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High Mass Resolution (high + mass_resolution)
Selected AbstractsHigh-Resolution LA-ICP-MS for Accurate Determination of Low Abundances of K, Sc and Other Trace Elements in Geological SamplesGEOSTANDARDS & GEOANALYTICAL RESEARCH, Issue 1 2010Julia Regnery LA-ICP-MS; haute résolution de masses; matériaux géologiques de référence; verres MPI-DING Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine K, Sc, Ti, V, Cr, Mn, Co, Ni and Zn in geological samples. Because the isotopes of these elements and the internal standard element (Ca) often have interferences from molecular ions when determined using quadrupole or sector-field ICP-MS in low mass resolution mode, ion intensities were measured at a high mass resolution of 4000. We investigated dynamic element fractionation, type and abundance of molecular ions using different geological reference materials. Highly resolved mass spectra were especially important for accurate low-abundance measurements. As a result, maximum "critical" concentration limits for each isotope were obtained, where a mass resolution of 4000 was necessary for reliable LA-ICP-MS analysis. To test the LA-ICP-MS technique, different international reference material glasses and powdered rock reference materials were analysed. Rock powders were fused to glass beads using an Ir-strip heater. Nearly all concentration values for the reference materials agreed with the reference values at the 95% confidence level. To demonstrate routine LA-ICP-MS analysis at a mass resolution of 4000, trace element data for Hawaiian basalts are also presented. La technique de spectrométrie de masse couplée à un plasma inductif et associée à un système d'ablation laser (LA-ICP-MS) a été utilisée pour la détermination des concentrations en K, Sc, Ti, V, Cr, Mn, Co, Ni and Zn dans des échantillons géologiques. Parce que les isotopes de ces éléments et l'élément utilisé comme standard interne (Ca) ont souvent des interférences liées à la formation d'ions moléculaires lorsqu'ils sont analysés par les techniques d'ICP-MS quadripolaire ou à secteur magnétique en mode basse résolution de masses, les intensités des ions ont été mesurées en mode haute résolution de masses de 4000. Nous avons étudié le fractionnement dynamique des éléments, le type et l'abondance des ions moléculaires en utilisant différents matériaux géologiques de référence. Les spectres de masse de haute résolution ont été particulièrement importants pour les mesures précises des faibles abondances. En conséquence, les limites maximales de concentration critique pour chaque isotope ont été obtenues, dans les cas où une résolution de masse de 4000 était nécessaire pour obtenir des analyses LA-ICP-MS fiables. Pour tester la technique LA-ICP-MS proposée, différents verres et poudres de matériaux de référence internationaux ont été analysés. Les poudres de roche ont été transformées en billes de verre par fusion dans un four automatique à chauffage par filament d'iridium. Presque toutes les concentrations obtenues pour les matériaux de référence sont en accord avec les valeurs de référence de la littérature à un niveau de confiance de 95%. Pour démontrer que la méthode présentée de LA-ICP-MS à résolution de masses de 4000 peut s'utiliser en routine, nous présentons également des données d'éléments traces de basaltes Hawaïens. [source] The Orbitrap: a new mass spectrometerJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 4 2005Qizhi Hu Abstract Research areas such as proteomics and metabolomics are driving the demand for mass spectrometers that have high performance but modest power requirements, size, and cost. This paper describes such an instrument, the Orbitrap, based on a new type of mass analyzer invented by Makarov. The Orbitrap operates by radially trapping ions about a central spindle electrode. An outer barrel-like electrode is coaxial with the inner spindlelike electrode and mass/charge values are measured from the frequency of harmonic ion oscillations, along the axis of the electric field, undergone by the orbitally trapped ions. This axial frequency is independent of the energy and spatial spread of the ions. Ion frequencies are measured non-destructively by acquisition of time-domain image current transients, with subsequent fast Fourier transforms (FFTs) being used to obtain the mass spectra. In addition to describing the Orbitrap mass analyzer, this paper also describes a complete Orbitrap-based mass spectrometer, equipped with an electrospray ionization source (ESI). Ions are transferred from the ESI source through three stages of differential pumping using RF guide quadrupoles. The third quadrupole, pressurized to less than 10,3 Torr with collision gas, acts as an ion accumulator; ion/neutral collisions slow the ions and cause them to pool in an axial potential well at the end of the quadrupole. Ion bunches are injected from this pool into the Orbitrap analyzer for mass analysis. The ion injection process is described in a simplified way, including a description of electrodynamic squeezing, field compensation for the effects of the ion injection slit, and criteria for orbital stability. Features of the Orbitrap at its present stage of development include high mass resolution (up to 150 000), large space charge capacity, high mass accuracy (2,5 ppm), a mass/charge range of at least 6000, and dynamic range greater than 10.3 Applications based on electrospray ionization are described, including characterization of transition-metal complexes, oligosaccharides, peptides, and proteins. Use is also made of the high-resolution capabilities of the Orbitrap to confirm the presence of metaclusters of serine octamers in ESI mass spectra and to perform H/D exchange experiments on these ions in the storage quadrupole. Copyright © 2005 John Wiley & Sons, Ltd. [source] High mass accuracy in-source collision-induced dissociation tandem mass spectrometry and multi-step mass spectrometry as complementary tools for fragmentation studies of quaternary ammonium herbicidesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2004Oscar Núñez Abstract Fragmentation studies using both an ion-trap mass analyzer and a hybrid quadrupole time-of-flight (Q-TOF) mass spectrometer were performed in order to establish the fragmentation pathways of organic molecules. A general strategy combining MSn data (n = 1,4) in an ion-trap analyzer with tandem mass spectrometry and in-source collision-induced dissociation tandem mass spectrometry (CID MS/MS) in a Q-TOF instrument was applied. The MSn data were used to propose a tentative fragmentation pathway following genealogical relationships. When several assignments were possible, MS/MS and in-source CID MS/MS (Q-TOF) allowed the elemental compositions of the fragments to be confirmed. Quaternary ammonium herbicides (quats) were used as test compounds and their fragmentation pathways were established. The elemental composition of the fragments was confirmed using the TOF analyzer with relative errors <0.0023 Da. Some fragments previously reported in the literature were reassigned taking advantage of the high mass resolution and accuracy of the Q-TOF instrument, which made it possible to solve losses where nitrogen was involved. Copyright © 2004 John Wiley & Sons, Ltd. [source] An integrated serum proteomic approach capable of monitoring the low molecular weight proteome with sequencing of intermediate to large peptidesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2009Karen Merrell The low-abundance, low molecular weight serum proteome has high potential for the discovery of new biomarkers using mass spectrometry (MS). Because the serum proteome is large and complex, defining relative quantitative differences for a molecular species between comparison groups requires an approach with robust separation capability, high sensitivity, as well as high mass resolution. Capillary liquid chromatography (cLC)/MS provides both the necessary separation technique and the sensitivity to observe many low-abundance peptides. Subsequent identification of potential serum peptide biomarkers observed in the cLC/MS step can in principle be accomplished by in series cLC/MS/MS without further sample preparation or additional instrumentation. In this report a novel cLC/MS/MS method for peptide sequencing is described that surpasses previously reported size limits for amino acid sequencing accomplished by collisional fragmentation using a tandem time-of-flight MS instrument. As a demonstration of the approach, two low-abundance peptides with masses of ,4000,5000,Da were selected for MS/MS sequencing. The multi-channel analyzer (MCA) was used in a novel way that allowed for summation of 120 fragmentation spectra for each of several customized collision energies, providing more thorough fragmentation coverage of each peptide with improved signal to noise. The peak list from this composite analysis was submitted to Mascot for identification. The two index peptides, 4279,Da and 5061,Da, were successfully identified. The peptides were a 39 amino acid immunoglobulin G heavy chain variable region fragment and a 47 amino acid fibrin alpha isoform C-terminal fragment. The method described here provides the ability both to survey thousands of serum molecules and to couple that with markedly enhanced cLC/MS/MS peptide sequencing capabilities, providing a promising technique for serum biomarker discovery. Copyright © 2009 John Wiley & Sons, Ltd. [source] |