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29 results on '"ND Zelinsky Institute of Organic Chemistry [Moscow, Russia]"'

1. Germanium-centered ion radicals

Author

Mikhail P. Egorov, Viatcheslav V. Jouikov, Elena N. Nikolaevskaya, Mikhail A. Syroeshkin, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Organogermanium compounds, Catenates, Germatranes, HOMO, LUMO, Cyclic voltammetry, Frontier molecular orbitals, Ion radicals, Oxidative addition, Anion radicals, Ionization energy, Redox catalysis, Digermenes, UV-Vis spectroscopy, DFT, Main group metal catalysis, Germylenes, Electron transfer, Electron affinity, [CHIM]Chemical Sciences, EPR, Cation radicals, SOMO
Abstract

International audience; Primary products of single-electron transfer to/from organogermanium compounds (anion radicals and cation radicals issued from reduction and oxidation, respectively) and their chemistry are considered through different approaches to the generation and study of organogermanium ion radicals; the relationship between the data obtained by various methods, including voltammetry, UV-Vis and photoelectron spectroscopy, and the possibilities of modern computational methods in this field are discussed. The chapter provides a systematized overview of literature data on the ion radicals of tetravalent organogermanium compounds, including germanium catenates, low-valent (germylenes, digermenes, phosphagermene) and hypercoordinated germanium derivatives, including germatranes. General aspects of the ion radical chemistry of organogermanium compounds, as well as its premise for the actively developing area of germylene catalysis in organic and organoelement synthesis are considered along with the possible prospects for the development of this field. © 2023 John Wiley and Sons, Inc. All rights reserved.

Published
2023
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2. Electrochemical Etching of Germanium in Ionic Liquids without the Use of Toxic and Corrosive Reagents

Author

Mikhail P. Egorov, Anna Ya. Kozmenkova, Viatcheslav Jouikov, Alexey S. Galushko, Mikhail A. Syroeshkin, Sofia D. Farafonova, Evgeniya A. Saverina, Valentine P. Ananikov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Mendeleev University of Chemical Technology of Russia, Nansen International Environmental and Remote Sensing Center - Russia (NIIERSC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), RFBR Russian Foundation for Basic Research (RFBR), Moscow City Government [21-33-70070], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, Energy Engineering and Power Technology, chemistry.chemical_element, Germanium, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, ionic liquids, Biomaterials, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, Electrochemical etching, Renewable Energy, Sustainability and the Environment, electrochemical etching, 021001 nanoscience & nanotechnology, 0104 chemical sciences, germanium, environmental compatibility, Chemical engineering, chemistry, Reagent, Ionic liquid, 0210 nano-technology, Porous medium, porous materials
Abstract

International audience; For the first time, the possibility of obtaining porous germanium from both single-crystal and polycrystalline starting materials using environmentally friendly (in contrast to the commonly used HF and HCl) imidazolium ionic liquids (IL) was shown. It was demonstrated that pore formation depended significantly on the viscosity of the IL, on the etching current density and etching time, and on defects and imperfections of the substrate surface. By varying these parameters, the rates of two competing processes - formation and growth of pores and electropolishing - could be adjusted, consequently allowing germanium with a various structured surface, including a porous surface. In particular, using a more viscous IL (for example, [BMIM][PF6] versus [BMIM][BF4]) made it possible to reduce the rate of dissolution of the germanium dioxide surface layer; as a result, the formation and growth of pores became a dominant process. At the same time, the dissolution rate of the already formed porous layer (electropolishing) increased with the etching current density and the number of defects and imperfections of the germanium surface.

Published
2021
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3. New Magnetic and Luminescent Dy(III) and Dy(III)/Y(III) Based Tetranuclear Silsesquioxane Cages

Author

Alena N. Kulakova, Luís D. Carlos, Karina Nigoghossian, Victor N. Khrustalev, Yannick Guari, Alexey N. Bilyachenko, Jérôme Long, Joulia Larionova, Elena S. Shubina, Gautier Félix, A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Peoples Friendship University of Russia [RUDN University] (RUDN), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Department of Physics and CICECO, and Universidade de Aveiro

Subjects
Inorganic Chemistry, chemistry.chemical_compound, chemistry, 010405 organic chemistry, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 010402 general chemistry, Luminescence, Hybrid material, 01 natural sciences, Silsesquioxane, 0104 chemical sciences, 3. Good health
Abstract

International audience; We report here the synthesis, structure, luminescence, and magnetic properties of three new cage-like tetranuclear silsesquioxanes (Et 4 N) 2 [(PhSiO 1..5) 8 (Y 0.75 Dy 0.25 O 1.5) 4 (O)(NO 2.5) 6 (EtOH) 2 (MeCN) 2 ] and (Cat) 2 [(PhSiO 1.5) 8 (DyO 1.5) 4 (O)(NO 2.5) 6 (EtOH) 2 (MeCN) 2 ] (Cat=Et 4 N or Ph 4 P). They present a characteristic greenyellow emission. The Y 3+ /Dy 3+ compound displays in addition a field-induced Single Molecule Magnet (SMM) behavior making it the first reported bifunctional magneto-luminescent silsesquioxane.

Published
2021
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4. Porous Silicon Preparation by Electrochemical Etching in Ionic Liquids

Author

Valentine P. Ananikov, Evgeniya A. Saverina, M. V. Gorbachevskii, Mikhail A. Syroeshkin, Daria Yu. Zinchenko, Viatcheslav Jouikov, Mikhail P. Egorov, Alexey S. Galushko, Sofia D. Farafonova, Andrei A. Novikov, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Gubkin Russian State University, Russian Science Foundation (RSF) [17-73-20281], Ministry of Science and Higher Education of the Russian Federation [0768-2020-0007], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Green chemistry, HF-free, Materials science, Silicon, General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Porous silicon, 01 natural sciences, Fluorescence, chemistry.chemical_compound, Electrochemical etching, Etching (microfabrication), [CHIM]Chemical Sciences, Environmental Chemistry, Renewable Energy, Sustainability and the Environment, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Anode, Confocal microscopy, Chemical engineering, chemistry, Ionic liquid, 0210 nano-technology
Abstract

International audience; Anodic etching of n-type {111} silicon in ionic liquid (IL) systems ([RMIM] [X], R = H, Bu; X = BF4-, PF6-), realized under galvanostatic conditions and at room temperature, allowed the formation of porous silicon surfaces with different pore morphology depending on the etching time, current density, and the IL used. The study of the effect of water content in IL on the etching process has shown a water content of 1% to be optimal. The role of the anion on the etching process was elucidated using 1-methylimidazolium tetrafluoroborate ([HMIM][BF4]) and 1-methylimidazolium hexafluorophosphate ([HMIM] [PF6]) IL systems. [HMIM] [BF4] was found to be most efficient for the formation of a silicon nanostructured array with a pore size of 30-80 nm. The thusprepared porous silicon samples show fluorescence in blue light (475 nm). The NMR spectra of [HMIM] [BF4] ionic liquid before and after etching do not show noticeable changes, which makes it possible to consider this IL as a potentially recyclable etching agent.

Published
2020
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5. 2‐Carboxyethylgermanium Sesquioxide as A Promising Anode Material for Li‐Ion Batteries

Author

Evgeniya A. Saverina, Viatcheslav Jouikov, Pavel A. Troshin, P. V. Stishenko, Mikhail P. Egorov, Roman R. Kapaev, Victoriya A. Balycheva, Mikhail A. Syroeshkin, Alexey S. Galushko, Valentine P. Ananikov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 17-73-20281, Russian Science Foundation, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, General Chemical Engineering, Substituent, Li-ion batteries, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Nanomaterials, anode materials, Sesquioxide, chemistry.chemical_compound, [CHIM]Chemical Sciences, Environmental Chemistry, General Materials Science, Graphite, chemistry.chemical_classification, Aqueous solution, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Anode, germanium, General Energy, chemistry, Chemical engineering, 0210 nano-technology
Abstract

International audience; Various forms of germanium and germanium-containing compounds and materials are actively investigated as energy-intensive alternatives to graphite as the anode of lithium-ion batteries. The most accessible form-germanium dioxide-has the structure of a 3D polymer, which accounts for its rapid destruction during cycling, and requires the development of further approaches to the production of nanomaterials and various composites based on it. For the first time, we propose here the strategy of using 2-carboxyethylgermanium sesquioxide ([O GeCH CH CO H] , 2-CEGS), in lieu of GeO , as a promising, energy-intensive, and stable new source system for building lithium-ion anodes. Due to the presence of the organic substituent, the formed polymer has a 1D or a 2D space organization, which facilitates the reversible penetration of lithium into its structure. 2-CEGS is common and commercially available, completely safe and non-toxic, insoluble in organic solvents (which is important for battery use) but soluble in water (which is convenient for manufacturing diverse materials from it). This paper reports the preparation of micro- (flower-shaped agglomerates of ≈1 μm thick plates) and nanoformed (needle-shaped nanoparticles of ≈500×(50-80) nm) 2-CEGS using methods commonly available in laboratories and industry such as vacuum and freeze-drying of aqueous solutions of 2-CEGS. Lithium half-cell anodes based on 2-CEGS show a capacity of ≈400 mAh g for microforms and up to ≈700 mAh g for nanoforms, which is almost two times higher than the maximal theoretical capacity of graphite. These anodes are stable during the cycling at various rates. The results of DFT simulations suggest that Li atoms form the stable Li O with the oxygen atoms of 2-CEGS, and actual charge-discharge cycles involve deoxygenated GeC H molecules. Thus, C chains loosen the anode structure compared to pure Ge, improving its ability to accommodate Li ions.

Published
2020
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6. 1,1'-Diphenyl-bis(silatrane) as the First Structurally Characterized bis(silatrane)

Author

Yu. Wang, D. M. Vakhrusheva, I. V. Krylova, A. Ya. Kozmenkova, E. N. Nikolaevskaya, B. N. Mankaev, M. E. Minyaev, M. A. Syroeshkin, M. P. Egorov, V. V. Jouikov, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Mendeleev University of Chemical Technology of Russia, and Russian Science FoundationRussian Science Foundation (RSF) [18-73-10180]

Subjects
General Chemical Engineering, redox properties, bis(silatranes), [CHIM]Chemical Sciences, General Chemistry, cyclic voltammetry, X-ray diffraction
Abstract

International audience; 1,1'-Diphenyl-bis(silatrane) (I) was obtained by the reaction of tris(1,3-dihydroxypropan-2-yl)amine (L) with PhSi(OEt)(3) in toluene. The molecular structure of complex I was established by X-ray diffraction (CIF file CCDC no. 2078347). Study of the redox properties of new bis(silatrane) I demonstrated that its radical ions generated by cyclic voltammetry are stable since the radical center located on the nitrogen atom is sterically protected within the bis(atrane) cage.

Published
2022
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7. Reductive Elimination at Pb(II) Center of an (Amino)plumbylene‐Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis

Author

Vladislava Timofeeva, José Miguel Léon Baeza, Raphael Nougué, Mikhail Syroeshkin, Rene Segundo Rojas Guerrero, Nathalie Saffon‐Merceron, Gül Altınbaş Özpınar, Saskia Rathjen, Thomas Müller, Antoine Baceiredo, Tsuyoshi Kato, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Pontificia Universidad Católica de Chile (UC), Université de Toulouse (UT), and Carl Von Ossietzky Universität Oldenburg = Carl von Ossietzky University of Oldenburg (OFFIS)

Subjects
Organic Chemistry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Catalysis
Abstract

International audience; A stable (amino)plumbylene-substituted phosphaketene 3 was synthesized by the successive reactions of PbCl 2 with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3, at 80 °C, leads to the transient formation of corresponding amino-and phosphanylidene-phosphaketenes (6 and 7), via a reductive elimination at the Pb II center forming new N-P and P-P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4, which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.

Published
2022
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8. An environment-friendly approach to produce nanostructured germanium anodes for lithium-ion batteries

Author

Alexey S. Galushko, Mikhail A. Syroeshkin, Pavel A. Troshin, Mikhail P. Egorov, Visweshwar Sivasankaran, Roman R. Kapaev, Viatcheslav Jouikov, Evgeniya A. Saverina, Valentine P. Ananikov, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Russian Science FoundationRussian Science Foundation (RSF) [16-13-00111, 17-73-20281], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, chemistry.chemical_element, Germanium, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, law.invention, symbols.namesake, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Environmental Chemistry, Electrolysis, Germanium dioxide, 021001 nanoscience & nanotechnology, Pollution, Nanocrystalline material, 0104 chemical sciences, Anode, chemistry, Chemical engineering, symbols, Lithium, Cyclic voltammetry, 0210 nano-technology, Raman spectroscopy
Abstract

International audience; In this paper, we propose a halogen-free process for the preparation of germanium micro-scale particles with a nano-structured surface morphology from germanium citrate, an easily accessible and environment-friendly precursor formed from germanium dioxide and citric acid in an aqueous medium. Electrodeposition of nanostructured Ge anodes on copper foil was performed via electrolysis of 1-5% germanium citrate solution in propylene glycol with addition of 5% acetic acid. Cyclic voltammetry data suggested that germanium citrate is an electrochemically inactive compound, but readily undergoes reduction by cathodic hydrogen released in the electrolysis. Such behaviour allows one to run the electrolysis under simple galvanostatic conditions without any need for controlling the potential. Furthermore, no diaphragm is required to separate the cathodic and anodic cell compartments. The electrodeposition produces black and compact films composed of similar to 200 nm germanium particles, which, in turn, consist of nanoparticles no larger than 25 nm in size (SEM and TEM data). XRD and Raman spectroscopy data lead to the conclusion that germanium precipitates in the amorphous phase; however, with an increase in the power of the He-Ne laser (632.8 nm) during Raman spectra recording, it transforms into a nanocrystalline form. Testing germanium anodes in lithium-ion half-cells showed a specific capacity of similar to 600 mA h g(-1) at 1-2C current rates, which is comparable to the best results achieved for Ge anodes produced using more sophisticated and less environment-friendly techniques.

Published
2020
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9. Special issue in honour of Michel Che : preface and recollections of his international influence on catalysis both fundamental and industrial

Author

Graham J. Hutchings, Boris N. Shelimov, Hervé Toulhoat, Christian Marcilly, Zbigniew Sojka, Patrick Maestro, Masakazu Anpo, Krystyna Dyrek, John Meurig Thomas, Catherine Louis, Jacques C. Vedrine, Can Li, Elio Giamello, Salvatore Coluccia, University of Cambridge [UK] (CAM), State Key Laboratory of Catalysis [Dalian Institute of Chemical Physics, Chinese Academy of Sciences], Dalian Institute of Chemical Physics - Chinese Academy of Sciences, Osaka Prefecture University, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Uniwersytet Jagielloński w Krakowie = Jagiellonian University (UJ), University of Torino, Università degli studi di Torino (UNITO), IFP Energies nouvelles (IFPEN), Solvay Research and Innovation, Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), School of Chemistry [Cardiff], and Cardiff University

Subjects
010405 organic chemistry, Chemistry, media_common.quotation_subject, Tribute, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Bridge (interpersonal), Catalysis, 0104 chemical sciences, Friendship, Honour, Physical and Theoretical Chemistry, Classics, media_common
Abstract

International audience; This special Issue of the Journal of Catalysis pays tribute to Professor Michel Che. In addition to the Editorial Preface, colleagues share their recollections of the vigorous endeavour he displayed throughout his scientific life to promote efficient international collaborations, as well as to bridge fundamental science and its applications. His human qualities are unanimously valued, which has left a trail marked with friendship.

Published
2021
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10. Identification of efficient promoters and selectivity trends in high temperature Fischer-Tropsch synthesis over supported iron catalysts

Author

Andrei Y. Khodakov, Petr A. Chernavskii, Robert Wojcieszak, Joris W. Thybaut, Alan J. Barrios, Vitaly V. Ordomsky, Yuan Luo, Mirella Virginie, Bang Gu, Deizi-Vanessa Peron, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Lomonosov Moscow State University [MSU], ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Universiteit Gent = Ghent University [UGENT], Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Universiteit Gent = Ghent University [Belgium] (UGENT), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Universiteit Gent = Ghent University (UGENT)

Subjects
Olefin fiber, Process Chemistry and Technology, Inorganic chemistry, chemistry.chemical_element, Fischer–Tropsch process, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Bismuth, Renewable fuels, Fischer-Tropsch, Iron catalysts, Promotion, High throughput, Light olefins, chemistry, Transition metal, Antimony, [CHIM]Chemical Sciences, 0210 nano-technology, Selectivity, Tin, ComputingMilieux_MISCELLANEOUS, General Environmental Science
Abstract

In this work, 29 elements were evaluated as promoters for silica supported iron catalysts for high temperature Fischer-Tropsch synthesis using a high-throughput experimentation unit. The selected promoters include alkali/alkaline metals, transition metals, precious metals and lanthanides. Several general selectivity trends were observed and discussed. The selectivity enhancement to light olefins requires maintaining low selectivity to methane and light paraffins and at the same time, slowing the chain growth to the C5+ hydrocarbons. A major increase in Fischer-Tropsch rate principally due to higher intrinsic site activity, was observed over the catalysts promoted with metals with low melting points such as tin, antimony, bismuth and lead. These promoted catalysts also exhibited better stability. The effect of the promotion with tin and antimony on the olefin selectivity was not noticeable, while the presence of bismuth and lead results in the major enhancement of the selectivity to light olefins, lower methane and C2-C4 paraffin selectivities.

Published
2020
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11. New Luminescent Tetranuclear Lanthanide-Based Silsesquioxane Cage-Like Architectures

Author

Jérôme Long, Joulia Larionova, Elena S. Shubina, Alexey N. Bilyachenko, Mikhail M. Levitsky, Gautier Félix, Victor N. Khrustalev, Ekaterina Mamontova, Alena N. Kulakova, Yannick Guari, A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Peoples’ Friendship University of Russia, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and ND Zelinsky Institute of Organic Chemistry [Moscow, Russia]

Subjects
Lanthanide, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Terbium, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Silsesquioxane, 3. Good health, 0104 chemical sciences, Crystallography, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Europium, Luminescence, Cage
Abstract

International audience; We report on the synthesis, structure, magnetic and luminescence properties investigations of four new cagelike lanthanide-based silsesquioxanes (Cat)2[(PhSiO1.5)8(LnO1.5)4(O)(NO2.5)6(EtOH)2(MeCN)2] (where Cat + = Et4N + , PPh4P + and Ln 3+ = Eu 3+ Tb 3+ and (Ph4P)4[(PhSiO1.5)8(TbO1.5)4(O)2(NO2.5)8]•10MeCN. They present an unusual prism-like topology of cage architectures and lanthanide-characteristic emission, which makes them the first luminescent cage-like lanthanide silsesquioxanes. One of the Tb 3+-based cages presents a magnetic spin-flip transition.

Published
2020
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12. Potential of Chemically Synthesized Oligosaccharides To Define the Carbohydrate Moieties of the Fungal Cell Wall Responsible for the Human Immune Response, Using Aspergillus fumigatus Galactomannan as a Model

Author

Vadim B. Krylov, Thierry Fontaine, Sarah Sze Wah Wong, Nikolay E. Nifantiev, Jean-Paul Latgé, Jean-Phillipe Bouchara, Dmitry A. Argunov, Alexander A. Karelin, Aspergillus, Institut Pasteur [Paris] (IP), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Groupe d'Étude des Interactions Hôte-Pathogène (GEIHP), Université d'Angers (UA), This work was supported by the Russian Science Foundation (grant 19-73-30017), the Agence Nationale pour la Recherche (grant AfuInf ANR-16-CE92-0039), and la Fondation pour la Recherche Médicale (grant DEQ20150331722 LATGE Equipe FRM 2015) to J.-P.L., ANR-16-CE92-0039,AfuInf,Protéome and polysaccharidome d'Aspergillus fumigatus lors des étapes précoces de l'infection(2016), Institut Pasteur [Paris], and Groupe d'Etude des Interactions Hôte-Parasite (GEIHP)

Subjects
0301 basic medicine, Antigens, Fungal, [SDV]Life Sciences [q-bio], lcsh:QR1-502, Oligosaccharides, chemokines, Polysaccharide, 01 natural sciences, Microbiology, Epitope, lcsh:Microbiology, Host-Microbe Biology, Aspergillus fumigatus, Immunomodulation, Mannans, Cell wall, immunology, Epitopes, 03 medical and health sciences, Galactomannan, chemistry.chemical_compound, Immune system, Cell Wall, glycoarray, Humans, antibodies, aspergillosis, skin and connective tissue diseases, Molecular Biology, [SDV.MP.MYC]Life Sciences [q-bio]/Microbiology and Parasitology/Mycology, chemistry.chemical_classification, Aspergillus, biology, 010405 organic chemistry, Galactose, Opinion/Hypothesis, biology.organism_classification, QR1-502, cytokines, 3. Good health, 0104 chemical sciences, 030104 developmental biology, chemistry, Biochemistry, galactomannan, biology.protein, Antibody
Abstract

Methodologies to identify epitopes or ligands of the fungal cell wall polysaccharides influencing the immune response of human pathogens have to date been imperfect. Using the galactomannan (GM) of Aspergillus fumigatus as a model, we have shown that synthetic oligosaccharides of distinct structures representing key fragments of cell wall polysaccharides are the most precise tools to study the serological and immunomodulatory properties of a fungal polysaccharide.

Published
2020
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13. Biotinylated Oligo-α-(1 → 4)- d -galactosamines and Their N-Acetylated Derivatives: α-Stereoselective Synthesis and Immunology Application

Author

Vadim B. Krylov, Ekaterina D. Kazakova, Isabel Valsecchi, Thierry Fontaine, Jean-Philippe Bouchara, Jean-Paul Latgé, Nikolay E. Nifantiev, Murielle Cornet, D. V. Yashunsky, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Centre Hospitalier Universitaire d'Angers (CHU Angers), PRES Université Nantes Angers Le Mans (UNAM), Groupe d'Étude des Interactions Hôte-Pathogène (GEIHP), Université d'Angers (UA), Thérapeutique Recombinante Expérimentale (TIMC-IMAG-TheREx ), Techniques de l'Ingénierie Médicale et de la Complexité - Informatique, Mathématiques et Applications Grenoble - UMR 5525 (TIMC-IMAG), VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Aspergillus, Institut Pasteur [Paris], Institut Pasteur [Paris] (IP), ANR-16-CE92-0039,AfuInf,Protéome and polysaccharidome d'Aspergillus fumigatus lors des étapes précoces de l'infection(2016), Thérapeutique Recombinante Expérimentale (TIMC-IMAG-TheREx), Techniques de l'Ingénierie Médicale et de la Complexité - Informatique, Mathématiques et Applications, Grenoble - UMR 5525 (TIMC-IMAG), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-IMAG-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-IMAG-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)

Subjects
Glycosylation, Stereochemistry, Glycoconjugate, medicine.drug_class, [SDV]Life Sciences [q-bio], Galactosaminogalactan, Galactosamine, 010402 general chemistry, Monoclonal antibody, 01 natural sciences, Biochemistry, Catalysis, Epitope, Aspergillus fumigatus, chemistry.chemical_compound, Structure-Activity Relationship, Colloid and Surface Chemistry, medicine, Humans, Glycosyl, Biotinylation, chemistry.chemical_classification, biology, Acetylation, Stereoisomerism, General Chemistry, biology.organism_classification, 0104 chemical sciences, chemistry
Abstract

International audience; Using 3-O-benzoyl-4,6-O-di-tert-butylsilylidene-2-azido-2-deoxy-selenogalactoside, biotinylated oligo-α-(1 → 4)-d-galactosamines comprising from two to six GalN units were prepared for the first time together with their N-acetylated derivatives. The combination of blocking groups used herein provided stereocontrol for the α-stereospecific glycosylation, to show also high efficiency of phenyl 2-azido-2-deoxy-selenogalactosides as glycosyl donors. The obtained glycoconjugates are related to fragments of exopolysaccharide galactosaminogalactan (GG) found in Aspergillus fumigatus, which is the most important airborne human fungal pathogen in industrialized countries. The synthesized glycoconjugates were arrayed on streptavidin-coated plates and used to investigate the GG epitopes recognized by mouse monoclonal antibodies against GG and by human antibodies in the sera of patients with aspergillosis. The obtained data showed that the oligo-α-(1 → 4)-d-galactosamines and their N-acetylated derivatives allowed the first precise analysis of the specificity of the antibody responses to this extremely complex fungal polysaccharide

Published
2020
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14. The sps Genes Encode an Original Legionaminic Acid Pathway Required for Crust Assembly in Bacillus subtilis

Author

Thomas Dubois, Frederic Krzewinski, Nao Yamakawa, Christelle Lemy, Audrey Hamiot, Loïc Brunet, Anne-Sophie Lacoste, Yuryi Knirel, Yann Guerardel, Christine Faille, DUBOIS, Thomas, APPEL À PROJETS GÉNÉRIQUE 2018 - La Mécanique des Fluides au Service de la Sécurité Alimentaire - - FEFS2018 - ANR-18-CE21-0010 - AAPG2018 - VALID, Equipements d'excellence - Plateau de microscopie de criblage à haut débit et d'analyse à très haute résolution - - Imaginex BioMed2010 - ANR-10-EQPX-0004 - EQPX - VALID, Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Plateformes Lilloises en Biologie et Santé - UAR 2014 - US 41 (PLBS), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Region Hauts-de-FranceGoToS3NuTeX, ANR-18-CE21-0010,FEFS,La Mécanique des Fluides au Service de la Sécurité Alimentaire(2018), ANR-10-EQPX-0004,Imaginex BioMed,Plateau de microscopie de criblage à haut débit et d'analyse à très haute résolution(2010), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Unité de Glycobiologie Structurale et Fonctionnelle (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Plateformes Lilloises en Biologie et Santé - UMS 2014 - US 41 (PLBS), Université de Lille, CNRS, Unité Matériaux et Transformations - UMR 8207 [UMET], Unité de Glycobiologie Structurale et Fonctionnelle (UGSF) - UMR 8576, and Plateformes Lilloises en Biologie et Santé - UAR 2014 - US 41 [PLBS]

Subjects
Bacillus subtilis, bacterial adhesion, crust, legionaminic acid, nonulosonic acid, spores, fungi, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Microbiology, QR1-502
Abstract

International audience; The crust is the outermost spore layer of most Bacillus strains devoid of an exosporium. This outermost layer, composed of both proteins and carbohydrates, plays a major role in the adhesion and spreading of spores into the environment. Recent studies have identified several crust proteins and have provided insights about their organization at the spore surface. However, although carbohydrates are known to participate in adhesion, little is known about their composition, structure, and localization. In this study, we showed that the spore surface of Bacillus subtilis is covered with legionaminic acid (Leg), a nine-carbon backbone nonulosonic acid known to decorate the flagellin of the human pathogens Helicobacter pylori and Campylobacter jejuni We demonstrated that the spsC, spsD, spsE, spsG, and spsM genes of Bacillus subtilis are required for Leg biosynthesis during sporulation, while the spsF gene is required for Leg transfer from the mother cell to the surface of the forespore. We also characterized the activity of SpsM and highlighted an original Leg biosynthesis pathway in B. subtilis Finally, we demonstrated that Leg is required for the assembly of the crust around the spores, and we showed that in the absence of Leg, spores were more adherent to stainless steel probably because of their reduced hydrophilicity and charge.IMPORTANCE Bacillus species are a major economic and food safety concern of the food industry because of their food spoilage-causing capability and persistence. Their persistence is mainly due to their ability to form highly resistant spores adhering to the surfaces of industrial equipment. Spores of the Bacillus subtilis group are surrounded by the crust, a superficial layer which plays a key role in their adhesion properties. However, knowledge of the composition and structure of this layer remains incomplete. Here, for the first time, we identified a nonulosonic acid (Leg) at the surfaces of bacterial spores (B. subtilis). We uncovered a novel Leg biosynthesis pathway, and we demonstrated that Leg is required for proper crust assembly. This work contributes to the description of the structure and composition of Bacillus spores which has been under way for decades, and it provides keys to understanding the importance of carbohydrates in Bacillus adhesion and persistence in the food industry.

Published
2020
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15. Specificity of human natural antibodies referred to as anti-Tn

Author

Sergey V. Khaidukov, Jacques LePendu, Nailya Khasbiullina, Tatiana V. Ovchinnikova, Polina Obukhova, Oxana Galanina, Horst Kunz, Yuriy A. Knirel, Nicolai V. Bovin, Nadezhda Shilova, Ola Blixt, Kira Dobrochaeva, Alexander Filatov, N. V. Antipova, Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry (IBCh RAS), Russian Academy of Sciences [Moscow] (RAS), Semiotik LLC [Moscow, Russian Federation], Gynecology and Perinatology Named after Academician V.I. Kulakov [Moscow, Russian Federation] (Ministry of Healthcare of Russian Federation), Ministry of Healthcare of Russian Federation, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Peoples Friendship University of Russia [RUDN University] (RUDN), Vysšaja škola èkonomiki = National Research University Higher School of Economics [Moscow] (HSE), University of Copenhagen = Københavns Universitet (KU), Institut fur Anorganische Chemie und Analytische Chemie [Mainz], Johannes Gutenberg - Universität Mainz (JGU), Institute of Immunology [Moscow, Russian Federation], Federal Medical-Biological Agency of Russia, Centre de Recherche en Cancérologie Nantes-Angers (CRCNA), Centre Hospitalier Universitaire d'Angers (CHU Angers), PRES Université Nantes Angers Le Mans (UNAM)-PRES Université Nantes Angers Le Mans (UNAM)-Hôtel-Dieu de Nantes-Institut National de la Santé et de la Recherche Médicale (INSERM)-Hôpital Laennec-Centre National de la Recherche Scientifique (CNRS)-Faculté de Médecine d'Angers-Centre hospitalier universitaire de Nantes (CHU Nantes), The work of KD, NK, and NB was supported by grant #14-50-00131 of the Russian Science Foundation. The work of SK and NS was supported by the grant #18-04-00749 of the Russian Foundation for the Basic Research. The work of AF was supported by the grant #18-29-07025 of the Russian Foundation for the Basic Research. The work of OG was supported by the grant from the French Embassy 'Bourses Metchnikov - séjours scientifiques 2015'. We are grateful to the Cellular and Tissular Imaging Core Facility of Nantes University (MicroPiCell). The tissue samples were kindly provided by Dr. J. Bara, Villejuif, France., University of Copenhagen = Københavns Universitet (UCPH), Johannes Gutenberg - Universität Mainz = Johannes Gutenberg University (JGU), Bernardo, Elizabeth, and National Research University Higher School of Economics [Moscow] (HSE)

Subjects
0301 basic medicine, Glycan, Glycans, Immunology, Tn antigen, Antibody Affinity, [SDV.CAN]Life Sciences [q-bio]/Cancer, Anti-Glycan antibodies, Epitope, Antigen-Antibody Reactions, Epitopes, Jurkat Cells, 03 medical and health sciences, 0302 clinical medicine, Affinity chromatography, [SDV.CAN] Life Sciences [q-bio]/Cancer, Antibody Specificity, Neoplasms, Humans, Antigens, Tumor-Associated, Carbohydrate, Amino Acid Sequence, Molecular Biology, Peptide sequence, Cancer, biology, Chemistry, Bacterial polysaccharide, Immunity, Innate, 3. Good health, 030104 developmental biology, Carbohydrate Sequence, Immunoglobulin M, Biochemistry, Natural antibodies, biology.protein, Paratope, Antibody, 030215 immunology
Abstract

International audience; To understand the role of human natural IgM known as antibodies against the carbohydrate epitope Tn, the antibodies were isolated using GalNAcα−Sepharose affinity chromatography, and their specificity was profiled using microarrays (a glycan array printed with oligosaccharides and bacterial polysaccharides, as well as a glycopeptide array), flow cytometry, and inhibition ELISA. The antibodies bound a restricted number of GalNAcα-terminated oligosaccharides better than the parent monosaccharide, e.g., 6-O-Su-GalNAcα and GalNAcα1−3Galβ1−3(4)GlcNAcβ. The binding with several bacterial polysaccharides that have no structural resemblance to the affinity ligand GalNAcα was quite unexpected. Given that GalNAcα is considered the key fragment of the Tn antigen, it is surprising that these antibodies bind weakly GalNAcα−OSer and do not bind a wide variety of GalNAcα−OSer/Thr-containing mucin glycopeptides. At the same time, we have observed specific binding to cells having Tn-positive glycoproteins containing similar glycopeptide motifs in a con-formationally rigid macromolecule. Thus, specific recognition of the Tn antigen apparently requires that the naturally occurring "anti-Tn" IgM recognize a complex epitope comprising the GalNAcα as an essential component and a fairly long amino acid sequence where the amino acids adjacent to GalNAcα do not contact the antibody paratope; i.e., the antibodies recognize a spatial epitope or a molecular pattern rather than a classical continuous sequence. In addition, we have not found any increase in the binding of natural antibodies when GalNAcα residues were clustered. These results may help in further development of anticancer vaccines based on synthetic Tn constructs.

Published
2020
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16. 1,1 '-Diphenyl-bis-germatrane with persistent radical cation

Author

Anna Ya. Kozmenkova, Mikhail A. Syroeshkin, Mikhail P. Egorov, Daria M. Vakhrusheva, Badma N. Mankaev, Irina V. Krylova, Viatcheslav Jouikov, Vitalijs Romanovs, Latvian Institute of Organic Synthesis, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Mendeleev University of Chemical Technology of Russia, Lomonosov Moscow State University (MSU), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Russian Science FoundationRussian Science Foundation (RSF) [18-73-10180], European Regional Development Fund ERDF - Latvia [1.1.1.2/VIAA/3/19/577], Latvian Institute of Organic Synthesis [Riga, Lituania], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, cyclic voltammetry, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, chemistry, Radical ion, radical cations, redox properties, actuator systems, [CHIM]Chemical Sciences, organogermanium compounds, Derivative (chemistry), metallatranes
Abstract

International audience; Bis-phenyl derivative of a novel family of bis-metallatranes, 1,1'-diphenyl-bis-germatrane, was synthesized and characterized. One-electron oxidation of this compound is electrochemically and chemically reversible providing a persistent radical cation.

Published
2020
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17. Synthesis, characterization and redox properties of Ar-C=N -> Ge <- N=C-Ar containing system

Author

Krylova, Irina, Saverina, Evgeniya A., Rynin, Stanislav S., Lalov, Andrey, Minyaev, Mikhail E., Nikolaevskaya, Elena N., Syroeshkin, Mikhail A., Egorov, Mikhail P., ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Russian Science FoundationRussian Science Foundation (RSF) [18-73-10180], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
radical ions, redox chemistry, [CHIM]Chemical Sciences, germanium complexes, Schiff bases, salens, DFT calculations, cyclic voltammetry
Abstract

International audience; New Schiff base germanate derivative containing the chain Ar-C=N -> Ge

Published
2020
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18. Composition of the Biofilm Matrix of Cutibacterium acnes Acneic Strain RT5

Author

Andrei V. Gannesen, Evelina L. Zdorovenko, Ekaterina A. Botchkova, Julie Hardouin, Sebastien Massier, Dmitry S. Kopitsyn, Maxim V. Gorbachevskii, Alexandra A. Kadykova, Alexander S. Shashkov, Marina V. Zhurina, Alexander I. Netrusov, Yuriy A. Knirel, Vladimir K. Plakunov, Marc G. J. Feuilloley, Winogradsky Institute of Microbiology, Russian Academy of Sciences [Moscow] (RAS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Polymères Biopolymères Surfaces (PBS), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Gubkin Russian State University, Lomonosov Moscow State University (MSU), Laboratoire de Microbiologie Signaux et Microenvironnement (LMSM), Normandie Université (NU)-Normandie Université (NU), Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), and Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Microbiology (medical), polysaccharides, lcsh:QR1-502, Matrix (biology), Polysaccharide, Microbiology, biofilm matrix, lcsh:Microbiology, Extracellular matrix, 03 medical and health sciences, Propionibacterium acnes, [SDV.BC.IC]Life Sciences [q-bio]/Cellular Biology/Cell Behavior [q-bio.CB], ComputingMilieux_MISCELLANEOUS, Original Research, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, biology, 030306 microbiology, Chemistry, Extraction (chemistry), Biofilm, Biofilm matrix, biology.organism_classification, Orbitrap mass spectrometry, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, proteins, surface-enhanced Raman spectroscopy, nuclear magnetic resonance, Biochemistry, Cutibacterium acnes, biofilms, Bacteria
Abstract

In skin, Cutibacterium acnes (former Propionibacterium acnes) can behave as an opportunistic pathogen, depending on the strain and environmental conditions. Acneic strains of C. acnes form biofilms inside skin–gland hollows, inducing inflammation and skin disorders. The essential exogenous products of C. acnes accumulate in the extracellular matrix of the biofilm, conferring essential bacterial functions to this structure. However, little is known about the actual composition of the biofilm matrix of C. acnes. Here, we developed a new technique for the extraction of the biofilm matrix of Gram-positive bacteria without the use of chemical or enzymatic digestion, known to be a source of artifacts. Our method is based on the physical separation of the cells and matrix of sonicated biofilms by ultracentrifugation through a CsCl gradient. Biofilms were grown on the surface of cellulose acetate filters, and the biomass was collected without contamination by the growth medium. The biofilm matrix of the acneic C. acnes RT5 strain appears to consist mainly of polysaccharides. The following is the ratio of the main matrix components: 62.6% polysaccharides, 9.6% proteins, 4.0% DNA, and 23.8% other compounds (porphyrins precursors and other). The chemical structure of the major polysaccharide was determined using a nuclear magnetic resonance technique, the formula being →6)-α-D-Galp-(1→4)-β-D-ManpNAc3NAcA-(1→6)-α-D-Glcp-(1→4)-β-D-ManpNAc3NAcA-(1→3)-β-GalpNAc-(1→. We detected 447 proteins in the matrix, of which the most abundant were the chaperonin GroL, the elongation factors EF-Tu and EF-G, several enzymes of glycolysis, and proteins of unknown function. The matrix also contained more than 20 hydrolases of various substrata, pathogenicity factors, and many intracellular proteins and enzymes. We also performed surface-enhanced Raman spectroscopy analysis of the C. acnes RT5 matrix for the first time, providing the surface-enhanced Raman scattering (SERS) profiles of the C. acnes RT5 biofilm matrix and biofilm biomass. The difference between the matrix and biofilm biomass spectra showed successful matrix extraction rather than simply the presence of cell debris after sonication. These data show the complexity of the biofilm matrix composition and should be essential for the development of new anti-C. acnes biofilms and potential antibiofilm drugs.

Published
2019
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19. Novel mouse monoclonal antibodies specifically recognizing β-(1→3)-D-glucan antigen

Author

Yury E. Tsvetkov, D. V. Yashunsky, Ivan K. Baykov, Yana A. Khlusevich, Alexander A. Karelin, Vadim B. Krylov, Sarah Sze Wah Wong, Vishukumar Aimanianda, Jean-Paul Latgé, Alevtina V. Bardashova, Nina V. Tikunova, Nikolay E. Nifantiev, Andrey L. Matveev, Ljudmila A. Emelyanova, Institute of Chemical Biology and Fundamental Medicine [Novosibirsk, Russia] (ICBFM SB RAS), Siberian Branch of the Russian Academy of Sciences (SB RAS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Novosibirsk State University (NSU), Aspergillus, Institut Pasteur [Paris], Mycologie moléculaire - Molecular Mycology, Institut Pasteur [Paris]-Centre National de la Recherche Scientifique (CNRS), Franco-German ANR-DFG (ANR-16-CE92-0031-01 AFUINTERACT to V. Kumar, (http://www.agence-nationale-recherche.fr) and the Franco-Indian CEFIPRA (Project N° 5403-1 to V. Kumar) grants., Centre National de la Recherche Scientifique (CNRS)-Institut Pasteur [Paris], Institut Pasteur [Paris] (IP), Institut Pasteur [Paris] (IP)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE92-0031,EpiFUS,Rôle de FUS dans la régulation des modifications épigénétiques : conséquences pour la sclérose latérale amyotrophique et la démence frontotemporale(2016)

Subjects
0301 basic medicine, Antifungal Agents, beta-Glucans, [SDV]Life Sciences [q-bio], MESH: Drug Synergism, Aspergillus fumigatus, MESH: Antibodies, Monoclonal, Mice, Cell Wall, Candida albicans, MESH: Animals, Bovine serum albumin, Fluconazole, MESH: Treatment Outcome, chemistry.chemical_classification, MESH: Microbial Sensitivity Tests, Multidisciplinary, biology, MESH: beta-Glucans, Candidiasis, Antibodies, Monoclonal, Drug Synergism, Oligosaccharide, MESH: Candidiasis, 3. Good health, Treatment Outcome, Biochemistry, Biotinylation, Medicine, MESH: Fluconazole, [SDV.IMM]Life Sciences [q-bio]/Immunology, Drug Therapy, Combination, Female, MESH: Aspergillus fumigatus, Research Article, Antigens, Fungal, medicine.drug_class, Science, 030106 microbiology, Microbial Sensitivity Tests, Monoclonal antibody, 03 medical and health sciences, MESH: Cell Wall, medicine, Animals, Humans, MESH: Mice, MESH: Antigens, Fungal, MESH: Humans, MESH: Candida albicans, [SDV.IMM.IMM]Life Sciences [q-bio]/Immunology/Immunotherapy, biology.organism_classification, MESH: Antifungal Agents, In vitro, Disease Models, Animal, MESH: Drug Therapy, Combination, 030104 developmental biology, chemistry, biology.protein, Hybridoma technology, MESH: Disease Models, Animal, MESH: Female
Abstract

International audience; β-(1→3)-D-Glucan is an essential component of the fungal cell wall. Mouse monoclonal antibodies (mAbs) against synthetic nona-β-(1→3)-D-glucoside conjugated with bovine serum albumin (BSA) were generated using hybridoma technology. The affinity constants of two selected mAbs, 3G11 and 5H5, measured by a surface plasmon resonance biosensor assay using biotinylated nona-β-(1→3)-D-glucan as the ligand, were approximately 11 nM and 1.9 nM, respectively. The glycoarray, which included a series of synthetic oligosaccharide derivatives representing β-glucans with different lengths of oligo-β-(1→3)-D-glucoside chains, demonstrated that linear tri-, penta- and nonaglucoside, as well as a β-(1→6)-branched octasaccharide, were recognized by mAb 5H5. By contrast, only linear oligo-β-(1→3)-D-glucoside chains that were not shorter than pentaglucosides (but not the branched octaglucoside) were ligands for mAb 3G11. Immunolabelling indicated that 3G11 and 5H5 interact with both yeasts and filamentous fungi, including species from Aspergillus, Candida, Penicillium genera and Saccharomyces cerevisiae, but not bacteria. Both mAbs could inhibit the germination of Aspergillus fumigatus conidia during the initial hours and demonstrated synergy with the antifungal fluconazole in killing C. albicans in vitro. In addition, mAbs 3G11 and 5H5 demonstrated protective activity in in vivo experiments, suggesting that these β-glucan-specific mAbs could be useful in combinatorial antifungal therapy.

Published
2019
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20. Upconversion of Reductants

Author

Febin Kuriakose, Vladislava A. Timofeeva, Evgeniya A. Saverina, Mikhail A. Syroeshkin, Igor V. Alabugin, Mikhail P. Egorov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Florida State University [Tallahassee] (FSU), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), 1800329, Directorate for Mathematical and Physical Sciences, 17-73-20281, Russian Science Foundation, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS)

Subjects
Exergonic reaction, upconversion, 010405 organic chemistry, Chemistry, photoredox catalysis, fragmentations, Photoredox catalysis, General Chemistry, radical anions, 010402 general chemistry, Photochemistry, electron transfer, 01 natural sciences, Redox, Chemical reaction, Catalysis, Photon upconversion, 0104 chemical sciences, Electron transfer, reductants, [CHIM]Chemical Sciences, Luminescence, Chain reaction, ComputingMilieux_MISCELLANEOUS
Abstract

The many applications of photon upconversion-conversion of low-energy photons into high-energy photons-raises the question of the possibility of "electron upconversion". In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20-25 kcal mol-1 of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron-upconverting systems-dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three-electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide-based medicines, firefly luminescence, and reductive repair of DNA photodamage.

Published
2019
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21. Reversible dimerization of anion radicals of carbonyl compounds and the electrosynthesis of pinacols. The case of 9-fluorenone

Author

A. S. Mendkovich, Vladimir A. Kokorekin, M. N. Mikhailov, Arona Ngom, Viatcheslav Jouikov, Diariatou Gningue-Sall, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Cheikh Anta Diop [Dakar, Sénégal] (UCAD), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Cyclic voltammetry, Hydrogen bond, Anion radical, General Chemical Engineering, Protonation, 02 engineering and technology, Chronoamperometry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrosynthesis, Photochemistry, 01 natural sciences, 0104 chemical sciences, Ion, chemistry.chemical_compound, chemistry, Electrochemistry, [CHIM]Chemical Sciences, Phenol, Digital simulation, 0210 nano-technology, Dimerization, Lithium Cation
Abstract

International audience; Reversible dimerization of the anion radicals of carbonyl compounds was studied by cyclic voltammetry, chronoamperometry, electrolysis, digital simulation and quantum chemical calculations using electroreduction of 9-fluorenone in DMF/0.1 M Bu4NClO4 as an example. The experimental data confirmed that this reaction is thermodynamically unfavorable as it was predicted by DFT calculations. In contrast with some other anion radicals, neither ion pairing of 9-fluorenone anion radicals with lithium cation nor their hydrogen bonding with water shifts the dimerization equilibrium to the dimeric product. Reversibility of the dimerization decreases in the presence of phenol due to the protonation of the dimeric dianion and to the irreversibility of dimerization of the anion radical – phenol complexes. The contribution of these two pathways to general hydrodimerization process is discussed. © 2020 Elsevier Ltd

Published
2020
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22. Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

Author

Valentine P. Ananikov, Evgueni Kirillov, Konstantin S. Rodygin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, Polymers and Plastics, Calcium carbide, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Materials Chemistry, Copolymer, medicine, [CHIM]Chemical Sciences, chemistry.chemical_classification, Poly(vinyl ethers), Organic Chemistry, Polymerization mechanism, Polymer, Vinyl ether, Stereocontrol in polymerization, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Vinyl ethers, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Acetylene, 0210 nano-technology, medicine.drug
Abstract

International audience; This review highlights recent progress in the synthesis and application of vinyl ethers (VEs) as monomers for modern homo- and co-polymerization processes. VEs can be easily prepared using a number of traditional synthetic protocols including a more sustainable and straightforward manner by reacting gaseous acetylene or calcium carbide with alcohols. The remarkably tunable chemistry of VEs allows designing and obtaining polymers with well-defined structures and controllable properties. Both VE homopolymerization and copolymerization systems are considered, and specific emphasis is given to the novel initiating systems and to the methods of stereocontrol.

Published
2020
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23. Germanium Dioxide and the Antioxidant Properties of Catechols

Author

Valery M. Pechennikov, Vera A. Zelenova, Irina V. Krylova, Galina E. Filonova, Elena N. Nikolaevskaya, Artem V. Kansuzyan, Mikhail P. Egorov, Viatcheslav Jouikov, Mikhail A. Syroeshkin, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sechenov First Moscow State Medical University, Russian Academy of Sciences [Moscow] (RAS), Ministry of Education and Science of the Russian Federation. Grant Number: ??‐755.2017.3, Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Germanium dioxide, Aqueous solution, 010405 organic chemistry, Diol, chemistry.chemical_element, Germanium, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Redox, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Reaction rate constant, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cyclic voltammetry, Acetonitrile
Abstract

International audience; Complexes of tetra‐ and hexa‐coordinated germanium AdrCat2Ge (1, AdrCat = adrenaline catecholate), AldCat2Ge (2, AldCat = 4‐formylcatecholate), AldCat3Ge(Et3NH)2 (3) were synthesized by the reaction of germanium dioxide with adrenaline and 3,4‐dihydroxybenzaldehyde in aqueous solution. The structures of the complexes were confirmed by 1H and 13C NMR and IR spectroscopy, HRMS, and elemental analysis. Cyclic voltammetry in phosphate buffer solutions (pH = 6.86) has shown the oxidation potentials Ep of these complexes to be shifted by ca. 330–360 mV to more positive potentials compared to the parent aromatic diols, which means that their electron‐releasing properties were diminished by about 7.6–8.3 kcal mol–1. A study of the kinetics of the reaction of these complexes with 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) free radical in the presence of 5 % acetonitrile reveals a decrease of approximately one order of magnitude in the radical scavenging activity of adrenaline and model 3,4‐dihydroxybenzaldehyde upon their complexation with Ge. The corresponding rate constants drop from (3.23 ± 0.07) × 103 L mol–1 s–1 (adrenaline) to (3.80 ± 0.20) × 102 L mol–1 s–1 for 1, and from (4.40 ± 0.20) × 103 L mol–1 s–1 (3,4‐dihydroxybenzaldehyde) to (4.45 ± 0.25) × 102 L mol–1 s–1 for 2 and 3 (germanium is equally capable to bind two or three molecules of the diol). Keeping in mind that 1,2‐diols are widespread in the living nature and often have important biological functions, these results will contribute to the understanding of role of germanium dioxide in metabolic mechanisms and to alert against unreasonable use of Ge preparations.

Published
2019
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24. Easily electroreducible halogen-free germanium complexes with biologically active pyridines

Author

Elena N. Nikolaevskaya, Mikhail P. Egorov, Alyona A. Starikova, Mikhail A. Syroeshkin, Pavel G. Shangin, Viatcheslav Jouikov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Russian Science Foundation [17-73-20281], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Germanium dioxide, Cyclic voltammetry, Pyridines, Inorganic chemistry, Catechols, chemistry.chemical_element, Germanium, Halogen free, 010402 general chemistry, Electrochemistry, DFT calculations, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Nicotinamide, 010405 organic chemistry, Chemistry, Biological activity, 3. Good health, 0104 chemical sciences, Anode
Abstract

The green conversion of germanium dioxide into soluble non-halogenated forms suitable for further processing occurs smoothly and in high yields under the action of 3,5-di-tert-butylbenzene-1,2-diol in presence of biologically active N-donor ligands L. The formed hexacoordinated germanium catecholate complexes (DTBCat)2GeL2 (DTBCat = 3,5-di-tert-butylcatecholate, L = nicotinic acid, nicotinamide and isoniazid) 1–3 are air stable and soluble in common organic solvents. These new complexes are easily reducible at a glassy carbon electrode in DMF/0.1 M Bu4NBF4 at the cathodic potentials remarkably less negative than those of the reduction of parent non-coordinated N-donor ligands L; the corresponding anodic shifts for 1–3 are 0.598, 1.009 and 0.978 V, respectively. The ease of the electrochemical reduction and the energy of electron donation from the ligands L to germanium in 1–3 are in good agreement with DFT B3LYP/def2tzvp analysis and the stabilization energies of these germanium complexes.

Published
2019
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25. Chemical Synthesis and Application of Biotinylated Oligo-α-(1 → 3)- d -Glucosides To Study the Antibody and Cytokine Response against the Cell Wall α-(1 → 3)- d -Glucan of Aspergillus fumigatus

Author

Nikolay E. Nifantiev, Sarah Sze Wah Wong, Jean-Philippe Bouchara, Maria V. Orekhova, Bozhena S. Komarova, Jean-Paul Latgé, John F. Kearney, Anne Beauvais, Vishukumar Aimanianda, Vadim B. Krylov, Yury E. Tsvetkov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Aspergillus, Institut Pasteur [Paris] (IP), Groupe d'Étude des Interactions Hôte-Pathogène (GEIHP), Université d'Angers (UA), University of Alabama at Birmingham [ Birmingham] (UAB), This work was supported in part by the Russian Science Foundation (grant 14-50-00126) and by the French ANR agency and Fondation de la Recherche Medicale (DEQ20150331722 LATGE Equipe FRM 2015)., Institut Pasteur [Paris], and Groupe d'Etude des Interactions Hôte-Parasite (GEIHP)

Subjects
0301 basic medicine, Streptavidin, Glycosylation, Stereochemistry, [SDV]Life Sciences [q-bio], MESH: Glucosides, Chemical synthesis, [SDV.IMM.II]Life Sciences [q-bio]/Immunology/Innate immunity, Article, Aspergillus fumigatus, MESH: Antibodies, Monoclonal, 03 medical and health sciences, chemistry.chemical_compound, MESH: Cell Wall, Glucosides, Cell Wall, MESH: Glucans, Humans, Glycosyl, Biotinylation, MESH: Biotinylation, Glucans, Glucan, chemistry.chemical_classification, MESH: Cytokines, MESH: Humans, biology, Organic Chemistry, Antibodies, Monoclonal, biology.organism_classification, MESH: Leukocytes, Mononuclear, 030104 developmental biology, chemistry, Polyclonal antibodies, biology.protein, Leukocytes, Mononuclear, Cytokines, [SDV.IMM]Life Sciences [q-bio]/Immunology, MESH: Aspergillus fumigatus
Abstract

International audience; Biotinylated hepta-, nona- and undeca-α-(1 → 3)-d-glucosides representing long oligosaccharides of α-(1 → 3)-d-glucan, one of the major components of the cell walls of the fungal pathogen Aspergillus fumigatus, were synthesized for the first time via a blockwise strategy. Convergent assembly of the α-(1 → 3)-d-glucan chains was achieved by glycosylation with oligoglucoside derivatives bearing 6- O-benzoyl groups. Those groups are capable of remote α-stereocontrolling participation, making them efficient α-directing tools even in the case of large glycosyl donors. Synthetic biotinylated oligoglucosides (and biotinylated derivatives of previously synthesized tri- and penta-α-(1 → 3)-d-glucosides) loaded on streptavidin microtiter plates were shown to be better recognized by anti-α-(1 → 3)-glucan human polyclonal antibodies and to induce higher cytokine responses upon stimulation of human peripheral blood mononuclear cells than their natural counterpart, α-(1 → 3)-d-glucan, immobilized on a conventional microtiter plate. Attachment of the synthetic oligosaccharides equipped with a hydrophilic spacer via the streptavidin-biotin pair allows better spatial presentation and control of the loading compared to the random sorption of natural α-(1 → 3)-glucan. Increase of oligoglucoside length results in their better recognition and enhancement of cytokine production. Thus, using synthetic α-(1 → 3)-glucan oligosaccharides, we developed an assay for the host immune response that is more sensitive than the assay based on native α-(1 → 3)-glucan.

Published
2018
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26. Spontaneous formation of nanofilms under interaction of 4th generation pyrydylphenylene dendrimer with proteins

Author

Svetlana A. Sorokina, Zinaida B. Shifrina, Victor S. Stroylov, Cédric Gaillard, Aleksandra K. Melnikova, Vladimir I. Muronetz, Yulia Yu. Stroylova, Thomas Haertlé, Moscow State University, Institute of Molecular Medicine, St. James's Hospital and Trinity College, Russian Academy of Sciences [Moscow] (RAS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Faculty of Bioengineering and Bioinformatics, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Department of Animal Nutrition and Feed Management, University of Life Sciences in Poznan, Teheran University, Partenaires INRAE, RFBR grant [15-38-70034, 16-33-00593], and French Government

Subjects
Dendrimers, Dendrimer-protein composites, Polymers and Plastics, Molecular model, In silico, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Molecular dynamics, chemistry.chemical_compound, Dendrimer, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, medicine, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Chymotrypsin, biology, Organic Chemistry, 021001 nanoscience & nanotechnology, Trypsin, 0104 chemical sciences, 3. Good health, Enzymes, chemistry, biology.protein, Biophysics, Lysozyme, 0210 nano-technology, Biosensor, medicine.drug
Abstract

The use of materials based on protein-polymer compositions is a promising method for solving a number of problems in biotechnology and medicine. In our work, we produced multilayer nanofilms based on 4th generation (G4) pyridylphenylene dendrimers with fully pyridine-based periphery containing a protein component. For dairy beta- and kappa-caseins, alpha-lactalbumin, recombinant sheep prion protein, lysozyme, trypsin, and alpha-chymotrypsin the ability to integrate into self-organizing structures about 230–710 nm thick, measured by atomic force microscopy, was found. The formation of nanofilms is dependent on the protein/dendrimer ratio in the initial solution. At the same time, the nanofilms are resistant to pH changes, and the action of detergents. We demonstrated that trypsin and chymotrypsin incorporated into the nanofilms still conserved proteolytic activities and were stable for at least 3 weeks. We have also conducted in silico molecular modeling of the G4 dendrimer interactions with lysozyme. Spatial structure of the dendrimer-protein complex was predicted and most probable variant remained almost intact under 100 ns molecular dynamics simulation conditions. We believe that dendrimer-protein systems are promising tools for possible applications in the development of new stable biomaterials and biosensors.

Published
2018
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27. Halogen-free GeO2 conversion electrochemical reduction vs. complexation in (DTBC)(2)Ge[Py(CN)(n)] (n=0...2) complexes

Author

Amel Farhati, Elena N. Nikolaevskaya, Mikhail A. Kiskin, Evgeniya A. Saverina, Mikhail P. Egorov, Viatcheslav Jouikov, Alyona A. Starikova, Mikhail A. Syroeshkin, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Russian Science Foundation [17-73-20281], Russian Academy of Science, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Chemistry, chemistry.chemical_element, Germanium, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Medicinal chemistry, Toluene, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Elemental analysis, Dimethylformamide, [CHIM]Chemical Sciences, 0210 nano-technology, Spectroscopy, Single crystal, Tetrahydrofuran
Abstract

International audience; 3,5-di-tert-Butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0…2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n and characterized by elemental analysis, NMR, IR and UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has been determined by X-ray single crystal analysis. UV-VIS spectra have shown that these complexes are stable in CH3CN, toluene and CH2Cl2 solutions; in contrast, they are rapidly decomposed by dimethylformamide and tetrahydrofuran. Complexes 1 and 2 (with 4-cyano and 3-cyanopyridine) are electrochemically reducible in toluene/1 M Bu4NPF6 at E = -1.3…-1.7 V vs. AgCl. The quantum-chemical study of these complexes is in accordance with the unsuccessful attempts to obtain analogous derivatives with 2-cyanopyridine and 2,6-dicyanopyridine.

Published
2018
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28. DFT study of dihydrogen addition to molybdenum π-heteroaromatic complexes: a prerequisite step for the catalytic hydrodenitrogenation process

Author

Mikhail S. Nechaev, Evgenii O. Fetisov, Igor P. Gloriozov, Denis A. Kissounko, Yuri F. Oprunenko, Jean-Yves Saillard, Samia Kahlal, Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota [Twin Cities], University of Minnesota System-University of Minnesota System, Department of Chemistry, Moscow State University, Department of Science, Arapahoe Community College (ACC), A.V. Topchiev Institute of Petrochemical Synthesis (TIPS), Russian Academy of Sciences [Moscow] (RAS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), The authors thank Alexander von Humboldt Stiftung (Bonn, Germany) for providing the workstation and other software accessories to perform DFT calculations. This work was supported by Russian Science Foundation (RSF grant 14-50-00126)., University of Minnesota [Twin Cities] (UMN), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hydride, Quinoline, chemistry.chemical_element, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Ring (chemistry), Photochemistry, Oxidative addition, Medicinal chemistry, Catalysis, Transition state, chemistry.chemical_compound, chemistry, Molybdenum, Materials Chemistry, Hydrodenitrogenation, [CHIM]Chemical Sciences
Abstract

International audience; The range of molybdenum hydride complexes that are sought to participate in the important catalytic hydrodenitrogenation process (HDN) of nitrogen containing polycyclic aromatic hydrocarbons were evaluated by DFT studies. The previously synthesized stable (η6-quinoline)Mo(PMe3)3 complex 1N, in which molybdenum is bonded to the heterocyclic ring, was chosen as a model. The hydrogenation of the quinone heterocycle, which was postulated as the initial step in the overall HDN reaction, is found to occur via three consecutive steps of the oxidative addition of dihydrogen to Mo in 1N. Successive transfer of hydrogen atoms from the metal to the heterocycle leads to the ultimate formation of the tetrahydrido molybdenum intermediate Mo(PMe3)4H413 and 2,2,3,3-tetrahydroquinoline C9H11N 14. All the involved intermediates and transition states have been fully characterized by DFT. This computational modeling of the hydrogenation of quinoline, as a part of extended HDN catalytic processes, provides a fundamental understanding of such mechanisms

Published
2015
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29. Synthesis of a Pentasaccharide and Neoglycoconjugates Related to Fungal α-(1→3)-Glucan and Their Use in the Generation of Antibodies to Trace Aspergillus fumigatus Cell Wall

Author

Maria V. Orekhova, Bozhena S. Komarova, Vishukumar Aimanianda, Rémi Beau, Yury E. Tsvetkov, Jean-Paul Latgé, Nikolay E. Nifantiev, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Aspergillus, Institut Pasteur [Paris], This work was supported RSF grant 14‐23‐00199 (NEN)., and Institut Pasteur [Paris] (IP)

Subjects
Glycoconjugate, Disaccharide, carbohydrates, Oligosaccharides, Aspergillus fumigatus, chemistry.chemical_compound, Mice, Biotin, Cell Wall, MESH: Animals, Bovine serum albumin, Glucans, [SDV.MP.MYC]Life Sciences [q-bio]/Microbiology and Parasitology/Mycology, chemistry.chemical_classification, Mice, Inbred BALB C, biology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Serum Albumin, Bovine, 3. Good health, imaging agents, MESH: Cattle, Biochemistry, Female, protecting groups, Antibody, MESH: Aspergillus fumigatus, Glycosylation, glycosylation, MESH: Mice, Inbred BALB C, Catalysis, Antibodies, MESH: Cell Wall, MESH: Glucans, MESH: Biotin, Animals, MESH: Glycoconjugates, MESH: Mice, MESH: Antibodies, Organic Chemistry, General Chemistry, biology.organism_classification, glycoconjugates, chemistry, biology.protein, Cattle, MESH: Oligosaccharides, MESH: Female, MESH: Serum Albumin, Bovine, Conjugate
Abstract

International audience; 3-Aminopropyl α-(1→3)-pentaglucoside, a fragment of α-(1→3)-glucan of the cell wall of Aspergillus fumigatus, has been synthesized in a blockwise approach. The application of mono- and disaccharide N-phenyltrifluoroacetimidates bearing a stereodirecting 6-O-benzoyl group was essential for stereoselective α-glucosylations. In the products, p-methoxyphenyl and levulinoyl groups served as orthogonal protecting groups for the anomeric position and 3-OH group, respectively. Their removal from shared blocks led to donors and acceptors that were used for the synthesis of pentasaccharides. Coupling of free α-(1→3)-pentaglucoside with biotin and bovine serum albumin (BSA) gave glycoconjugate tools for mycological studies. Immunization of mice with the BSA conjugate induced the generation of antibodies that recognize α-(1→3)-glucan on A. fumigatus cell wall and distinguish its morphotypes. This discovery represents a first step to the development of a diagnostic test system and a vaccine to detect and fight this life-threatening pathogen.

Published
2015
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