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11.
Comparison of the activation time effects and the internal energy distributions for the CID,PQD and HCD excitation modes
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Farid Ichou Adrian Schwarzenberg Denis Lesage Sandra Alves Christophe Junot Xavier Machuron‐Mandard Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2014,49(6):498-508
Reproducibility among different types of excitation modes is a major bottleneck in the field of tandem mass spectrometry library development in metabolomics. In this study, we specifically evaluated the influence of collision voltage and activation time parameters on tandem mass spectrometry spectra for various excitation modes [collision‐induced dissociation (CID), pulsed Q dissociation (PQD) and higher‐energy collision dissociation (HCD)] of Orbitrap‐based instruments. For this purpose, internal energy deposition was probed using an approach based on Rice–Rampserger–Kassel–Marcus modeling with three thermometer compounds of different degree of freedom (69, 228 and 420) and a thermal model. This model treats consecutively the activation and decomposition steps, and the survival precursor ion populations are characterized by truncated Maxwell–Boltzmann internal energy distributions. This study demonstrates that the activation time has a significant impact on MS/MS spectra using the CID and PQD modes. The proposed model seems suitable to describe the multiple collision regime in the PQD and HCD modes. Linear relationships between mean internal energy and collision voltage are shown for the latter modes and the three thermometer molecules. These results suggest that a calibration based on the collision voltage should provide reproducible for PQD, HCD to be compared with CID in tandem in space instruments. However, an important signal loss is observed in PQD excitation mode whatever the mass of the studied compounds, which may affect not only parent ions but also fragment ions depending on the fragmentation parameters. A calibration approach for the CID mode based on the variation of activation time parameter is more appropriate than one based on collision voltage. In fact, the activation time parameter in CID induces a modification of the collisional regime and thus helps control the orientation of the fragmentation pathways (competitive or consecutive dissociations). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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Adrián Schwarzenberg Farid Ichou Richard B. Cole Xavier Machuron‐Mandard Christophe Junot Denis Lesage Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2013,48(5):576-586
Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non‐volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI‐MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MSn) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision‐induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an ‘identification tree’ based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the ‘identification tree’. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Isocyanates can cause occupational asthma. By using available HPLC-UVF methods, isocyanates can be quantified only at levels above 1% of the Permissible Exposure Limits (PEL). Once sensitized, workers can react to concentrations below these limits of detection (LOD) making these methods insufficiently sensitive to adequately evaluate trace amounts of isocyanates present in air or in materials at safe levels for sensitized workers. This article describes a novel method for isocyanate analysis allowing the quantification of 2,4TDI and 2,6TDI monomers at very low concentrations using HPLC-CIS-MS-MS. The method's sensitivity increases with a decrease in the alkali radius. The LOD is 0.039 ng mL(-1) for 2,4TDI and 0.100 ng mL(-1) for 2,6TDI in solution when lithium is the alkali adduct, which is 20 times more sensitive than HPLC-UVF method. This new method allows determination in foam at levels of 0.078 ng g(-1) for 2,4TDI and 0.200 ng g(-1) for 2,6TDI respectively, for a 0.5 g foam sample. This is more than 100 times more sensitive than other methods for determining free monomers in solid materials. Analytical reproducibility and precision are better than 92% and 93% for both diisocyanate monomers. The use of HPLC-UVF conventional method failed to detect unreacted isocyanates in foam samples, but TDI monomers were quantified by HPLC-CIS-MS-MS. 相似文献
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R P Saint-Arroman M Chabanas A Baudouin C Copéret J M Basset A Lesage L Emsley 《Journal of the American Chemical Society》2001,123(16):3820-3821
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Philippe Franck Beáta Dajka-Halász Katrien Monsieurs Bert U.W. Maes 《Tetrahedron》2008,64(26):6030-6037
Pd-catalyzed cyclodehydrohalogenation involving oxidative addition of aromatic C-Br or activated azaheteroaromatic C-Cl bonds and C(sp2)-H activation have been investigated at high reaction temperatures (180-200 °C). This allowed the fast (10-30 min) synthesis of a variety of azaheteroaromatic ring systems (dibenzo[f,h]phthalazine, dibenzo[f,h]cinnoline, benzofuro[2,3-d]pyridazine, 5H-pyridazino[4,5-b]indole, 7H-indolo[2,3-c]quinoline and 5H-δ-carboline) in moderate to good yields. 相似文献
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Carboxylic‐Acid‐Passivated Metal Oxide Nanocrystals: Ligand Exchange Characteristics of a New Binding Motif
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Jonathan De Roo Dr. Yolanda Justo Katrien De Keukeleere Freya Van den Broeck Prof. Dr. José C. Martins Prof. Dr. Isabel Van Driessche Prof. Dr. Zeger Hens 《Angewandte Chemie (International ed. in English)》2015,54(22):6488-6491
Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO2 and ZrO2 NCs using 1H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self‐adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X‐type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X‐type ligands yielding a combined X2 binding motif that allows for self‐adsorption and exchange for L‐type ligands. 相似文献
20.
Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products
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Dr. Ahmed M. Debela Dr. Mayreli Ortiz Dr. Valerio Beni Prof. Serge Thorimbert Dr. Denis Lesage Prof. Richard B. Cole Prof. Ciara K. O'Sullivan Prof. Bernold Hasenknopf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17721-17727
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 [SiW11O39{Sn(CH2)2CO}]8? and [P2W17O61{Sn(CH2)2CO}]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. 相似文献