Host–Guest Chemistry of a Bis‐Calix[4]pyrrole Derivative Containing a trans/cis‐Switchable Azobenzene Unit with Several Aliphatic Bis‐Carboxylates

The azobenzene unit used as a photochemically and thermally switchable linker in the assembly of a bis‐calix[4]pyrrole receptor provides a means to modulate the binding of bis‐carboxylates of significant biological importance in cancer research. Conversely, the complexation of different bis‐anionic guests has significant kinetic effects on both the photochemical and thermal trans/cis isomerization of the azobenzene unit.     

A mixed hp FEM for the approximation of fourth‐order singularly perturbed problems on smooth domains

We consider fourth‐order singularly perturbed problems posed on smooth domains and the approximation of their solution by a mixed Finite Element Method on the so‐called Spectral Boundary Layer Mesh. We show that the method converges uniformly, with respect to the singular perturbation parameter, at an exponential rate when the error is measured in the energy norm. Numerical examples illustrate our theoretical findings.     

Cheating as a dynamic marketing strategy in monopoly,cartel and duopoly

In 2015 it was discovered that Volkswagen had manipulated the exhaust emissions of its (diesel) cars. Since then, numerous other automotive car manufacturers were strongly suspected to violate against the same emission standards. This paper investigates how and why firms (monopoly, cartel and duopoly) engage in cheating, more precisely, promising attributes that are actually not part of the product. Firms make claims in order to better market their product but risk damaging their future reputation. The upshot of the paper is the stark difference between open loop and Markov perfect oligopolistic equilibrium outcomes. More precisely, the latter mitigates cheating substantially even below the levels attained by monopolies and cartels (unless consumers have a very short memory), which is contrary to the outcome in the limiting static version of the game. Therefore, revealing the true state (e.g., by mandating strict inspections) could force firms to use this information and play in Markov instead of open loop strategies.

     

Imaging of the formerly bonded area of individual fibre to fibre joints with SEM and AFM

Besides the determination of the force and the energy needed to break individual fibre to fibre joints, the investigation of the formerly bonded area (FBA) is of essential importance to learn more about the failure mechanisms of fibre–fibre bonds in general. In this study the surfaces of paper fibres and the FBA of fibre–fibre joints after the determination of the breaking force as well as the bonding energy were analysed by means of low voltage scanning electron microscopy and atomic force microscopy. A comparison between the contact zone of fibres broken at different loading rates as well as under cyclic loading showed that there seems to be no significant difference in the appearance of the FBA in these cases. Only minor delamination of the cell wall could be found in the bonding zone, which indicates no mechanical interlocking of fibrils in the bonding zone. Furthermore, it is shown that some glues used for specimen preparation of fibre–fibre bond strength measurement are forming a glue film on the fiber surface and migrate into the bonding region.     

A prochelator peptide designed to use heterometallic cooperativity to enhance metal ion affinity

A peptide has been designed so that its chelating affinity for one type of metal ion regulates its affinity for a second, different type of metal ion. The prochelator peptide (PCP), which is a fusion of motifs evocative of calcium loops and zinc fingers, forms a 1 : 2 Zn : peptide complex at pH 7.4 that increases its affinity for Zn²⁺ ∼3-fold in the presence of Tb³⁺ (log β₂ from 13.8 to 14.3), while the 1 : 1 luminescent complex with Tb³⁺ is brighter, longer lived, and 20-fold tighter in the presence of Zn²⁺ (log K from 6.2 to 7.5). This unique example of cooperative, heterometallic allostery in a biologically compatible construct suggests the possibility of designing conditionally active metal-binding agents that could respond to dynamic changes in cellular metal status.     

Numerical study of adhesive and cohesive failure of structured interfaces

In this contribution, a numerical study is presented, which addresses the failure behaviour of structured interfaces within a computational homogenisation scheme. Different local phenomena, e.g. the surface roughness and different local failure types like cohesive failure of the polymer and adhesive failure of the local interface and their effects on the overall interface characteristics are investigated. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Collective Total Synthesis of 4-Azafluorenone Alkaloids

4-Azafluorenones are typically obtained by acid-mediated cyclization of 2-arylnicotinates. However, this approach fails to give 5-oxygenated 4-azafluorenones due to lactonization of 2-(2-alkoxy)phenylnicotinate intermediates. Herein, we report two modifications of established approaches to 4-azafluorenone synthesis that, either in combination or by themselves, enable the flexible preparation of 4-azafluorenones with diverse oxygenation patterns in the benzenoid ring. Undesired lactonization was circumvented via tert-butyl hydroperoxide (TBHP)-mediated radical cyclization of 2-aryl-3-(hydroxymethyl)pyridines. In the absence of suitable protecting groups for phenolic intermediates, bromide substituents were regioselectively introduced as latent hydroxy groups and later converted under palladium catalysis. We present the first total syntheses of five 4-azafluorenone alkaloids muniranine, darienine, 5,8-dimethoxy-7-hydroxyonychine, 5,6,7,8-tetramethoxyonychine, and 6,8-dihydroxy-7-methoxyonychine in addition to new total syntheses of six 4-azafluorenone alkaloids and one related pyridocoumarin alkaloid.