194 research outputs found

    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

    The impact of leaving group anomericity on the structure of glycosyl cations of protected galactosides

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    It has been reported that fragments produced by glycosidic bond breakage in mass spectrometry‐based experiments can retain a memory of their anomeric configuration, which has major implications for glycan sequencing. Herein, we use cryogenic vibrational spectroscopy and ion mobility‐mass spectrometry to study the structure of B‐type fragments of protected galactosides. Cationic fragments were generated from glycosyl donors carrying trichloroacetimidate or thioethyl leaving groups of different anomeric configuration. The obtained infrared signatures indicate that the investigated fragments exhibit an identical structure, which suggests that there is no anomeric memory in B‐type ions of fully protected monosaccharides

    Magnon delocalization in ferromagnetic chains with long-range correlated disorder

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    We study one-magnon excitations in a random ferromagnetic Heisenberg chain with long-range correlations in the coupling constant distribution. By employing an exact diagonalization procedure, we compute the localization length of all one-magnon states within the band of allowed energies EE. The random distribution of coupling constants was assumed to have a power spectrum decaying as S(k)1/kαS(k)\propto 1/k^{\alpha}. We found that for α<1\alpha < 1, one-magnon excitations remain exponentially localized with the localization length ξ\xi diverging as 1/E. For α=1\alpha = 1 a faster divergence of ξ\xi is obtained. For any α>1\alpha > 1, a phase of delocalized magnons emerges at the bottom of the band. We characterize the scaling behavior of the localization length on all regimes and relate it with the scaling properties of the long-range correlated exchange coupling distribution.Comment: 7 Pages, 5 figures, to appear in Phys. Rev.

    The Effect of Contrast Medium SonoVue® on the Electric Charge Density of Blood Cells

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    The effect of contrast medium SonoVue® on the electric charge density of blood cells (erythrocytes and thrombocytes) was measured using a microelectrophoretic method. We examined the effect of adsorbed H+ and OH− ions on the surface charge of erythrocytes or thrombocytes. Surface charge density values were determined from electrophoretic mobility measurements of blood cells performed at various pH levels. The interaction between solution ions and the erythrocyte’s or thrombocyte’s surface was described by a four-component equilibrium model. The agreement between the experimental and theoretical charge variation curves of the erythrocytes and thrombocytes was good at pH 2–9. The deviation observed at a higher pH may be caused by disregarding interactions between the functional groups of blood cells

    A review of data mining in knowledge management: applications/findings for transportation of small and medium enterprises

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    A core subfeld of knowledge management (KM) and data mining (DM) constitutes an integral part of the knowledge discovery in database process. With the explosion of information in the new digital age, research studies in the DM and KM continue to heighten up in the business organisations, especially so, for the small and medium enterprises (SMEs). DM is crucial in supporting the KM application as it processes the data to useful knowledge and KM role next, is to manage these knowledge assets within the organisation systematically. At the comprehensive appraisal of the large enterprise in the transportation sector and the SMEs across various industries—it was gathered that there is limited research case study conducted on the application of DM–KM on the transportation SMEs in specifc. From the extensive review of the case studies, it was uncovered that majority of the organisations are not leveraging on the use of tacit knowledge and that the SMEs are adopting a more traditional use of ICTs to its KM approach. In addition, despite DM–KM is being widely implemented—the case studies analysis reveals that there is a limitation in the presence of an integrated DM–KM assessment to evaluate the outcome of the DM–KM application. This paper concludes that there is a critical need for a novel DM–KM assessment plan template to evaluate and ensure that the knowledge created and implemented are usable and relevant, specifcally for the SMEs in the transportation sector. Therefore, this research paper aims to carry out an in-depth review of data mining in knowledge management for SMEs in the transportation industry

    Demonstration of cooling by the Muon Ionization Cooling Experiment

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    The use of accelerated beams of electrons, protons or ions has furthered the development of nearly every scientific discipline. However, high-energy muon beams of equivalent quality have not yet been delivered. Muon beams can be created through the decay of pions produced by the interaction of a proton beam with a target. Such ‘tertiary’ beams have much lower brightness than those created by accelerating electrons, protons or ions. High-brightness muon beams comparable to those produced by state-of-the-art electron, proton and ion accelerators could facilitate the study of lepton–antilepton collisions at extremely high energies and provide well characterized neutrino beams1,2,3,4,5,6. Such muon beams could be realized using ionization cooling, which has been proposed to increase muon-beam brightness7,8. Here we report the realization of ionization cooling, which was confirmed by the observation of an increased number of low-amplitude muons after passage of the muon beam through an absorber, as well as an increase in the corresponding phase-space density. The simulated performance of the ionization cooling system is consistent with the measured data, validating designs of the ionization cooling channel in which the cooling process is repeated to produce a substantial cooling effect9,10,11. The results presented here are an important step towards achieving the muon-beam quality required to search for phenomena at energy scales beyond the reach of the Large Hadron Collider at a facility of equivalent or reduced footprint6

    Transverse Emittance Reduction in Muon Beams by Ionization Cooling

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    Accelerated muon beams have been considered for next-generation studies of high-energy lepton-antilepton collisions and neutrino oscillations. However, high-brightness muon beams have not yet been produced. The main challenge for muon acceleration and storage stems from the large phase-space volume occupied by the beam, derived from the muon production mechanism through the decay of pions from proton collisions. Ionization cooling is the technique proposed to decrease the muon beam phase-space volume. Here we demonstrate a clear signal of ionization cooling through the observation of transverse emittance reduction in beams that traverse lithium hydride or liquid hydrogen absorbers in the Muon Ionization Cooling Experiment (MICE). The measurement is well reproduced by the simulation of the experiment and the theoretical model. The results shown here represent a substantial advance towards the realization of muon-based facilities that could operate at the energy and intensity frontiers.Comment: 23 pages and 5 figure

    First demonstration of ionization cooling by the Muon Ionization Cooling Experiment

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    High-brightness muon beams of energy comparable to those produced by state-of-the-art electron, proton and ion accelerators have yet to be realised. Such beams have the potential to carry the search for new phenomena in lepton-antilepton collisions to extremely high energy and also to provide uniquely well-characterised neutrino beams. A muon beam may be created through the decay of pions produced in the interaction of a proton beam with a target. To produce a high-brightness beam from such a source requires that the phase space volume occupied by the muons be reduced (cooled). Ionization cooling is the novel technique by which it is proposed to cool the beam. The Muon Ionization Cooling Experiment collaboration has constructed a section of an ionization cooling cell and used it to provide the first demonstration of ionization cooling. We present these ground-breaking measurements.Comment: 19 pages and 6 figure
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