游戏永恒

与以往相比,马克斯·杜德勒的建筑似乎更直接地从源头接近目标。任何可能妨碍材料与建筑内在联系的部分都被排除在外—这一点在柏林的洪堡大学新图书馆格林兄弟中心可以明显见到。竖向支撑以一种非常紧密的节奏顺次排列,其间隔密度远高于正常要求。没有为附加装饰或者表面肌理的翻新留下任何余地。结构忠实于自身,形成了自己的"装饰",既不能增也不能减。它深深地扎根于它所建造的场地,并与背景相一致,这种背景是与"准确(分布)"联系在一起的,莱昂·巴蒂斯塔·阿尔伯蒂将其解释为一种先天判断能力的结果。从这个意义来讲,杜德勒的建筑是直接而准确的。他避     

Interleukin‐4‐Clicked Surfaces Drive M2 Macrophage Polarization

Driving macrophage (M?) polarization into the M2 phenotype provides potential against inflammatory diseases. Interleukin‐4 (IL‐4) promotes polarization into the M2‐M? phenotype, but its systemic use is constrained by dose‐limiting toxicity. Consequently, we developed IL‐4‐decorated surfaces aiming at sustained and localized activity. IL‐4 muteins were generated by genetic code expansion; Lys42 was replaced by unnatural amino acids (uAAs). Both muteins showed cell‐stimulation ability and binding affinity to IL4Rα similar to those of wt‐IL‐4. Copper‐catalyzed (CuAAC) and copper‐free strain‐promoted (SPAAC) 1,3‐dipolar azide–alkyne cycloadditions were used to site‐selectively anchor IL‐4 to agarose surfaces. These surfaces had sustained IL‐4 activity, as demonstrated by TF‐1 cell proliferation and M2, but not M1, polarization of M‐CSF‐generated human M?. The approach provides a blueprint for the engineering of cytokine‐activated surfaces profiled for sustained and spatially controlled activity.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Time‐resolved investigation of Cu(In,Ga)Se2 growth and Ga gradient formation during fast selenisation of metallic precursors

Ga segregation at the backside of Cu(In,Ga)Se₂ solar cell absorbers is a commonly observed phenomenon for a large variety of sequential fabrication processes. Here, we investigate the correlation between Se incorporation, phase formation and Ga segregation during fast selenisation of Cu–In–Ga precursor films in elemental selenium vapour. Se incorporation and phase formation are analysed by real‐time synchrotron‐based X‐ray diffraction and fluorescence analysis. Correlations between phase formation and depth distributions are gained by interrupting the process at several points and by subsequent ex situ cross‐sectional electron microscopy and Raman spectroscopy. The presented results reveal that the main share of Se incorporation takes place within a few seconds during formation of In–Se at the top part of the film, accompanied by outdiffusion of In out of a ternary Cu–In–Ga phase. Surprisingly, CuInSe₂ starts to form at the surface on top of the In–Se layer, leading to an intermediate double graded Cu depth distribution. The remaining Ga‐rich metal phase at the back is finally selenised by indiffusion of Se. On the basis of a proposed growth model, we discuss possible strategies and limitations for the avoidance of Ga segregation during fast selenisation of metallic precursors. Solar cells made from samples selenised with a total annealing time of 6.5 min reached conversion efficiencies of up to 14.2 % (total area, without anti‐reflective coating). The evolution of the Cu(In,Ga)Se₂ diffraction signals reveals that the minimum process time for high‐quality Cu(In,Ga)Se₂ absorbers is limited by cation ordering rather than Se incorporation. Copyright © 2014 John Wiley & Sons, Ltd.     

Microstructure of the HMX‐Based PBX KS32 after Mechanical Loading

Non‐destructive X‐ray diffraction techniques were applied in order to monitor the influence of mechanical and shock‐loading on the microstructure of the plastic‐bonded high explosive KS32. The investigations uncovered damage to embedded coarse HMX crystals and to the binder system HTPB‐IPDI. Damage to the crystals occurred already during the kneading process in terms of deformation twinning. On higher loading between 400 MPa (static) and 480 MPa (dynamic) also crystal fracture was observed. The change in the binder structure was found after both static and dynamic loading, but not in the cured, differently kneaded samples. Moreover, the change in binder structure after dynamic loading was verified by dynamic mechanical analysis, and interpreted as a partial damage of the binder rubber shell around the explosive particles. The results are compared to literature data from imaging techniques.     

Carbon nanotubes‐filled thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)‐filled thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X‐ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of ? NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40341.     

Synthese und Konformationsanalyse von Pyranophanonen und Pyrylophanium-Verbindungen mit intraannularen Substituenten

Synthesis and Conformational Analysis of Pyranophanones and Pyrylophanium Compounds with Intraannular Substituents The synthesis of [3.3]dithiapyranophanone 6 and 11 is accomplished by use of the two-components-dilution-principle. Pyrolysis of their bis(sulfones) 7 and 12 gives the [2.2]pyranophanones 8 , 9 and 13 . Under preservation of conformation the intraannular carbonyl-function is used for the synthesis of methylpyranophanoles 14 , 16 and 17 . The synthesis of pyrylophanium compounds 15 and 18 is possible by elimination in trifluoroacetic acid. 6 exhibits anti-conformation within its crystal-structure and like 7 reveals temperature-dependent behavior in solution. Using 6 as an example, a combination of ¹³C-NMR-spectroscopy, forcefield-calculation and computer-simulation is applied for the first time to give evidence for molecular-dynamic processes of cyclophanes. 8 and 9 are the syn- and anti-conformers of the desired product, as shown by X-ray structural analysis. 13 reveals anti-conformation within its crystal structure as well as in solution. The conformational analysis of other new phanes described here is based on the ¹H-NMR-spectra of these pyrolysis products. As expected the intraannular substituents of Pyrylophanium-lons 15 and 18 show the characteristic upfield-shift within their ¹H-NMR-spectra.     

Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

Photochemistry of Acylazides. VIII. Do Acylnitrenes React like 1,3-Dipoles? The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2 . But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloaddition is modestly stereoselective by steric hindrance within the cyclic enolether 3b . Very small de-values were found with chiral substituents in the acylazide 13 . The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.