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2016



  • K. Plevová, L. Chang, E. Martin, Q. Llopis, L. Dechoux, et S. Thorimbert, « Regio- and Stereoselective Preparation of β,γ-Unsaturated Carboxylic Acids by One-Pot Sequential Double 1,6-Addition of Grignard Reagents to Methyl Coumalate », Advanced Synthesis & Catalysis, vol. 358, nᵒ 20, p. 3293-3297, 2016.
    Résumé : An efficient regio- and stereoselective metal-catalyzed addition of two Grignard reagents (homo-coupling, 2 RMgX or hetero-coupling, R1MgX+R2MgX) to methyl coumalate (methyl 2-oxo-2H-pyran-5-carboxylate) is described. This synthetic approach opens the access to a wide variety of functionalized β,γ-unsaturated carboxylic acids in a modular way. Control of the chemo- and stereoselectivity of this one-pot procedure is discussed.
    Mots-clés : 6-π electrocyclic ring opening, CHEMBIO, double 1,6-conjugate addition, Grignard reagents, metal catalysis, POLE 3, unsaturated acids.


  • C. Przybylski, J. M. Benito, V. Bonnet, C. O. Mellet, et J. M. García Fernández, « Deciphering of polycationic carbohydrate based non-viral gene delivery agents by ESI-LTQ-Orbitrap using CID/HCD pairwise tandem mass spectrometry », RSC Adv., vol. 6, nᵒ 82, p. 78803-78817.


  • C. Przybylski, J. M. Benito, V. Bonnet, C. O. Mellet, et J. M. García Fernández, « Toward a suitable structural analysis of gene delivery carrier based on polycationic carbohydrates by electron transfer dissociation tandem mass spectrometry », Analytica Chimica Acta, vol. 948, p. 62-72.


  • H. Qi, J. Wolfe, D. Fichou, et Z. Chen, « Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst », Scientific Reports, vol. 6, p. 30882.
    Résumé : Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light.
    Mots-clés : NASCO, POLE 2.


  • V. Rajeshkumar, M. Courté, D. Fichou, et M. C. Stuparu, « Synthesis and Properties of Large Polycyclic Aromatic Hydrocarbons with Planar and Non-Planar Structural Motifs », European Journal of Organic Chemistry, vol. 2016, nᵒ 36, p. 6010-6014.
    Résumé : Implementation of non-planar aromatic motifs in the molecular design of π-conjugated materials represents a paradigm shift that is interesting from a fundamental research viewpoint but remains largely underdeveloped. To further facilitate this cause, we report on the synthesis and properties of two large polycyclic aromatic compounds (38 carbon atoms). In one compound the planar π-system pyrene is linked to bowl-shaped hydrocarbon corannulene through a C=C bond, which is referred to as “corannulene–vinylpyrene”. Photochemical treatment of this compound results in annulation of both aromatic nuclei and formation of the other large fused structure with ten six-membered aromatic rings, referred to as “corannulene–benzopyrene”. Photophysical and electrochemical studies reveal that the properties of these two structurally related hybrid materials arise from an extended π-conjugation between the planar and non-planar motifs and varies depending upon their molecular structure.
    Mots-clés : Annulation, Arenes, cyclization, Fused-ring systems, NASCO, POLE 2, polycycles.


  • V. Rajeshkumar, C. Marc, D. Fichou, et M. C. Stuparu, « Synthesis and Properties of a Buckybowl/Buckyball Dyad », Synlett, vol. 27, nᵒ 14, p. 2101-2104.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : NASCO, POLE 2.

  • J. Ramirez Hernandez, F. Chemla, F. Ferreira, O. Jackowski, J. Oble, A. Perez-Luna, et G. Poli, « tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions », Chimia, vol. 70, nᵒ 1, p. 84-92.
    Résumé : The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon–nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.
    Mots-clés : amination, Chiral Nucleophiles, POLE 1, ROCS, Tert-Butanesulfinamide.


  • B. Rasolonjatovo, B. Pitard, T. Haudebourg, V. Bennevault, et P. Guégan, « Synthesis of tetraarm star block copolymer based on polytetrahydrofuran and poly(2-methyl-2-oxazoline) for gene delivery applications », European Polymer Journal, sept. 2016.
    Résumé : New star shaped block copolymers were synthesized according to a core first strategy, with a hydrophobic polytetrahydrofuran (PTHF) central block and a poly(2-methyl-2-oxazoline) (PMeOx) external block. First, the cationic polymerization of THF was initiated from a tetrafunctional triflate ester synthesized in situ. The chain ends were functionalized by quenching the polymerization with an excess of MeOx, that allowed for the MeOx polymerization under microwave in a subsequent step. Demonstration of the expected structures was carried out at each step of the polymerization. The controlled molar mass of the star copolymers was kept below 5000 g mol−1 in order to mimick the structure of the efficient poloxamines for gene transfer applications. Formulations containing various concentrations of star block copolymers were intramuscularly injected in mice. Efficient gene transfer was measured at formulations with very low concentration of copolymer compared to reference standard containing Lutrol®.
    Mots-clés : CROP, Gene therapy, POLE 4, Poly(2-methyl-2-oxazoline), POLYMERES.

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    E. Rathahao-Paris, S. Alves, C. Junot, et J. - C. Tabet, « High resolution mass spectrometry for structural identification of metabolites in metabolomics », Metabolomics, vol. 12, nᵒ 1, p. 10.
    Résumé : High resolution mass spectrometry (HRMS) is increasingly used to produce metabolomics data. Thanks to its high mass resolution and mass measurement accuracy, it is also very useful for metabolite identification. Nevertheless, a rigorous methodology is required. This manuscript describes different steps involved in the structural elucidation of metabolites and demonstrates the utility of HRMS for such purpose. After a brief overview of HRMS performances in terms of mass measurement accuracy, peak resolution, isotopic clusters/patterns and the instrumentation used, the first section is devoted to the data processing generally performed to reduce the data set size. Based on the mass accuracy measurements, different post-acquisition data processing procedures have been developed for complex mixture analysis and can be used in metabolomics. The second section describes protocols used to process putative metabolite annotations or identifications with HRMS data, based on elemental composition determined from accurately measured m/z value and mass spectral databases. Non-classical approaches are also proposed for tentative structure elucidation of unknown metabolites. Finally, limitations of the proposed workflow for metabolite structure elucidation are discussed and possible improvements are proposed.
    Mots-clés : CSOB, POLE 3.


  • E. Ressouche, S. Pensec, B. Isare, G. Ducouret, et L. Bouteiller, « Rational Design of Urea-Based Two-Component Organogelators », ACS Macro Letters, vol. 5, nᵒ 2, p. 244-247.
    Résumé : Low molecular weight gelators are versatile and responsive gel-forming systems. However, it is still a challenge to develop a new organogelator for a precise application, i.e., to gel a predetermined liquid. We propose a simple concept of a two-component gelling system that can be rationally adapted to gel liquids ranging in polarity from silicone oil to acetonitrile.
    Mots-clés : POLE 4, POLYMERES.


  • E. Ressouche, S. Pensec, B. Isare, J. Jestin, et L. Bouteiller, « Two-Component Self-Assemblies: Investigation of a Synergy between Bisurea Stickers », Langmuir, vol. 32, nᵒ 44, p. 11664-11671.
    Résumé : It is of interest to develop two-component systems for added flexibility in the design of supramolecular polymers, nanofibers, or organogels. Bisureas are known to self-assemble by hydrogen bonding into long supramolecular objects. We show here that mixing aromatic bisureas with slightly different structures can yield surprisingly large synergistic effects. A strong increase in viscosity is observed when a bisurea with the sterically demanding 2,4,6-trimethylbenzene spacer is combined with a bisurea bearing no methyl group in position 2 of the aromatic spacer (i.e., 4-methylbenzene or 4,6-dimethylbenzene). This effect is the consequence of a change in the supramolecular assembly triggered by the composition of the mixture. The mixture of complementary bisureas forms rodlike objects that are more stable by about 1 kJ/mol and that are thicker than the rodlike objects formed by both parent systems.
    Mots-clés : POLE 4, POLYMERES.


  • K. Ridier, A. Mondal, C. Boilleau, O. Cador, B. Gillon, G. Chaboussant, B. Le Guennic, K. Costuas, et R. Lescouëzec, « Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex », Angewandte Chemie, vol. 128, nᵒ 12, p. 4031-4035, mars 2016.


  • C. Rinfray, V. Brasiliense, G. Izzet, F. Volatron, S. Alves, C. Combellas, F. Kanoufi, et A. Proust, « Electron Transfer to a Phosphomolybdate Monolayer on Glassy Carbon: Ambivalent Effect of Protonation », Inorganic Chemistry, vol. 55, nᵒ 14, p. 6929-6937.
    Résumé : The polyoxomolybdate hybrid TBA3[PMo11O39{Sn(C6H4)C≡C(C6H4)N2}] KMoSn[N2+] was prepared through Sonogashira-type coupling between TBA4[PMo11O39{Sn(C6H4)I}] KMoSn[I] and an excess of 3,3-diethyl-1-(4-ethynylphenyl)triaz-1-ene bearing a protected diazonium function, followed by its deprotection by the addition of trifluoroacetic acid (TFA). This enlarges the family of organic–inorganic polyoxomolybdate-based hybrids, which has been far less investigated than their related polyoxotungstates. The diazonium function allows for the electrochemical grafting on glassy carbon, and the KMoSn-modified electrode was further probed by cyclic voltammetry. The PMo11Sn core was found to be highly sensitive to protonation, and five bielectronic proton-coupled electron transfer processes were detected in the presence of an excess of TFA, thus corresponding to the injection of up to 10 electrons in the potential range between 0.15 and −0.45 V/SCE. The gain observed in the thermodynamic potentials is however detrimental to the apparent kinetics of the electron transfer, which drops from 500 s–1 in the absence of acid to 12 s–1 in the presence of an excess of TFA.
    Mots-clés : CSOB, E-POM, POLE 2, POLE 3.


  • A. Rivera-Hernández, B. J. Fallon, S. Ventre, C. Simon, M. - H. Tremblay, G. Gontard, E. Derat, M. Amatore, C. Aubert, et M. Petit, « Regio- and Stereoselective Hydrosilylation of Unsymmetrical Alkynes Catalyzed by a Well-Defined, Low-Valent Cobalt Catalyst », Organic Letters, vol. 18, nᵒ 17, p. 4242-4245.
    Résumé : Herein, the use of a well-defined low-valent cobalt(I) catalyst [HCo(PMe3)4] capable of performing the highly regio- and stereoselective hydrosilylation of internal alkynes is reported. The reaction can be applied to a variety of hydrosilanes, symmetrical and unsymmetrical alkynes, giving in many cases a single hydrosilylation isomer. Experimental and theoretical studies suggest the key step to be a hydro-cobaltation and that the reaction proceeds through a classical Chalk–Harrod mechanism.
    Mots-clés : MACO, POLE 1.


  • S. Roland, X. Ling, et M. - P. Pileni, « N-Heterocyclic Carbene Ligands for Au Nanocrystal Stabilization and Three-Dimensional Self-Assembly », Langmuir, vol. 32, nᵒ 31, p. 7683-7696.
    Résumé : N-Heterocyclic carbenes (NHCs) have emerged as a new class of ligands for materials chemistry that appears particularly relevant for the stabilization and functionalization of metal nanoparticles (NPs). The particular properties and high synthetic flexibility of NHCs make them highly attractive tools for the development of new (nano)materials and the fundamental study of their properties. The relationships between the NHC structure and NP structure/properties, including physical, biological, and self-assembly properties, remain largely unknown. In the past decade, many efforts have been made to gain more fundamental understanding in this area. In this feature article, we present our contribution in this field focusing on the formation of NHC-coated Au nanocrystals (NCs), their stability, and their ability to self-assemble into 3D crystalline structures called supracrystals. First, the formation of NHC-stabilized Au NCs is discussed by comparing different NHC structures, NHC-based Au precursors, and synthesis methods. This study shows the major role of the NHC structure in obtaining both stable NHC-coated Au NCs and narrow size distributions. In a second part, a comparative study of the oxygen resistance of NHC- and thiol-coated NCs is presented, demonstrating the enhanced stability of NHC-coated Au NCs to oxygen-based treatments. Finally, the self-assembly of NHC-coated Au NCs into 3D Au superlattices is presented. The formation of large organized domains of several micrometers is described from the design of NHCs tailored with long alkyl chains. In these different contexts, efforts have been made to gain a more in-depth understanding of the behavior of NHC ligands at the surface of NCs. These results show that the NHC-based approach to nanomaterials has many assets for opening a new research area in the supracrystal world.
    Mots-clés : GOBS, POLE 3.


  • B. Rudolf, A. Kubicka, M. Salmain, M. Palusiak, A. J. Rybarczyk-Pirek, et S. Wojtulewski, « Synthesis and characterization of new M(II) carbonyl complexes (M = Fe or Ru) including an η1-N-maleimidato ligand. Reactivity studies with biological thiols », Journal of Organometallic Chemistry, vol. 801, p. 101-110, 2016.
    Résumé : Herein we report the preparation and characterization of the iron and ruthenium organometallic maleimides (η5-Cp*)Fe(CO)2(η1-maleimidato) (Cp* = pentamethyl cyclopentadienyl) and (η5-Cp)Ru(CO)2(η1-maleimidato). The molecular structure of the ru

    thenium complex was confirmed by X-ray diffraction study. The reactivity of the metallocarbonyl maleimide derivatives toward biologically meaningful thiols, namely cysteine ethyl ester hydrochloride, glutathione (GSH) and human serum albumin (HSA) was investigated. To get better insight into the reaction mechanism, kinetic studies of the reaction with GSH and HSA were performed as well as quantum-chemical calculations and QTAIM analysis. We found out that the reactivity of the organometallic maleimides towards thiols depended on: 1) the metal present in the structure, 2) the nature of the capping aromatic ligand due to differences in electron donating capabilities and steric demands and 3) additional interactions like hydrogen bonding in (η5-Cp*)Fe(CO)2(η1-maleimidato) and carbonyl … carbonyl interactions in (η5-Cp)Ru(CO)2(η1-maleimidato).
    Mots-clés : Bioorganometallic chemistry, CHEMBIO, cysteine thiols, Maleimides, Metal carbonyls, Organometallic, POLE 3.


  • V. Scalcon, A. Citta, A. Folda, A. Bindoli, M. Salmain, I. Ciofini, S. Blanchard, J. de Jésús Cázares-Marinero, Y. Wang, P. Pigeon, G. Jaouen, A. Vessières, et M. P. Rigobello, « Enzymatic oxidation of ansa-ferrocifen leads to strong and selective thioredoxin reductase inhibition in vitro », Journal of Inorganic Biochemistry, vol. 165, p. 146-151.
    Résumé : This paper reports the inhibitory effect on the cytosolic thioredoxin reductase (TrxR1) in vitro by the ansa-ferrocifen derivative (ansa-FcdiOH, 1). We found that 1 decreased only slightly enzyme activity (IC50 = 8 μM), while 1*, the species generated by enzymatic oxidation by the HRP (horseradish peroxidase)/H2O2 mixture, strongly inhibited TrxR1 (IC50 = 0.15 μM). At the same concentrations, neither 1 nor 1* had effect on glutathione reductase (GR). The most potent TrxR1 inhibitor did not appear to be the corresponding quinone methide as it was the case for ferrocifens of the acyclic series, or the stabilized carbocation as in the osmocifen series, but rather the quinone methide radical. This hypothesis was confirmed by ab-initio calculations of the species generated by oxidation of 1 and by EPR spectroscopy. BIAM (biotin-conjugated iodoacetamide) assay showed that 1* targeted both cysteine and selenocysteine of the C-terminal redox center of TrxR1.
    Mots-clés : Ansa-ferrocifen, CHEMBIO, E-POM, Enzymatic oxidation, Ferrocene, POLE 2, POLE 3, Quinone methide radical, Thioredoxin reductase.


  • V. Scalcon, S. Top, H. Z. S. Lee, A. Citta, A. Folda, A. Bindoli, W. K. Leong, M. Salmain, A. Vessières, G. Jaouen, et M. P. Rigobello, « Osmocenyl-tamoxifen derivatives target the thioredoxin system leading to a redox imbalance in Jurkat cells », Journal of Inorganic Biochemistry, vol. 160, p. 296-304, 2016.
    Résumé : The synthesis and the biological effects of two ferrocifen analogs in the osmium series, namely the monophenolic complex 1, the tamoxifen-like complex 2 and their oxidized quinone methide (QM) derivatives, 1-QM and 2-QM, are reported. Inhibition of purified thioredoxin reductase (TrxR) is observed with 1 and 2 only after their enzymatic oxidation by the hydrogen peroxide/horseradish peroxidase (H2O2/HRP) system with IC50 of 2.4 and 1.2 μM respectively. However, this inhibition is larger than that obtained with the corresponding quinone methides (IC50 = 5.4 μM for 1-QM and 3.6 μM for 2-QM). The UV–Vis spectra of 1 or 2 incubated in the presence of H2O2/HRP show that the species generated is not a quinone methide, but probably the corresponding cation. In Jurkat cells, 2 shows high toxicity (IC50 = 7.4 μM), while 1 is less effective (IC50 = 42 μM). Interestingly, a significant inhibition of TrxR activity is observed in cells incubated with 2 (about 70% inhibition with 15 μM) while the inhibition induced by 1 is much weaker (about 30% inhibition with 50 μM). This strong inhibition of TrxR by 2 leads to accumulation of thioredoxin and peroxiredoxin 3 in oxidized form and to a decrease of the mitochondrial membrane potential (MMP). These results show that cytotoxicity of the osmocifens depends on their oxidation within the cell and that inhibition of thioredoxin reductase by oxidized species is a key factor in rationalizing the cytotoxicity of these complexes on Jurkat cells.
    Mots-clés : CHEMBIO, Jurkat cancer cells, Osmocene, Osmocenyl-tamoxifen, POLE 3, ROS, Thioredoxin reductase.


  • H. Sesolis, J. Dubarle-Offner, C. K. M. Chan, E. Puig, G. Gontard, P. Winter, A. L. Cooksy, V. W. W. Yam, et H. Amouri, « Highly Phosphorescent Crystals of Square-Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD-DFT Calculations », Chemistry – A European Journal, vol. 22, nᵒ 24, p. 8032-8037.
    Résumé : A novel class of chiral luminescent square-planar platinum complexes with a π-bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo- or hetero-chiral arrangement at the supramolecular level, displaying non-covalent Pt–Pt and π–π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD-DFT calculation is obtained to rationalize this unique behavior.
    Mots-clés : ARC, molecular aggregation, noncovalent interactions, photophysical properties, Platinum, POLE 1, supramolecular chirality.


  • C. Shen, D. Fichou, et Q. Wang, « Interfacial Engineering for Quantum-Dot-Sensitized Solar Cells », Chemistry – An Asian Journal, vol. 11, nᵒ 8, p. 1183-1193.
    Résumé : Quantum-dot-sensitized solar cells (QDSCs) are promising solar-energy-conversion devices, as low-cost alternatives to the prevailing photovoltaic technologies. Compared with molecular dyes, nanocrystalline quantum dot (QD) light absorbers exhibit higher molar extinction coefficients and a tunable photoresponse. However, the power-conversion efficiencies (PCEs) of QDSCs are generally below 9.5 %, far behind their molecular sensitizer counterparts (up to 13 %). These low PCEs have been attributed to a large free-energy loss during sensitizer regeneration, energy loss during the charge-carrier transport and transfer processes, and inefficient charge separation at the QD/electrolyte interfaces, and various interfacial engineering strategies for enhancing the PCE and cell stability have been reported. Herein, we review recent progress in the interfacial engineering of QDSCs and discuss future prospects for the development of highly efficient and stable QDSCs.
    Mots-clés : nanostructures, NASCO, POLE 2, quantum dots, renewable resources, sensitizers, solar cells.


  • Y. Si, C. Grazon, G. Clavier, J. Rieger, J. F. Audibert, B. Sclavi, et R. Méallet-Renault, « Rapid and accurate detection of Escherichia coli growth by fluorescent pH-sensitive organic nanoparticles for high-throughput screening applications. », Biosensors & bioelectronics, vol. 75, p. 320-327, 2016.
    Résumé : Abstract: Rapid detection of bacterial growth is an important issue in the food industry and for medical research. Here we present a novel kind of...
    Mots-clés : POLE 4, POLYMERES.


  • S. Sladkevich, A. - L. Dupont, M. Sablier, D. Seghouane, et R. B. Cole, « Understanding paper degradation: identification of products of cellulosic paper decomposition at the wet-dry “tideline” interface using GC-MS », Analytical and Bioanalytical Chemistry, vol. 408, nᵒ 28, p. 8133-8147.
    Résumé : Cellulose paper degradation products forming in the “tideline” area at the wet-dry interface of pure cellulose paper were analyzed using gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) and high-resolution electrospray ionization-mass spectrometry (ESI-MS, LTQ Orbitrap) techniques. Different extraction protocols were employed in order to solubilize the products of oxidative cellulose decomposition, i.e., a direct solvent extraction or a more laborious chromophore release and identification (CRI) technique aiming to reveal products responsible for paper discoloration in the tideline area. Several groups of low molecular weight compounds were identified, suggesting a complex pathway of cellulose decomposition in the tidelines formed at the cellulose-water-oxygen interface. Our findings, namely the appearance of a wide range of linear saturated carboxylic acids (from formic to nonanoic), support the oxidative autocatalytic mechanism of decomposition. In addition, the identification of several furanic compounds (which can be, in part, responsible for paper discoloration) plus anhydro carbohydrate derivatives sheds more light on the pathways of cellulose decomposition. Most notably, the mechanisms of tideline formation in the presence of molecular oxygen appear surprisingly similar to pathways of pyrolytic cellulose degradation. More complex chromophore compounds were not detected in this study, thereby revealing a difference between this short-term tideline experiment and longer-term cellulose aging.
    Mots-clés : CSOB, POLE 3.


  • P. Srivastava, M. Ghasemi, N. Ray, A. Sarkar, J. Kocabova, S. Lachmanova, M. Hromadova, S. Boujday, S. Cauteruccio, P. Thakare, E. Licandro, C. Fosse, et M. Salmain, « Fischer carbene mediated covalent grafting of a peptide nucleic acid on gold surfaces and IR optical detection of DNA hybridization with a transition metalcarbonyl label », Applied Surface Science, vol. 385, p. 47-55, 2016.
    Résumé : Amine-reactive surfaces comprising N-hydroxysuccinimide ester groups as well as much more unusual Fischer alkoxymetallocarbene groups were generated on gold-coated surfaces via self-assembled monolayers of carboxy- and azido-terminated thiolates, respectively. These functions were further used to immobilize homothymine peptide nucleic acid (PNA) decamer in a covalent fashion involving the primary amine located at its N-terminus. These stepwise processes were monitored by polarization modulation reflection – absorption infrared spectroscopy (PM-RAIRS) that gave useful information on the molecular composition of the organic layers. PNA grafting and hybridization with complementary DNA strand were successfully transduced by quartz crystal microbalance (QCM) measurements. Unfortunately, attempts to transduce the hybridization optically by IR in a label-free fashion were inconclusive. Therefore we undertook to introduce an IR reporter group, namely a transition metalcarbonyl (TMC) entity at the 5′ terminus of complementary DNA. Evidence for the formation of PNA-DNA heteroduplex was brought by the presence of ν(CO) bands in the 2000 cm−1 region of the IR spectrum of the gold surface owing to the metalcarbonyl label.
    Mots-clés : 11-mercaptoundecanoic acid, 4-methylbenzylhydrylamine, AFM, Atomic force microscopy, Azide-alkyne cycloaddition, CHEMBIO, diisopropylethylamine, DIPEA, Fischer-type carbene complex, Genosensor, hexafluoroisopropanol, HFIP, MBHA, MUA, N, N', N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, nanoshaving, NS, ODN, oligonucleotide, PBS, Peptide nucleic acid, phosphate buffered saline, PM-RAIRS, PNA, polarization-modulation reflection-absorption infrared spectroscopy, POLE 3, qcm-d, quartz crystal microbalance with dissipation, SAM, SEA, Self-assembled monolayer, single strand DNA, ssDNA, Staphylococcal enterotoxin A, tapping mode, TEA, TM, TMC, transition metalcarbonyl, triethylamine, TSTU.


  • Y. - O. Teng, H. - Y. Zhao, J. Wang, H. Liu, M. - L. Gao, Y. Zhou, K. - L. Han, Z. - C. Fan, Y. - M. Zhang, H. Sun, et P. Yu, « Synthesis and anti-cancer activity evaluation of 5-(2-carboxyethenyl)-isatin derivatives », European Journal of Medicinal Chemistry, vol. 112, p. 145-156.
    Résumé : A series of novel di- or trisubstituted isatin derivatives were designed and synthesized in 5–6 steps in 25–45% overall yields. Their structures were confirmed by 1H NMR and 13C NMR as well as LC-MS. The anticancer activity of the fourty-three new isatin derivatives against human T lymphocyte cells Jurkat was evaluated by MTT assay in vitro. SAR study suggested that the combination of 1-benzyl and 5-[trans-2-(methoxycarbonyl)ethen-1-yl] substitution greatly enhanced their cytotoxic activity. Among them, compound 2h was shown to have a significant cytotoxic activity with an IC50 value of 0.03 μM, more than 330-fold higher than that of it's mother molecule isatin. Investigation of the cell morphology changes and annexin-V/PI staining study demonstrated that compound 2h inhibited the proliferation of Jurkat cells by inducing apoptosis. Since compound 2h induced the dissipation of mitochondrial membrane potential and the activation of caspase-3, it was obvious that compound 2h inhibited the proliferation of Jurkat cells through the mitochondrial apoptotic pathway. Other than this, compound 2h exerted inhibition effect to many other tumor cells and only showed weak cytotoxic to human normal cells suggesting that compound 2h possessed a broad range of anticancer spectrum and high safety to normal cells.
    Mots-clés : Anti-tumor agents, Apoptosis, GOBS, Isatin derivatives, Jurkat cells, POLE 3, proliferation.
  • C. Train, G. Rikken, et M. Verdaguer, « Non-Centrosymmetric Molecular Magnets », in Molecular Magnetic Materials: Concepts and Applications,, First Edition., Wiley-VCH Verlag GmbH & Co. KGaA., p. 299-321.
    Mots-clés : HorsPole, magnet, Magnetism, Verdaguer.


  • A. Vanitcha, C. Damelincourt, G. Gontard, N. Vanthuyne, V. Mouriès-Mansuy, et L. Fensterbank, « Bis-phosphine allene ligand: coordination chemistry and preliminary applications in catalysis », Chemical Communications, vol. 52, nᵒ 41, p. 6785-6788.
    Résumé : A 1,3-bis-diphenylphosphine allene can give rise to new coordination complexes with palladium, platinum and gold metals. These complexes were fully characterized by NMR, HRMS and X-ray diffraction analysis. For gold(I), the corresponding dinuclear complex has been used in a series of diagnostic catalytic reactions and gave promising preliminary results in asymmetric catalysis.
    Mots-clés : MACO, POLE 1.


  • E. Velasquez, J. Rieger, F. Stoffelbach, F. D'Agosto, M. Lansalot, P. - E. Dufils, et J. Vinas, « Surfactant-free poly(vinylidene chloride) latexes via one-pot RAFT-mediated aqueous polymerization », Polymer, vol. 106, p. 275-284.


  • G. Vincent, S. Cheli, R. Martinez Mallorquin, A. Abramovitch, S. Beauvière, C. Gomez, F. Brebion, I. Marek, M. Malacria, J. P. Goddard, et L. Fensterbank, « Oxidation of bis-sulfinyl carbanions as the pivot of ionic/radical tandem reactions », Comptes Rendus Chimie, vol. 19, nᵒ 3, p. 403-411.
    Mots-clés : Alkylidene bis-sulfoxide, conjugate addition, MACO, POLE 1, Radical, Red-ox, Tandem.

  • H. Wang, R. Xu, Y. Shi, L. Si, P. Jiao, Z. Fan, X. Han, X. Wu, X. Zhou, F. Yu, Y. Zhang, L. Zhang, L. Zhang, D. Zhou, et S. Xiao, « Design, synthesis and biological evaluation of novel L-ascorbic acid-conjugated pentacyclic triterpene derivatives as potential influenza virus entry inhibitors », European Journal of Medicinal Chemistry, vol. 110, p. 376-388.
    Résumé : Since the influenza viruses can rapidly evolve, it is urgently required to develop novel anti-influenza agents possessing a novel mechanism of action. In our previous study, two pentacyclic triterpene derivatives (Q8 and Y3) have been found to have anti-influenza virus entry activities. Keeping the potential synergy of biological activity of pentacyclic triterpenes and l-ascorbic acid in mind, we synthesized a series of novel l-ascorbic acid-conjugated pentacyclic triterpene derivatives (18-26, 29-31, 35-40 and 42-43). Moreover, we evaluated these novel compounds for their anti-influenza activities against A/WSN/33 virus in MDCK cells. Among all evaluated compounds, the 2,3-O,O-dibenzyl-6-deoxy-l-ascorbic acid-betulinic acid conjugate (30) showed the most significant anti-influenza activity with an EC50 of 8.7 μM, and no cytotoxic effects on MDCK cells were observed. Time-of-addition assay indicated that compound 30 acted at an early stage of the influenza life cycle. Further analyses revealed that influenza virus-induced hemagglutination of chicken red blood cells was inhibited by treatment of compound 30, and the interaction between the influenza hemagglutinin (HA) and compound 30 was determined by surface plasmon resonance (SPR) with a dissociation constant of KD = 3.76 μM. Finally, silico docking studies indicated that compound 30 and its derivative 31 were able to occupy the binding pocket of HA for sialic acid receptor. Collectively, these results suggested that l-ascorbic acid-conjugated pentacyclic triterpenes were promising anti-influenza entry inhibitors, and HA protein associated with viral entry was a promising drug target.
    Mots-clés : Animals, antiviral agents, Ascorbic Acid, Dogs, Drug design, Entry inhibitor, GOBS, Hemagglutinin, Hemagglutinin Glycoproteins, Influenza Virus, humans, Influenza A Virus, H1N1 Subtype, Influenza virus, Influenza, Human, l-ascorbic acid, Madin Darby Canine Kidney Cells, Molecular Docking Simulation, Orthomyxoviridae Infections, Pentacyclic triterpene, pentacyclic triterpenes, POLE 3, Sialic acid receptor, Virus Internalization.

  • H. Wang, Y. Cui, R. Zou, Z. Cheng, W. Yao, Y. Mao, et Y. Zhang, « Synthesis of oligosaccharides using per-O-trimethylsilyl-glycosyl iodides as glycosyl donor », Carbohydrate Research, vol. 427, p. 1-5.
    Résumé : Trimethylsilyl (TMS) protecting group has been found to be very useful for the simultaneous protection of both the glycosyl donor- and the acceptor-substrates in oligosaccharide synthesis. Thus, while the per-O-trimethylsilylated glycosyl iodides served as the glycosyl donor, those bearing selectively exposed primary hydroxyl groups were found suitable as the glycosyl acceptor for the reaction. The cheap and commercially available trialkylamine, triethylamine was found to be an effective promoter for the glycosylation. Importantly, the reaction was α-stereospecific and gave the products in 58%-78% yields.
    Mots-clés : Glycosyl iodide, GOBS, POLE 3, triethylamine, Trimethylsilyl group, α-Glycosylation.

  • X. - T. Wang, Z. - Y. Zhu, L. Zhao, H. - Q. Sun, M. Meng, J. - Y. Zhang, et Y. - M. Zhang, « Structural characterization and inhibition on α-d-glucosidase activity of non-starch polysaccharides from Fagopyrum tartaricum », Carbohydrate Polymers, vol. 153, p. 679-685.
    Résumé : In the present study, the crude polysaccharide was extracted from Fagopyrum tartaricum and purified by Sephadex G-25 and G-75 column to produce a polysaccharide fraction termed TBP-II. Its average molecular weight was 26kDa. The structural characterization of TBP-II was investigated by gas chromatography, periodate oxidation-Smith degradation, Methylation and NMR. Congo red was applied to explore its advanced structures. The results revealed that chemical composition and structural characteristic of TBP-II was mainly consisted of galactose, arabinose, xylose and glucose with a molar ratio of 0.7:1:6.3:74.2. The backbone of TBP-II was composed of (1→4)-linked α-d-glucopyranosyl (Glcp), while the branches comprised of (1→3)-linked α-d-glucopyranosyl (Glcp), (1→6)-linked α-d-galactopyranosyl (Galp) and (1→2,4)-linked α-d-rhamnopyranosyl (Rhap). The structure of TBP-II was 1,3 and 1,6-branched-galactorhamnoglucan that had a linear backbone of (1→4)-linked α-d-glucopyranose (Glcp). Using Congo red assay showed that it was absent of triple helix structure. The α-d-glucosidase inhibitory activity of TBP-II was determined using acarbose as positive control. The result showed that the inhibition rate depended on the concentration of polysaccharides.
    Mots-clés : Acetic acid (PubChem CID: 176), Butanol (PubChem CID: 263), Characterization, Chloroform (PubChem CID: 6212), Dimethyl sulfoxide (PubChem CID: 679), Ethanol (PubChem CID: 702), Fagopyrum tartaricum, GOBS, POLE 3, Polysaccharide, Sodium hydroxide (PubChem CID:14798), Trifluoroacetic acid(PubChem CID: 6422), α-d-glucosidase.


  • Y. Wang, M. - A. Richard, S. Top, P. M. Dansette, P. Pigeon, A. Vessières, D. Mansuy, et G. Jaouen, « Ferrocenyl Quinone Methide–Thiol Adducts as New Antiproliferative Agents: Synthesis, Metabolic Formation from Ferrociphenols, and Oxidative Transformation », Angewandte Chemie International Edition, vol. 128, nᵒ 35, p. 10587-10590, 2016.
    Résumé : Ferrociphenols (FCs) and their oxidized, electrophilic quinone methide metabolites (FC-QMs) are organometallic compounds related to tamoxifen that exhibit strong antiproliferative properties. To evaluate the reactivity of FC-QMs toward cellular nucleophiles, we studied their reaction with selected thiols. A series of new compounds resulting from the addition of these nucleophiles, the FC-SR adducts, were thus synthesized and completely characterized. Such conjugates are formed upon metabolism of FCs by liver microsomes in the presence of NADPH and thiols. Some of the FC-SR adducts exhibit antiproliferative properties comparable to those of their FC precursors. Under oxidizing conditions they either revert to their FC-QM precursors or transform into new quinone methides (QMs) containing the SR moiety, FC-SR-QM. These results provide interesting data about the reactivity and mechanism of antiproliferative effects of FCs, and also open the way to a new series of organometallic antitumor compounds.
    Mots-clés : CHEMBIO, Glutathion, Lebermikrosome, Michael-Addition, Organometallverbindungen, POLE 3, Tumortherapeutika.


  • Z. Xia, O. Khaled, V. Mouriès-Mansuy, C. Ollivier, et L. Fensterbank, « Dual Photoredox/Gold Catalysis Arylative Cyclization of o-Alkynylphenols with Aryldiazonium Salts: A Flexible Synthesis of Benzofurans », The Journal of Organic Chemistry, vol. 81, nᵒ 16, p. 7182-7190.
    Résumé : A new method for the arylative cyclization of o-alkynylphenols with aryldiazonium salts via dual photoredox/gold catalysis is described. The reaction proceeds smoothly at room temperature in the absence of base and/or additives and offers an efficient approach to benzofuran derivatives. The scope of the transformation is wide, and the limitations are discussed. The reaction is proposed to proceed through a photoredox-promoted generation of a vinylgold(III) intermediate that undergoes reductive elimination to provide the heterocyclic coupling adduct.
    Mots-clés : MACO, POLE 1.

  • S. Xiao, L. Si, Z. Tian, P. Jiao, Z. Fan, K. Meng, X. Zhou, H. Wang, R. Xu, X. Han, G. Fu, Y. Zhang, L. Zhang, et D. Zhou, « Pentacyclic triterpenes grafted on CD cores to interfere with influenza virus entry: A dramatic multivalent effect », Biomaterials, vol. 78, p. 74-85.
    Résumé : Multivalent effect plays an important role in biological processes, particularly in the specific recognition of virus with its host cell during the first step of infection. Here we report the synthesis of multivalent pentacyclic triterpene grafted on cyclodextrin core and potency of against influenza entry activity. Nine star-shaped compounds containing six, seven and eight pentacyclic triterpene pharmacophore on cyclodextrin scaffold were prepared by way of copper-catalyzed azide-alkyl cycloaddition reaction under microwave activation. Some of the multimers exhibited much potent antiviral activity against H1N1 virus (A/WSN/33), even equivalent or superior to oseltamivir. The most active compound 31, a heptavalent oleanolic acid-β-cyclodextrin conjugate, shows an up to 125-fold potency enhancement by its IC50 value over the corresponding monovalent conjugate and oleanolic acid, disclosing a clear multivalent effect. Further studies show that three compounds 31-33 exhibited broad spectrum inhibitory activity against other two human influenza A/JX/312 (H3N2) and A/HN/1222 (H3N2) viruses with the IC50 values at 2.47-14.90 μM. Most importantly, we found that compound 31, one of the best representative conjugate, binds tightly to the viral envelope hemagglutinin with a dissociation constant of KD = 2.08 μM, disrupting the interaction of hemagglutinin with the sialic acid receptor and thus the attachment of viruses to host cells. Our study might establish a strategy for the design of new pharmaceutical agents based on multivalency so as to block influenza virus entry into host cells.
    Mots-clés : Animals, Dogs, Entry inhibitor, GOBS, Hemagglutinin, Influenza A Virus, H1N1 Subtype, Influenza virus, Madin Darby Canine Kidney Cells, Membrane Fusion, Multivalent effect, Pentacyclic triterpene, POLE 3, Triterpenes.


  • S. Xiao, Q. Wang, L. Si, X. Zhou, Y. Zhang, L. Zhang, et D. Zhou, « Synthesis and biological evaluation of novel pentacyclic triterpene α-cyclodextrin conjugates as HCV entry inhibitors », European Journal of Medicinal Chemistry, vol. 124, p. 1-9.
    Résumé : Hepatitis C virus (HCV) entry is a key target for the treatment of chronic HCV infection. In our continuing efforts to identify novel potential anti-HCV entry inhibitors, a series of water-soluble triazole-bridged α-cyclodextrin-pentacyclic triterpene conjugates were easily synthesized with moderate to good yields. These novel compounds were fully identified and characterized by 1D and 2D NMR spectroscopy and ESI-HRMS. The anti-HCV entry activities were determined based on HCVpp/VSVGpp entry assays. The best results were found for compounds 15 and 18, which displayed the most promising anti-HCV entry activities with average IC50 values of 1.18 μM and 0.25 μM, respectively. In addition, the in vitro cytotoxicity activity of the two compounds against MDCK cells showed no toxicity at 100 μM. Five different binding assays were set up to identify the action mechanism. The results showed that the compounds exert their inhibitory activity at the post-binding step and subsequently prevent virus entry.
    Mots-clés : click chemistry, GOBS, HCV entry inhibitor, Pentacyclic triterpene, POLE 3, α-Cyclodextrin.


  • Y. Xiao, X. Su, L. Sosa-Vargas, E. Lacaze, B. Heinrich, B. Donnio, D. Kreher, F. Mathevet, et A. - J. Attias, « Chemical engineering of donor–acceptor liquid crystalline dyads and triads for the controlled nanostructuration of organic semiconductors », Crystal Engineering Communications, vol. 18, nᵒ 25, p. 4787-4798, juin 2016.
    Résumé : Multi-segregated columnar structures provide a geometrically ideal scheme for ambipolar organic semiconductors, but are not easy to design. A set of novel materials with dyad and triad architectures based on 2 different discotic cores is reported and the conditions of emergence of such complex structures are investigated. The designed molecules associate together electron-donor triphenylene cores (D) and perylene or naphthalene diimides as acceptor moieties (A), both entities being linked via alkyl chain spacers. The evaluation in solution of their HOMO/LUMO energy levels by cyclic voltammetry demonstrates the preservation of the individual features of the D and A units. Their thermal and self-organization behaviors were studied by polarized-light optical microscopy, differential scanning calorimetry, temperature-dependent small-angle X-ray scattering and dilatometry, which permitted detailed investigation of the self-organization behaviour. These D–A compounds turned out to spontaneously self-organize into columnar mesophases at room temperature, with the D and A moieties segregated into either alternated stacks within mixed columns or in distinct columns, the latter providing an ideal configuration for 1D hole and electron transport pathways. In view of potential applications of the triad/dyad template, thin films of these self-organized materials were also probed by atomic force microscopy and grazing incidence X-ray scattering.
    Mots-clés : POLE 4, POLYMERES.

  • Y. Yang, J. He, Y. Suo, L. Lv, J. Wang, C. Huo, Z. Zheng, Z. Wang, J. Li, W. Sun, et Y. Zhang, « Anti-inflammatory effect of taurocholate on TNBS-induced ulcerative colitis in mice », Biomedicine & Pharmacotherapy = Biomedecine & Pharmacotherapie, vol. 81, p. 424-430.
    Résumé : Taurocholate is a natural conjugated bile acid. The aim of this study was to evaluate the anti-inflammatory effect of taurocholate in TNBS-induced ulcerative colitis in mice. The colitis were induced by rectal administration of TNBS. After 24h, the experimental animals were treated with sulfasalazine (SASP, 500mg/kg/day) and taurocholate (20, 40 and 60mg/kg) for 7 consecutive days. The anti-inflammatory effects of taurocholate for colitis were assessed by body weight, colonic weight and length, macroscopic scores, and histopathological examinations. In addition, the colonic tissue levels of myeloperoxidase (MPO) activity, interleukin (IL)-1β, interferon (IFN-γ) and tumour necrosis factor-α (TNF-α) were also determined to assess the effect of taurocholate. Compared with the model group, treatment with taurocholate (20, 40 and 60mg/kg) significantly inhibited the body weight loss, improved colonic weight and length, and decreased macroscopic and histopathological scores. Furthermore, the activity accumulation of MPO and the colonic tissue levels of IL-1β, IFN-γ and TNF-α were also decreased by administration of taurocholate. All the findings of this study suggested that taurocholate has the anti-inflammatory effect in ulcerative colitis in mice and indicated it as a good candidate to treat inflammatory bowel disease.
    Mots-clés : Anti-inflammatory effect, Cytokines, GOBS, POLE 3, Taurocholate, TNBS, Ulcerative colitis.

  • Y. Yang, J. He, Y. Suo, Z. Zheng, J. Wang, L. Lv, C. Huo, Z. Wang, J. Li, W. Sun, et Y. Zhang, « Tauroursodeoxycholate improves 2,4,6-trinitrobenzenesulfonic acid-induced experimental acute ulcerative colitis in mice », International Immunopharmacology, vol. 36, p. 271-276.
    Résumé : Ulcerative colitis is a chronic nonspecific inflammatory disease of unknown cause. The aim of this study was to evaluate the anti-inflammatory effect of tauroursodeoxycholate in 2, 4, 6-trinitrobenzenesulfonic acid-induced experimental colitis in mice. After the induction of colitis for 24h, the mice were administrated orally with tauroursodeoxycholate (20, 40 and 60mg/kg) and sulfasalazine (500mg/kg) by gavage for 7 consecutive days. The inhibition effects were evaluated by the body of weight change, survival rate, macroscopical and histological evaluations. Besides, myeloperoxidase (MPO) activity, interleukin (IL)-1β, interferon (IFN)-γ and tumour necrosis factor-α (TNF-α) in colon tissue were also determined by enzyme-linked immunosorbent assay. Treatment with different doses of tauroursodeoxycholate (20, 40 and 60mg/kg) significantly improved the body weight change, decreased the macroscopic and histopathological scores. Compared with the model group, the accumulation of MPO activity, the colonic tissue levels of IL-1β, IFN-γ and TNF-α were significantly reduced in the tauroursodeoxycholate treated groups. Moreover, tauroursodeoxycholate assuaged the symptoms of colitis. These results suggested that tauroursodeoxycholate has an anti-inflammatory effect in TNBS-induced ulcerative colitis in mice.
    Mots-clés : Cytokines, GOBS, POLE 3, Tauroursodeoxycholate, Trinitrobenzenesulfonic acid, Ulcerative colitis.


  • E. Zaborova, A. Six, H. Amokrane, F. Charra, F. Mathevet, A. - J. Attias, et D. Kreher, « Synthesis of new dithia[3.3]parapara- and metapara-cyclophane based tectons: toward an universal surface-confined 2D/3D molecular binding motif », Pure and Applied Chemistry, vol. 88, nᵒ 10-11, p. 1005–1025.
    Résumé : A series of new paraphenylene-based 2D and 3D tectons has been designed for supramolecular self-assembly on both HOPG and Au. Several versatile chemical strategies have been developed to reach the target tectons, bearing either metaparacyclophane or paraparacyclophane cores, functionalized or not, allowing the obtention soon of more complex 3D tectons bearing functional unit such as chromophores. Moreover, preliminary STM results show that these compounds can successfully self-assemble both on HOPG and Au(111) substrates at liquid-solid interface, encouraging us in finding an universal surface-confined 2D/3D molecular binding motif. This feature combined with the preliminary results of the self-assembly on the plasmonic substrate Au(111) open-up opportunities in the field of Nanoscience.
    Mots-clés : POLE 4, POLYMERES.

  • Y. Zhang, D. Lu, M. Sollogoub, et Y. Zhang, « Carbohydrate–carbohydrate interaction: from hypothesis to confirmation », in Carbohydrate Chemistry, p. 238-254.
    Résumé : Carbohydrates play important roles in a wide range of biological processes. Since the first hypothesis about carbohydrate–carbohydrate interaction (CCI) was proposed by Hakomori et al., an increasing interest has been placed on CCI, using a variety of techniques. Based on all these studies, Lewisx–Lewisx interaction (a typical CCI) has been now confirmed to be specific, homotypic, and mediated by the presence of divalent cations such as Ca2+. In this review, a detailed overview of the process from hypothesis to confirmation of carbohydrate–carbohydrate interaction is summarized.
    Mots-clés : GOBS, POLE 3.

  • Y. Zhou, H. - Y. Zhao, D. Jiang, L. - Y. Wang, C. Xiang, S. - P. Wen, Z. - C. Fan, Y. - M. Zhang, N. Guo, Y. - O. Teng, et P. Yu, « Low toxic and high soluble camptothecin derivative 2-47 effectively induces apoptosis of tumor cells in vitro », Biochemical and Biophysical Research Communications, vol. 472, nᵒ 3, p. 477-481.
    Résumé : The cytotoxic activity of camptothecin derivatives is so high that these compounds need to be further modified before their successful application as anti-cancer agents clinically. In this study, we reported the synthesis and biological evaluation of a novel camptothecin derivative called compound 2-47. The changes in structure did not reduce its activity to inhibit DNA topoisomerase I. Compound 2-47 induced apoptosis of many tumor cells including leukemia cells K562, Jurkat, HL-60, breast cancer cell BT-549, colon cancer cell HT-29 and liver cancer cell HepG2 with a half maximal inhibitory concentration (IC50) of 2- to 3-fold lower than HCPT as a control. In particular, 2-47 inhibited the proliferation of Jurkat cells with an IC50 of as low as 40 nM. By making use of Jurkat cell as a model, following treatment of Jurkat cells, compound 2-47 activated caspase-3 and PARP, resulting in a decreased Bcl-2/Bax ratio. These data showed that compound 2-47 induces Jurkat cell death through the mitochondrial apoptotic pathway. In addition, compound 2-47 showed a decreased cytotoxic activity against normal cells and an improved solubility in low-polar solvent. For example, compound 2-47 solutes in CHCl3 130-fold higher than HCPT. Taken together, our data demonstrated that camptothecin derivative 2-47 notably inhibits the tumor cell proliferation through mitochondrial-mediated apoptosis in vitro.
    Mots-clés : Apoptosis, camptothecin, Camptothecin derivatives, Cell Line, Tumor, DNA topoisomerase I, Dose-Response Relationship, Drug, Drug design, GOBS, humans, Neoplasms, Experimental, POLE 3, Solubility, Treatment Outcome.

  • X. Zhu, M. Sollogoub, et Y. Zhang, « Biological applications of hydrophilic C60 derivatives (hC60s)- a structural perspective », European Journal of Medicinal Chemistry, vol. 115, p. 438-452.
    Résumé : Reactive oxygen species (ROS) generation and radical scavenging are dual properties of hydrophilic C60 derivatives (hC60s). hC60s eliminate radicals in dark, while they produce reactive oxygen species (ROS) in the presence of irradiation and oxygen. Compared to the pristine C60 suspension, the aqueous solution of hC60s is easier to handle in vivo. hC60s are diverse and could be placed into two general categories: covalently modified C60 derivatives and pristine C60 solubilized non-covalently by macromolecules. In order to present in detail, the above categories are broken down into 8 parts: C60(OH)n, C60 with carboxylic acid, C60 with quaternary ammonium salts, C60 with peptide, C60 containing sugar, C60 modified covalently or non-covalently solubilized by cyclodextrins (CDs), pristine C60 delivered by liposomes, functionalized C60-polymer and pristine C60 solubilized by polymer. Each hC60 shows the propensity to be ROS producer or radical scavenger. This preference is dependent on hC60s structures. For example, major application of C60(OH)n is radical scavenger, while pristine C60/γ-CD complex usually serves as ROS producer. In addition, the electron acceptability and innate hydrophobic surface confer hC60s with O2 uptake inhibition, HIV inhibition and membrane permeability. In this review, we summarize the preparation methods and biological applications of hC60s according to the structures.
    Mots-clés : Biological applications, GOBS, Hydrophilic C(60) derivatives, POLE 3, Radical scavenger, ROS generation.


  • Z. - Y. Zhu, L. Chen, F. Liu, L. - J. Chen, M. Meng, H. - Q. Sun, et Y. - M. Zhang, « Preparation and activity evaluation of chrysin-β-d-galactopyranoside », Archives of Pharmacal Research, vol. 39, nᵒ 10, p. 1433-1440.
    Résumé : Chrysin-β-d-galactopyranoside was efficiently synthesized, evaluated for its inhibitory activities against H22 cell lines compared with chrysin, the scavenging of hydroxyl radical, DPPH radical and superoxide anion, inhibitory effect against bacteria and fungi. The structures of all compounds were fully characterized by spectroscopic data (NMR, MS). The anti-tumor, antioxidant and antimicrobial activities of chrysin-β-d-galactopyranoside were proved to be enhanced significantly compared with chrysin.
    Mots-clés : GOBS, POLE 3.

  • Z. - Y. Zhu, D. Cui, H. Gao, F. - Y. Dong, X. -cui Liu, F. Liu, L. Chen, et Y. -min Zhang, « Efficient synthesis and activity of beneficial intestinal flora of two lactulose-derived oligosaccharides », European Journal of Medicinal Chemistry, vol. 114, p. 8-13.
    Résumé : Lactulose is considered as a prebiotic because it promotes the intestinal p

    roliferation of Lactobacillus acidophilus which is added to various milk products. Moreover, lactulose is used in pharmaceuticals as a gentle laxative and to treat hyperammonemia. This study was aimed at the total synthesis of two Lactulose-derived oligosaccharides: one is 3-O-β-d-galactopyranosyl-d-fructose, d-fructose and β-d-galactose bounded together with β-1,3-glycosidic bound, the other is 1-O-β-d-galactopyranosyl-d-fructose, d-fructose and β-d-galactose bounded together with β-1,1-glycosidic bound, which were accomplished in seven steps from d-fructose and β-d-galactose and every step of yield above 75%. This synthetic route provided a practical and effective synthetic strategy for galactooligosaccharides, starting from commercially available monosaccharides. Then we evaluated on their prebiotic properties in the search for potential agents of regulating and improving the intestinal flora of human. The result showed that the prebiotic properties of Lactulose-derived oligosaccharides was much better than Lactulose. Among them, 3-O-β-d-galactopyranosyl-d-fructose displayed the most potent activity of proliferation of L. acidophilus.
    Mots-clés : GOBS, Lactobacillus acidophilus, Lactulose, Lactulose-derived oligosaccharides, POLE 3, Prebiotics.

  • Z. - Y. Zhu, F. Dong, X. Liu, Q. Lv, Y. Yang, F. Liu, L. Chen, T. Wang, Z. Wang, et Y. Zhang, « Effects of extraction methods on the yield, chemical structure and anti-tumor activity of polysaccharides from Cordyceps gunnii mycelia », Carbohydrate Polymers, vol. 140, p. 461-471.
    Résumé : This study was to investigate the effects of different extraction methods on the yield, chemical structure and antitumor activity of polysaccharides from Cordyceps gunnii (C. gunnii) mycelia. Five extraction methods were used to extract crude polysaccharides (CPS), which include room-temperature water extraction (RWE), hot-water extraction (HWE), microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and cellulase-assisted extraction (CAE). Then Sephadex G-100 was used for purification of CPS. As a result, the antitumor activities of CPS and PPS on S180 cells were evaluated. Five CPS and purified polysaccharides (PPS) were obtained. The yield of CPS by microwave-assisted extraction (CPSMAE) was the highest and its anti-tumor activity was the best and its macromolecular polysaccharide (3000-1000kDa) ratio was the largest. The PPS had the same monosaccharide composition, but their obvious difference was in the antitumor activity and the physicochemical characteristics, such as intrinsic viscosity, specific rotation, scanning electron microscopy and circular dichroism spectra.
    Mots-clés : Acetic acid (PubChem CID: 176), Acetic anhydride (PubChem CID: 7918), Antitumor activity, Cellulase (PubChem CID: 3084041), Chemical structure, Chloroform (PubChem CID: 6212), Cordyceps gunnii, Dimethylsulfoxide (PubChem CID: 21912085), Ethanol (PubChem CID: 702), Extraction method, GOBS, Methanol (PubChem CID: 887), N-butyl alcohol (PubChem CID: 263), POLE 3, Polysaccharide, Pyridine (PubChem CID: 1049), Trifluoroacetic acid (PubChem CID: 6422).


  • Z. - Y. Zhu, M. - Z. Guo, F. Liu, Y. Luo, L. Chen, M. Meng, X. - T. Wang, et Y. - M. Zhang, « Preparation and inhibition on α-d-glucosidase of low molecular weight polysaccharide from Cordyceps militaris », International Journal of Biological Macromolecules, vol. 93, Part A, p. 27-33.
    Résumé : The structural properties and the inhibition on α-d-glucosidase activity of the low molecular weight (LCMPs-II) obtained from the optimized acid hydrolysis of the Cordyceps militaris polysaccharides (CMPs) were investigated in this paper. The LCMPs-II with a molecular weight of 28 KDa mainly composed of rhamnose, xylose and glucose with the molar ratio of 1: 2.19: 6.73 was separated from LCMPs-I which was the acid hydrolysis product of CMPs by chromatography on Sephadex G-100 column. The solubility of LCMPs-II was tested to be 32.12 ± 1.05 g in 100 mL distilled water under 25 °C. Its solubility was almost as twice as that of CMPs. Afterward, the structural features of LCMPs-II was investigated by a combination of chemical and instrumental analysis such as the specific rotation determination, FT-IR, periodate oxidation-Smith degradation, Congo-red, GC, scanning electron microscope and NMR. The results showed that the optical rotation of LCMPs-II was +25° and it was 1,3-branched-rhamnoxyloglucan which had a linear backbone of (1 → 4)-linked α-d-glucopyranose (α-d-Glcp units).
    Mots-clés : Acid hydrolysis, Cordyceps militaris, GOBS, Inhibitory activity, POLE 3.
  • Z. - Y. Zhu, Y. Li, H. - Q. Sun, L. - J. Chen, Y. - L. Tang, X. - C. Liu, et Y. - M. Zhang, « Screening of Cordyceps Strains and Optimization of Its Solid-State Fermentation Conditions on Bioconversion of Astragalus Residue », Cellulose Chemistry and Technology, vol. 50, nᵒ 2, p. 257-263.
    Résumé : The Astragalus residue is produced after the extraction of Astragalus polysaccharides (APS). In Astragalus residue, the main ingredient is crude fiber. The crude fiber is considered to be the main source for green chemicals, bio-fuels and bio-based products. In this study, we used five kinds of Cordyceps as fermentation strains and Astragalus residue as fermentation substrate for solid-state fermentation. Crude fiber degradation rate after fermentation was considered as the main indicator. The mannitol content and soluble sugar content of the fermentation product were used as secondary indicators. The experiments were carried out by screening the solid-state fermentation strains, optimizing the solid-state fermentation conditions and studying the pilot-scale cultivation of solid-state fermentation. From the results of screening the solid-state fermentation strains, we selected the Paecilomyces bainier strain for further investigation. The fermentation conditions were optimized with four single factors, including fermentation time, solid fermentation inoculum size, pH value of solid medium and fermentation substrate thickness. The single-factor tests revealed that the optimum conditions were the following: fermentation time of 25 days, fermentation substrate pH of the initial value, inoculum of 20% and fermentation substrate thickness of 1.0 cm.
    Mots-clés : Astragalus residue, Cordyceps Paecilomyces sinensis, GOBS, POLE 3, solid-state fermentation.


  • Z. - Y. Zhu, F. Liu, H. Gao, H. Sun, M. Meng, et Y. - M. Zhang, « Synthesis, characterization and antioxidant activity of selenium polysaccharide from Cordyceps militaris », International Journal of Biological Macromolecules, vol. 93, Part A, p. 1090-1099.
    Résumé : A purified selenium-containing derivatives of Cordyceps militaris polysaccharide synthesized using H2SeO3/HNO3 and BaCl2 as a catalyst was investigated in this paper. The reaction condition was optimized by selecting different reaction temperature and period. Afterward, the one with the highest Se content was purified by ultra-filtration device with a molecular cut off size of 10KDa. Followed by its structural characterizations. Results of IFR and 13C NMR spectroscopy indicated that C-6 substitution was predominant in selenized polysaccharide. The modified polysaccharide with molecular weight of 1998 KDa was mainly consisted of mannose, glucose and galactose in the mole ratios of with the mole ratios of 1:28.63:1.41. Thermogravimetric and morphological analyses of the samples were carried out by AFS, SEM and AFM. In addition, the in vitro antioxidant results suggested that selenium-containing polysaccharide should be applied as a novel selenium source in dietary supplements, with potent antioxidant properties.
    Mots-clés : Cordyceps militaris, GOBS, POLE 3, polysaccharides, Selenize, structure.

  • Z. - Y. Zhu, X. - C. Liu, F. - Y. Dong, M. - Z. Guo, X. - T. Wang, Z. Wang, et Y. - M. Zhang, « Influence of fermentation conditions on polysaccharide production and the activities of enzymes involved in the polysaccharide synthesis of Cordyceps militaris », Applied Microbiology and Biotechnology, vol. 100, nᵒ 9, p. 3909-3921.
    Résumé : The influence of different fermentation conditions on intracellular polysaccharide (IPS) production and activities of the phosphoglucomutase (PGM), UDPG-pyrophosphorylase (UGP), phosphoglucose isomerase (PGI), UDPG-dehydrogenase (UGD), and glucokinase (GK) implicated in metabolite synthesis in Cordyceps militaris was evaluated. The highest IPS production (327.57 ± 6.27 mg/100 mL) was obtained when the strain was grown in the optimal medium containing glucose (40 g · L(-1)), beef extract (10 g · L(-1)), and CaCO3 (0.5 g · L(-1)), and the initial pH and temperature were 7 and 25 °C, respectively. The activities of PGM, UGP, and PGI were proved to be influenced by the fermentation conditions. A strong correlation between the activities of these enzymes and the production of IPS was found. The transcription level of the pgm gene (encoding PGM) was 1.049 times and 1.467 times compared to the ugp gene and pgi gene (encoding UGP and PGI), respectively, in the optimal culture medium. This result indicated that PGM might be the highly key enzyme to regulate the biosynthesis of IPS of C. militaris in a liquid-submerged culture. Our study might be helpful for further research on the pathway of polysaccharide biosynthesis aimed to improve the IPS production of C. militaris.
    Mots-clés : biosynthesis, Cordyceps militaris, Enzyme activity, GOBS, Intracellular polysaccharides, POLE 3.

  • Z. - Y. Zhu, X. - C. Liu, X. - N. Fang, H. - Q. Sun, X. - Y. Yang, et Y. - M. Zhang, « Structural characterization and anti-tumor activity of polysaccharide produced by Hirsutella sinensis », International Journal of Biological Macromolecules, vol. 82, p. 959-966.
    Résumé : HSP-III, a novel homogeneous polysaccharide with 513.89 kDa molecular weight, was fractionated from submerged cultures of Hirsutella sinensis by Sevag and chromatography on Sephadex G-100 column. The total sugar content of HSP-III was amounted to 89.87%. Based on the results of high performance gel permeation chromatogram (HPGPC), FT-IR, NMR spectroscopy, GC, periodate oxidation-smith degradation and methylation analysis, it showed that HSP-III was mainly composed of mannose and galactose, and a small amount of rhamnose, arabinose, xylose, and glucose. The molar ratio of Rha:Ara:Xyl:Man:Glu:Gal was 1.00:2.44:13.11:74.13:13.80:54.39. The main chain of HSP-III was majorly composed of (1→3) glucose. The tumor inhibition ratio on H22 cell was 79.04% at 100 μg/mL of HSP-III.
    Mots-clés : Anti-tumor activity, Antineoplastic Agents, Ascomycota, Cell Line, Tumor, Cell Survival, Fungal Polysaccharides, GOBS, humans, Magnetic Resonance Spectroscopy, Methylation, Molecular Weight, Periodic Acid, POLE 3, Polysaccharide, Spectroscopy, Fourier Transform Infrared, structure, Structure-Activity Relationship.

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