low limit of detection and a high fluorescence quantum yield was designed and synthesized to detect SO 2 derivatives based on the coumarin-thiophene dye, which was fused with a coumarin moiety and 2-thiophenecarboxaldehyde. The probe DTCC exhibited a fast response time (less than 10 s), satisfactory selectivity for SO 2 derivatives in the presence of other ROS and excellent sensitivity for SO 2 derivatives with a low limit of detection (0.23 μM) as well as a wide linear range (0–100 μM). Furthermore, the probe DTCC was successfully applied in fluorescence imaging in SH-SY5Y neuroblastoma cells with excellent membrane permeability and stability. It was also employed in monitoring the total SO 2 derivatives in several real TCM samples. These results illustrate that the probe DTCC has an excellent capability for monitoring SO 2 derivatives in living cells and real TCM samples.
    Mots-clés : GOBS, POLE 3.

  • Y. Yang, J. Li, C. Wei, Y. He, Y. Cao, Y. Zhang, W. Sun, B. Qiao, et J. He, « Amelioration of nonalcoholic fatty liver disease by swertiamarin in fructose-fed mice », Phytomedicine, vol. 59, p. 152782, 2019.

  • D. Zhang, Y. Zhang, Y. Fan, M. - N. Rager, V. Guérineau, L. Bouteiller, M. - H. Li, et C. M. Thomas, « Polymerization of Cyclic Carbamates: A Practical Route to Aliphatic Polyurethanes », Macromolecules, vol. 52, nᵒ 7, p. 2719-2724, avr. 2019.
    Résumé : A new polymerization system is reported that provides aliphatic polyurethanes with novel structures from the anionic ring-opening polymerization of five-membered carbamates. By use of a bifunctional initiating system, the anionic ring-opening polymerization of cyclic carbamates gives unimodal polymers with Đ values generally narrow. A series of PUs with controlled molecular weights were synthesized by changing the reaction conditions. Detailed analysis of the reaction demonstrates that repeated acylations of in situ formed urethane anions lead to the formation of the polyurethane.
    Mots-clés : POLYMERES.
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  • L. Zhang, P. Chen, A. Loiseau, D. Brouri, S. Casale, M. Salmain, S. Boujday, et B. Liedberg, « Spatially Controlled Reduction and Growth of Silver in Hollow Gold Nanoshell Particles », The Journal of Physical Chemistry C, vol. 123, nᵒ 16, p. 10614-10621, 2019.
    Résumé : Spatially controlled reactions at the nanoscale have attracted increasing interest for fundamental chemistry and for the engineering of novel functional materials. Herein, we demonstrate that pH-triggered reduction of silver ions preferentially occurs at the inner walls of porous and citrate-capped gold nanoshell (AuNS) particles. The reaction initially relies on the presence of sacrificial silver ions inside the AuNS particles as well as in the surrounding preparation solution, and it proceeds upon external addition of silver ions until a solid silver core is formed inside the AuNS particles. Subsequent reduction of silver occurs on the external surface of the solidified AuNS, resulting in a layered and compositionally complex nanoparticle containing both silver and gold. Growth experiments performed in the dark, under white light illumination, as well as near resonance suggest that the reduction reaction is not guided by a plasmonic field enhancement effect. This is in contrast to the recently proposed hot spot mechanism of silver reduction at the rim of nanoholes in a periodic gold array. Our observations point toward a confinement process that proceeds via a continuous supply of silver ions that diffuse from the external solution through the porous shell into the inner volume of the AuNS particles where they become reduced.
    Mots-clés : CHEMBIO, POLE 3.
    Note Note
    <p>doi: 10.1021/acs.jpcc.8b11864</p>

  • L. Zhang, D. Hu, M. Salmain, B. Liedberg, et S. Boujday, « Direct quantification of surface coverage of antibody in IgG-Gold nanoparticles conjugates », Talanta, vol. 204, p. 875-881, nov. 2019.
    Résumé : It is of paramount importance to be able to accurately quantify surface coverage of antibodies on gold nanoparticles (AuNP) so as to optimise the sensitivity of AuNP-based immunosensors. Herein, we developed a fluorescence-based method to directly quantify rabbit immunoglobulin G (IgG) used as antibody model bound to AuNP. Rabbit IgG was first labelled with fluorescein-5-isothiocyanate (FITC) prior to conjugation to AuNP via either physisorption or chemisorption. IgG-conjugated AuNP were treated with NaCN to dissolve the AuNP and restore the fluorescence emission that was quenched in the presence of the metallic colloids, followed by quantification of fluorescein by spectrofluorimetry. This direct assay gave about 4 IgG bound to each 15-nm diameter AuNP for both immobilization strategies. This surface coverage value was in good agreement with that determined from the theoretical value calculated from the Localized Surface Plasmon Resonance (LSPR) band shift. For comparison, we also applied two indirect methods based on the quantitation of excess IgG remaining in the supernatant using fluorescence assay or enzyme-linked immunosorbent assay (ELISA). The indirect assays, either fluorescence or ELISA, commonly used to assess the antibody coverage on AuNP, overestimated the IgG surface coverage to a large extent, since up to 3 to 4 times higher coverages were measured. Therefore, the direct fluorescence method reported in this paper appears as a valuable method for quantification of surface coverage of antibody on AuNP.
    Mots-clés : Adsorption, CHEMBIO, Fluorescence, Gold nanoparticles, Immunoglobulin G (IgG), POLE 3, Quantification.

  • L. Zhang, M. Salmain, B. Liedberg, et S. Boujday, « Naked Eye Immunosensing of Food Biotoxins Using Gold Nanoparticle-Antibody Bioconjugates », ACS Applied Nano Materials, vol. 2, nᵒ 7, p. 4150-4158, 2019.
    Résumé : Colorimetric immunoassays using gold nanoparticles (AuNP) form a special class of assays where AuNP act as a transducer to monitor binding events between an antigen and an antibody. Indeed, AuNP display unique optical properties that can been exploited in various ways to develop biosensors. One of the most striking properties of colloidal AuNP (and more generally of noble metal nanomaterials) is their extremely high extinction coefficient in the visible range of the spectrum owing to the localized surface plasmon resonance (LSPR) phenomenon. This feature makes AuNP detectable down to very low concentrations by absorption spectroscopy or even by the naked eye. Herein we took advantage of the high detectability of AuNP to design a solid-phase, sandwich-type, colorimetric immunosensor aiming at the detection of staphylococcal enterotoxin A (SEA). A test zone comprised of a polyclonal anti-SEA antibody was created at the surface of amino-functionalized glass slides via high affinity binding to covalently immobilized Protein A. The same antibody was conjugated to 13 nm diameter AuNP to afford the nanoimmunoprobe. After the glass slides were successively exposed to SEA and AuNP-antibody bioconjugate, a distinct red spot appeared at the detection zone from as low as 1 ng SEA in buffer. Quantification of SEA in the 10–500 ng/mL range was established using a benchtop UV–visible spectrometer by integration of the LSPR band centered at 530 nm. Eventually, this biosensor was applied to the detection of SEA in milk with a limit of detection of 1.5 ng/mL.
    Mots-clés : CHEMBIO, POLE 3.
    Note Note
    <p>doi: 10.1021/acsanm.9b00598</p>

  • Z. Zhao, N. Barrett, Q. Wu, D. Martinotti, L. Tortech, R. Haumont, M. Pellen, et E. K. H. Salje, « Interaction of low-energy electrons with surface polarity near ferroelastic domain boundaries », Physical Review Materials, vol. 3, nᵒ 4, p. 043601, avr. 2019.
    Résumé : We derive surface polarity at and near ferroelastic domain boundaries from molecular dynamics simulations based on an ionic spring model. Interatomic gradient forces lead to flexoelectricity which, in turn, generates polarity at the surface and in twin boundaries. We then derive generic properties of electron scattering spectra equivalent to those observed in low-energy electron microscopy (LEEM) and mirror electron microscopy (MEM) experiments. Negatively (positively) charged surfaces reflect (attract) incident electrons with low kinetic energy. The electron images reveal the valley and ridge surface structures near the intersection of the twin boundary and the surface. Polarity in surface layers is predicted to be visible in LEEM and MEM spectra at neutral surfaces, but much less when surfaces are charged. Inward polarity reflects electrons similar to negative surface charges, and outward polarity backscatters electrons like positive surface charges. Both the polarity in the twin boundary and the physical topography scatter electrons, consistent with experimental LEEM and MEM experiments on CaTiO3 with (001) and (111) surface terminations.
    Mots-clés : E-POM, POLE 2.
    Pièce jointe Full Text PDF 9.3 Mo (source)

  • Z. Zhao, S. Ruan, X. Ma, Q. Feng, Z. Xie, Z. Nie, P. Fan, M. Qian, X. He, S. Wu, Y. Zhang, et X. Zheng, « Challenges Faced with Small Molecular Modulators of Potassium Current Channel Isoform Kv1.5 », Biomolecules, vol. 10, nᵒ 1, p. 10, déc. 2019.
    Résumé : The voltage-gated potassium channel Kv1.5, which mediates the cardiac ultra-rapid delayed-rectifier (IKur) current in human cells, has a crucial role in atrial fibrillation. Therefore, the design of selective Kv1.5 modulators is essential for the treatment of pathophysiological conditions involving Kv1.5 activity. This review summarizes the progress of molecular structures and the functionality of different types of Kv1.5 modulators, with a focus on clinical cardiovascular drugs and a number of active natural products, through a summarization of 96 compounds currently widely used. Furthermore, we also discuss the contributions of Kv1.5 and the regulation of the structure-activity relationship (SAR) of synthetic Kv1.5 inhibitors in human pathophysiology. SAR analysis is regarded as a useful strategy in structural elucidation, as it relates to the characteristics that improve compounds targeting Kv1.5. Herein, we present previous studies regarding the structural, pharmacological, and SAR information of the Kv1.5 modulator, through which we can assist in identifying and designing potent and specific Kv1.5 inhibitors in the treatment of diseases involving Kv1.5 activity.
    Mots-clés : GOBS, POLE 3.

  • Z. Zhao, H. Song, J. Xie, T. Liu, X. Zhao, X. Chen, X. He, S. Wu, Y. Zhang, et X. Zheng, « Research progress in the biological activities of 3,4,5-trimethoxycinnamic acid (TMCA) derivatives », European Journal of Medicinal Chemistry, vol. 173, p. 213-227, 2019.

  • C. Zheng, T. Bavaro, S. Tengattini, A. G. Mascherpa, M. Sollogoub, Y. Zhang, et M. Terreni, « Chemoenzymatic Synthesis of Glycoconjugates Mediated by Regioselective Enzymatic Hydrolysis of Acetylated 2-Amino Pyranose Derivatives », European Journal of Organic Chemistry, vol. 2019, nᵒ 22, p. 3622-3631, juin 2019.

  • C. Zheng, H. Guan, Y. Liu, Z. Li, T. Bavaro, M. Terreni, M. Sollogoub, J. Xu, et Y. Zhang, « Chemoenzymatically synthesized ganglioside GM3 analogues with inhibitory effects on tumor cell growth and migration », European Journal of Medicinal Chemistry, vol. 165, p. 107-114, 2019.

  • C. Zheng, M. Terreni, M. Sollogoub, et Y. Zhang, « Ganglioside GM3 and Its Role in Cancer », Current Medicinal Chemistry, vol. 26, nᵒ 16, p. 2933-2947, août 2019.
    Résumé : Ganglioside GM3 is strongly related with human tumors, such as lung, brain cancers and melanomas, and more and more evidences have revealed that GM3 possesses powerful effects on cancer development and progression. GM3 is over expressed on several types of cancers, and can be as a tumor-associated carbohydrate antigen, used for immunotherapy of cancers. GM3 can also inhibit tumor cells growth by anti-angiogenesis or motility and so on. Especially, GM3 has effects on the EGFR tyrosine kinase signaling, uPAR-related signaling and glycolipid-enriched microdomains, which are essential for cancer signaling conduction. It is obvious that GM3 will be a promising target for cancer treatment.
    Mots-clés : GOBS, POLE 3.

  • Q. Zhu, B. Paci, A. Generosi, S. Renaudineau, P. Gouzerh, X. Liang, C. Mathieu, C. Rountree, G. Izzet, A. Proust, N. Barrett, et L. Tortech, « Conductivity via Thermally Induced Gap States in a Polyoxometalate Thin Layer », The Journal of Physical Chemistry C, vol. 123, nᵒ 3, p. 1922-1930, janv. 2019.

  • S. Zhu, A. T. Tran, Y. Hirokami, G. Gontard, O. Khaled, Y. Zhang, A. Kato, Y. Blériot, et M. Sollogoub, « Bi(OTf)3-mediated intramolecular epoxide opening for bicyclic azepane synthesis », Journal of Carbohydrate Chemistry, vol. 38, nᵒ 2, p. 139-149, févr. 2019.


  • 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.
    Pièce jointe Full Text PDF 450.4 ko (source)

  • 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.

  • C. K. Barik, R. Ganguly, Y. Li, C. Przybylski, M. Salmain, et W. K. Leong, « Embedding a Ruthenium-Based Structural Mimic of the [Fe]-Hydrogenase Cofactor into Papain », Inorganic Chemistry, vol. 57, nᵒ 19, p. 12206-12212, sept. 2018.
    Mots-clés : CHEMBIO, CSOB, POLE 3.

  • 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.

  • S. ben Moussa, A. Mehri, M. Gruselle, P. Beaunier, G. Costentin, et B. Badraoui, « Combined effect of magnesium and amino glutamic acid on the structure of hydroxyapatite prepared by hydrothermal method », Materials Chemistry and Physics, vol. 212, p. 21-29, juin 2018.
    Résumé : Magnesium modified calcium hydroxyapatite of different Mg/Ca compositions have been synthesized using the hydrothermal method in the presence of glutamic acid. The resulting materials have been characterized by X-ray powder diffraction, chemical analysis, IR Spectroscopy and Transmission Electron Microscopy (TEM). X-ray diffraction analysis shows that the resulting materials consist of a single phase having an apatitic structure. IR spectroscopy highlights the presence of carboxylic groups for the organic moieties grafted onto the apatitic surface. The surface properties of apatite samples are determined.
    Mots-clés : Apatite surface, ARC, Glutamic acid, Hybrid compound, Hydrothermal method, POLE 1.

  • 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) 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.
    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.
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