Galactic archaeology: IMF and depletion in the "thin disk"

We determine the initial mass function (IMF) of the ``thin disk'' by means of a direct comparison between synthetic stellar samples (for different matching choices of IMF, star formation rate SFR and depletion) and a complete (volume-limited) sample of single stars near the galactic plane (|z| < 25pc), selected from the Hipparcos catalogue (d < 100pc, M_v < +4.0). Our synthetic samples are computed from first principles: stars are created with a random distribution of mass M_* and age t_* which follow a given (genuine) IMF and SFR(t_*). They are then placed in the HR diagram by means of a grid of empirically well-tested evolution tracks. The quality of the match (synthetic versus observed sample) is assessed by means of star counts in specific regions in the HR diagram. 7 regions are located along the MS (main sequence, mass sensitive), while 4 regions represent different evolved (age-sensitive) stages of the stars. The counts of evolved stars, in particular, give valuable evidence of the history of the ``thin disk'' (apparent) star formation and lift the ambiguities in models restricted to MS star counts.Comment: 10 pages, 3 figures, submitted to MNRA

Letter to Sound Rules for Accented Lexicon Compression

This paper presents trainable methods for generating letter to sound rules from a given lexicon for use in pronouncing out-of-vocabulary words and as a method for lexicon compression. As the relationship between a string of letters and a string of phonemes representing its pronunciation for many languages is not trivial, we discuss two alignment procedures, one fully automatic and one hand-seeded which produce reasonable alignments of letters to phones. Top Down Induction Tree models are trained on the aligned entries. We show how combined phoneme/stress prediction is better than separate prediction processes, and still better when including in the model the last phonemes transcribed and part of speech information. For the lexicons we have tested, our models have a word accuracy (including stress) of 78% for OALD, 62% for CMU and 94% for BRULEX. The extremely high scores on the training sets allow substantial size reductions (more than 1/20). WWW site: http://tcts.fpms.ac.be/synthesis/mbrdicoComment: 4 pages 1 figur

X-ray Emission from Haloes of Simulated Disc Galaxies

Bolometric and 0.2-2 keV X-ray luminosities of the hot gas haloes of simulated disc galaxies have been calculated at redshift z=0. The TreeSPH simulations are fully cosmological and the sample of 44 disc galaxies span a range in characteristic circular speeds of V_c = 130-325 km/s. The galaxies have been obtained in simulations with a considerable range of physical parameters, varying the baryonic fraction, the gas metallicity, the meta-galactic UV field, the cosmology, the dark matter type, and also the numerical resolution. The models are found to be in agreement with the (few) relevant X-ray observations available at present. The amount of hot gas in the haloes is also consistent with constraints from pulsar dispersion measures in the Milky Way. Forthcoming XMM and Chandra observations should enable much more stringent tests and provide constraints on the physical parameters. We find that simple cooling flow models over-predict X-ray luminosities by up to two orders of magnitude for high (but still realistic) cooling efficiencies relative to the models presented here. Our results display a clear trend that increasing cooling efficiency leads to decreasing X-ray luminosities at z=0. The reason is found to be that increased cooling efficiency leads to a decreased fraction of hot gas relative to total baryonic mass inside of the virial radius at present. At gas metal abundances of a third solar this hot gas fraction becomes as low as just a few percent. We also find that most of the X-ray emission comes from the inner parts (inner about 20 kpc) of the hot galactic haloes. Finally, we find for realistic choices of the physical parameters that disc galaxy haloes possibly were more than one order of magnitude brighter in soft X-ray emission at z=1, than at present.Comment: 8 pages, 7 figures, MNRAS LaTeX forma

Glycan analysis by ion mobility-mass spectrometry and gas-phase spectroscopy

Due to the existence of numerous isomers, the in-depth analysis of glycans represents a major challenge. Currently, the majority of glycans are analysed using mass spectrometry (MS)-based techniques, which can provide information on regioisomers but usually fail to differentiate stereoisomers. A promising approach to overcome this limitation is to implement ion mobility spectrometry (IMS) as an additional gas-phase separation dimension. This review highlights recent developments in which IM-MS was used as a tool for comprehensive glycan analysis or as rapid screening method for glycan feature analysis. Furthermore, we summarize a series of very recent investigations in which gas-phase spectroscopy is applied to study glycans and discuss the potential of the hyphenation between IM-MS and infrared (IR) spectroscopy as a future tool for glycomics and glycoproteomics

Analytical challenges of glycosaminoglycans at biological interfaces

The analysis of glycosaminoglycans (GAGs) is a challenging task due to their high structural heterogeneity, which results in diverse GAG chains with similar chemical properties. Simultaneously, it is of high importance to understand their role and behavior in biological systems. It has been known for decades now that GAGs can interact with lipid molecules and thus contribute to the onset of atherosclerosis, but their interactions at and with biological interfaces, such as the cell membrane, are yet to be revealed. Here, analytical approaches that could yield important knowledge on the GAG-cell membrane interactions as well as the synthetic and analytical advances that make their study possible are discussed. Due to recent developments in laser technology, we particularly focus on nonlinear spectroscopic methods, especially vibrational sum-frequency generation spectroscopy, which has the potential to unravel the structural complexity of heterogeneous biological interfaces in contact with GAGs, in situ and in real time

Analyzing the higher order structure of proteins with conformer-selective ultraviolet photodissociation

The top-down approach in protein sequencing requires simple methods in which the analyte can be readily dissociated at every position along the backbone. In this context, ultraviolet photodissociation (UVPD) recently emerged as a promising tool because, in contrast to slow heating techniques such as collision induced dissociation (CID), the absorption of UV light is followed by a rather statistically distributed cleavage of backbone bonds. As a result, nearly complete sequence coverage can be obtained. It is well-known, however, that gas-phase proteins can adopt a variety of different, sometimes coexisting conformations and the influence of this structural diversity on the UVPD fragmentation behavior is not clear. Using ion mobility-UVPD-mass spectrometry we recently showed that UVPD is sensitive to the higher order structure of gas-phase proteins. In particular, the cis/trans isomerization of certain proline peptide bonds was shown to significantly influence the UVPD fragmentation pattern of two extended conformers of 11+ ubiquitin. Building on these results, we here provide conformer-selective UVPD data for 7+ ubiquitin ions, which are known to be present in a much more diverse and wider ensemble of different structures, ranging from very compact to highly extended species. Our data show that certain conformers fall into groups with similar UVPD fragmentation pattern. Surprisingly, however, the conformers within each group can differ tremendously in their collision cross section. This indicates that the multiple coexisting conformations typically observed for 7+ ubiquitin are caused by a few, not easily inter-convertible, subpopulations

Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy

The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds

Chemical Evolution of Galaxies

Chemical evolution of galaxies brings together ideas on stellar evolution and nucleosynthesis with theories of galaxy formation, star formation and galaxy evolution, with all their associated uncertainties. In a new perspective brought about by the Hubble Deep Field and follow-up investigations of global star formation rates, diffuse background etc., it has become necessary to consider the chemical composition of dark baryonic matter as well as that of visible matter in galaxies.Comment: 6 pages, AAS LaTeX macros v5.0, Millennium Essay to appear in PASP, Feb 200

Evidence for Solar Metallicities in Massive Star-forming Galaxies at z>~2

We present results of near-IR spectroscopic measurements of 7 star-forming galaxies at 2.1<z<2.5. Drawn from a large spectroscopic survey of galaxies photometrically pre-selected by their U_nGR colors to lie at z~2, these galaxies were chosen for their bright rest-frame optical luminosities (K_s<=20.0). Most strikingly, the majority of the sample of 7 galaxies exhibit [NII]/Ha nebular emission line ratios indicative of at least solar HII region metallicities, at a lookback time of 10.5 Gyr. The broadband colors of the K_s-bright sample indicate that most have been forming stars for more than a Gyr at z~2, and have already formed stellar masses in excess of 10^11 Msun. The descendants of these galaxies in the local universe are most likely metal-rich and massive spiral and elliptical galaxies, while plausible progenitors for them can be found among the population of z~3 Lyman Break Galaxies. While the K_s-bright z~2 galaxies appear to be highly evolved systems, their large Ha luminosities and uncorrected Ha star-formation rates of 24-60 Msun/yr indicate that active star formation is still ongoing. The luminous UV-selected objects presented here comprise more than half of the high-redshift (z>1.5) tails of current K-band-selected samples such as the K20 and Gemini Deep Deep surveys.Comment: 15 pages including 5 figures. Accepted for publication in Ap