The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides – A Simple and Versatile Approach to ortho‐Functionalized Arylphosphine Oxides

Alkyldiphenylphosphine oxides typically undergo α‐deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho‐phosphinoyllithium intermediates are subject to functionalization and C C bond forming reactions, thus providing a convenient approach to new phosphine oxides and phosphine‐borane complexes, which have a good potential for an approach to new ligands for catalysis.

     

Acylierung von Heterocyclen mit Kohlensäurederivaten. I. Kinetik und Mechanismus der Reaktion von 2-Aminobenzimidazolen mit Arylcyanaten

Acylation of Heterocycles with Carbonic Acid Derivatives. I. Kinetics and Mechanism of the Reaction of 2-Aminobenzimidazoles with Aryl Cyanates The second order rate constants for the reaction of 2-amino-benzimidazoles (2-ABI) with aryl cyanates forming 2-amino-benzimidazole aryl ester imide 3 have been determined in dependence on substituent effects by u. v. measurements. The results are interpreted by a six-membered cyclic transition state in which the electrophilic attack of the cyanate on the endocyclic N atom is catalyzed by an H bridge interaction of the exocyclic amino group of 2-ABI with the OCN group.     

Influence of pectin properties and processing conditions on thermal pectin degradation

Texture degradation of fruits and vegetables during thermal processing is partly due to pectin depolymerization. In this contribution we investigate the influence of pectin properties (degree and pattern of methoxylation) and processing conditions (pH 2.0, 3.0, 5.0 and 7.0; temperatures of 80 up to 110 °C) on pectin degradation rate constants. Pectins with different degrees and patterns of methoxylation were prepared and heated, the extent of acid hydrolysis, β-elimination and demethoxylation was assayed as a function of treatment time. As the degree of methoxylation and pH decreased, β-elimination rate constants decreased while acid hydrolysis rate constants increased. Demethoxylation rate constants were minimal at pH 3.0 and increased both at lower and higher pH. Reaction rate constants were not considerably influenced by the pattern of methoxylation. All reaction rate constants increased with increasing temperature. As β-elimination rates are reduced by competing demethoxylation, both rate constants were compared. The ratio of these reaction rate constants showed no trend with pH. However, an increase in degree of methoxylation or temperature resulted in a more pronounced increase in β-elimination rate constants than in demethoxylation rate constants.     

Influence of thermal ageing on the stability of polymer bulk heterojunction solar cells

A new approach is presented in order to improve the thermal stability of polymer: [6-6]-phenyl C₆₁ butyric acid methyl ester (PCBM) bulk heterojunction solar cells. The central idea in this approach is the use of a polymer with high glass transition temperature (T_g), well above the normal operating temperatures of the devices. In this paper, a PPV-derivative with a T_g of 150 °C was used as an electron donor and the thermal stability of the obtained solar cells was compared with solar cells based on the reference material poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) with a T_g of 45 °C. The use of the material with higher glass transition temperature resulted in a significant improvement of the thermal stability of the photovoltaic parameters. Furthermore, a systematic transmission electron microscope (TEM) study demonstrates that the better thermal stability of performance coincides with a more stable active layer morphology. Both improvements are attributed to the reduced free movement of the electron donor material (PCBM) within the active layer of the solar cell.     

Studies of a thermomechanically treated Al-Zn-Mg alloy

The influence of subgrain structure on the precipitation process in an Al-4.2 wt% Zn-1.6 wt% Mg alloy was studied and correlated with its mechanical properties for ageing temperatures of 110, 142 and 165° C.     

Comparison of methods for determination of microbial biomass in wastewater

Microbial biomass in wastewater was determined by methods used in environmental microbiology and by a method used in wastewater engineering based on a conceptual model simulating fundamental microbial processes in wastewater from measured oxygen uptake rates. The methods originating from environmental microbiology are based on staining and counting of cells for the determination of total cell biomass (acridine orange and DAPI), physiological state of cells (LIVE/DEAD BacLight) and activity of cells (reduction of the redox dye CTC and microautoradiography). Depending on the staining method applied, cell biomasses yielded 15-86% of the biomass defined by the model, and good correlations between cell biomass and model biomass were found. Cell biomass, oxygen uptake and acetate uptake were measured in wastewater, where acetate was added. Substrate uptake rates were found not to be proportional to the increases in cell biomass, suggesting that only a small fraction of the cell biomass was responsible for the main part of the substrate uptake. Despite the differences found between cell biomass and model biomass, it was recommended to use the conceptual model as an engineering tool for simulation of microbial processes and wastewater quality changes. However, there should be a clear distinction between the terms 'model biomass', 'cell biomass' and different activity measurements of cells.