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Accueil > Les équipes > Glycochimie Organique Biologique et Supramoléculaire (GOBS) > Publications

Publications

publié le , mis à jour le

2013



  • J. D. Howe, N. Smith, M. J. - R. Lee, N. Ardes-Guisot, B. Vauzeilles, J. Désiré, A. Baron, Y. Blériot, M. Sollogoub, D. S. Alonzi, et T. D. Butters, « Novel imino sugar α-glucosidase inhibitors as antiviral compounds », Bioorganic & Medicinal Chemistry, vol. 21, nᵒ 16, p. 4831-4838.
    Résumé : Abstract Deoxynojirimycin (DNJ) based imino sugars display antiviral activity in the tissue culture surrogate model of Hepatitis C (HCV), bovine viral diarrhoea virus (BVDV), mediated by inhibition of ER α-glucosidases. Here, the antiviral activities of neoglycoconjugates derived from deoxynojirimycin, and a novel compound derived from deoxygalactonojirimycin, by click chemistry with functionalised adamantanes are presented. Their antiviral potency, in terms of both viral infectivity and virion secretion, with respect to their effect on α-glucosidase inhibition, are reported. The distinct correlation between the ability of long alkyl chain derivatives to inhibit ER α-glucosidases and their anti-viral effect is demonstrated. Increasing alkyl linker length between DNJ and triazole groups increases α-glucosidase inhibition and reduces the production of viral progeny RNA and the maturation of the envelope polypeptide. Disruption to viral glycoprotein processing, with increased glucosylation on BVDV E2 species, is representative of α-glucosidase inhibition, whilst derivatives with longer alkyl linkers also show a further decrease in infectivity of secreted virions, an effect proposed to be distinct from α-glucosidase inhibition.
    Mots-clés : Bovine viral diarrhea virus, Endoplasmic reticulum, Glucosidases, GOBS, Imino sugars, Neoglycoconjugates, POLE 3.


  • U. Jacquemard, P. Harpainter, et S. Roland, « Introduction of bulky tert-butyl substituents on the core of N,N′-diaryl N-heterocyclic carbenes through the corresponding vicinal diamines », Tetrahedron Letters, vol. 54, nᵒ 35, p. 4793-4795.
    Résumé : Abstract Highly bulky N,N′-diaryl imidazolinium salts substituted by one or two tert-butyl groups on the heterocyclic backbone and the corresponding silver N-heterocyclic carbene complexes are obtained by the addition of tert-butyl magnesium chloride or tert-butyl lithium on symmetrical 1,2-bisimines derived from 2,6-diisopropylaniline, 2,6-diethylaniline and 2,4,6-trimethylaniline.
    Mots-clés : Carbene ligands, Chiral ligands, GOBS, Imidazoliniums, POLE 3, Silver complexes, Vicinal diamines.


  • I. k Ahmed, R. Farha, Z. Huo, C. Allain, X. Wang, H. Xu, M. Goldmann, B. Hasenknopf, et L. Ruhlmann, « Porphyrin–polyoxometalate hybrids connected via a Tris-alkoxo linker for the generation of photocurrent », Electrochimica Acta, vol. 110, p. 726-734.


  • E. Leclerc, X. Pannecoucke, M. Ethève-Quelquejeu, et M. Sollogoub, « Fluoro-C-glycosides and fluoro-carbasugars, hydrolytically stable and synthetically challenging glycomimetics », Chemical Society Reviews, vol. 42, nᵒ 10, p. 4270-4283.
    Résumé : Fluoro-C-glycosides and fluoro-carbasugars are a particular subclass of hydrolytically stable glycomimetics that are expected to have different, hopefully improved properties thanks to the stereoelectronic features of the fluoroalkyl moiety. This review summarizes the studies devoted to the synthesis of such Carbohydrate chemistry
    Mots-clés : GOBS, POLE 3.

  • J. Liang, J. He, S. Zhu, W. Zhao, Y. Zhang, Y. Ito, et W. Sun, « Preparation of Main Iridoid Glycosides in Fructus Corni by Macroporous Resin Column Chromatography and Countercurrent Chromatography », Journal of Liquid Chromatography & Related Technologies, vol. 36, nᵒ 8, p. 983-999.
    Résumé : Loganin, sweroside, and morroniside, three main iridoid glycosides from Fructus Corni were successfully separated by macroporous resin column chromatography and countercurrent chromatography (CCC). In the first step, D101 macroporous resin was selected for cleaning-up, water was used to elute the column to remove the undesired constituents and then 50% aqueous ethanol was used to elute the targets. The total content of three iridoid glycosides was 51.1% in this process. In the second step, the obtained crude sample was then isolated by CCC using a two-phase solvent system composed of dichloromethane-methanol-n-butanol-water-acetic acid (5:5:2:4:0.1, v/v/v/v/v). From 100mg of a crude sample, 12.6mg of loganin, 5.9mg of sweroside, and 28.5mg of morroniside were obtained with purities of 98.6%, 97.3%, and 99.1% and total recoveries of 90.4%, 91.8%, and 89.1%, respectively, after a two-step purification. The HPLC quantitative analysis and response surface methodology were used for optimization of the separation condition and the target compounds were identified by ESI-MS, 1H NMR, and 13C NMR.
    Mots-clés : cells, constituents, countercurrent chromatography, Fructus Corni, GOBS, hsccc, inflammation, loganin, macroporous resin column chromatography, mice, morroniside, officinalis, POLE 3, purification, scopolamine, sweroside.

  • X. Ling, N. Schaeffer, S. Roland, et M. - P. Pileni, « Nanocrystals: Why Do Silver and Gold N-Heterocyclic Carbene Precursors Behave Differently? », Langmuir, vol. 29, nᵒ 41, p. 12647-12656.
    Résumé : Synthesizing stable Au and Ag nanocrystals of narrow size distribution from metal-N-heterocyclic carbene (NHC) complexes remains a challenge, particularly in the case of Ag and when NHC ligands with no surfactant-like properties are used. The formation of nanocrystals by one-phase reduction of metal-NHCs (metal = Au, Ag) bearing common NHC ligands, namely 1,3-diethylbenzimidazol-2-ylidene.(L-1), 1,3-bis(mesityl)imidazol-2-ylidene (L-2), and 1,3-bis(2,6-(Pr2C6H3)-Pr-i)imidazol-2-ylidene (L-3), is presented herein. We show that both Au and Ag nanocrystals displaying narrow size distribution can be formed by reduction with amine boranes. The efficiency of the process and the average size and size distribution of the nanocrystals markedly depend on the nature of the metal and NHC ligand, on the sequence in the reactant addition (i.e., presence or absence of thiol during the reduction step), and on the presence or absence of oxygen. Dodecanethiol was introduced to produce stable nanocrystals associated with narrow size distributions. A specific reaction is observed with Ag NHCs in the presence of thiols whereas Au-NHCs remain unchanged. Therefore, different organometallic species are involved in the reduction step to produce the seeds. This can be correlated to the lack of effect of NHCs on Ag nanocrystal size. In contrast, alteration of Au nanocrystal average size can be achieved with a NHC ligand of great steric bulk (L-3). This demonstrates that a well-defined route for a given metal cannot be extended to another metal.
    Mots-clés : Catalysis, chemistry, complexes, GOBS, Heterocycles, layered structure, metal nanoparticles, nucleation, phase synthesis, POLE 3, size, solid-state, system.


  • K. Micoine, M. Malacria, E. Lacôte, S. Thorimbert, et B. Hasenknopf, « Regioselective Double Organic Functionalization of Polyoxotungstates through Electrophilic Addition of Aromatic Isocyanates to [P2W17O61(SnR)]7– », European Journal of Inorganic Chemistry, vol. 2013, nᵒ 10-11, p. 1737–1741.
    Résumé : The direct attachment of several different organic molecules to a single polyoxometalate remains a challenge in the field of functionalized polyoxometalates. In this paper, we show that an organotin-functionalized Dawson-type polyoxotungstate [P2W17O61(SnR)]7– reacts with aromatic isocyanates ArNCO to yield new doubly functionalized compounds [P2W17O61(SnR)(CONHAr)]6–. Both organic moieties, Ar and R, can be varied independently; we have tested nine Ar and three R groups. Therefore, this synthetic methodology represents a way to graft two distinct functional molecules directly onto a polyoxometalate.
    Mots-clés : CHEMBIO, COS, Electrophilic addition, GOBS, Heterocycles, MACO, organic–inorganic hybrid composites, POLE 1, POLE 3, Polyoxometalates, SUPRA, synthesis design, Tungsten.

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  • B. Riflade, J. Oble, L. Chenneberg, E. Derat, B. Hasenknopf, E. Lacôte, et S. Thorimbert, « Hybrid polyoxometalate palladacycles: DFT study and application to the Heck reaction », Tetrahedron, vol. 69, nᵒ 27–28, p. 5772-5779, 2013.
    Résumé : The phosphovanadotungstate polyanion [P2W15V3O62]9− is a powerful support to stabilize palladacycles conjugated to the inorganic framework via an organic ligand. The insertion can be directed toward sp2 or sp3 C–H insertion upon appropriate choice of the substitution pattern on the organic ligand. DFT modeling indicates that the strong withdrawing effect of the POM transmitted through the conjugated carbonyl was responsible for this easy insertion. The palladacycles led to the formation of stilbene via a Mizoroki–Heck reaction. However it is likely that the POMs act as Pd-reservoirs for the formation of nanoparticles.
    Mots-clés : catalysis, CHEMBIO, COS, C–H insertion, GOBS, Heck reaction, Heterocycles, Hybrid polyoxometalate, MACO, Palladacycles, POLE 1, POLE 3, SSO, SUPRA.


  • C. s Allain, D. Schaming, N. Karakostas, M. Erard, J. - P. Gisselbrecht, S. Sorgues, I. Lampre, L. Ruhlmann, et B. Hasenknopf, « Synthesis, electrochemical and photophysical properties of covalently linked porphyrin–polyoxometalates », Dalton Transactions, vol. 42, nᵒ 8, p. 2745-2754.
    Résumé : Two covalently linked porphyrin–polyoxometalate hybrids have been prepared: an Anderson-type hexamolybdate [N(C4H9)4]3[MnMo6O18{(OCH2)3CNHCO(ZnTPP)}2] with two pendant zinc(ii)-tetraphenylporphyrins, and a Dawson-type vanadotungstate [N(C4H9)4]5H[P2V3W15O59{(OCH2)3CNHCO(ZnTPP)}] with one porphyrin. Electroch
    Mots-clés : GOBS, POLE 3, SUPRA.

  • M. - P. Santoni, F. Nastasi, S. Campagna, G. S. Hanan, B. Hasenknopf, et I. Ciofini, « Understanding the redox properties of dinuclear ruthenium(II) complexes by a joint experimental and theoretical analysis », Dalton Transactions, vol. 42, nᵒ 15, p. 5281-5291.
    Résumé : A combined experimental and theoretical approach has been used to investigate the redox properties of two dinuclear Ru(II) complexes, 2a and 2b, containing the planar dpt-ph-dpt bridging ligand (dpt-ph-dpt = 1 '', 4 ''-bis(2,4-dipyrid-2'-yl-1,3,5-triazin-6-yl) benzene). The redox properties of the free bridging ligand and the X-ray structure of 2a have also been reported, together with the X-ray structure of a related mononuclear compound, for comparison purposes. The photophysical processes of 2a and 2b have also been studied by pump-probe transient absorption spectroscopy. Compounds 2a and 2b are able to reversibly collect six and eight electrons, respectively, upon electrochemical reduction at mild potentials (>-2.0 V vs. SCE). A detailed assignment of the various reduction processes to specific subunits of the dinuclear arrays has been made possible by calculation of the HOMOs and LUMOs of native and bireduced species. For example, computation allowed us to clarify the redox behavior of 2b: the first reduction processes of this compound occur at almost coincident potentials, with successive electrons added on the same subunit (namely, the bridging ligand). Charge redistribution towards the other subunits of the molecular framework upon second reduction, revealed by calculation performed on the bireduced species, is the key to interpreting this peculiar behavior. Inter-ligand electron hopping interconverts the MLCT state involving the peripheral ligand to that of the (lower-lying) MLCT state that involves the bridging ligand. This process is faster than 350 fs in 2a, where its driving force is higher than 0.2 eV, whereas it occurs with a time constant of about 6 ps in 2b, having a smaller driving force for the process. Both compounds decay to the ground state, with MLCT emission on the nanosecond time scale, however a faster component of such decay is kinetically evidenced, indicating a process of about 200-250 ps in both cases, which is tentatively assigned to relatively slow diffusive solvent dynamics.
    Mots-clés : absorption-spectra, artificial photosynthesis, electrochemical oxidation, electron-transfer, energy-gap law, GOBS, photocatalytic hydrogen-production, photophysical properties, POLE 3, SUPRA, transfer excited-states, transition-metal-complexes, tridentate ligands.


  • M. Sollogoub, « Site-Selective Heterofunctionalization of Cyclodextrins: Discovery, Development, and Use in Catalysis », Synlett, vol. 24, nᵒ 20, p. 2629-2640.


  • S. Xiao, M. Yang, F. Yu, L. Zhang, D. Zhou, P. Sinaÿ, et Y. Zhang, « Synthesis of four mono-functionalized α-cyclodextrin derivatives for further confirming DIBAL-H-promoted bis-de-O-methylation mechanism », Tetrahedron, vol. 69, nᵒ 20, p. 4053-4060.
    Résumé : Abstract In our previous studies, a mechanism for DIBAL-H promoted regioselective bis-de-O-methylation of per-O-methylated cyclodextrin (CD) was proposed based on per-O-methylated β-CDs. As a further step to this work, four per-O-methylated α-CD derivatives (6, 7, 11, and 18) with mono functional group at the secondary rim have been designed and synthesized. Using DIBAL-H as a chemical ‘scalpel’, we found that (1) only the O-methyl at C-2A of 6 could be easily removed and (2) the O-methyl at C 3 B could be firstly regioselectively removed slowly, followed by a rapid removal of the second O-methyl at C 2 A to provide 3. Combined with our previous studies, we think that not only O-3B-methyl but also O-2A and O-3B are necessary for the formation of ‘tweezers’ during DIBAL-H promoted bis-de-O-methylation reaction of per-O-methylated CD.
    Mots-clés : DIBAL-H, GOBS, Mechanism, POLE 3, Synthesis, α-Cyclodextrin.


  • M. z de Person, A. Coffre, R. Skanji, M. Ben Messaouda, M. Abderraba, Y. Zhang, et F. Moussa, « Mechanism and number of adducts of photo-addition of glycine methyl-ester to [60] fullerene », Tetrahedron, vol. 69, nᵒ 33, p. 6826-6831.
    Résumé : Abstract Recently, it has been shown that visible light irradiation of a mixture of C60 and glycine methyl-ester in the presence of oxygen is a direct route to sequentially synthesize higher FP poly-adducts. However, the involved mechanism and the maximum number of pyrrolidine adducts per C60 molecule remained to be ascertained. Using high resolution mass spectrometry and HPLC–MS, we show here that the most probable mechanism involves a first step of azomethine ylide (AMY) formation followed by its [2+3] cyclo-addition to C60, and that the hexakis-adduct is the highest FP poly-adduct (FPPA) obtained under these conditions. Some FPPA and AMY dimers are also identified in the final mixture.
    Mots-clés : Azomethine ylide, Dimers, Fullerenes, GOBS, HPLC–MS, Photo-addition, POLE 3, Pyrrolidines.


  • E. Zaborova, M. Guitet, G. Prencipe, Y. Blériot, M. Ménand, et M. Sollogoub, « An “Against the Rules” Double Bank Shot with Diisobutylaluminum Hydride To Allow Triple Functionalization of α-Cyclodextrin », Angewandte Chemie International Edition, vol. 52, nᵒ 2, p. 639–644, 2013.
    Mots-clés : concave cycles, Cyclodextrin, GOBS, heterofunctionalization, mechanistic studies, POLE 3, selectivity.

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  • X. Zhang, Y. Ito, J. Liang, Q. Su, Y. Zhang, J. Liu, et W. Sun, « Preparative isolation and purification of five steroid saponins from Dioscorea zingiberensis C.H.Wright by counter-current chromatography coupled with evaporative light scattering detector », Journal of Pharmaceutical and Biomedical Analysis, vol. 84, p. 117-123.
    Résumé : A counter-current chromatography (CCC) method was successfully applied to separate and purify steroid saponins from the traditional Chinese medicine Dioscorea zingiberensis C.H.Wright for the first time. Ethyl acetate–n-butanol–methanol–water (4:1:2:4, v/v) was used as the two-phase solvent system, and evaporative light scattering detector (ELSD) was used as the detector in this method. The method separated in a single run the following five steroid saponins: 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranol-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranoside (Compound A); 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[β-d-glucopyranosyl(1 → 3)-α-l-rhamnopyranosyl(1 → 2)]-β-d-glucopyranoside (Compound B); 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[α-l-rhamnopyranosyl(1 → 4)]-β-d-glucopyranoside (Compound C); 26-O-β-d-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-{α-l-rhamnopyranosyl-(1 → 4)-[β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranosyl-(1 → 2)]}-β-d-glucopyranoside (Compound D); and 26-O-β-d-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-[β-d-glucopyranosyl-(1 → 4)-α-l-rhamnopyranosyl(1 → 2)]-β-d-glucopyranoside (Compound E). Their structural identification of the five steroid saponins was performed by means of ESI-MS, and 13C NMR.
    Mots-clés : counter-current chromatography, Dioscorea zingiberensis C.H. Wright, Evaporative light scattering detector, GOBS, POLE 3, Steroid saponins, traditional chinese medicine.


  • W. Zhao, C. Sun, J. He, L. Chen, Y. Zhang, et W. Sun, « The possible mechanisms of Picrasma quassiodes (D. Don) Benn. in the treatment of colitis induced by 2,4,6-trinitrobenzene sulfonic acid in mice », Journal of Ethnopharmacology, vol. 145, nᵒ 2, p. 424-430.


  • W. Zhao, J. Yu, Q. Su, J. Liang, L. Zhao, Y. Zhang, et W. Sun, « Antihypertensive effects of extract from Picrasma quassiodes (D. Don) Benn. in spontaneously hypertensive rats », Journal of Ethnopharmacology, vol. 145, nᵒ 1, p. 187-192.

  • Z. - Y. Zhu, Y. Liu, C. - L. Si, J. Yuan, Q. Lv, Y. - Y. Li, G. - L. Dong, A. - J. Liu, et Y. - M. Zhang, « Sulfated modification of the polysaccharide from Cordyceps_gunnii mycelia and its biological activities », Carbohydrate Polymers, vol. 92, nᵒ 1, p. 872-876.
    Résumé : A chemically new sulfated polysaccharide (SPS50) was prepared from the water soluble polysaccharide (PS50), isolated from Cordyceps_gunnii mycelia, by concentrated sulfuric acid method. The yield of crude SPS50 was 62.34% and its specific rotation was [alpha](D)(20) = 36.75 degrees. The structural characteristics of this chemically sulfated polysaccharide were determined based on the infrared analysis (IR), high performance liquid chromatography (HPLC) and sodium dodecyl sulfate polyacrylamide gel electropheresis (SDS-PAGE). Its biological properties including anti-oxidant and anti-tumor activities were also investigated. The results showed that the anti-oxidant capacity of SPS50 was not as good as SP50 and the anti-tumor activity of SPS50 was much better than PS50. SPS50 showed evident growth inhibition on K562 cells. The tumor inhibition ratio of SPS50 against K562 cells was 69.92%. (C) 2012 Elsevier Ltd. All rights reserved.
    Mots-clés : Anti-oxidant activity, Anti-tumor activity, anticoagulant, antitumor-activity, Cordyceps_gunnii, derivatives, GOBS, high-molecular-weight, POLE 3, Polysaccharide, Sulfated modification.
  • 2012



    • G. a Izzet, M. Ménand, B. Matt, S. Renaudineau, L. - M. Chamoreau, M. Sollogoub, et A. Proust, « Cyclodextrin-Induced Auto-Healing of Hybrid Polyoxometalates », Angewandte Chemie International Edition, vol. 51, nᵒ 2, p. 487–490.
      Mots-clés : auto-healing, Cyclodextrins, E-POM, GOBS, Host–guest systems, POLE 2, POLE 3, Polyoxometalates, POM.


    • L. Amorim, F. Marcelo, J. Désiré, M. Sollogoub, J. Jiménez-Barbero, et Y. Blériot, « Synthesis and conformational analysis of bicyclic mimics of α- and β-d-glucopyranosides adopting the biologically relevant 2,5B conformation », Carbohydrate Research, vol. 361, p. 219-224.
      Résumé : The synthesis of three conformationally locked d-glucopyranoside analogs displaying the hydroxyl pattern of the parent sugar is described. A two carbon bridge connecting the C-2 and C-5 atoms of the pyranose ring allows a torsion of the sugar ring toward a 2,5B conformation as confirmed by conformational analysis. This conformation is strongly believed to be adopted by the oxacarbenium ion-like transition state of several inverting glucosidases.
      Mots-clés : Bicycle, Boat conformation, Glucopyranose, Glycosidase, GOBS, POLE 3.


    • J. Deschamp, M. Mondon, S. Nakagawa, A. Kato, D. S. Alonzi, T. D. Butters, Y. Zhang, M. Sollogoub, et Y. Blériot, « Towards a stable noeuromycin analog with a d-manno configuration: Synthesis and glycosidase inhibition of d-manno-like tri- and tetrahydroxylated azepanes », Bioorganic & Medicinal Chemistry, vol. 20, nᵒ 2, p. 641-649.
      Résumé : Noeuromycin is a highly potent albeit unstable glycosidase inhibitor due to its hemiaminal function. While stable d-gluco-like analogs have been reported, no data are available for d-manno-like structures. A series of tri- and tetrahydroxylated seven-membered iminosugars displaying either a d-manno-or a l-gulo-like configuration, were synthesized from methyl α-d-mannopyranoside using a reductive amination-mediated ring expansion as the key step. Screening towards a range of commercial glycosidases demonstrated their potency as competitive glycosidase inhibitors while cellular assay showed selective albeit weak glycoprotein processing mannosidase inactivation.
      Mots-clés : Azepane, Glycosidase, GOBS, Iminosugar, Inhibition, POLE 3, Sugar mimic.

    • V. Dubee, M. Arthur, H. Fief, S. Triboulet, J. - L. Mainardi, L. Gutmann, M. Sollogoub, L. B. Rice, M. Etheve-Quelquejeu, et J. - E. Hugonnet, « Kinetic Analysis of Enterococcus faecium L,D-Transpeptidase Inactivation by Carbapenems », Antimicrobial Agents and Chemotherapy, vol. 56, nᵒ 6, p. 3409-3412.
      Résumé : Bypass of classical penicillin-binding proteins by the L,D-transpeptidase of Enterococcus faecium (Ldt(fm)) leads to high-level ampicillin resistance in E. faecium mutants, whereas carbapenems remain the lone highly active beta-lactams. Kinetics of Ldt(fm) inactivation was determined for four commercial carbapenems and a derivative obtained by introducing a minimal ethyl group at position 2. We show that the bulky side chains of commercial carbapenems have both positive and negative effects in preventing hydrolysis of the acyl enzyme and impairing drug binding.
      Mots-clés : antibiotics, biosynthesis, clavulanate, GOBS, meropenem, mycobacterium-tuberculosis, peptidoglycan cross-linking, POLE 3, resistance, transpeptidase.

    • N. Dupre, C. Brazel, L. Fensterbank, M. Malacria, S. Thorimbert, B. Hasenknopf, et E. Lacôte, « Self-Buffering Hybrid Gold-Polyoxometalate Catalysts for the Catalytic Cyclization of Acid-Sensitive Substrates », Chemistry-a European Journal, vol. 18, nᵒ 41, p. 12962-12965, 2012.
      Mots-clés : allenes, asymmetric enamine catalysts, carbene nhc complexes, CHEMBIO, COS, Cycloisomerization, epoxidation, GOBS, Gold, Heterocycles, heteropoly compounds, highly efficient, Hydroamination, intercluster compound, MACO, organic-inorganic hybrid composites, oxidation, POLE 1, POLE 3, Polyoxometalates, polyoxotungstates, protonation, SUPRA.


    • L. Eloy, A. - S. Jarrousse, M. - L. Teyssot, A. Gautier, L. Morel, C. Jolivalt, T. Cresteil, et S. Roland, « Anticancer Activity of Silver–N-Heterocyclic Carbene Complexes: Caspase-Independent Induction of Apoptosis via Mitochondrial Apoptosis-Inducing Factor (AIF) », ChemMedChem, vol. 7, nᵒ 5, p. 805–814.
      Résumé : Fourteen silver(I) complexes bearing N-heterocyclic carbene (NHC) ligands were prepared and evaluated for anticancer activity. Some of these were found to exhibit potent antiproliferative activity toward several types of human cancer cell lines, including drug-resistant cell lines, with IC50 values in the nanomolar range. An initial investigation into the mechanism of cell death induced by this family of silver(I) complexes was carried out. Cell death was shown to result from the activation of apoptosis without involvement of primary necrosis. In HL60 cells, silver–NHCs induce depolarization of the mitochondrial membrane potential (ΔΨm) and likely allow the release of mitochondrial proteins to elicit early apoptosis. This effect is not related to the overproduction of reactive oxygen species (ROS). In addition, apoptosis is not associated with the activation of caspase-3, but is triggered by the translocation of apoptosis-inducing factor (AIF) and caspase-12 from mitochondria and the endoplasmic reticulum, respectively, into the nucleus to promote DNA fragmentation and ultimately cell death. No modification in cell-cycle distribution was observed, indicating that silver–NHCs are not genotoxic. Finally, the use of a fluorescent complex showed that silver–NHCs target mitochondria. Altogether, these results demonstrate that silver–NHCs induce cancer cell death independent of the caspase cascade via the mitochondrial AIF pathway.
      Mots-clés : apoptosis-inducing factor, cancer, Carbene ligands, CHEMBIO, GOBS, Heterocycles, mode of action, POLE 3, silver.


    • Z. Guan, L. - H. Zhang, P. Sinaÿ, et Y. Zhang, « Study on Metal-Induced Reactions of α-Diazocarbonyl Glucosides », Journal of Organic Chemistry, vol. 77, nᵒ 20, p. 8888-8895.
      Résumé : Conversions of diazocarbonyl carbohydrate compounds catalyzed by a series of rhodium and copper catalysts in conventional heating or microwave conditions were investigated. C?H insertion product was obtained in the presence of Rh2(OAc)4. Intermolecular reactions rather than intramolecular reactions occurred in the presence of copper catalysts.
      Mots-clés : GOBS, POLE 3.


    • M. Guitet, S. A. de Beaumais, Y. Blériot, B. Vauzeilles, Y. Zhang, M. Ménand, et M. Sollogoub, « Cyclodextrins selectively modified on both rims using an O-3-debenzylative post-functionalisation, a consequence of the Sorrento meeting », Carbohydrate Research, vol. 356, p. 278-281.
      Résumé : A de-O-benzylation reaction induced by I2–Et3SiH and developed by Iadonisi et al. on mono- and disaccharides was applied to per- or polybenzylated α-cyclodextrins to furnish compounds deprotected at position 3 of all sugar units. This methodology allows the straightforward post-functionalisation of the secondary rim of cyclodextrins already functionalised on their primary rim.
      Mots-clés : Chemoselective, Cyclodextrin, Deprotection, GOBS, POLE 3, Post-functionalisation, Regioselective.


    • H. Li, Y. Zhang, S. Favre, P. Vogel, M. Sollogoub, et Y. Blériot, « Synthesis of branched seven-membered 1-N-iminosugars and their evaluation as glycosidase inhibitors », Carbohydrate Research, vol. 356, p. 110-114.
      Résumé : Four branched tetra- and pentahydroxylated azepanes have been synthesized from a common azepane precursor through dihydroxylation followed by deoxygenation. They have been assayed as glycosidase inhibitors on a panel of 22 glycosidases and one methylated azepane displayed selective, competitive, and moderate inhibition toward bovine kidney α-l-fucosidase.
      Mots-clés : Azepane, Glycosidase, GOBS, Iminosugar, Inhibitor, POLE 3.

    • J. Liang, J. He, S. Zhu, W. Zhao, Y. Zhao, Y. Zhang, et W. Sun, « An Expeditious Method Combining Multi-Components Determination And Fingerprinting Based On Ultra Performance Liquid Chromatography-Photo Diode Array-Tandem Mass Spectrometry And Chemometrics: Application For Authentication And Quality Evaluation Of Cornus Officinalis Sieb. Et Zucc », Analytical Letters, vol. 45, nᵒ 15, p. 2109-2124.
      Résumé : Selective and efficient analytical methods for authentication and quality evaluation of herbal medicines are significant and necessary. An expeditious method combining multi-components determination and fingerprinting based on ultra-performance liquid chromatography-photo diode array-tandem mass spectrometry (UPLC-PDA -MS/MS) and chemometrics for authentication and quality evaluation of Cornus Officinalis Sieb. et Zucc was developed. Tandem mass spectrometer operating in multiple reaction monitoring (MRM

      ) was used for determination of three characteristic constituents (morroniside, sweroside, and loganin) in C. Officinalis. Meanwhile, UPLC fingerprint of C. Officinalis was established and the data set was submitted for classification to a suite of chemometrics method. Combing main biologically active components content level and chemometrics analysis, the effects of cultivation area, harvesting, and storage time on the quality of C. Officinalis were investigated. The study reveals that multi-components determination coupled with fingerprinting could be applied for authentication and quality evaluation of C. Officinalis which is accurate, efficient, and reliable.
      Mots-clés : Chemometrics, Cornus Officinalis Sieb. et Zucc, Fingerprint, fructus, GOBS, hplc, inflammation, loganin, mice, morroniside, Multi-components determination, POLE 3, Quality evaluation, uplc-ms/ms, uplc-pda-ms/ms.


    • J. Pérez-Castells, M. Fontanella, A. Ardá, F. J. Canãda, M. Sollogoub, Y. Blériot, et J. Jiménez-Barbero, « Conformational analysis of seven-membered 1-N-iminosugars by NMR and molecular modelling », New Journal of Chemistry, vol. 36, nᵒ 4, p. 1008-1013.
      Résumé : The conformational analysis of a series of tri- and tetrahydroxyazepanes 1–6 designed as noeuromycin mimics has been carried out using 1H NMR spectroscopy assisted by molecular mechanics, molecular dynamics and Monte Carlo calculations. A marked flexibility for these compounds has been found. Superimposition
      Mots-clés : GOBS, POLE 3.


    • H. Qu, Y. Zhang, X. Chai, et W. Sun, « Isoforsythiaside, an antioxidant and antibacterial phenylethanoid glycoside isolated from Forsythia suspensa », Bioorganic Chemistry, vol. 40, p. 87-91.
      Résumé : The isolation, structural elucidation, antioxidant effect and antibacterial activity of isoforsythiaside, a novel phenylethanoid glycoside isolated from Forsythia suspensa, were described. The antioxidant activity was estimated using the 1-diphenyl-2-picrylhydrazyl scavenging activity method and the in vitro antimicrobial activity was evaluated by the microtitre plate method. The results showed that this compound had strong activities. Owing to these properties, the study can be further extended to exploit for the possible application of isoforsythiaside as the alternative antioxidants and antibacterial agents from natural origin.
      Mots-clés : Antibacterial, Antioxidant, Forsythia suspensa, Forsythiaside, GOBS, Isoforsythiaside, POLE 3, Structural elucidation.


    • J. Rieger, T. Antoun, S. - H. Lee, M. Chenal, G. Pembouong, J. Lesage de la Haye, I. Azcarate, B. Hasenknopf, et E. Lacôte, « Synthesis and Characterization of a Thermoresponsive Polyoxometalate–Polymer Hybrid », Chemistry – A European Journal, vol. 18, nᵒ 11, p. 3355–3361.
      Résumé : We report the synthesis of the first organo-POM with thermoresponsive properties. Our concept will provide chemists with a new tool to design POMs whose solubility is reversibly controllable through an external stimulus. POM–polymer TBA7[POM]-poly(N,N-diethylacrylamide) (POM–PDEAAm), was prepared by grafting PDEAAm-NH2 (obtained by RAFT polymerization) onto the activated Dawson acyl-POM, α2-[P2W17O61SnCH2CH2C(O)]6−. Extensive MS analysis was used to monitor the chain-functionalization steps and to confirm the formation of the hybrid. Aqueous solutions of the (NH4)7[POM–PDEAAm] exhibited a LCST of 38 °C. Thus, the solubility/aggregation of the hybrid was reversibly controlled by changing the temperature. Above 38 °C, the solution became cloudy, and cleared again upon cooling. Dynamic light scattering (DLS) revealed the formation of small aggregates in the range 100 nm. We assumed that the charged POM head units prevented the formation of the larger-scattering aggregates that are usually observed for PDEAAm, and promoted the formation of micelle-like structures. The conjugate exhibited a temperature transition, which was different from that of the polymer and depended on the counterions associated with the POM. This result demonstrates the potential for merging organic (in this case, polymer) and inorganic structures to afford materials that exhibit new properties.
      Mots-clés : aggregation, COS, GOBS, MACO, organic-inorganic hybrid composites, POLE 1, POLE 3, POLE 4, POLYMERES, polymerization, Polyoxometalates, SUPRA, thermoresponsive polymers.


    • M. - P. Santoni, A. K. Pal, G. S. Hanan, M. - C. Tang, K. Venne, A. Furtos, P. Ménard-Tremblay, C. Malveau, et B. Hasenknopf, « Coordination-driven self-assembly of polyoxometalates into discrete supramolecular triangles », Chemical Communications, vol. 48, nᵒ 2, p. 200-202.
      Résumé : Pd(ii)-directed self-assembly of a 3-pyridyl grafted Lindqvist hexavanadate led to the formation of a unique trimeric species, as confirmed by a variety of techniques, including pulsed-field gradient NMR spectroscopy and high-resolution ESI mass spectrometry.
      Mots-clés : GOBS, POLE 3, SUPRA.


    • R. Skanji, M. Ben Messaouda, Y. Zhang, M. Abderrabba, H. Szwarc, et F. Moussa, « Sequential photo-addition of glycine methyl-ester to [60]fullerene », Tetrahedron, vol. 68, nᵒ 12, p. 2713-2718.
      Résumé : While direct photo-addition of glycine-methyl-esters (GME) to [60]fullerene (C60) can yield a complex product mixture, only a fulleropyrrolidine (FP) mono-adduct has been characterized and the mechanism remains to be ascertained. We show here that visible light irradiation of a mixture of C60 and GME in the presence of oxygen is a direct route to synthesize sequentially higher FP poly-adducts through an unprecedented cyclization–deamination mechanism. Each step of this mechanism leads to a FP adduct involving the correlated addition of two GME radicals and the departure of an ammonia molecule.
      Mots-clés : C60-Polyadducts, Fulleropyrrolidine, Glycine-methyl-esters, GOBS, Photo-additions, POLE 3, [60]Fullerene.


    • S. L. Xiao, D. M. Zhou, M. Yang, F. Yu, L. H. Zhang, P. Sinaÿ, et Y. M. Zhang, « Synthesis of two mono-deoxy β-cyclodextrin derivatives as useful tools for confirming DIBAL-H promoted bis-de-O-methylation mechanism », Chinese Chemical Letters, vol. 23, nᵒ 12, p. 1315-1318.
      Résumé : Diisobutylaluminium hydride (DIBAL-H) promotes secondary rim regioselective bis-de-O-methylation of permethylated β-cyclodextrin (β-CD) to give diol 2. To gain an insight into the mechanism of this remarkable regioselective behavior, two corresponding permethylated β-CDs with an alcohol function at either 2- or 3-position were synthesized in our previous study. As a step further to this work, the two compounds were subjected to deoxygenation reaction with tributyltin hydride in the present of 2,2′-azobisisobutyronitrile affording the corresponding 2- and 3-deoxy permethylated β-CD derivatives (19 and 16). The structures of these two compounds were characterized by 1D and 2D NMR and HRMS. Compounds 16 and 19 were unable to react with DIBAL-H which suggests that O-2A and O-3B are necessary for DIBAL-H promoted bis-de-O-methylation reaction of permethylated β-CD.
      Mots-clés : Cyclodextrin (CD), Deoxy, DIBAL-H, GOBS, Mechanism, POLE 3, Synthesis.


    • S. -long Xiao, Q. Wang, F. Yu, Y. -yun Peng, M. Yang, M. Sollogoub, P. Sinaÿ, Y. -min Zhang, L. -he Zhang, et D. -min Zhou, « Conjugation of cyclodextrin with fullerene as a new class of HCV entry inhibitors », Bioorganic & Medicinal Chemistry, vol. 20, nᵒ 18, p. 5616-5622.
      Résumé : An α-cyclodextrin–[60]fullerene conjugate with a flexible linker at the secondary face of α-cyclodextrin has been prepared, which displays significant water solubility and, more importantly, acts as a new class of HCV entry inhibitor with IC50 at 0.17 μM level.
      Mots-clés : Conjugate, Fullerene, GOBS, HCV entry, POLE 3, α-Cyclodextrin.


    • S. - H. Yan, Y. - Y. Zhao, H. - S. Zeng, Y. Zhang, R. - C. Lin, et W. - J. Sun, « Chemical composition and antioxidant activities of extracts from <i>Apocyni Veneti Folium</i> », Natural Product Research, vol. 26, nᵒ 7, p. 600-608.

    • W. Zhao, J. He, Y. Zhang, Y. Ito, Q. Su, et W. Sun, « Preparative Isolation and Purification of Alkaloids from Picrasma Quassiodes (d. Don) Benn. by High-Speed Countercurrent Chromatography », Journal of Liquid Chromatography & Related Technologies, vol. 35, nᵒ 11, p. 1597-1606.
      Résumé : By using a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (2: 2: 2: 2, v/v/v/v), a high-speed counter-current chromatography technique was successfully used for isolation and purification of three alkaloids from Picrasma quassiodes (D. Don) Benn. for the first time. A total of 22.1 mg of 3-methylcanthin-2,6-dione, 4.9 mg of 4-methoxy-5-hydroxycanthin-6-one and 1.2 mg of 1-methoxycarbonyl-beta-carboline were obtained from 100 mg of crude extract of Picrasma quassiodes (D. Don) Benn. in less than 5 hr, with purities of 89.30%, 98.32%, and 98.19%, respectively. The target compounds were identified by ESI-MS, H-1 NMR, and C-13 NMR.
      Mots-clés : 1-methoxycarbonyl-beta-carboline, 3-methylcanthin-2,6-dione, 4-methoxy-5-hydroxycanthin-6-one, Alkaloids, beta-carboline alkaloids, GOBS, high-speed countercurrent chromatography, Picrasma quassiodes, POLE 3, separation.

    • Y. - Y. Zhao, X. - L. Cheng, F. Wei, X. - Y. Xiao, W. - J. Sun, Y. Zhang, et R. - C. Lin, « Serum metabonomics study of adenine-induced chronic renal failure in rats by ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry », Biomarkers, vol. 17, nᵒ 1, p. 48-55.
      Résumé : An ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC Q-TOF MS) metabonomics approach was employed to study the serum metabolic profiling of adenine-induced chronic renal failure (CRF) rats. Acquired data were subjected to principal component analysis (PCA) for differentiating the CRF and the normal control groups. Potential biomarkers were screened by using S-plot and were identified by the accurate mass, isotopic pattern and MS/MS fragments information obtained from UPLC Q-TOF MS analysis. Significant differences in the serum level of creatinine, amino acids and LysoPCs were observed, indicating the perturbations of amino acid metabolism and phospholipid metabolism in adenine-induced CRF rats. This research proved that metabonomics is a promising tool for disease research.
      Mots-clés : activation, biomarkers, Chronic renal failure, GOBS, inborn-errors, kidney, metabolism, metabonomics, nmr-spectroscopy, pathway, POLE 3, principal component analysis, rats, serum, tof ms, uplc, uplc q-tof ms.

    • Z. - Y. Zhu, J. Chen, C. - L. Si, N. Liu, H. - Y. Lian, L. - N. Ding, Y. Liu, et Y. - M. Zhang, « Immunomodulatory effect of polysaccharides from submerged cultured Cordyceps gunnii », Pharmaceutical Biology, vol. 50, nᵒ 9, p. 1103-1110.
      Résumé : Context: The genus Cordyceps (Clavicipitaceae) is a group of entomopathogenic fungi that is widely used as tonic food or invigorant with broad-spectrum medicinal properties in China. Cordyceps gunnii (Berk.) Berk (C. gunnii), is also well known as the Chinese rare caterpillar fungus and has similar pharmacological activities with Cordyceps sinensis (C. sinensis). Polysaccharides (PS) from various Cordyceps species have demonstrated many interesting biological activities, including antitumor, immunopotentiation, hypoglycemic, and hypocholesterolemic activities. Objective: To investigate the effect of C. gunnii PS on the immunostimulatory antitumor function and expression of immune related cytokines in normal, immuno-suppressive, and H22-bearing mice, respectively. Methods: C. gunnii PS were extracted with hot water at 80 C for 2 h. Normal, immuno-suppressive, and H22-bearing mice were treated with PS respectively. By detecting the value of macrophage phagocytic index, proliferation of lymphocytes, natural killer (NK) cell activity and expression of related cytokines, interleukin (IL-4), tumor necrosis factor-alpha (TNF-alpha) and interferon-gamma (IFN-gamma), and tumor inhibition index in H22-bearing mice additionally, the effect of PS on immunostimulatory antitumor function and its mechanism were studied. Results: The total sugar content of the PS was determined to be 95% after purification. PS markedly increased the thymus and spleen indexes, the macrophage phagocytosis, the proliferation of splenic cells, and the level of IFN-gamma and TNF-alpha. In tumor growth inhibition test, PS showed remarkable inhibition effects. Conclusion: PS from the C. gunnii could enhance nonspecific immunological function, humoral immunity, cellular immunity in mice, and inhibit tumor growth.
      Mots-clés : Antitumor, Cordyceps, expression, GOBS, mice, nonspecific immunity, POLE 3, polysaccharides.


    • Z. - Y. Zhu, H. - Y. Lian, C. - L. Si, Y. Liu, N. Liu, J. Chen, L. - N. Ding, Q. Yao, et Y. Zhang, « The chromatographic analysis of oligosaccharides and preparation of 1-kestose and nystose in yacon », International Journal of Food Sciences and Nutrition, vol. 63, nᵒ 3, p. 338-342.
      Mots-clés : analysis, glucose-oxidase, GOBS, mixed-enzyme-system, oligosaccharide, POLE 3, separation, yacon.
      Pièce jointe


    • Z. - Y. Zhu, N. Liu, Y. Liu, C. - L. Si, R. - Q. Liu, J. Chen, C. - J. Liu, A. - J. Liu, et Y. - M. Zhang, « Chemical analysis of a polysaccharide from <i>Cristaria plicata</i> (Leach) », International Journal of Food Sciences and Nutrition, vol. 63, nᵒ 4, p. 506-511.
      Mots-clés : anodonta-cygnea, chemical composition, GOBS, hyriopsis-cumingii, isolation, mussel, POLE 3, Polysaccharide, purification, structure.
      Pièce jointe

    • Z. -yuan Zhu, N. Liu, C. -ling Si, Y. Liu, L. -na Ding, C. Jing, A. -jun Liu, et Y. -min Zhang, « Structure and anti-tumor activity of a high-molecular-weight polysaccharide from cultured mycelium of Cordyceps gunnii », Carbohydrate Polymers, vol. 88, nᵒ 3, p. 1072-1076.
      Résumé : Cordyceps gunnii (berk.) Berk (C. Gunnii) is well known as a Chinese rare caterpillar fungus and has similar pharmacological activity with C. sinensis. In this work, a high-molecular-weight polysaccharide (CPS) was isolated and purified from the mycelia of C. gunnii. The total sugar content of CPS was amounted to 92.84%. The result of HPLC indicated that CPS was a homogeneous polysaccharide. The estimated average molecular weight of CPS was 3.72 x 10(6) Da. The specific rotation of CPS was recorded [alpha](D)(25) = +134.2 degrees. Its characteristic was determined by chemical analysis, gas chromatography, IR spectroscopy and NMR data. The results showed that CPS was mainly composed of glucose, and a small amount of rhamnose, arabinose, xylose, mannose and galactose with a molar ratio of Rha:Ara:Xyl:Man:Glu:Gal = 3.0:2.6:1.0:1.3:106.0:2.8. The main chain of CPS was majorly composed of alpha-(1 -> 4) glucose. The tumor inhibition ratio on K562 cell by CPS was 56.65%. (C) 2012 Elsevier Ltd. All rights reserved.
      Mots-clés : antioxidant activity, Antitumor, cells, Characteristic, Cordyceps gunnii, GOBS, High-molecular-weight polysaccharide, mice, militaris, POLE 3, purification, sinensis.
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      Z. - Y. Zhu, Q. Yao, Y. Liu, C. - L. Si, J. Chen, N. Liu, H. - Y. Lian, L. - N. Ding, et Y. - M. Zhang, « Highly efficient synthesis and antitumor activity of monosaccharide saponins mimicking components of Chinese folk medicine Cordyceps sinensis », Journal of Asian Natural Products Research, vol. 14, nᵒ 5, p. 429-435.
      Résumé : Ergosterol 3-O-beta-D-glucopyranoside (1a) and ergosterol 3-O-beta-D-galactopyranoside (1b) were highly efficiently synthesized and evaluated for their inhibitory activities against two tumor cell lines. The structures of these compounds were extensively confirmed by H-1, C-13 NMR, IR, and HRMS. Compounds 1a and 1b exhibited interesting cytotoxic profiles. The antitumor activity of compound 1a was higher than that of 1b.
      Mots-clés : Cordyceps sinensis, Ergosterol, Glycosylation, GOBS, POLE 3, saponins.

    2011

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