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1. Antiviral and apoptosis modulating potential of fluorinated derivatives of uracil

Author

Naumenko, Krystyna; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Golovan, Anna; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Zelena, Lubov; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Shermolovich, Yuriy; Institute of organic chemistry of National Academy of Sciences of Ukraine Murmanska str., 5, Kyiv, Ukraine, 02660, Ganna, Gudz; Institute of organic chemistry of National Academy of Sciences of Ukraine Murmanska str., 5, Kyiv, Ukraine, 02660, Zagorodnya, Svіtlana; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Naumenko, Krystyna; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Golovan, Anna; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Zelena, Lubov; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143, Shermolovich, Yuriy; Institute of organic chemistry of National Academy of Sciences of Ukraine Murmanska str., 5, Kyiv, Ukraine, 02660, Ganna, Gudz; Institute of organic chemistry of National Academy of Sciences of Ukraine Murmanska str., 5, Kyiv, Ukraine, 02660, and Zagorodnya, Svіtlana; D. K. Zabolotny Institute of Microbiology and Virology of National Academy of Sciences of Ukraine Akademika Zabolotnoho str., 154, Kyiv, Ukraine, 03143

Abstract

The Epstein-Barr virus (EBV) is the first virus that has been classified as a human oncology virus. The ability of EBV to immortalize the cells of the human body is the highest among all known transforming viruses. Fluorine-containing nucleoside analogs represent a significant class of the chemotherapeutics widely used in the treatment for a lot of diseases. They have been playing a major role in treating tumor and virus either as selective inhibitors of enzymes for cancer or viral replication or as nucleic acid chain terminators which interrupt the replication of cancer cells or a virus.Aim. The purpose of this study was to analyze the potential antiviral and apoptosis modulating activity of fluorinated derivatives of uracil by using in silico and in vitro methods.Materials and methods. Two analogs (compound G26 and G27) on the base of 5-(p-tolilsulfonil)-6(polyfluoroalkyl)uracil were used in the study. The studies were conducted on cultures of Raji (latent infected EBV) and B95-8 (chronically producing virus) B-lymphoma cells. Trypan blue assay, MTT-method, neutral red uptake assay, PCR, flow cytometry, and web-servers PASS, PharmMapper were used.Results. According to PASS prediction, all compounds may possess the antiviral activity and anticancer activity. The in vitro study let to reveal the low level of cytotoxicity of these uracil derivatives. Anti-EBV activity was observed for all compounds and EC50 values were 75 and 65 µg/ml. Using PharmMapper, it has been shown that the targets are enzymes necessary for the replication of viral DNA (protease, kinase) and proteins that provide an apoptotic cascade (MAPK, cytochrome). For compound G27, several peaks on the histogram were observed, which may be evidence of changes in the cell cycle of lymphoblastoid cultures.Conclusions. In this way, the results of the present research shown an antiviral and apoptosis modulating activity of derivatives based on uracil. The data assumed by in silico methods can be used to mode, Першим вірусом класифікованим, як онкологічний був вірус Епштейна-Барр. Метою роботи було дослідити біологічні властивості фторованих похідних на основі урацилу. Згідно прогнозування PASS, сполуки G26 та G27 можуть мати противірусну активність. Анти-ВЕБ активність in vitro була показана для обох досліджуваних сполук. Таким чином, похідні урацилу є перспективними для створення нових антивірусних агентів

Published
2018

2. GigaSOM.jl: High-performance clustering and visualization of huge cytometry datasets

Author

University of Luxembourg: High Performance Computing - ULHPC [research center], Luxembourg Centre for Systems Biomedicine (LCSB): Bioinformatics Core (R. Schneider Group) [research center], ELIXIR CZ LM2018131 (MEYS) [sponsor], FNR AFR-RIKEN bilateral program (TregBar 2015/11228353) [sponsor], FNR PRIDE Doctoral Training Unit program (PRIDE/11012546/NEXTIMMUNE) [sponsor], Institute of Organic Chemistry and Biochemistry of the CAS (RVO: 61388963) [sponsor], ELIXIR Staff Exchange programme 2020 [sponsor], Kratochvil, Miroslav(*), Hunewald, Oliver(*), Heirendt, Laurent, Verissimo, Vasco, Vondrášek, Jiří, Satagopam, Venkata, Schneider, Reinhard, Trefois, Christophe, Ollert, Markus, University of Luxembourg: High Performance Computing - ULHPC [research center], Luxembourg Centre for Systems Biomedicine (LCSB): Bioinformatics Core (R. Schneider Group) [research center], ELIXIR CZ LM2018131 (MEYS) [sponsor], FNR AFR-RIKEN bilateral program (TregBar 2015/11228353) [sponsor], FNR PRIDE Doctoral Training Unit program (PRIDE/11012546/NEXTIMMUNE) [sponsor], Institute of Organic Chemistry and Biochemistry of the CAS (RVO: 61388963) [sponsor], ELIXIR Staff Exchange programme 2020 [sponsor], Kratochvil, Miroslav(*), Hunewald, Oliver(*), Heirendt, Laurent, Verissimo, Vasco, Vondrášek, Jiří, Satagopam, Venkata, Schneider, Reinhard, Trefois, Christophe, and Ollert, Markus

Abstract

Background: The amount of data generated in large clinical and phenotyping studies that use single-cell cytometry is constantly growing. Recent technological advances allow the easy generation of data with hundreds of millions of single-cell data points with >40 parameters, originating from thousands of individual samples. The analysis of that amount of high-dimensional data becomes demanding in both hardware and software of high-performance computational resources. Current software tools often do not scale to the datasets of such size; users are thus forced to downsample the data to bearable sizes, in turn losing accuracy and ability to detect many underlying complex phenomena. Results: We present GigaSOM.jl, a fast and scalable implementation of clustering and dimensionality reduction for flow and mass cytometry data. The implementation of GigaSOM.jl in the high-level and high-performance programming language Julia makes it accessible to the scientific community and allows for efficient handling and processing of datasets with billions of data points using distributed computing infrastructures. We describe the design of GigaSOM.jl, measure its performance and horizontal scaling capability, and showcase the functionality on a large dataset from a recent study. Conclusions: GigaSOM.jl facilitates the use of commonly available high-performance computing resources to process the largest available datasets within minutes, while producing results of the same quality as the current state-of-art software. Measurements indicate that the performance scales to much larger datasets. The example use on the data from a massive mouse phenotyping effort confirms the applicability of GigaSOM.jl to huge-scale studies.

Published
2020

3. 4-Амінозаміщені 1,6-дигідропіразоло[3,4-e][1,4]діазепіни: синтез, ямр-спектральне та квантово-хімічне дослідження

Author

Kemskіі, S. V.; Institute of Organic Chemistry of the NAS of Ukraine, Boyko, Yu. S.; Institute of Organic Chemistry of the NAS of Ukraine, Bolbut, A. V.; Institute of Organic Chemistry of the NAS of Ukraine, Suykov, S. Yu.; Institute of Organic Chemistry of the NAS of Ukraine, Kyrylchuk, A. A.; Institute of Organic Chemistry of the NAS of Ukraine, Vovk, M. V.; Institute of Organic Chemistry of the NAS of Ukraine, Kemskіі, S. V.; Institute of Organic Chemistry of the NAS of Ukraine, Boyko, Yu. S.; Institute of Organic Chemistry of the NAS of Ukraine, Bolbut, A. V.; Institute of Organic Chemistry of the NAS of Ukraine, Suykov, S. Yu.; Institute of Organic Chemistry of the NAS of Ukraine, Kyrylchuk, A. A.; Institute of Organic Chemistry of the NAS of Ukraine, and Vovk, M. V.; Institute of Organic Chemistry of the NAS of Ukraine

Abstract

Відзначена роль структурної модифікації 1,4-бензодіазепінових систем діалкіламіногрупами, яка раніше була успішно використана для одержання низки важливих похідних із комплексом специфічних біологічних властивостей. В поданій статті значно розширений спектр гетероанельованих діазепінів шляхом розробки препаративно зручного варіанту синтезу нових амінозаміщених піразоло[3,4-e][1,4]діазепінів. З цією метою детально досліджена реакція 4-хлоро-1,6-дигідропіразоло[3,4-e][1,4]діазепінів із первинними алкіл(арил)амінами та вторинними циклоалкіламінами. Встановлено, що така взаємодія перебігає при 8-10-годинному кип’ятінні в етанолі і у випадку первинних та вторинних алкіламінів приводить до гідрохлоридів 4-аміно-1,6-дигідропіразоло[3,4-e][1,4]діазепінів, а в разі ариламінів – до відповідних вільних основ з високими виходами. З’ясовано, що реакція з вторинними амінами дуже чутлива до їх просторових параметрів, тому діетил- або діізопропіламіни не схильні до взаємодії з 4-хлоропохідними 1,6-дигідропіразоло[3,4-e][1,4]діазепінів. Структура синтезованих сполук не суперечить результатам елементного аналізу, хроматомас-, ІЧ- та ЯМР-спектрів. Для надійного віднесення сигналів циклоалкіламінозамісників у відповідних 1,6-дигідропіразоло[3,4-e][1,4]діазепінах використані методики COSY та EXSY. Спектральні зміни в процесі протонування 5-циклоалкіламінопіразолодіазепінів узгоджуються з результатами квантово-хімічного моделювання, згідно із яким найвигіднішою є структура з протонованим атомом азоту в положенні 5 піразолодіазепінової системи., The role of the structural modification of 1,4-benzodiazepine systems with dialkylamino groups previously used successfully for a number of important derivatives possessing a complex of specific biological properties has been noted. This paper significantly expands the variety of hetero-annelated diazepines by developing a preparatively convenient synthetic route of new amino substituted pyrazol[3,4-e][1,4]diazepines. For this purpose, the reaction of 4-chloro-1,6-dihydropyrazolo[3,4-e][1,4]diazepines with the primary alkyl (aryl) amines and the secon- dary cycloalkylamines has been studied in detail. It has been found that this interaction occurs under 8-10 hour reflux in ethanol and for the primary and secondary alkylamines it leads to 4-amino-1,6-dihydropyrazolo[3,4-e] [1,4]diazepine hydrochlorides, and in case of aryl amines – to their corresponding free bases with high yields. The reaction of the secondary amines has been shown to be very sensitive to their steric parameters: dietyl- or diisopropylamines do not interact with 4-chloro derivatives of 1,6-dihydropyrazolo[3,4-e][1,4]diazepines. The structure of the compounds synthesized is consistent with the results of elemental analysis, LS/MS-, IR- and NMR-spectra. The COSY and EXSY methods were used for reliable identification of signals of cycloalkylamino substituents of 1,6 dihydropyrazolo[3,4-e][1,4]diazepines. Changes in NMR-spectra during protonation of 5-cycloalkylaminopyrazolodiazepines correspond to the results of quantum chemical simulations, according to them the preferred structure is the one with the protonated nitrogen atom in position 5 of the pyrazolodiazepine system., Отмечена роль структурной модификации 1,4-бензодиазепиновых систем диалкиламиногруппами, которая ранее была успешно использована для получения ряда важных производных c комплексом специфических биологических свойств. В данной статье значительно расширен спектр гетероаннелированных диазепинов путём разработки препаративно удобного варианта синтеза новых аминозамещенных пиразол[3,4-e] [1,4] диазепинов. С этой целью подробно исследована реакция 4-хлор-1,6- дигидропиразоло[3,4-e][1,4] диазепинов с первичными алкил(арил)аминами и вторичными циклоалкиламинами. Установлено, что такое взаимодействие протекает при 8-10-часовом кипячении в этаноле и в случае первичных и вторичных алкиламинов приводит к гидрохлоридам 4-амино-1,6-дигидропиразоло[3,4-e][1,4]диазепинов, а в случае ариламинов – к соответствующим свободным основаниям с высокими выходами. Показано, что реакция со вторичными аминами чувствительна к их пространственным параметрам, и диэтил- или диизопропиламины не склонны к взаимодействию с 4-хлорпроизводными 1,6-дигидропиразоло[3,4-e][1,4] диазепинов. Структура синтезированных соединений не противоречит данным элементного анализа, хроматомасс-, ИК- и ЯМР-спектров. Для надежного отнесения сигналов циклоалкиламинозаместителей в соответствующих 1,6-дигидропиразоло[3,4-e][1,4]диазепинах использованы методики COSY и EXSY. Спектральные изменения в процессе протонирования 5-циклоалкиламинопиразолодиазепинов согласуются с результатами квантово-химического моделирования, согласно которым наиболее выгодной является структура с протонированным атомом азота в положении 5 пиразолодиазепиновой системы.

Published
2016

4. Inside Cover: Access to Organometallic Arylcobaltcorrins through Radical Synthesis: 4???Ethylphenylcobalamin, a Potential ???Antivitamin???B 12 ??? (Angew. Chem. Int. Ed. 9/2013)

Author

Department of Biological Chemistry, University of Michigan, Ann Arbor (USA), Institute of Organic Chemistry and Centre of Molecular Biosciences, University of Innsbruck, Innrain 80/82, 6020 Innsbruck (Austria) http://homepage.uibk.ac.at/???c72602/kraeutler.htm, Department of Engineering Science, Aarhus University (Denmark), Institute of Molecular Biosciences, University of Graz (Austria), Ruetz, Markus, Gherasim, Carmen, Gruber, Karl, Fedosov, Sergey, Banerjee, Ruma, Kr??utler, Bernhard, Department of Biological Chemistry, University of Michigan, Ann Arbor (USA), Institute of Organic Chemistry and Centre of Molecular Biosciences, University of Innsbruck, Innrain 80/82, 6020 Innsbruck (Austria) http://homepage.uibk.ac.at/???c72602/kraeutler.htm, Department of Engineering Science, Aarhus University (Denmark), Institute of Molecular Biosciences, University of Graz (Austria), Ruetz, Markus, Gherasim, Carmen, Gruber, Karl, Fedosov, Sergey, Banerjee, Ruma, and Kr??utler, Bernhard

Published
2013

5. Reaction pathways at the initial steps of trioxane polymerisationElectronic supplementary information (ESI) available. See DOI: 10.1039/c8cy01691g

Author

Hoffmann, Matthias, BizzarriCurrent address: Institute of Organic Chemistry, Claudia, (KIT), Karlsruhe Institute of Technology, Fr, Leitner, Walter, MüllerCurrent address: Rheinische Fachhochschule Köln gGmbH, Thomas E., and Prozesste, Professur für Verfahrens- und

Abstract

Cleavage and (re)formation of oxymethylene moieties are essential steps during the build-up of polyoxymethylene (POM), a technically relevant high-performance polymer. To reveal how the catalyst accomplishes the cleavage of oxymethylene moieties, the kinetics of the ring-opening of trioxane was studied. Thereby insights into the initial phase of the growth of oxymethylene chains were obtained. The chain length of short oligomers was controlled with acetic anhydride as transfer agent. With a high ratio of acetic anhydride to trioxane, the first homologues of the series, trioxymethylene diacetate, dioxymethylene diacetate and monooxymethylene diacetate were obtained in excellent yield. The homologues show distinct features in the NMR and IR spectra that were related to their reactivity during chain propagation. Formation of intermediate hemi-acetal oxonium moieties is suggested to be a key step in the reaction pathway. Such molecular level insight may be a crucial factor for further tailoring production and properties of polyoxymethylene as well as introducing oligomeric oxymethylene diacetates to new application fields.

Published
2018
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6. Prenylated p-Hydroxyacetophenone Derivatives from the Giant Senecio johnstonii

Author

The University of Michigan, Ann Arbor, MI 48109-1048, U.S.A., Institute for Organic Chemistry, Technical University of Berlin, D-1000, Berlin 12, F.R.G., Dupre, S., Bohlmann, F., Knox, E., The University of Michigan, Ann Arbor, MI 48109-1048, U.S.A., Institute for Organic Chemistry, Technical University of Berlin, D-1000, Berlin 12, F.R.G., Dupre, S., Bohlmann, F., and Knox, E.

Abstract

The extract of the aerial parts of S. johnstonii afforded five known prenylated p-hydroxyacetophenone derivatives, scopoletin and 5-pentadecyl resorcinol together with the tridecyl derivative. The chemotaxonomic situation is discussed briefly.

Published
2006

7. Competition between stacking and hydrogen bonding: theoretical study of the phenol⋯Ar cation and neutral complex and comparison to experiment.

Author

Jiří Černý, Xin Tong, Pavel HobzaPhoton Science Institute Fellow. Present address: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic., and Klaus Müller-Dethlefs

Abstract

Experimental results obtained previously for vdW-bonded and H-bonded phenol⋯argon (PhOH⋯Ar) complexes in their S0 and D0 states are combined with ab initio quantum-chemical theoretical results. Such a combination allows us to present a “complete” description of the geometry, relative energies, interaction energies and enthalpies of PhOH⋯Ar complexes. Based on a minimum-energy-path study, the transition structures and barrier heights related to transitions between stable conformers are also presented. For the presented structures, the agreement between the theoretical interaction enthalpy at 0 K with experimentally obtained values is very good. On the other hand, for numerical harmonic-frequency calculations we find a very poor performance for the neutral PhOH⋯Ar complex and complete failure for the studied complexes in their cationic form. [ABSTRACT FROM AUTHOR]

Published
2008

10. Liquid crystalline properties of unsymmetrical bent-core compounds containing chiral moietiesElectronic supplementary information (ESI) available: Synthetic procedures and analytical data for all the compounds discussed here, textural photographs of SmCsphase under electric field. See http://dx.doi.org/10.1039b419479a

Author

ReddyPresent address: Institute of Organic Chemistry, R. Amaranatha, University, Martin-Luther, Kurt-Mothes-Str.2, 0, Sadashiva, B. K., and Baumeister, U.

Abstract

The synthesis, characterization and mesomorphic properties of new unsymmetrical bent-core compounds containing chiral moieties are reported. These compounds have been derived from either 3-hydroxybenzoic acid or 2,7-dihydroxynaphthalene as the central unit. The chiral group is incorporated either within the bent-core structure as a linking group or is appended in the terminal position. The influence of the position of the chiral moiety on the mesomorphic properties has been investigated. The bent-core compounds containing a chiral group octan-2-ol in the terminal chain exhibit a direct transition from chiral calamitic phases such as SmC, SmCγto a polar banana phase with a two-dimensional lattice ColobPA on decreasing temperature. In order to prove this phase sequence, the corresponding compound with a racemic octan-2-ol group at the terminal chain has been synthesized. The preliminary observations and investigations are presented for comparison with the chiral compound. Possible explanations for this unusual phase sequence and the models for the ColobPA SmCSPA phase are also discussed on the basis of X-ray and electric field experiments.

Published
2005
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11. Methanol synthesis over ZnO: A structure-sensitive reaction

Author

Wilmer, H., Kurtz, M., Klementiev, K. V., TkachenkoOn leave from Institute of Organic Chemistry, O. P., Sciences, Russian Academy of, Moscow., Grünert, W., Hinrichsen, O., Birkner, A., Rabe, S., Merz, K., Driess, M., Wöll, C., and Muhler, M.

Abstract

In order to identify active sites on ZnO powdered catalysts in methanol synthesis a total of five ZnO samples with different degrees of crystallinity were characterized by means of N2physisorption, XRD, TEM, and EXAFS. With respect to catalysis, high-pressure methanol synthesis was performed as a test reaction. A linear area-activity relationship for the highly crystalline materials was obtained, but at high BET surface areas a strong deviation from linearity was found. The observed phenomena provide evidence for a structure-sensitivity, suggesting that a specific active site is favored for methanol formation. Based on earlier work with polycrystalline ZnO powder and with respect to the current theoretical and experimental work with ZnO single crystals, the polar ZnO faces are assumed to be highly relevant for the catalytic activity under methanol synthesis conditions.

Published
2003
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12. The structure of zinc and copper oxide species hosted in porous siliceous matrices

Author

TkachenkoOn leave from N. D. Zelinsky Institute of Organic Chemistry, O. P., Science, Russian Academy of, Mo, Klementiev, K. V., Löffler, E., Ritzkopf, I., Schüth, F., Bandyopadhyay, M., Grabowski, S., Gies, H., Hagen, V., Muhler, M., Lu, Lianhai, Fischer, R. A., and Grünert, W.

Abstract

Microporous and mesoporous siliceous phases MFI, FAU, MCM-48, MCM-41, and SBA-15 were modified with zinc viaaqueous and organometallic routes and characterized with techniques that reflect the structure of the matrix, the distribution of zinc over the matrix, and the structure of the zinc oxide species XRD, nitrogen physisorption, IR spectroscopy, XPS, X-ray absorption fine structure XAFS, UV-Vis spectroscopy. For comparison, MFI and MCM-48 were modified with copper alone and characterised by XPSX-ray induced Auger electron spectroscopy and XAFS. From the results, it can be concluded that zinc interacts strongly with the siliceous surfaces, which prevents the formation of ZnO aggregates even when the coverage exceeds the monolayer limit. While zinc could be well distributed over FAU and mesoporous matrices by treatment with diethyl zinc, it remained on the external surface of MFI, possibly due to pore entrance narrowing by adsorbed species. For MCM-48 and MCM-41, the formation of a thin, probably monolayer surface zinc silicate coating was concluded from the data. With an aqueous impregnation technique, strong changes in the pore system of MCM-48 were noted, which indicate rupture of pore walls and partial structural damage. Different from zinc, copper forms small oxide aggregates upon introduction into micro and mesoporous siliceous matrices.

Published
2003
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13. Heterodimeric capsules formed by tetratosyl and tetratolyl urea calix[4]arenesCCDC reference number 653881. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b716368a.

Author

Michael Bolte, Iris Thondorf, Volker Böhmer, Valentyn RudzevichPermanent address: Institute of Organic Chemistry, NAS of Ukraine, Murmanska Str. 5, 02094 Kyiv-94, Ukraine., and Yuliya Rudzevich

Subjects
CRYSTALLOGRAPHY, HYDROGEN bonding, UREA, X-rays
Abstract

Predictions made by MD simulations for size, shape and guest inclusion of a heterodimer formed by a tetratosyl and a tetratolyl urea calix[4]arene and for its hydrogen bonding system have been entirely confirmed by a single crystal X-ray structure. [ABSTRACT FROM AUTHOR]

Published
2008
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14. A catenane consisting of a large ring threaded through both cyclic units of a handcuff-like compoundElectronic supplementary information (ESI) available: A numbered figure of the molecules 3, 52and 12for the 1H NMR assignment. See http://dx.doi.org/10.1039b509745b

Author

Frey, Julien, KrausPresent address: Institute of Organic Chemistry, Tomáš, Biochemistry, 2, Flemingovo nam., Prag, 16610, Heitz, Valérie, and Sauvage, Jean-Pierre

Abstract

The template effect of copperi allowed the preparation of a new catenane constructed around a bis-macrocyclic unit; a double ring-closing metathesis reaction afforded the central ring which is threaded through both rings of the bis-macrocycle.

Published
2005
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15. SYNTHESIS OF GROUP IV ORGANOMETALLIC POLYMERS AND RELATED COMPOUNDS

Author

INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), Leusink, A. J., Noltes, J. G., Budding, H. A., Van Der Kerk, G. J. M., INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), Leusink, A. J., Noltes, J. G., Budding, H. A., and Van Der Kerk, G. J. M.

Abstract

The synthesis and characterization are described of linear polymers, having a carbon chain regularly interrupted by the Group IV elements silicon, germanium, tin, or lead. Such polymers were obtained by means of: (1) poly- addition reactions involving an organotin dihydride and either a dienic, a diynic, or a monoynic compound; (2) Wurtz-type poly-condensations involving appropriate combinations of p-chlorophyenyl and chloro derivatives of the Group IV elements. The synthesis and polymerization of vinyl-type Group IV organometallic monomers is dealt with briefly. Furthermore, interesting Group IV metal-containing heterocycles were prepared and also a few polymers containing, in addition to Group IV atoms, other, other heteroelements in their backbone. All polymer-forming reactions were studied by carrying out model reactions on a low-molecular weight level.

Published
1965

16. Synthesis of Organotin Polymers by Poly-Addition

Author

INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), Noltes, J. G., van der Kerk, G. J., INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), Noltes, J. G., and van der Kerk, G. J.

Abstract

The results of a synthetic program directed towards the preparation of IVth main group organometallic polymers are presented. The main body of the report is concerned with the synthesis of linear polymers having a carbon chain regularly interrupted by tin (and in some cases other IVth group) atoms Such polymers have been obtained by means of true poly-addition reactions (hydrogen transfer polymerization) involving an organotin dihydride and either a dienic or a diynic or a monoyni C coumpound The synthesis of lVth group organometal-substituted polystyrenes carbon chain polymers containing the organometallic moiety as a substituent group as well as of a series of poly-p-phenylenesilanes-polymers consisting of chains of p-phenylene groups connected by dialkyl(aryl) silane groups are dealt with briefly.

Published
1962

17. THE SYNTHESIS OF IVTH GROUP ORGANOMETALLIC POLYMERS AND RELATED COMPOUNDS.

Author

INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), LEUSINK,A. J., Noltes,J. G., Budding,H. A., Van der Kerk,G. J. M., INSTITUTE FOR ORGANIC CHEMISTRY TNO UTRECHT (NETHERLANDS), LEUSINK,A. J., Noltes,J. G., Budding,H. A., and Van der Kerk,G. J. M.

Abstract

The synthesis and characterization are described of linear polymers, having a carbon chain regularly interrupted by the Group IV elements silicon, germanium, tin or lead. Such polymers were obtained by means of: (1) poly-addition reactions involving an organotin dihydride and either a dienic, a diynic or a monoynic compound; (2) Wurtz-type poly-condensations involving appropriate combinations of p-chlorophenyl and chloro derivatives of the Group IV elements. The synthesis and polymerization of vinyl-type IVth group organometallic monomers is dealt with briefly. Furthermore, interesting IVth group metal-containing heterocyoles were prepared and also a few polymers, containing in addition to Group IV atoms other hetero-elements in their backbone. All polymer-forming reactions have been studied by carrying out model reactions on a low-molecular weight level. (Author)

Published
1964

18. Persistent Organic Pollutants Burden, Trophic Magnification and Risk in a Pelagic Food Web from Coastal NW Mediterranean Sea

Author

Geneviève Deviller, Chia-Ting Chen, Begoña Jiménez, Juan Muñoz-Arnanz, Daniela Bănaru, Javier Castro-Jiménez, Richard Sempéré, Institut méditerranéen d'océanologie (MIO), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), institute of organic chemistry (IQOG-GSIC), Madrid, Spain (IQOC-CSIC), IQOG-CSIC-Institute of organic chemistry (IQOG-CSIC), Madrid, Spain (IQOG-CSIC), DERAC Environmental Risk Assessment Chem, Labex OT-Med (no. ANR-11-LABX-0061) – MEDPOPFrench Government Investissements d’Avenir (ANR) through the A*MIDEX project (no ANR-11-IDEX-0001-02) PARME CNRS EC2CO project, and ANR-19-CE34-0001,CONTAMPUMP,Plancton: pompe biologique de contaminants dans les écosystèmes marins (CONTAMPUMP)?(2019)

Subjects
Food Chain, Polychlorinated Dibenzodioxins, cephalopods, plankton, cephalopods, 010501 environmental sciences, Dioxins, 01 natural sciences, Zooplankton, Flame retardants, Persistent Organic Pollutants, Polybrominated diphenyl ethers, Halogenated Diphenyl Ethers, Mediterranean Sea, Animals, Humans, Environmental Chemistry, 14. Life underwater, PCBs, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Trophic level, [SDU.OCEAN]Sciences of the Universe [physics]/Ocean, Atmosphere, biology, plankton, Pelagic zone, General Chemistry, Environmental exposure, Dibenzofurans, Polychlorinated, biology.organism_classification, Polychlorinated Biphenyls, Bioaccumulation, 6. Clean water, Food web, Atlantic bonito, Fish, 13. Climate action, Environmental chemistry, Environmental science, Sarda, Dibenzofurans, Environmental Monitoring
Abstract

The storage capacity, trophic magnification and risk of sixty-two POPs have been evaluated in a well-characterized pelagic food web (including phytoplankton, zooplankton, six fish, and two cephalopods species) from an impacted area in NW Mediterranean Sea. Our results show the high capacity of the planktonic compartment for the storage of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), consistent with their estimated low trophic magnification factors (TMF) of 0.2-2.0 (PBDEs) and of 0.3-1.1 (PCDD/Fs). ∑PBDEs dominated in the zooplankton size-class 200-1000 μm (∼330 ng g-1 lw, median), whereas ∑PCDD/Fs accumulated preferentially in phytoplankton size-class 0.7-200 μm (875 pg g-1 lw, median). In contrast, polychlorinated biphenyls (PCBs) were preferentially bioaccumulated in the higher trophic levels (six fish species and two cephalopods) with TMFs = 0.8-3.9, reaching median concentrations of 4270 and 3140 ng g-1 lw (∑PCBs) in Atlantic bonito (Sarda sarda) and chub mackerel (Scomber colias), respectively. For these edible species, the estimated weekly intakes of dioxin-like POPs for humans based on national consumption standards overpassed the EU tolerable weekly intake. Moreover, the concentrations of nondioxin-like PCBs in S. sarda were above the EU maximum levels in foodstuffs, pointing to a risk. No risk evidence was found due to consumption of all other edible species studied, neither for PBDEs. The integrated burden of POPs in the food web reached ∼18 μg g-1 lw, representing a dynamic stock of toxic organic chemicals in the study area. We show that the characterized food web could be a useful and comprehensive "bioindicator"of the chemical pollution status of the study area, opening new perspectives for the monitoring of toxic chemicals in Mediterranean coastal waters., This work was funded by the Labex OT-Med (no. ANR-11- LABX-0061) −MEDPOP, funded by the French Government Investissements d’Avenir (ANR) through the A*MIDEX project (no ANR-11-IDEX-0001-02) and contributes to the MER- MEX/MISTRALS program. It also received financial support from the PARME CNRS EC2CO project. D. Bănaru had the benefit of leave within the ANR CONTAMPUMP project (no ANR-19-CE34-0001) and C.-T. Chen received PhD funding from French Ministry of National Education, Research and Technology. A financial contribution was obtained too from the Ministry of Agriculture and Fisheries, Food and Environ- ment (MAPAMA), project 15CAES004. J.M-A. acknowledges his contract under projects 15CAES004 and 17CAES004. We thank Bastian Carré for his help for lipid analyses and Christian Re for his assistance in sample preparation.

Published
2021
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19. Cysteine oxidation and disulfide formation in the ribosomal exit tunnel

Author

Schulte, Linda, Mao, Jiafei, Reitz, Julian, Sreeramulu, Sridhar, Kudlinzki, Denis, Hodirnau, Victor-Valentin, Meier-Credo, Jakob, Saxena, Krishna, Buhr, Florian, Langer, Julian D., Blackledge, Martin, Frangakis, Achilleas S., Glaubitz, Clemens, Schwalbe, Harald, Institute of Organic Chemistry and Chemical Biology, Goethe-Universität Frankfurt am Main, Institute for Biophysical Chemistry & Centre for Biomolecular Magnetic Resonance, Goethe-University Frankfurt, 60438 Frankfurt am Main, Germany, Institute for Biophysics, Buchmann Institute for Molecular Life Science, Institute of Science and Technology [Austria] (IST Austria), Max Planck Institute of Biophysics [Frankfurt am Main] (MPIBP), Max-Planck-Gesellschaft, Center for Biomolecular Magnetic Resonance, Goethe-Universität Frankfurt am Main-Institute for Organic Chemistry and Chemical Biology, Institut de biologie structurale (IBS - UMR 5075), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institute of Biophysical Chemistry, Center for Biomolecular Magnetic Resonance (BMRZ), Reitz, Julian [0000-0002-0393-0655], Meier-Credo, Jakob [0000-0003-1026-1573], Blackledge, Martin [0000-0003-0935-721X], Frangakis, Achilleas S [0000-0002-8067-6611], Glaubitz, Clemens [0000-0002-3554-6586], Schwalbe, Harald [0000-0001-5693-7909], Apollo - University of Cambridge Repository, and Institute of Science and Technology [Klosterneuburg, Austria] (IST Austria)

Subjects
Models, Molecular, MESH: Oxidation-Reduction, Protein Folding, Magnetic Resonance Spectroscopy, MESH: Mutation, Protein Conformation, Science, MESH: Protein Folding, Article, Mass Spectrometry, MESH: Protein Conformation, ddc:570, MESH: S-Nitrosothiols, MESH: Disulfides, Cysteine, Disulfides, gamma-Crystallins, lcsh:Science, MESH: Glutathione, MESH: Mass Spectrometry, S-Nitrosothiols, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], MESH: gamma-Crystallins, MESH: Magnetic Resonance Spectroscopy, Cryoelectron Microscopy, food and beverages, MESH: Cysteine, Glutathione, Protein Biosynthesis, MESH: Protein Biosynthesis, Mutation, ddc:540, lcsh:Q, Molecular modelling, MESH: Cryoelectron Microscopy, Structural biology, Solution-state NMR, Oxidation-Reduction, Ribosomes, MESH: Ribosomes, MESH: Models, Molecular
Abstract

Understanding the conformational sampling of translation-arrested ribosome nascent chain complexes is key to understand co-translational folding. Up to now, coupling of cysteine oxidation, disulfide bond formation and structure formation in nascent chains has remained elusive. Here, we investigate the eye-lens protein γB-crystallin in the ribosomal exit tunnel. Using mass spectrometry, theoretical simulations, dynamic nuclear polarization-enhanced solid-state nuclear magnetic resonance and cryo-electron microscopy, we show that thiol groups of cysteine residues undergo S-glutathionylation and S-nitrosylation and form non-native disulfide bonds. Thus, covalent modification chemistry occurs already prior to nascent chain release as the ribosome exit tunnel provides sufficient space even for disulfide bond formation which can guide protein folding., As protein synthesis takes place, newly synthesized polypeptide chain passes through the ribosomal exit tunnel, which can accommodate up to 70 residues in the case of a helical peptide. Here the authors show that oxidation of cysteine residues in the nascent chain can occur within the ribosome exit tunnel, where sufficient space exists for the formation of disulfide bonds.

Published
2020
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20. Translation of non-standard codon nucleotides reveals minimal requirements for codon-anticodon interactions

Author

Ronald Micura, Aaron Siewert, Eric Westhof, Christoph Kreutz, Johannes Kremser, Catherina Gasser, Thomas Philipp Hoernes, Elisabeth Fuchs, Alexander Hüttenhofer, Michael Andreas Juen, Herbert Lindner, Klaus Faserl, Xinying Shi, Claudia Höbartner, Matthias D. Erlacher, Simpson Joseph, Innsbruck Medical University [Austria] (IMU), Institute of Organic Chemistry, University of Innsbruck, Institute of Organic Chemistry, Center for Molecular Biosciences, Univ, Architecture et Réactivité de l'ARN (ARN), Institut de biologie moléculaire et cellulaire (IBMC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Innsbruck Biocenter, and Innsbrück Biocenter

Subjects
0301 basic medicine, Pyridones, Science, [SDV]Life Sciences [q-bio], information science, General Physics and Astronomy, Wobble base pair, Computational biology, Cytidine, Ribosome, General Biochemistry, Genetics and Molecular Biology, Article, 03 medical and health sciences, Viral Proteins, Bacteriophage T7, medicine, Protein biosynthesis, Anticodon, Escherichia coli, Receptor, Serotonin, 5-HT2C, Humans, Nucleotide, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Inosine, 2-Aminopurine, Codon, lcsh:Science, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Messenger RNA, Multidisciplinary, Base Sequence, Chemistry, RNA, Hydrogen Bonding, [SDV.BBM.BM]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Molecular biology, General Chemistry, DNA-Directed RNA Polymerases, RNA, Transfer, Gly, 030104 developmental biology, HEK293 Cells, Protein Biosynthesis, Transfer RNA, bacteria, lcsh:Q, Ribosomes, medicine.drug
Abstract

The precise interplay between the mRNA codon and the tRNA anticodon is crucial for ensuring efficient and accurate translation by the ribosome. The insertion of RNA nucleobase derivatives in the mRNA allowed us to modulate the stability of the codon-anticodon interaction in the decoding site of bacterial and eukaryotic ribosomes, allowing an in-depth analysis of codon recognition. We found the hydrogen bond between the N1 of purines and the N3 of pyrimidines to be sufficient for decoding of the first two codon nucleotides, whereas adequate stacking between the RNA bases is critical at the wobble position. Inosine, found in eukaryotic mRNAs, is an important example of destabilization of the codon-anticodon interaction. Whereas single inosines are efficiently translated, multiple inosines, e.g., in the serotonin receptor 5-HT2C mRNA, inhibit translation. Thus, our results indicate that despite the robustness of the decoding process, its tolerance toward the weakening of codon-anticodon interactions is limited., The recognition of the mRNA codon by the tRNA anticodon is crucial for protein synthesis. Here the authors introduce non-standard nucleotides in bacterial and eukaryotic mRNA to reveal the minimal hydrogen bond requirement of codon-anticodon interaction for efficient and accurate translation.

Published
2018
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21. Radical polymerization of radical-labeled monomers: The triarylmethyl-based radical monomer as an example

Author

Elena G. Bagryanskaya, Olga Yu. Rogozhnikova, Mariya V. Edeleva, Tatiana I. Troitskaya, Sylvain R. A. Marque, Victor M. Tormyshev, Novosibirsk State University (NSU), N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Vorozhtsov Novosibirsk Institute of Organic Chemistry (RAS, SB, NN )

Subjects
Polymers and Plastics, Chemistry, Organic Chemistry, Radical polymerization, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Monomer, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract

WOS:000449661700006; Recent development of spin-labeled nitroxide-mediated polymerization (NMP) involving successful polymer preparation with high livingness and narrow dispersity in the presence of persistent trityl-based stable radicals attached to the initiators (90% recovery of a trityl radical signal after the polymerization) led us to the preparation of stable organic radical polymers based on trityl radical-substituted monomers using NMP as the method of polymerization despite the claims in the literature about its expected failure. Here, we present successful radical polymerization and NMP of a trityl radical-based tri- and mono-monomer yielding more than 90% recovery of the trityl radical signal. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2656-2664

Published
2018
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22. Acyclonucleosides bearing coplanar arylethynyltriazole nucleobases: synthesis, structural analysis, and biological evaluation

Author

Jianhua Yao, Mimi Chen, Mengyao Li, Suo Yaxiong, Yi Xia, Ling Peng, Zhengwei Zhou, Chongqing University [Chongqing], Shanghai Institute of Organic Chemistry - Chinese Academy of Sciences, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Shanghai Institute of Organic Chemistry-Chinese Academy of Sciences, and PENG, Ling

Subjects
0301 basic medicine, Stereochemistry, [SDV]Life Sciences [q-bio], Triazole, Sonogashira coupling, [SDV.CAN]Life Sciences [q-bio]/Cancer, Catalysis, Nucleobase, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, [SDV.CAN] Life Sciences [q-bio]/Cancer, Materials Chemistry, medicine, Molecule, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Biological evaluation, [CHIM.MATE] Chemical Sciences/Material chemistry, Nucleoside analogue, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, [SDV] Life Sciences [q-bio], [SDV.IB.BIO] Life Sciences [q-bio]/Bioengineering/Biomaterials, 030104 developmental biology, chemistry, 030220 oncology & carcinogenesis, Nucleoside, medicine.drug
Abstract

International audience; Nucleoside derivatives are an important class of molecules in the search for bioactive compounds. In our continuing efforts to develop novel nucleoside analogs, we used the Sonogashira cross-coupling reaction to synthesize 1,2,4-triazole acyclonucleosides bearing various arylethynyl groups on the triazole nucleobase. By employing 3-iodotriazole nucleoside as the coupling substrate, the Sonogashira reaction proceeded efficiently even with alkynes, which are notoriously unreactive and challenging. Further crystal structural analysis unveiled the coplanar feature of the 3-arylethynyltriazole motifs, suggesting their potential as surrogates for large planar aromatic systems or nucleobases. Most importantly, several synthesized compounds displayed interesting antiproliferative activity against various cancer cells and induced apoptosis, highlighting that this family of triazole nucleosides might show promise as anticancer candidates.

Published
2017
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23. The effect of the oxophilic Tb(III) cation on C ON bond homolysis in alkoxyamines

Author

Sylvain R. A. Marque, Elena G. Bagryanskaya, Irina Yu. Bagryanskaya, Evgeny V. Tretyakov, Polina Kaletina, Gérard Audran, Dmitriy Parkhomenko, Mariya V. Edeleva, Svetlana I. Zhivetyeva, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Novosibirsk State University (NSU), N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, and Vorozhtsov Novosibirsk Institute of Organic Chemistry (RAS, SB, NN )

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Nitroxyl, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, 3. Good health, Homolysis, Inorganic Chemistry, Metal, chemistry.chemical_compound, Reaction rate constant, chemistry, visual_art, Materials Chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Alkyl
Abstract

WOS:000430904400002; Recently, we reported on the activation of the C-ON bond homolysis in alkoxyamines R1R2NOR3 using the coordination of the alkyl fragment R-3 with metal cations Cu(II) and Zn(II). Here, we report the selective coordination of the diethylphosphoryl group carried by the nitroxyl fragment by the oxophilic metal cation Tb(III). Coordination on the nitroxyl fragment afford a slight 2-fold decrease in the C-ON bond homolysis rate constant kd. (C) 2018 Elsevier B.V. All rights reserved.

Published
2018
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24. How intramolecular coordination bonding (ICB) controls the homolysis of the C-ON bond in alkoxyamines

Author

Mariya V. Edeleva, Anna A. Iurchenkova, Polina Kaletina, Gérard Audran, Tung To Hai, Elena G. Bagryanskaya, Svetlana I. Zhivetyeva, Sergey A. Cherkasov, Irina Yu. Bagryanskaya, Sylvain R. A. Marque, Jean-Patrick Joly, Evgeny V. Tretyakov, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Novosibirsk State University (NSU), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Vorozhtsov Novosibirsk Institute of Organic Chemistry (RAS, SB, NN ), GRAMAT (DAM/GRAMAT), Direction des Applications Militaires (DAM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
chemistry.chemical_classification, General Chemical Engineering, Intermolecular force, Nitroxyl, Protonation, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, 3. Good health, Homolysis, chemistry.chemical_compound, chemistry, Computational chemistry, Intramolecular force, Molecule, [CHIM]Chemical Sciences, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology, Alkyl
Abstract

WOS:000481879400050; International audience; Because the C-ON bond homolysis rate constant k(d) is an essential parameter of alkoxyamine reactivity, it is especially important to tune k(d) without a major alteration of the structure of the molecule. Recently, several approaches have become known, e.g., protonation of functional groups and formation of metal complexes. In this paper, coordination reactions of [Zn(hfac)(2)(H2O)(2)] with a series of new SG1-based alkoxyamines affording complexes with different structures are presented. The k(d) values of the complexed forms of the alkoxyamines were compared to those of free and protonated ones to reveal the contribution of the electron-withdrawing property and structure stabilization. Together with previously published data, this work provides clues to the design of alkoxyamines that can be effectively activated upon coordination with metal ions. Furthermore, our results provide insight into the mechanism underlying the influence of complexation on the reactivity of alkoxyamines. This led us to describe different types of coordination: intramolecular in nitroxyl fragment, intramolecular in alkyl fragment, intramolecular between alkyl and nitroxyl fragment, and intermolecular one. All of them exhibit different trends which are dramatically altered by changes in conformation.

Published
2019
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25. Quantifying the Strength of a Salt Bridge by Neutron Scattering and Molecular Dynamics

Author

Philip E. Mason, Pavel Jungwirth, Elise Duboué-Dijon, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Laboratoire de biochimie théorique [Paris] (LBT (UPR_9080)), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)-Institut de biologie physico-chimique (IBPC (FR_550)), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] (ASCR), Université Paris Diderot - Paris 7 (UPD7)-Institut de biologie physico-chimique (IBPC), and Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Quantitative Biology::Biomolecules, Aqueous solution, Materials science, 010304 chemical physics, Force field (physics), Neutron diffraction, Guanidinium Cation, Neutron scattering, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Molecular dynamics, Chemical physics, 0103 physical sciences, Side chain, General Materials Science, Salt bridge, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The molecular structure and strength of a model salt bridge between a guanidinium cation as the charged side chain group of arginine and the carboxylic group of acetate in an aqueous solutions is characterized by a combination of neutron diffraction with isotopic substitution and molecular dynamics simulations. Being able to recover the second order difference signal, the present neutron scattering experiments provide direct information about ion pairing in the investigated solution. At the same time, these measurements serve as benchmarks for assessing the quality of the force field employed in the simulation. We show that a standard non-polarizable force field, which tends to overestimate the strength of salt bridges, does not reproduce the structural features from neutron scattering pertinent to ion pairing. In contrast, a quantitative agreement with experiment is obtained when electronic polarization effects are accounted for in a mean-field way via charge scaling. Such simulations are then used to quantify the weak character of a fully hydrated salt bridge. Finally, on top of the canonical hydrogen-bonding binding mode between guanidinium and acetate, these simulations also point to another interaction motif involving an out-of-plane hydrophobic contact of the methyl group of acetate with the guanidinium cation.

Published
2019
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26. Enantiopure C 1 -Cyclotriveratrylene with a Reversed Spatial Arrangement of the Substituents

Author

Cédric Colomban, Lorenzo Di Bari, Alexandre Martinez, Marion Jean, Michel Giorgi, Nicolas Vanthuyne, Marcin Górecki, Augustin Long, Muriel Albalat, Jean-Pierre Dutasta, Institut des Sciences Moléculaires de Marseille (ISM2), Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), University of Pisa - Università di Pisa, Institute of Organic Chemistry Polish Academy of Sciences, Laboratoire de Chimie, Ecole Normale Supérieure de Lyon and CNRS, Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Institute of Organic Chemistry [Warsaw], Polska Akademia Nauk = Polish Academy of Sciences (PAN), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Polska Akademia Nauk (PAN), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Absolute configuration, Cyclotriveratrylene, 010402 general chemistry, Biochemistry, Physical and Theoretical Chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, chemistry.chemical_compound, Enantiopure drug, chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Cyclophane
Abstract

International audience; Cyclotriveratrylene (CTV) is a macrocyclic cyclophane presenting a bowl-shaped conformation, used as building block to construct cryptophane and hemi-cryptophane capsules. A method to synthesize new enantiopure CTV derivatives with an unprecedented spatial arrangement of their substituents, exhibiting C 1 symmetry, is described. The absolute configuration was assigned by ECD spectroscopy coupled with modeling. A statistical model has allowed for optimization of the proportion of C 1 CTV, and the modularity of this approach is also highlighted.

Published
2019
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27. Adding attractive semio-chemical trait refines the taxonomy of Alpinobombus (Hymenoptera: Apidae)

Author

Thomas Lecocq, Paolo Biella, Denis Michez, Pierre Rasmont, Nicolas Brasero, Baptiste Martinet, Irena Valterová, Laboratoire de Zoologie [Mons], University of Mons [Belgium] (UMONS), Unité de Recherches Animal et Fonctionnalités des Produits Animaux (URAFPA), Institut National de la Recherche Agronomique (INRA)-Université de Lorraine (UL), University of South Bohemia, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), European Union's Horizon 2020 project INTERACT (730938), Czech Science Foundation (GACR GP14-10035P), University of South Bohemia (GA JU 152/2016/P), European Project: 0730938(2007), Université de Mons (UMons), Université de Lorraine (UL)-Institut National de la Recherche Agronomique (INRA), laboratoire de Zoologie, Université de Mons-Hainaut, Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences [Prague] (ASCR), Martinet, B, Brasero, N, Lecocq, T, Biella, P, Valterova, I, Michez, D, and Rasmont, P

Subjects
0106 biological sciences, 0301 basic medicine, Entomology, Species complex, taxonomie, [SDV]Life Sciences [q-bio], trait fonctionnel, Zoology, species, Hymenoptera, [SDV.BID.SPT]Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, 010603 evolutionary biology, 01 natural sciences, chemical trait, specie, bumblebees, species, cephalic labial gland secretions, arcto-alpine distribution, chemical trait, Alpinobombus, taxonomy, apidae, 03 medical and health sciences, apidae, taxonomie, trait fonctionnel, sécrétion glandulaire, taxonomy, cephalic labial gland secretions, cephalic labial gland secretion, Invertebrate Zoology, bumblebees, arcto-alpine distribution, Alpinobombus, sécrétion glandulaire, biology, Apidae, bumblebee, biology.organism_classification, Zoologie des invertébrés, 030104 developmental biology, Taxon, Insect Science, Trait, Taxonomy (biology)
Abstract

International audience; AbstractSpecies taxonomy of bumblebees (Bombus Latreille, 1802) is well known to be problematic due to a potentially high intra-specific variability of morphological traits while different species can converge locally to the same color pattern (cryptic species). Assessing species delimitation remains challenging because it requires to arbitrarily select variable traits whose accuracy continues to be debated. Integrative taxonomic approach seems to be very useful for this group as different independent traits are assessed to propose a rational taxonomic hypothesis. Among operational criteria to assess specific status, the reproductive traits involved in the pre-mating recognition (i.e., the male cephalic labial gland secretions, CLGS) have been premium information. Since these secretions are supposed to be species-specific, these chemical traits can bring essential information where species delimitation is debated. Here, we describe and compare the CLGS of 161 male specimens of nine Alpinobombus taxa: alpinus, balteatus, helleri, hyperboreus, kirbiellus, natvigi, neoboreus, polaris, and pyrrhopygus. We aim also to test the congruence between this new information (reproductive traits) and published genetic dataset. Our results emphasized six distinct groups with diagnostic major compounds: (a) alpinus + helleri with hexadec-9-en-1-ol; (b) polaris + pyrrhopygus with two major compounds hexadec-9-en-1-ol and hexadec-9-enal; (c) balteatus with tetradecyl acetate; (d) kirbiellus with geranyl geranyl acetate; (e) hyperboreus + natvigi with octadec-11-en-1-ol; (f) neoboreus with octadec-9-en-1-ol. Based on this new information, we can confirm the species status of B. alpinus, B. balteatus, B. hyperboreus, B. kirbiellus, B. neoboreus, and B. polaris. We also confirm the synonymy of helleri (Alps) with alpinus (Sweden). However, the specific status of natvigi (Alaska) and pyrrhopygus (Sweden) is questionable and these taxa do not have specific CLGS composition.

Published
2018
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28. Can Arginine Inhibit Insulin Aggregation? A Combined Protein Crystallography, Capillary Electrophoresis, and Molecular Simulation Study

Author

Pavel Jungwirth, Tim Ganderton, Vladimír Palivec, Cristina M. Viola, Elise Duboué-Dijon, Tomáš Křížek, Andrzej M. Brzozowski, Kryštof Březina, Jiří Jiráček, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Laboratoire de biochimie théorique [Paris] (LBT (UPR_9080)), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)-Institut de biologie physico-chimique (IBPC (FR_550)), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Charles University [Prague] (CU), University of York [York, UK], Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] (ASCR), Université Paris Diderot - Paris 7 (UPD7)-Institut de biologie physico-chimique (IBPC), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Charles University [Prague]

Subjects
0301 basic medicine, Arginine, medicine.medical_treatment, Plasma protein binding, 02 engineering and technology, Molecular Dynamics Simulation, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, 03 medical and health sciences, Molecular dynamics, Capillary electrophoresis, In vivo, 0103 physical sciences, Materials Chemistry, medicine, [CHIM.CRIS]Chemical Sciences/Cristallography, Humans, Insulin, Physical and Theoretical Chemistry, 010302 applied physics, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Chemistry, Osmolar Concentration, Electrophoresis, Capillary, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Electrophoresis, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], 030104 developmental biology, Ionic strength, Biophysics, Protein Multimerization, 0210 nano-technology, Protein Binding
Abstract

The oligomeric state of the storage form of human insulin in pancreas, which may be affected by several endogenous components of beta-cells storage granules such as arginine, is not known. Here, the effect of arginine on insulin oligomerisation is investigated independently by protein crystallography, molecular dynamics simulations and capillary electrophoresis. The combined results point to a strong effect of ionic strength on insulin assembly. Molecular simulations and electrophoretic measurements at low/mM salt concentrations show no significant effect of arginine on insulin aggregation. In contrast, crystallographic data at high/molar ionic strength indicate inhibition of insulin hexamerization by arginine due to its binding at site relevant for intermolecular contacts, which was also observed in MD simulations. Our results thus bracket the in vivo situation in pancreatic beta-cells storage granules, where the ionic strength is estimated to be in the hundreds of millimolar to sub-molar range. The present findings add to molecular understanding of in vivo insulin oligomerization and storage, with additional implications for insulin stability in arginine-rich injections.

Published
2018
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29. The cephalic labial gland secretions of two socially parasitic bumblebees Bombus hyperboreus ( Alpinobombus ) and Bombus inexspectatus ( Thoracobombus ) question their inquiline strategy

Author

Brasero, Nicolas, Martinet, Baptiste, Lecocq, Thomas, Lhomme, Patrick, Biella, Paolo, Valterova, Irena, Urbanová, Klára, Cornalba, Maurizio, Hines, Heather, Rasmont, Pierre, Université de Mons (UMons), Unité de Recherches Animal et Fonctionnalités des Produits Animaux (URAFPA), Institut National de la Recherche Agronomique (INRA)-Université de Lorraine (UL), Laboratoire de Zoologie (Research Institute of Biosciences), University of South Bohemia, Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences [Prague] (ASCR), Università di Pavia, laboratoire de Zoologie, Université de Mons-Hainaut, Laboratoire de Zoologie [Mons], University of Mons [Belgium] (UMONS), Pennsylvania State University (Penn State), Penn State System, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Università degli Studi di Pavia, Brasero, N, Martinet, B, Lecocq, T, Lhomme, P, Biella, P, Valterova, I, Urbanova, K, Cornalba, M, Hines, H, Rasmont, P, Università degli Studi di Pavia = University of Pavia (UNIPV), and European Project: 244090,EC:FP7:ENV,FP7-ENV-2009-1,STEP(2010)

Subjects
Male, Social parasitism, Animal, Bombus inexspectatus, [SDV.BID.EVO]Life Sciences [q-bio]/Biodiversity/Populations and Evolution [q-bio.PE], inquiline strategy, bumblebee, Bees, Bombus hyperboreus, Bombus inexspectatu, Animal Communication, bumblebees, Exocrine Glands, cephalic labial gland secretions, cephalic labial gland secretion, Animals, Female, Bombus hyperboreu, Social Behavior, Bee, ComputingMilieux_MISCELLANEOUS, Exocrine Gland
Abstract

Social parasitic Hymenopterans have evolved morphological, chemical, and behavioral adaptations to overcome the sophisticated recognition and defense systems of their social host to invade host nests and exploit their worker force. In bumblebees, social parasitism appeared in at least 3 subgenera independently: in the subgenus Psithyrus consisting entirely of parasitic species, in the subgenus Alpinobombus with Bombus hyperboreus, and in the subgenus Thoracobombus with B. inexspectatus. Cuckoo bumblebee males utilize species-specific cephalic labial gland secretions for mating purposes that can impact their inquiline strategy. We performed cephalic labial gland secretions in B. hyperboreus, B. inexspectatus and their hosts. Males of both parasitic species exhibited high species specific levels of cephalic gland secretions, including different main compounds. Our results showed no chemical mimicry in the cephalic gland secretions between inquilines and their host and we did not identify the repellent compounds already known in other cuckoo bumblebees.

Published
2018
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30. Synthesis of an enantiomerically pure inherently chiral calix[4]arene phosphonic acid and its evaluation as an organocatalyst

Author

Eric Manoury, V. I. Boiko, Jean-Claude Daran, Oleksandr A. Yesypenko, Andrii Karpus, Vitaly I. Kalchenko, Zoia Voitenko, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Taras Shevchenko University of Kiev, Institute of Organic Chemistry, National Academy of Sciences of Ukraine, National Academy of Sciences of Ukraine (NASU), and Institute of Organic Chemistry of NASU [Kyiv]

Subjects
Organophosphorus compounds, Aromatic compounds, 010405 organic chemistry, Organic Chemistry, Epoxide, Reaction products, Molecules, 010402 general chemistry, Inherent chirality, 01 natural sciences, Hydrocarbons, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Organocatalysis, Calixarene, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Enantiomer, Brønsted–Lowry acid–base theory, Benzoic acid
Abstract

International audience; A facile method for the preparation of enantiomerically pure inherently chiral calix[4]arene phosphonic acid (cR,pR)-7 in four steps starting from the readily available and previously synthesized (cS)-enantiomer of calix[4]arene acetic acid 1 or its methyl ester 2 was developed. The first tests of this unique calixarene Brönsted acid with inherent chirality in organocatalysis of the aza-Diels–Alder reaction of imines with Danishefsky’s diene and epoxide ring opening by benzoic acid were performed. The calixarene phosphonic acid (cR,pR)-7 shows good catalytic activities but with low enantioselectivities in these reactions.

Published
2018
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31. Following the cold: geographical differentiation between interglacial refugia and speciation in the arcto-alpine species complex Bombus monticola (Hymenoptera: Apidae)

Author

Martinet, Baptiste, Lecocq, Thomas, Brasero, Nicolas, Biella, Paolo, Urbanová, Klára, Valterová, Irena, Cornalba, Maurizio, Gjershaug, Jan Ove, Michez, Denis, Rasmont, Pierre, Université de Mons (UMons), Unité de Recherches Animal et Fonctionnalités des Produits Animaux (URAFPA), Institut National de la Recherche Agronomique (INRA)-Université de Lorraine (UL), University of South Bohemia, Czech Academy of Sciences [Prague] (ASCR), Czech University of Life Science, Università di Pavia, Norwegian Institute for Nature Research (NINA), Belgian FRS (Fonds de la Recherche Scientifique), Czech Science Foundation (GACR GP14-10035P), University of South Bohemia (GA JU 152/2016/P), Institute of Organic Chemistry and Biochemistry of the Academy of Sciences of the Czech Republic (61388963), European Community's Seventh Framework Program, STEP Project (Status and Trends of European Pollinators) (244090), European Union's Horizon project INTERACT (730938), Laboratoire de Zoologie [Mons], University of Mons [Belgium] (UMONS), Czech Academy of Sciences [Prague] (CAS), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech University of Life Sciences Prague (CZU), Università degli Studi di Pavia = University of Pavia (UNIPV), European Project: 244090,EC:FP7:ENV,FP7-ENV-2009-1,STEP(2010), and Università degli Studi di Pavia

Subjects
refuge interglaciaire, différenciation spécifique, taxonomie, [SDV.BA]Life Sciences [q-bio]/Animal biology, Zoology and botany: 480 [VDP], bombus, integrative taxonomic approach, post-glacial warming, bumblebees, Marqueur mitochondrial, taxonomy, Following the cold: speciation in B. monticola Arcto-alpine regions, interrefugia differentiation, spéciation, cold-adapted species, europe, Zoologiske og botaniske fag: 480 [VDP]
Abstract

Cold-adapted species are expected to have reached their largest distribution range during a part of the Ice Ages whereas postglacial warming has led to their range contracting toward high-latitude and high-altitude areas. This has resulted in an extant allopatric distribution of populations and possibly to trait differentiations (selected or not) or even speciation. Assessing inter-refugium differentiation or speciation remains challenging for such organisms because of sampling difficulties (several allopatric populations) and disagreements on species concept. In the present study, we assessed postglacial inter-refugia differentiation and potential speciation among populations of one of the most common arcto-alpine bumblebee species in European mountains, Bombus monticola Smith, 1849. Based on mitochondrial DNA/nuclear DNA markers and eco-chemical traits, we performed integrative taxonomic analysis to evaluate alternative species delimitation hypotheses and to assess geographical differentiation between interglacial refugia and speciation in arcto-alpine species. Our results show that trait differentiations occurred between most Southern European mountains (i.e. Alps, Balkan, Pyrenees, and Apennines) and Arctic regions. We suggest that the monticola complex actually includes three species: B. konradini stat.n. status distributed in Italy (Central Apennine mountains), B. monticola with five subspecies, including B. monticola mathildis ssp.n. distributed in the North Apennine mountains ; and B. lapponicus. Our results support the hypothesis that post-Ice Age periods can lead to speciation in cold-adapted species through distribution range contraction. We underline the importance of an integrative taxonomic approach for rigorous species delimitation, and for evolutionary study and conservation of taxonomically challenging taxa. Following the cold: geographical differentiation between interglacial refugia and speciation in the arcto-alpine species complex Bombus monticola (Hymenoptera: Apidae)

Published
2018
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32. Assessing Ge-132 as an antioxidant in organic and water-containing media

Author

Viatcheslav Jouikov, Mikhail A. Syroeshkin, Andrey V. Lalov, Valery M. Pechennikov, Antonina A. Vishtorskaya, Irina V. Krylova, Evgeniya A. Saverina, Mikhail P. Egorov, Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences [Moscow] (RAS), 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), This work was supported by Grant МК-755.2017.3. High resolution mass spectra were recorded in the Department of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow., 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
Antioxidant, DPPH, Radical, medicine.medical_treatment, HRMS, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, law.invention, Inorganic Chemistry, chemistry.chemical_compound, Sesquioxide, Ultraviolet visible spectroscopy, law, germanium sesquioxides, Materials Chemistry, medicine, Physical and Theoretical Chemistry, Electron paramagnetic resonance, Quenching (fluorescence), 010405 organic chemistry, Organic Chemistry, Ge-132, 6. Clean water, cyclic voltammetry, 0104 chemical sciences, antioxidants, chemistry, EPR, Cyclic voltammetry, UV spectroscopy, Nuclear chemistry
Abstract

International audience; The antioxidant activity of Ge-132 (2-carboxyethylgermanium sesquioxide, [(O0.5)3GeCH2CH2COOH]n), a widely used organic germanium dietary supplement, was assessed by cyclic voltammetry and through its interaction with a stable radical 2,2,-diphenyl-1-picrylhydrazyl (DPPH) monitored by UV-Vis and EPR spectroscopy in water, CH3CN, DMF, MeOH, and their mixtures with water. The results obtained by these methods are coherent in that Ge-132 can manifest its antioxidant activity only in the absence of water because the latter hydrolyses its Ge-O-Ge fragment responsible for quenching free radicals. Thus, contrary to a common use of Ge-132 as a water-soluble agent, it can act as an antioxidant solely in a lipid environment, which is important for understanding the mechanism of its biological activity.

Published
2018
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33. Binding of Divalent Cations to Insulin: Capillary Electrophoresis and Molecular Simulations

Author

Hector Martinez-Seara, Jana Hladilkova, Elise Duboué-Dijon, Pavel Coufal, Pauline Delcroix, Tomáš Křížek, Pavel Jungwirth, Laboratoire de biochimie théorique [Paris] (LBT (UPR_9080)), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)-Institut de biologie physico-chimique (IBPC (FR_550)), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Lund University [Lund], Charles University [Prague] (CU), Université Paris Diderot - Paris 7 (UPD7)-Institut de biologie physico-chimique (IBPC), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] (ASCR), and Charles University [Prague]

Subjects
Cations, Divalent, Salt (chemistry), Protonation, 02 engineering and technology, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Divalent, Molecular dynamics, chemistry.chemical_compound, Capillary electrophoresis, Materials Chemistry, Humans, Insulin, Magnesium, Carboxylate, Physical and Theoretical Chemistry, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], chemistry.chemical_classification, Aqueous solution, Electrophoresis, Capillary, Water, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Electrophoresis, Zinc, chemistry, Calcium, 0210 nano-technology, Protein Binding
Abstract

International audience; In the present study, we characterize the binding of divalent cations to insulin in aqueous salt solutions by means of capillary electrophoresis and molecular dynamics simulations. The results show a strong pH dependence. At low pH, at which all the carboxylate groups are protonated and the protein has an overall positive charge, all the cations exhibit only weak and rather unspecific interactions with insulin. In contrast, at close to neutral pH, when all the carboxylate groups are deprotonated and negatively charged, the charge-neutralizing effect of magnesium, calcium, and zinc, in particular, on the electrophoretic mobility of insulin is significant. This is also reflected in the results of molecular dynamics simulations showing accumulation of cations at the protein surface, which becomes smaller in magnitude upon effective inclusion of electronic polarization via charge rescaling.

Published
2018
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34. Asymmetric Choreography in Pairs of Orthogonal Rotors

Author

Jiří Kaleta, Antonio Rodríguez-Fortea, Patrick Batail, Cécile Mézière, Magali Allain, Josef Michl, Enric Canadell, P. Wzietek, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, European Research Council, Academy of Sciences of the Czech Republic, National Science Foundation (US), Centre National de la Recherche Scientifique (France), Région des Pays de la Loire, Ministère de l'Europe et des Affaires étrangères (France), departament de quimica fisica i quimica inorganica i quimica analitica i quimica organica, Universitat Rovira i Virgili, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Laboratoire de Physique des Solides, Université Paris-Sud - Paris 11 (UP11), Institute of Organic Chemistry and Biochemistry (Institute of Organic Chemistry and Biochemistry), Institute of Organic Chemistry and Biochemistry, MOLTECH-ANJOU (MOLTECH-ANJOU), Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Consejo Superior de Investigaciones Científicas [Spain] (CSIC), Laboratoire de Physique des Solides d'Orsay (LPS), and Universirté d'Orsay

Subjects
Diffraction, General Chemical Engineering, Mechanical properties, Crystal structure, 010402 general chemistry, 01 natural sciences, Molecular physics, Article, lcsh:Chemistry, chemistry.chemical_compound, Potential energy, [CHIM.CRIS]Chemical Sciences/Cristallography, Molecule, [CHIM]Chemical Sciences, Reaction rate theory, Nanodevices, ComputingMilieux_MISCELLANEOUS, Rotor (mathematics), Physics, 010405 organic chemistry, General Chemistry, Molecular rotation, 0104 chemical sciences, Pentane, chemistry, lcsh:QD1-999, Crystal structures, Relaxation (physics), Single crystal, Molecular structure
Abstract

An asymmetric mechanism for correlated motion occurring in noninteracting pairs of adjacent orthogonal 1,4-bis(carboxyethynyl)bicyclo[1.1.1]pentane (BCP) rotators 1 in the solid state is unraveled and shown to play an important role in understanding the dynamics in the crystalline rotor, Bu4N+[1–]·H2O. Single crystal X-ray diffraction and calculation of rotor–rotor interaction energies combined with variable-temperature, variable-field 1H spin–lattice relaxation experiments led to the identification and microscopic rationalization of two distinct relaxation processes., Work in Bellaterra and Tarragona was supported by the Spanish Ministerio de Economía y Competitividad (projects FIS2015-64886-C5-4-P and CTQ2017-87269-P) and Generalitat de Catalunya (2014GR301 and 2014GR199). E.C. acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under grant SEV-2015-0496. J.K. and J.M. gratefully acknowledge financial support from the European Research Council under the European Community’s Framework Programme (FP7/2007-2013) ERC grant agreement no. 227756 and the Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic (RVO: 61388963). This material is based upon work supported by the National Science Foundation under grant no. CHE-1566435. Work at Orsay was supported by the CNRS. Work at Angers was supported by the CNRS and the Région des Pays de la Loire grant MOVAMOL. Joint work at Angers, Orsay, and Prague was supported by the Ministère de l’Europe et des Affaires Etrangères under the grant PHC Barrande no. 864563J.

Published
2018
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35. Gating the electron transfer at a monocopper centre through the supramolecular coordination of water molecules within a protein chamber mimic

Author

Jan Řezáč, Aurélien de la Lande, Antony Memboeuf, Yves Le Mest, Bénédicte Douziech, Claudio Iacobucci, Thierry Prangé, Olivia Reinaud, Dany Jeanne Dit Fouque, Nicolas Le Poul, Grégory Thiabaud, Benoit Colasson, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Laboratoire pour l'utilisation du rayonnement électromagnétique (LURE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-MENRT-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] (ASCR), and LCP, Université Paris-Sud, UMR 8000 CNRS, 91405 Orsay, France

Subjects
010405 organic chemistry, Chemistry, Supramolecular chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Redox, 0104 chemical sciences, Ion, Metal, Electron transfer, Crystallography, Covalent bond, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, visual_art, Calixarene, visual_art.visual_art_medium, Molecule, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

Functionality of enzymes is strongly related to water dynamic processes., Functionality of enzymes is strongly related to water dynamic processes. The control of the redox potential for metallo-enzymes is intimately linked to the mediation of water molecules in the first and second coordination spheres. Here, we report a unique example of supramolecular control of the redox properties of a biomimetic monocopper complex by water molecules. It is shown that the copper complex based on a calix[6]arene covalently capped with a tetradentate [tris(2-methylpyridyl)amine] (tmpa) core, embedding the metal ion in a hydrophobic cavity, can exist in three different states. The first system displays a totally irreversible redox behaviour. It corresponds to the reduction of the 5-coordinate mono-aqua-CuII complex, which is the thermodynamic species in the +II state. The second system is detected at a high redox potential. It is ascribed to an “empty cavity” or “water-free” state, where the CuI ion sits in a 4-coordinate trigonal environment provided by the tmpa cap. This complex is the thermodynamic species in the +I state under “dry conditions”. Surprisingly, a third redox system appears as the water concentration is increased. Under water-saturation conditions, it displays a pseudo-reversible behaviour at a low scan rate at the mid-point from the water-free and aqua species. This third system is not observed with the Cu-tmpa complex deprived of a cavity. In the calix[6]cavity environment, it is ascribed to a species where a pair of water molecules is hosted by the calixarene cavity. A molecular mechanism for the CuII/CuI redox process with an interplay of (H2O)x (x = 0, 1, 2) hosting is proposed on the basis of computational studies. Such an unusual behaviour is ascribed to the unexpected stabilization of the CuI state by inclusion of the pair of water molecules. This phenomenon strongly evidences the drastic influence of the interaction between water molecules and a hydrophobic cavity on controlling the thermodynamics and kinetics of the CuII/CuI electron transfer process.

Published
2018
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36. Variability in Sexual Pheromones Questions their Role in Bumblebee Pre-Mating Recognition System

Author

Pierre Rasmont, Irena Valterová, Baptiste Martinet, Thomas Lecocq, Roland de Jonghe, Nicolas Brasero, Klára Urbanová, Laboratoire de Zoologie [Mons], University of Mons [Belgium] (UMONS), Unité de Recherches Animal et Fonctionnalités des Produits Animaux (URAFPA), Institut National de la Recherche Agronomique (INRA)-Université de Lorraine (UL), Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] (ASCR), Czech University of Life Sciences, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), and Czech University of Life Sciences Prague (CZU)

Subjects
0106 biological sciences, Male, Entomology, Zoology, 010603 evolutionary biology, 01 natural sciences, Biochemistry, Gas Chromatography-Mass Spectrometry, Exocrine Glands, Pollinator, Animals, Mating, Sex Attractants, Ecology, Evolution, Behavior and Systematics, Bumblebee, ComputingMilieux_MISCELLANEOUS, Principal Component Analysis, biology, Courtship display, [SDV.BID.EVO]Life Sciences [q-bio]/Biodiversity/Populations and Evolution [q-bio.PE], General Medicine, Bees, biology.organism_classification, 010602 entomology, Taxon, Sex pheromone, Female, Subgenus
Abstract

Sex-specific chemical secretions have been widely used as diagnostic characters in chemotaxonomy. The taxonomically confused group of bumblebees has reaped the benefit of this approach through the analyses of cephalic labial gland secretions (CLGS). Most of currently available CLGS descriptions concern species from the West-Palearctic region but few from the New World. Here, the CLGS of four East-Palearctic species Bombus deuteronymus, B. filchnerae, B. humilis, and B. exil (subgenus Thoracobombus) are analysed. Our results show high levels of variability in the major compounds in B. exil. In contrast, we describe a low differentiation in CLGS compounds between B. filchnerae and its phylogenetically closely related taxon B. muscorum. Moreover, the chemical profiles of B. filchnerae and B. muscorum are characterized by low concentrations of the C16 component, which is found in higher concentrations in the other Thoracobombus species. This raises the possibility that courtship behavior as well as environmental constraints could affect the role of the bumblebee males' CLGS.

Published
2018
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37. Symmetry Breaking in Pyrrolo[3,2‐ b ]pyrroles: Synthesis, Solvatofluorochromism and Two‐photon Absorption

Author

Bolesław Kozankiewicz, Marzena Banasiewicz, Daniel T. Gryko, Aleksander Rebane, Alexander Mikhaylov, Cloé Azarias, Łukasz G. Łukasiewicz, Denis Jacquemin, Hye Gun Ryu, Kyo Han Ahn, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Modélisation Et Spectroscopie (ModES), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN), Department of Cell Biology [New Haven], Yale University School of Medicine-Howard Hughes Medical Institute (HHMI), Institute of Organic Chemistry, and Institute of Organic Chemistry Polish Academy of Sciences

Subjects
010405 organic chemistry, Chemistry, donor-acceptor systems, structure-activity relationship, Organic Chemistry, General Chemistry, Dihedral angle, Chromophore, 010402 general chemistry, Photochemistry, Triple bond, 01 natural sciences, Biochemistry, Two-photon absorption, 0104 chemical sciences, fused-ring systems, Crystallography, Dipole, Excited state, [CHIM]Chemical Sciences, Symmetry breaking, fluorescence, dyes/pigments, Ground state
Abstract

International audience; Five centrosymmetric and one dipolar pyrrolo[3,2-b]pyrroles, possessing either two or one strongly electron-withdrawing nitro group have been synthesized in a straightforward manner from simple building blocks. For the symmetric compounds, the nitroaryl groups induced spontaneous breaking of inversion symmetry in the excited state, thereby leading to large solvatofluorochromism. To study the origin of this effect, the series employed peripheral structural motifs that control the degree of conjugation via altering of dihedral angle between the 4-nitrophenyl moiety and the electron-rich core. We observed that for compounds with a larger dihedral angle, the fluorescence quantum yield decreased quickly when exposed to even moderately polar solvents. Reducing the dihedral angle (i.e., placing the nitrobenzene moiety in the same plane as the rest of the molecule) moderated the dependence on solvent polarity so that the dye exhibited significant emission, even in THF. To investigate at what stage the symmetry breaking occurs, we measured two-photon absorption (2PA) spectra and 2PA cross-sections (σ2PA ) for all six compounds. The 2PA transition profile of the dipolar pyrrolo[3,2-b]pyrrole, followed the corresponding one-photon absorption (1PA) spectrum, which provided an estimate of the change of the permanent electric dipole upon transition, ≈18 D. The nominally symmetric compounds displayed an allowed 2PA transition in the wavelength range of 700-900 nm. The expansion via a triple bond resulted in the largest peak value, σ2PA =770 GM, whereas altering the dihedral angle had no effect other than reducing the peak value two- or even three-fold. In the S0 →S1 transition region, the symmetric structures also showed a partial overlap between 2PA and 1PA transitions in the long-wavelength wing of the band, from which a tentative, relatively small dipole moment change, 2-7 D, was deduced, thus suggesting that some small symmetry breaking may be possible in the ground state, even before major symmetry breaking occurs in the excited state

Published
2017
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38. Asexual queen succession mediates an accelerated colony life cycle in the termite Silvestritermes minutus

Author

Klára Dolejšová, Yves Roisin, Sophie Frechault, Romain Fougeyrollas, Jan Křivánek, David Sillam-Dussès, Virginie Roy, Robert Hanus, Institut d'écologie et des sciences de l'environnement de Paris (iEES Paris), Institut National de la Recherche Agronomique (INRA)-Sorbonne Université (SU)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), Centre National de la Recherche Scientifique (CNRS), Institut National de la Recherche Agronomique (INRA), Institut de Recherche pour le Développement (IRD [France-Ouest]), Université Paris Diderot - Paris 7 (UPD7), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Faculty of Science, Suez Canal University. Ismailia. Egypt, Institut d'écologie et des sciences de l'environnement de Paris (iEES), Institut National de la Recherche Agronomique (INRA)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université libre de Bruxelles (ULB), Institut d'écologie et des sciences de l'environnement de Paris (iEES Paris ), Institut de Recherche pour le Développement (IRD)-Sorbonne Université (SU)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Sorbonne Université (SU), EA4443 Laboratoire d'Ethologie Expérimentale et Comparée (LEEC), Université Paris 13 (UP13), Université Sorbonne Paris Cité (USPC), Czech Science Foundation [14-12774S], Grant Agency of the Charles University in Prague [358815], CAS, Prague [RVO: 61388963], Institut d'écologie et des sciences de l'environnement de Paris (IEES (UMR_7618 / UMR_D_242 / UMR_A_1392 / UM_113) ), Université Pierre et Marie Curie (Paris 6), Chemistry of Social Insects, The Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences [Prague] (ASCR), Institut d'écologie et des sciences de l'environnement de Paris (IEES), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Recherche Agronomique (INRA), Université Libre de Bruxelles [Bruxelles] (ULB), UMR 242, and Sorbonne Universités

Subjects
Male, 0106 biological sciences, 0301 basic medicine, life history, Modes of reproduction, Genotype, media_common.quotation_subject, [SDV]Life Sciences [q-bio], termites, Zoology, Isoptera, Alate, Biology, 010603 evolutionary biology, 01 natural sciences, 03 medical and health sciences, Genetics, Animals, parthenogenesis, Neoteny, Ecology, Evolution, Behavior and Systematics, Sex allocation, media_common, Life Cycle Stages, Reproduction, Parthenogenesis, breeding system, Sexual reproduction, 030104 developmental biology, Biological dispersal, Female, asexual queen succession, Silvestritermes minutus, Microsatellite Repeats
Abstract

Mixed modes of reproduction, combining sexual processes with thelytokous parthenogenesis, occur in all major clades of social insects. In several species of termites, queens maximize their genetic input into nondispersing replacement queens through parthenogenesis, while maintaining genetically diverse sterile offspring and dispersing reproductives via sexual reproduction. This so-called asexual queen succession (AQS) has multiple independent origins and its presumed advantages are diverse as well, ranging from multiplication of colony reproductive potential to extension of its life-span beyond that of the foundress. However, how AQS shapes colony life cycles under natural conditions remains poorly known. The neotropical termite Silvestritermes minutus inhabits small but conspicuous nests, offering a unique opportunity to investigate the impact of AQS on life history. We report on its breeding system, life cycle and sex allocation using social structure census in 137 nests and genotyping of 12 colonies at 12 microsatellite loci. We show that colonies are established by an outbred pair of primary reproductives. In less than 2 years, the foundress is replaced by multiple neotenic queens, arising mostly through automixis with central fusion. Sterile castes, male and most (93%) female dispersers are produced sexually. Colony reproduction is usually restricted to a single dispersal of alates with unbiased sex ratio, taking place after 3 years. We conclude that S. minutus benefits from AQS to maximize colony growth rate and alate production within a very short life cycle rather than to extend colony lifespan. This highlights the versatile role of AQS in different cases of its polyphyletic origin.

Published
2017
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39. IL-33 polymorphisms are associated with increased risk of hay fever and reduced regulatory T cells in a birth cohort

Author

Jean-Charles Dalphin, Andreas Böck, Jon Genuneit, Sabina Illi, Charlotte Braun-Fahrländer, Sven Michel, Josef Riedler, Dominique A. Vuitton, Erika von Mutius, Marjut Roponen, Juha Pekkanen, Maximilian Schieck, P. C. Schröder, Bianca Schaub, Juliane Weber, Remo Frei, Roger Lauener, Vera Isabel Casaca, Caroline Roduit, Petra Ina Pfefferle, Anna Lluis, Michael Kabesch, Université de Montpellier (UM), Universität Duisburg-Essen [Essen], Children's Hospital, University hospital of Zurich [Zurich], Christine Kühne – Centre for Allergy Research and Education (CK-CARE), Institute of Epidemiology, Universität Ulm - Ulm University [Ulm, Allemagne], Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), University of Basel (Unibas), Swiss Tropical and Public Health Institute [Basel], Kardinal Schwarzenberg’sches Krankenhaus, Carcinogénèse épithéliale : facteurs prédictifs et pronostiques - UFC (EA 3181) (CEF2P / CARCINO), Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre Hospitalier Régional Universitaire de Besançon (CHRU Besançon), Laboratoire Chrono-environnement - CNRS - UBFC (UMR 6249) (LCE), Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), University of Munich, University of Zurich, Schaub, Bianca, Université de Montpellier ( UM ), Christine Kühne – Centre for Allergy Research and Education ( CK-CARE ), Universität Ulm, Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague, University of Basel ( Unibas ), Carcinogénèse épithéliale : facteurs prédictifs et pronostiques - UFC ( CEF2P / CARCINO ), Centre Hospitalier Régional Universitaire [Besançon] ( CHRU Besançon ) -Université Bourgogne Franche-Comté ( UBFC ) -Université de Franche-Comté ( UFC ), Laboratoire Chrono-environnement ( LCE ), and Université Bourgogne Franche-Comté ( UBFC ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Franche-Comté ( UFC )

Subjects
0301 basic medicine, Male, Risk, Allergy, Genotype, Immunology, IL1RL1, 610 Medicine & health, Polymorphism, Single Nucleotide, T-Lymphocytes, Regulatory, Allergic inflammation, [ SDV.EE.SANT ] Life Sciences [q-bio]/Ecology, environment/Health, Cohort Studies, 03 medical and health sciences, Gene Frequency, 10183 Swiss Institute of Allergy and Asthma Research, Germany, Immunology and Allergy, Medicine, Humans, Genetic Predisposition to Disease, IL-2 receptor, 2735 Pediatrics, Perinatology and Child Health, Allele, Child, Cells, Cultured, 2. Zero hunger, [SDV.EE.SANT]Life Sciences [q-bio]/Ecology, environment/Health, 2403 Immunology, business.industry, FOXP3, Rhinitis, Allergic, Seasonal, Forkhead Transcription Factors, medicine.disease, Interleukin-33, 3. Good health, Minor allele frequency, 030104 developmental biology, Suppressor of Cytokine Signaling 3 Protein, 10036 Medical Clinic, Child, Preschool, Pediatrics, Perinatology and Child Health, 2723 Immunology and Allergy, Hay fever, Female, business
Abstract

Background: IL-33 polymorphisms influence the susceptibility to asthma. IL-33 indirectly induces Th2-immune responses via dendritic cell activation, being important for development of atopic diseases. Furthermore, IL-33 upregulates regulatory T cells (Tregs), which are critical for healthy immune homeostasis. This study investigates associations between IL-33 polymorphisms during the development of childhood atopic diseases and underlying mechanisms including immune regulation of Tregs. Methods: Genotyping of IL-33-polymorphisms (rs928413, rs1342326) was performed by MALDI-TOF-MS in 880 of 1133 PASTURE/EFRAIM children. In 4.5-year-old German PASTURE/EFRAIM children (n = 99), CD4(+) CD25(high)FOXP3(+) Tregs were assessed by flow cytometry following 24-h incubation of PBMCs with PMA/ionomycin, LPS or without stimuli (U). SOCS3, IL1RL1, TLR4 mRNA expression and sST2 protein levels ex vivo were measured in PASTURE/EFRAIM children by real-time PCR or ELISA, respectively. Health outcomes (hay fever, asthma) were assessed by questionnaires at the age of 6 years. Results: rs928413 and rs1342326 were positively associated with hay fever (OR = 1.77, 95% CI = 1.02-3.08;OR = 1.79, 95% CI = 1.04-3.11) and CD4(+) CD25(high)FOXP3(+) Tregs (%) decreased in minor allele homozygotes/heterozygotes compared to major allele homozygotes (p(U) = 0.004;p(LPS) = 0.005;p(U) = 0.001;p(LPS) = 0.012). SOCS3 mRNA expression increased in minor allele homozygotes and heterozygotes compared with major allele homozygotes for both IL-33-polymorphisms (p (rs928413) = 0.032, p(rs1342326) = 0.019) and negatively correlated to Tregs. Conclusions: IL-33-polymorphisms rs928413 and rs1342326 may account for an increased risk of hay fever with the age of 6 years. Lower Tregs and increased SOCS3 in combined heterozygotes and minor allele homozygotes may be relevant for hay fever development, pointing towards dysbalanced immune regulation and insufficient control of allergic inflammation.

Published
2016

40. The role of the glucose-sensing transcription factor carbohydrate-responsive element-binding protein pathway in termite queen fertility

Author

Maryline Favier, Robert Hanus, Virginie Roy, Michael Poulsen, David Sillam-Dussès, Mireille Vasseur-Cognet, Institut d'écologie et des sciences de l'environnement de Paris (iEES), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Recherche Agronomique (INRA), Laboratoire d'Ethologie Expérimentale et Comparée (LEEC), Université Sorbonne Paris Cité (USPC)-Université Paris 13 (UP13), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Department for Food Chemistry, National Food Institute, Danish Technical University, Centre for Social Evolution (CSE), Department of Biology [Copenhagen], Faculty of Science [Copenhagen], University of Copenhagen = Københavns Universitet (KU)-University of Copenhagen = Københavns Universitet (KU)-Faculty of Science [Copenhagen], University of Copenhagen = Københavns Universitet (KU)-University of Copenhagen = Københavns Universitet (KU)-Department of Plant and Environmental Sciences [Copenhagen], University of Copenhagen = Københavns Universitet (KU)-University of Copenhagen = Københavns Universitet (KU), Institut Cochin (IC UM3 (UMR 8104 / U1016)), Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), This work was supported by a maturation grant from the Institute of Research for Development (IRD) received by D.S.D. and M.V.C. (RVO: 61388963), Czech Science Foundation (14-12774S) to R.H. and a Villum Kann Rasmussen Foundation Young Investigator Fellowship (VKR10101) to M.P., Institut d'écologie et des sciences de l'environnement de Paris ( IEES ), Institut National de la Recherche Agronomique ( INRA ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Université Paris-Est Créteil Val-de-Marne - Paris 12 ( UPEC UP12 ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire d'Ethologie Expérimentale et Comparée ( LEEC ), Université Paris 13 ( UP13 ) -Université Sorbonne Paris Cité ( USPC ), Institute of Organic Chemistry and Biochemistry [Praha], Czech Academy of Sciences [Prague] ( ASCR ), Centre for Social Evolution, Section for Ecology and Evolution, Department of Biology, University of Copenhagen ( KU ), Institut Cochin ( UM3 (UMR 8104 / U1016) ), Université Paris Descartes - Paris 5 ( UPD5 ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National de la Recherche Agronomique (INRA)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université Paris 13 (UP13)-Université Sorbonne Paris Cité (USPC), Department of Plant and Environmental Sciences [Copenhagen], University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH)-Faculty of Science [Copenhagen], University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH)-Department of Biology [Copenhagen], University of Copenhagen = Københavns Universitet (UCPH)-University of Copenhagen = Københavns Universitet (UCPH), Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Bos, Mireille, Institut d'écologie et des sciences de l'environnement de Paris (IEES), Czech Academy of Sciences [Prague] (ASCR), and Vasseur-Cognet, Mireille

Subjects
0301 basic medicine, Immunology, education, Isoptera, Biology, phenotypic plasticity, General Biochemistry, Genetics and Molecular Biology, reproduction, 03 medical and health sciences, Downregulation and upregulation, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Animals, Tissue Distribution, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Protein Interaction Maps, Carbohydrate-responsive element-binding protein, lcsh:QH301-705.5, Gene, Transcription factor, carbohydrate-responsive element-binding protein, transcription factor, social insects, lipogenesis, [ SDV.BBM ] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Research Articles, Phylogeny, General Neuroscience, Research, Correction, Pyruvate carboxylase, Up-Regulation, Fatty acid synthase, 030104 developmental biology, Fertility, Glucose, lcsh:Biology (General), ChREBP Pathway, Biochemistry, Lipogenesis, biology.protein, Insect Proteins, Female, Signal Transduction, Transcription Factors
Abstract

Termites are among the few animals that themselves can digest the most abundant organic polymer, cellulose, into glucose. In mice and Drosophila , glucose can activate genes via the transcription factor carbohydrate-responsive element-binding protein (ChREBP) to induce glucose utilization and de novo lipogenesis. Here, we identify a termite orthologue of ChREBP and its downstream lipogenic targets, including acetyl-CoA carboxylase and fatty acid synthase. We show that all of these genes, including ChREBP, are upregulated in mature queens compared with kings, sterile workers and soldiers in eight different termite species. ChREBP is expressed in several tissues, including ovaries and fat bodies, and increases in expression in totipotent workers during their differentiation into neotenic mature queens. We further show that ChREBP is regulated by a carbohydrate diet in termite queens. Suppression of the lipogenic pathway by a pharmacological agent in queens elicits the same behavioural alterations in sterile workers as observed in queenless colonies, supporting that the ChREBP pathway partakes in the biosynthesis of semiochemicals that convey the signal of the presence of a fertile queen. Our results highlight ChREBP as a likely key factor for the regulation and signalling of queen fertility.

Published
2016
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41. Non-Pincer-Type Mononuclear Scandium Alkylidene Complexes: Synthesis, Bonding, and Reactivity

Author

Laurent Maron, Jiliang Zhou, Yaofeng Chen, Xuebing Leng, Xuefei Zhao, Chen Wang, Shanghai Institute of Organic Chemistry-Chinese Academy of Sciences, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Shanghai Institute of Organic Chemistry - Chinese Academy of Sciences, Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-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)-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 sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Imine, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Cycloaddition, 0104 chemical sciences, Pincer movement, Bond length, chemistry.chemical_compound, Phenylacetylene, Nucleophile, [CHIM]Chemical Sciences, Reactivity (chemistry), Scandium
Abstract

International audience; The first non‐pincer‐type mononuclear scandium alkylidene complexes were synthesized and structurally characterized. These complexes exhibited short Sc−C bond lengths and even one of the shortest reported to date (2.1134(18) Å). The multiple character of the Sc−C bond was highlighted by a DFT calculation. This was confirmed by experimental reactivity study where the complex underwent [2+1] cycloaddition with elemental selenium and [2+2] cycloaddition with imine. DFT calculation also revealed a strong nucleophilic behavior of the alkylidene complex that was experimentally demonstrated by the C−H bond activation of phenylacetylene

Published
2016

42. Resistance to the nucleotide analogue cidofovir in HPV(+) cells: a multifactorial process involving UMP/CMP kinase 1

Author

Tim De Schutter, Marcela Krečmerová, Lieve Naesens, Graciela Andrei, Dimitrios Topalis, Robert Snoeck, Tatiane C Nogueira, Chahrazade El Amri, Jan Balzarini, Rega Institute for Medical Research [Leuven, België], Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Vieillissement Cellulaire Intégré et Inflammation (VCII), Adaptation Biologique et Vieillissement = Biological Adaptation and Ageing (B2A), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Rega Institute for Medical Research, Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences [Prague] (ASCR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and HAL UPMC, Gestionnaire

Subjects
0301 basic medicine, UMP-CMP kinase, viruses, Uterine Cervical Neoplasms, Uridine Triphosphate, chemistry.chemical_compound, 0302 clinical medicine, Papillomaviridae, Phosphorylation, human papillomavirus, Uridine triphosphate, Cervical cancer, Nucleoside-phosphate kinase, biology, Multidrug resistance-associated protein 2, virus diseases, 3. Good health, Oncology, 030220 oncology & carcinogenesis, Female, cervical carcinoma, Cytosine, Cidofovir, Research Paper, Cytidine Triphosphate, Organophosphonates, [SDV.CAN]Life Sciences [q-bio]/Cancer, Microbial Sensitivity Tests, [SDV.MHEP.GEO]Life Sciences [q-bio]/Human health and pathology/Gynecology and obstetrics, cidofovir, 03 medical and health sciences, [SDV.CAN] Life Sciences [q-bio]/Cancer, Cell Line, Tumor, medicine, Humans, NTP metabolism, Solute Carrier Proteins, Papillomavirus Infections, Transporter, medicine.disease, biology.organism_classification, Virology, [SDV.MHEP.GEO] Life Sciences [q-bio]/Human health and pathology/Gynecology and obstetrics, 030104 developmental biology, chemistry, Drug Resistance, Neoplasm, Cancer research, ATP-Binding Cassette Transporters, Nucleoside-Phosphate Kinase, HeLa Cells
Abstract

Human papillomavirus (HPV) is responsible for cervical cancer, and its role in head and neck carcinoma has been reported. No drug is approved for the treatment of HPV-related diseases but cidofovir (CDV) exhibits selective antiproliferative activity.In this study, we analyzed the effects of CDV-resistance (CDVR) in two HPV(+) (SiHaCDV and HeLaCDV) and one HPV(-) (HaCaTCDV) tumor cell lines. Quantification of CDV metabolites and analysis of the sensitivity profile to chemotherapeutics was performed. Transporters expression related to multidrug-resistance (MRP2, P-gp, BCRP) was also investigated.Alterations of CDV metabolism in SiHaCDV and HeLaCDV, but not in HaCaTCDV, emerged via impairment of UMP/CMPK1 activity. Mutations (P64T and R134M) as well as down-regulation of UMP/CMPK1 expression were observed in SiHaCDV and HeLaCDV, respectively. Altered transporters expression in SiHaCDV and/or HeLaCDV, but not in HaCaTCDV, was also noted.Taken together, these results indicate that CDVR in HPV(+) tumor cells is a multifactorial process. ispartof: Oncotarget vol:7 issue:9 pages:10386-10401 ispartof: location:United States status: published

Published
2016
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43. Stereospecific Polymerization of Bulky Methacrylates Using Organocatalyst in Strong Donating Solvent via Self-Controlled Mechanism

Author

Yangyang Sun, Ambre Carpentier, Yixin Zhang, Biwei Weng, Yaoyao Ling, Laurent Maron, Miao Hong, Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences [Beijing] (CAS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and University of Chinese Academy of Sciences [Beijing] (UCAS)

Subjects
Polymers and Plastics, Organic Chemistry, COORDINATION POLYMERIZATION, ANIONIC-POLYMERIZATION, PROTON-TRANSFER POLYMERIZATION, MEDIATED POLYMERIZATION, METHYL-METHACRYLATE, LIVING POLYMERIZATION, Inorganic Chemistry, N-HETEROCYCLIC CARBENES, Materials Chemistry, [CHIM]Chemical Sciences, RADICAL POLYMERIZATION, (METH)ACRYLIC MONOMERS, POLAR DIVINYL MONOMERS
Published
2022
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44. Molecular Simulations of Halomethanes at the Air/Ice Interface

Author

Céline Toubin, Maurice Monnerville, Eva Pluhařová, Martina Roeselová, Stéphane Briquez, Alena Habartová, Laureline Hormain, Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Czech science Foundation (Grant 13-06181S), Institute of Organic Chemistry and Biochemistry (AS CR via RVO 61388963), PHC-Barrande (26513PA) funded by the french Ministry of Foreign Affairs and the Czech Ministry of Education, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ozone, Bromine, Halomethane, chemistry.chemical_element, chemistry.chemical_compound, Molecular dynamics, Adsorption, chemistry, 13. Climate action, Chemical physics, Atmospheric chemistry, Halogen, Chlorine, Organic chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract

International audience; Halogenated organics are emitted into the atmosphere from a variety of sources of both natural and anthropogenic origin. Their uptake at the surface of aerosols can affect their reactivity, for example, in processes that take part in ozone destruction due to production of reactive chlorine, bromine, and iodine radicals. Classical molecular dynamics (MD) simulations are carried out to investigate the interaction of small halomethane molecules of atmospheric relevance with a crystalline ice surface. The following halomethanes were studied: CH3Cl, CH2Cl2, CHCl3, CH3Br, CH2Br2, and CHBr3. MD simulations provide an invaluable insight into the adsorption behavior of halomethanes species. The adsorption energy is increasing as the number of halogen atoms is increasing. Moreover, brominated methanes exhibit a stronger interaction with the ice than their chlorinated analogs. Implications for the atmospheric chemistry are discussed.

Published
2015
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45. Methods for species delimitation in bumblebees (Hymenoptera, Apidae, Bombus ): towards an integrative approach

Author

Jean-Yves Rasplus, Pierre Rasmont, Irena Valterová, Alexandre Dewulf, Nicolas Brasero, Thibaut De Meulemeester, Manuel Dehon, Denis Michez, Thomas Lecocq, Simon Dellicour, Laboratoire de Zoologie [Mons], University of Mons [Belgium] (UMONS), Evolutionary Biology and Ecology [Brussels], Université libre de Bruxelles (ULB), Naturalis Biodiversity Center [Leiden], Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Centre de Biologie pour la Gestion des Populations (UMR CBGP), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut National de la Recherche Agronomique (INRA)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Université de Montpellier (UM)-Institut de Recherche pour le Développement (IRD [France-Sud])-Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Fonds pour la recherche dans l'industrie et l'agriculture (FRIA), FRIA, European Community [244090], Institute of Organic Chemistry and Biochemistry of the Academy of Sciences of the Czech Republic [RVO: 61388963], network Bibliotheque du Vivant - CNRS, Museum National d'Histoire Naturelle (MNHN), Institut National de la Recherche Agronomique (INRA), Belgian F.R.S.-FNRS, European Project: 244090,EC:FP7:ENV,FP7-ENV-2009-1,STEP(2010), Unité de Recherches Animal et Fonctionnalités des Produits Animaux (URAFPA), Institut National de la Recherche Agronomique (INRA)-Université de Lorraine (UL), Biology and Ecology, Université de Mons (UMons), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), laboratoire de Zoologie, Université de Mons-Hainaut, Université Libre de Bruxelles [Bruxelles] (ULB), Institute of Organic Chemistry and Biochemistry, and Czech Academy of Sciences [Prague] (ASCR)

Subjects
0106 biological sciences, 0303 health sciences, biology, Apidae, Ecology, Hymenoptera, Subspecies, biology.organism_classification, [SDV.BID.SPT]Life Sciences [q-bio]/Biodiversity/Systematics, Phylogenetics and taxonomy, 010603 evolutionary biology, 01 natural sciences, Genetic differentiation, 03 medical and health sciences, Evolutionary biology, Genetics, Animal Science and Zoology, Taxonomy (biology), Molecular Biology, ComputingMilieux_MISCELLANEOUS, Ecology, Evolution, Behavior and Systematics, Bumblebee, 030304 developmental biology
Abstract

International audience; Delimitation of closely related species is often hindered by the lack of discrete diagnostic morphological characters. This is exemplified in bumblebees (genus Bombus). There have been many attempts to clarify bumblebee taxonomy by using alternative features to discrete morphological characters such as wing shape, DNA, or eco-chemical traits. Nevertheless each approach has its own limitations. Recent studies have used a multisource approach to gather different lines of speciation evidence in order to draw a strongly supported taxonomic hypothesis in bumblebees. Yet, the resulting taxonomic status is not independent of selected evidence and of consensus methodology (i.e. unanimous procedure, majority, different weighting of evidence). In this article, we compare taxonomic conclusions for a group of taxonomically doubtful species (the Bombus lapidarius-group) obtained from the four commonly used lines of evidence for species delimitation in bumblebees (geometric morphometric of wing shape, genetic differentiation assessment, sequence-based species delimitation methods and differentiation of cephalic labial gland secretions). We ultimately aim to assess the usefulness of these lines of evidence as components of an integrative decision framework to delimit bumblebee species. Our results show that analyses based on wing shape do not delineate any obvious cluster. In contrast, nuclear/mitochondrial, sequence-based species delimitation methods, and analyses based on cephalic labial gland secretions are congruent with each other. This allows setting up an integrative decision framework to establish strongly supported species and subspecies status within bumblebees.

Published
2015
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46. Improvement of the quadratic non-linear optical properties of pyrimidine chromophores by N-methylation and tungsten pentacarbonyl complexation

Author

Xiaoyang Che, Filip Bureš, Jean-Yves Saillard, Julien Vallet, Alberto Barsella, Sylvain Achelle, Bertrand Caro, Samia Kahlal, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), 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), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Technology, University of Pardubice, Faculty of Chemical Technology, 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), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, 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
Pyrimidine, Chemistry, Process Chemistry and Technology, General Chemical Engineering, chemistry.chemical_element, Second-harmonic generation, Nonlinear optics, N methylation, Chromophore, Tungsten, Ring (chemistry), Photochemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Nonlinear system, chemistry.chemical_compound, Computational chemistry
Abstract

International audience; In this contribution, we report the synthesis of two series of compds.: 4-​(arylvinyl)​-​1-​methylpyrimidinium derivs. and tungsten pentacarbonyl complexes of 4-​(arylvinyl)​pyrimidines. Their second order non-​linear properties, measured by Elec.-​Field Induced Second Harmonic generation (EFISH) method, and their photophys. behavior were thoroughly investigated and compared to the corresponding 4-​(arylvinyl)​pyrimidines. A strong enhancement of the NLO response was obsd. upon methylation or complexation by W(CO)​5 of the pyrimidine ring. DFT theor. calcns. were performed to provide complementary insights on the structure-​properties relationships in particular concerning the amplitude of the NLO response.

Published
2015
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47. Asexual queen succession in the higher termite Embiratermes neotenicus

Author

David Sillam-Dussès, Virginie Roy, Romain Fougeyrollas, Chantal Poteaux, Yves Roisin, Klára Dolejšová, Robert Hanus, Institut d'écologie et des sciences de l'environnement de Paris (iEES), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Recherche Agronomique (INRA), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Faculty of Science, Suez Canal University. Ismailia. Egypt, Université Paris Nord (Paris 13), Evolutio nary Biology and Ecology, Université libre de Bruxelles (ULB), Belgian National Fund for Scientific Research (FRFC) [2.4594.12], Czech Science Foundation [14-12774S], Grant Agency of the Charles University in Prague [580413], Institute of Organic Chemistry and Biochemistry, AS CR [RVO: 61388963], and Institut National de la Recherche Agronomique (INRA)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
reproductive strategies, Genotype, [SDV]Life Sciences [q-bio], Molecular Sequence Data, Parthenogenesis, education, termites, Zoology, General Biochemistry, Genetics and Molecular Biology, termitidae, Electron Transport Complex IV, Reticulitermes, Genus, Animals, Neoteny, Research Articles, General Environmental Science, General Immunology and Microbiology, biology, Ecology, Sequence Analysis, DNA, General Medicine, biology.organism_classification, breeding system, Biological Evolution, thelytokous parthenogenesis, Termitidae, Haplotypes, Genetic structure, isoptera, Insect Proteins, Queen (butterfly), Thelytoky, General Agricultural and Biological Sciences
Abstract

Asexual queen succession (AQS), in which workers, soldiers and dispersing reproductives are produced sexually while numerous non-dispersing queens arise through thelytokous parthenogenesis, has recently been described in three species of lower termites of the genus Reticulitermes . Here, we show that AQS is not an oddity restricted to a single genus of lower termites, but a more widespread strategy occurring also in the most advanced termite group, the higher termites (Termitidae). We analysed the genetic structure in 10 colonies of the Neotropical higher termite Embiratermes neotenicus (Syntermitinae) using five newly developed polymorphic microsatellite loci. The colonies contained one primary king accompanied either by a single primary queen or by up to almost 200 neotenic queens. While the workers, the soldiers and most future dispersing reproductives were produced sexually, the non-dispersing neotenic queens originated through thelytokous parthenogenesis of the founding primary queen. Surprisingly, the mode of thelytoky observed in E. neotenicus is most probably automixis with central fusion, contrasting with the automixis with terminal fusion documented in Reticulitermes . The occurrence of AQS based on different mechanisms of ploidy restoration raises the hypothesis of an independent evolutionary origin of this unique reproductive strategy in individual lineages of lower and higher termites.

Published
2015
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49. Modern Approaches to Synthetic Design of Chiral α-Tertiary Amines Based on Trifluoromethylcontaining Ketimines: A Review

Author

Sukach, Volodymyr, Tkachuk, V., Gillaizeau, Isabelle, Vovk, Mykhailo, Institute of Organic Chemistry, National Academy of Sciences of Ukraine (NASU), Enamine Ltd, Institut de Chimie Organique et Analytique (ICOA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
nucleophilic addition, α-tertiary amines, asymmetric synthesis, metal complex catalysis, [CHIM]Chemical Sciences, organocatalysis, General Chemistry, trifluoromethyl group, ketimines
Abstract

International audience; Enantioselective construction methods of chiral derivatives of α-tertiary amines using acyclic and cyclic trifluoromethylketimines are considered. The importance of a trifluoromethyl group in the structure of ketimine substrates for effective asymmetric addition of C-nucleophilic reagents in the presence of metal complex catalysts or organocatalysts is emphasized. The practical application of these chiral products in medicinal chemistry is covered.

Published
2022
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50. 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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