1,495 research outputs found

    Letter to Sound Rules for Accented Lexicon Compression

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    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

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

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    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

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    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

    Strongly entangled light from planar microcavities

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    The emission of entangled light from planar semiconductor microcavities is studied and the entanglement properties are analyzed and quantified. Phase-matching of the intra-cavity scattering dynamics for multiple pump beams or pulses, together with the coupling to external radiation, leads to the emission of a manifold of entangled photon pairs. A decomposition of the emitted photons into two parties leads to a strong entanglement of the resulting bipartite system. For the quantification of the entanglement, the Schmidt number of the system is determined by the construction of Schmidt number witnesses. It is analyzed to which extend the resources of the originally strongly entangled light field are diminished by dephasing in propagation channels.Comment: 9 pages, 5 figures, extended versio

    Dextran as internal calibrant for N-glycan analysis by liquid chromatography coupled to ion mobility-mass spectrometry

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    LC–MS is one of the most important tools for the comprehensive characterization of N-glycans. Despite many efforts to speed up glycan analysis via optimized sample preparation (e.g., faster enzyme digestion in combination with instant or rapid labeling dyes), a major bottleneck remains the rather long measurement times of HILIC chromatography. Further compli- cation arises from the necessity to concomitantly calibrate with an external standard to allow for accurate retention times and the conversion into more robust GU values. Here we demonstrate the use of an internal calibration strategy for HILIC chromatography to speed up glycan analysis. By reducing the number of utilized dextran oligosaccharides, the calibrant can be spiked directly into the sample such that external calibration runs are no longer required. The minimized dextran ladder shows accurate GU calibration with a minor deviation of well below 1% and can be applied without modifications in sample preparation or data processing. We further demonstrate the simultaneous use of the minimized dextran ladder as calibrant for the estimation of CCS values in traveling wave ion mobility spectrometry. In both cases, the minimized dextran ladder enables the measurement of calibrant and sample in a single HPLC run without losing information or accuracy

    RNAi-mediated silencing of MLL-AF9 reveals leukemia-associated downstream targets and processes

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    Background: The translocation t(9;11)(p22;q23) leading to the leukemogenic fusion gene MLL-AF9 is a frequent translocation in infant acute myeloid leukemia (AML). This study aimed to identify genes and molecular processes downstream of MLL-AF9 (alias MLL-MLLT3) which could assist to develop new targeted therapies for such leukemia with unfavorable prognosis. Methods: In the AML cell line THP1 which harbors this t(9; 11) translocation, endogenous MLL-AF9 was silenced via siRNA while ensuring specificity of the knockdown and its efficiency on functional protein level. Results: The differential gene expression profile was validated for leukemia-association by gene set enrichment analysis of published gene sets from patient studies and MLL-AF9 overexpression studies and revealed 425 differentially expressed genes. Gene ontology analysis was consistent with a more differentiated state of MLL-AF9 depleted cells, with involvement of a wide range of downstream transcriptional regulators and with defined functional processes such as ribosomal biogenesis, chaperone binding, calcium homeostasis and estrogen response. We prioritized 41 gene products as candidate targets including several novel and potentially druggable effectors of MLL-AF9 (AHR, ATP2B2, DRD5, HIPK2, PARP8, ROR2 and TAS1R3). Applying the antagonist SCH39166 against the dopamine receptor DRD5 resulted in reduced leukemic cell characteristics of THP1 cells. Conclusion: Besides potential new therapeutic targets, the described transcription profile shaped by MLL-AF9 provides an information source into the molecular processes altered in MLL aberrant leukemia

    Neutrinos And Big Bang Nucleosynthesis

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    The early universe provides a unique laboratory for probing the frontiers of particle physics in general and neutrino physics in particular. The primordial abundances of the relic nuclei produced during the first few minutes of the evolution of the Universe depend on the electron neutrinos through the charged-current weak interactions among neutrons and protons (and electrons and positrons and neutrinos), and on all flavors of neutrinos through their contributions to the total energy density which regulates the universal expansion rate. The latter contribution also plays a role in determining the spectrum of the temperature fluctuations imprinted on the Cosmic Background Radiation (CBR) some 400 thousand years later. Using deuterium as a baryometer and helium-4 as a chronometer, the predictions of BBN and the CBR are compared to observations. The successes of, as well as challenges to the standard models of particle physics and cosmology are identified. While systematic uncertainties may be the source of some of the current tensions, it could be that the data are pointing the way to new physics. In particular, BBN and the CBR are used to address the questions of whether or not the relic neutrinos were fully populated in the early universe and, to limit the magnitude of any lepton asymmetry which may be concealed in the neutrinos.Comment: Accepted for publication in the Proceedings of Nobel Symposium 129, "Neutrino Physics"; to appear in Physics Scripta, eds., L Bergstrom, O. Botner, P. Carlson, P. O. Hulth, and T. Ohlsso

    Structure and composition of the benthic macroinvertebrate community on wetland and irrigated rice cultivation.

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    Wetlands are environmentally and economically important ecosystems. The irrigated rice crops are considered artificial wetlands, because they offer food and refuge to different aquatic communities. The benthic macroinvertebrates are used to study environmental quality. The knowledge from the organisms which inhabit the natural and artificial wetlands can help to verify less harmful management practices in the agroecosystems. AIM: The aim of this research was to analyze and compare the benthic macroinvertebrate community from a wetland and an experimental kind of rice cultivation. METHODS: It was used dip nets 1 mm mesh every 15 days, with six repetitions in each place, from January to March 2010. After washing and screening them in the laboratory, the organisms were identified using stereoscope microscope and identification keys, and classified according to their functional trophic group. RESULTS: The whole organisms collected were 33,293 specimens. It was found 34 taxa, being 26 founded in the rice crops and 31 on the wetland. The natural wetland shows greater abundance, being responsible for 90.47% from the total abundance in this study. In the rice crop the abundance and the richness increased in the course of collection. However, it did not reach the values founded in the wetlands during the cultivation period. The most found groups in the two environmental were Belostomatidae and Planorbidae, while Hyalellidae and Elmidae were found only in the wetland, being a stress indicator in the wetland. CONCLUSIONS: The community structure including abundance, richness and composition was statistical different between wetlands and rice cultivation

    Plate-height model of ion mobility-mass spectrometry

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    In the past decade, ion mobility spectrometry (IMS) in combination with mass spectrometry (IM-MS) became a widely employed technique for the separation and structural characterization of ionic species in the gas phase. Similarly to chromatography, where studies on the mechanism of band broadening and adequate plate-height equations have been aiding method development and promoting advancements in column technology, a suitable resolving power theory of drift tube ion mobility-mass spectrometry (DTIM-MS) is essential to stimulate further progress in this emerging field of separation science. In the present study, therefore, we explore dispersion processes in detail and present a plate-height model of ion mobility-mass spectrometry. We quantify the effects of five major dispersion processes that contribute to zone broadening and determine the resolving power in DTIM-MS: diffusion, Coulomb repulsion, electric field inhomogeneities, the finite initial spread of the ion cloud and dispersion outside the mobility cell. A solution is provided to account for the nonuniform separation field in IM-MS in the presence of multiple compartments. The equations – derived from first principles – serve as the basis for formulating an expression that is similar in nature to van Deemter's plate-height equation for chromatography. A comprehensive set of experiments was performed on a custom-built DTIM-MS instrument to evaluate the accuracy of the plate-height model, resulting in satisfactory agreement between experiment and theory. Building on these findings, the plate-height equation was employed to explore the influence of drift gas pressure, injection pulse-width and the mobility of ions on resolving power from a theoretical point of view. Our findings may aid instrument design and development in the future, as well as the optimization of measurement conditions to improve ion mobility separations. By employing the plate-height concept and the general formalism of differential migration processes to describe zone spreading in IM-MS, we aim to find a common ground between this emerging method and such well-established techniques as HPLC or CZE. We also hope that the work presented here will facilitate a broader acceptance of IMS as a separation method of great potential by the communities of chromatography and electrophoresis, as well as that of mass spectrometry

    Plate-height model of ion mobility-mass spectrometry: Part 2-Peak-to-peak resolution and peak capacity

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    In a previous work, we explored zone broadening and the achievable plate numbers in linear drift tube ion mobility-mass spectrometry through developing a plate-height model [1]. On the basis of these findings, the present theoretical study extends the model by exploring peak-to-peak resolution and peak capacity in ion mobility separations. The first part provides a critical overview of chromatography-influenced resolution equations, including refinement of existing formulae. Furthermore, we present exact resolution equations for drift tube ion mobility spectrometry based on first principles. Upon implementing simple modifications, these exact formulae could be readily extended to traveling wave ion mobility separations and to cases when ion mobility spectrometry is coupled to mass spectrometry. The second part focuses on peak capacity. The well-known assumptions of constant plate number and constant peak width form the basis of existing approximate solutions. To overcome their limitations, an exact peak capacity equation is derived for drift tube ion mobility spectrometry. This exact solution is rooted in a suitable physical model of peak broadening, accounting for the finite injection pulse and subsequent diffusional spreading. By borrowing concepts from the theoretical toolbox of chromatography, we believe that the present study will help in integrating ion mobility spectrometry into the unified language of separation science
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