The effects of Cl-induced alloying in Pt–Sn/Al2O3 catalysts on butane/H2 reactions

The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)–Sn(4.5%)/Al₂O₃ catalysts have been correlated with selectivities for butane/H₂ reactions. Particles of Pt⁰ fin Cl-free catalysts were partly covered by Sn⁰, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1:1 Pt⁰–Sn⁰ alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.     

Combination of computational prescreening and experimental library construction can accelerate enzyme optimization by directed evolution

Chiral compounds can be produced efficiently by using biocatalysts. However, wild-type enzymes often do not meet the requirements of a production process, making optimization by rational design or directed evolution necessary. Here, we studied the lipase-catalyzed hydrolysis of the model substrate 1-(2-naphthyl)ethyl acetate both theoretically and experimentally. We found that a computational equivalent of alanine scanning mutagenesis based on QM/MM methodology can be applied to identify amino acid positions important for the activity of the enzyme. The theoretical results are consistent with concomitant experimental work using complete saturation mutagenesis and high-throughput screening of the target biocatalyst, a lipase from Bacillus subtilis. Both QM/MM-based calculations and molecular biology experiments identify histidine 76 as a residue that strongly affects the catalytic activity. The experiments demonstrate its important influence on enantioselectivity.     

Chemical inhibitors when timing is critical: a pharmacological concept for the maturation of T cell contacts

Cellular signal transduction proceeds through a complex network of molecular interactions and enzymatic activities. The timing of these molecular events is critical for the propagation of a signal and the generation of a specific cellular response. To define the timing of signalling events, we introduce the combination of high-resolution confocal microscopy with the application of small-molecule inhibitors at various stages of signal transduction in T cells. Inhibitors of Src-family tyrosine kinases and actin dynamics were employed to dissect the role of the lymphocyte-specific tyrosine kinase Lck in the formation and maintenance of T cell receptor/CD3-dependent contacts. Anti-CD3epsilon-coated coverslips served as a highly defined stimulus. The kinetics of the recruitment of the yellow fluorescent protein-tagged signalling protein ZAP-70 were detected by high-resolution confocal microscopy. The analysis revealed that at 5 min after receptor engagement, Lck activity was required for maintenance of contacts. In contrast, after 20 min of receptor engagement, the contacts were Lck-independent. The relevance of the timing of inhibitor application provides a pharmacological concept for the maturation of T cell-substrate contacts.     

Development of polarization ratio model for sea surface wind field retrieval from TerraSAR-X HH polarization data

In this article, the polarization ratio (PR) of TerraSAR-X (TS-X) vertical–vertical (VV) and horizontal–horizontal (HH) polarization data acquired over the ocean is investigated. Similar to the PR of C-band synthetic aperture radar (SAR), the PR of X-band SAR data also shows significant dependence on incidence angle. The normalized radar cross-section (NRCS) in VV polarization data is generally larger than that in HH polarization for incidence angles above 23°. Based on the analysis, two PR models proposed for C-band SAR were retuned using TS-X dual-polarization data. A new PR model, called X-PR hereafter, is proposed as well to convert the NRCS of TS-X in HH polarization to that in VV polarization. By using the developed geophysical model functions of XMOD1 and XMOD2 and the tuned PR models, the sea surface field is retrieved from the TS-X data in HH polarization. The comparisons with in situ buoy measurements show that the combination of XMOD2 and X-PR models yields a good retrieval with a root mean square error (RMSE) of 2.03 m s^–1 and scatter index (SI) of 22.4%. A further comparison with a high-resolution analysis wind model in the North Sea is also presented, which shows better agreement with RMSE of 1.76 m s^–1 and SI of 20.3%. We also find that the difference between the fitting of the X-PR model and the PR derived from TS-X dual-polarization data is close to a constant. By adding the constant to the X-PR model, the accuracy of HH polarization sea surface wind speed is further improved with the bias reduced by 0.3 m s^–1. A case acquired at the offshore wind farm in the East China Sea further demonstrates that the improvement tends to be more effective for incidence angles above 40°.     

UR: SMART–A tool for analyzing social media content

Information Systems and e-Business Management - The digital transformation, with its ongoing trend towards electronic business, confronts companies with increasingly growing amounts of data which...     

Rethinking technology on the boundaries of life and work

Technology is often seen as seamless, or making (life/work) boundaries go away. Ubicomp designs for that and for seamlessness in general. However, there may be better ways of understanding boundaries, as to design technologies in the space of changing work/life boundaries, which is the topic of this special issue. This paper makes a theoretical argument to insist that boundaries are not fixed, neither can or should they be made away with technologically, through seamless technologies. Based on this argument, it discusses various presumed technology-mediated boundaries of work and home, life, etc., as they can be found in the Ubicomp, CSCW and HCI literature: The ways in which work and work technologies are stereotypically connected to effectiveness and hard labor, and non-work technologies to fun and enjoyment; the ways in which technologies move back and forth between mediating work activity and non-work; the role of place and time boundaries in relation to the ability to work any time, anywhere and the metaphors used to address these boundaries; and the perceived boundaries of private versus public, and the new boundaries created by technologies in and across our lives and work. Using an empirical case, the paper offers an alternative use of boundaries as resources to be activated and used in design. It suggests that we need to more carefully design technologies that provide seamfulness on these specific and dynamic boundaries.     

Relationship between the attenuation of downwelling irradiance at 490 nm with the attenuation of PAR (400 nm-700 nm) in the Baltic Sea

The vertical attenuation coefficient of diffuse downwelling irradiance at 490 nm (K_d 490) is a parameter that we routinely derive from SeaWiFS images of the Baltic Sea. Here, through model simulations, we examine the relationship between K_d(490), and the vertical attenuation coefficient of PAR (K_d PAR), as this later coefficient determines the light available for aquatic photosynthesis. A simple semi-analytical model is used to predict K_d(490) and K_d(PAR), as a function of the concentrations of chlorophyll, colored dissolved organic material (CDOM), suspended inorganic, and suspended organic particulate material. A series of model simulations based on variations in these optically significant constituents over a range realistic for the Baltic Sea, are used to define the relationship between the two attenuation coefficients.

Kd(PAR)=0.6677Kd^0.6763(490).     

Thermodynamic modeling of the Na–Al–Ti–H system and Ti dissolution in sodium alanates

Thermodynamic assessments were made to optimize thermodynamic models and parameter fits to selected experimental and first principles hypothetical predicted phase data within the Na–Al–Ti–H system. This enabled thermodynamic modeling of Ti solubility within the sodium alanates: NaAlH₄ and Na₃AlH₆, and the relative stability of Ti-bearing phases. The modeling provides insights into the role of Ti originating from Ti-based activating agents commonly referred to as ‘catalysts’ in promoting reversibility of the Na–Al–H dehydrogenation and rehydrogenation reactions under moderate temperature and pressure conditions relevant to H storage applications. Preliminary assessments were made to evaluate H solubility in bcc-Ti and hcp-Ti, and stability of the hydride δ-TiH₂. To model possible Ti dissolution in NaAlH₄ and α-Na₃AlH₆, sub-lattice models were applied. A repulsive interaction is predicted by first principles calculations when Ti is dissolved in NaAlH₄ or α-Na₃AlH₆, which becomes stronger with increasing temperature. Although Ti is virtually insoluble in NaAlH₄ or α-Na₃AlH₆, a small addition of TiCl₃ will induce a thermodynamic driving force for formation of TiH₂ and/or TiAl₃. The addition of pure Ti shows a weaker effect than TiCl₃ and leads to formation of TiH₂ only. Based on a combined interpretation of present thermodynamic modeling and prior experimental observations, the TiAl₃ and TiH₂ phases are ascribed to have a catalytic effect, not a thermodynamic destabilization effect, on the reversibility of the dehydrogenation/rehydrogenation reactions in the Na–Al–H system.     

The process map as an instrument to standardize processes: design and application at a financial service provider

The standardization of processes and the identification of shared business services in a service-oriented architecture (SOA) are currently widely discussed. Above all in practice, however, there still is a lack of appropriate instruments to support these tasks. In this paper an approach for a process map is introduced which allows for a systematic presentation—as complete as possible—of the processes in an enterprise (division). After a consistent refinement of the process has taken place by means of aggregation/disaggregation respectively, generalization/specialization relations, it is possible to identify primarily functional similarities of the detailed sub-processes. The application of the process map at a financial service provider (FSP) highlights how these similarities can be taken as a basis to standardize processes and to identify shared services.     

Experimental quantification of annular dark-field images in scanning transmission electron microscopy

This paper reports on a method to obtain atomic resolution Z-contrast (high-angle annular dark-field) images with intensities normalized to the incident beam. The procedure bypasses the built-in signal processing hardware of the microscope to obtain the large dynamic range necessary for consecutive measurements of the incident beam and the intensities in the Z-contrast image. The method is also used to characterize the response of the annular dark-field detector output, including conditions that avoid saturation and result in a linear relationship between the electron flux reaching the detector and its output. We also characterize the uniformity of the detector response across its entire area and determine its size and shape, which are needed as input for image simulations. We present normalized intensity images of a SrTiO(3) single crystal as a function of thickness. Averaged, normalized atom column intensities and the background intensity are extracted from these images. The results from the approach developed here can be used for direct, quantitative comparisons with image simulations without any need for scaling.