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

1. Détection des métabolites urinaires par spectrométrie de masse à très haute résolution : comparaison entre les approches DI /ESI-FTICR et LC/ESI-LTQ-Orbitrap

Author

Xue, Baiyi, Alves, Sandra, Tabet, Jean-Claude, Cole, Richard B., Paris, Alain, Rathahao, Estelle, Junot, Christophe, Ingénierie Procédés Aliments (GENIAL), Institut National de la Recherche Agronomique (INRA)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM), 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), Méthodologies d'Analyse de Risque Alimentaire (MET@RISK), Institut National de la Recherche Agronomique (INRA), 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), Ingénierie Procédés Aliments ( GENIAL ), Institut National de la Recherche Agronomique ( INRA ) -AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] ( CNAM ), 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 ), Méthodologies d'Analyse de Risque Alimentaire ( MET@RISK ), Institut National de la Recherche Agronomique ( INRA ), Laboratoire d'Etude du Métabolisme des Médicaments ( LEMM ), Service de Pharmacologie et Immunoanalyse ( SPI ), Département Médicaments et Technologies pour la Santé ( DMTS ), Direction de Recherche Fondamentale (CEA) ( DRF (CEA) ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-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 ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Département Médicaments et Technologies pour la Santé ( DMTS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay, Institut National de la Recherche Agronomique (INRA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA), 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), 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)-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 la Recherche Agronomique (INRA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM), HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA), and ProdInra, Archive Ouverte

Subjects
[SDV] Life Sciences [q-bio], [ SDV ] Life Sciences [q-bio], [SDV]Life Sciences [q-bio]
Abstract

Détection des métabolites urinaires par spectrométrie de masse à très haute résolution : comparaison entre les approches DI /ESI-FTICR et LC/ESI-LTQ-Orbitrap. 7. Journées Scientifiques du Réseau Français de Métabolomique et Fluxomique

Published
2013

2. 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

3. 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

4. [(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

5. 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

6. Cyclodextrin Complexation Studies as the First Step for Repurposing of Chlorpromazine

Author

Christine Cézard, Audrey Solgadi, Lars Herfindal, Luc de Chaisemartin, François-Xavier Legrand, Christina Sizun, David Landy, Gillian Barratt, Zhiqiang Wang, Cédric Przybylski, Gestionnaire HAL, Sorbonne Université, Université Paris-Saclay, Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV), Université du Littoral Côte d'Opale (ULCO), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), 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), Ingénierie et Plateformes au Service de l'Innovation Thérapeutique (IPSIT), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), 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)-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), Service d'hématologie et immunologie, Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-AP-HP - Hôpital Bichat - Claude Bernard [Paris], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Université Paris Cité (UPCité), Inflammation, microbiome, immunosurveillance (MI2), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Saclay, University of Bergen (UiB), 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)-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), and Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Université de Paris (UP)

Subjects
Magnetic Resonance Spectroscopy, Chlorpromazine, Chemistry, Pharmaceutical, Enthalpy, Pharmaceutical Science, 02 engineering and technology, Molecular Dynamics Simulation, 030226 pharmacology & pharmacy, Repurposin, Sugammadex, 03 medical and health sciences, Molecular dynamics, 0302 clinical medicine, Drug Stability, Cyclodextrin,Chlorpromazine, Inclusion complex, Sugammadex, Photodegradation, Repurposin, Photodegradation, [CHIM] Chemical Sciences, medicine, Cyclodextrin, [CHIM]Chemical Sciences, chemistry.chemical_classification, Cyclodextrins, Drug Carriers, Inclusion complex, Chemistry, beta-Cyclodextrins, Drug Repositioning, Isothermal titration calorimetry, 021001 nanoscience & nanotechnology, Binding constant, Combinatorial chemistry, 3. Good health, Delayed-Action Preparations, Drug delivery, Liposomes, Thermodynamics, 0210 nano-technology, CSOB, medicine.drug, gamma-Cyclodextrins
Abstract

International audience; The antipsychotic drug chlorpromazine (CPZ) has potential for the treatment of acute myeloid leukemia, if central nervous system side-effects resulting from its passage through the blood-brain barrier can be prevented. A robust drug delivery system for repurposed CPZ would be drug-in-cyclodextrin-in-liposome that would redirect the drug away from the brain while avoiding premature release in the circulation. As a first step, CPZ complexation with cyclodextrin (CD) has been studied. The stoichiometry, binding constant, enthalpy, and entropy of complex formation between CPZ and a panel of CDs was investigated by isothermal titration calorimetry (ITC). All the tested CDs were able to include CPZ, in the form of 1:1, 1:2 or a mixture of 1:1 and 1:2 complexes. In particular, a substituted γ-CD, sugammadex (the octasodium salt of octakis(6-deoxy-6-S-(2-carboxyethyl)-6-thio)cyclomaltooctaose), formed exclusively 1:2 complexes with an extremely high association constant of 6.37 × 10 9 M −2. Complexes were further characterized by heat capacity changes, one-and twodimensional (ROESY) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics simulations. Finally, protection of CPZ against photodegradation by CDs was assessed. This was accelerated rather than reduced by complexation with CD. Altogether these results provide a molecular basis for the use of CD in delayed release formulations for CPZ.

Published
2020

7. CpeF Is the Bilin Lyase That Ligates the Doubly Linked Phycoerythrobilin on β-Phycoerythrin in the Cyanobacterium \emphFremyella\emph Diplosiphon

Author

Jacob P. Frick, David M. Kehoe, M. Nazim Boutaghou, Wendy M. Schluchter, Andrian Gutu, Jonathan A. Karty, Richard B. Cole, Carla V. Hernandez, Christina M. Kronfel, Leanora S. Hernandez, University of New Orleans, Department of Biology (Kehoe's Lab), Indiana University [Bloomington], Indiana University System-Indiana University System, Mass Spectrometry Facility, Indiana University System-Indiana University System-Department of Chemistry, Indiana University System, 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), Department of Biological Sciences [New Orleans], The University of New Orleans, Dpt of Chemistry [New Orleans], and University of New Orleans, New Orleans

Subjects
0301 basic medicine, 030102 biochemistry & molecular biology, biology, POLE 3, Protein subunit, Phycobiliprotein, Phycoerythrobilin, Cell Biology, Lyase, Biochemistry, CPEB, 03 medical and health sciences, chemistry.chemical_compound, 030104 developmental biology, chemistry, biology.protein, [CHIM]Chemical Sciences, Phycobilisome, Bilin, Molecular Biology, Phycoerythrin, CSOB
Abstract

Phycoerythrin (PE) is a green light–absorbing protein present in the light-harvesting complex of cyanobacteria and red algae. The spectral characteristics of PE are due to its prosthetic groups, or phycoerythrobilins (PEBs), that are covalently attached to the protein chain by specific bilin lyases. Only two PE lyases have been identified and characterized so far, and the other bilin lyases are unknown. Here, using in silico analyses, markerless deletion, biochemical assays with purified and recombinant proteins, and site-directed mutagenesis, we examined the role of a putative lyase-encoding gene, cpeF, in the cyanobacterium Fremyella diplosiphon. Analyzing the phenotype of the cpeF deletion, we found that cpeF is required for proper PE biogenesis, specifically for ligation of the doubly linked PEB to Cys-48/Cys-59 residues of the CpeB subunit of PE. We also show that in a heterologous host, CpeF can attach PEB to Cys-48/Cys-59 of CpeB, but only in the presence of the chaperone-like protein CpeZ. Additionally, we report that CpeF likely ligates the A ring of PEB to Cys-48 prior to the attachment of the D ring to Cys-59. We conclude that CpeF is the bilin lyase responsible for attachment of the doubly ligated PEB to Cys-48/Cys-59 of CpeB and together with other specific bilin lyases contributes to the post-translational modification and assembly of PE into mature light-harvesting complexes.

Published
2019

8. 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

9. 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

10. 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

11. 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

12. 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

13. Rapid Photoinduced Charge Injection into Covalent Polyoxometalate\textendash Bodipy Conjugates

Author

Black, Fiona A., Jacquart, Aurélie, Toupalas, Georgios, Alves, Sandra, Proust, Anna, Clark, Ian P., Gibson, Elizabeth A., Izzet, Guillaume, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK., School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK. Code (UMR, EA, ...), 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), 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), Edifices PolyMétalliques (E-POM), Central Laser Facility (CLF), STFC Rutherford Appleton Laboratory (RAL), and Science and Technology Facilities Council (STFC)-Science and Technology Facilities Council (STFC)

Subjects
POLE 3, POLE 2, [CHIM]Chemical Sciences, E-POM, CSOB
Published
2018

14. 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

15. 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

16. 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

17. 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

18. 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

19. 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

20. Unusual Post-Spray Proton Transfer to Protein Using Acetone Spray in Desorption Electrospray Ionization

Author

Jean-Claude Tabet, Nicolas Auzeil, Anna Warnet, Institut Parisien de Chimie Moléculaire (IPCM), Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), Laboratoire de Chimie et Toxicologie Analytique et Cellulaire (EA 4463), Université Paris Descartes - Paris 5 (UPD5), Chimie Structurale Organique et Biologique (CSOB), 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)-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 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), 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 ionization, Lysozyme, Analytical chemistry, MS, Ion, Solvent, chemistry.chemical_compound, DESI, Adsorption, chemistry, Aprotic solvent, Ionization, Labelling, Acetone, Mass spectrum, Cationization, [CHIM]Chemical Sciences
Abstract

International audience; Although acetone, in DESI ionisation generally leads to protein aggregation, in this study we report unexpected multi-proton transfers to lysozyme using this aprotic solvent as a charged spray. The DESI/acetone mass spectrum of lysozyme displays (i) a significant increase in the average charge state (Zav) and (ii) an incomplete H+/Ca2+ exchange, even though the overall contribution of cationised species is high, relative to those from spraying with a methanol/water solvent. This behavior is contrary to that expected from gas phase basicity, because GBacetone >GBmethanol. Decreasing the amount of sample deposited on the target (from 50 to 0.050 pmole) leads to a charge state increase, as seen in ESI, but not in the extent of cationisation. Moreover, the DESI signal duration is extended with sprayed acetone even though the total ionic current is significantly lowered. With a d6-acetone spray, no incorporation of a deuteron occurs, and the ionization yield is strongly decreased for multi-protonated lysoi+ lysozyme. This is in contrast to that observed with a d4-methanol spray, which displays a distribution of 48 deuterons in the lyso9+ ion as shown in high resolution with a LTQ/Orbitrap instrument. This unexpected behavior of the (CD3)2CO spray suggests that protons do not originate from acetone. Furthermore, dry argon post-flow on the target surface results in the lysozyme signal suppression, whereas with a humid argon flow, the signal is regenerated. On the other hand, an argon stream bubbling in heavy water, yields incorporation of several deuterons. The interpretation of this behavior is explained by considering the acetone radical ions at the surface of the primary droplets (and/or offspring droplets and/or at the wet sample surface), being able to react with ambient moisture (or with traces of water adsorbed at liquid phase). Under these conditions, enough protons are produced to generate multi-charged solvated lysozyme aggregates which then become desolvated in the reduced pressure in the skimmer area.

Published
2015

21. High resolution mass spectrometry for quantitative analysis and untargeted screening of algal toxins in mussels and passive samplers

Author

Manoella Sibat, Pearse McCarron, Zouher Amzil, Christine Herrenknecht, Philipp Hess, Richard B. Cole, Zita Zendong, Institute for Marine Biosciences, Consiglio Nazionale delle Ricerche [Roma] (CNR), Mer, molécules et santé EA 2160 (MMS), Université de Nantes - UFR des Sciences Pharmaceutiques et Biologiques, Université de Nantes (UN)-Université de Nantes (UN)-Le Mans Université (UM)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN), Laboratoire Phycotoxines, Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), Phytoxins laboratory, Nantes, 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 Français de Recherche pour l'Exploitation de la Mer - Atlantique (IFREMER Atlantique), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Le Mans Université (UM)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Université de Nantes - UFR des Sciences Pharmaceutiques et Biologiques, Laboratoire Phycotoxines (PHYC), Dynamiques des Écosystèmes Côtiers (DYNECO), Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER), 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
Matrix effects, Monitoring, Ion suppression in liquid chromatography–mass spectrometry, Orbitrap, Mass spectrometry, Tandem mass spectrometry, Biochemistry, Analytical Chemistry, law.invention, Matrix (chemical analysis), chemistry.chemical_compound, law, Tandem Mass Spectrometry, Animals, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Shellfish, Chromatography, Organic Chemistry, Domoic acid, General Medicine, Reference Standards, Triple quadrupole mass spectrometer, Bivalvia, Passive sampling, chemistry, 13. Climate action, Environmental chemistry, Marine toxins, Marine toxin, SPATT, Chromatography, Liquid
Abstract

Measurement of marine algal toxins has traditionally focussed on shellfish monitoring while, over the last decade, passive sampling has been introduced as a complementary tool for exploratory studies. Since 2011, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been adopted as the EU reference method (No.15/2011) for detection and quantitation of lipophilic toxins. Traditional LC-MS approaches have been based on low-resolution mass spectrometry (LRMS), however, advances in instrument platforms have led to a heightened interest in the use of high-resolution mass spectrometry (HRMS) for toxin detection. This work describes the use of HRMS in combination with passive sampling as a progressive approach to marine algal toxin surveys. Experiments focused on comparison of LRMS and HRMS for determination of a broad range of toxins in shellfish and passive samplers. Matrix effects are an important issue to address in LC-MS; therefore, this phenomenon was evaluated for mussels (Mytilus galloprovincialis) and passive samplers using LRMS (triple quadrupole) and HRMS (quadrupole time-of-flight and Orbitrap) instruments. Matrix-matched calibration solutions containing okadaic acid and dinophysistoxins, pectenotoxin, azaspiracids, yessotoxins, domoic acid, pinnatoxins, gymnodimine A and 13-desmethyl spirolide C were prepared. Similar matrix effects were observed on all instruments types. Most notably, there was ion enhancement for pectenotoxins, okadaic acid/dinophysistoxins on one hand, and ion suppression for yessotoxins on the other. Interestingly, the ion selected for quantitation of PTX2 also influenced the magnitude of matrix effects, with the sodium adduct typically exhibiting less susceptibility to matrix effects than the ammonium adduct. As expected, mussel as a biological matrix, quantitatively produced significantly more matrix effects than passive sampler extracts, irrespective of toxin. Sample dilution was demonstrated as an effective measure to reduce matrix effects for all compounds, and was found to be particularly useful for the non-targeted approach. Limits of detection and method accuracy were comparable between the systems tested, demonstrating the applicability of HRMS as an effective tool for screening and quantitative analysis. HRMS offers the advantage of untargeted analysis, meaning that datasets can be retrospectively analysed. HRMS (full scan) chromatograms of passive samplers yielded significantly less complex data sets than mussels, and were thus more easily screened for unknowns. Consequently, we recommend the use of HRMS in combination with passive sampling for studies investigating emerging or hitherto uncharacterised toxins.

Published
2015

22. 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

23. 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

24. Identification of glyceollin metabolites derived from conjugation with glutathione and glucuronic acid in male ZDSD rats by online liquid chromatography-electrospray ionization tandem mass spectrometry

Author

Syeda S. Quadri, Stephen M. Boue, Richard B. Cole, Robert E. Stratford, Dpt of Chemistry [New Orleans], University of New Orleans, New Orleans, University of Louisiana, Southern Regional Research Center, USDA-ARS : Agricultural Research Service, 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
Male, phytoalexins, Spectrometry, Mass, Electrospray Ionization, Pterocarpans, Electrospray ionization, Glucuronidation, Tandem mass spectrometry, Mass spectrometry, Article, phase II metabolism, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, Glucuronic Acid, Tandem Mass Spectrometry, [CHIM]Chemical Sciences, Animals, Mercapturic acid, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, Glyceollin, phytoestrogens, reactive oxygen species, 0303 health sciences, Chromatography, Chemistry, Plant Extracts, General Chemistry, Glucuronic acid, phytochemicals, Glutathione, Rats, Rats, Zucker, 030220 oncology & carcinogenesis, Seeds, Microsomes, Liver, phase I metabolism, Soybeans, General Agricultural and Biological Sciences, Conjugate, Chromatography, Liquid
Abstract

Glyceollin-related metabolites produced in rats following oral glyceollin administration were screened in plasma, feces, and urine, and these metabolites were identified by precursor and product ion scanning using liquid chromatography coupled online with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Precursor ion scanning in the negative ion (NI) mode was used to identify all glyceollin metabolites based on production of a diagnostic radical product ion (m/z 148) upon decomposition. Using this approach, precursor peaks of interest were found at m/z 474 and 531. Tandem mass spectra of these two peaks allowed us to characterize them as byproducts of glutathione conjugation. The peak at m/z 474 was identified as the deprotonated cysteinyl conjugate of glyceollins with an addition of an oxygen atom, whereas m/z 531 was identified as the deprotonated cysteinylglyceine glyceollin conjugate plus an oxygen. These results were confirmed by positive ion (PI) mode analyses. Mercapturic acid conjugates of glyceollins were also identified in NI mode. In addition, glucuronidation of glyceollins was observed, giving a peak at m/z 513 corresponding to the deprotonated conjugate. Production of glucuronic acid conjugates of glyceollins was confirmed in vitro in rat liver microsomes. Neither glutathione conjugation byproducts nor glucuronic acid conjugates of glyceollins have been previously reported.

Published
2014

25. Evaluation of horse urine sample preparation methods for metabolomics using LC coupled to HRMS

Author

Marie-Agnès Popot, Alain Paris, Christophe Junot, Patrice Garcia, Yves Bonnaire, Natali Stojiljkovic, Jean-Claude Tabet, Laboratoire des Courses Hippiques (LCH), 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), Physiologie de la Nutrition et du Comportement Alimentaire (PNCA), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, 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), National Association of Research and Technology, French Institute for the horse and horse riding, and Fédération Nationale des Courses Françaises

Subjects
Chromatography, Chemistry, [SDV]Life Sciences [q-bio], Clinical Biochemistry, General Medicine, Urine, Repeatability, Analytical Chemistry, Preparation method, Medical Laboratory Technology, Metabolomics, Metabolome, Animals, Sample preparation, Horses, General Pharmacology, Toxicology and Pharmaceutics, Drug analysis, Urine sample, Chromatography, Liquid
Abstract

Background: Horse urine is the medium of choice for the implementation of metabolomic approaches aimed at improving horse doping control. However, drug analysis in this biofluid is a challenging task due to the presence of large amounts of interfering compounds. Methodology & Results: A comparative study of sample preparation has been conducted to evaluate five sample-preparation methods, namely acetonitrile precipitation, proteinase K hydrolysis, membrane filtration and sample dilution with water by factors of five and 20, for metabolome analysis using liquid chromatography coupled to high resolution mass spectrometry. Assessment was performed at both global and targeted levels, by using a few thousand features obtained from peak detection software, and internal standards and 100 annotated or identified metabolites. Conclusion: By considering the number of detected signals, their intensity and their detection repeatability, acetonitrile precipitation was selected as the most efficient sample-preparation method for the analysis of horse urine metabolome in liquid chromatography coupled to high resolution mass spectrometry conditions.

Published
2014

26. Le développement de méthode d’empreintes métabolomiques à haut débit et à ultra haute résolution pour le phénotypage métabolique et l’identification structurale de biomarqueurs

Author

Xue, Baiyi, Alves, Sandra, Tabet, Jean-Claude, Cole, Richard B., Paris, Alain, Junot, Christophe, Rathahao, Estelle, Ingénierie Procédés Aliments (GENIAL), Institut National de la Recherche Agronomique (INRA)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), 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), Méthodologies d'Analyse de Risque Alimentaire (MET@RISK), Institut National de la Recherche Agronomique (INRA), 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)-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)-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 la Recherche Agronomique (INRA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM), HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA), 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), 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), Institut National de la Recherche Agronomique (INRA)-AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] (CNAM)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA), and ProdInra, Archive Ouverte

Subjects
[SDV] Life Sciences [q-bio], [SDV]Life Sciences [q-bio]
Abstract

Le développement de méthode d’empreintes métabolomiques à haut débit et à ultra haute résolution pour le phénotypage métabolique et l’identification structurale de biomarqueurs. 7. Journées Scientifiques du Réseau Français de Métabolomique et Fluxomique

Published
2013

27. 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

28. 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

29. 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

30. 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

31. 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

32. 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

33. An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

Author

Helena Osterholz, Amna Ijaz, Juliana D'Andrilli, Christina K. Remucal, Nicholas D. Schmitt, Patrick G. Hatcher, Simeon Schum, Rosalie K. Chu, Richard B. Cole, Mary J. Thomas, Rachel L. Sleighter, Nikola Tolić, Nikola Radoman, Lynn Mazzoleni, Hongmei Chen, Aron Stubbins, Ryan H. S. Hutchins, Phoebe Zito, Chen He, Shuzhen Zhang, Jitao Lv, Thorsten Dittmar, Mark P. Barrow, Jeffrey A. Hawkes, Gabriel Singer, Remy Gavard, Stephanie M. Berg, Jeffrey N. Agar, Hugh E. Jones, Núria Catalán, Carsten Simon, David C. Podgorski, Gerd Gleixner, William Kew, Beatriz E. Noriega-Ortega, Diana Catalina Palacio Lozano, Nancy J. Hess, Quan Shi, Maryam Khaksari, US Geological Survey [Boulder], United States Geological Survey [Reston] (USGS), Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), College of Physical Science and Technology [Nanning], Guangxi University [Nanning], 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), Max Planck Institute for Biogeochemistry (MPI-BGC), Max-Planck-Gesellschaft, Department of Chemistry and Biochemistry, Old Dominion University [Norfolk] (ODU), Centre Ingénierie et Santé (CIS-ENSMSE), École des Mines de Saint-Étienne (Mines Saint-Étienne MSE), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), China University of Petroleum, Leibniz Institute of Freshwater Ecology & Inland Fisheries, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (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), 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
0106 biological sciences, 010504 meteorology & atmospheric sciences, Chemistry, 010604 marine biology & hydrobiology, Electrospray ionization, Sediments fluvials, Ocean Engineering, Oceanografi, hydrologi och vattenresurser, Mass spectrometry, 01 natural sciences, Characterization (materials science), River sediments, Oceanography, Hydrology and Water Resources, Compostos orgànics, 13. Climate action, Environmental chemistry, Organic compounds, Dissolved organic carbon, [CHIM]Chemical Sciences, Composition (visual arts), 0105 earth and related environmental sciences
Abstract

High‐resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive‐ion and negative‐ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified ~1000 common ions in both negative‐ and positive‐ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance‐weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments Research Funding: Beatriu de Pinos. Grant Number: 2016‐00215 Division of Chemical, Bioengineering, Environmental, and Transport Systems. Grant Number: 1802388 Engineering and Physical Sciences Research Council. Grant Number: EP/L015307/1 French National FT‐ICR network. Grant Number: FR 3624 CNRS H2020 European Research Council. Grant Number: ERC‐STG 716196 H2020 Marie Skłodowska‐Curie Actions. Grant Number: CHROME‐839709 National Science Foundation. Grant Number: AGS‐1531454 Newton Fund. Grant Number: 275910721 NIH. Grant Number: S10OD018475 Vetenskapsrådet. Grant Number: 2018‐04618

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