Low Mass Range Research Articles

Nitrocellulose Film Substrate Minimizes Fragmentation in Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry Analysis of Triacylglycerols

The potential of matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) for the analysis of intact triacylglycerols (TAGs) is generally limited by the extensive in-source prompt fragmentation. The sequential deposition of matrix and TAGs over the stainless steel target precoated with a thin layer of nitrocellulose (NC) drastically reduced fragmentation in the MALDI-TOF MS profiling of oils and fats. The NC MALDI-TOF MS profiles of native and thermally stressed virgin olive oil and butter are reported as case studies, along with test analyses of a standard mixture of mono-, di-, and triacylglycerols. Mass spectra were almost completely devoid of both fragment and matrix ion signals, thus disclosing relevant information, especially in the low molecular mass range. The detection of several partial acylglycerols of low abundance and minor TAGs that are barely observed with other techniques also provided evidence for an increased dynamic range of NC MALDI-TOF MS that was due to the minimization of suppressive effects. The NC film substrate also improved the shot-to-shot and sample-to-sample reproducibility of the ion production through the exhibition of a more homogeneous matrix/analyte cocrystallization, thus enabling MALDI-based measurements to a consistent quantification of TAGs.

Laser desorption/ionization mass spectrometric analysis of small molecules using fullerene‐derivatized silica as energy‐absorbing material

In spite of the growing acceptance of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the analysis of a wide variety of compounds, including polymers and proteins, its use in analyzing low-molecular-weight molecules (<1000 m/z) is still limited. This is mainly due to the interference of matrix molecules in the low-mass range. Here the derivatized fullerenes covalently bound to silica particles with different pore sizes are applied as thin layer for laser desorption/ionization (LDI) mass spectrometric analysis. Thus, an interference of intrinsic matrix ions can be eliminated or minimized in comparison with the state-of-the-art weak organic acid matrices. The desorption/ionization ability of the developed fullerene-silica materials depends on the applied laser power, sample preparation and pore size of the silica particles. Thus, fullerene-silica serves as an LDI support for mass spectrometric analysis of molecules (<1500 Da). The performance of the fullerene-silica is demonstrated by the mass analysis of variety of small molecules such as carbohydrates, amino acids, peptides, phospholipids and drugs.

A dark matter candidate from Lorentz invariance in 6D

We study the unique 6 dimensional orbifold with chiral fermions where a stable dark matter candidate is present due to Lorentz invariance on the orbifold, with no additional discrete symmetries imposed by hand. We propose a model of Universal Extra Dimensions where a scalar photon of few hundred GeV is a good candidate for dark matter. The spectrum of the model is characteristic of the geometry, and it has clear distinctive features compared to previous models of Kaluza-Klein dark matter. The 5 dimensional limit of this model is the minimal model of natural Kaluza-Klein dark matter. Notwithstanding the low mass range preferred by cosmology, the model will be a challenge for the LHC due to the relatively small splitting between the states in the same KK level.

Liquid chromatography/tandem mass spectrometric analysis of 7,10-dihydroxyoctadecenoic acid, its isotopomers, and other 7,10-dihydroxy fatty acids formed byPseudomonas aeruginosa42A2

Pseudomonas aeruginosa is an opportunistic pathogen, which oxidizes oleic acid to 7(S),10(S)-dihydroxy-8(E)-octadecenoic acid (7,10-(OH)(2)-18:1) of biological and industrial interest. Electrospray tandem mass spectrometric (MS/MS) analysis of hydroxylated fatty acids usually generates characteristic fragments containing the carboxylate anion and formed by alpha-cleavage at the oxidized carbon. These fragments indicate the positions of the hydroxyl group. In contrast, liquid chromatography (LC)/MS/MS analysis of 7,10-(OH)(2)-18:1 yielded a series of other ions with structural information. To study the fragmentation mechanism, we prepared (2)H- and (18)O-labeled isotopomers. We also performed MS(3) analysis of the major ions, and for comparison we generated the corresponding 7,10-dihydroxy metabolites of 16:1n-7, 18:2n-6, and 20:1n-11 with a protein extract of P. aeruginosa. The MS/MS spectra of 7,10-(OH)(2)-18:1 and its isotopomers, 7,10-(OH)(2)-16:1, and 7,10-(OH)(2)-20:1, contained a series of prominent fragments that all hold the omega end. The 8,9-double bond was not essential for this fragmentation, as 7,10-(OH)(2)-18:0, and its isotopomers, formed essentially the same fragments in the lower mass range. In contrast, 7,10-dihydroxy-8(E),12(Z)-octadecadienoic acid (7,10-(OH)(2)-18:2) fragmented by alpha-cleavage at the oxidized carbons with formation of carboxylate anions. Our results demonstrate that C(16)-C(20) fatty acids with a 7,10-dihydroxy-8(E) functionality undergo charge-driven fragmentation after charge migration to the omega-end, whereas the main ions of 7,10-(HO)(2)-18:2 retain charge at the carboxyl group.

H I-SELECTED GALAXIES AS A PROBE OF QUASAR ABSORPTION SYSTEMS

We investigate the properties of HI-rich galaxies detected in blind radio surveys within the hierarchical structure formation scenario using a semi-analytic model of galaxy formation. By drawing a detailed comparison between the properties of HI-selected galaxies and HI absorption systems, we argue a link between the local galaxy population and quasar absorption systems, particularly for Damped Ly-alpha absorption (DLA) systems and sub-DLA systems. First, we evaluate how many HI-selected galaxies exhibit HI column densities as high as those of DLA systems. We find that HI-selected galaxies with HI masses M(HI) > 10^8 solar masses have gaseous disks that produce HI column densities comparable to those of DLA systems. We conclude that DLA galaxies where the HI column densities are as high as those of DLA systems, contribute significantly to the population of HI-selected galaxies at M(HI) > 10^8 solar masses. Second, we find that star formation rates (SFRs) correlate tightly with HI masses rather than B- (and J-) band luminosities. In the low-mass range M(HI) < 10^8 solar masses, sub-DLA galaxies replace DLA galaxies as the dominant population. The number fraction of sub-DLA galaxies relative to galaxies reaches 40%-60% at HI masses 10^8 solar masses and 30%-80% at 10^7 solar masses. The HI-selected galaxies at 10^7 solar masses are a strong probe of sub-DLA systems that place stringent constraints on galaxy formation and evolution.

Distribution of T-Scores and Z-Scores in a University Cohort with an Emphasis on Elevated Bone Mineral Density (BMD)

We used DXA data from the most recent (2005-2006) National Health and Nutrition Examination Survey to identify men with femoral neck osteoporosis (T-score -2.5), using both male and female normative references. Prevalence estimates based on bone mineral density (BMD) were compared with self-reported prevalence of osteoporosis. Corresponding national prevalence estimates were obtained using survey sample weights. Logistic regression was used to assess the association between subject characteristics and osteoporosis (based on female norms) among men aged 50 and older. Based on female norms, estimates of osteoporosis ranged from 0.6% of men in their fifties to 8.8% of men eighty and older; corresponding estimates using male norms ranged from 2.0% to 11.6%. Projecting to the US population, this corresponds to 0.7 million (95% CI: 0.4-1.0 million) men with low femoral neck bone mass using female norms, and 1.2 million (95% CI: 0.8-1.7 million) men using male norms. A generational effect was noted between BMD-based and self-reported osteoporosis prevalence estimates. More subjects in their fifties reported having been diagnosed and treated for osteoporosis than met BMD criteria, while more men eighty and older met BMD criteria than reported diagnosis or treatment. After adjustment for age, a number of differences were noted between men 50 and older with and without osteoporosis. Osteoporotic men were shorter (mean height 166 vs. 175 cm, p 5 0.01), and more likely to report being unable to perform tasks around the home/yard (21.6% vs. 2.0%, p 5 0.01), walk or bicycle (23.4% vs. 1.4%, p ! 0.01), and engage in moderate activities (30.4% vs. 2.5%, p ! 0.01) than their non-osteoporotic peers. Estimates of the number of US men with low femoral neck bone mass range from 0.7 to 1.2 million depending on the normative reference used. Men with osteoporosis are shorter than their non-osteoporotic peers and report greater functional disability than their peers. More research is needed to understand the functional consequences of male osteoporosis by different criteria

Spectral Fingerprints of Habitability

The emerging field of extrasolar planet search has shown an extraordinary ability to combine research by astrophysics, chemistry, biology and geophysics into a new and exciting interdisciplinary approach to understand our place in the universe. Are there other worlds like ours? How can we characterize those planets and assess if they are habitable? After a decade rich in giant exoplanet detections, observation techniques have now reached the ability to find planets of less than 10 M_Earth (so called Super-Earths) that may potentially be habitable. The detection and characterization of Earth-like planet is approaching rapidly with dedicated space observatories already in operation (Corot) or in development phase (Kepler, James Webb Space Telescope, Extremely Large Telescope (ELT), Darwin/TPF). Space missions like CoRoT (CNES, Rouan et al. 1998) and Kepler (NASA, Borucki et al. 1997) will give us statistics on the number, size, period and orbital distance of planets, extending to terrestrial planets on the lower mass range end as a first step, while missions like Darwin/TPF are designed to characterize their atmospheres. In this chapter we discuss how we can read a planet's spectral fingerprint and characterize if it is potentially habitable. We discuss the first steps to detect a habitable planet and set biomarker detection in context in Section 1. In Section 2 we focus on biomarkers, their signatures at different wavelengths, abiotic sources and cryptic photosynthesis – using Earth as our primary example – the only habitable planet we know of so far. Section 3 concentrates on planets around different stars, and Section 4 summarizes the chapter.

Assessment of Suitability of Magnetic Beads for Purification of Rat Plasma in Proteomic Analyses by Matrix-Assisted Laser Desorption IonizationTime-of-Flight MS

Plasma is a complex matrix and has to be clarified or fractionated to obtain informative MS data. Although there are a number of prefractionation methods to clean up complex biological matrixes before proteomic analysis, these methods require large sample volumes and are costly and time-consuming. Alternatively, recently introduced magnetic beads (MB) appear to be attractive in overcoming these difficulties. Therefore, we were interested in investigating the applicability of MB in the clarification of rat plasma samples for proteome analyses. For this purpose, we used complementary supports, such as hydrophobic interaction chromatography-based MB (MB-C18) and weak cation-exchange chromatography-based MB (MB-WCX). MB-based fractionated samples were either spotted directly or underwent tryptic digestion before matrix-assisted laser desorption ionization (MALDI) spotting. Samples from both MB separation techniques gave clean and well-resolved MALDI-time-of-flight MS spectra in the low molecular mass range of 1-10 kDa with alpha-cyano-4-hydroxycinnamic acid as the matrix. Both techniques gave approximately 300 analyte peaks in this mass range. Our results showed that both MB-based separation procedures gave complementary mass spectral information. This approach provided information on the identity of a number of less-abundant and more-abundant proteins in plasma. Our findings suggest that this MB-based proteomic approach can be valuable in conducting faster screening of plasma samples for protein profiling.

Improved flow pattern map for accurate prediction of the heat transfer coefficients during condensation of R-134a in smooth horizontal tubes and within the low-mass flux range

This paper presents an improved flow pattern map for predicting the heat transfer coefficients during condensation of R-134a inside a smooth horizontal tube. Experimental tests were conducted over the low-mass flux range of 75–300 kg/m 2 s, at a nominal saturation temperature of 40 °C, and with the test section vapour qualities ranging from 0.76 down to 0.03. This represents points within the annular, intermittent and stratified flow regimes. The results were used to modify the Thome–El Hajal flow pattern map to include a transition region between the stratified-wavy and annular or intermittent flow regimes. The revised flow pattern-based heat transfer correlation predicted the experimental data to a mean deviation of less than 6%.

Probing Minicharged Particles with Tests of Coulomb’s Law

Minicharged particles arise in many extensions of the standard model. Their contribution to the vacuum polarization modifies Coulomb's law via the Uehling potential. In this Letter, we argue that tests for electromagnetic fifth forces can therefore be a sensitive probe of minicharged particles. In the low mass range < or approximately equal to microeV existing constraints from Cavendish type experiments provide the best model-independent bounds on minicharged particles.

GALICS. II: the [ α/Fe] -mass relation in elliptical galaxies

We aim at reproducing the mass- and sigma-[alpha/Fe] relations in the stellar populations of early-type galaxies by means of a cosmologically motivated assembly history for the spheroids. We implement a detailed treatment for the chemical evolution of H, He, O and Fe in GalICS, a semi-analytical model for galaxy formation which successfully reproduces basic low- and high-redshift galaxy properties. The contribution of supernovae (both type Ia and II) as well as low- and intermediate-mass stars to chemical feedback are taken into account. We find that this chemically improved GalICS does not produce the observed mass- and sigma-[alpha/Fe] relations. The slope is too shallow and scatter too large, in particular in the low and intermediate mass range. The model shows significant improvement at the highest masses and velocity dispersions, where the predicted [alpha/Fe] ratios are now marginally consistent with observed values. We show that this result comes from the implementation of AGN (plus halo) quenching of the star formation in massive haloes. A thorough exploration of the parameter space shows that the failure of reproducing the mass- and sigma-[alpha/Fe] relations can partly be attributed to the way in which star formation and feedback are currently modelled. The merger process is responsible for a part of the scatter. We suggest that the next generation of semi-analytical model should feature feedback (either stellar of from AGN) mechanisms linked to single galaxies and not only to the halo, especially in the low and intermediate mass range. The integral star formation history of a single galaxy determines its final stellar [alpha/Fe] as it might be expected from the results of closed box chemical evolution models. (abridged)

HI-selected Galaxies As a Probe of Quasar Absorption Systems

AbstractWe investigate the properties of local HI-selected galaxies detected in blind radio surveys by using semi-analytic galaxy formation models in the hierarchical structure formation scenario. By drawing a detailed comparison between the properties of the HI-selected galaxies and the quasar absorption systems, we investigate a link between the local galaxy population and the quasar absorption systems, particularly for Damped Lymanα absorption (DLA) systems (NHI ≥ 1020.3 cm−2) and sub-DLA systems (1019 &lt; NHI &lt; 1020.3 cm−2).We find that DLA galaxies, in which the HI column densities are as high as those of DLA systems, contribute primarily to the population of local HI-selected galaxies at MHI ≥ 108M⊙. By contrast, in the low-mass range MHI ≤ 107M⊙, sub-DLA galaxies replace DLA galaxies as the dominant population. The HI-selected galaxies would be a strong probe of DLA/sub-DLA systems.

Characterizing Spatial and Temporal Variability of Dissolved Gases in Aquatic Environments with in situ Mass Spectrometry

The TETHYS mass spectrometer is intended for long-term in situ observation of dissolved gases and volatile organic compounds in aquatic environments. Its design maintains excellent low mass range sensitivity and stability during long-term operations, enabling characterization of low-frequency variability in many trace dissolved gases. Results are presented from laboratory trials and a 300-h in situ trial in a shallow marine embayment in Massachusetts, U.S.A. This time series consists of over 15000 sample measurements and represents the longest continuous record made by an in situ mass spectrometer in an aquatic environment. These measurements possess sufficient sampling density and duration to apply frequency analysis techniques for study of temporal variability in dissolved gases. Results reveal correlations with specific environmental periodicities. Numerical methods are presented for converting mass spectrometer ion peak ratios to absolute-scale dissolved gas concentrations across wide temperature regimes irrespective of ambient pressure, during vertical water column profiles in a hypoxic deep marine basin off the coast of California, U.S.A. Dissolved oxygen concentration values obtained with the TETHYS instrument indicate close correlation with polarographic oxygen sensor data across the entire depth range. These methods and technology enable observation of aquatic environmental chemical distributions and dynamics at appropriate scales of resolution.

A top-heavy stellar initial mass function in starbursts as an explanation for the high mass-to-light ratios of ultra-compact dwarf galaxies

It has been shown recently that the dynamical V-band mass-to-light ratios of compact stellar systems with masses from 10^6 to 10^8 Solar masses are not consistent with the predictions from simple stellar population (SSP) models. Top-heavy stellar initial mass functions (IMFs) in these so-called ultra compact dwarf galaxies (UCDs) offer an attractive explanation for this finding, the stellar remnants and retained stellar envelopes providing the unseen mass. We therefore construct a model which quantifies by how much the IMFs of UCDs would have to deviate in the intermediate-mass and high-mass range from the canonical IMF in order to account for the enhanced M/L_V ratio of the UCDs. The deduced high-mass IMF in the UCDs depends on the age of the UCDs and the number of faint products of stellar evolution retained by them. Assuming that the IMF in the UCDs is a three-part power-law equal to the canonical IMF in the low-mass range and taking 20% as a plausible choice for the fraction of the remnants of high-mass stars retained by UCDs, the model suggests the exponent of the high-mass IMF to be approximately 1.6 if the UCDs are 13 Gyr old (i.e. almost as old as the Universe) or approximately 1.0 if the UCDs are 7 Gyr old, in contrast to 2.3 for the Salpeter-Massey IMF. If the IMF was as top-heavy as suggested here, the stability of the UCDs might have been threatened by heavy mass loss induced by the radiation and evolution of massive stars. The central densities of UCDs must have been in the range 10^6 to 10^7 Solar masses per cubic parsec when they formed with star formation rates of 10 to 100 Solar masses per year.

Development of Quadrupole Mass Spectrometers Using Rapid Prototyping Technology

In this report, we present a prototype design of a quadrupole mass filter (QMF) with hyperbolic electrodes, fabricated at the University of Liverpool using digital light processing (DLP), a low-cost and lightweight 3D rapid prototyping (RP) technique. Experimental mass spectra are shown for H(2)(+), D(2)(+), and He(+) ions to provide proof of principle that the DLP mass filter is working as a mass analyzer in the low-mass range (1 to 10 amu). The performance of the DLP QMF has also been investigated for individual spectral peaks. Numerical simulations of the instrument were performed by coupling CPO and Liverpool QMS-2 programs to model both the ion source and mass filter, respectively, and the instrument is shown to perform as predicted by theory. DLP thus allows miniaturization of mass spectrometers at low cost, using hyperbolic (or other) geometries of mass analyzer electrodes that provide optimal ion manipulation and resolution for a given application. The potential of using RP fabrication techniques for developing miniature and microscale mass analyzers is also discussed.

Liquid chromatography–tandem quadrupole mass spectrometry and comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry measurement of targeted metabolites of Methylobacterium extorquens AM1 grown on two different carbon sources

Complementary methods using liquid chromatography–tandem quadrupole mass spectrometry (LC–MS/MS) and comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC–TOF-MS) were developed and applied to determine targeted metabolites involved in central carbon metabolism [including tricarboxylic acid cycle, serine cycle, ethylmalonyl-coenzyme A (ethylmalonyl-CoA) pathway and poly-β-hydroxybutyrate cycle] of the bacterium Methylobacterium extorquens AM1 grown on two carbon sources, ethylamine (C2) and succinate (C4). Nucleotides, acyl-CoAs and a few volatile metabolites in cell extracts of M. extorquens AM1 were readily separated using either hydrophilic interaction liquid chromatography or reversed-phase liquid chromatography, and detected with good sensitivity by MS/MS. However, volatile intermediates within a low mass range (<300 m/ z), especially at low abundance (such as glyoxylic acid and others <500 nM), were more effectively analyzed by GC × GC–TOF-MS which often provided better sensitivity, resolution and reproducibility. The complementary nature of the LC-based and GC-based methods allowed the comparison of 39 metabolite concentrations (the lowest level was at 139.3 nM). The overlap between the LC-based and GC-based methods of seven metabolites provided a basis to check for consistency between the two methods, and thus provided some validation of the quantification accuracy. The abundance change of 20 intermediates further suggested differences in pathways linked to C2 and C4 metabolism.

A Synthetic Germanium‐Bismuth Glass for the Coarse Mass Calibration of SIMS Instruments

This short technical note describes a simple technique for synthesising an optimised binary glass for performing coarse mass table calibrations of secondary ion mass spectrometers. A Ge‐Bi glass doped with five selected trace elements was used to anchor the entire mass table up to m/z ≥ 209 at an accuracy of &lt; 0.5 dalton. Using this material it has been possible to calibrate coarsely the mass table of a Cameca ims 6f instrument in less than five minutes, thereby greatly simplifying the switch from low mass range to high mass range measurements. Although not suitable for the quantification of geological materials, the ease of synthesis and its utility for rapidly performing what is an otherwise time consuming process makes this material a useful tool for SIMS instruments which offer a multiple mass range capability.

Sub-keV neutrino and dark matter physics with ultra-low-energy Germanium detector

We present in the poster the status of an R&D program towards the goal of an ultra-low-energy germanium (ULEGe) detector at threshold of 100 eV with an active target mass on the order of 1 kg and a background near threshold at the range of 1 event/kg-keV-day [1]. The scientific objectives include the studies of neutrino-nucleus coherent scattering and neutrino magnetic moments, as well as WIMP dark matter searches at the low WIMP mass range. Such detectors would also have potential implications in reactor monitoring for security purposes. A threshold of 220 eV has been demonstrated with a prototype 4-channel ULEGe array with a total mass of 20 g [2]. Competitive limits have been derived for WIMP-nucleon couplings for WIMPs with mass less than 10 GeV. Scale-up plans are described.

Fifteen new T dwarfs discovered in the UKIDSS Large Area Survey

We present the discovery of fifteen new T2.5-T7.5 dwarfs (with estimated distances between ~24-93pc, identified in the first three main data releases of the UKIRT Infrared Deep Sky Survey. This brings the total number of T dwarfs discovered in the Large Area Survey (to date) to 28. These discoveries are confirmed by near infrared spectroscopy, from which we derive spectral types on the unified scheme of Burgasser et al. (2006). Seven of the new T dwarfs have spectral types of T2.5-T4.5, five have spectral types of T5-T5.5, one is a T6.5p, and two are T7-7.5. We assess spectral morphology and colours to identify T dwarfs in our sample that may have non-typical physical properties (by comparison to solar neighbourhood populations). The colours of the full sample of LAS T dwarfs show a possible trend to bluer Y-J with decreasing effective temperature beyond T8. By accounting for the main sources of incompleteness (selection, follow-up and spatial) as well as the effects of unresolved binarity and Malmquist bias, we estimate that there are 17+-4 >=T4 dwarfs in the J<=19 volume of the LAS second data release. Comparing this to theoretical predictions is most consistent with a sub-stellar mass function exponent alpha between -1.0 and 0. This is consistent with the latest 2MASS/SDSS constraint (which is based on lower number statistics), and is significantly lower than the alpha~1.0 suggested by L dwarf field populations, possibly a result of the lower mass range probed by the T dwarf class.

Robust and Sensitive iTRAQ Quantification on an LTQ Orbitrap Mass Spectrometer

Isobaric stable isotope tagging reagents such as tandem mass tags or isobaric tags for relative and absolute quantification enable multiplexed quantification of peptides via reporter ion signals in the low mass range of tandem mass spectra. Until recently, the poor recovery of low mass fragments observed in tandem mass spectra acquired on ion trap mass spectrometers precluded the use of these reagents on this widely available instrument platform. The Pulsed Q Dissociation (PQD) technique allows negotiating this limitation but suffers from poor fragmentation efficiency, which has raised doubts in the community as to its practical utility. Here we show that by carefully optimizing instrument parameters such as collision energy, activation Q, delay time, ion isolation width, number of microscans, and number of trapped ions, low m/z fragment ion intensities can be generated that enable accurate peptide quantification at the 100 amol level. Side by side comparison of PQD on an LTQ Orbitrap with CID on a five-year old Q-Tof Ultima using complex protein digests shows that whereas precision of quantification of 10-15% can be achieved by both approaches, PQD quantifies twice as many proteins. PQD on an LTQ Orbitrap also outperforms "higher energy collision induced dissociation" on the same instrument using the recently introduced octapole collision cell in terms of lower limit of quantification. Finally, we demonstrate the significant analytical potential of iTRAQ quantification using PQD on an LTQ Orbitrap by quantitatively measuring the kinase interaction profile of the small molecule drug imatinib in K-562 cells. This article gives practical guidance for the implementation of PQD, discusses its merits, and for the first time, compares its performance to higher energy collision-induced dissociation.