3D‐morphology reconstruction of nanoscale phase‐separation in polymer memory blends

In many organic electronic devices functionality is achieved by blending two or more materials, typically polymers or molecules, with distinctly different optical or electrical properties in a single film. The local scale morphology of such blends is vital for the device performance. Here, a simple approach to study the full 3D morphology of phase‐separated blends, taking advantage of the possibility to selectively dissolve the different components is introduced. This method is applied in combination with AFM to investigate a blend of a semiconducting and ferroelectric polymer typically used as active layer in organic ferroelectric resistive switches. It is found that the blend consists of a ferroelectric matrix with three types of embedded semiconductor domains and a thin wetting layer at the bottom electrode. Statistical analysis of the obtained images excludes the presence of a fourth type of domains. The criteria for the applicability of the presented technique are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1231–1237     

Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

Spectral estimates for saddle point matrices arising in weak constraint four‐dimensional variational data assimilation

We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds.