8,275 research outputs found

    Production of hydrogen by unmixed steam reforming of methane

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    Unmixed steam reforming is an alternative method of catalytic steam reforming that uses separate air and fuel–steam feeds, producing a reformate high in H2 content using a single reactor and a variety of fuels. It claims insensitivity to carbon formation and can operate autothermally. The high H2 content is achieved by in situ N2 separation from the air using an oxygen transfer material (OTM), and by CO2 capture using a solid sorbent. The OTM and CO2 sorbent are regenerated during the fuel–steam feed and the air feed, respectively, within the same reactor. This paper describes the steps taken to choose a suitable CO2-sorbent material for this process when using methane fuel with the help of microreactor tests, and the study of the carbonation efficiency and regeneration ability of the materials tested. Elemental balances from bench scale experiments using the best OTM in the absence of the CO2 sorbent allow identifying the sequence of the chemical reaction mechanism. The effect of reactor temperature between 600 and on the process outputs is investigated. Temperatures of 600 and under the fuel–steam feed were each found to offer a different set of desirable outputs. Two stages during the fuel–steam feed were characterised by a different set of global reactions, an initial stage where the OTM is reduced directly by methane, and indirectly by hydrogen produced by methane thermal decomposition, in the second stage, steam reforming takes over once sufficient OTM has been reduced. The implications of these stages on the process desirable outputs such as efficiency of reactants conversion, reformate gas quality, and transient effects are discussed

    The Thermodynamics of Ligand Association and Molecular Recognition of Cationic and Metallated Porphyrins and Ruthenium Complexes with Model DNA Constructs

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    Molecular recognition, particularly as it applies to strong binding interactions between complementary ligand/receptor molecules in solution, is important in such varied areas as molecular biology, pharmacology, synthetic chemistry, and chemical detection. Strong binding is the additive result of a number of specific, weak, non-covalent interactions occurring between complementary molecules. This dissertation reports on the energetics of forming complexes between small molecules and model DNA constructs. Ligands included cationic and metallated cationic porphyrins and polyheterocyclic ruthenium compounds. DNA receptors included double stranded B-DNAs (hairpin and short linear sequences) as well G-quadruplex DNAs. Thermodynamic data were collected using isothermal titration calorimetry, circular dichroism spectropolarimetry, ultraviolet-visible spectroscopy, and mass spectrometry. The measured thermodynamic parameters included the changes in free energy, enthalpy and entropy for ligand/receptor complex formation as well as the stoichiometry of the stable complexes. The first section of this dissertation reports that the binding of cationic porphyrins to model G-quadruplex DNA may proceed through two pathways, end stacking and intercalation. Modulating the number of pyridinium groups on a pyridinium substituted porphyrin yielded differing binding thermodynamics leading to the understanding that a balance of surface area, charge, and geometry affect the ability of a porphyrin to bind to G-quadruplex DNA. Further investigations into the binding of metallated porphyrins developed the understanding that the geometry of the central metal ion affected not only the thermodynamics but could also inhibit the intercalative mode. It was previously shown that the high affinity binding for binuclear polyheterocyclic ruthenium compounds proceeds through an intercalative mode. To further understand the binding process and the structureunction relationship of the ligand components, the binding of smaller mononuclear complexes that were representative of portions of the binuclear complex was examined in this dissertation. While limiting the intercalative ability lowered the binding affinity, the mononuclear complex with the full intercalating bridge was able bind to DNA with a higher affinity than the binuclear complex. These studies have been successful in part in determining the contributions of numerous weak interactions including: charge (Coulombic interactions), H-bonding, hydrophobic interactions, and solvent structure (solvation changes), to the overall energetics of this molecular recognition process. The first section of this dissertation reports that the binding of cationic porphyrins to model G-quadruplex DNA may proceed through two pathways, end stacking and intercalation. Modulating the number of pyridinium groups on a pyridinium substituted porphyrin yielded differing binding thermodynamics leading to the understanding that a balance of surface area, charge, and geometry affect the ability of a porphyrin to bind to G-quadruplex DNA. Further investigations into the binding of metallated porphyrins developed the understanding that the geometry of the central metal ion affected not only the thermodynamics but could also inhibit the intercalative mode. It was previously shown that the high affinity binding for binuclear polyheterocyclic ruthenium compounds proceeds through intercalation. To further understand the binding process and the structureunction relationship of the ligand components, the binding of smaller mononuclear complexes that were representative of portions of the binuclear complex was examined in this dissertation. While limiting the intercalative ability lowered the binding affinity, the mononuclear complex with the full intercalating bridge was able bind to DNA with a higher affinity than the binuclear complex. These studies have been successful in part in determining the contributions of numerous weak interactions including: charge (Coulombic interactions), H-bonding, hydrophobic interactions, and solvent structure (solvation changes), to the overall energetics of this molecular recognition process

    Microwave-stimulated Raman adiabatic passage in a Bose-Einstein condensate on an atom chip

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    We report the achievement of stimulated Raman adiabatic passage (STIRAP) in the microwave frequency range between internal states of a Bose-Einstein condensate (BEC) magnetically trapped in the vicinity of an atom chip. The STIRAP protocol used in this experiment is robust to external perturbations as it is an adiabatic transfer, and power-efficient as it involves only resonant (or quasi-resonant) processes. Taking into account the effect of losses and collisions in a non-linear Bloch equations model, we show that the maximum transfer efficiency is obtained for non-zero values of the one- and two-photon detunings, which is confirmed quantitatively by our experimental measurements

    The European Institute for Innovation through Health Data

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    The European Institute for Innovation through Health Data (i~HD, www.i-hd.eu) has been formed as one of the key sustainable entities arising from the Electronic Health Records for Clinical Research (IMI-JU-115189) and SemanticHealthNet (FP7-288408) projects, in collaboration with several other European projects and initiatives supported by the European Commission. i~HD is a European not-for-profit body, registered in Belgium through Royal Assent. i~HD has been established to tackle areas of challenge in the successful scaling up of innovations that critically rely on high-quality and interoperable health data. It will specifically address obstacles and opportunities to using health data by collating, developing, and promoting best practices in information governance and in semantic interoperability. It will help to sustain and propagate the results of health information and communication technology (ICT) research that enables better use of health data, assessing and optimizing their novel value wherever possible. i~HD has been formed after wide consultation and engagement of many stakeholders to develop methods, solutions, and services that can help to maximize the value obtained by all stakeholders from health data. It will support innovations in health maintenance, health care delivery, and knowledge discovery while ensuring compliance with all legal prerequisites, especially regarding the insurance of patient's privacy protection. It is bringing multiple stakeholder groups together so as to ensure that future solutions serve their collective needs and can be readily adopted affordably and at scale

    A Mesoscopic Resonating Valence Bond system on a triple dot

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    We introduce a mesoscopic pendulum from a triple dot. The pendulum is fastened through a singly-occupied dot (spin qubit). Two other strongly capacitively islands form a double-dot charge qubit with one electron in excess oscillating between the two low-energy charge states (1,0) and (0,1); this embodies the weight of the pendulum. The triple dot is placed between two superconducting leads as shown in Fig. 1. Under well-defined conditions, the main proximity effect stems from the injection of resonating singlet (valence) bonds on the triple dot. This gives rise to a Josephson current that is charge- and spin-dependent. Consequences in a SQUID-geometry are carefully investigated.Comment: final version to appear in PR

    Effect of trap symmetry and atom-atom interactions on a trapped atom interferometer with internal state labelling

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    In this paper, we study the dynamics of a trapped atom interferometer with internal state labelling in the presence of interactions. We consider two situations: an atomic clock in which the internal states remain superposed, and an inertial sensor configuration in which they are separated. From the average spin evolution, we deduce the fringe contrast and the phase-shift. In the clock configuration, we recover the well-known identical spin rotation effect (ISRE) which can significantly increase the spin coherence time. We also find that the magnitude of the effect depends on the trap geometry in a way that is consistent with our recent experimental results in a clock configuration [M. Dupont-Nivet, and al., New J. Phys., 20, 043051 (2018)], where ISRE was not observed. In the case of an inertial sensor, we show that despite the spatial separation it is still possible to increase the coherence time by using mean field interactions to counteract asymmetries of the trapping potential.Comment: 18 pages, 5 figure

    Experimental study of the role of trap symmetry in an atom-chip interferometer above the Bose-Einstein condensation threshold

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    We report the experimental study of an atom-chip interferometer using ultracold rubidium 87 atoms above the Bose-Einstein condensation threshold. The observed dependence of the contrast decay time with temperature and with the degree of symmetry of the traps during the interferometer sequence is in good agreement with theoretical predictions published in [Dupont-Nivet et al., NJP 18, 113012 (2016)]. These results pave the way for precision measurements with trapped thermal atoms.Comment: 11 pages, 4 figure
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