Synthesis and Thin Film Phase Behaviour of Functional Rod‐Coil Block Copolymers Based on Poly(para‐phenylenevinylene) and Poly(lactic acid)

We report the synthesis of a series of block copolymers consisting of a rod‐like semiconducting poly(2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (DEH‐PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self‐assembling templates for bulk heterojunction donor–acceptor layers in organic solar cells. A lamellar microphase‐separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.

     

Localized electropolymerization on oxidized boron-doped diamond electrodes modified with pyrrolyl units

This paper describes the functionalization of oxidized boron-doped diamond (BDD) electrodes with N-(3-trimethoxysilylpropyl)pyrrole (TMPP) and the influence of this layer on the electrochemical transfer kinetics as well as on the possibility of forming strongly adhesive polypyrrole films on the BDD interface through electropolymerization. Furthermore, localized polymer formation was achieved on the TMPP-modified BDD interface using the direct mode of a scanning electrochemical microscope (SECM) as well as an electrochemical scanning near-field optical microscope (E-SNOM). Depending on the method used polypyrrole dots with diameters in the range of 1-250 microm are electrogenerated.     

Biocatalytic deuterium- and hydrogen-transfer using over-expressed ADH-'A': enhanced stereoselectivity and 2H-labeled chiral alcohols

Employing the over-expressed highly organic solvent tolerant alcohol dehydrogenase ADH-'A' from Rhodococcus ruber DSM 44541, versatile building blocks, which were not accessible by the wild type catalyst, were obtained in > 99% e.e.; furthermore, employing d8-2-propanol as deuterium source, stereoselective biocatalytic deuterium transfer was made feasible to furnish enantiopure deuterium labeled sec-alcohols on a preparative scale employing a single enzyme.     

Probing the substrate specificity of the catalytically self-sufficient cytochrome P450 RhF from a Rhodococcus sp

Analysis of the substrate specificity of the self-sufficient cytochrome P450 RhF revealed that the enzyme tends to catalyse the dealkylation of substituted alkyl-aryl ethers with shorter alkyl moieties more readily than equivalent compounds with longer alkyl groups.     

A Pulsed EPR and DFT Investigation of the Stabilization of Coordinated Phenoxyl Radicals in a Series of Cobalt Schiff-Base Complexes

We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co^II, [Co(1)], leads to the formation of an unusual coordinated Co^III-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino Co^II complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine Co^II salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].     

Young-type interference in (e, 2e) ionization of H(2)

We have investigated the electron impact single ionization of the hydrogen molecule, with fully determined kinematics. The experimental and theoretical results are compared with He ionization under the same conditions. The results indicate that the ejected electron angular distribution for H(2) is modified due to Young-type interference between ionization amplitudes for scattering from the two centers in the hydrogen molecule. The observable result is a suppression of the backward scattering (recoil) peak compared with the binary peak.     

Forecasting the underlying potential governing the time series of a dynamical system

We introduce a technique of time series analysis, potential forecasting, which is based on dynamical propagation of the probability density of time series. We employ polynomial coefficients of the orthogonal approximation of the empirical probability distribution and extrapolate them in order to forecast the future probability distribution of data. The method is tested on artificial data, used for hindcasting observed climate data, and then applied to forecast Arctic sea-ice time series. The proposed methodology completes a framework for ‘potential analysis’ of tipping points which altogether serves anticipating, detecting and forecasting nonlinear changes including bifurcations using several independent techniques of time series analysis. Although being applied to climatological series in the present paper, the method is very general and can be used to forecast dynamics in time series of any origin.     

A Class of Gorenstein Artin Algebras of Embedding Dimension Four

In this article, we study height four graded Gorenstein ideals I in k[x, y, z, w] such that I ₂ is of height one and generated by three quadrics. After a suitable linear change of variables, I ∩ k[x, y, z] is either Gorenstein or of type two. The former case was studied by Iarrobino and Srinivasan [8 Iarrobino , A. , Srinivasan , H. ( 2005 ). Artininan Gorenstein algebras of embedding dimension four: components of ? Gor (H) for H = (1, 4, 7,…, 1) . Journal of Pure and Applied Algebra 201 : 62 – 96 .[Crossref], [Web of Science ®] , [Google Scholar]] where they give the structure of the ideal and its resolution. We study the latter case and give the structure of these ideals and their minimal resolution. We also explicitly write the form of the generators of I and the maps in the free resolution of R/I.     

The algorithmic beauty of plant roots – an L-System model for dynamic root growth simulation

Understanding the impact of root architecture on plant resource efficiency is important, in particular, in the light of upcoming shortages of mineral fertilizers and changed environmental conditions. In the 1950s, a great number of root systems of European cultivated plants were excavated and studied by L. Kutschera (1960). Her work gave enormous insight into the variety of root system architectures and helped to realize the importance of belowground processes to plant productivity. We analysed the resulting hand drawings by using mathematical modelling and found root system parameters for a newly developed parametric L-System model. In this way we were able to first reproduce the illustrations, second computationally analyse root system traits and finally access the dynamic root architecture development.