Search

Your search keyword '"Chimie Structurale Organique et Biologique (CSOB)"' showing total 90 results
Start Over Author "Chimie Structurale Organique et Biologique (CSOB)"
90 results on '"Chimie Structurale Organique et Biologique (CSOB)"'

1. Mise en évidence d’état d’exposition aux pesticides par une analyse rapide d’empreintes métabolomiques sur un instrument FTMS et un traitement chimiométrique

Author

Habchi , Baninia, Alves , Sandra, Paris , Alain, Lecluse , Yannick, Gauduchon , Pascal, Lebailly , Pierre, Rutledge , Douglas, Rathahao , Estelle, Ingénierie, Procédés, Aliments (GENIAL), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, 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), Molécules de Communication et Adaptation des Micro-Organismes (MCAM), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU), 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), 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), Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Réseau Francophone de Métabolomique et Fluxomique (RFMF). FRA., Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM), 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 ), Molécules de Communication et Adaptation des Micro-Organismes ( MCAM ), Muséum National d'Histoire Naturelle ( MNHN ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Caen Normandie ( UNICAEN ), and Normandie Université ( NU )

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

en cours de publication...en cours de publication...; Mise en évidence d’état d’exposition aux pesticides par une analyse rapide d’empreintes métabolomiques sur un instrument FTMS et un traitement chimiométrique. 9èmes Journées Scientifiques du Réseau Français de Métabolomique et Fluxomique

Published
2015

2. Décomposition de la variance d’origine métabolique selon le cultivar, la dose du maïs génétiquement modifié par incorporation dans l’aliment et le genre du modèle-animal utilisé pour évaluer les aliments GM

Author

Paris, Alain, Gauthier, Marine, Butin, L, Alves, Sandra, Adel-Patient, Karine, Wal, Jean-Michel, Rathahao, Estelle, Méthodologies d'Analyse de Risque Alimentaire (MET@RISK), Institut National de la Recherche Agronomique (INRA), Unité Mixte de Recherche sur les Herbivores - UMR 1213 (UMRH), Institut National de la Recherche Agronomique (INRA)-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS), Laboratoire d'Etudes et de Recherches en Immunoanalyses (LERI), Service de Pharmacologie et Immunoanalyse (SPI), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Médicaments et Technologies pour la Santé (MTS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité d'Immuno-Allergie Alimentaire (UIAA - UR 496), Ingénierie, Procédés, Aliments (GENIAL), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, Unité Mixte de Recherches sur les Herbivores - UMR 1213 (UMRH), VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Institut National de la Recherche Agronomique (INRA), 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), 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 National de la Recherche Agronomique (INRA)-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Méthodologies d'Analyse de Risque Alimentaire ( MET@RISK ), Institut National de la Recherche Agronomique ( INRA ), Unité Mixte de Recherches sur les Herbivores ( UMR 1213 Herbivores ), VetAgro Sup ( VAS ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Institut National de la Recherche Agronomique ( INRA ), Laboratoire d'Etudes et de Recherches en Immunoanalyses ( LERI ), 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, 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 ), Unité d'Immuno-Allergie Alimentaire ( UIAA - UR 496 ), Ingénierie Procédés Aliments ( GENIAL ), and Institut National de la Recherche Agronomique ( INRA ) -AgroParisTech-Conservatoire National des Arts et Métiers [CNAM] ( CNAM )

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

(Session Applications de la métabolomique en nutrition-santé) en cours de publication.(Session Applications de la métabolomique en nutrition-santé)en cours de publication.; Décomposition de la variance d’origine métabolique selon le cultivar, la dose du maïs génétiquement modifié par incorporation dans l’aliment et le genre du modèle-animal utilisé pour évaluer les aliments GM. 9. Journées Scientifiques du Réseau Français de Métabolomique et Fluxomique

Published
2015

3. Benchmarking higher energy collision dissociation (HCD) by investigation of binding energies of gas-phase host-guest complexes of hemicryptophane cages

Author

Parisa Bayat, David Gatineau, Denis Lesage, Alexandre Martinez, Richard B. Cole, 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), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), 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), and Arcane Labex

Subjects
Ions, Benchmarking, [CHIM]Chemical Sciences, Thermodynamics, Spectroscopy, Mass Spectrometry
Abstract

International audience; Synthesis of host molecules that feature well-defined characteristics for molecular recognition of guest molecules is often a major aim of synthetic host–guest (H–G) chemistry. A key consideration in evaluating the selectivity of hosts and the affinities of guests is the measurement of binding energies of obtained H–G complexes. In contrast to nuclear magnetic resonance (NMR) or fluorescence measurements that are capable of measuring binding strengths in solution, mass spectrometry offers the opportunity to measure gas-phase binding energies. Presented in this article is a higher energy collision dissociation (HCD) approach for determining critical energies of dissociation of H–G complexes. Experiments were performed on electrospray ionization (ESI)-generated H–G pairs in an LTQ-XL/Orbitrap hybrid instrument. The presented HCD approach requires preliminary calibration of the internal energy distribution of generated ions that was achieved by the use of activation parameters that were known from previous low-energy collision-induced dissociation (low-energy CID) experiments. Internal energy deposition was modeled based on a truncated Maxwell–Boltzmann distribution and characteristic temperature (Tchar). Using this method, critical energies of dissociation were determined for 10 H–G biologically relevant complexes of the heteroditopic hemicryptophane cage host (Host). Obtained results are compared with those found previously by low-energy CID. The use of this HCD technique is relatively straightforward, although its implementation does require knowledge (or a presumption) about the Arrhenius pre-exponential factor of the complexes to obtain their critical energies of dissociation.

Published
2022

4. 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

5. 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

6. 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

7. [(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

8. 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

9. Tutorial: Ion Activation in Tandem Mass Spectrometry Using Ultra-High Resolition Spectroscopy

Author

Bayat, Parisa, Lesage, Denis, Cole, Richard B., Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)

Subjects
POLE 3, [CHIM]Chemical Sciences, CSOB
Published
2020

10. A bis‐chelating (O^N^O)/(N^N) ligand for the synthesis of heterobimetallic Pt(II)/Re(I) complexes: tools for the optimization of a new class of Pt(II) anticancer agents

Author

Bertrand, Benoît, Botuha, Candice, Forte, Jeremy, Dossmann, Héloïse, Salmain, Michèle, Chemical Biology (CHEMBIO), 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), and Chimie Structurale Organique et Biologique (CSOB)

Subjects
heterobimetallic complexes, Synthesis, Bioorganometallic chemistry, cancer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry
Abstract

International audience; The two independent (O^N^O) and (N^N) coordination sites of a newly synthesized bis 2-(hydroxyphenyl)-1,2,4-triazole platform have been exploited to prepare four monometallic neutral (O^N^O)Pt(II) complexes carrying DMSO, pyridine, triphenylphosphine or N-heterocyclic carbene (NHC) as fourth ligand. Then the second (N^N) coordination site was used to introduce an IR-active rhenium tricarbonyl entity, affording the four corresponding heterobimetallic neutral Pt(II)/Re(I) complexes as well as a cationic Pt(II)/Re(I) derivative. X-ray crystallographic studies showed that distortion of the organic platform occurred to accommodate the coordination geometry of both metal centers. No ligand exchange and no transchelation occurred upon incubation of the Pt(II) complexes in aqueous environment or in the presence of Fe(III), respectively. The ligand and the complexes antiproliferative activity was first screened on the triple negative breast cancer cell line MDA-MB-231. Then the IC50 of the most active candidates was determined on a wider panel of human cancer cells (MDA-MB-231, MCF-7 and A2780) as well as on a non-tumorigenic cell line (MCF-10A). Low micromolar activities were reached for the complexes carrying a DMSO ligand, making them the first examples of highly active though hydrolytically stable Pt(II) complexes. Finally, the characteristic mid-IR signature of the Re(CO)3 fragment in the Pt/Re heterobimetallic complexes was used to quantify their uptake in breast cancer cells.

Published
2020

11. 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

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

Author

Mayreli Ortiz, Markéta Svobodová, Ciara K. O'Sullivan, Denis Lesage, Bernold Hasenknopf, Serge Thorimbert, Richard B. Cole, Ahmed M. Debela, Glycochimie Organique Biologique et Supramoléculaire (GOBS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Chimie Structurale Organique et Biologique (CSOB), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
DNA, Bacterial, Yersinia pestis, [SDV]Life Sciences [q-bio], Sequence (biology), 010402 general chemistry, Polymerase Chain Reaction, 01 natural sciences, Redox, Catalysis, chemistry.chemical_compound, [CHIM]Chemical Sciences, Nucleotide, A-DNA, Electrodes, ComputingMilieux_MISCELLANEOUS, Polymerase, chemistry.chemical_classification, biology, Nucleotides, 010405 organic chemistry, Organic Chemistry, Electrochemical Techniques, General Chemistry, Tungsten Compounds, biology.organism_classification, Electrophoresis, Gel, Pulsed-Field, 0104 chemical sciences, Biochemistry, chemistry, Polyoxometalate, biology.protein, Gold, DNA
Abstract

Redox-labeled nucleotides are of increasing interest for the fabrication of next generation molecular tools and should meet requirements of being thermally stable, sensitive, and compatible with polymerase-mediated incorporation while also being electrochemically discriminable. The synthesis and characterization of Keggin and Dawson polyoxometalate-deoxynucleotide (POM-dNTP) bioconjugates linked through 7-deaza-modified purines is described. The modified POM-dNTPs were used for polymerase-based amplification of a DNA sequence specific for Yersinia pestis and the amplified DNA detected using an electrochemical DNA sensor. This highlights the potential of polyoxometalates as thermally stable, sensitive and polymerase-compatible redox labels for exploitation in bioanalytical applications.

Published
2017

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

Author

Thyago S. Rodrigues, Denis Lesage, Wender A. Silva, Gunter Ebeling, Heibbe C. B. de Oliveira, Richard B. Cole, Jairton Dupont, Marcos N. Eberlin, Brenno A. D. Neto, University of Brasilia, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Universidade Federal do Rio Grande do Sul [Porto Alegre] (UFRGS), University of Campinas [Campinas] (UNICAMP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Estadual de Campinas = University of Campinas (UNICAMP)

Subjects
education.field_of_study, 010405 organic chemistry, Transition metal carbene complex, Inorganic chemistry, Population, Ionic bonding, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Ion, chemistry.chemical_compound, Deprotonation, chemistry, Structural Biology, Ionic liquid, [CHIM]Chemical Sciences, Molecule, Reactivity (chemistry), education, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract

Negatively charge-tagged N-heterocyclic carbenes have been formed in solution via deprotonation of imidazolium ions bearing acid side groups and transferred to the gas phase via ESI(-)-MS. The structure of the putative and apparently stable gaseous carbenes formed in such conditions were then probed via reactions with carbon dioxide using a triple quadrupole mass spectrometer particularly optimized for ion/molecule reactions of ESI-generated ions. Complete conversion to imidazolium carboxylates was achieved, which seems to demonstrate the efficiency of the transfer, the gas-phase stability, and the long-lived nature of these unprecedented charge-tagged carbenes and their predominance in the ionic population. Comprehensive studies on the intrinsic reactivity of N-heterocyclic carbenes with silent charge tags are therefore possible. Graphical Abstract ᅟ.

Published
2017

14. Revisiting the Intermolecular Fujiwara Hydroarylation of Alkynes

Author

Nelson H. Morgon, Marla N. Godoi, Marcos N. Eberlin, Richard B. Cole, Denis Lesage, Vanessa G. Santos, Thaís Regiani, Pablo David G. Martinez, Héloïse Dossmann, Carlos Roque D. Correia, Francisco de Azambuja, University of Campinas (UNICAMP), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Estadual de Campinas = University of Campinas (UNICAMP)

Subjects
010405 organic chemistry, Computational chemistry, Chemistry, Organic Chemistry, Intermolecular force, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience; no abstract

Published
2017

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

Author

Franziska D. Zitzmann, Detlev Belder, Sebastian Thurmann, Yannick Krauke, Christian Sonnendecker, Andrea A. Robitzki, Wolfgang Zimmermann, Cédric Przybylski, Kate Monks, Nicole Heinke, Leipzig University, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Universität Leipzig [Leipzig], and Institut für Analytische Chemie

Subjects
Spectrometry, Mass, Electrospray Ionization, POLE 3, Cell Survival, Complex formation, Supramolecular chemistry, Bacillus, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Catalysis, Cell Line, Bacterial Proteins, [CHIM]Chemical Sciences, Humans, Fragmentation (cell biology), Fluvastatin, chemistry.chemical_classification, Cyclodextrins, Chromatography, 010405 organic chemistry, 010401 analytical chemistry, Electrophoresis, Capillary, Stereoisomerism, General Chemistry, Reversed-phase chromatography, General Medicine, 3. Good health, 0104 chemical sciences, Mefloquine, Electrophoresis, Enzyme, chemistry, Pharmaceutical Preparations, Glucosyltransferases, Enantiomer, CSOB
Abstract

Large-ring cyclodextrins (CD) are cyclic glucans composed of 9 or more α-1,4-linked glucose units. They are minor side products of bacterial glucanotransferases (CGTases, EC 2.4.1.19) and have previously been available only in very small amounts for studies of their properties in supramolecular complex formation reactions. We engineered a CGTase to synthesize mainly large-ring CD facilitating their preparation in larger amounts. By reversed phase chromatography, we obtained single CD samples composed of 10 to 12 glucose units (CD10, CD11, and CD12) with a purity of >90 %. Their identity was confirmed by high resolution mass spectrometry and fragmentation analysis. We demonstrated the non-toxicity of CD10-CD12 for human cell lines by a cell proliferation assay and impedimetric monitoring. We then showed that CD10 and CD11 are efficient chiral selectors for the capillary electrophoretic separation of the enantiomeric pharmaceuticals fluvastatin, mefloquine, carvedilol, and primaquine.

Published
2019

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

Author

Abed Bil, Takwa Khanchouche, Véronique Bonnet, José Kovensky, Cédric Przybylski, Urjwan Alali, David Mathiron, Rémi Beaulieu, Mohammed Benazza, Aurélie Vallin, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plateforme Analytique (PFA), Université de Picardie Jules Verne (UPJV), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
POLE 3, medicine.medical_treatment, Saccharomyces cerevisiae, 010402 general chemistry, 01 natural sciences, Biochemistry, medicine, Monosaccharide, [CHIM]Chemical Sciences, Glycoside Hydrolase Inhibitors, Physical and Theoretical Chemistry, IC50, Acarbose, chemistry.chemical_classification, Cyclodextrins, Molecular Structure, Cyclodextrin, 010405 organic chemistry, Chemistry, Insulin, Organic Chemistry, Glycoside, alpha-Glucosidases, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Propargyl, Click chemistry, Click Chemistry, Glycoconjugates, CSOB, medicine.drug
Abstract

New inhibitors of α-glucosidase based on perglycosylated cyclodextrins were synthesized via click-chemistry and compared to acarbose. , The homeostasis disruption of d -glucose causes diabetes, a dramatic chronic disease worldwide. Type 1 diabetes is a successfully treatable form, where blood d -glucose is regulated by insulin treatment. In contrast type 2 diabetes, the non-insulin dependent kind, is problematic. The control of the d -glucose blood level via intestinal α- d -glucosidase inactivation can be achieved by using competitive inhibitors, such as iminosugars ( e.g. acarbose) or sulfonium sugar derivatives ( e.g. salacinol). Recently, an unprecedented result showed that multivalent diamond nanoparticles grafted with unmodified sugars displayed α-glucosidase inhibition at low micromolar concentrations. Herein we describe the synthesis of multivalent glycoclusters using cyclodextrins (CDs) as scaffolds and an assessment of their role as inhibitors of α- d -glucosidase. The glycoclusters were efficiently obtained from per-azido α, β and γ-CD derivatives and propargyl glycosides using click-chemistry under microwave irradiation. The methodology was successfully applied to various protected and non-protected propargylated monosaccharides, including both O - and S -glycosides, giving clear evidence of its versatility. The targeted 6- per -glycosylated CDs were isolated in moderate to excellent yields (30\textendash 90%) by silica gel chromatography. The results showed inhibition of α-glucosidase from Saccharomyces cerevisiae with IC 50 values in the 32\textendash 132 μM range, lower than that of acarbose (IC 50 = ∼250 μM), a well-known competitive inhibitor used in the clinical treatment of type 2 diabetes. Preliminary experiments suggest a mixed-type non-competitive inhibition mode for these new glycoclusters.

Published
2019

17. 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

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

Author

Maxime C. Bridoux, Nolwenn Floch, Alexandre Sonnette, Gabriel Gaiffe, Richard B. Cole, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Central de la Préfecture de Police, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Dart, Kendrick mass, POLE 3, Chemistry, 010401 analytical chemistry, Analytical chemistry, 010402 general chemistry, Orbitrap, Mass spectrometry, 01 natural sciences, DART ion source, 0104 chemical sciences, Analytical Chemistry, law.invention, law, Mass spectrum, [CHIM]Chemical Sciences, Plastic explosive, computer, CSOB, Semtex, computer.programming_language
Abstract

The coupling of an atmospheric pressure ionization source (Direct Analysis in Real Time, DART) and a high-resolution mass spectrometer (Orbitrap) has enabled the rapid and efficient analysis of a variety of energetic formulations. This approach was used to generate mass spectra for 83 plastic explosives and polymer samples in less than 2 min per sample. To manually interpret and identify all of the constituent polymers and other interesting features in the acquired mass spectra is a tedious and time-consuming challenge. Instead, a methodology based on the systematic calculation of Kendrick mass defects (KMDs) was developed and implemented. Its application allowed the identification of the polymeric support present in each energetic formulation. The presence of polyisobutylene in PG2 has been confirmed thanks to this approach, and a mixture of polyisobutylene, polybutadiene, and polystyrene has been confirmed in the Semtex 10 formulation. The developed methodology has also permitted the observation of changes that occur to the polymeric composition of these formulations after a blast. It appears that the most adequate way to describe post blast polymer samples is that they are less oxygenated and, above all, more unsaturated than the original starting material. These conclusions were deduced with the aid of principal component analysis, which served to establish the main factors that differentiate the samples.

Published
2019

19. 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

20. 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

21. Caractérisation globale d'explosifs et de substances connexes (polymères, liants et plastifiants) à l'état de traces sur des prélèvements solides reposant sur la spectrométrie de masse à haute-résolution

Author

Gaiffe, Gabriel, 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), Sorbonne Université, and Richard B. Cole

Subjects
Polymeres, [CHIM.POLY]Chemical Sciences/Polymers, Mass spectrometry, DART, ASAP, Formulations énergétiques, Electrospray, Spectrométrie de masse, Energetic formulations, Polymères
Abstract

The manufacture and the illicit traffic of explosives result in the increasing use of explosive devices during attacks. The identification of explosives is a major issue for the fight against terrorism. However, the wide variety of energetic formulations make their characterization complex by a single technique. This thesis focused on mass spectrometry by seeking to improve the detection of explosive molecules embedded in energetic formulations and by investigating the processes involved in the technique of anion attachment used to improve the sensitivity of detection. It appears that chloride and nitrate attachment is the most appropriate technique to produce an intense signal. A hypothesis has been advanced based on CID and IRMPD experiments. The work also focused on characterizing the matrix surrounding the explosives to create a database. These analyzes are performed using ASAP and DART sources, to limit material losses, with the prospect of working on samples in trace amounts. These methods have shown their ability to produce mass spectra for fluorinated polymers that are difficult to analyze. In order to obtain a spectral fingerprint for the polymers and to be able to compare the spectra of these polymers, a Kendrick mass defect analysis method was developed and allowed to identify the polymers in a mixture. An analysis was made on real samples of explosives to compare the chemical species present pre and post explosion.; La fabrication et le trafic illicite d’explosifs ont pour conséquence l’usage croissant d’engins explosifs lors d’attentats. L'identification d'explosifs est un enjeu majeur pour la lutte contre le terrorisme. La grande variété de formulations énergétiques rend cependant complexe leur caractérisation par une seule technique. Cette thèse s’est focalisé sur la spectrométrie de masse en cherchant à améliorer la détection de molécules explosives incluses dans des formulations énergétiques et en investiguant les processus mis en œuvre dans la technique de l’attachement d’anion permettant l’amélioration de la sensibilité de détection. Il apparaît que l’attachement de chlorure et de nitrate est la technique la plus appropriée à produire un signal intense. Une hypothèse a été avancée en se basant sur des expériences de CID et d’IRMPD. Le travail a aussi porté sur la caractérisation de la matrice environnant les explosifs pour créer une base de données. Ces analyses sont réalisées à l’aide des sources ASAP et DART, pour limiter les pertes de matière, avec en perspectives le travail sur des échantillons à l’état de traces. Ces méthodes ont montré leur capacité à produire des spectres de masse pour des polymères fluorés difficilement analysables. Afin d’obtenir une empreinte spectrale des polymères et de pouvoir comparer les spectres de ces polymères, une méthode d’analyse des défauts de masse de Kendrick a été développée et a permis d’identifier les polymères dans un mélange. Une analyse a été faite sur des échantillons réels d’explosifs pour comparer les espèces chimiques présentes pré et post explosion.

Published
2018

22. 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

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

Author

Maxime C. Bridoux, Gabriel Gaiffe, Richard B. Cole, Sabrina Lacpatia, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), LCPP - laboratoire central de la préfecture de police, DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Kendrick mass, POLE 3, 010401 analytical chemistry, Analytical chemistry, chemistry.chemical_element, Polymer, 010402 general chemistry, Mass spectrometry, Orbitrap, 01 natural sciences, Polyvinylidene fluoride, 0104 chemical sciences, Analytical Chemistry, law.invention, chemistry.chemical_compound, chemistry, law, Fluorine, [CHIM]Chemical Sciences, Hexafluoropropylene, Chlorotrifluoroethylene, CSOB
Abstract

Fluorinated polymers are a diverse and important class of polymers with unique applications. However, characterization of fluorinated polymers by conventional mass spectrometric methods is challenging because (i) their high fluorine contents make them insoluble or only sparingly soluble in most common solvents and (ii) commonly used matrices employed for MALDI do not desorb or ionize them efficiently. In this work, atmospheric-solid-analysis-probe (ASAP) high-resolution orbitrap mass spectrometry (HRMS) was used as a new tool for the molecular characterization of various fluorinated polymers, including polyvinylidene fluoride (PVDF) and fluorinated copolymers containing PVDF and chlorotrifluoroethylene (KEL-F 800) or PVDF and hexafluoropropylene (Viton A and Tecnoflon). The major peaks of the observed distributions were assigned compositions, but the high number of species required the use of an alternative method to treat such complex data. Kendrick-mass defects (KMD) were calculated on the basis of the "common-to-all" vinylidene difluoride repeating unit. By plotting the KMD as a function of the nominal Kendrick masses (NKM), specific patterns based on homologous series emerged. Kendrick maps were therefore drawn to simplify the mass spectra and provide confident peak assignments through homologous-series recognition. A specific fingerprint for each polymer has been identified, and the ability to discern the four species present in a blend through KMD analysis was demonstrated.

Published
2018

24. 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

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

Author

Christine Costanza, Richard B. Cole, Maxime C. Bridoux, Gabriel Gaiffe, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Central de la Préfecture de Police, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
POLE 3, Electrospray ionization, 010401 analytical chemistry, Analytical chemistry, Pentaerythritol tetranitrate, 010402 general chemistry, Tandem mass spectrometry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, Adduct, Ion, chemistry.chemical_compound, Deprotonation, chemistry, Molecule, [CHIM]Chemical Sciences, CSOB, Spectroscopy
Abstract

The development of rapid, efficient, and reliable detection methods for the characterization of energetic compounds is of high importance to security forces concerned with terrorist threats. With a mass spectrometric approach, characteristic ions can be produced by attaching anions to analyte molecules in the negative ion mode of electrospray ionization mass spectrometry (ESI-MS). Under optimized conditions, formed anionic adducts can be detected with higher sensitivities as compared with the deprotonated molecules. Fundamental aspects pertaining to the formation of anionic adducts of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), 1,3,5-trinitro-1,3,5-triazinane (RDX), pentaerythritol tetranitrate (PETN), nitroglycerin (NG), and 1,3,5-trinitroso-1,3,5-triazinane energetic (R-salt) compounds using various anions have been systematically studied by ESI-MS and ESI tandem mass spectrometry (collision-induced dissociation) experiments. Bracketing method results show that the gas-phase acidities of PETN, RDX, and HMX fall between those of HF and acetic acid. Moreover, PETN and RDX are each less acidic than HMX in the gas phase. Nitroglycerin was found to be the most acidic among the nitrogen-rich explosives studied. The ensemble of bracketing results allows the construction of the following ranking of gas-phase acidities: PETN (1530-1458 kJ/mol) > RDX (approximately 1458 kJ/mol) > HMX (approximately 1433 kJ/mol) > nitroglycerin (1427-1327.8 kJ/mol).

Published
2018

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

Author

Parisa Bayat, Denis Lesage, Richard B. Cole, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)

Subjects
chemistry.chemical_classification, Collision-induced dissociation, POLE 3, 010401 analytical chemistry, Glycosidic bond, 010402 general chemistry, Photochemistry, Mass spectrometry, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, chemistry.chemical_compound, Reaction rate constant, chemistry, Fragmentation (mass spectrometry), Lithium chloride, [CHIM]Chemical Sciences, Dissolution, CSOB, Spectroscopy
Abstract

The dissolution mechanism of oligosaccharides in N,N-dimethylacetamide/lithium chloride (DMAc/LiCl), a solvent used for cellulose dissolution, and the capabilities of low-energy collision-induced dissociation (low-energy CID), collision-induced dissociation (CID), and higher energy collision dissociation (HCD) for structural analysis of carbohydrates were investigated. Comparing the spectra obtained using 3 techniques shows that, generally, when working with monolithiated sugars, CID spectra provide more structurally informative fragments, and glycosidic bond cleavage is the main pathway. However, when working with dilithiated sugars, HCD spectra can be more informative providing predominately cross-ring cleavage fragments. This is because HCD is a nonresonant activation technique, and it allows a higher amount of energy to be deposited in a short time, giving access to more endothermic decomposition pathways as well as consecutive fragmentations. The difference in preferred dissociation pathways of monolithiated and dilithiated sugars indicates that the presence of the second lithium strongly influences the relative rate constants for cross-ring cleavages vs glycosidic bond cleavages, and disfavors the latter. Regarding the dissolution mechanism of sugars in DMAc/LiCl, CID and HCD experiments on dilithiated and trilithiated sugars reveal that intensities of product ions containing 2 Li+ or 3 Li+ , respectively, are higher than those bearing only 1 Li+ . In addition, comparing the fragmentation spectra (both HCD and CID) of LiCl-adducted lithiated sugar and NaCl-adducted sodiated sugar shows that while, in the latter case, loss of NaCl is dominant, in the former case, loss of HCl occurs preferentially. The compiled evidence implies that there is a strong and direct interaction between lithium and the saccharide during the dissolution process in the DMAc/LiCl solvent system.

Published
2018

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

Author

Sukanya Pandeti, Jean-Claude Tabet, Jagadeshwar Reddy Thota, Naga Veera Yerra, Pavankumar Pallerla, CSIR Indian Institute of Chemical Technology [Hyderabad] (IICT), Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Spectrometry, Mass, Electrospray Ionization, POLE 3, Endothelin A Receptor Antagonists, Electrospray ionization, Pharmaceutical formulation, Tandem mass spectrometry, Mass spectrometry, 01 natural sciences, Analytical Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Hydrolysis, 0302 clinical medicine, Drug Stability, Liquid chromatography–mass spectrometry, Tandem Mass Spectrometry, Ammonium formate, [CHIM]Chemical Sciences, Spectroscopy, Chromatography, High Pressure Liquid, Sulfonamides, Chromatography, Photolysis, 010401 analytical chemistry, Organic Chemistry, 0104 chemical sciences, Endothelin B Receptor Antagonists, Pyrimidines, 030228 respiratory system, chemistry, Degradation (geology), Oxidation-Reduction, CSOB
Abstract

Rationale Stress testing of a drug candidate is an important step in the drug discovery and development process. The presence of degradation products in a drug affects the quality as well as the safety and efficacy of drug formulation. Hence, it is essential to develop an efficient analytical method which could be useful for the separation, identification and characterization of all possible degradation products (DPs) of a drug. Macitentan (MT) is an endothelin receptor antagonist (ERA) drug used to treat high blood pressure in the lungs. Comprehensive stress testing of MT was carried out as per ICH guidelines to understand the degradation profile of the drug. Methods MT was subjected to various stress conditions such as acidic, basic, neutral hydrolysis, oxidation, photolysis and thermal conditions; and the resulting degradation products were investigated using liquid chromatography/diode-array detection/electrospray ionization high-resolution mass spectrometry (LC/DAD/ESI-HRMS) and tandem mass spectrometry (MS/MS) techniques. An efficient and simple ultra-high-performance liquid chromatography (UHPLC) method has been developed using an Accucore C18 column (4.6 × 150 mm, 2.6 μm) using a gradient elution of 5 mM ammonium formate and acetonitrile as mobile phases. Results MT was found to degrade under acid and base hydrolysis stress conditions; whereas it was stable under oxidation, neutral hydrolysis, thermal and photolytic conditions. MT formed nine DPs (DP1 to DP9) and one DP (DP10) under acidic and basic hydrolytic conditions, respectively. All the degradation products (DP1 to DP10) were identified and characterized by LC/MS/MS in positive ion mode with accurate mass measurements. Conclusions MT was found to be labile under hydrolytic conditions. The structures of the DPs were characterized by appropriate mechanisms. The proposed method can be effectively used for the characterization of MT and its DPs.

Published
2018

28. 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

29. 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

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

Author

Sandra Alves, Jean-Claude Tabet, Bessem Brahim, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)

Subjects
Spectrometry, Mass, Electrospray Ionization, POLE 3, Stereochemistry, Electrospray ionization, Peptide, 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), Ion, chemistry.chemical_compound, Fragmentation (mass spectrometry), Physics::Atomic and Molecular Clusters, [CHIM]Chemical Sciences, Binding site, Nuclear Experiment, Spectroscopy, chemistry.chemical_classification, Ions, Quantitative Biology::Biomolecules, Binding Sites, 010401 analytical chemistry, General Medicine, DNA, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, chemistry, Peptides, CSOB, Single strand
Abstract

Gas-phase fragmentation of single strand DNA-peptide noncovalent complexes is investigated in positive and negative electrospray ionization modes.Collision-induced dissociation experiments, performed on the positively charged noncovalent complex precursor ions, have confirmed the trend previously observed in negative ion mode, i.e. a high stability of noncovalent complexes containing very basic peptidic residues (i.e. R K) and acidic nucleotide units (i.e. Thy units), certainly incoming from the existence of salt bridge interactions. Independent of the ion polarity, stable noncovalent complex precursor ions were found to dissociate preferentially through covalent bond cleavages of the partners without disrupting noncovalent interactions. The resulting DNA fragment ions were found to be still noncovalently linked to the peptides. Additionally, the losses of an internal nucleic fragment producing "three-body" noncovalent fragment ions were also observed in both ion polarities, demonstrating the spectacular salt bridge interaction stability. The identical fragmentation patterns (regardless of the relative fragment ion abundances) observed in both polarities have shown a common location of salt bridge interaction certainly preserved from solution. Nonetheless, most abundant noncovalent fragment ions (and particularly three-body ones) are observed from positively charged noncovalent complexes. Therefore, we assume that, independent of the preexisting salt bridge interaction and zwitterion structures, multiple covalent bond cleavages from single-stranded DNA/peptide complexes rely on an excess of positive charges in both electrospray ionization ion polarities.

Published
2017

31. A study of procyanidin binding to Histatin 5 using Electrospray Ionization Tandem Mass Spectrometry (ESI-MS/MS) and molecular simulations

Author

Nalaka S. Rannulu, Joshua Shraberg, Richard B. Cole, Steven W. Rick, 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
Spectrometry, Mass, Electrospray Ionization, Electrospray ionization, Molecular Sequence Data, General Physics and Astronomy, Peptide, Histatins, Tandem mass spectrometry, Mass spectrometry, Antioxidants, Catechin, chemistry.chemical_compound, Tandem Mass Spectrometry, Biflavonoids, Humans, [CHIM]Chemical Sciences, Proanthocyanidins, Amino Acid Sequence, Physical and Theoretical Chemistry, Saliva, Procyanidin B1, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Chromatography, Molecular Docking Simulation, chemistry, Docking (molecular), Histatin, Ion cyclotron resonance
Abstract

Tannins act as antioxidants, anticarcinogens, cardio-protectants, anti-inflammatory and anti-microbial agents and bind to salivary peptides by hydrophilic and hydrophobic mechanisms. Electrospray Ionization Mass Spectrometry (ESI-MS) has been used to assess both hydrophilic and hydrophobic components of noncovalent binding in protein complexes. In the present study, direct infusion Electrospray-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ES-FTICR MS) is used to assess relative binding affinities of procyanidin tannin stereoisomers for salivary peptides arising from aqueous solutions. The condensed tannins procyanidin B1, B2, B3, and B4 demonstrate significantly different binding affinities for the salivary peptide Histatin 5. Rigid docking combined with molecular dynamics optimization is used to investigate procyanidin-Histatin 5 binding mechanisms and as a basis to rationalize trends found in the corresponding ES-FTICR MS experiments. The relative binding affinities of the four procyanidin rotamers are different in the gas and liquid phases. The simulation results indicate that many of the same contact points are made in both phases, but there is a increase in strong electrostatic interactions and an decrease in π-π contacts upon transfer from the liquid to the gas phase. The simulations reveal that the tannin interactions can make close contacts with a variety of amino acid residues on the peptide.

Published
2015

32. New insights into dissociation of deprotonated 2,4-dinitrotoluene by combined high-resolution mass spectrometry and density functional theory calculations

Author

Adrian Schwarzenberg, Xavier Machuron-Mandard, Jean-Claude Tabet, Richard B. Cole, Héloïse Dossmann, 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 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), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie 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), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Electrospray ionization, Organic Chemistry, Analytical chemistry, Mass spectrometry, Analytical Chemistry, Ion, Deprotonation, Fragmentation (mass spectrometry), Quadrupole, [CHIM]Chemical Sciences, Density functional theory, Quadrupole ion trap, ComputingMilieux_MISCELLANEOUS, Spectroscopy
Abstract

RATIONALE 2,4-Dinitrotoluene (2,4-DNT) is a nitroaromatic explosive which is commonly found in environmental samples close to training points, firing places, and manufacturers. Mass spectrometry analysis of this compound shows one main product ion that distinguishes it from the other isomers of DNT. We present here a detailed mechanistic study on the formation of this ion. METHODS 2,4-DNT was analyzed using negative electrospray ionization high-resolution mass spectrometry (ESI-HRMS) using a linear ion trap quadrupole LTQ-Orbitrap XL mass spectrometer. Collision-induced dissociation (CID) experiments were performed on the [M–H]– ion obtained. Density functional theory (DFT) calculations were used to support experimental observations. RESULTS Fragmentation of deprotonated 2,4-DNT [M–H]– (m/z 181) yields a main product ion at m/z 116. The mechanism of formation of this diagnostic product ion is not obvious and it has never been rationalized. Calculations were performed to probe different mechanistic variants, which are discussed in this work. CONCLUSIONS Analysis of possible pathways to form the m/z 116 ion from the m/z 181 precursor shows that its formation is likely to proceed first via NO• loss, followed by eliminations of H2O and then HO•. Copyright © 2014 John Wiley & Sons, Ltd.

Published
2014

33. 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

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

Author

Christophe Junot, Mylène Marie, Fanny Leroux, Jérôme Cotton, Céline Ducruix, Jean-Claude Tabet, Bruno Corman, Simon Broudin, Profilomic [Boulogne-Billancourt], Profilomic, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay

Subjects
Metabolite, Food Contamination, Mass spectrometry, computer.software_genre, 01 natural sciences, Mass Spectrometry, 03 medical and health sciences, chemistry.chemical_compound, Metabolomics, Data Mining, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, Pollutant, 0303 health sciences, Chromatography, 010401 analytical chemistry, food and beverages, Honey, General Chemistry, Pesticide, Honey samples, Food Analysis, 0104 chemical sciences, chemistry, 13. Climate action, Environmental chemistry, Data mining, General Agricultural and Biological Sciences, Xenobiotic, computer, Chromatography, Liquid
Abstract

Analytical methods for food control are mainly focused on restricted lists of well-known contaminants. This paper shows that liquid chromatography-high-resolution mass spectrometry (LC/ESI-HRMS) associated with the data mining tools developed for metabolomics can address this issue by enabling (i) targeted analyses of pollutants, (ii) detection of untargeted and unknown xenobiotics, and (iii) detection of metabolites useful for the characterization of food matrices. A proof-of-concept study was performed on 76 honey samples. Targeted analysis indicated that 35 of 83 targeted molecules were detected in the 76 honey samples at concentrations below regulatory limits. Furthermore, untargeted metabolomic-like analyses highlighted 12 chlorinated xenobiotics, 1 of which was detected in lavender honey samples and identified as 2,6-dichlorobenzamide, a metabolite of dichlobenil, a pesticide banned in France since 2010. Lastly, multivariate statistical analyses discriminated honey samples according to their floral origin, and six discriminating metabolites were characterized thanks to the MS/MS experiments.

Published
2014

35. 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

36. 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

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

Author

Jean-Claude Tabet, Ekaterina Darii, Yves Gimbert, Alain Perret, Sandra Alves, Génomique métabolique (UMR 8030), Genoscope - Centre national de séquençage [Evry] (GENOSCOPE), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de Génotypage (CNG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Models, Molecular, Spectrometry, Mass, Electrospray Ionization, Clinical Biochemistry, Ionic bonding, Glucose-6-Phosphate, Protonation, 010402 general chemistry, Arginine, 01 natural sciences, Biochemistry, Dissociation (chemistry), Analytical Chemistry, chemistry.chemical_compound, Deprotonation, Isomerism, Tandem Mass Spectrometry, [CHIM]Chemical Sciences, Guanidine, ComputingMilieux_MISCELLANEOUS, Chromatography, Hydrogen bond, 010401 analytical chemistry, Fructosephosphates, Glucosephosphates, Hydrogen Bonding, Cell Biology, General Medicine, 0104 chemical sciences, chemistry, Covalent bond, Zwitterion, Thermodynamics
Abstract

Non-covalent complexes (NCC) between hexose monophosphates (HexP) and arginine (R) were analyzed using ESI MS and MS/MS in negative mode under different (hard, HC and soft, SC) desolvation conditions. High resolution mass spectrometry (HRMS) revealed the presence of different ionic species, namely, homo- and heteromultimers of R and HexP. Deprotonated heterodimers and corresponding sodiated species were enhanced under HC likely due to a decrease in available charge number associated with the reduction of H + /Na + exchange. The quantum calculations showed that the formation of covalent systems is very little exothermic, therefore, such systems are disfavored. Desolvation dependent CID spectra of deprotonated [(HexP+R)‒H] − complexes demonstrated that they can exist within the hydrogen bond (HB) and salt bridge (SB) forms, yielding either NCC separation or covalent bond cleavages, respectively. Although HB forms are the main species, they cannot survive under HC; therefore, the minor SB forms became detectable. Energy-resolved mass spectrometry (ERMS) experiments revealed diagnostic fragment ions from both SB and HB forms, providing evidence that these isomeric forms are inconvertible. SB formation should result from the ionic interactions of highly acidic group of HexP with strongly basic guanidine group of arginine and thus requires an arginine zwitterion (ZW) form. This was confirmed by quantum calculations. Ion-ion interactions are significantly affected by the presence of sodium cation as demonstrated by the fragmentation patterns of sodiated complex species. Regarding CID data, only SB between protonated amino group of R and deprotonated phosphate group of HexP could be suggested, but the primary amine is not enough basic then, the SB must be fleeting. Nevertheless, the observation of the covalent bond cleavages suggests the presence of structures with a free negative charge able to induce fragmentations. Indeed, according to quantum calculations, solvated salt (SS) systems involving Na + /COO − salt solvated by neutral phosphate and negative charge on sugar ring are preferentially formed.

Published
2017

38. 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

39. The Background to Electrospray

Author

Richard B. Cole, Bing Guan, University of New Orleans, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Electrospray, History, POLE 3, William Henley, 02 engineering and technology, Jean-Antoine Nollet, Malcolm Dole, William Gilbert, Lord Kelvin, 01 natural sciences, Lord Rayleigh, William Thomson, 0103 physical sciences, Mass analyzer, Geoffrey Taylor, Harold Ransburg, [CHIM]Chemical Sciences, 010306 general physics, Literature, John Ellicott, business.industry, Environmental ethics, W. A. Macky, 021001 nanoscience & nanotechnology, Sir Thomas Browne, John Zeleny, Electrospray history, Electrostatic attraction, Electrospray development, Stephen Gray, John William Strutt, 0210 nano-technology, business, CSOB
Abstract

International audience; This article traces the development of electrospray back to its earliest beginnings. Many readers may be surprised to learn that descriptions of the electrostatic attraction of liquids to surfaces appear in the scientific literature as early as the year 1600, and that true electrospray experiments are documented to have been performed in the eighteenth century. Progress in the development of electrospray is detailed through these earliest observations and subsequent ingenious applications, mathematical descriptions, and, finally, coupling to mass analyzer instrumentation.

Published
2016

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

Author

Richard B. Cole, Jean E. Boulicault, Sandra Alves, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
POLE 3, Chemistry, 010401 analytical chemistry, Cationic polymerization, Analytical chemistry, 010402 general chemistry, Mass spectrometry, 01 natural sciences, 0104 chemical sciences, Adduct, Ion, Crystallography, Electron transfer, Fragmentation (mass spectrometry), Structural Biology, Mass spectrum, [CHIM]Chemical Sciences, Sample preparation, CSOB, Spectroscopy
Abstract

MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe(3+) > Al(3+) > Li(+) > Ga(3+) > Co(2+) > Cr(3+) > Cu(2+) > [Mn(2+), Mg(2+)] > [Na(+), K(+)]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion. Graphical Abstract ᅟ.

Published
2016

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

Author

Uwe Linne, Mohamed A. Marahiel, Jean-Claude Tabet, Richard B. Cole, Carlos Afonso, Marie Pérot-Taillandier, Sylvie Rebuffat, Séverine Zirah, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Molécules de Communication et Adaptation des Micro-organismes (MCAM), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Philipps Universität Marburg, Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Histoire naturelle de l'Homme préhistorique (HNHP), Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Université de Perpignan Via Domitia (UPVD), Fachbereich Chemie der Philipps-Universität Marburg (WZMW), Philipps Universität Marbug, Department of chemistry, University of Marburg, Laboratoire de Chimie Structurale Organique et Biologique, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Philipps Universität Marburg = Philipps University of Marburg, Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Muséum national d'Histoire naturelle (MNHN)-Université de Perpignan Via Domitia (UPVD)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Spectrometry, Mass, Electrospray Ionization, Topoisomer, Electrospray, Protein Conformation, Analytical chemistry, Electrons, Peptide, 010402 general chemistry, Mass spectrometry, Vibration, 01 natural sciences, Analytical Chemistry, Ion, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Tandem Mass Spectrometry, Computational chemistry, Spectroscopy, Fourier Transform Infrared, Ions, chemistry.chemical_classification, Quantitative Biology::Biomolecules, Electron-capture dissociation, Chemistry, 010401 analytical chemistry, Stereoisomerism, Cyclotrons, Resonance (chemistry), 0104 chemical sciences, Gases, Protons, Peptides, Ion cyclotron resonance
Abstract

International audience; Characterizing the conformation of biomolecules by mass spectrometry still represents a challenge. With their knotted structure involving a N-terminal macrolactam ring where the C-terminal tail of the peptide is threaded and sterically trapped, lasso peptides constitute an attractive model for developing methods for characterizing gas-phase conformation, through comparison with their unknotted topoisomers. Here, the kinetics of electron capture dissociation (ECD) of a lasso peptide, capistruin, was investigated by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry and compared to that of its branched-cyclic topoisomer, lactam-capistruin. Both peptides produced rather similar ECD spectra but showed different extent of H(*) transfer from c(i)' to z(j)(*) ions. Time-resolved double-resonance experiments under ECD conditions were performed to measure the formation rate constants of typical product ions. Such experiments showed that certain product ions, in particular those related to H(*) transfer, proceeded through long-lived complexes for capistruin, while fast dissociation processes predominated for lactam-capistruin. The formation rate constants of specific ECD product ions enabled a clear differentiation of the lasso and branched-cyclic topoisomers. These results indicate that the formation kinetics of ECD product ions constitute a new way to explore the conformation of biomolecules and distinguish between topoisomers and, more generally, conformers.

Published
2012

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

Author

Mayreli Ortiz, Richard B. Cole, Ahmed M. Debela, Bernold Hasenknopf, Serge Thorimbert, Denis Lesage, Valerio Beni, Ciara K. O'Sullivan, Glycochimie Organique Biologique et Supramoléculaire (GOBS), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Laboratoire de Synthèse Organique et Organométallique (UMR CNRS 7201), Université Pierre et Marie Curie - Paris 6 (UPMC), Chimie Structurale Organique et Biologique (CSOB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[SDV]Life Sciences [q-bio], 010402 general chemistry, 01 natural sciences, Polymerase Chain Reaction, Catalysis, law.invention, Nucleic acid thermodynamics, chemistry.chemical_compound, Polymerase chain reaction optimization, law, Primer dimer, Multiplex polymerase chain reaction, Electrochemistry, Organic chemistry, [CHIM]Chemical Sciences, Polymerase chain reaction, ComputingMilieux_MISCELLANEOUS, DNA Primers, 010405 organic chemistry, Chemistry, Organic Chemistry, Nucleic Acid Hybridization, General Chemistry, DNA, Tungsten Compounds, Combinatorial chemistry, 0104 chemical sciences, Real-time polymerase chain reaction, Primer (molecular biology)
Abstract

The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11 O39 {Sn(CH2 )2 CO}](8-) and [P2 W17 O61 {Sn(CH2 )2 CO}](6-) have been used to link to a 5'-NH2 terminated 21-mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM-labeled primers was demonstrated through hybridization with a surface-immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.

Published
2015

43. 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

44. 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

45. 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

46. 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

47. Direct introduction Fourier transform mass spectrometry (FTMS) for metabolomic fingerprint

Author

Habchi, Baninia, Alves, Sandra, Paris, Alain, Lécluse, Yannick, Gauduchon, Pascal, Lebailly, Pierre, Rutledge, Douglas, Rathahao, Estelle, Ingénierie, Procédés, Aliments (GENIAL), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, 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), Molécules de Communication et Adaptation des Micro-Organismes (MCAM), Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université de Caen Normandie (UNICAEN), Normandie Université (NU), 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), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and 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)

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

Direct introduction Fourier transform mass spectrometry (FTMS) for metabolomic fingerprint. XX. Rencontres du Club Jeune de la Société Française de Spectrométrie de Masse

Published
2015

48. Development and validation of an isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry method for the reliable quantification of 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) and 14 other explosives and their degradation products in environmental water samples

Author

Daniel Léonço, Maxime C. Bridoux, Cécile Hubert, Jean-Claude Tabet, 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), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National de l'Environnement Industriel et des Risques (INERIS), Synthèse, Structure et Fonction de Molécules Bioactives (SSFMB), and Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Detection limit, Chromatography, Aqueous solution, Collision-induced dissociation, Chemistry, Analytical chemistry, Isotope dilution, Mass spectrometry, Analytical Chemistry, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Liquid chromatography–mass spectrometry, TATB, Mass spectrum, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

A comprehensive method for the determination and characterization of 15 common explosive compounds in water samples by ultra-high pressure liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (APCI-MS/MS) is presented. The method allows the determination of 10 nitroaromatics, two nitroamines and three nitrate ester compounds. Among these, 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) was quantified and detected for the first time in our knowledge at trace levels (0.2 µg/L). Furthermore, the collision induced dissociation (CID) mass spectrum of TATB is discussed and a fragmentation mechanism is proposed. The signal for each explosive was normalized by isotopically-enriched congeners used as internal standards. The limits of detection (LOD) reached 20 ng/L, depending on the type of energetic molecule, which are adequate for water samples and the linearity was verified from 1.4 to 2 orders of magnitude. The sensitivity of the UHPLC-APCI-MS/MS approach allows direct injection of aqueous samples without preceding extraction for concentration. Besides, the method displays a good reliability with low signal suppression in various matrices such as spring water, mineral water, acidified water or ground water. The effectiveness of the method is demonstrated by the analysis of underground water samples containing traces of explosives from test fields in France.

Published
2015

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

Author

Aleksandar Lolić, C. Charvy, Sandra Alves, Jean-Claude Tabet, Tatjana Tripkovic, Rada Baošić, Snežana D. Nikolić-Mandić, Chimie Structurale Organique et Biologique (CSOB), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), University of Belgrade [Belgrade], and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Bovine collagen, Electrospray ionization, Analytical chemistry, Tempera, 010402 general chemistry, Orbitrap, Mass spectrometry, Tandem mass spectrometry, 01 natural sciences, Orthodox icons, law.invention, law, Ionization, MALDI-TOF MS/MS, [CHIM]Chemical Sciences, Spectroscopy, proteinaceous binders, ComputingMilieux_MISCELLANEOUS, Chromatography, Chemistry, 010401 analytical chemistry, General Medicine, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, ESI-LTQ-Orbitrap, egg tempera, visual_art, Quadrupole, visual_art.visual_art_medium
Abstract

Proteomic approach in combination with mass spectrometry demonstrates a great potential for identification of proteinaceous materials in works of art. In this study we used a linear trap quadrupole Orbitrap (LTQ-Orbitrap), a state-of-the-art mass spectrometer for parts per million accuracy analyses of peptides behind tryptic hydrolysis. After the efficiency of the proteomic method was confirmed for reference and model samples, micro-samples from historical paintings were for the first time analysed using this technique. Superior performances of the liquid chromatography–mass spectrometry approach using a LTQ-Orbitrap mass spectrometer allowed identification of egg yolk peptides in two samples from nineteenth-century Orthodox icons, indicating egg tempera as the painting technique. Accurate precursor ion masses, in the range of ±2 ppm, and retention times of tryptic peptides strengthen protein identification. Additionally, in all historical samples the presence of animal glues suggested that the ground layer was likely bound using bovine collagen. Comparing to results acquired using matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry in our previous study, here we achieved higher ion scores and protein scores, better sequence coverage and more identified proteins. In fact, a combination of the two mass spectrometric techniques provided overlapping and complementary data, related to the detection of peptides with different physicochemical properties.

Published
2015

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

Author

Schwarzenberg, Adrián, Dossmann, Héloïse, Cole, Richard B., Machuron‐Mandard, Xavier, Tabet, Jean-Claude, 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), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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
[CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences
Abstract

International audience; 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-MS(n) ) 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 MS(n) 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 CH2 O 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, CH2 O 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

Published
2014

Catalog

Books, media, physical & digital resources
See catalog results