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Publications

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2020



  • P. Bayat, D. Lesage, et R. B. Cole, « Tutorial: Ion activation in tandem Mass spectrometry using ultra-high resolition spectroscopy », Mass Spectrometry Reviews, p. mas.21623, févr. 2020.


  • C. Tugny, N. del Rio, M. Koohgard, N. Vanthuyne, D. Lesage, K. Bijouard, P. Zhang, J. Meijide Suárez, S. Roland, E. Derat, O. Bistri-Aslanoff, M. Sollogoub, L. Fensterbank, et V. Mouriès-Mansuy, « β-Cyclodextrin–NHC–Gold(I) Complex (β-ICyD)AuCl: A Chiral Nanoreactor for Enantioselective and Substrate-Selective Alkoxycyclization Reactions », ACS Catalysis, vol. 10, nᵒ 11, p. 5964-5972, juin 2020.
    Résumé : 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.
    Mots-clés : CSOB, GOBS, MACO, POLE 1, POLE 3.
    Pièce jointe Full Text PDF 2.2 Mo (source)


  • Z. Wang, D. Landy, C. Sizun, C. Cézard, A. Solgadi, C. Przybylski, L. de Chaisemartin, L. Herfindal, G. Barratt, et F. - X. Legrand, « Cyclodextrin complexation studies as the first step for repurposing of chlorpromazine », International Journal of Pharmaceutics, vol. 584, p. 119391, 2020.

2019



  • U. Alali, A. Vallin, A. Bil, T. Khanchouche, D. Mathiron, C. Przybylski, R. Beaulieu, J. Kovensky, M. Benazza, et V. Bonnet, « The uncommon strong inhibition of α-glucosidase by multivalent glycoclusters based on cyclodextrin scaffolds », Organic & Biomolecular Chemistry, vol. 17, nᵒ 30, p. 7228-7237, 2019.
    Résumé : 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 (30–90%) by silica gel chromatography. The results showed inhibition of α-glucosidase from Saccharomyces cerevisiae with IC 50 values in the 32–132 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.
    Mots-clés : CSOB, POLE 3.


  • P. Bayat, D. Gatineau, D. Lesage, S. Marhabaie, A. Martinez, et R. B. Cole, « Investigation of activation energies for dissociation of host-guest complexes in the gas phase using low-energy collision induced dissociation », Journal of Mass Spectrometry, vol. 54, nᵒ 5, p. 437-448, 2019.


  • M. Cassé, C. Nisole, H. Dossmann, Y. Gimbert, J. - M. Fourquez, L. Haberkorn, C. Ollivier, et L. Fensterbank, « Trifluoromethyl radical triggered radical cyclization of <italic>N</italic>-benzoyl ynamides leading to isoindolinones », SCIENCE CHINA Chemistry, vol. 62, nᵒ 11, p. 1542-1546, oct. 2019.
    Résumé : Under photocatalytic reductive conditions, trifluoromethyl radical addition onto an ynamide followed by cyclization on a benzoyl moiety produces diverse isoindolinone platforms with good yields. The selectivity of the radical cyclization, <italic>N</italic>-benzoyl vs. <italic>N</italic>-benzyl as radical acceptor and the <italic>E</italic>/<italic>Z</italic> ratio of isomers have been rationalized by modeling.
    Mots-clés : CSOB, MACO, POLE 1, POLE 3.
    Pièce jointe Full Text PDF 1.6 Mo (source)


  • B. Colsch, A. Damont, C. Junot, F. Fenaille, et J. - C. Tabet, « Experimental evidence that electrospray-produced sodiated lysophosphatidyl ester structures exist essentially as protonated salts », European Journal of Mass Spectrometry, vol. 25, nᵒ 3, p. 333-338, 2019.


  • A. Damont, M. - F. Olivier, A. Warnet, B. Lyan, E. Pujos-Guillot, E. L. Jamin, L. Debrauwer, S. Bernillon, C. Junot, J. - C. Tabet, et F. Fenaille, « Proposal for a chemically consistent way to annotate ions arising from the analysis of reference compounds under ESI conditions: A prerequisite to proper mass spectral database constitution in metabolomics », Journal of Mass Spectrometry, vol. 54, nᵒ 6, p. 567-582, 2019.


  • G. Gaiffe, R. B. Cole, A. Sonnette, N. Floch, et M. C. Bridoux, « Identification of Postblast Residues by DART-High Resolution Mass Spectrometry Combined with Multivariate Statistical Analysis of the Kendrick Mass Defect », Analytical Chemistry, vol. 91, nᵒ 13, p. 8093-8100, juill. 2019.


  • M. Girardi, D. Platzer, S. Griveau, F. Bedioui, S. Alves, A. Proust, et S. Blanchard, « Assessing the Electrocatalytic Properties of the Cp*RhIII2+-Polyoxometalate Derivative [H2PW11O39RhIIICp*(OH2)]3– towards CO2 Reduction », European Journal of Inorganic Chemistry, vol. 2019, nᵒ 3-4, p. 387-393, 2019.
    Résumé : Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high activation energy barrier. Of molecular catalysts, metal complexes with polypyridyl ligands are well represented, among which the [Cp*Rh(bpy)Cl]+ and [M(bpy)(CO)3X] (M = Re, Mn) complexes. As redox non-innocent ligand, the bipyridine ligand is generally involved in the reduction mechanisms. It is thus tempting to replace it by other redox non-innocent ligands such as vacant polyoxometalates (POMs). We have thus prepared [α-H2PW11O39RhIIICp*(OH2)]3– which is closely related to [Cp*RhIII(bpy)Cl]+ by substitution of the monovacant [PW11O39]7– Keggin-type POM for the bipyridine ligand. Its activity towards CO2 reduction has been assessed in acetonitrile in the presence of water. Compared to [Cp*Rh(bpy)Cl]+ that produces formate selectively over CO and H2, the POM derived catalyst favors proton reduction over CO2 reduction.
    Mots-clés : Carbon dioxide fixation, CSOB, E-POM, Non-innocent ligands, POLE 2, POLE 3, Polyoxometalates, Redox chemistry.
    Pièce jointe Full Text PDF 974.1 ko (source)


  • T. Hautbergue, E. L. Jamin, R. Costantino, S. Tadrist, L. Meneghetti, J. - C. Tabet, L. Debrauwer, I. P. Oswald, et O. Puel, « Combination of Isotope Labeling and Molecular Networking of Tandem Mass Spectrometry Data To Reveal 69 Unknown Metabolites Produced by <i>Penicillium nordicum</i> », Analytical Chemistry, vol. 91, nᵒ 19, p. 12191-12202, 2019.


  • E. L. Jamin, C. Jacques, L. Jourdes, J. - C. Tabet, N. Borotra, S. Bessou-Touya, L. Debrauwer, et H. Duplan, « Identification of lipids of the stratum corneum by high performance thin layer chromatography and mass spectrometry », European Journal of Mass Spectrometry, vol. 25, nᵒ 3, p. 278-290, 2019.


  • C. M. Kronfel, C. V. Hernandez, J. P. Frick, L. S. Hernandez, A. Gutu, J. A. Karty, M. N. Boutaghou, D. M. Kehoe, R. B. Cole, et W. M. Schluchter, « CpeF is the bilin lyase that ligates the doubly linked phycoerythrobilin on β-phycoerythrin in the cyanobacterium <i>Fremyella diplosiphon</i> », Journal of Biological Chemistry, p. jbc.RA118.007221, janv. 2019.


  • D. Lesage, S. Mezzache, Y. Gimbert, H. Dossmann, et J. - C. Tabet, « Extended kinetic method and RRKM modeling to reinvestigate proline’s proton affinity and approach the meaning of effective temperature », European Journal of Mass Spectrometry, p. 146906671882205, janv. 2019.


  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, et J. M. García Fernández, « Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions », Frontiers in Chemistry, vol. 7, p. 72, 2019.
    Résumé : The presence of a doubly-linked naphthylene clip at the O-2I and O-3II positions in the secondary ring of -cyclodextrin (CD) derivatives promoted their self-assembly into head-to-head supramolecular dimers in which the aromatic modules act either as cavity extension walls (if the naphthalene moiety is 1,8-disubstituted) or as folding screens that separate the individual CD units (if 2,3-disubstituted). Dimer architecture is governed by the conformational properties of the monomer constituents, as determined by NMR, fluorescence, circular dichroism and computational techniques. In a second supramolecular organization level, the topology of the assembly directs host-guest interactions and, reciprocally, guest inclusion impacts the stability of the supramolecular edifice. Thus, inclusion of adamantane carboxylate, a well-known CD cavity-fitting guest, was found to either preserve the dimeric arrangement, leading to multicomponent species, or elicit dimer disruption. The ensemble of results highlights the potential of the approach to program self-organization and external stimuli responsiveness of CD devices in a controlled manner while keeping full diastereomeric purity.
    Mots-clés : CSOB, POLE 3.


  • C. Przybylski, V. Bonnet, et R. R. Vivès, « A microscale double labelling of GAG oligosaccharides compatible with enzymatic treatment and mass spectrometry », Chemical Communications, vol. 55, nᵒ 29, p. 4182-4185, 2019.


  • C. Przybylski, H. Ramoul, V. Bonnet, M. Abad, et N. Jarroux, « Harnessing Polyisobutylene by Rotaxanation with γ-Cyclodextrin: Opportunities for Making Smart Molecular Necklaces », Macromolecular Chemistry and Physics, vol. 220, nᵒ 5, p. 1800502, mars 2019.
    Résumé : Abstract A new type of polyrotaxane based on the threading of ?-cyclodextrins (?-CDs) along a highly hydrophobic polymer, polyisobutylene (PIB), is successfully prepared and finely characterized. The used radical coupling associated with tuned reaction time and temperature leads to a fast and controlled necklace synthesis with low reagent consumption. Synthesis exhibits appealing conversion and threading rates with almost 100% and 62?73%, respectively. A combination of well-established SEC and NMR techniques, with a more forefront MALDI-TOF MS approach, provides details on the original PIB and the resulting polyrotaxanes (M w, M n, PDI, and average number of ?-CD threaded). Interestingly, tetramethylguanidinium-2-(4-hydroxyphenylazo)benzoate in DMF for MALDI analysis is revealed as a suitable matrix to overcome solubility troubles widely observed with PIB. Moreover, rotaxanation appears as an alternative to the grafting of polar groups to modify/handle hydrophobic polymers. Such an approach offers new opportunities to achieve the synthesis, with unambiguous evidence, of new supramolecular necklaces based on highly hydrophobic polymers.
    Mots-clés : CSOB, cyclodextrins, mass spectrometry, POLE 3, polyisobutylene, polyrotaxane, radical coupling.
    Note Note
    <p>doi: 10.1002/macp.201800502</p>


  • I. Seffouh, C. Przybylski, A. Seffouh, R. El Masri, R. R. Vivès, F. Gonnet, et R. Daniel, « Mass spectrometry analysis of the human endosulfatase Hsulf-2 », Biochemistry and Biophysics Reports, vol. 18, p. 100617, 2019.
    Résumé : The human 6-O-endosulfatases HSulf-1 and -2 catalyze the region-selective hydrolysis of the 6-O-sulfate group of the glucosamine residues within sulfated domains of heparan sulfate, thereby ensuring a unique and original post-biosynthetic modification of the cell surface proteoglycans. While numerous studies point out the role of HSulf-2 in crucial physiological processes as well as in pathological conditions particularly in cancer, its structural organization in two chains and its functional properties remain poorly understood. In this study, we report the first characterization by mass spectrometry (MS) of HSulf-2. An average molecular weight of 133,115 Da was determined for the whole enzyme by MALDI-TOF MS, i.e. higher than the naked amino acid backbone (98,170 Da), highlighting a significant contribution of post-translational modifications. The HSulf-2 protein sequence was determined by Nano-LC-MS/MS, leading to 63% coverage and indicating at least four N-glycosylation sites at Asn 108, 147, 174 and 217. These results provide a platform for further structural investigations of the HSulf enzymes, aiming at deciphering the role of each chain in the substrate binding and specificities and in the catalytic activities.
    Mots-clés : 6--Endosulfatase, CSOB, Formylglycine, Heparan sulfate, HSulf-2, Mass spectrometry, POLE 3, Sulfatase.


  • C. Sonnendecker, S. Thürmann, C. Przybylski, F. D. Zitzmann, N. Heinke, Y. Krauke, K. Monks, A. A. Robitzki, D. Belder, et W. Zimmermann, « Large‐Ring Cyclodextrins as Chiral Selectors for Enantiomeric Pharmaceuticals », Angewandte Chemie International Edition, 2019.


  • N. Stojiljkovic, F. Leroux, S. Bubanj, M. - A. Popot, A. Paris, J. - C. Tabet, et C. Junot, « Tracking main environmental factors masking a minor steroidal doping effect using metabolomic analysis of horse urine by liquid chromatography–high-resolution mass spectrometry », European Journal of Mass Spectrometry, vol. 25, nᵒ 3, p. 339-353, 2019.


  • J. - C. Tabet, « A 50-year career working and teaching in the fast-moving field of mass spectrometry research », European Journal of Mass Spectrometry, vol. 25, nᵒ 2, p. 195-201, 2019.


  • M. Thomas, L. Stuani, E. Darii, C. Lechaplais, E. Pateau, J. - C. Tabet, M. Salanoubat, P. - L. Saaidi, et A. Perret, « De novo structure determination of 3-((3-aminopropyl)amino)-4-hydroxybenzoic acid, a novel and abundant metabolite in Acinetobacter baylyi ADP1 », Metabolomics, vol. 15, nᵒ 3, p. 45, 2019.


  • Z. Xia, V. Corcé, F. Zhao, C. Przybylski, A. Espagne, L. Jullien, T. L. Saux, Y. Gimbert, H. Dossmann, V. Mouriès-Mansuy, C. Ollivier, et L. Fensterbank, « Photosensitized oxidative addition to gold( i ) enables alkynylative cyclization of o -alkylnylphenols with iodoalkynes », Nature Chemistry, vol. 11, nᵒ 9, p. 797-805, sept. 2019.
    Résumé : Studies into gold-catalysed cross-coupling reactions have expanded over recent decades; however, oxidative addition to gold(i) complexes remains challenging. Now it has been shown that a dual catalytic transformation involving iridium photosensitization to trigger oxidative addition to organogold intermediates enables C(sp2)–C(sp) cross-coupling reactions that are useful for the alkynylation of benzofurans.
    Mots-clés : CHEMBIO, CSOB, MACO, POLE 1, POLE 3.
    Pièce jointe Full Text PDF 1.8 Mo (source)

2018



  • L. Bacri, H. Mamad-Hemouch, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, et J. Pelta, « Biomimetic ion channels formation by emulsion based on chemically modified cyclodextrin nanotubes », Faraday Discussions, 2018.


  • P. Barbier Saint Hilaire, U. M. Hohenester, B. Colsch, J. - C. Tabet, C. Junot, et F. Fenaille, « Evaluation of the High-Field Orbitrap Fusion for Compound Annotation in Metabolomics », Analytical Chemistry, vol. 90, nᵒ 5, p. 3030-3035, mars 2018.


  • C. K. Barik, R. Ganguly, Y. Li, C. Przybylski, M. Salmain, et W. K. Leong, « Embedding a Ruthenium-Based Structural Mimic of the [Fe]-Hydrogenase Cofactor into Papain », Inorganic Chemistry, vol. 57, nᵒ 19, p. 12206-12212, sept. 2018.
    Mots-clés : CHEMBIO, CSOB, POLE 3.


  • P. Bayat, D. Gatineau, D. Lesage, V. Robert, A. Martinez, et R. B. Cole, « Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling », Journal of The American Society for Mass Spectrometry, nov. 2018.


  • P. Bayat, D. Lesage, et R. B. Cole, « 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 », Journal of Mass Spectrometry, vol. 53, nᵒ 8, p. 705-716, 2018.


  • F. A. Black, A. Jacquart, G. Toupalas, S. Alves, A. Proust, I. P. Clark, E. A. Gibson, et G. Izzet, « Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates », Chemical Science, vol. 9, nᵒ 25, p. 5578-5584, 2018.
    Mots-clés : CSOB, E-POM, POLE 2, POLE 3.


  • B. Brahim, J. - C. Tabet, et S. Alves, « Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of “three-body” noncovalent fragment ions », European Journal of Mass Spectrometry, vol. 24, nᵒ 1, p. 168-177, 2018.


  • de Jesús Cázares-Marinero José, Przybylski Cédric, et Salmain Michèle, « Proteins as Macromolecular Ligands for Metal-Catalysed Asymmetric Transfer Hydrogenation of Ketones in Aqueous Medium », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 12, p. 1383-1393, 2018.
    Résumé : Biohybrid catalysts resulting from the dative anchoring of half-sandwich organometallic complexes [M(arene)(H2O)x(Cl)y]n+ (M = RuII, arene = ?6-benzene, p-cymene or mesitylene; M = IrIII, RhIII, arene = ?5-Cp*; x = 1?3, y = 0?2, n = 0?2) to bovine beta-lactoglobulin (?LG) or hen egg white lysozyme showed unprecedented behaviour. These constructs were shown to catalyse the asymmetric transfer hydrogenation of aryl ketones in water with sodium formate as hydrogen donor at a much faster rate than the complexes alone. Full conversion of the benchmark substrate 2,2,2-trifluoroacetophenone was reached with an ee of 86?% for the most selective biohybrid. Surprisingly, even the crude biohybrid gave a good ee despite the presence of non-protein-bound metal species in the reaction medium. Other aryl ketones were reduced in the same way, and the highest ee was obtained for ortho-substituted acetophenone derivatives. Furthermore, treatment of ?LG with dimethyl pyrocarbonate resulted in a noticeable decrease of the activity and selectivity of the biohybrid, indicating that the sole accessible histidine residue (His146) was probably involved in the coordination and activation of Ru(benzene). This work underscores that protein scaffolds are efficient chiral ligands for asymmetric catalysis. The use of sodium formate instead of dihydrogen makes this approach safe, inexpensive and environmentally friendly.
    Mots-clés : Artificial metalloenzymes, Asymmetric catalysis, CHEMBIO, CSOB, Hydrogenation, Mass spectrometry, POLE 3, Ruthenium.
    Note Note
    <p>doi: 10.1002/ejic.201701359</p>


  • S. Douix, H. Dossmann, E. Nicol, D. Duflot, et A. Giuliani, « Spectroscopy and Photodissociation of the Perfluorooctanoate Anion », Chemistry - A European Journal, sept. 2018.


  • G. Gaiffe, M. C. Bridoux, C. Costanza, et R. B. Cole, « A systematic tandem mass spectrometric study of anion attachment for improved detection and acidity evaluation of nitrogen-rich energetic compounds », Journal of Mass Spectrometry, vol. 53, nᵒ 1, p. 21-29, 2018.


  • G. Gaiffe, R. B. Cole, S. Lacpatia, et M. C. Bridoux, « Characterization of Fluorinated Polymers by Atmospheric-Solid-Analysis-Probe High-Resolution Mass Spectrometry (ASAP/HRMS) Combined with Kendrick-Mass-Defect Analysis », Analytical Chemistry, vol. 90, nᵒ 10, p. 6035-6042, mai 2018.


  • D. Gatineau, D. Lesage, H. Clavier, H. Dossmann, C. H. Chan, A. Milet, A. Memboeuf, R. B. Cole, et Y. Gimbert, « Bond dissociation energies of carbonyl gold complexes: a new descriptor of ligand effects in gold( <span style="font-variant:small-caps;">i</span> ) complexes? », Dalton Transactions, vol. 47, nᵒ 43, p. 15497-15505, 2018.


  • B. Habchi, S. Alves, D. Jouan-Rimbaud Bouveresse, B. Appenzeller, A. Paris, D. N. Rutledge, et E. Rathahao-Paris, « Potential of dynamically harmonized Fourier transform ion cyclotron resonance cell for high-throughput metabolomics fingerprinting: control of data quality », Analytical and Bioanalytical Chemistry, vol. 410, nᵒ 2, p. 483-490, 2018.


  • B. Habchi, A. Kassouf, Y. Padellec, E. Rathahao-Paris, S. Alves, D. N. Rutledge, J. Maalouly, et V. Ducruet, « An untargeted evaluation of food contact materials by flow injection analysis-mass spectrometry (FIA-MS) combined with independent components analysis (ICA) », Analytica Chimica Acta, 2018.


  • H. Mamad-Hemouch, L. Bacri, C. Huin, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, et J. Pelta, « Versatile cyclodextrin nanotube synthesis with functional anchors for efficiency ion channel formation: design, characterization and ion conductance », Nanoscale, 2018.
    Mots-clés : CSOB, Cyclodextrin, POLE 3.


  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, et J. M. García Fernández, « Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins », The Journal of Organic Chemistry, vol. 83, nᵒ 10, p. 5588-5597, mai 2018.


  • E. Rathahao-Paris, S. Alves, N. Boussaid, N. Picard-Hagen, V. Gayrard, P. - L. Toutain, J. - C. Tabet, D. N. Rutledge, et A. Paris, « Evaluation and validation of an analytical approach for high-throughput metabolomic fingerprinting using direct introduction–high-resolution mass spectrometry: Applicability to classification of urine of scrapie-infected ewes », European Journal of Mass Spectrometry, p. 146906671880645, oct. 2018.


  • A. Tomer, B. T. Kusema, J. - F. Paul, C. Przybylski, E. Monflier, M. Pera-Titus, et A. Ponchel, « Cyclodextrin-assisted low-metal Ni-Pd/Al2O3 bimetallic catalysts for the direct amination of aliphatic alcohols », Journal of Catalysis, vol. 368, p. 172-189, 2018.


  • N. V. Yerra, P. Pallerla, S. Pandeti, J. - C. Tabet, et J. R. Thota, « Characterization of degradation products of macitentan under various stress conditions using liquid chromatography/mass spectrometry », Rapid Communications in Mass Spectrometry, vol. 32, nᵒ 13, p. 1075-1084, juill. 2018.

2017



  • P. Barbier Saint Hilaire, A. Warnet, Y. Gimbert, U. M. Hohenester, G. Giorgi, M. - F. Olivier, F. Fenaille, B. Colsch, C. Junot, et J. - C. Tabet, « Mechanistic study of competitive releases of H2O, NH3 and CO2 from deprotonated aspartic and glutamic acids: Role of conformation », Journal of Chromatography B, vol. 1047, p. 64-74, mars 2017.
    Résumé : 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 8.4 kJ/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.
    Mots-clés : CSOB, Electrospray high-resolution mass spectrometry, POLE 3, Regioselective dissociation, Unexpected cleavage of aspartate anion.


  • J. Blass, J. Brunke, F. Emmerich, C. Przybylski, V. M. Garamus, A. Feoktystov, R. Bennewitz, G. Wenz, et M. Albrecht, « Interactions between shape-persistent macromolecules as probed by AFM », Beilstein Journal of Organic Chemistry, vol. 13, p. 938-951, mai 2017.


  • P. - E. Bodet, I. Salard, C. Przybylski, F. Gonnet, C. Gomila, J. Ausseil, et R. Daniel, « Efficient recovery of glycosaminoglycan oligosaccharides from polyacrylamide gel electrophoresis combined with mass spectrometry analysis », Analytical and Bioanalytical Chemistry, vol. 409, nᵒ 5, p. 1257-1269, 2017.


  • E. Darii, S. Alves, Y. Gimbert, A. Perret, et J. - C. Tabet, « Meaning and consequence of the coexistence of competitive hydrogen bond/salt forms on the dissociation orientation of non-covalent complexes », Journal of Chromatography B, vol. 1047, p. 45-58, mars 2017.
    Résumé : 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.
    Mots-clés : CSOB, POLE 3.


  • G. A. Garcia, H. Dossmann, L. Nahon, S. Daly, et I. Powis, « Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions », ChemPhysChem, vol. 18, nᵒ 5, p. 500-512, mars 2017.

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    Résumé : 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. It 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.
    Mots-clés : circular dichroism, CSOB, photoelectron circular dichroism, photoelectron spectroscopy, photoionization, Photophysics, POLE 3.


  • D. Gatineau, A. Memboeuf, A. Milet, R. B. Cole, H. Dossmann, Y. Gimbert, et D. Lesage, « Experimental bond dissociation energies of benzylpyridinium thermometer ions determined by threshold-CID and RRKM modeling », International Journal of Mass Spectrometry, 2017.


  • M. N. Godoi, F. de Azambuja, P. D. G. Martinez, N. H. Morgon, V. G. Santos, T. Regiani, D. Lesage, H. Dossmann, R. B. Cole, M. N. Eberlin, et C. R. D. Correia, « Revisiting the Intermolecular Fujiwara Hydroarylation of Alkynes », European Journal of Organic Chemistry, vol. 2017, nᵒ 13, p. 1794-1803, avr. 2017.

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