An ionene with spirane structure (spiroionene)

The secondary diamine 1,3,5,7-tetrahydro[1,2c:4,5c'] benzodipyrrole (3) and 1,2,4,5-tetrabromomethylbenzene (1) form a polymeric ionene with spirane structure through a repetitive alkylation reaction. The structure of the product could be proven by¹³C-NMR spectroscopy by comparison with suitable reference compounds. Solutions in aqueous methanol exhibit a typical polyelectrolyte effect. Variation of the counterions produces sufficient solubility in organic solvents. From the crystal structure of a similar model compound one can conclude that the synthesized polymer has a rod-like shape.     

Development and characterization of a biocompatible OH-modified copolymer based on polyurethane

Different polyurethanes were synthesized by varying the diol as well as the diisocyanate components and chain extenders. Polyurethanes with OH-groups were obtained by photo- and thermoinitiation of the radical polymerization of hydroxy alkyl acrylates in the presence of the polyurethanes. The polymers were evaluated with respect to their biocompatibility by measuring the cell spreading, the rates of DNA- and protein synthesis and the swelling behaviour. The differences in the surfaces and the bulks between the selected basic polyurethane and the functionalized modification were determined and characterized by XPS, FTIR-ATR and ¹³C-FT-NMR-spectroscopy. The mechanical data of Tecoflex EG 60D® and Pellethane 2363–80AE® were compared with the data of the synthesized polyurethanes.     

Processing and morphology of molecularly imprinted nylon thin films

The characterization of thin, selectively imprinted films of nylon‐6 was performed. Amino acids were used as template molecules. Spin‐cast films were prepared with sizes ranging from 2 μm to 300 nm, depending on the nylon and template concentration in the casting solution. The morphological characteristics of the film surface were examined by atomic force microscopy, and the structure within the films was observed by freeze‐fracture scanning electron microscopy. The film activity was clearly coordinated with the appearance of nanometer‐sized pores both on the surface and within the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2919–2926, 2006     

Aqueous heterophase polymerization of styrene—a study by means of multi-angle laser light scattering

An online multi-angle laser light scattering study of ab initio surfactant-free styrene emulsion polymerization reveals unexpected results regarding the development of the dispersity during the whole reaction starting from mixing styrene and water at reaction temperature. The experimentally observed change in the dispersity, which is an indirect measure of the average characteristic size of the colloidal objects, allows the identification of three characteristic intervals. During interval A the equilibration of styrene in water is characterized by the formation of styrene domains, which increase in number and size until an equilibrium state is reached. This means that there is virtually no homogeneous/molecular styrene in water solution but rather nanodroplets of about 200 nm in diameter (assuming spherical shape) are formed. During interval B, after initiation of the polymerization and particle formation, the dispersity increases again as the average size decreases and the number of scattering objects increases. The polymer particles suck up the monomer from the monomer nanodroplets, which leads to the disappearance of the nanodroplets and to a decrease in the average size. During interval C the average size increases again due to the predominantly growth of the polystyrene particles.     

The participation of soluble factors in the ω-oxidation of fatty acids in the liver of the sheep

The removal of soluble components from an ovine hepatic microsomal preparation decreased the ω-hydroxylation of dodecanoic and hexadecanoic acids. The results suggest that one or more soluble components play a role in the microsomal ω-hydroxylation of fatty acids. The possible roles in the reaction of catalase (known to stimulate the microsomal desaturations of fatty acids and alkylglycerols) and superoxide dismutase were investigated. The addition of these enzymes to the complete (but not the washed) microsomal preparation stimulated both the initial ω-hydroxylation reaction and the subsequent dehydrogenation reactions of the ω-oxidation pathway. The similarity of the effects of catalase and superoxide dismutase and stimulation of two different steps of the ω-oxidation pathway suggest that these agents are acting indirectly by removing active oxygen species rather than directly on the enzymes of microsomal fatty acid ω-hydroxylation.     

Zur kinetik der acrylnitril-polymerisation

The heterogeneous bulk polymerization of acrylonitrile initiated by AIBN has been studied by means of an improved dilatometric technique and a new method of analysis, where the initial reaction rate (v_w)₀ results from the intercept of a straight line in a \documentclass{article}\pagestyle{empty}\begin{document}$ \frac {\ln \left( 1 \hbox{---} {\rm U} \right)} {{\rm e}^{{- 0,5} {\rm k}_{\rm s}{\rm t} \hbox{---} 1}}$\end{document} versus t plot. It has been found that the initial reaction rate is proportional to the square root of the initial catalyst concentration S₀. The ratio of the rate coefficients of propagation and termination\documentclass{article}\pagestyle{empty}\begin{document}$\frac { {\rm k}_{\rm a} } { {\rm k}_{ {\rm w}^{2} } } $\end{document} could be calculated from the slope of a straight line passing through the origin in a plot of (v_w)₀ versus \documentclass{article}\pagestyle{empty}\begin{document}$\sqrt { {\rm S}_{0} }$\end{document} and yielded a value of 280 mol 1^?1.     

Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

Organic Nanoparticles with Polypropyleneoxide Chains as Support for Metallocene Catalysts: Ethylene Homopolymerization and Ethylene/α-olefin Copolymerization

Summary Novel organic nanoparticles functionalized with nucleophilic polypropyleneoxide (PPO) chains on their surfaces for supporting metallocene catalysts in heterogeneous olefin polymerization are presented. The nanoparticles (60–100 nm) were obtained by miniemulsion polymerization of styrene, divinylbenzene and PPO functionalized styrene. It is demonstrated that Me₂Si(2MeBenzlnd)₂ZrCl₂/MAO supported on these nanoparticles is suitable for the homopolymerization of ethylene, resulting in excellent product morphologies and high activities. lt is shown that by varying the MAO/Zr ratios and Zr concentrations the activities and productivities of the catalysts as well as the qualities of the polyethylene products can be tuned. These new supported catalysts are also suitable for the copolymerization of ethylene with several comonomers (1-hexene, 1-octene, 1-decene or norbornene). As the obtained product properties like crystallinity, melting temperature or bulk density match the results of silica supported systems, these organic nanoparticles can be considered as alternative carriers in comparison to the established inorganic ones.     

Closed‐Loop Identification for Control of Linear Parameter Varying Systems

This paper deals with system identification for control of linear parameter varying systems. In practical applications, it is often important to be able to identify small plant changes in an incremental manner without shutting down the system and/or disconnecting the controller; unfortunately, closed‐loop system identification is more difficult than open‐loop identification. In this paper we prove that the so‐called Hansen scheme, a technique known from linear time‐invariant systems theory for transforming closed‐loop system identification problems into open‐loop‐like problems, can be extended to accommodate linear parameter varying systems as well. We investigate the identified subsystem's parameter dependency and observe that, under mild assumptions, the identified subsystem is affine in the parameter vector. Various identification methods are compared in direct and Hansen Scheme setups in simulation studies, and the application of the Hansen Scheme is seen to improve the identification performance.