Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions

In the context of solar-to-chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron-transfer processes of three novel zinc(II)-gold(III) bis(porphyrin) dyads [Zn^II(P)–Au^III(P)]⁺ are presented (P: tetraaryl porphyrin). Time-resolved spectroscopic studies indicated ultrafast dynamics (k >10¹⁰ s⁻¹) after visible-light excitation, which finally yielded a charge-shifted state [Zn^II(P ^{⋅ +})–Au^II(P)]⁺ featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (k ≈3×10⁸ s⁻¹). The [Zn^II(P ^{⋅ +})–Au^II(P)]⁺ charge-shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)–gold(II) bis(porphyrin) Zn^II(P)–Au^II(P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X-band EPR, gold L₃-edge X-ray absorption near edge structure (XANES) and paramagnetic ¹H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in Zn^II(P)–Au^II(P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple.     

High birefringence and large negative dielectric anisotropy phenyl-tolane liquid crystals

Two phenyl-tolane compounds with two pairs of (2,3) lateral difluoro substitutions were synthesized and their properties evaluated. These compounds exhibit a high birefringence (Δn ∼ 0.35) and a large negative dielectric anisotropy (Δε∼ -8). These two important features make the phenyl-tolane compounds useful as a dopant in a negative Δε liquid-crystal mixture to enhance the performance of the host mixture, or as a negative component in a dual-frequency liquid-crystal mixture to improve the dielectric anisotropy and birefringence and lower the crossover frequency.     

Computing Particle Surface Areas and Contact Areas from Three‐Dimensional Tomography Data of Particulate Materials

Microtomography is an emerging technique for particle and particulate‐materials characterization. To use this technology effectively, robust and accurate computational algorithms are needed to compute relevant particle properties, including particle surface area and particle‐particle contact area. However, the most accurate algorithms that have been developed for computing the exposed (void/solid) surface area in a microtomography image cannot be used directly for computing surface areas or particle‐particle contact areas for individual particles in a dense packing. This paper presents an algorithm for extracting particle contact areas from a digitized, segmented image of a packed granular material, which in turn can be used to find individual particle surface areas (even if the complete surfaces are not exposed because of contacts in the packing). Results show that small errors in the binary surface‐area computations are magnified in the course of determining particle contact areas; the total error in the computation depends mainly on the size of the contact area in voxel units.     

Synthesis and mesomorphic properties of super high birefringence isothiocyanato bistolane liquid crystals

Four series of high birefringence bistolane liquid crystals containing isothiocyanato termal groups were synthesized and characterized. As well as the phenyl group, both biphenyl and naphthyl moieties were introduced to enhance the birefringence. These bistolane compounds exhibit reasonably low melting points and high birefringence of 0.5-0.8. A eutectic mixture was formulated from these compounds exhibiting a wide nematic range, high figure-of-merit and low viscosity.     

Video technology in the assessment of an in-service teacher learning program

Video technology offers the possibility to make instructional situations available for discussion in teacher learning projects. For the confrontation with videotaped instructional situations, the teachers' rating of characteristics for instructional quality plays an imminent role. As criteria for instructional quality are often linked to the goals of the teacher learning project, the teachers' views offer possibilities to evaluate these projects. For the example of instructional situations in german classrooms concerning geometrical proof, differences in judgements on instructional quality are analysed. The study focuses on data of a cluster analysis showing initial divergencies in the rating of videotaped instructional situations and it describes how the teachers'views evolve.     

Dihydroxyquingdainone Induces Apoptosis in Leukaemia and Lymphoma Cells via the Mitochondrial Pathway in a Bcl-2- and Caspase-3-Dependent Manner and Overcomes Resistance to Cytostatic Drugs In Vitro

Isatis tinctoria and its indigo dyes have already provided highly active anti-leukaemic lead compounds, with the focus mainly being on indirubin, whereas indigo itself is inactive. There are many more indigoids to find in this plant extract, for example, quingdainone, an indigoid derived from tryptanthrin. We present here a new synthesis of hitherto neglected substituted quingdainones, which is very necessary due to their poor solubility behaviour, and a structure-dependent anti-leukaemic activity study of a number of compounds. Substituted α-phenylaminoacrylic acid was synthesised by hydrogen sulfide extrusion from an analogue mercaptoacetic acid, available from the condensation of rhodanin and a substituted tryptanthrin. It is shown that just improving water solubility does not increase anti-leukaemic activity, since a quingdainone carboxylic acid is inactive compared to dihydroxyquingdainone. The most effective compound, dihydroxyquingdainone with an AC₅₀ of 7.5 µmole, is further characterised, revealing its ability to overcome multidrug resistance in leukaemia cells (Nalm-6/BeKa) with p-glycoprotein expression.