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Mass Spectrometric Experiments (mass + spectrometric_experiment)
Selected AbstractsAzido-Nitrene Is Probably the N4 Molecule Observed in Mass Spectrometric ExperimentsCHEMINFORM, Issue 40 2003Nguyen Minh Tho Nguyen Minh Tho Abstract For Abstract see ChemInform Abstract in Full Text. [source] Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxidesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 9 2003David Rondeau Abstract Organic peroxides such as the cumene hydroperoxide I (Mr = 152 u), the di- tert -butyl peroxide II (Mr = 146 u) and the tert -butyl peroxybenzoate III (Mr = 194 u) were analyzed by atmospheric pressure chemical ionization mass spectrometry using a water,methanol mixture as solvent with a low flow-rate of mobile phase and unusual conditions of the source temperature (,50 °C) and probe temperature (70,200 °C). The mass spectra of these compounds show the formation of (i) an [M + H]+ ion (m/z 153) for the hydroperoxide I, (ii) a stable adduct [M + CH3OH2]+ ion (m/z 179) for the dialkyl peroxide II and (iii) several protonated adduct species such as protonated molecules (m/z 195) and different protonated adduct ions (m/z 227, 389 and 421) for the peroxyester III. Tandem mass spectrometric experiments, exact mass measurements and theoretical calculations were performed for characterize these gas-phase ionic species. Using the double-well energy potential model illustrating a gas-phase bimolecular reaction, three important factors are taken into account to propose a qualitative interpretation of peroxide behavior toward the CH3OH2+, i.e. thermochemical parameters () and two kinetic factors such as the capture constant of the initial stable ion,dipole and the magnitude of the rate constant of proton transfer reaction into the loose proton bond cluster. Copyright © 2003 John Wiley & Sons, Ltd. [source] Advanced glycation end products: a highly complex set of biologically relevant compounds detected by mass spectrometry,JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 4 2001Annunziata Lapolla Abstract Structural information on ,AGE-peptides,' a class of substances belonging to advanced glycation end products (AGE) and originating by proteolysis of glycated proteins, was gained through various analytical approaches on the mixture produced by proteinase K digestion of in vitro glycated bovine serum albumin. Both matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS) were employed, and the results were compared with those from conventional spectroscopic methods (UV, fluorescence, gel permeation). The data acquired by the various techniques all depict the digestion mixtures as highly complex, with components exhibiting molecular mass in the range 300,3500 Da. In the analysis of HPLC/ESI-MS data, identification of AGE-peptides was facilitated by 3D mapping. Structural information was gained by means of multiple mass spectrometric experiments. Copyright © 2001 John Wiley & Sons, Ltd. [source] Porous silicon surfaces for metabonomics: Detection and identification of nucleotides without matrix interferencePHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 6 2007D. Gómez Abstract In present work, porous silicon surfaces (PSS) have been developed for time of flight mass spectrometric experiments (TOF-MS) in the monitoring of nucleotides, commonly found as metabolites in the cell. The mass range of the studied molecules (, 400 amu) is common to several important messengers and other metabolites. Different porosified surfaces have been developed by means of electrochemical etching and different degree of porosity and pore size achieved as function of silicon dopant concentration, silicon resistivity, current density and the presence or absence of illumination along the process. As main conclusion, it can be said that an interesting commercial nucleotide (Cyclic adenosine monophosphate, c-AMP) has been detected on low concentrations (,hundreds of femtomols) for some of the fabricated porous surfaces. Taking into account that these concentrations are similar to the ones found in real samples, this result opens the possibility to the fabrication of DIOS (Desorption Ionization On Silicon) chips for the detection of nucleotides in biological fluids. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electron ionisation mass spectral studies of bridgehead-fused ,2 -norbornanethiazolinesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 6 2009Antonio García Martínez The electron ionisation (EI) mass spectra of a series of bridgehead-fused ,2 -norbornanethiazolines, a new class of bridgehead-norbornane derivatives, have been studied and their cleavage mechanisms rationalised on the basis of the substituent shifts as well as on the identification of relevant peaks through accurate mass measurements and collision-induced dissociation tandem mass spectrometric experiments. The fragmentation patterns of isomeric pairs of 6,6- and 10,10-dimethylnorbornanethiazolines are almost identical, probably due to an initial isomerisation of molecular ion previous to the fragmentation. In general, the dominant peaks in the spectra of all the studied compounds originate from initial , -cleavages of C(5),C(6) or C(1),C(10) bonds, followed by concomitant homolytic cleavage of C(1),C(9) and C(7),C(10) bonds. The driving force for this fragmentation pathway, directed by the gem -dimethyl group, is the formation of a highly stabilised thiazolilmethyl cation which constitutes the base peak in all the spectra and allows the identification of these interesting ligands. Copyright © 2009 John Wiley & Sons, Ltd. [source] Formation of iminium ions by fragmentation of a2 ionsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2004Alex G. Harrison Tandem mass spectrometric experiments have been carried out on the protonated amides H-Gly-Ala-NH2, H-Ala-Gly-NH2, H-Ala-Val-NH2, H-Val-Ala-pNA, H-Leu-Phe-NH2, H-Phe-Leu-NH2, H-Phe-Tyr-NH2 and H-Tyr-Phe-NH2 with particular emphasis on the fragmentation of the isomeric a2 ions derived therefrom. Primary fragmentation reactions of the protonated amides involve formation of the y1, and b2 ions with further fragmentation of the b2 ion to form the a2 ion which fragments to form iminium ions. Collision-induced dissociation studies of the mass-selected a2 ions were carried out. For the Gly-Ala, Ala-Gly and Val-Ala a2 ions, weak signals were observed corresponding to loss of CO from the a2 ion. With the exception of the Gly-Ala, Ala-Gly and Val-Ala a2 ions, both possible iminium ions (a1 and the internal iminium ion) are observed with the most abundant being that formed by proton attachment to the imine of higher proton affinity. The results provide strong support for the recently proposed (El Aribi et al. J. Am. Chem. Soc. 2003; 125: 9229) mechanism of fragmentation of a2 ions which involves elimination of CO from the a2 ion to form a proton-bound complex of two imines. Based on this mechanism ab initio calculations of the total energies of the a2 ions and the transition states for fragmentation have been carried out giving the energy barrier for fragmentation of each a2 ion. The experimental results are interpreted in terms of these energetics data, unimolecular rate constants calculated by using the RRKM theory, and the imine proton affinities. Copyright © 2004 John Wiley & Sons, Ltd. [source] Identification of 1-hydroxypyrene glucuronide in tissue of marine polychaete Nereis diversicolor by liquid chromatography/ion trap multiple mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 16 2002Anders M. B. Giessing 1-Hydroxypyrene glucuronide is identified as the single major aqueous metabolite of the tetracyclic aromatic hydrocarbon pyrene, in tissue from a deposit-feeding marine polychaete, Nereis diversicolor. Identification was performed using an ion trap mass spectrometer fitted with an atmospheric pressure chemical ionization (APCI) probe and connected to a high-performance liquid chromatography/diode array detector (HPLC/DAD) system. Besides 1-hydroxypyrene, the 339-nm UV trace of tissue samples from pyrene-exposed worms showed only one dominant peak that could be related to pyrene metabolism. Negative APCI-MS of this supposed 1- hydroxypyrene conjugate gave a characteristic signal at m/z 429 corresponding to the molecular ion of 1-hydroxypyrene glucuronide plus eluent adducts ([M,,,H,+,2H2O],). Fragmentation pathways were studied by isolating the abundant ion at m/z 429 in the ion trap and performing multiple mass spectrometric experiments (MSn). The fragmentations observed were consistent with the proposed identification. Two low intensity LC peaks that could be related to pyrene metabolism by their DAD absorption spectra were also present in the 339-nm UV chromatogram of tissue samples. However, these peaks could not be identified by their mass spectra in negative ion mode due to ion suppression by very abundant co-eluting impurities. The present method shows that LC/MSn is a fast and useful analytical tool for identification of aqueous polycyclic aromatic hydrocarbon biotransformation products in samples from relatively small marine invertebrates with limited sample preparation. Copyright © 2002 John Wiley & Sons, Ltd. [source] Structural studies of wheat flour glutenin polymers by CD spectroscopyBIOPOLYMERS, Issue 4 2004S. Fisichella Abstract A dissolution procedure of unreduced glutenin polymers of three wheat flour varieties (WRU 6981, Alisei 1, and Alisei 2) by sonication in the presence of SDS (sodium dodecyl sulphate), after the elimination of albumins, globulins, and gliadins, was achieved, and the molecular weight distribution of glutenin polymers obtained by this method was measured by matrix assisted laser desorption ionization,time of flight (MALDI-TOF) mass spectrometry. A structural study by CD spectroscopy at different temperatures of WRU 6981 glutenin polymer and of 1Ax1 high- Mr (relative molecular mass) glutenin subunit, which is the only high- Mr subunit contained in WRU 6981 flour, was undertaken to understand if the information obtained from the single subunit were applicable to the total polymer. CD spectroscopy also has been employed to study the glutenin polymers obtained by Alisei 1 and Alisei 2 wheat flours; Alisei 1 biotype contained 1Bx7 and 1Dx2+1Dy12 high-Mr subunits, whereas the Alisei 2 biotype contained only 1Bx7 and 1Dy12 subunits. A conformational study was undertaken by CD spectroscopy at different temperatures and in the presence of some chemical denaturant agents, such as urea and sodium dodecyl sulphate, in order to obtain information about their intrinsic stability and to verify if the 1Dx2 subunit presence determined a different structural behavior between Alisei 1 and Alisei 2 polymers. MALDI-TOF mass spectrometric experiments showed that the glutenin polymers molecular weights were in the mass range of 500,000,5,000,000. CD spectra indicated that a single conformational state did not predominate in the temperature range studied but equilibrium between two distinct conformational states existed; moreover, all the changes induced by urea and by SDS followed a multistep transition process. © 2004 Wiley Periodicals, Inc. Biopolymers, 2004 [source] A Combined ESI- and MALDI-MS(/MS) Study of Peripherally Persulfonylated Dendrimers: False Negative Results by MALDI-MS and Analysis of Defects,CHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2005Thorsten Felder Dipl.-Chem. Abstract Mass spectrometry, in particular MALDI-MS, has often been used as a valuable means to characterize dendritic molecules with respect to their molecular masses. Also, it is a valuable tool for analyzing potential defects in their structure which result from incomplete synthetic steps. This article presents a comparison of ESI and MALDI mass spectrometric experiments on dendrimers persulfonylated at their periphery. While the ESI mass spectra easily permit impurities and defects to be identified and thus provide evidence for sample purity, reactions with acidic matrices occur during the MALDI process. The resulting defects are identical to those expected from incomplete substitution. Thus, in these cases, MALDI-MS yields false negative results. With mass-selected, ESI-generated ions, collision experiments were performed in an FT-ICR mass spectrometer cell to provide detailed insight into the fragmentation patterns of the various dendrimers. Different fragmentation patterns are observed depending on the exact structure of the dendrimer. Also, the nature of the charge is important. The fragmentation reactions for protonated species differ much from those binding a sodium or potassium ion. These differences can be traced back to different sites for binding H+ versus Na+ or K+. Tandem MS experiments on mass-selected dendrimer ions with defects can be used to distinguish different types of defects. A concise structural assignment can thus be made on the basis of these experiments. Even mixtures of two isobaric defect variants with the same elemental composition can be identified. Massenspektrometrie, insbesondere MALDI-MS wurde oft als wertvolle Analysenmethode für die Charakterisierung von Dendrimeren hinsichtlich ihrer Molekülmasse, aber auch hinsichtlich einer Analyse potentieller Strukturdefekte eingesetzt, die aus unvollständig verlaufenden Synthesestufen resultieren. In diesem Artikel berichten wir über einen Vergleich von ESI- und MALDI-massenspektrometrischen Experimenten mit an ihrer Peripherie persulfonylierten Dendrimeren. Während die ESI-Massenspektren eine einfache Identifizierung von Verunreinigungen und Defekten erlauben und damit eine Reinheitskontrolle ermöglichen, laufen während der Ionisierung mittels MALDI Reaktionen mit sauren Matrices ab, die genau solche Defekte erzeugen, wie man sie aus einer unvollständigen Synthese erwarten würde. MALDI-MS führt hier also zu einem falsch-negativen Ergebnis. Mit massenselektierten Ionen aus der Electrospray-Ionisierung wurden Stoßexperimente in einer FT-ICR-Zelle durchgeführt, um einen detaillierten Einblick in das Fragmentierungsmuster der verschiedenen Dendrimere zu erhalten. Man beobachtet unterschiedliche Fragmentierungsmuster in Abhängigkeit von der genauen Struktur der Dendrimere. Auch die Art der Ladung ist wichtig, da die Fragmentierungswege der protonierten Dendrimere sich deutlich von denen ihrer Na+ - und K+ -Addukte unterscheiden. Diese Unterschiede können auf unterschiedliche Bindungsstellen für H+gegenüber Na+oder K+zurückgeführt werden. Tandem MS-Experimente mit massenselektierten, strukturdefekten Dendrimer-Ionen erlauben eine genaue Unterscheidung verschiedener Typen von Defekten. Sie können daher für eine detaillierte Strukturaufklärung verwendet werden. Sogar Mischungen zweier isobarer Defektvarianten mit gleicher Elementarzusammensetzung werden zuverlässig identifiziert. [source] | ||||||||||