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Mass Range (mass + range)
Selected AbstractsCharacterization of natural wax esters by MALDI-TOF mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2009Vladimír Vrkoslav Abstract The applicability of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) to the analysis of wax esters (WEs) was investigated. A series of metal salts of 2,5-dihydroxybenzoic acid (DHB) was synthesized and tested as possible matrices. Alkali metal (Li, Na, K, Rb, Cs) and transition metal (Cu, Ag) salts were studied. The matrix properties were evaluated, including solubility in organic solvents, threshold laser power that should be applied for successful desorption/ionization of WEs, the nature of the matrix ions and the mass range occupied by them, and the complexity of the isotope clusters for individual metals. Lithium salt of dihydroxybenzoic acid (LiDHB) performed the best and matrices with purified lithium isotopes (6LiDHB or 7LiDHB) were recommended for WEs. Three sample preparation procedures were compared: (1) mixing the sample and matrix in a glass vial and deposition of the mixture on a MALDI plate (Mix), (2) deposition of sample followed by deposition of matrix (Sa/Ma), and (3) deposition of matrix followed by deposition of sample (Ma/Sa). Morphology of the samples was studied by scanning electron microscopy. The best sample preparation technique was Ma/Sa with the optimum sample to matrix molar ratio 1 : 100. Detection limit was in the low picomolar range. The relative response of WEs decreased with their molecular weight, and minor differences between signals of saturated and monounsaturated WEs were observed. MALDI spectra of WEs showed molecular adducts with lithium [M + Li]+. Fragments observed in postsource decay (PSD) spectra were related to the acidic part of WEs [RCOOH + Li]+ and they were used for structure assignment. MALDI with LiDHB was used for several samples of natural origin, including insect and plant WEs. A good agreement with GC/MS data was achieved. Moreover, MALDI allowed higher WEs to be analyzed, up to 64 carbon atoms in Ginkgo biloba leaves extract. Copyright © 2008 John Wiley & Sons, Ltd. [source] Preparative separation of a multicomponent peptide mixture by mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2006Xinli Yang Abstract We report on the first multiplex preparative separation by mass spectrometry of bio-organic molecules in the 200,350 Da mass range that is typical for synthetic drugs. A five-component mixture consisting of two di- and three tripeptides has been separated by mass using a specially designed mass spectrometer. The instrument for preparative separations consists of an electrospray ionization (ESI) source, ion transfer optics, an electrostatic sector, and an inhomogeneous-field magnetic mass analyzer that achieves linear mass dispersion of ion beams. Protonated peptides produced by electrospray were separated, nondestructively landed on a 16-channel array of dry collector plates, and reconstituted in solution. The preparation procedures and the instrumental conditions have been optimized to maximize the ion currents. The significant features of the special mass spectrometer are high ion currents and simultaneous separation and collection of mixture components. Copyright © 2006 John Wiley & Sons, Ltd. [source] Rapid screening and characterization of drug metabolites using a new quadrupole,linear ion trap mass spectrometerJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2003Gérard Hopfgartner Abstract The application of a new hybrid RF/DC quadrupole,linear ion trap mass spectrometer to support drug metabolism and pharmacokinetic studies is described. The instrument is based on a quadrupole ion path and is capable of conventional tandem mass spectrometry (MS/MS) as well as several high-sensitivity ion trap MS scans using the final quadrupole as a linear ion trap. Several pharmaceutical compounds, including trocade, remikiren and tolcapone, were used to evaluate the capabilities of the system with positive and negative turbo ionspray, using either information-dependent data acquisition (IDA) or targeted analysis for the screening, identification and quantification of metabolites. Owing to the MS/MS in-space configuration, quadrupole-like CID spectra with ion trap sensitivity can be obtained without the classical low mass cutoff of 3D ion traps. The system also has MS3 capability which allows fragmentation cascades to be followed. The combination of constant neutral loss or precursor ion scan with the enhanced product ion scan was found to be very selective for identifying metabolites at the picogram level in very complex matrices. Owing to the very high cycle time and, depending on the mass range, up to eight different MS experiments could be performed simultaneously without compromising chromatographic performance. Targeted product ion analysis was found to be complementary to IDA, in particular for very low concentrations. Comparable sensitivity was found in enhanced product ion scan and selected reaction monitoring modes. The instrument is particularly suitable for both qualitative and quantitative analysis. Copyright © 2003 John Wiley & Sons, Ltd. [source] The Monitor project: rotation periods of low-mass stars in M50MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 4 2009Jonathan Irwin ABSTRACT We report on the results of a time-series photometric survey of M50 (NGC 2323), a ,130 Myr open cluster, carried out using the Cerro Tololo Inter-American Observatory (CTIO) 4-m Blanco telescope and Mosaic-II detector as part of the Monitor project. Rotation periods were derived for 812 candidate cluster members over the mass range 0.2 ,M/M,, 1.1. The rotation period distributions show a clear mass-dependent morphology, statistically indistinguishable from those in NGC 2516 and M35 taken from the literature. Due to the availability of data from three observing runs separated by ,10 and 1 month time-scales, we are able to demonstrate clear evidence for evolution of the photometric amplitudes, and hence spot patterns, over the 10 month gap. We are not able to constrain the time-scales for these effects in detail due to limitations imposed by the large gaps in our sampling, which also prevent the use of the phase information. [source] Are fossil groups a challenge of the cold dark matter paradigm?MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 2 2009Stefano Zibetti ABSTRACT We study six groups and clusters of galaxies suggested in the literature to be ,fossil' systems (i.e. to have luminous diffuse X-ray emission and a magnitude gap of at least 2 mag R between the first and the second ranked member within half of the virial radius), each having good quality X-ray data and Sloan Digital Sky Survey (SDSS) spectroscopic or photometric coverage out to the virial radius. The poor cluster AWM 4 is clearly established as a fossil system, and we confirm the fossil nature of four other systems (RX J1331.5+1108, RX J1340.6+4018, RX J1256.0+2556 and RX J1416.4+2315), while the cluster RX J1552.2+2013 is disqualified as fossil system. For all systems, we present the luminosity functions within 0.5 and 1 virial radius that are consistent, within the uncertainties, with the universal luminosity function of clusters. For the five bona fide fossil systems, having a mass range 2 × 1013,3 × 1014 M,, we compute accurate cumulative substructure distribution functions (CSDFs) and compare them with the CSDFs of observed and simulated groups/clusters available in the literature. We demonstrate that the CSDFs of fossil systems are consistent with those of normal observed clusters and do not lack any substructure with respect to simulated galaxy systems in the cosmological , cold dark matter (,CDM) framework. In particular, this holds for the archetype fossil group RX J1340.6+4018 as well, contrary to earlier claims. [source] The poorly constrained cluster disruption time-scale in the Large Magellanic CloudMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 3 2008Geneviève Parmentier ABSTRACT We use Monte Carlo simulations, combined with homogeneously determined age and mass distributions, based on multiwavelength photometry, to constrain the cluster formation history and the rate of bound cluster disruption in the Large Magellanic Cloud (LMC) star cluster system. We evolve synthetic star cluster systems formed with a power-law initial cluster mass function (ICMF) of spectral index ,=,2 assuming different cluster disruption time-scales. For each of these cluster disruption time-scales, we derive the corresponding cluster formation rate (CFR) required to reproduce the observed cluster age distribution. We then compare, in a ,Poissonian',2 sense, model mass distributions and model two-dimensional distributions in log(mass) versus log(age) space of the detected surviving clusters to the observations. Because of the bright detection limit (MlimV,,4.7 mag) above which the observed cluster sample is complete, one cannot constrain the characteristic cluster disruption time-scale for a 104 M, cluster, tdis4[where the disruption time-scale depends on cluster mass as tdis=tdis4(Mcl/104 M,),, with ,, 0.62], to better than a lower limit, tdis4, 1 Gyr. We conclude that the CFR has been increasing steadily from 0.3 clusters Myr,1 5 Gyr ago to a present rate of (20,30) clusters Myr,1 for clusters spanning a mass range of ,100,107 M,. For older ages, the derived CFR depends sensitively on our assumption of the underlying CMF shape. If we assume a universal Gaussian ICMF, then the CFR has increased steadily over a Hubble time from ,1 cluster Gyr,1 15 Gyr ago to its present value. On the other hand, if the ICMF has always been a power law with a slope close to ,=,2, the CFR exhibits a minimum some 5 Gyr ago, which we tentatively identify with the well-known age gap in the LMC's cluster age distribution. [source] Stellar contents and star formation in the young star cluster Be 59MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 3 2008A. K. Pandey ABSTRACT We present UBV Ic CCD photometry of the young open cluster Be 59 with the aim to study the star formation scenario in the cluster. The radial extent of the cluster is found to be ,10 arcmin (2.9 pc). The interstellar extinction in the cluster region varies between E(B,V) , 1.4 to 1.8 mag. The ratio of total-to-selective extinction in the cluster region is estimated as 3.7 ± 0.3. The distance of the cluster is found to be 1.00 ± 0.05 kpc. Using near-infrared (NIR) colours and slitless spectroscopy, we have identified young stellar objects (YSOs) in the open cluster Be 59 region. The ages of these YSOs range between <1 and ,2 Myr, whereas the mean age of the massive stars in the cluster region is found to be ,2 Myr. There is evidence for second-generation star formation outside the boundary of the cluster, which may be triggered by massive stars in the cluster. The slope of the initial mass function, ,, in the mass range 2.5 < M/M,, 28 is found to be ,1.01 ± 0.11 which is shallower than the Salpeter value (,1.35), whereas in the mass range 1.5 < M/M,, 2.5 the slope is almost flat. The slope of the K -band luminosity function is estimated as 0.27 ± 0.02, which is smaller than the average value (,0.4) reported for young embedded clusters. Approximately 32 per cent of H, emission stars of Be 59 exhibit NIR excess indicating that inner discs of the T Tauri star (TTS) population have not dissipated. The Midcourse Space Experiment (MSX) and IRAS-HIRES images around the cluster region are also used to study the emission from unidentified infrared bands and to estimate the spatial distribution of optical depth of warm and cold interstellar dust. [source] Supermassive black hole mass functions at intermediate redshifts from spheroid and AGN luminosity functionsMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 1 2006Naoyuki Tamura ABSTRACT Redshift evolution of supermassive black hole mass functions (BHMFs) is investigated up to z, 1. BHMFs at intermediate redshifts are calculated in two ways. One way is from early-type galaxy luminosity functions (LFs); we assume an MBH,Lsph correlation at a redshift by considering a passive evolution of Lsph in the local relationship. The resultant BHMFs (spheroid-BHMFs) from LFs of red-sequence galaxies indicate a slight decrease of number density with increasing redshift at MBH, 107.5,8 M,. Since a redshift evolution in slope and zeropoint of the MBH,Lsph relation is unlikely to be capable of making such an evolution in BHMF, the evolution of the spheroid-BHMFs is perhaps due mainly to the decreasing normalization in the galaxy LFs. We also derive BHMFs from LFs of morphologically selected early-type galaxies. The resultant BHMFs are similar to those from the red-sequence galaxies, but show a small discrepancy at z, 1 corresponding to an increase of supermassive black hole (SMBH) number density by ,0.3 dex. We also investigate how spheroid-BHMFs are affected by uncertainties existing in the derivation in detail. The other way of deriving a BHMF is based on the continuity equation for number density of SMBHs and LFs of active galactic nucleus (AGN). The resultant BHMFs (AGN-BHMFs) show no clear evolution out to z= 1 at MBH, 108 M,, but exhibit a significant decrease with redshift in the lower mass range. Interestingly, these AGN-BHMFs are quite different in the range of MBH, 108 M, from those derived by Merloni (2004), where the fundamental plane of black hole activity is exploited. Comparison of the spheroid-BHMFs with the AGN-BHMFs suggests that at MBH, 108 M,, the spheroid-BHMFs are broadly consistent with the AGN-BHMFs out to z, 1. Although the decrease of SMBH number density with redshift suggested by the spheroid-BHMFs is slightly faster than that suggested by the AGN-BHMFs, we presume this to be due at least partly to a selection effect on the LFs of red-sequence galaxies; the colour selection could miss spheroids with blue colours. The agreement between the spheroid-BHMFs and the AGN-BHMFs appears to support that most of the SMBHs are already hosted by massive spheroids at z, 1 and they evolve without significant mass growth since then. [source] Background radiation from sterile neutrino decay and reionizationMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 1 2005M. Mapelli ABSTRACT Sterile neutrinos are one of the most promising warm dark matter (WDM) candidates. By considering their radiative- and pion-decay channels, we derive the allowed contribution of sterile neutrinos to the X-ray, optical and near-infrared (NIR) cosmic backgrounds. The X-ray background puts a strong constraint on the mass of radiatively decaying neutrinos (m,s, 14 keV), whereas the allowed mass range for pion-decay neutrinos (for a particle lifetime > 4 × 1017 s) is 150 ,m,s/MeV , 500. Taking into account these constraints, we find that sterile neutrinos do not significantly contribute to the optical and NIR background. We further consider the impact of sterile neutrinos on reionization. We find that the Thomson optical depth due to sterile neutrinos is ,e= (0.4,3) × 10,2 in the case of radiative decays and it is ,10,3 for the pion-decay channel. We conclude that these particles must have played only a minor role in cosmic reionization history. [source] Disc formation and the origin of clumpy galaxies at high redshiftMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY: LETTERS (ELECTRONIC), Issue 1 2009Oscar Agertz ABSTRACT Observations of high-redshift galaxies have revealed a multitude of large clumpy rapidly star-forming galaxies. Their formation scenario and their link to present-day spirals are still unknown. In this Letter, we perform adaptive mesh refinement simulations of disc formation in a cosmological context that are unrivalled in terms of mass and spatial resolution. We find that the so-called ,chain-galaxies' and ,clump-clusters' are a natural outcome of early epochs of enhanced gas accretion from cold dense streams as well as tidally and ram-pressured stripped material from minor mergers and satellites. Through interaction with the hot halo gas, this freshly accreted cold gas settles into a large disc-like system, not necessarily aligned to an older stellar component, that undergoes fragmentation and subsequent star formation, forming large clumps in the mass range 107,109 M,. Galaxy formation is a complex process at this important epoch when most of the central baryons are being acquired through a range of different mechanisms , we highlight that a rapid mass loading epoch is required to fuel the fragmentation taking place in the massive arms in the outskirts of extended discs, an accretion mode that occurs naturally in the hierarchical assembly process at early epochs. [source] Origin and evolution of magnetarsMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY: LETTERS (ELECTRONIC), Issue 1 2008Lilia Ferrario ABSTRACT We present a population synthesis study of the observed properties of the magnetars investigating the hypothesis that they are drawn from a population of progenitors that are more massive than those of the normal radio pulsars. We assume that the anomalous X-ray emission is caused by the decay of a toroidal or tangled up field that does not take part in the spin-down of the star. Our model assumes that the magnetic flux of the neutron star is distributed as a Gaussian in the logarithm about a mean value that is described by a power law , where Mp is the mass of the progenitor. We find that we can explain the observed properties of the magnetars for a model with ,0= 2 × 1025 G cm2 and ,= 5 if we suitably parametrize the time evolution of the anomalous X-ray luminosity as an exponentially decaying function of time. Our modelling suggests that magnetars arise from stars in the high-mass end (20 M,,Mp, 45 M,) of this distribution. The lower mass progenitors are assumed to give rise to the radio pulsars. The high value of , can be interpreted in one of two ways. It may indicate that the magnetic flux distribution on the main sequence is a strong function of mass and that this is reflected in the magnetic fluxes of the neutron stars that form from this mass range (the fossil field hypothesis). The recent evidence for magnetic fluxes similar to those of the magnetars in a high fraction (,25 per cent) of massive O-type stars lends support to such a hypothesis. Another possibility is that the spin of the neutron star is a strong function of the progenitor mass, and it is only for stars that are more massive than ,20 M, that magnetar-type fields can be generated by the ,,, dynamo mechanism (the convective dynamo hypothesis). In either interpretation, it has to be assumed that all or a subset of stars in the mass range ,20,45 M,, which on standard stellar evolution models lead to black holes via the formation of a fall-back disc, must give rise to magnetars. Unlike with the radio pulsars, the magnetars only weakly constrain the birth spin period, due to their rapid spin-down. Our model predicts a birthrate of ,1.5,3 × 10,3 yr,1 for the magnetars. [source] A well-characterised peak identification list of MALDI MS profile peaks for human blood serumPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 18 2010Ali Tiss Abstract MALDI MS profiling, using easily available body fluids such as blood serum, has attracted considerable interest for its potential in clinical applications. Despite the numerous reports on MALDI MS profiling of human serum, there is only scarce information on the identity of the species making up these profiles, particularly in the mass range of larger peptides. Here, we provide a list of more than 90 entries of MALDI MS profile peak identities up to 10,kDa obtained from human blood serum. Various modifications such as phosphorylation were detected among the peptide identifications. The overlap with the few other MALDI MS peak lists published so far was found to be limited and hence our list significantly extends the number of identified peaks commonly found in MALDI MS profiling of human blood serum. [source] Proteomic analysis of human bronchoalveolar lavage fluid: expression profiling of surfactant-associated protein A isomers derived from human pulmonary alveolar proteinosis using immunoaffinity detectionPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 1 2003Chang He Abstract Human bronchoalveolar lavage fluid (BALF) proteins from pulmonary alveolar proteinosis (PAP) obtained by washing the epithelial lining of the lung with phosphate-buffered saline, were separated using high resolution two-dimensional gel electrophoresis (2-DE) under denaturing and reducing conditions. By Western blotting, the proteins were transferred from polyacrylamide gel onto a chemical resilient membrane. The surfactant-associated protein A (SP-A) isomers were then identified with enhanced chemiluminescence detection (ECL) using antibody-antigen reaction. Some of the gels were treated with silver staining after 2-DE. The molecular masses of SP-A isomers in BALF from PAP ranged from 20.5 to 26, 26 to 32, and 32 to 42 kDa, respectively; and isoelectric points (pI) were in pH range of 4.5,5.4 under denaturing and reducing conditions. In the mass range of 20.5,26 kDa and pI of 4.5,5.4, there were five isomers, and in mass range of 26,32 kDa and pI of 4.5 to 5.4, there were at least eight isomers on the ECL detection film. However, in the mass range of 32,42 kDa and pI of 4.5,5.4, there were three isomers separated one from another but there was also a cluster of overlapping spots on the ECL detection film. Thus, this communication describes a characteristic 2-DE pattern of SP-A isomers in BALF from PAP as follows. (1) The five isomers of mass 20.5,26 kDa and pI of 4.5,5.4; (2) the eight isomers of mass 26,32 kDa and pI of 4.5,5.4; and (3) the three isomers of mass 32,42 kDa and pI of 4.5,5.4. [source] Limitations of mass spectrometric methods for the characterization of polydisperse materials,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2010Alan A. Herod This paper is a review of work on the characterization of coal liquids and petroleum residues and asphaltenes over several decades in which various mass spectrometric methods have been investigated. The limitations of mass spectrometric methods require exploration in order to understand what the different analytical methods can reveal about environmental pollution by these kinds of samples and, perhaps more importantly, what they cannot reveal. The application of mass spectrometry to environmental problems generally requires the detection and determination of the concentration of specific pollutants released into the environment by accident or design. The release of crude petroleum or coal liquids into the environment can be detected and tracked during biodegradation processes through specific chemicals such as alkanes or polyaromatic hydrocarbons (PAHs). However, petroleum asphaltenes are polydisperse materials of unknown mass range and chemical structures and, therefore, there are no individual chemicals to detect. It is necessary to determine methods of detection and the ranges of mass of such materials. This can only be achieved through fractionation to reduce the polydispersity of the initial sample. Comparison of mass spectrometric results with results from an independent analytical method such as size-exclusion chromatography with a suitable eluent is advisable to confirm that all the sample has been detected and mass discrimination effects avoided. Copyright © 2010 John Wiley & Sons, Ltd. [source] Strategy for the elucidation of elemental compositions of trace analytes based on a mass resolution of 100 000 full width at half maximumRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2010Anton Kaufmann Elemental compositions (ECs) can be elucidated by evaluating the high-resolution mass spectra of unknown or suspected unfragmented analyte ions. Classical approaches utilize the exact mass of the monoisotopic peak (M,+,0) and the relative abundance of isotope peaks (M,+,1 and M,+,2). The availability of high-resolution instruments like the Orbitrap currently permits mass resolutions up to 100 000 full width at half maximum. This not only allows the determination of relative isotopic abundances (RIAs), but also the extraction of other diagnostic information from the spectra, such as fully resolved signals originating from 34S isotopes and fully or partially resolved signals related to 15N isotopes (isotopic fine structure). Fully and partially resolved peaks can be evaluated by visual inspection of the measured peak profiles. This approach is shown to be capable of correctly discarding many of the EC candidates which were proposed by commercial EC calculating algorithms. Using this intuitive strategy significantly extends the upper mass range for the successful elucidation of ECs. Copyright © 2010 John Wiley & Sons, Ltd. [source] On the high-resolution mass analysis of the product ions in tandem time-of-flight (TOF/TOF) mass spectrometers using a time-dependent re-acceleration techniqueRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2010Sergey Kurnosenko The time-dependent reacceleration of product ions produced as a result of dissociation of a single precursor ion in a tandem time-of-flight mass spectrometer is considered for the first time. Analytical expressions for the shapes of electric pulses bringing all the kinetic energies of the product ions to the same value are derived for two cases: forward acceleration mode and deceleration, followed by re-acceleration in the reversed direction (reversed mode). Secondary time-of-flight focusing resulting from the re-acceleration in the reversed mode is shown to be mass-dependent and, when averaged over a wide mass range, the focusing is tight enough to provide mass resolution exceeding 10,000. After time-dependent re-acceleration, additional compression of the ion packet width leading to better mass resolution can be obtained by decelerating the ions in a constant field. Copyright © 2009 John Wiley & Sons, Ltd. [source] The utility of ultra-performance liquid chromatography/electrospray ionisation time-of-flight mass spectrometry for multi-residue determination of pesticides in strawberryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2008Michael J. Taylor The utility of ultra-performance liquid chromatography/orthogonal-acceleration time-of flight mass spectrometry (UPLC/TOFMS) for the rapid qualitative and quantitative analysis of 100 pesticides targeted in strawberry was assessed by comparing results with those obtained using a validated in-house UPLC tandem mass spectrometry (MS/MS) multi-residue method. Crude extracts from retail strawberry samples received as part of the 2007 annual UK pesticide residues in food surveillance programme were screened for the presence of pesticide residues using UPLC/TOFMS. Accurate mass measurement of positive and negative ions allowed their extraction following ,full mass range data acquisition' with negligible interference from background or co-eluting species observed during UPLC gradient separation (in a cycle time of just 6.5,min per run). Extracted ion data was used to construct calibration curves and to detect and identify any incurred residues (i.e. pesticides incorporated in or on the test material following application during cultivation, harvest and storage). Calibration using matrix-matched standards was performed over a narrow concentration range of 0.005,0.04,mg,kg,1 with determination coefficients (r2) ,0.99 for all analytes with the exception of malathion/fenarimol/fludioxanil (r2,=,0.98), quassia/pymetrazine (r2,=,0.97) and fenthion sulfone (r2,=,0.95). Residues found in selected samples ranged from 0.025,0.28,mg,kg,1 and were in excellent agreement with results obtained using UPLC/MS/MS. Mass measurement accuracies of ,5,ppm were achieved consistently throughout the separation, mass range and concentration range of interest thus providing the opportunity to obtain discrete elemental compositions of target ions. © Crown copyright 2008. Reproduced with the permission of Her Majesty's Stationery Office. Published by John Wiley & Sons, Ltd. [source] Mass spectrometry in the characterization of ambers.RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 5 2008Amber is a fossil resin constituted of organic polymers derived through complex maturation processes of the original plant resin. A classification of eight samples of amber of different geological age (Miocene to Triassic) and geographical origin is here proposed using direct mass spectrometric techniques, i.e. laser desorption ionization (LDI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI), in order to obtain a fingerprint related to the amber origin. Differences and similarities were detected among the spectra with the four methods, showing quite complex spectra, full of ionic species in the mass range investigated (up to m/z 2000). The evaluation required statistical analysis involving multivariate techniques. Cluster analysis or principal component analysis (PCA) generally did not show a clear clustering with respect to the age of samples, except for the APPI method, which allowed a satisfying clustering. Using the total ion current (TIC) obtained by the different analytical approaches on equal quantities of the different amber samples and plotted against the age, the only significant correlation appeared to be that involving APPI. To validate the method, four amber samples from Cretaceous of Spain were analyzed. Also in this case a significant correlation with age was found only with APPI data. PCA obtained with TIC values from all the MS methods showed a fair grouping of samples, according to their age. Three main clusters could be detected, belonging to younger, intermediate and older fossil resins, respectively. This MS analysis on crude amber, either solid or extract, followed by appropriate multivariate statistical evaluation, can provide useful information on amber age. The best results are those obtained by APPI, indicating that the quantity of amber soluble components that can be photoionized decreases with increasing age, in agreement with the formation of highly stable, insoluble polymers. Copyright © 2008 John Wiley & Sons, Ltd. [source] Electron transfer dissociation in the hexapole collision cell of a hybrid quadrupole-hexapole Fourier transform ion cyclotron resonance mass spectrometerRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 3 2008Desmond A. Kaplan Electron transfer dissociation (ETD) of proteins is demonstrated in a hybrid quadrupole-hexapole Fourier transform ion cyclotron resonance mass spectrometer (Qh-FTICRMS). Analyte ions are selected in the mass analyzing quadrupole, accumulated in the hexapole linear ion trap, reacted with fluoranthene reagent anions, and then analyzed via an FTICR mass analyzer. The hexapole trap allows for a broad fragment ion mass range and a high ion storage capacity. Using a 3,T FTICRMS, resolutions of 60,000 were achieved with mass accuracies averaging below 1.4,ppm. The high resolution, high mass accuracy ETD spectra provided by FTICR obviates the need for proton transfer reaction (PTR) charge state reduction of ETD product ions when analyzing proteins or large peptides. This is demonstrated with the ETD of ubiquitin and apomyoglobin yielding sequence coverages of 37 and 20%, respectively. We believe this represents the first reported successful combination of ETD and a FTICRMS. Copyright © 2008 John Wiley & Sons, Ltd. [source] The molecular scanner in microscope modeRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 22 2006Stefan L. Luxembourg The combination of microscope mode matrix-assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS) with protein identification methodology: the molecular scanner, was explored. The molecular scanner approach provides improvement of sensitivity of detection and identification of high-mass proteins in microscope mode IMS. The methodology was tested on protein distributions obtained after separation by sodium dodecyl sulfate/polyacrylamide gel electrophoresis (SDS-PAGE). High-quality, high-spatial-resolution ion images were recorded on a TRIFT-II ion microscope after gold coating of the MALDI sample preparation on the poly(vinylidenedifluoride) capture membranes. The sensitivity of the combined method is estimated to be 5 pmol. The minimum amount of sample consumed, needed for identification, was estimated to be better than 100 fmol. Software tools were developed to analyze the spectral data and to generate broad mass range and single molecular component microscope mode ion images and single mass-to-charge ratio microprobe mode images. Copyright © 2006 John Wiley & Sons, Ltd. [source] Nano-high-performance liquid chromatography in combination with nano-electrospray ionization Fourier transform ion-cyclotron resonance mass spectrometry for proteome analysisRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2003Christian Ihling Fourier transform ion-cyclotron resonance (FTICR) mass spectrometry offers several advantages for the analysis of biological samples, including excellent mass resolution, ultra-high mass measurement accuracy, high sensitivity, and wide mass range. We report the application of a nano-HPLC system coupled to an FTICR mass spectrometer equipped with nanoelectrospray source (nano-HPLC/nano-ESI-FTICRMS) for proteome analysis. Protein identification in proteomics is usually conducted by accurately determining peptide masses resulting from enzymatic protein digests and comparing them with theoretically digested protein sequences from databases. A tryptic in-solution digest of bovine serum albumin was used to optimize experimental conditions and data processing. Spots from Coomassie Blue and silver-stained two-dimensional (2D) gels of human thyroid tissue were excised, in-gel digested with trypsin, and subsequently analyzed by nano-HPLC/nano-ESI-FTICRMS. Additionally, we analyzed 1D-gel bands of membrane preparations of COS-6 cells from African green monkey kidney as an example of more complex protein mixtures. Nano-HPLC was performed using 1-mm reverse-phase C-18 columns for pre-concentration of the samples and reverse-phase C-18 capillary columns for separation, applying water/acetonitrile gradient elution conditions at flow rates of 200,nL/min. Mass measurement accuracies smaller than 3,ppm were routinely obtained. Different methods for processing the raw data were compared in order to identify a maximum number of peptides with the highest possible degree of automation. Parallel identification of proteins from complex mixtures down to low-femtomole levels makes nano-HPLC/nano-ESI-FTICRMS an attractive approach for proteome analysis. Copyright © 2003 John Wiley & Sons, Ltd. [source] Investigation and correction of the gene-derived sequence of glutenin subunit 1Dx2 by matrix-assisted laser desorption/ionisation mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 20 2002Vincenzo Cunsolo Direct matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) analysis of a mixture of tryptic peptides was used to verify the gene-derived amino acid sequence of the high molecular weight (HMW) subunit 1Dx2 of bread wheat. Analysis of the digest was performed by recording several MALDI mass spectra of the mixture at low, medium and high mass ranges, and optimising the matrix and the acquisition parameters for each mass range. This resulted in coverage of the whole sequence except for a short fragment T3 (3 amino acids), which was not detected. It also allowed the insertion of a Pro residue in position 59 to be identified. The results obtained provide evidence for the lack of a substantial level of glycosylation or other post-translational modifications of subunit 1Dx2, and demonstrate that MALDI-MS is the most useful method presently available for the direct verification of the gene-derived sequences of HMW glutenin subunits and similar proteins. Copyright © 2002 John Wiley & Sons, Ltd. [source] Short pulse laser mass spectrometry of nitrotoluenes: ionization and fragmentation behaviorRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 5 2002Christian Weickhardt The mass spectra of all isomers of mononitrotoluene, four isomers of dinitrotoluene and of 2,4,6,-trinitrotoluene, obtained by multiphoton ionization utilizing ultrashort laser pulses with center wavelengths of either 206,nm or 412,nm, are presented and discussed. Under these ionization conditions all nitrotoluenes exhibit a high degree of fragmentation which increases with the degree of substitution. For the compounds having a nitro group in position 2 and/or 6 a pronounced ortho effect leading to the loss of OH is observed. The fragmentation patterns in the lower mass range are typical for alkylated aromatic substances. While no fundamental differences between the mass spectra obtained with the two wavelengths were observed, the visible light in all cases resulted in a broader variety of fragments and additional signals in the higher mass range. The latter can be used for isomer identification. Copyright © 2002 John Wiley & Sons, Ltd. [source] Maturation of the lantibiotic subtilin: matrix-assisted laser desorption/ionization time-of-flight mass spectrometry to monitor precursors and their proteolytic processing in crude bacterial culturesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2002Torsten Stein Bacillus subtilis synthesizes the lanthionine containing 32-amino-acid peptide antibiotic (lanti-biotic) subtilin from a ribosomally generated 56-amino-acid precursor pre-propeptide by extensive posttranslational modifications. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to monitor the production of matured subtilin within crude samples taken from B. subtilis culture media without prior fractionation. The processing reaction of subtilin was blocked with the serine protease inhibitor phenylmethylsulfonyl fluoride and different subtilin precursor peptides in the molecular mass range up to 6220 were observed. Two of these species were isolated by reversed-phase high-performance liquid chromatography (HPLC) and structurally analyzed by post-source decay MALDI-TOFMS. We provide evidence that the precursor species comprise the posttranslational modified C-terminal part of subtilin to which leader peptide moieties with different chain lengths are attached. These antimicrobial-inactive species could be processed to antibiotic-active subtilin by incubation with culture media of different subtilin-nonproducing B. subtilis strains as indicated by a combination of antimicrobial growth assays and MALDI-TOFMS analyses. These achievements are strong evidence for the sensitivity of MALDI-TOFMS methodology that allows straightforward investigations of analytes even in complex mixtures without time-consuming sample preparations. Copyright © 2001 John Wiley & Sons, Ltd. [source] Ion rotating motion in a gas-filled radio-frequency quadrupole ion guide as a new technique for structural and kinetic investigations of ionsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 20 2001Valeri V. Raznikov An ion rotating excitation mode of operation of a segmented gas-filled radio-frequency quadrupole (RFQ) ion guide for a high-resolution orthogonal time-of-flight (TOF) mass spectrometer is described. It is shown theoretically, by computer simulation and experimentally, that ion rotating excitation in a gas-filled RFQ has several advantages over other types of ion oscillation excitation. The main advantages are an approximately twofold increase in average ion kinetic energy for the same maximal deviation from the RFQ axis and therefore an increase of about this factor of average internal excitation energy of ions, and the extended mass range of fragment ions that can be observed. The new method of ion decomposition by ion rotation around the axis of an RFQ ion guide was experimentally implemented and tested using a home-built ,SIN-COS' generator to supply the excitation voltage. This generator enables control of phase shift and amplitude of excitation voltages applied to quadrupole rods smoothly from the data acquisition program running on a PC. Copyright © 2001 John Wiley & Sons, Ltd. [source] Differential Capture of Serum Proteins for Expression Profiling and Biomarker Discovery in Pre- and Posttreatment Head and Neck Cancer Samples,THE LARYNGOSCOPE, Issue 1 2008Gary L. Freed MD Abstract Introduction: A long-term goal of our group is to develop proteomic-based approaches to the detection and use of protein biomarkers for improvement in diagnosis, prognosis, and tailoring of treatment for head and neck squamous cell cancer (HNSCC). We have previously demonstrated that protein expression profiling of serum can identify multiple protein biomarker events that can serve as molecular fingerprints for the assessment of HNSCC disease state and prognosis. Methods: An automated Bruker Daltonics (Billerica, MA) ClinProt matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometer was used. Magnetic chemical affinity beads were used to differentially capture serum proteins prior to MALDI-TOF analysis. The resulting spectra were analyzed using postprocessing software and a pattern recognition genetic algorithm (ClinProt 2.0). An HNSCC cohort of 48 sera samples from 24 patients consisting of matched pretreatment and 6 to 12 month posttreatment samples was used for further analysis. Low-mass differentially expressed peptides were identified using MALDI-TOF/TOF. Results: In the working mass range of 1,000 to 10,000 m/z, approximately 200 peaks were resolved for ionic bead capture approaches. For spectra generated from weak cation bead capture, a k-nearest neighbor genetic algorithm was able to correctly classify 94% normal from pretreatment HNSCC samples, 80% of pretreatment from posttreatment samples, and 87% of normal from posttreatment samples. These peptides were then analyzed by MALDI-TOF/TOF mass spectometry for sequence identification directly from serum processed with the same magnetic bead chemistry or alternatively after gel electrophoresis separation of the captured proteins. We were able to compare this with similar studies using surface-enhanced laser desorption ionization (SELDI)-TOF to show this method as a valid tool for this process with some improvement in the identification of our groups. Conclusions: This initial study using new high-resolution MALDI-TOF mass spectrometry coupled with bead fractionation is suitable for automated protein profiling and has the capability to simultaneously identify potential biomarker proteins for HNSCC. In addition, we were able to show improvement with the MALDI-TOF in identifying groups with HNSCC when compared with our prior data using SELDI-TOF. Using this MALDI-TOF technology as a discovery platform, we anticipate generating biomarker panels for use in more accurate prediction of prognosis and treatment efficacies for HNSCC. [source] Proteomic analysis of the venom from the endoparasitoid wasp Pteromalus puparum (Hymenoptera: Pteromalidae)ARCHIVES OF INSECT BIOCHEMISTRY AND PHYSIOLOGY (ELECTRONIC), Issue 1 2010Jia-Ying Zhu Abstract Parasitoid venom is a complex mixture of active substances with diversified biological functions. Because of its range of activities, venom is an important resource with respect to potential application in agriculture and medicine. Only a limited number of peptides, proteins, and enzymes have been identified and characterized from parasitoid venom. Here we describe a proteomic analysis of the venom from the endoparasitoid wasp Pteromalus puparum (Hymenoptera: Pteromalidae). Venom resolved by two-dimensional electrophoresis yielded 56 protein spots with major proteins in the pI range 4,7 and molecular mass range of 25,66.2,kDa. The amino acid sequences of the proteins were identified by mass spectrometry. Several venom proteins such as calreticulin, venom acid phosphatase, serine protease, arginine kinase, serine protease homolog, aminotransferase-like venom protein, and heat shock protein 70, were identified in silico based on their amino acid sequences. The full-length cDNAs of calreticulin and arginine kinase were cloned. Calreticulin showed 62% identity with calreticulin in the venom of Cotesia rubecula. Arginine kinase showed a high level of sequence identity (92%) with its counterpart in the venom of Cyphononyx dorsalis. RT-PCR analysis revealed that the transcript levels of calreticulin and arginine kinase were developmentally changed, suggesting a possible correlation with the oviposition process. This study contributes to our appreciation of a parasitoid wasp venom composition. © 2010 Wiley Periodicals, Inc. [source] Optical and infrared photometry of new very low-mass stars and brown dwarfs in the , Orionis clusterASTRONOMISCHE NACHRICHTEN, Issue 9 2004V. J. S. Béjar Abstract We present an RI photometric survey covering an area of 430 arcmin2 around the multiple star , Orionis. The observations were conducted with the 0.8 m IAC-80 Telescope at the Teide Observatory. The survey limiting R and I magnitudes are 22.5 and 21, and completeness magnitudes 21 and 20, respectively. We have selected 53 candidates from the I vs. R,I colour-magnitude diagram (I = 14,20) that follow the previously known photometric sequence of the cluster. Adopting an age of 2,4 Myr for the cluster, we find that these objects span a mass range from 0.35 M, to 0.015 M,. We have performed J -band photometry of 52 candidates and Ks photometry for 12 of them, with the result that 50 follow the expected infrared sequence for the cluster, thus confirming with great confidence that the majority of the candidates are bona fide members. JHKs photometry from the Two Micron All Sky Survey (2MASS) is available for 50 of the candidates and are in good agreement with our data. Out of 48 candidates, which have photometric accuracies better than 0.1 mag in all bands, only three appear to show near-infrared excesses. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [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] The distribution of ejected subhaloes and its implication for halo assembly biasMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 4 2009Huiyuan Wang ABSTRACT Using a high-resolution cosmological N -body simulation, we identify the ejected population of subhaloes, which are haloes at redshift z= 0 but were once contained in more massive ,host' haloes at high redshifts. The fraction of the ejected subhaloes in the total halo population of the same mass ranges from 9 to 4 per cent for halo masses from ,1011 to ,1012 h,1 M,. Most of the ejected subhaloes are distributed within four times the virial radius of their hosts. These ejected subhaloes have distinct velocity distribution around their hosts in comparison to normal haloes. The number of subhaloes ejected from a host of given mass increases with the assembly redshift of the host. Ejected subhaloes in general reside in high-density regions, and have a much higher bias parameter than normal haloes of the same mass. They also have earlier assembly times, so that they contribute to the assembly bias of dark matter haloes seen in cosmological simulations. However, the assembly bias is not dominated by the ejected population, indicating that large-scale environmental effects on normal haloes are the main source for the assembly bias. [source] | |||||||||||||