Author: "Chimie Structurale Organique et Biologique (CSOB)" / Topic: 01 natural sciences - Searchworks@Jio Institute Digital Library Search Results

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53 results on '"Chimie Structurale Organique et Biologique (CSOB)"'

1. First Direct Evidence of Interpartner Hydride/Deuteride Exchanges for Stored Sodiated Arginine/Fructose-6-phosphate Complex Anions within Salt-Solvated Structures

Author: Yves Gimbert, Sandra Alves, François Fenaille, Ekaterina Darii, Alain Perret, Amina S. Woods, Jean-Claude Tabet, Annelaure Damont, Génomique métabolique (UMR 8030), Genoscope - Centre national de séquençage [Evry] (GENOSCOPE), Université Paris-Saclay-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 Paris-Saclay-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)-Centre National de la Recherche Scientifique (CNRS)-Université d'Évry-Val-d'Essonne (UEVE), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Médicaments et Technologies pour la Santé (MTS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), DMTS, Université Paris Saclay, CEA, INRAE, SPI, Synthèse, Structure et Fonction de Molécules Bioactives (SSFMB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Service de Pharmacologie et Immunoanalyse (SPI), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA))
Subjects: chemistry.chemical_classification, Hydride, Electrospray ionization, 010401 analytical chemistry, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, chemistry.chemical_compound, Crystallography, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Structural Biology, Molecule, Non-covalent interactions, Isotopologue, Carboxylate, Isomerization, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract: International audience; Mass spectrometric investigations of noncovalent binding between low molecular weight compounds revealed the existence of gas-phase (GP) noncovalent complex (NCC) ions involving zwitterionic structures. ESI MS is used to prove the formation of stable sodiated NCC anions between fructose (F6P) and arginine (R) moieties. Theoretical calculations indicate a folded solvated salt (i.e., sodiated carboxylate interacting with phosphate) rather than a charge-solvated form. Under standard CID conditions, [(F6P+R-H+Na)-H]− competitively forms two major product ions (PIs) through partner splitting [(R-H+Na) loss] and charge-induced cross-ring cleavage while preserving the noncovalent interactions (noncovalent product ions (NCPIs)). MS/MS experiments combined with in-solution proton/deuteron exchanges (HDXs) demonstrated an unexpected labeling of PIs, i.e., a correlated D-enrichment/D-depletion. An increase in activation time up to 3000 ms favors such processes when limited to two H/D exchanges. These results are rationalized by interpartner hydride/deuteride exchanges (⟨HDX⟩) through stepwise isomerization/dissociation of sodiated NCC-d11 anions. In addition, the D-enrichment/D-depletion discrepancy is further explained by back HDX with residual water in LTQ (selective for the isotopologue NCPIs as shown by PI relaxation experiments). Each isotopologue leads to only one back HDX unlike multiple HDXs generally observed in GP. This behavior shows that NCPIs are zwitterions with charges solvated by a single water molecule, thus generating a back HDX through a relay mechanism, which quenches the charges and prevents further back HDX. By estimating back HDX impact on D-depletion, the interpartner ⟨HDX⟩ complementarity was thus illustrated. This is the first description of interpartner ⟨HDX⟩ and selective back HDX validating salt-solvated structures.
Published: 2021

2. Benzophenone Photoreactivity in a Lipid Bilayer To Probe Peptide/Membrane Interactions: Simple System, Complex Information

Author: Gilles Clodic, Emmanuelle Sachon, Lucrèce Matheron, Carla Kirschbaum, Leïla Bechtella, Marine Cosset, Gérard Bolbach, Astrid Walrant, Sandrine Sagan, Institut de Biologie Intégrative (IFR-BI), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-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)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), University of Cambridge [UK] (CAM), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris
Subjects: Ultraviolet Rays, Lipid Bilayers, Peptide, Cell-Penetrating Peptides, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Analytical Chemistry, Benzophenones, chemistry.chemical_compound, Tandem Mass Spectrometry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Benzophenone, Non-covalent interactions, Amino Acid Sequence, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Lipid bilayer, Phospholipids, chemistry.chemical_classification, Chemistry, Fatty Acids, 010401 analytical chemistry, Combinatorial chemistry, 0104 chemical sciences, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Cholesterol, Cross-Linking Reagents, Membrane, Oxidation-Reduction
Abstract: International audience; Affinity photo-cross-linking coupled to mass spec-trometry, using benzophenone (Bzp)-functionalized peptides, was used to study the noncovalent interactions of cell-penetrating peptides and lipid membranes. Using biomimetic lipid vesicles composed of saturated and unsaturated negatively charged lipids, DMPG (14:0), DPPG (16:0), DOPG (18:1 cis Δ 9), 18:1 (trans Δ 9) PG, and DLoPG (18:2 cis Δ 9, 12), allowed observation of all the classical and less common reactivities of Bzp described in the literature by direct MS analysis: CC double bond formation on saturated fatty acids, covalent adducts formation via classical C−C bond, and Paterno-Buchi oxetane formation followed or not by fragmentation (retro-Paterno-Buchi) as well as photosensitization of unsaturated lipids leading to lipid dimers. All these reactions can occur concomitantly in a single complex biological system: a membrane-active peptide inserted within a phospholipid bilayer. We also detect oxidation species due to the presence of radical oxygen species. This work represents a noteworthy improvement for the characterization of interacting partners using Bzp photo-cross-linking, and it shows how to exploit in an original way the different reactivities of Bzp in the context of a lipid membrane. We propose an analytical workflow for the interpretation of MS spectra, giving access to information on the CPP/lipid interaction at a molecular level such as depth of insertion or membrane fluidity in the CPP vicinity. An application of this workflow illustrates the role of cholesterol in the CPP/lipids interaction.
Published: 2019

3. [(C^C)Au(N^N)]+ complexes as a new family of anticancer candidates: synthesis, characterization and exploration of the antiproliferative properties

Author: Geoffrey Gontard, Michèle Salmain, Uttara Basu, Philip Spence, Denis Lesage, Jérémy Forté, Henrik Hoffmeister, Edwyn Remadna, Silva Khodjoyan, Benoît Bertrand, Héloïse Dossmann, Ingo Ott, Zoë A. E. Waller, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Chimie Structurale Organique et Biologique (CSOB), Technische Universität Braunschweig = Technical University of Braunschweig [Braunschweig], University of East Anglia [Norwich] (UEA), and University College of London [London] (UCL)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Stereochemistry, Phenanthroline, Thioredoxin reductase, Organic Chemistry, General Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health, Amino acid, chemistry.chemical_compound, Bipyridine, chemistry, Organogold Compounds, Chelation, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Derivative (chemistry)
Abstract: International audience; A library of eleven cationic gold(III) complexes of the general formula [(C^C)Au(N^N)] + when C^C is either biphenyl or 4,4’-ditertbutyldiphenyl and N^N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C^N^C)Au(NHC)] + structure. This makes the [(C^C)Au(N^N)] + complexes a new class of organogold compounds with an original mode of action
Published: 2021

4. β-Cyclodextrin-NHC-Gold(I) Complex (β-ICyD)AuCl: A Chiral Nanoreactor for Enantioselective and Substrate-Selective Alkoxycyclization Reactions

Author: Denis Lesage, Sylvain Roland, Kajetan Bijouard, Jorge Meijide Suárez, Matthieu Sollogoub, Etienne Derat, Louis Fensterbank, Olivia Bistri-Aslanoff, Nicolas Vanthuyne, Natalia del Rio, Pinglu Zhang, Mehdi Koohgard, Coralie Tugny, Virginie Mouriès-Mansuy, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Glycochimie Organique Biologique et Supramoléculaire (GOBS), Méthodes et Application en Chimie Organique (MACO), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and ANR-17-CE07-0036,CaSPair,Paires de Lewis séparées par une cavité, une nouvelle plateforme pour la conversion catalytique de petites molécules(2017)
Subjects: POLE 3, POLE 1, Nanoreactor, cavity, 010402 general chemistry, 01 natural sciences, Catalysis, [CHIM]Chemical Sciences, Metrics & More Article Recommendations gold(I), chemistry.chemical_classification, cyclodextrins, Cyclodextrin, 010405 organic chemistry, Ligand, Chemistry, Enantioselective synthesis, selectivity, Substrate (chemistry), asymmetric catalysis, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, GOBS, Selectivity, MACO, CSOB
Abstract: International audience; NHC-capped β-cyclodextrin (β-ICyD) was used as a ligand for gold-catalyzed alkoxycyclization reactions. The cavity was found to be responsible for a triple selectivity: (i) the asymmetric shape of the cavity of β-ICyD induced highly stereoselective cyclizations, (ii) the shape of the interior favored the formation of a six-membered ring in the absence of a nucleophile, and finally, (iii) the encapsulation of the metal inside the cavity disfavored the addition of sterically hindered alcohols. Highly enantioselective and substrate-selective alkoxycyclizations of enynes are therefore promoted by the cavity-based molecular reactor (β-ICyD)AuCl.
Published: 2020

5. PCR Incorporation of Polyoxometalate Modified Deoxynucleotide Triphosphates and Their Application in Molecular Electrochemical Sensing of Yersinia pestis

Author: Mayreli Ortiz, Markéta Svobodová, Ciara K. O'Sullivan, Denis Lesage, Bernold Hasenknopf, Serge Thorimbert, Richard B. Cole, Ahmed M. Debela, Glycochimie Organique Biologique et Supramoléculaire (GOBS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Chimie Structurale Organique et Biologique (CSOB), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: DNA, Bacterial, Yersinia pestis, [SDV]Life Sciences [q-bio], Sequence (biology), 010402 general chemistry, Polymerase Chain Reaction, 01 natural sciences, Redox, Catalysis, chemistry.chemical_compound, [CHIM]Chemical Sciences, Nucleotide, A-DNA, Electrodes, ComputingMilieux_MISCELLANEOUS, Polymerase, chemistry.chemical_classification, biology, Nucleotides, 010405 organic chemistry, Organic Chemistry, Electrochemical Techniques, General Chemistry, Tungsten Compounds, biology.organism_classification, Electrophoresis, Gel, Pulsed-Field, 0104 chemical sciences, Biochemistry, chemistry, Polyoxometalate, biology.protein, Gold, DNA
Abstract: Redox-labeled nucleotides are of increasing interest for the fabrication of next generation molecular tools and should meet requirements of being thermally stable, sensitive, and compatible with polymerase-mediated incorporation while also being electrochemically discriminable. The synthesis and characterization of Keggin and Dawson polyoxometalate-deoxynucleotide (POM-dNTP) bioconjugates linked through 7-deaza-modified purines is described. The modified POM-dNTPs were used for polymerase-based amplification of a DNA sequence specific for Yersinia pestis and the amplified DNA detected using an electrochemical DNA sensor. This highlights the potential of polyoxometalates as thermally stable, sensitive and polymerase-compatible redox labels for exploitation in bioanalytical applications.
Published: 2017

6. Charge-tagged N-heterocyclic carbenes (NHC): Direct transfer from ionic liquid solutions and long-lived nature in the gas phase

Author: Thyago S. Rodrigues, Denis Lesage, Wender A. Silva, Gunter Ebeling, Heibbe C. B. de Oliveira, Richard B. Cole, Jairton Dupont, Marcos N. Eberlin, Brenno A. D. Neto, University of Brasilia, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Universidade Federal do Rio Grande do Sul [Porto Alegre] (UFRGS), University of Campinas [Campinas] (UNICAMP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Estadual de Campinas = University of Campinas (UNICAMP)
Subjects: education.field_of_study, 010405 organic chemistry, Transition metal carbene complex, Inorganic chemistry, Population, Ionic bonding, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Ion, chemistry.chemical_compound, Deprotonation, chemistry, Structural Biology, Ionic liquid, [CHIM]Chemical Sciences, Molecule, Reactivity (chemistry), education, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract: Negatively charge-tagged N-heterocyclic carbenes have been formed in solution via deprotonation of imidazolium ions bearing acid side groups and transferred to the gas phase via ESI(-)-MS. The structure of the putative and apparently stable gaseous carbenes formed in such conditions were then probed via reactions with carbon dioxide using a triple quadrupole mass spectrometer particularly optimized for ion/molecule reactions of ESI-generated ions. Complete conversion to imidazolium carboxylates was achieved, which seems to demonstrate the efficiency of the transfer, the gas-phase stability, and the long-lived nature of these unprecedented charge-tagged carbenes and their predominance in the ionic population. Comprehensive studies on the intrinsic reactivity of N-heterocyclic carbenes with silent charge tags are therefore possible. Graphical Abstract ᅟ.
Published: 2017

7. Revisiting the Intermolecular Fujiwara Hydroarylation of Alkynes

Author: Nelson H. Morgon, Marla N. Godoi, Marcos N. Eberlin, Richard B. Cole, Denis Lesage, Vanessa G. Santos, Thaís Regiani, Pablo David G. Martinez, Héloïse Dossmann, Carlos Roque D. Correia, Francisco de Azambuja, University of Campinas (UNICAMP), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Estadual de Campinas = University of Campinas (UNICAMP)
Subjects: 010405 organic chemistry, Computational chemistry, Chemistry, Organic Chemistry, Intermolecular force, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract: International audience; no abstract
Published: 2017

8. Large-Ring Cyclodextrins as Chiral Selectors for Enantiomeric Pharmaceuticals

Author: Franziska D. Zitzmann, Detlev Belder, Sebastian Thurmann, Yannick Krauke, Christian Sonnendecker, Andrea A. Robitzki, Wolfgang Zimmermann, Cédric Przybylski, Kate Monks, Nicole Heinke, Leipzig University, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Universität Leipzig [Leipzig], and Institut für Analytische Chemie
Subjects: Spectrometry, Mass, Electrospray Ionization, POLE 3, Cell Survival, Complex formation, Supramolecular chemistry, Bacillus, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Catalysis, Cell Line, Bacterial Proteins, [CHIM]Chemical Sciences, Humans, Fragmentation (cell biology), Fluvastatin, chemistry.chemical_classification, Cyclodextrins, Chromatography, 010405 organic chemistry, 010401 analytical chemistry, Electrophoresis, Capillary, Stereoisomerism, General Chemistry, Reversed-phase chromatography, General Medicine, 3. Good health, 0104 chemical sciences, Mefloquine, Electrophoresis, Enzyme, chemistry, Pharmaceutical Preparations, Glucosyltransferases, Enantiomer, CSOB
Abstract: Large-ring cyclodextrins (CD) are cyclic glucans composed of 9 or more α-1,4-linked glucose units. They are minor side products of bacterial glucanotransferases (CGTases, EC 2.4.1.19) and have previously been available only in very small amounts for studies of their properties in supramolecular complex formation reactions. We engineered a CGTase to synthesize mainly large-ring CD facilitating their preparation in larger amounts. By reversed phase chromatography, we obtained single CD samples composed of 10 to 12 glucose units (CD10, CD11, and CD12) with a purity of >90 %. Their identity was confirmed by high resolution mass spectrometry and fragmentation analysis. We demonstrated the non-toxicity of CD10-CD12 for human cell lines by a cell proliferation assay and impedimetric monitoring. We then showed that CD10 and CD11 are efficient chiral selectors for the capillary electrophoretic separation of the enantiomeric pharmaceuticals fluvastatin, mefloquine, carvedilol, and primaquine.
Published: 2019

9. The Uncommon Strong Inhibition of α-Glucosidase by Multivalent Glycoclusters Based on Cyclodextrin Scaffolds

Author: Abed Bil, Takwa Khanchouche, Véronique Bonnet, José Kovensky, Cédric Przybylski, Urjwan Alali, David Mathiron, Rémi Beaulieu, Mohammed Benazza, Aurélie Vallin, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plateforme Analytique (PFA), Université de Picardie Jules Verne (UPJV), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: POLE 3, medicine.medical_treatment, Saccharomyces cerevisiae, 010402 general chemistry, 01 natural sciences, Biochemistry, medicine, Monosaccharide, [CHIM]Chemical Sciences, Glycoside Hydrolase Inhibitors, Physical and Theoretical Chemistry, IC50, Acarbose, chemistry.chemical_classification, Cyclodextrins, Molecular Structure, Cyclodextrin, 010405 organic chemistry, Chemistry, Insulin, Organic Chemistry, Glycoside, alpha-Glucosidases, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Propargyl, Click chemistry, Click Chemistry, Glycoconjugates, CSOB, medicine.drug
Abstract: New inhibitors of α-glucosidase based on perglycosylated cyclodextrins were synthesized via click-chemistry and compared to acarbose. , The homeostasis disruption of d -glucose causes diabetes, a dramatic chronic disease worldwide. Type 1 diabetes is a successfully treatable form, where blood d -glucose is regulated by insulin treatment. In contrast type 2 diabetes, the non-insulin dependent kind, is problematic. The control of the d -glucose blood level via intestinal α- d -glucosidase inactivation can be achieved by using competitive inhibitors, such as iminosugars ( e.g. acarbose) or sulfonium sugar derivatives ( e.g. salacinol). Recently, an unprecedented result showed that multivalent diamond nanoparticles grafted with unmodified sugars displayed α-glucosidase inhibition at low micromolar concentrations. Herein we describe the synthesis of multivalent glycoclusters using cyclodextrins (CDs) as scaffolds and an assessment of their role as inhibitors of α- d -glucosidase. The glycoclusters were efficiently obtained from per-azido α, β and γ-CD derivatives and propargyl glycosides using click-chemistry under microwave irradiation. The methodology was successfully applied to various protected and non-protected propargylated monosaccharides, including both O - and S -glycosides, giving clear evidence of its versatility. The targeted 6- per -glycosylated CDs were isolated in moderate to excellent yields (30\textendash 90%) by silica gel chromatography. The results showed inhibition of α-glucosidase from Saccharomyces cerevisiae with IC 50 values in the 32\textendash 132 μM range, lower than that of acarbose (IC 50 = ∼250 μM), a well-known competitive inhibitor used in the clinical treatment of type 2 diabetes. Preliminary experiments suggest a mixed-type non-competitive inhibition mode for these new glycoclusters.
Published: 2019

10. Identification of Postblast Residues by DART-High Resolution Mass Spectrometry Combined with Multivariate Statistical Analysis of the Kendrick Mass Defect

Author: Maxime C. Bridoux, Nolwenn Floch, Alexandre Sonnette, Gabriel Gaiffe, Richard B. Cole, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Central de la Préfecture de Police, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Dart, Kendrick mass, POLE 3, Chemistry, 010401 analytical chemistry, Analytical chemistry, 010402 general chemistry, Orbitrap, Mass spectrometry, 01 natural sciences, DART ion source, 0104 chemical sciences, Analytical Chemistry, law.invention, law, Mass spectrum, [CHIM]Chemical Sciences, Plastic explosive, computer, CSOB, Semtex, computer.programming_language
Abstract: The coupling of an atmospheric pressure ionization source (Direct Analysis in Real Time, DART) and a high-resolution mass spectrometer (Orbitrap) has enabled the rapid and efficient analysis of a variety of energetic formulations. This approach was used to generate mass spectra for 83 plastic explosives and polymer samples in less than 2 min per sample. To manually interpret and identify all of the constituent polymers and other interesting features in the acquired mass spectra is a tedious and time-consuming challenge. Instead, a methodology based on the systematic calculation of Kendrick mass defects (KMDs) was developed and implemented. Its application allowed the identification of the polymeric support present in each energetic formulation. The presence of polyisobutylene in PG2 has been confirmed thanks to this approach, and a mixture of polyisobutylene, polybutadiene, and polystyrene has been confirmed in the Semtex 10 formulation. The developed methodology has also permitted the observation of changes that occur to the polymeric composition of these formulations after a blast. It appears that the most adequate way to describe post blast polymer samples is that they are less oxygenated and, above all, more unsaturated than the original starting material. These conclusions were deduced with the aid of principal component analysis, which served to establish the main factors that differentiate the samples.
Published: 2019

11. Combined use of direct analysis in real-time/Orbitrap mass spectrometry and micro-Raman spectroscopy for the comprehensive characterization of real explosive samples

Author: Richard B. Cole, Maxime C. Bridoux, Adrian Schwarzenberg, Sébastien Schramm, DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Explosive material, Polymers, Analytical chemistry, Real weapons, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Biochemistry, Analytical Chemistry, Direct Analysis in Real Time, chemistry.chemical_compound, symbols.namesake, Dioctyl sebacate, Raman microscopy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Sample preparation, ComputingMilieux_MISCELLANEOUS, Paper in Forefront, chemistry.chemical_classification, Chemistry, 010401 analytical chemistry, Plasticizer, Polymer, DART ion source, 0104 chemical sciences, symbols, Orbitrap MS, Explosives, Raman spectroscopy
Abstract: Direct Analysis in Real Time (DART™) high-resolution Orbitrap™ mass spectrometry (HRMS) in combination with Raman microscopy was used for the detailed molecular level characterization of explosives including not only the charge but also the complex matrix of binders, plasticizers, polymers, and other possible organic additives. A total of 15 defused military weapons including grenades, mines, rockets, submunitions, and mortars were examined. Swabs and wipes were used to collect trace (residual) amounts of explosives and their organic constituents from the defused military weapons and micrometer-size explosive particles were transferred using a vacuum suction-impact collection device (vacuum impactor) from wipe and swap samples to an impaction plate made of carbon. The particles deposited on the carbon plate were then characterized using micro-Raman spectroscopy followed by DART-HRMS providing fingerprint signatures of orthogonal nature. The optical microscope of the micro-Raman spectrometer was first used to localize and characterize the explosive charge on the impaction plate which was then targeted for identification by DART-HRMS analysis in both the negative and positive modes. Raman spectra of the explosives TNT, RDX and PETN were acquired from micrometer size particles and characterized by the presence of their characteristic Raman bands obtained directly at the surface of the impaction plate nondestructively without further sample preparation. Negative mode DART-HRMS confirmed the types of charges contained in the weapons (mainly TNT, RDX, HMX, and PETN; either as individual components or as mixtures). These energetic compounds were mainly detected as deprotonated species [M–H]−, or as adduct [M + 35Cl]−, [M + 37Cl]−, or [M + NO3]− anions. Chloride adducts were promoted in the heated DART reagent gas by adding chloroform vapors to the helium stream using an “in-house” delivery method. When the polarity was switched to positive mode, DART-HRMS revealed a very complex distribution of polymeric binders (mainly polyethylene glycols and polypropylene glycols), plasticizers (e.g., dioctyl sebacate, tributyl phosphate), as well as wax-like compounds whose structural features could not be precisely assigned. In positive mode, compounds were identified either as protonated molecules or ammonium adduct species. These results clearly demonstrate the complementarity of micro-Raman microscopy combined with DART-MS. The former technique provides structural information on the type of explosives present at the surface of the sample, whereas the latter provides not only a confirmation of the nature of the explosive charge but also useful additional information regarding the nature of the complex organic matrix of binders, plasticizers, polymers, oils, and potentially other organic additives and contaminants present in the sample. Combining these two techniques provides a powerful tool for the screening, comprehensive characterization, and differentiation of particulate explosive samples for forensic sciences and homeland security applications. Graphical Abstract Comprehensive characterization of explosive particles collected from swipe samples by micro-Raman and DART™-HRMS Electronic supplementary material The online version of this article (doi:10.1007/s00216-016-9691-9) contains supplementary material, which is available to authorized users.
Published: 2016

12. Bond dissociation energies of carbonyl gold complexes: a new descriptor of ligand effects in gold(i) complexes?

Author: Héloïse Dossmann, Richard B. Cole, Antony Memboeuf, Yves Gimbert, Anne Milet, Hervé Clavier, Chen-Hui Chan, Denis Lesage, David Gatineau, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), 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), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), 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), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: 010405 organic chemistry, Ligand, Bond strength, Chemistry, 010402 general chemistry, Tandem mass spectrometry, 01 natural sciences, Bond-dissociation energy, Dissociation (chemistry), 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Computational chemistry, Electronic effect, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene
Abstract: International audience; Ligand electronic effects in gold(I) chemistry have been evaluated by means of the experimental determination of M-CO bond dissociation energies for 16 [L-Au-CO] + complexes, bearing L ligands widely used in gold catalysis. Energy-resolved analyzes have been achieved using tandem mass spectrometry with collision induced dissociation. Coupled to DFT calculations, this approach enables the quantification of ligand effects based on the LAu-CO bond strength. Further energy decomposition analysis gives access to detailed insights of this bond's properties. Whereas small differences are observed between phosphine-and phosphite-containing gold complexes, carbene ligands are shown to stabilize much more efficiently the gold-carbonyl bond.
Published: 2018

13. Spectroscopy and Photodissociation of the Perfluorooctanoate Anion

Author: Alexandre Giuliani, Suzie Douix, Héloïse Dossmann, Edith Nicol, Denis Duflot, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), 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), Département Caractérisation et Elaboration des Produits Issus de l'Agriculture (CEPIA), Institut National de la Recherche Agronomique (INRA), GENCI-TGCC [2018-A0010806820], Ile-de-France region through DIM Analytics, Agence Nationale de la Recherche Scientifique, France [ANR-08-BLAN-0065], CaPPA project (Chemical and Physical Properties of the Atmosphere) - French National Research Agency (ANR) through the PIA (Programme d'Investissement d'Avenir) [ANR-10-LABX-005], French Ministere de l'Enseignement Superieur et de la Recherche, Hauts de France Region, European Funds for Regional Economical Development, National FT-ICR network [FR 3624 CNRS], École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS)
Subjects: atmospheric chemistry, 010504 meteorology & atmospheric sciences, Mass spectrometry, Photochemistry, 01 natural sciences, Catalysis, Ion, chemistry.chemical_compound, Ultraviolet visible spectroscopy, UV/Vis spectroscopy, Spectroscopy, 0105 earth and related environmental sciences, mass spectrometry, photochemistry, 010401 analytical chemistry, Organic Chemistry, Photodissociation, Relaxation (NMR), perfluoro compounds, General Chemistry, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, 13. Climate action, Atmospheric chemistry, Perfluorooctanoic acid, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Perfluorocarbons, a class of fully fluorinated compounds, are highly persistent and toxic pollutants that are receiving increasing attention due to their widespread environmental distribution. In this study, attention was focused on one compound in particular, namely, perfluorooctanoic acid (PFOA). The first investigation of the UV/VUV photochemistry of the PFOA anion in the gas phase by action spectroscopy of selected ions is reported. Two main relaxation channels were identified: photodissociation and photodetachment. Absolute cross sections for the individual observed processes were measured. DFT calculations and natural transition orbital analysis were carried out to help in the interpretation of the experimental results.
Published: 2018

14. Characterization of Fluorinated Polymers by Atmospheric-Solid-Analysis-Probe High-Resolution Mass Spectrometry (ASAP/HRMS) Combined with Kendrick-Mass-Defect Analysis

Author: Maxime C. Bridoux, Gabriel Gaiffe, Richard B. Cole, Sabrina Lacpatia, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), LCPP - laboratoire central de la préfecture de police, DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Kendrick mass, POLE 3, 010401 analytical chemistry, Analytical chemistry, chemistry.chemical_element, Polymer, 010402 general chemistry, Mass spectrometry, Orbitrap, 01 natural sciences, Polyvinylidene fluoride, 0104 chemical sciences, Analytical Chemistry, law.invention, chemistry.chemical_compound, chemistry, law, Fluorine, [CHIM]Chemical Sciences, Hexafluoropropylene, Chlorotrifluoroethylene, CSOB
Abstract: Fluorinated polymers are a diverse and important class of polymers with unique applications. However, characterization of fluorinated polymers by conventional mass spectrometric methods is challenging because (i) their high fluorine contents make them insoluble or only sparingly soluble in most common solvents and (ii) commonly used matrices employed for MALDI do not desorb or ionize them efficiently. In this work, atmospheric-solid-analysis-probe (ASAP) high-resolution orbitrap mass spectrometry (HRMS) was used as a new tool for the molecular characterization of various fluorinated polymers, including polyvinylidene fluoride (PVDF) and fluorinated copolymers containing PVDF and chlorotrifluoroethylene (KEL-F 800) or PVDF and hexafluoropropylene (Viton A and Tecnoflon). The major peaks of the observed distributions were assigned compositions, but the high number of species required the use of an alternative method to treat such complex data. Kendrick-mass defects (KMD) were calculated on the basis of the "common-to-all" vinylidene difluoride repeating unit. By plotting the KMD as a function of the nominal Kendrick masses (NKM), specific patterns based on homologous series emerged. Kendrick maps were therefore drawn to simplify the mass spectra and provide confident peak assignments through homologous-series recognition. A specific fingerprint for each polymer has been identified, and the ability to discern the four species present in a blend through KMD analysis was demonstrated.
Published: 2018

15. Revealing cooperative binding of polycationic cyclodextrins with DNA oligomers by capillary electrophoresis coupled to mass spectrometry

Author: Juan M. Benito, José M. García Fernández, Carmen Ortiz Mellet, Cédric Przybylski, Véronique Bonnet, Ministerio de Economía y Competitividad (España), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Instituto de Investigaciones Químicas (IIQ), Universidad de Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: POLE 3, Cooperative effects, DNA, Single-Stranded, dnaN, Gene delivery, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Biochemistry, Mass Spectrometry, Polymerization, Analytical Chemistry, chemistry.chemical_compound, Capillary electrophoresis, [CHIM]Chemical Sciences, Environmental Chemistry, Hill number, Spectroscopy, Cyclodextrins, Drug Carriers, Chromatography, Base Sequence, 010405 organic chemistry, Oligonucleotide, Electrophoresis, Capillary, Cooperative binding, DNA, 0104 chemical sciences, Polycationic cyclodextrins, chemistry, CE-MS, Nucleic acid, CSOB
Abstract: Gene delivery is critical for the development of nucleic acid-based therapies against a range of severe diseases. The conception of non-viral (semi)synthetic vectors with low cytotoxicity and virus-like efficiency is gathering a lot of efforts, but it represents a fantastic challenge still far from accomplishment. Carbohydrate-based scaffolds offer interesting features towards this end, such as easy availability, relatively cheap cost, tuning properties and a good biocompatibility. The lack of analytical methods providing quantitative and qualitative data on their binding properties with oligonucleotides (DNA/RNA), with a minimal time and sample consumption, represents a limitation for these channels. Here, we attempted to fill the gap by hyphenation of capillary electrophoresis with mass spectrometry (CE-MS). This coupling strategy allows discriminating free and complexed DNA oligomers with cationic cyclodextrins (CDs), determining the stoichiometry where the highest observed is always DNA: n/3(CD), and unambiguously assigning the partners through m/z detection. Very reliable data were obtained with migration time within 5.5 (standard deviation < 0.5%) and 25 min (standard deviation < 1.1%) for UV and MS detection, respectively. Furthermore, varying the nitrogen/phosphorus ratio (N/P), key parameters relating to the thermodynamics e.g. the micro and macroscopic dissociation constants K and K, respectively (both in low μM range) and the Gibbs free energy ΔG (−16.3 to −26.9 kJ mol), and also the cooperativity as Hill number (nH between 0.98 and 15.75) of the supramolecular process can be delineated, providing a unique tool for the high throughput screening and selection of efficient gene delivery carriers., The authors thank Genopole-France and the Conseil Régional d’Ile-de-France and the Spanish Ministerio de Economia y Competitividad (MinECo, contract no. SAF2013-44021-R and CTQ2015-64425-C2-1-R).
Published: 2018

16. A Systematic Tandem Mass Spectrometric Study of Anion Attachment for Improved Detection and Acidity Evaluation of Nitrogen-Rich Energetic Compounds

Author: Christine Costanza, Richard B. Cole, Maxime C. Bridoux, Gabriel Gaiffe, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Central de la Préfecture de Police, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: POLE 3, Electrospray ionization, 010401 analytical chemistry, Analytical chemistry, Pentaerythritol tetranitrate, 010402 general chemistry, Tandem mass spectrometry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, Adduct, Ion, chemistry.chemical_compound, Deprotonation, chemistry, Molecule, [CHIM]Chemical Sciences, CSOB, Spectroscopy
Abstract: The development of rapid, efficient, and reliable detection methods for the characterization of energetic compounds is of high importance to security forces concerned with terrorist threats. With a mass spectrometric approach, characteristic ions can be produced by attaching anions to analyte molecules in the negative ion mode of electrospray ionization mass spectrometry (ESI-MS). Under optimized conditions, formed anionic adducts can be detected with higher sensitivities as compared with the deprotonated molecules. Fundamental aspects pertaining to the formation of anionic adducts of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), 1,3,5-trinitro-1,3,5-triazinane (RDX), pentaerythritol tetranitrate (PETN), nitroglycerin (NG), and 1,3,5-trinitroso-1,3,5-triazinane energetic (R-salt) compounds using various anions have been systematically studied by ESI-MS and ESI tandem mass spectrometry (collision-induced dissociation) experiments. Bracketing method results show that the gas-phase acidities of PETN, RDX, and HMX fall between those of HF and acetic acid. Moreover, PETN and RDX are each less acidic than HMX in the gas phase. Nitroglycerin was found to be the most acidic among the nitrogen-rich explosives studied. The ensemble of bracketing results allows the construction of the following ranking of gas-phase acidities: PETN (1530-1458 kJ/mol) > RDX (approximately 1458 kJ/mol) > HMX (approximately 1433 kJ/mol) > nitroglycerin (1427-1327.8 kJ/mol).
Published: 2018

17. Low-Energy Collision-Induced Dissociation (Low-Energy CID), Collision-Induced Dissociation (CID), and Higher Energy Collision Dissociation (HCD) Mass Spectrometry for Structural Elucidation of Saccharides and Clarification of Their Dissolution Mechanism i

Author: Parisa Bayat, Denis Lesage, Richard B. Cole, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)
Subjects: chemistry.chemical_classification, Collision-induced dissociation, POLE 3, 010401 analytical chemistry, Glycosidic bond, 010402 general chemistry, Photochemistry, Mass spectrometry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, chemistry.chemical_compound, Reaction rate constant, chemistry, Fragmentation (mass spectrometry), Lithium chloride, [CHIM]Chemical Sciences, Dissolution, CSOB, Spectroscopy
Abstract: The dissolution mechanism of oligosaccharides in N,N-dimethylacetamide/lithium chloride (DMAc/LiCl), a solvent used for cellulose dissolution, and the capabilities of low-energy collision-induced dissociation (low-energy CID), collision-induced dissociation (CID), and higher energy collision dissociation (HCD) for structural analysis of carbohydrates were investigated. Comparing the spectra obtained using 3 techniques shows that, generally, when working with monolithiated sugars, CID spectra provide more structurally informative fragments, and glycosidic bond cleavage is the main pathway. However, when working with dilithiated sugars, HCD spectra can be more informative providing predominately cross-ring cleavage fragments. This is because HCD is a nonresonant activation technique, and it allows a higher amount of energy to be deposited in a short time, giving access to more endothermic decomposition pathways as well as consecutive fragmentations. The difference in preferred dissociation pathways of monolithiated and dilithiated sugars indicates that the presence of the second lithium strongly influences the relative rate constants for cross-ring cleavages vs glycosidic bond cleavages, and disfavors the latter. Regarding the dissolution mechanism of sugars in DMAc/LiCl, CID and HCD experiments on dilithiated and trilithiated sugars reveal that intensities of product ions containing 2 Li+ or 3 Li+ , respectively, are higher than those bearing only 1 Li+ . In addition, comparing the fragmentation spectra (both HCD and CID) of LiCl-adducted lithiated sugar and NaCl-adducted sodiated sugar shows that while, in the latter case, loss of NaCl is dominant, in the former case, loss of HCl occurs preferentially. The compiled evidence implies that there is a strong and direct interaction between lithium and the saccharide during the dissolution process in the DMAc/LiCl solvent system.
Published: 2018

18. Characterization of Degradation Products of Macitentan under Various Stress Conditions Using Liquid Chromatography/Mass Spectrometry

Author: Sukanya Pandeti, Jean-Claude Tabet, Jagadeshwar Reddy Thota, Naga Veera Yerra, Pavankumar Pallerla, CSIR Indian Institute of Chemical Technology [Hyderabad] (IICT), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Spectrometry, Mass, Electrospray Ionization, POLE 3, Endothelin A Receptor Antagonists, Electrospray ionization, Pharmaceutical formulation, Tandem mass spectrometry, Mass spectrometry, 01 natural sciences, Analytical Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Hydrolysis, 0302 clinical medicine, Drug Stability, Liquid chromatography–mass spectrometry, Tandem Mass Spectrometry, Ammonium formate, [CHIM]Chemical Sciences, Spectroscopy, Chromatography, High Pressure Liquid, Sulfonamides, Chromatography, Photolysis, 010401 analytical chemistry, Organic Chemistry, 0104 chemical sciences, Endothelin B Receptor Antagonists, Pyrimidines, 030228 respiratory system, chemistry, Degradation (geology), Oxidation-Reduction, CSOB
Abstract: Rationale Stress testing of a drug candidate is an important step in the drug discovery and development process. The presence of degradation products in a drug affects the quality as well as the safety and efficacy of drug formulation. Hence, it is essential to develop an efficient analytical method which could be useful for the separation, identification and characterization of all possible degradation products (DPs) of a drug. Macitentan (MT) is an endothelin receptor antagonist (ERA) drug used to treat high blood pressure in the lungs. Comprehensive stress testing of MT was carried out as per ICH guidelines to understand the degradation profile of the drug. Methods MT was subjected to various stress conditions such as acidic, basic, neutral hydrolysis, oxidation, photolysis and thermal conditions; and the resulting degradation products were investigated using liquid chromatography/diode-array detection/electrospray ionization high-resolution mass spectrometry (LC/DAD/ESI-HRMS) and tandem mass spectrometry (MS/MS) techniques. An efficient and simple ultra-high-performance liquid chromatography (UHPLC) method has been developed using an Accucore C18 column (4.6 × 150 mm, 2.6 μm) using a gradient elution of 5 mM ammonium formate and acetonitrile as mobile phases. Results MT was found to degrade under acid and base hydrolysis stress conditions; whereas it was stable under oxidation, neutral hydrolysis, thermal and photolytic conditions. MT formed nine DPs (DP1 to DP9) and one DP (DP10) under acidic and basic hydrolytic conditions, respectively. All the degradation products (DP1 to DP10) were identified and characterized by LC/MS/MS in positive ion mode with accurate mass measurements. Conclusions MT was found to be labile under hydrolytic conditions. The structures of the DPs were characterized by appropriate mechanisms. The proposed method can be effectively used for the characterization of MT and its DPs.
Published: 2018

19. Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins

Author: Juan M. Benito, Carmen Ortiz Mellet, Cédric Przybylski, Francisco Mendicuti, Thais Carmona, José M. García Fernández, Tania Neva, University of Sevilla, Universidad de Alcalá - University of Alcalá (UAH), Instituto de Investigaciones Químicas (IIQ), Universidad de Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), European Commission, Universidad de Alcalá, Junta de Andalucía, Ministerio de Economía y Competitividad (España), and Universidad de Sevilla
Subjects: POLE 3, 010405 organic chemistry, Chemistry, Organic Chemistry, 010402 general chemistry, Topology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Monomer, Planar, Self assembling, Ovoid, Moiety, [CHIM]Chemical Sciences, Xylylene, CSOB, Topology (chemistry)
Abstract: The topology of ß-cyclodextrin can be molded, from toroidal to ovoid basket-shaped, by the installation of an o- or m-xylylene moiety connecting two consecutive d-glucopyranosyl units through the secondary O-2(I) and O-3(II) positions. This strategy can be exploited advantageously to precast the cavity for preferential inclusion of globular or planar guests as well as to privilege dimeric or monomeric species in water solution., This study was supported by the Spanish Ministerio de Economía y Competitividad (contract numbers CTQ2015-64425-C2-1-R, CTQ2016-80600-P and SAF2016-76083-R), the Junta de Andalucía (contract number FQM2012-1467), the UAH (CCGP2017-EXP/027) and the European Regional Development Funds (FEDER and FSE). Technical assistance from the research support services of the University of Seville (CITIUS) is also acknowledged. T.N. acknowledges the Junta de Andalucía for a doctoral fellowship.
Published: 2018

20. Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of 'three-body' noncovalent fragment ions

Author: Sandra Alves, Jean-Claude Tabet, Bessem Brahim, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)
Subjects: Spectrometry, Mass, Electrospray Ionization, POLE 3, Stereochemistry, Electrospray ionization, Peptide, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), Ion, chemistry.chemical_compound, Fragmentation (mass spectrometry), Physics::Atomic and Molecular Clusters, [CHIM]Chemical Sciences, Binding site, Nuclear Experiment, Spectroscopy, chemistry.chemical_classification, Ions, Quantitative Biology::Biomolecules, Binding Sites, 010401 analytical chemistry, General Medicine, DNA, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, chemistry, Peptides, CSOB, Single strand
Abstract: Gas-phase fragmentation of single strand DNA-peptide noncovalent complexes is investigated in positive and negative electrospray ionization modes.Collision-induced dissociation experiments, performed on the positively charged noncovalent complex precursor ions, have confirmed the trend previously observed in negative ion mode, i.e. a high stability of noncovalent complexes containing very basic peptidic residues (i.e. R K) and acidic nucleotide units (i.e. Thy units), certainly incoming from the existence of salt bridge interactions. Independent of the ion polarity, stable noncovalent complex precursor ions were found to dissociate preferentially through covalent bond cleavages of the partners without disrupting noncovalent interactions. The resulting DNA fragment ions were found to be still noncovalently linked to the peptides. Additionally, the losses of an internal nucleic fragment producing "three-body" noncovalent fragment ions were also observed in both ion polarities, demonstrating the spectacular salt bridge interaction stability. The identical fragmentation patterns (regardless of the relative fragment ion abundances) observed in both polarities have shown a common location of salt bridge interaction certainly preserved from solution. Nonetheless, most abundant noncovalent fragment ions (and particularly three-body ones) are observed from positively charged noncovalent complexes. Therefore, we assume that, independent of the preexisting salt bridge interaction and zwitterion structures, multiple covalent bond cleavages from single-stranded DNA/peptide complexes rely on an excess of positive charges in both electrospray ionization ion polarities.
Published: 2017

21. Differentiation of isomeric dinitrotoluenes and aminodinitrotoluenes using electrospray high resolution mass spectrometry

Author: Adrian Schwarzenberg, Héloïse Dossmann, Jean-Claude Tabet, Richard B. Cole, Xavier Machuron-Mandard, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), 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: Electrospray, Chemistry, 010401 analytical chemistry, Analytical chemistry, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), Fourier transform ion cyclotron resonance, 0104 chemical sciences, Ion, Fragmentation (mass spectrometry), [CHIM]Chemical Sciences, Molecule, Explosive detection, Quadrupole ion trap, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract: Explosive detection and identification play an important role in the environmental and forensic sciences. However, accurate identification of isomeric compounds remains a challenging task for current analytical methods. The combination of electrospray multistage mass spectrometry (ESI-MSn) and high resolution mass spectrometry (HRMS) is a powerful tool for the structure characterization of isomeric compounds. We show herein that resonant ion activation performed in a linear quadrupole ion trap allows the differentiation of dinitrotoluene isomers as well as aminodinitrotoluene isomers. The explosive-related compounds: 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2-amino-4,6-dinitrotoluene (2A-4,6-DNT) and 4-amino-2,6-dinitrotoluene (4A-2,6-DNT) were analyzed by ESI-MS in the negative ion mode; they produced mainly deprotonated molecules [M − H]−. Subsequent low resolution MSn experiments provided support for fragment ion assignments and determination of consecutive dissociation pathways. Resonant activation of deprotonated dinitrotoluene isomers gave different fragment ions according to the position of the nitro and amino groups on the toluene backbone. Fragment ion identification was bolstered by accurate mass measurements performed using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS). Notably, unexpected results were found from accurate mass measurements performed at high resolution for 2,6-DNT where a 30-Da loss was observed that corresponds to CH2O departure instead of the expected isobaric NO• loss. Moreover, 2,4-DNT showed a diagnostic fragment ion at m/z 116, allowing the unambiguous distinction between 2,4- and 2,6-DNT isomers. Here, CH2O loss is hindered by the presence of an amino group in both 2A-4,6-DNT and 4A-2,6-DNT isomers, but nevertheless, these isomers showed significant differences in their fragmentation sequences, thus allowing their differentiation. DFT calculations were also performed to support experimental observations. Copyright © 2014 John Wiley & Sons, Ltd.
Published: 2014

22. High-Resolution Mass Spectrometry Associated with Data Mining Tools for the Detection of Pollutants and Chemical Characterization of Honey Samples

Author: Christophe Junot, Mylène Marie, Fanny Leroux, Jérôme Cotton, Céline Ducruix, Jean-Claude Tabet, Bruno Corman, Simon Broudin, Profilomic [Boulogne-Billancourt], Profilomic, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay
Subjects: Metabolite, Food Contamination, Mass spectrometry, computer.software_genre, 01 natural sciences, Mass Spectrometry, 03 medical and health sciences, chemistry.chemical_compound, Metabolomics, Data Mining, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, Pollutant, 0303 health sciences, Chromatography, 010401 analytical chemistry, food and beverages, Honey, General Chemistry, Pesticide, Honey samples, Food Analysis, 0104 chemical sciences, chemistry, 13. Climate action, Environmental chemistry, Data mining, General Agricultural and Biological Sciences, Xenobiotic, computer, Chromatography, Liquid
Abstract: Analytical methods for food control are mainly focused on restricted lists of well-known contaminants. This paper shows that liquid chromatography-high-resolution mass spectrometry (LC/ESI-HRMS) associated with the data mining tools developed for metabolomics can address this issue by enabling (i) targeted analyses of pollutants, (ii) detection of untargeted and unknown xenobiotics, and (iii) detection of metabolites useful for the characterization of food matrices. A proof-of-concept study was performed on 76 honey samples. Targeted analysis indicated that 35 of 83 targeted molecules were detected in the 76 honey samples at concentrations below regulatory limits. Furthermore, untargeted metabolomic-like analyses highlighted 12 chlorinated xenobiotics, 1 of which was detected in lavender honey samples and identified as 2,6-dichlorobenzamide, a metabolite of dichlobenil, a pesticide banned in France since 2010. Lastly, multivariate statistical analyses discriminated honey samples according to their floral origin, and six discriminating metabolites were characterized thanks to the MS/MS experiments.
Published: 2014

23. Mechanistic study of competitive releases of H 2 O, NH 3 and CO 2 from deprotonated aspartic and glutamic acids: Role of conformation

Author: Gianluca Giorgi, Anna Warnet, Ulli Martin Hohenester, Benoit Colsch, François Fenaille, Jean-Claude Tabet, Pierre Barbier Saint Hilaire, Christophe Junot, Yves Gimbert, Marie Françoise Olivier, Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Centro Interdipartimentale di Analisi e Determinazioni Structurali, Università degli Studi di Siena = University of Siena (UNISI), Laboratoire d'Etude du Métabolisme des Médicaments (LEMM), Service de Pharmacologie et Immunoanalyse (SPI), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Médicaments et Technologies pour la Santé (MTS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Steric effects, Anions, Stereochemistry, Decarboxylation, Clinical Biochemistry, Molecular Conformation, Glutamic Acid, 010402 general chemistry, 01 natural sciences, Biochemistry, Cyclopropane, Analytical Chemistry, chemistry.chemical_compound, Ammonia, Models, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Aspartic acid, Nucleophilic substitution, Methylene, Electrospray high-resolution mass spectrometry, Regioselective dissociation, Unexpected cleavage of aspartate anion, Aspartic Acid, Carbon Dioxide, Models, Molecular, Spectrometry, Mass, Electrospray Ionization, Stereoisomerism, Water, Protons, Cell Biology, ComputingMilieux_MISCELLANEOUS, Chromatography, Chemistry, Spectrometry, 010401 analytical chemistry, Electrospray Ionization, Molecular, General Medicine, Glutamic acid, Mass, 0104 chemical sciences, 13. Climate action, Intramolecular force
Abstract: The aims of this study were to highlight the impact of minor structural differences (e.g. an aminoacid side chain enlargement by one methylene group), on ion dissociation under collision-induced dissociation conditions, and to determine the underlying chemical mechanisms. Therefore, we compared fragmentations of deprotonated aspartic and glutamic acids generated in negative electrospray ionization. Energy-resolved mass spectrometry breakdown curves were recorded and MS3 experiments performed on an Orbitrap Fusion for high-resolution and high-mass accuracy measurements. Activated fragmentations were performed using both the resonant and non-resonant excitation modes (i.e., CID and HCD, respectively) in order to get complementary information on the competitive and consecutive dissociative pathways. These experiments showed a specific loss of ammonia from the activated aspartate but not from the activated glutamate. We mainly focused on this specific observed loss from aspartate. Two different mechanisms based on intramolecular reactions (similar to those occurring in organic chemistry) were proposed, such as intramolecular elimination (i.e. Ei-like) and nucleophilic substitution (i.e. SNi-like) reactions, respectively, yielding anions as fumarate and α lactone from a particular conformation with the lowest steric hindrance (i.e. with antiperiplanar carboxyl groups). The detected deaminated aspartate anion can then release CO2 as observed in the MS3 experimental spectra. However, quantum calculations did not indicate the formation of such a deaminated aspartate product ion without loss of carbon dioxide. Actually, calculations displayed the double neutral (NH3+CO2) loss as a concomitant pathway (from a particular conformation) with relative high activation energy instead of a consecutive process. This disagreement is apparent since the concomitant pathway may be changed into consecutive dissociations according to the collision energy i.e., at higher collision energy and at lower excitation conditions, respectively. The latter takes place by stabilization of the deaminated aspartate solvated with two residual molecules of water (present in the collision cell). This desolvated anion formed is an α lactone substituted by a methylene carboxylate group. The vibrational excitation acquired by [(D-H)-NH3]-during its isolation is enough to allow its prompt decarboxylation with a barrier lower than 8.4kJ/mol. In addition, study of glutamic acid-like diastereomers constituted by a cyclopropane, hindering any side chain rotation, confirms the impact of the three-dimensional geometry on fragmentation pathways. A significant specific loss of water is only observed for one of these diastereomers. Other experiments, such as stable isotope labeling, need to be performed to elucidate all the observed losses from activated aspartate and glutamate anions. These first mechanistic interpretations enhance understanding of this dissociative pathway and underline the necessity of studying fragmentation of a large number of various compounds to implement properly new algorithms for de novo elucidation of unknown metabolites.
Published: 2017

24. Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

Author: Steven F. Daly, Ivan Powis, Laurent Nahon, Héloïse Dossmann, Gustavo A. Garcia, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), University of Nottingham, UK (UON), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Scattering, media_common.quotation_subject, 02 engineering and technology, Photoionization, Electron, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Asymmetry, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Ion, Dipole, Excited state, Ionization, Physics::Atomic and Molecular Clusters, [CHIM]Chemical Sciences, Physics::Atomic Physics, Physics::Chemical Physics, Physical and Theoretical Chemistry, Atomic physics, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, media_common
Abstract: Electron-ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly-oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally-resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward-backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck-Condon simulations of the photoelectron spectra. A previously proposed quasi-diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation, and provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate, and which are then only weakly excited in the Franck-Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes.
Published: 2017

25. Meaning and consequence of the coexistence of competitive hydrogen bond/salt forms on the dissociation orientation of non-covalent complexes

Author: Jean-Claude Tabet, Ekaterina Darii, Yves Gimbert, Alain Perret, Sandra Alves, Génomique métabolique (UMR 8030), Genoscope - Centre national de séquençage [Evry] (GENOSCOPE), Université Paris-Saclay-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 Paris-Saclay-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 d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de Génotypage (CNG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Models, Molecular, Spectrometry, Mass, Electrospray Ionization, Clinical Biochemistry, Ionic bonding, Glucose-6-Phosphate, Protonation, 010402 general chemistry, Arginine, 01 natural sciences, Biochemistry, Dissociation (chemistry), Analytical Chemistry, chemistry.chemical_compound, Deprotonation, Isomerism, Tandem Mass Spectrometry, [CHIM]Chemical Sciences, Guanidine, ComputingMilieux_MISCELLANEOUS, Chromatography, Hydrogen bond, 010401 analytical chemistry, Fructosephosphates, Glucosephosphates, Hydrogen Bonding, Cell Biology, General Medicine, 0104 chemical sciences, chemistry, Covalent bond, Zwitterion, Thermodynamics
Abstract: Non-covalent complexes (NCC) between hexose monophosphates (HexP) and arginine (R) were analyzed using ESI MS and MS/MS in negative mode under different (hard, HC and soft, SC) desolvation conditions. High resolution mass spectrometry (HRMS) revealed the presence of different ionic species, namely, homo- and heteromultimers of R and HexP. Deprotonated heterodimers and corresponding sodiated species were enhanced under HC likely due to a decrease in available charge number associated with the reduction of H + /Na + exchange. The quantum calculations showed that the formation of covalent systems is very little exothermic, therefore, such systems are disfavored. Desolvation dependent CID spectra of deprotonated [(HexP+R)‒H] − complexes demonstrated that they can exist within the hydrogen bond (HB) and salt bridge (SB) forms, yielding either NCC separation or covalent bond cleavages, respectively. Although HB forms are the main species, they cannot survive under HC; therefore, the minor SB forms became detectable. Energy-resolved mass spectrometry (ERMS) experiments revealed diagnostic fragment ions from both SB and HB forms, providing evidence that these isomeric forms are inconvertible. SB formation should result from the ionic interactions of highly acidic group of HexP with strongly basic guanidine group of arginine and thus requires an arginine zwitterion (ZW) form. This was confirmed by quantum calculations. Ion-ion interactions are significantly affected by the presence of sodium cation as demonstrated by the fragmentation patterns of sodiated complex species. Regarding CID data, only SB between protonated amino group of R and deprotonated phosphate group of HexP could be suggested, but the primary amine is not enough basic then, the SB must be fleeting. Nevertheless, the observation of the covalent bond cleavages suggests the presence of structures with a free negative charge able to induce fragmentations. Indeed, according to quantum calculations, solvated salt (SS) systems involving Na + /COO − salt solvated by neutral phosphate and negative charge on sugar ring are preferentially formed.
Published: 2017

26. Clarification of the 30 Da releases from the [M-H]−and M−•ions of trinitrotoluene by electrospray high resolution mass spectrometry

Author: Adrian Schwarzenberg, Jean-Claude Tabet, Héloïse Dossmann, Cécile Hubert, Richard B. Cole, Xavier Machuron-Mandard, Unité de chimie organique moléculaire et macromoléculaire (UCO2M), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Détection et de Géophysique (CEA) (LDG), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Electrospray, Chromatography, Protein mass spectrometry, Chemistry, 010401 analytical chemistry, High resolution, 010402 general chemistry, Mass spectrometry, 01 natural sciences, 0104 chemical sciences, Ion, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, 13. Climate action, [CHIM]Chemical Sciences, Trinitrotoluene, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract: International audience; Although some nitroaromatic compounds can naturally occur in the environment, the vast majority of them come from anthropogenic sources. Indeed, nitroaromatic compounds such as 2,4,6-trinitrotoluene (TNT) and related-compounds are widely used as chemicals or synthetic intermediates in industrial manufacturing of explosives, dyes, pharmaceuticals, polyurethane foams and pesticides. [1] Considering the proven toxicity of nitroaromatic compounds on living organisms [2] , and their significance in the forensic sciences, much attention has been given to these compounds [3]. Thus, nitroaromatic compounds have been extensively studied by mass spectrometry (MS) coupled with different ionization sources. At first, classical vacuum ionization techniques such as Electron Ionization (EI) [4, 5] and Chemical Ionization (CI) [5-7] were widely used to examine nitroaromatic compounds. Upon the development of atmospheric pressure ionization (API) techniques, atmospheric pressure chemical ionization (APCI) [8] and electrospray ionization (ESI) [9] became established as preferred techniques to analyze nitroaromatic compounds [10]. In particular, ESI of TNT in the negative ion mode can produce competitive processes : (i) deprotonation [M-H]-and (ii) electrochemical reduction M •-. [11, 12] Afterwards, Collision-Induced-Dissociation (CID) has been extensively used for structural as well as quantitative information [13] TNT samples are commonly analyzed at low resolution by tandem mass spectrometry. Under CID conditions, these negatively charged molecular species dissociate by competitive losses of either OH • (implicating the "ortho effect", Scheme 1), or by loss of NO • (after NO 2 /ONO isomerization). In addition, NO 2  release was also observed. Scheme 1. Stepwise OH  release implicating the "ortho effect" promoted by the radical anion [M] •-(m/z 227) of TNT. In this study, we have used a standard solution (1 mg/mL in MeOH:ACN (1:1)) of 2,4,6-trinitrotoluene (TNT), obtained from AccuStandard Europe (Niederbipp, Switzerland). TNT was prepared by dilution at 1 µg mL-1 in H 2 O/MeOH (1:1), then infused at a flow rate of 5 µL min-1 into an LTQ-Orbitrap XL mass spectrometer (Thermo Fisher Scientific, Courtaboeuf, France) and ionized by ESI in the negative ion mode. The employed spray voltage was-2.5 kV giving mainly the deprotonated molecule [M-H]-at m/z 226 and the
Published: 2014

27. The Background to Electrospray

Author: Richard B. Cole, Bing Guan, University of New Orleans, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Electrospray, History, POLE 3, William Henley, 02 engineering and technology, Jean-Antoine Nollet, Malcolm Dole, William Gilbert, Lord Kelvin, 01 natural sciences, Lord Rayleigh, William Thomson, 0103 physical sciences, Mass analyzer, Geoffrey Taylor, Harold Ransburg, [CHIM]Chemical Sciences, 010306 general physics, Literature, John Ellicott, business.industry, Environmental ethics, W. A. Macky, 021001 nanoscience & nanotechnology, Sir Thomas Browne, John Zeleny, Electrospray history, Electrostatic attraction, Electrospray development, Stephen Gray, John William Strutt, 0210 nano-technology, business, CSOB
Abstract: International audience; This article traces the development of electrospray back to its earliest beginnings. Many readers may be surprised to learn that descriptions of the electrostatic attraction of liquids to surfaces appear in the scientific literature as early as the year 1600, and that true electrospray experiments are documented to have been performed in the eighteenth century. Progress in the development of electrospray is detailed through these earliest observations and subsequent ingenious applications, mathematical descriptions, and, finally, coupling to mass analyzer instrumentation.
Published: 2016

28. Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

Author: Richard B. Cole, Jean E. Boulicault, Sandra Alves, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: POLE 3, Chemistry, 010401 analytical chemistry, Cationic polymerization, Analytical chemistry, 010402 general chemistry, Mass spectrometry, 01 natural sciences, 0104 chemical sciences, Adduct, Ion, Crystallography, Electron transfer, Fragmentation (mass spectrometry), Structural Biology, Mass spectrum, [CHIM]Chemical Sciences, Sample preparation, CSOB, Spectroscopy
Abstract: MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe(3+) > Al(3+) > Li(+) > Ga(3+) > Co(2+) > Cr(3+) > Cu(2+) > [Mn(2+), Mg(2+)] > [Na(+), K(+)]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion. Graphical Abstract ᅟ.
Published: 2016

29. Determination of Peptide Topology through Time-Resolved Double-Resonance under Electron Capture Dissociation Conditions

Author: Uwe Linne, Mohamed A. Marahiel, Jean-Claude Tabet, Richard B. Cole, Carlos Afonso, Marie Pérot-Taillandier, Sylvie Rebuffat, Séverine Zirah, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Molécules de Communication et Adaptation des Micro-organismes (MCAM), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Philipps Universität Marburg, Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Histoire naturelle de l'Homme préhistorique (HNHP), Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Université de Perpignan Via Domitia (UPVD), Fachbereich Chemie der Philipps-Universität Marburg (WZMW), Philipps Universität Marbug, Department of chemistry, University of Marburg, Laboratoire de Chimie Structurale Organique et Biologique, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Philipps Universität Marburg = Philipps University of Marburg, Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Muséum national d'Histoire naturelle (MNHN)-Université de Perpignan Via Domitia (UPVD)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Spectrometry, Mass, Electrospray Ionization, Topoisomer, Electrospray, Protein Conformation, Analytical chemistry, Electrons, Peptide, 010402 general chemistry, Mass spectrometry, Vibration, 01 natural sciences, Analytical Chemistry, Ion, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Tandem Mass Spectrometry, Computational chemistry, Spectroscopy, Fourier Transform Infrared, Ions, chemistry.chemical_classification, Quantitative Biology::Biomolecules, Electron-capture dissociation, Chemistry, 010401 analytical chemistry, Stereoisomerism, Cyclotrons, Resonance (chemistry), 0104 chemical sciences, Gases, Protons, Peptides, Ion cyclotron resonance
Abstract: International audience; Characterizing the conformation of biomolecules by mass spectrometry still represents a challenge. With their knotted structure involving a N-terminal macrolactam ring where the C-terminal tail of the peptide is threaded and sterically trapped, lasso peptides constitute an attractive model for developing methods for characterizing gas-phase conformation, through comparison with their unknotted topoisomers. Here, the kinetics of electron capture dissociation (ECD) of a lasso peptide, capistruin, was investigated by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry and compared to that of its branched-cyclic topoisomer, lactam-capistruin. Both peptides produced rather similar ECD spectra but showed different extent of H(*) transfer from c(i)' to z(j)(*) ions. Time-resolved double-resonance experiments under ECD conditions were performed to measure the formation rate constants of typical product ions. Such experiments showed that certain product ions, in particular those related to H(*) transfer, proceeded through long-lived complexes for capistruin, while fast dissociation processes predominated for lactam-capistruin. The formation rate constants of specific ECD product ions enabled a clear differentiation of the lasso and branched-cyclic topoisomers. These results indicate that the formation kinetics of ECD product ions constitute a new way to explore the conformation of biomolecules and distinguish between topoisomers and, more generally, conformers.
Published: 2012

30. Biofunctionalization of Polyoxometalates with DNA Primers, Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products

Author: Mayreli Ortiz, Richard B. Cole, Ahmed M. Debela, Bernold Hasenknopf, Serge Thorimbert, Denis Lesage, Valerio Beni, Ciara K. O'Sullivan, Glycochimie Organique Biologique et Supramoléculaire (GOBS), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Laboratoire de Synthèse Organique et Organométallique (UMR CNRS 7201), Université Pierre et Marie Curie - Paris 6 (UPMC), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDV]Life Sciences [q-bio], 010402 general chemistry, 01 natural sciences, Polymerase Chain Reaction, Catalysis, law.invention, Nucleic acid thermodynamics, chemistry.chemical_compound, Polymerase chain reaction optimization, law, Primer dimer, Multiplex polymerase chain reaction, Electrochemistry, Organic chemistry, [CHIM]Chemical Sciences, Polymerase chain reaction, ComputingMilieux_MISCELLANEOUS, DNA Primers, 010405 organic chemistry, Chemistry, Organic Chemistry, Nucleic Acid Hybridization, General Chemistry, DNA, Tungsten Compounds, Combinatorial chemistry, 0104 chemical sciences, Real-time polymerase chain reaction, Primer (molecular biology)
Abstract: The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11 O39 {Sn(CH2 )2 CO}](8-) and [P2 W17 O61 {Sn(CH2 )2 CO}](6-) have been used to link to a 5'-NH2 terminated 21-mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM-labeled primers was demonstrated through hybridization with a surface-immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.
Published: 2015

31. High fidelity approach for proteomic scale enrichment and identification of N‐termini

Author: Jonathan C. Lansing, Yanjie Jiang, James A. Madsen, Richard B. Cole, Victor Farutin, Dpt of Chemistry [New Orleans], University of New Orleans, New Orleans, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), University of New Orleans, and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lysis, Lysine, medicine.disease_cause, 01 natural sciences, Dissociation (chemistry), 03 medical and health sciences, chemistry.chemical_compound, medicine, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Instrumentation, Escherichia coli, Spectroscopy, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, chemistry.chemical_classification, Sulfonyl, 0303 health sciences, Chromatography, Elution, 010401 analytical chemistry, Condensed Matter Physics, 0104 chemical sciences, Enzyme, chemistry, Isothiocyanate
Abstract: A novel workflow was designed for the large-scale identification of protein N-terminal sequences. The workflow started with converting lysine to homoarginine, followed by reaction with sulfonation of N-termini by 4-sulfophenyl isothiocyanate (SPITC). Upon trypsin digestion, the SPITC modified N-terminal peptides were enriched by electrostatic repulsion hydrophilic interaction (ERLIC) chromatography in which the internal and C-terminal peptides eluted at the void volume, and the SPITC peptides were retained in the column due to the hydrophilicity and electrostatic attraction of the sulfonyl group to the stationary phase. Upon higher-energy collisional induced dissociation (HCD) SPITC peptides in ESI generated predominately y-type ion series; such simplification of spectra enables the identification of N-termini with high confidence. The appearance of b1 + SPITC product ions upon HCD further boosts the confidence for N-terminal identifications. This method was applied to an Escherichia coli cell lysate, thus allowing the identification of 358 high confidence N-terminal peptides representing 274 distinct E. coli proteins as certain proteins were found to have multiple N-terminal peptides due to cleavage from various cellular enzymes. Confidence in N-terminal assignments is further heightened since 224 of the unique proteins identified from N-terminal peptides were also identified in the analysis of flow-through fractions.
Published: 2015

32. Electron detachment/photodetachment dissociation of lasso peptides

Author: Jean-Claude Tabet, Carlos Afonso, Marie Pérot-Taillandier, Quentin Enjalbert, Rodolphe Antoine, Séverine Zirah, Philippe Dugourd, Sylvie Rebuffat, Richard B. Cole, Molécules de Communication et Adaptation des Micro-organismes (MCAM), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Topoisomer, Collision-induced dissociation, Electron-capture dissociation, Chemistry, Stereochemistry, 010401 analytical chemistry, Peptide, 010402 general chemistry, Condensed Matter Physics, Mass spectrometry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, Fragmentation (mass spectrometry), Covalent bond, Computational chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Instrumentation, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract: Lasso peptides are bioactive peptides produced by bacteria, characterized by a mechanically interlocked topology where the C-terminal tail of the peptide is threaded through and trapped within an N-terminal macrolactam ring. The structural characterization of lasso peptides and differentiation from their unthreaded topoisomers by mass spectrometry are challenging tasks. We previously explored the fragmentation mechanisms of lasso peptides in positive ion mode and showed several signatures of the lasso topology under collision induced dissociation (CID) and electron capture dissociation. Here we analyzed the dissociation of the multiply-deprotonated microcin J25 (MccJ25), a 21-residue lasso peptide produced by Escherichia coli, together with its non-lasso topoisomer and several variants generated by site-directed mutagenesis, under different modes of activation. The fragmentation patterns obtained by CID for the threaded and unthreaded structures were very similar. By contrast, electron detachment dissociation (EDD) as well as activated-electron photodetachment dissociation (a-EPD) revealed very different dissociation pathways for the two topoisomers. The doubly deprotonated topoisomers showed a different deprotonation pattern, Tyr20 residue being deprotonated for MccJ25 only, yielding the singly charged [c19−C2H4O] product ion. MccJ25 also triggered several two-peptide product ions diagnostic of the lasso topology, including the [(c8)*(z2)] species, which could be maintained by either a covalent or a non-covalent linkage.
Published: 2015

33. Electrospray ionization linear trap quadrupole Orbitrap in analysis of old tempera paintings: application to nineteenth‐century Orthodox icons

Author: Aleksandar Lolić, C. Charvy, Sandra Alves, Jean-Claude Tabet, Tatjana Tripkovic, Rada Baošić, Snežana D. Nikolić-Mandić, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), University of Belgrade [Belgrade], and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Bovine collagen, Electrospray ionization, Analytical chemistry, Tempera, 010402 general chemistry, Orbitrap, Mass spectrometry, Tandem mass spectrometry, 01 natural sciences, Orthodox icons, law.invention, law, Ionization, MALDI-TOF MS/MS, [CHIM]Chemical Sciences, Spectroscopy, proteinaceous binders, ComputingMilieux_MISCELLANEOUS, Chromatography, Chemistry, 010401 analytical chemistry, General Medicine, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, ESI-LTQ-Orbitrap, egg tempera, visual_art, Quadrupole, visual_art.visual_art_medium
Abstract: Proteomic approach in combination with mass spectrometry demonstrates a great potential for identification of proteinaceous materials in works of art. In this study we used a linear trap quadrupole Orbitrap (LTQ-Orbitrap), a state-of-the-art mass spectrometer for parts per million accuracy analyses of peptides behind tryptic hydrolysis. After the efficiency of the proteomic method was confirmed for reference and model samples, micro-samples from historical paintings were for the first time analysed using this technique. Superior performances of the liquid chromatography–mass spectrometry approach using a LTQ-Orbitrap mass spectrometer allowed identification of egg yolk peptides in two samples from nineteenth-century Orthodox icons, indicating egg tempera as the painting technique. Accurate precursor ion masses, in the range of ±2 ppm, and retention times of tryptic peptides strengthen protein identification. Additionally, in all historical samples the presence of animal glues suggested that the ground layer was likely bound using bovine collagen. Comparing to results acquired using matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry in our previous study, here we achieved higher ion scores and protein scores, better sequence coverage and more identified proteins. In fact, a combination of the two mass spectrometric techniques provided overlapping and complementary data, related to the detection of peptides with different physicochemical properties.
Published: 2015

34. Vacuum Ultraviolet Photoionization Study of Gas Phase Vitamins A and B1 Using Aerosol Thermodesorption and Synchrotron Radiation

Author: Barbara Cunha de Miranda, Marie Pérot-Taillandier, Gustavo A. Garcia, Carlos Afonso, Adrian Schwarzenberg, Héloïse Dossmann, Denis Lesage, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, Vacuum, Ultraviolet Rays, Photoemission spectroscopy, Molecular Conformation, Synchrotron radiation, Electrons, 02 engineering and technology, Electron, Photoionization, 010402 general chemistry, 01 natural sciences, Ion, Ionization, Physics::Atomic and Molecular Clusters, [CHIM]Chemical Sciences, Thiamine, Physical and Theoretical Chemistry, Vitamin A, Aerosols, Chemistry, Temperature, Photochemical Processes, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Thermodynamics, Gases, Ionization energy, Atomic physics, 0210 nano-technology, Valence electron, Synchrotrons
Abstract: International audience; Gas-phase studies of biomolecules are often difficult to initiate because of the thermolability of these systems. Such studies are nevertheless important to determine fundamental intrinsic properties of the molecules. Here we present the valence shell photoionization of gas-phase vitamins A and B1 close to their ionization threshold. The study was performed by means of an aerosol thermodesorption source coupled to an electron/ion coincidence spectrometer and synchrotron radiation (SOLEIL facility, France). Ion yield curves were recorded for both molecules over a few electronvolt energy range and the threshold photoelectron spectrum was also obtained for vitamin A. Some fundamental properties were extracted for both ions such as adiabatic and the three first vertical ionization energies of retinol (IEad = 6.8 ± 0.2 eV and IEvert = 7.4, 8.3, and 9.2 eV) and dissociation appearance energies for the main fragment ions of vitamin B1. Analysis of the data was supported by ab initio calculations which show a very good agreement with the experimental observations.
Published: 2014

35. Efficient Mono- and Bifunctionalization of Polyolefin Dendrimers by Olefin Metathesis

Author: Eric Cloutet, Didier Astruc, Denise Méry, Jean-Claude Blais, Catia Ornelas, Jaime Ruiz Aranzaes, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des polymères organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Institut de Chimie du CNRS (INC), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_element, Stereoisomerism, Polyenes, Alkenes, 010402 general chemistry, Metathesis, 01 natural sciences, Ruthenium, Catalysis, dendrimers, chemistry.chemical_compound, organometallic re, iron, Dendrimer, Organometallic Compounds, Salt metathesis reaction, Molecule, Organic chemistry, ComputingMilieux_MISCELLANEOUS, Group 2 organometallic chemistry, Molecular Structure, Olefin metathesis, ferrocenes, 010405 organic chemistry, General Medicine, General Chemistry, 0104 chemical sciences, Polyolefin, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, metathesis
Abstract: International audience
Published: 2005

36. A revisit of high collision energy effects on collision‐induced dissociation spectra using matrix‐assisted laser desorption/ionization tandem time‐of‐flight mass spectrometry (MALDI‐LIFT‐TOF/TOF): application to the sequencing of RNA/DNA chimeras: CID fragmentation of DNA

Author: Jean-Claude Tabet, Florence Mauger, Ivo Gut, Institut de Génomique d'Evry (IG), Institut de Biologie François JACOB (JACOB), 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 Paris-Saclay, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centro Nacional de Análisi Genómico (CNAG), Centro Nacional de Análisis Genómico, Centre National de Génotypage (CNG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Paris-Saclay-Institut de Biologie François JACOB (JACOB), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Ribonucleotide, Collision-induced dissociation, Stereochemistry, Analytical chemistry, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Analytical Chemistry, chemistry.chemical_compound, [CHIM]Chemical Sciences, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Ions, Sequence Analysis, RNA, Chemistry, Oligonucleotide, 010401 analytical chemistry, Organic Chemistry, DNA, Sequence Analysis, DNA, 0104 chemical sciences, Thymine, Matrix-assisted laser desorption/ionization, Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization, RNA, Time-of-flight mass spectrometry
Abstract: RATIONALE High-energy collision-induced dissociation (CID) spectra of isomeric RNA/DNA chimeras using matrix-assisted laser desorption/ionization time-of-flight LIFT mass spectrometry (MALDI-LIFT-TOF/TOF) can potentially be applied for an exhaustive fragment characterization in a nucleic acid sequencing scheme. These chimeras contain deoxynucleotides and at the 3'-end a ribonucleotide with a 3'-phosphate group. METHODS Deprotonated RNA/DNA chimeras of 4-, 5-, 7- and 10-mers are analyzed by CID. This enhances consecutive dissociations from both the precursor and prompt product anions generated by MALDI and metastable fragmentations prior to entering the LIFT cell. RESULTS Gas-phase fragmentations of 4- and 5-mers produced many fragment ions, from base release prior to consecutive cleavage of the nucleotide phosphate bond linkage phosphate. The unusual a4− product ion is a specific and diagnostic dissociation of the 4-mer if the ribonucleotide contains cytosine. As the size of RNA/DNA chimeras increase, several abundant product ions are generated mainly from zwitterionic forms (deprotonated phosphate ester and protonated base sites): [(M-H)–BiH]−, [ai–BiH]−, wj−, [wj, (ai-BiH)]− (if Bi ≠ T) as internal product ion, and more rarely [wj–BiH]−. The absence of the majority of the [ai–BiH]− series although the wj− series suggested that the higher critical energy processes with a loose transition state are favored yielding the wj− series. A large number of abundant fragment ions are detected which enable each isomer to be sequenced. CONCLUSIONS This sequencing method is high-throughput, accurate and could be used to sequence isomers of up to 10-mers and also oligonucleotides of unknown sequence. However, RNA/DNA chimeras without thymine must be sufficiently concentrated to reach desorption of deprotonated molecular species to be selected in LIFT to produce all fragment ions within measurable abundances. Copyright © 2014 John Wiley & Sons, Ltd.
Published: 2014

37. Photoelectron circular dichroism and spectroscopy of trifluoromethyl‐ and methyl‐oxirane: a comparative study

Author: Steven F. Daly, Héloïse Dossmann, Laurent Nahon, Ivan Powis, Gustavo A. Garcia, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Nottingham, UK (UON), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Circular dichroism, Chemistry, General Physics and Astronomy, 02 engineering and technology, Photoionization, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Electron spectroscopy, 0104 chemical sciences, Ion, Ab initio quantum chemistry methods, Ionization, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Atomic physics, 0210 nano-technology, Valence electron, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract: Photoelectron circular dichroism (PECD), a forward–backward asymmetry along the light propagation direction observed in the angular distribution of photoelectrons formed in the ionization of a chiral gas phase target with circularly polarized light, is becoming an established technique for chiral differentiation. In this work some of the fundamental and analytical properties of PECD are confirmed and explored further through a comparative study of the valence shell photoionization of enantiomerically pure trifluoromethyl-oxirane and methyl-oxirane, namely the sensitivity of PECD to the initial orbital and to chemical substitution. The recorded PECD experimental data and corresponding continuum multiple scattering calculations for the outermost orbitals obtained at various photon energies reveal the dramatic effect of substituting the CF3 and CH3 groups attached at the asymmetric chiral center. The previously unknown trifluoromethyl-oxirane ion spectroscopy and the fragmentation pattern measured by threshold electron/ion coincidence techniques over the first four eVs above the ionization threshold are also presented in this work and assigned through the use of ab initio calculations. The state-selected photochemistry and threshold electron spectroscopy of methyl-oxirane have additionally been recorded to complement previous spectroscopic studies.
Published: 2014

38. Structural studies of the sBBI/trypsin non‐covalent complex using covalent modification and mass spectrometry: Structural studies of the sBBI/trypsin non‐covalent complex

Author: Guanalini Saravanamuthu, Ekaterina Darii, Jean-Claude Tabet, Ivo Gut, Centre National de Génotypage (CNG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centro Nacional de Análisi Genómico (CNAG), Centro Nacional de Análisis Genómico, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0303 health sciences, Chromatography, Chemistry, Stereochemistry, 010401 analytical chemistry, Organic Chemistry, Mass spectrometry, Tandem mass spectrometry, Trypsin, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, Analytical Chemistry, Ion, 03 medical and health sciences, Covalent bond, Desorption, medicine, Molecule, [CHIM]Chemical Sciences, Spectroscopy, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, medicine.drug
Abstract: RATIONALE The study of protein recognition sites is crucial for understanding the mechanisms of protein interaction. Mass spectrometry can be a method of choice for the investigation of the contact surface within the protein non-covalent complexes. METHODS Probing the reactivity of essential amino acid residues of soybean Bowman-Birk inhibitor (sBBI) within the non-covalent sBBI/bovine trypsin complex was performed using covalent labeling by the BS3 cross-linker and charge tag with a quaternary ammonium group in combination with matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) and tandem mass spectrometry (MS/MS) analysis. RESULTS Significant modulation of the reactivity of essential K16 and S17 residues in the sBBI molecule upon binding to trypsin was established. The studies of sBBI proteolytic peptides with the same structure but carrying different labels using metastable dissociation in LIFT mode demonstrated that fragmentation pathways were oriented by used modification (BS3 cross-linker or charge tag). CONCLUSIONS The effectiveness of the mass spectrometric approach including covalent modification for exploring protein-protein interaction sites has been demonstrated. The alteration of the reactivity of functionally important amino acid residues in the sBBI molecule is most likely related to changes in their microenvironment. It has been suggested that in the presence of charge tags fragmentation in LIFT mode proceeds through the formation of salt bridges between quaternary ammonium groups and acidic residues due to the occurrence of zwitterions (including basic and acidic residues). Despite the presence of one or several charge tags, fragmentation takes place yielding modulated bi/yj ion series depending on the positions of the tags. Copyright © 2014 John Wiley & Sons, Ltd.
Published: 2014

39. Annotation of the human serum metabolome by coupling three liquid chromatography methods to high-resolution mass spectrometry

Author: Samia Boudah, Lydie Oliveira, Marie-Françoise Olivier, Jean-Claude Tabet, Christophe Junot, Sandrine Aros-Calt, François Fenaille, Laboratoire d'Etude du Métabolisme des Médicaments (LEMM), Service de Pharmacologie et Immunoanalyse (SPI), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Médicaments et Technologies pour la Santé (MTS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay
Subjects: Electrospray, Databases, Factual, Metabolite, Clinical Biochemistry, Analytical chemistry, Tandem mass spectrometry, 01 natural sciences, Biochemistry, Analytical Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Metabolomics, Tandem Mass Spectrometry, Ionization, Metabolome, [CHIM]Chemical Sciences, Humans, Organic Chemicals, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Chromatography, Chemistry, Hydrophilic interaction chromatography, 010401 analytical chemistry, Cell Biology, General Medicine, 0104 chemical sciences, Gas chromatography–mass spectrometry, Blood Chemical Analysis, Chromatography, Liquid
Abstract: This work aims at evaluating the relevance and versatility of liquid chromatography coupled to high resolution mass spectrometry (LC/HRMS) for performing a qualitative and comprehensive study of the human serum metabolome. To this end, three different chromatographic systems based on a reversed phase (RP), hydrophilic interaction chromatography (HILIC) and a pentafluorophenylpropyl (PFPP) stationary phase were used, with detection in both positive and negative electrospray modes. LC/HRMS platforms were first assessed for their ability to detect, retain and separate 657 metabolite standards representative of the chemical families occurring in biological fluids. More than 75% were efficiently retained in either one LC-condition and less than 5% were exclusively retained by the RP column. These three LC/HRMS systems were then evaluated for their coverage of serum metabolome. The combination of RP, HILIC and PFPP based LC/HRMS methods resulted in the annotation of about 1328 features in the negative ionization mode, and 1358 in the positive ionization mode on the basis of their accurate mass and precise retention time in at least one chromatographic condition. Less than 12% of these annotations were shared by the three LC systems, which highlights their complementarity. HILIC column ensured the greatest metabolome coverage in the negative ionization mode, whereas PFPP column was the most effective in the positive ionization mode. Altogether, 192 annotations were confirmed using our spectral database and 74 others by performing MS/MS experiments. This resulted in the formal or putative identification of 266 metabolites, among which 59 are reported for the first time in human serum.
Published: 2013

40. Characterization of protein-hapten conjugates by mass spectrometry

Author: Gérard Bolbach, Florence Gonnet, Andrée Marquet, Nelly Gourlaouën, Dominique Florentin, Laboratoire de Chimie Organique Biologique, Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0303 health sciences, Chromatography, biology, Chemistry, Polyatomic ion, Matrix isolation, General Chemistry, 010402 general chemistry, Mass spectrometry, 01 natural sciences, 0104 chemical sciences, Catalysis, 03 medical and health sciences, biology.protein, Molecule, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Bovine serum albumin, Hapten, 030304 developmental biology, Conjugate
Abstract: An hapten 1 designed for the production of catalytic antibodies was synthesized after coupling its precursor 2 to bovine serum albumin (BSA). The conjugates BSA- 2 and BSA- 1 were characterized by MALDI mass spectrometry. This paper shows that besides the average number of molecules bound to the protein deduced from the molecular ion peak shift, the MALDI technique can also give access to their distribution, bv simulation of the peak.
Published: 1998

41. Formation and characterization of gaseous adducts of carbon dioxide to magnesium, (CO2)MgX- (X=OH, Cl, Br)

Author: Denis Lesage, Einar Uggerud, Héloïse Dossmann Soldi-Lose, Jean-Claude Tabet, Carlos Afonso, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre for Theoretical and Computational Chemistry [Oslo] (CTCC), Department of Chemistry [Oslo], Faculty of Mathematics and Natural Sciences [Oslo], University of Oslo (UiO)-University of Oslo (UiO)-Faculty of Mathematics and Natural Sciences [Oslo], University of Oslo (UiO)-University of Oslo (UiO), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and University of Oslo (UiO)
Subjects: Models, Molecular, Inorganic chemistry, Halide, chemistry.chemical_element, 010402 general chemistry, Crystallography, X-Ray, Medicinal chemistry, 01 natural sciences, Catalysis, Adduct, chemistry.chemical_compound, Nucleophile, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Nucleophilic substitution, [CHIM]Chemical Sciences, Magnesium, Alkyl, chemistry.chemical_classification, Carbon Monoxide, Molecular Structure, 010405 organic chemistry, Carbon fixation, Water, General Chemistry, General Medicine, Carbon Dioxide, Bromine, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Carbon dioxide, Chlorine
Abstract: International audience; A good fix: The structure and chemical reactivity of a reduced form of CO(2) bonded to magnesium, XMg(η(2) -O(2) C)(-) , is reported. Upon reaction with water it loses CO, while it adds CH(3) upon reaction with alkyl halides, thereby signifying nucleophilicity of the carbon atom in XMg(η(2) -O(2) C)(-) in S(N) 2 reactions.
Published: 2011

42. Do Platinum(II) and Palladium(II) Phosphinito Phosphinous Acids Generate the Same Type of Reactive Intermediate in Alkyne Coordination? A Gas-Phase Study with Phenylethyne and Propargyl Acetate

Author: Denis Lesage, Yves Gimbert, Magdalena Karanik, Jean-Claude Tabet, Stéphane Humbel, Paola Nava, Laurent Giordano, Gérard Buono, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-07-BLAN-0267,SPOs Preligands,Oxyde de Phosphine Secondaires OPS: Preligands en Catalyse et Catalyse Asymétrique(2007), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Acetylide, Norbornadiene, Organic Chemistry, Reactive intermediate, chemistry.chemical_element, Alkyne, 010402 general chemistry, Photochemistry, 01 natural sciences, Cycloaddition, 0104 chemical sciences, Catalysis, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Polymer chemistry, Propargyl, Physical and Theoretical Chemistry, Palladium
Abstract: International audience; The structure and behavior of the catalytic species involved in the PAPd- and PAPt-catalyzed formal [2 + 1] cycloaddition between an alkyne and norbornadiene have been studied by combined mass spectrometry experiments and density functional theory calculations. The first step of this reaction, the coordination of the catalyst with the alkyne, is also investigated under collision-activated reaction conditions. Two different structures are proposed for the key intermediates: an acetylide structure for Pd and a metallacarbene for Pt.
Published: 2011

43. Tracking gold acetylides in gold(i)-catalyzed cycloisomerization reactions of enynes

Author: Yves Gimbert, Florian Jaroschik, Jean-Philippe Goddard, Max Malacria, Magdalena Karanik, Antoine Simonneau, Denis Lesage, Régis Guillot, Louis Fensterbank, Jean-Claude Tabet, Vincent Gandon, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétéroéléments et Coordination (DCPH), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie organique et bioorganique (COB), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie organique et bioorganique EA 4566, Ecole Nationale Supérieure de Chimie de Mulhouse, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)
Subjects: 010405 organic chemistry, Electrospray ionization, General Chemistry, Propargyl alcohol, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Cycloisomerization, chemistry, Organogold chemistry, Moiety, Organic chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Propargyl bromide, ComputingMilieux_MISCELLANEOUS
Abstract: The intermediacy of gold acetylides in the gold(I)-catalyzed cycloisomerization of enynes was questioned. While dinuclear gold complexes are observed under electrospray ionization conditions, the solution reactivity of gold acetylides also leads to the conclusion of their high affinity for the second coordination of a gold moiety, leading to dinuclear gold complexes. However, the involvement of gold acetylides and the corresponding diaurated species in the elementary steps of cycloisomerization mechanisms of enynes appears unlikely.
Published: 2011

44. Gas phase self-association of Eudistomin U controlled by gas phase acidity and origin of its interaction with nucleobases

Author: Françoise Fournier, Ying Xu, Carlos Afonso, Yves Gimbert, Ren Wen, Xiaochun Dong, Jean-Claude Tabet, Synthèse, Structure et Fonction de Molécules Bioactives (SSFMB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemistry and Biochemistry Department (University of Maryland), University of Maryland [College Park], University of Maryland System-University of Maryland System, Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Pharmacy, Fudan University, Fudan University [Shanghai], Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Guanine, Electrospray ionization, Dimer, 010401 analytical chemistry, Analytical chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Ion, Nucleobase, Crystallography, chemistry.chemical_compound, Deprotonation, Polarizability, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Instrumentation, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract: Electrospray ionization mass spectrometry was used to investigate the intrinsic chemical properties of β-carbolines: Eudistomin U (as EU) and 5-Br-Eudistomin U (as BrEU) yielding self-association in negative ion mode. It was observed that the deprotonated homodimer of EU was more stable in the gas phase than BrEU. Indeed, BrEU presents a higher polarizability that could influence the dimerization energy. On the contrary, the stability energies calculated at B3LYP/6-31+G*//AM1 level showed a small difference for these two dimers. To understand the experimental stability variation, the experimental and theoretical gas phase acidities of these two β-carbolines have been estimated. It has been shown that EU is less acidic than BrEU in the gas phase, which could explain the lower stability of the [2BrEU-H]− dimer. In addition, the investigation of non-covalent interaction of β-carbolines and nucleobases has been carried out. It was experimentally demonstrated that the deprotonated heterodimer's relative stability scale was [Gua + M−H]− >> [Thy + M−H]− > [Ade + M−H]−, but the Cyt/β-carboline complexes were not observed. However, the absence of Cyt/β-carboline complexes could be explained by the great acidity difference between Cyt and β-carbolines, yielding unstable non-covalent complexes. The studied β-carbolines showed a particular affinity with guanine which suggested a strong interaction, from a structural and reactivity point of view. Calculated reaction pathways rationalize the set of experimental results concerning the heterodimer stabilisation reflected by the V1/2 value of breakdown curves of deprotonated heterodimers.
Published: 2009

45. The Role of Water in Platinum-Catalyzed Cycloisomerization of 1,6-Enynes: A Combined Experimental and Theoretical Gas Phase Study

Author: Sigrid Baumgarten, Max Malacria, Yves Gimbert, Jean-Philippe Goddard, Vincent Gandon, Louis Fensterbank, Denis Lesage, Jean-Claude Tabet, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie organique et bioorganique (COB), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Synthèse Organique et Organométallique (UMR CNRS 7201), Université Pierre et Marie Curie - Paris 6 (UPMC), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie organique et bioorganique EA 4566, Ecole Nationale Supérieure de Chimie de Mulhouse, and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)
Subjects: chemistry.chemical_classification, Coordination sphere, Double bond, 010405 organic chemistry, Organic Chemistry, Alkyne, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Catalysis, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Cycloisomerization, chemistry, Nucleophile, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Platinum, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract: PtII-catalyzed cycloisomerization of a 1,6-enyne proceeds quickly in CHCl3 at room temperature, and also in the gas phase. However, calculations predict a slow reaction, because of the formation of a very stable chelate that undergoes oxidative cyclization at a high energy cost. The electrophilic activation of the alkyne followed by nucleophilic attack of the double bond to generate a cyclopropyl carbene would lead to a faster reaction, but the decomplexation of the double bond to generate an unsaturated platinum species is also energetically disfavored. However, decomplexation can be envisaged if an adventitious molecule of water enters the coordination sphere of the metal. This crucial role of water in PtII-catalyzed cycloisomerization of enynes, initially sensed some years ago (Echavarren et al., J. Am. Chem. Soc.2001, 123, 10511) is now supported by mass spectrometry studies.
Published: 2009

46. Gas-Phase Study of Phenylacetylene and Norbornadiene on a Palladium(II) Phosphinous Acid Complex: Importance of the Order of Introduction of the Organic Partners

Author: Laurent Giordano, Jean-Claude Tabet, Gérard Buono, Yves Gimbert, Denis Lesage, Anne Milet, Stéphane Humbel, Reddy Thota, Laboratoire de Synthèse Organique et Organométallique (UMR CNRS 7201), Université Pierre et Marie Curie - Paris 6 (UPMC), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Chimie Théorique (DCM - CT), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Norbornadiene, Organic Chemistry, Reactive intermediate, Cationic polymerization, chemistry.chemical_element, Alkyne, 010402 general chemistry, Photochemistry, 01 natural sciences, Medicinal chemistry, Cycloaddition, Dissociation (chemistry), 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Phenylacetylene, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Palladium
Abstract: Palladium(II) acetate complexes with phosphinous acids such as tert-butyl(phenyl)phosphinous acid (PAPd) have been successfully applied in a new [2 + 1] cycloaddition reaction between norbornadiene (NBD) and phenylacetylene (PhCCH) to produce exo-phenylmethylidenecyclopropane in the solution phase. In the present study, collision-activated reaction (CAR)/collision-induced dissociation (CID) mass spectral experiments were performed on a cationic Pd(II) complex (Pd(OPPhtBu)2H ion, [a]+). These experiments were useful for the identification of the reactive intermediates in the gas phase. On the basis of the results of the collision-activated reactions on this particular Pd(II) complex ion with phenylacetylene and norbornadiene, we demonstrated the essential role of the order of addition of organic partners on the efficiency to form the diadduct ion [a + PhCCH + NBD]+. Theoretical calculations combined with mass spectrometry experiments support first a change in coordination mode of alkyne (η2 into η1) prior ...
Published: 2009

47. Collision induced dissociation-based characterization of nucleotide peptides: fragmentation patterns of microcin C7-C51, an antimicrobial peptide produced by Escherichia coli

Author: Vanessa W. Petit, Sylvie Rebuffat, Séverine Zirah, Jean-Claude Tabet, Laboratoire de chimie et biochimie des substances naturelles, Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Spectrometry, Mass, Electrospray Ionization, Collision-induced dissociation, antimicrobial peptide, Peptide, 010402 general chemistry, Tandem mass spectrometry, Mass spectrometry, 01 natural sciences, Fragmentation (mass spectrometry), Bacteriocins, Structural Biology, fragmentation, microcin C51, Escherichia coli, Nucleotide, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Spectroscopy, mass spectrometry, chemistry.chemical_classification, Nucleotides, 010401 analytical chemistry, Microcin, 0104 chemical sciences, Anti-Bacterial Agents, chemistry, Biochemistry, Electrospay-ionization, Nucleic acid, collision-induced-dissociation, Peptides
Abstract: International audience; Covalent protein-nucleic acid conjugates form an original class of compounds that occur in nature or can be generated in vitro through cross-linking to investigate domains involved in protein/nucleic acid interactions. Their mass spectrometry fragmentation patterns are poorly characterized. We have used electrospray-ionization mass spectrometry (ESI-MS) combined with collision-induced dissociation (CID) to characterize microcin C7-C51, an antimicrobial nucleotide peptide that targets aspartyl-tRNA synthetase and inhibits translation. The fragments of microcin C7-C51 were analyzed in positive- and negative-ion modes and compared with those of the corresponding unmodified heptapeptide and to the derived aspartyl-adenylate. The positive- and negative-ion mode fragments of microcin C7-C51 provided information on both the nucleotide and peptide moieties. Accurate mass measurement obtained using an LTQ Orbitrap instrument was a key factor for a comprehensive interpretation of the fragments. The experimental results obtained permitted the proposal of stepwise fragmentation pathways involving ion-dipole complexes. The data provide a better understanding of nucleotide peptide fragmentation in the gas phase.
Published: 2008

48. Theoretical and gas-phase studies of specific cationized purine base quartet

Author: Claude Pepe, Sakina Mezzache, Sandra Alves, Jean-Paul Paumard, Jean-Claude Tabet, Synthèse, Structure et Fonction de Molécules Bioactives (SSFMB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Dynamique Interactions et Réactivité (LADIR), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Models, Molecular, Spectrometry, Mass, Electrospray Ionization, Guanine, Stereochemistry, Electrospray ionization, Metal ions in aqueous solution, Molecular Conformation, Lithium, 010402 general chemistry, 01 natural sciences, Phase Transition, Analytical Chemistry, Adduct, chemistry.chemical_compound, Tetramer, Cations, Computer Simulation, Spectroscopy, Hypoxanthine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010401 analytical chemistry, Organic Chemistry, Sodium, Xanthine, Alkali metal, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, Models, Chemical, Purines, Potassium, Gases
Abstract: International audience; Guanine tetraplexes are biological non-covalent systems stabilized by alkali cations. Thus, self-clustering of guanine, xanthine and hypoxanthine with alkali cations (Na(+), K(+) and Li(+)) is investigated by electrospray ionization mass spectrometry (ESI-MS) in order to provide new insights into G-quartets, hydrogen-bonded complexes. ESI assays displayed magic numbers of tetramer adducts with Na(+), Li(+) and K(+), not only for guanine, but also for xanthine bases. The optimized structures of guanine and xanthine quartets have been determined by B3LYP hybrid density functional theory calculations. Complexes of metal ions with quartets are classified into different structure types. The optimized structures obtained for each quartet explain the gas-phase results. The gas-phase binding sequence between the monovalent cations and the xanthine quartet follows the order Li(+) > Na(+) > K(+), which is consistent with that obtained for the guanine quartet in the literature. The smallest stabilization energy of K(+) and its position versus the other alkali metal ions in guanine and xanthine quartets is consistent with the fact that the potassium cation can be located between two guanine or xanthine quartets, for providing a [gua(or (xan))(8)+K](+) octamer adduct. Even if an abundant octamer adduct with K(+) for xanthine was detected by ESI-MS, it was not the case for guanine.
Published: 2007

49. Prix Nobel de chimie 2002. Spectrométrie de masse et résonance magnétique nucléaire

Author: Sylvie Rebuffat, Jean-Claude Tabet, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Muséum national d'Histoire naturelle (MNHN), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010401 analytical chemistry, 0103 physical sciences, General Medicine, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 010306 general physics, 01 natural sciences, Humanities, General Biochemistry, Genetics and Molecular Biology, Analysis method, 0104 chemical sciences
Abstract: En 2002, le Prix Nobel de Chimie a été décerné à trois grands scientifiques, John B. Fenn et Koichi Tanaka pour la spectrométrie de masse et Kurt Wüthrich pour la résonance magnétique nucléaire. Il récompense ainsi les idées innovantes qui ont conduit à développer, à l’interface chimie-biologie, des méthodologies spectroscopiques majeures initialement introduites en chimie analytique. La découverte de nouvelles méthodes douces d’ionisation en spectrométrie de masse, et la conception d’une stratégie d’attributions séquentielles des signaux de résonance magnétique nucléaire de biopolymères, ont permis l’application de ces deux méthodologies puissantes et complémentaires à la détermination de structures de macromolécules du vivant, protéines, acides nucléiques (ADN, ARN) et polysaccharides, etc. Par l’élucidation de leurs édifices (structures planes et tridimensionnelles) et des mécanismes moléculaires régissant leurs interactions, ces travaux fournissent des clés précieuses pour la compréhension des mécanismes moléculaires du vivant., The Nobel Prize in Chemistry for 2002 has been awarded to two powerful spectroscopic methodologies through three valorous scientists, John Fenn and Koichi Tanaka, for mass spectrometry and Kurt Wüthrich for nuclear magnetic resonance. These techniques were previously known for their intensive use in chemical analysis. They are now developed at the chemistry/biology interface. Two new methods of soft ionization in mass spectrometry and a strategy of sequential assignment of nuclear magnetic resonance signals of biopolymers now allow the use of these powerful and complementary methodologies for the structural analysis of biological macromolecules, proteins, nucleic acids (DNA, RNA) and polysaccharides. Through the elucidation of their planar and three-dimensional structures and of the molecular mechanisms that govern their interactions, these techniques now may afford precious clues for understanding the molecular mechanisms of life.
Published: 2003

50. Dendritic stars by ring-opening-metathesis polymerization from ruthenium-carbene initiators

Author: Georges Bravic, Jean-Claude Blais, Sylvain Gatard, Eric Cloutet, Sylvain Nlate, Didier Astruc, Laboratoire de chimie organique et organométallique (LCOO), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des polymères organiques (LCPO), Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Institut de Chimie du CNRS (INC), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB)
Subjects: Dendrimers, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, Metathesis, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Ruthenium, 0104 chemical sciences, Polymerization, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Dendrimer, Polymer chemistry, Carbenes, Ring-opening metathesis polymerisation, Reversible addition−fragmentation chain-transfer polymerization, Ionic polymerization, Acyclic diene metathesis
Abstract: International audience; Dendrimers are a rich and appealing field of polymer chemistry. Organic polymerization form dendritic initiators also offers a route to highly branched polymers, and indeed these have been obtained, amongest other methods, ...
Published: 2003

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