Gasphasenkomplexe zwischen Kobaltchlorid und Aluminiumchlorid

CoCl₂ forms two gaseous complexes in the presence of gaseous Aluminiumchlorid: The equilibria were investigated by dynamic vapour pressure measurements (transpiration and chemical transport), by optical spectroscopy and by quenching the equilibrium gasphase followed by analysis of the condensates. The chromophor in the gaseous complexes appears to be tetrahedral CoCl₄.     

Quantitative detection of phosphoproteins by combination of two-dimensional difference gel electrophoresis and phosphospecific fluorescent staining

Here we combine a standard two-dimensional difference gel electrophoresis (DIGE) protocol with subsequent post-staining of gels with phosphospecific fluorescent Pro-Q Diamond dye. The combination of these two methods for fluorescence detection of proteins allows quantitative detection of phosphoproteins in 2-DE-gels. We established this protocol within a functional proteomics experiment. Mammary epithelial cells (EpH4) were stimulated in culture by epidermal growth factor (EGF), endosomal fractions prepared after subcellular fractionation and phosphorylated proteins successfully detected on endosomes. For instance, Endo A cytokeratin, known as phosphoprotein and differentiation marker inducible by MAPK signaling, was identified by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). With this protocol, all steps of combined proteome and phosphoproteome profiling experiments are significantly simplified and accelerated, taking full advantage of both methods in terms of specificity, sensitivity and accuracy of quantification.     

The palladium-catalyzed cross-coupling reaction of carboxylic anhydrides with arylboronic acids: a DFT study

The mechanism of the cross-coupling of phenylboronic acid with acetic anhydride, a viable model of the widely used Suzuki reaction, has been studied by DFT calculations at the BP86/6-31G level of theory. Two alternative catalytic cycles have been investigated, one starting from a neutral Pd(0)L(2) complex, the other from an anionic "Jutand-type" [Pd(0)L(2)X](-) species. The reaction profiles are in good agreement with the experimental findings, as both pathways require only moderate activation energies. Both pathways are dominated by cis-configured square-planar palladium(II)diphosphine intermediates. Despite careful investigations, we did not find in this model reaction any evidence for five-coordinate palladium(II) intermediates, which are commonly believed to cause the profound effects of counterions in palladium-catalyzed transformations. Instead, our calculations suggest that the higher catalytic activity of anionic complexes, such as [Pd(PMe(3))(2)OAc](-), may arise from their stronger ability to coordinate to carbon electrophiles. The transmetalation sequence is the same for both catalytic cycles, involving the dissociation of one phosphine ligand from the palladium. In the decisive transition state, in which the phenyl group is transferred from boron to palladium, the acetate base is found to be in a bridging coordination between these two atoms.     

Awakening effects of simulated sonic booms and aircraft noise on men and women

In the course of several studies, 22 male and female subjects, ranging in age from 5–75 years, have been stimulated while asleep by simulated sonic booms (ranging in intensity from 0·6 to 5·0 lb/ft² (239·5 N/m²), as if measured out of doors at ground level) and by indoor recordings of subsonic jet flyover noise (ranging in intensity from 101 to 119 PNdB, as if measured out of doors). The summarized results of these studies suggest that (i) children (5–8 years of age) are uniformly unaffected by noise during sleep; (ii) older subjects are more sensitive to noise than younger subjects; (iii) women are more sensitive to noise during sleep than are men; (iv) within an age group, individuals may vary widely with respect to their relative sensitivities to noise during sleep; and (v) the frequency of behavioral awakening is a function of the intensity of both the simulated sonic booms and the subsonic jet flyover noise.     

Bindungsverh?ltnisse in Bicyclo(1.1.0)butanderivaten

Ohne Zusammenfassung

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Bonding conditions in bicyclo(1.1.0)butane derivatives

     

Theoretical and experimental investigations of the temperature dependent continuous wave lasing characteristics and the switch-on dynamics of an InAs/InGaAs quantum-dot semiconductor laser

We investigate spectrally resolved continuous wave (CW) and spectrally and time-resolved switch-on emission properties of an InAs/InGaAs quantum-dot laser. The temperature and injection current dependence of the excited-state and ground-state emission dynamics is studied in the range between 20 °C and 50 °C under CW and gain-switching operation. All the experimental results are found to be in good agreement with simulation results based on a multi-population rate equation model incorporating all of the peculiar properties of the quantum-dot material as homogeneous and inhomogeneous broadening of the emission linewidth, different dynamics for electrons and holes, cascaded and direct capture paths of carriers from the wetting layer into the dot and Auger non-radiative recombination. This coincidence between simulations and experiments allows explaining the complicated behavior of the CW characteristics and the switch-on dynamics in the investigated temperature range.     

On Configurational-Force-Driven Crack Propagation and Adaptive Mesh Refinement in Finite Inelasticity

We introduce a consistent variational framework for inelasticity at finite strains, yielding dual balances in physical and material space as the Euler equations. The formulation is employed for the simultaneous usage of configurational forces as both driving forces for crack propagation as well as h-adaptive mesh refinement. The theoretical basis builds upon a global balance of internal and external power, where the mechanical response is exclusively governed by two scalar functions, the free energy function and a dissipation potential. The resulting variational structure is exploited in the context of fracture mechanics and yields evolution equations for internal variables. In the discrete setting, we present a geometry model fully separated from the finite element mesh structure that represents structural changes of the material configuration due to crack propagation. Advanced meshing algorithms provide an optimal discretization at the crack tip. Local and global criteria are obtained via error estimators based on configurational forces being interpreted as indicators of an energetic misfit due to an insufficient discretization. The numerical handling is decomposed into a staggered algorithm scheme for the dual set of equilibrium equations in material and physical space and efficient mesh generation tools. Exemplary numerical examples are considered to illustrate the method and to underline the effects of inelastic material behaviour in the presented context. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Robert Leslie Ellisʼs work on philosophy of science and the foundations of probability theory

The goal of this paper is to provide an extensive account of Robert Leslie Ellis?s largely forgotten work on philosophy of science and probability theory. On the one hand, it is suggested that both his ‘idealist’ renovation of the Baconian theory of induction and a ‘realism’ vis-à-vis natural kinds were the result of a complex dialogue with the work of William Whewell. On the other hand, it is shown to what extent the combining of these two positions contributed to Ellis?s reformulation of the metaphysical foundations of traditional probability theory. This parallel is assessed with reference to the disagreement between Ellis and Whewell on the nature of (pure) mathematics and its relation to scientific knowledge.     

Evidence for the Existence of (SiP6H2)2– and its Homologs as Examples of Binary Nortricyclane‐Type Zintl Anions

The extraction of stoichiometric ternary K/Si/P, K/Ge/P, and K/Si/As solid mixtures with en/crypt‐222 afforded compounds with binary anions of the respective groups 14/15 elemental combination. Although the analysis of the products turned out to be extremely difficult owing to their intrinsically poor crystallinity and low solubility, we have evidence that one of them contains (SiP₆H₂)^2– anions. Preliminary data from the two other compounds indicate the existence of the heavier Ge/P and Si/As variants as well. The combination of all analytical results, including X‐ray crystallography, energy‐dispersive X‐ray (EDX) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and nuclear magnetic resonance (NMR) spectroscopy, point towards the named composition of the anions and their doubly protonated nature. By this, they represent the first binary Zintl anions of the Si/P and Si/As elemental combination and complement the recent endeavors to synthesize binary Zintl anions of the light(er) p‐block elements. We discuss our attempts to elucidate the clusters' identity and provide our results as the most probable interpretation of the data, additionally corroborated by quantum chemical analyses.     

Decarboxylative ipso Amination of Activated Benzoic Acids

In the presence of a bimetallic Pd/Cu system with 1,10‐phenanthroline as the ligand and either air or N‐methylmorpholine N‐oxide as the oxidant, electron‐deficient benzoic acids undergo oxidative decarboxylative coupling with unprotected amines. This operationally simple aniline synthesis is widely applicable with respect to the amine and gives good yields, even on multigram scale. The orthogonality of this reaction to other Pd‐catalyzed cross‐couplings allows the concise synthesis of multisubstituted arenes by sequential C?C, C?Cl, and C?N functionalizations. Mechanistic investigations suggest the intermediacy of a hypervalent Pd species.