Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand.

The steric effects of substituents on five-membered rings are less pronounced than those on six-membered rings because of the difference in bond angles. Thus, the regioselectivities of reactions of five-membered heteroarenes that occur with selectivities dictated by steric effects, such as the borylation of C-H bonds, have been poor in many cases. We report that the silylation of five-membered-ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of [Ir(cod)(OMe)]2 (cod=1,5-cyclooctadiene) and a phenanthroline ligand or a new pyridyl-imidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C-H bonds of these rings under conditions that the borylation of C-H bonds with previously reported catalysts formed mixtures of products or products that are unstable. The heteroarylsilane products undergo cross-coupling reactions and substitution reactions with ipso selectivity to generate heteroarenes that bear halogen, aryl, and perfluoroalkyl substituents

Software implementation for calculating the Chern and Z2Z_2 topological invariants with WIEN2k

We present two modules that expand functionalities of the all-electron full-potential density functional theory package WIEN2k for computation of the Chern and $Z_2$ topological invariants. Characterization of topological properties relies on two methods: computing an evolution of hybrid Wannier charge centers for $Z_2$ topological insulators (construction of maximally localized Wannier functions is not needed) and computing the Berry phase for a multitude of Wilson loops that discretize a 2D Brillouin zone for Chern insulators as well as for mapping the Berry curvature. The implementation is validated by testing on well-known materials that feature topologically non-trivial electronic states.Comment: 13 pages, 5 figure

Effects of restricted basilar papillar lesions and hair cell regeneration on auditory forebrain frequency organization in adult European Starlings

The frequency organization of neurons in the forebrain Field L complex (FLC) of adult starlings was investigated to determine the effects of hair cell (HC) destruction in the basal portion of the basilar papilla (BP) and of subsequent HC regeneration. Conventional microelectrode mapping techniques were used in normal starlings and in lesioned starlings either 2 d or 6-10 weeks after aminoglycoside treatment. Histological examination of the BP and recordings of auditory brainstem evoked responses confirmed massive loss of HCs in the basal portion of the BP and hearing losses at frequencies >2 kHz in starlings tested 2 d after aminoglycoside treatment. In these birds, all neurons in the region of the FLC in which characteristic frequencies (CFs) normally increase from 2 to 6 kHz had CF in the range of 2-4 kHz. The significantly elevated thresholds of responses in this region of altered tonotopic organization indicated that they were the residue of prelesion responses and did not reflect CNS plasticity. In the long-term recovery birds, there was histological evidence of substantial HC regeneration. The tonotopic organization of the high-frequency region of the FLC did not differ from that in normal starlings, but the mean threshold at CF in this frequency range was intermediate between the values in the normal and lesioned short-recovery groups. The recovery of normal tonotopicity indicates considerable stability of the topography of neuronal connections in the avian auditory system, but the residual loss of sensitivity suggests deficiencies in high-frequency HC function

Green consumerism, green perceived value, and restaurant revisit intention: Millennials' sustainable consumption with moderating effect of green perceived quality

Adopting green practices does not always guarantee customer retention and loyalty. Employing the theoretical lens of cue utilization theory, we conceptualize green perceived quality as sending internal and external cues which help consumers form judgments about product quality and perceived value. Based on a survey of 280 restaurant customers, we hypothesize and report a positive and significant influence of both green consumerism and green perceived value on customer revisit intention. Further, the results confirm the moderating role of green perceived quality. From a practical point of view, managers interested in benefiting from the green practices of their restaurants should focus on increasing their customers' evaluation and overall judgment of the environmental quality of both their food and services

Effect of various electron and hole transport layers on the performance of CsPbI3-based perovskite solar cells: A numerical investigation in DFT, SCAPS-1D, and wxAMPS frameworks

CsPbI3 has recently received tremendous attention as a possible absorber of perovskite solar cells (PSCs). However, CsPbI3-based PSCs have yet to achieve the high performance of the hybrid PSCs. In this work, we performed a density functional theory (DFT) study using the Cambridge Serial Total Energy Package (CASTEP) code for the cubic CsPbI3 absorber to compare and evaluate its structural, electronic, and optical properties. The calculated electronic band gap (Eg) using the GGA-PBE approach of CASTEP was 1.483 eV for this CsPbI3 absorber. Moreover, the computed density of states (DOS) exhibited the dominant contribution from the Pb-5d orbital, and most charge also accumulated for the Pb atom as seen from the electronic charge density map. Fermi surface calculation showed multiband character, and optical properties were computed to investigate the optical response of CsPbI3. Furthermore, we used IGZO, SnO2, WS2, CeO2, PCBM, TiO2, ZnO, and C60 as the electron transport layers (ETLs), and Cu2O, CuSCN, CuSbS2, Spiro-MeOTAD, V2O5, CBTS, CFTS, P3HT, PEDOT: PSS, NiO, CuO, and CuI as the hole transport layers (HTLs) to identify the best HTL/CsPbI3/ETL combinations using the SCAPS-1D solar cell simulation software. Among 96 device structures, the best-optimized device structure, ITO/TiO2/CsPbI3/CBTS/Au was identified, which exhibited an efficiency of 17.9%. The effect of absorber and ETL thickness, series resistance, shunt resistance, and operating temperature was also evaluated for the six best devices along with their corresponding generation rate, recombination rate, capacitance-voltage, current density-voltage, and quantum efficiency characteristics. The obtained results from SCAPS-1D were also compared with wxAMPS simulation software.Comment: 34 pages, 12 figures, Supporting Information (3 figures

Material migration and fuel retention studies during the JET carbon divertor campaigns

The first divertor was installed in the JET machine between 1992 and 1994 and was operated with carbon tiles and then beryllium tiles in 1994–5. Post-mortem studies after these first experiments demonstrated that most of the impurities deposited in the divertor originate in the main chamber, and that asymmetric deposition patterns generally favouring the inner divertor region result from drift in the scrape-off layer. A new monolithic divertor structure was installed in 1996 which produced heavy deposition at shadowed areas in the inner divertor corner, which is where the majority of the tritium was trapped by co-deposition during the deuterium-tritium experiment in 1997. Different divertor geometries have been tested since such as the Gas-Box and High-Delta divertors; a principle objective has been to predict plasma behaviour, transport and tritium retention in ITER. Transport modelling experiments were carried out at the end of four campaigns by puffing 13C-labelled methane, and a range of diagnostics such as quartz-microbalance and rotating collectors have been installed to add time resolution to the post-mortem analyses. The study of material migration after D-D and D-T campaigns clearly revealed important consequences of fuel retention in the presence of carbon walls. They gave a strong impulse to make a fundamental change of wall materials. In 2010 the carbon divertor and wall tiles were removed and replaced with tiles with Be or W surfaces for the ITER-Like Wall Project

First mirror test in JET for ITER: Complete overview after three ILW campaigns

The First Mirror Test for ITER has been carried out in JET with mirrors exposed during: (i) the third ILW campaign (ILW-3, 2015-2016, 23.33 h plasma) and (ii) all three campaigns, i.e. ILW-1 to ILW-3: 2011-2016, 63,52 h in total. All mirrors from main chamber wall show no significant changes of the total reflectivity from the initial value and the diffuse reflectivity does not exceed 3% in the spectral range above 500 nm. The modified layer on surface has very small amount of impurities such as D, Be, C, N, O and Ni. All mirrors from the divertor (inner, outer, base under the bulk W tile) lost reflectivity by 20-80% due to the beryllium-rich deposition also containing D, C, N, O, Ni and W. In the inner divertor N reaches 5 x 10(17) cm(-2), W is up to 4.3 x 10(17) cm(-2), while the content of Ni is the greatest in the outer divertor: 3.8 x 10(17) cm(-2). Oxygen-18 used as the tracer in experiments at the end of ILW-3 has been detected at the level of 1.1 x 10(16) cm(-2). The thickness of deposited layer is in the range of 90 nm to 900 nm. The layer growth rate in the base (2.7 pm s(-1)) and inner divertor is proportional to the exposure time when a single campaign and all three are compared. In a few cases, on mirrors located at the cassette mouth, flaking of deposits and erosion occurred

Kompetenznetz E-Learning Hessen

Mit dem Kompetenznetz e-learning-hessen.de vernetzen sich die hessischen Hochschulen mit Hilfe der Koordination und Unterstützung durch das httc und Förderung durch das Hessische Ministerium für Wissenschaft und Kunst rund um das Thema E-Learning. Dieser Beitrag beschreibt die Ziele des Netzwerks, dessen Maßnahmen und Elemente und die bisherigen Erfahrungen und seine Entwicklung seit dem Jahr 2000. Mit der abschließenden Bewertung werden Anhaltspunkte für eine erfolgreiche Vernetzung von Hochschulen und ein Ausblick auf die geplanten Aktivitäten des hessischen Netzwerkes in den nächsten Jahren gegeben. (DIPF/ Orig.