Triphilic pentablock copolymers with perfluoroalkyl segment in central position

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.     

Methodological reflections on a three-step-design combining observation,stimulated recall and interview

In this paper a tripartite qualitative design combining abservation, stimulated recall and interview is presented and discussed. This three-step-design makes it possible to get insight into the interaction of internal and external processes when solving mathematical tasks. The data analysis depends on the research question and the methodological approach. In the light of two research projects in mathematics education two different methods of data analysis are presented and methodologically reflected.     

Acoustic anisotropy and birefringence in fibre-reinforced composite materials

All nine elastic moduli of an orthotropic composite material, namely, polypropylene reinforced with glass fiber, are determined from the measured values of the bulk acoustic wave velocities along specific directions in the planes of symmetry of the material. These data are used to calculate the angular dependences of phase velocities, polarization vectors, and directions of ray velocities of bulk waves in the composite. It is demonstrated that the difference in the velocities of shear waves polarized along and across the glass fiber gives rise to an acoustic birefringence and can lead to an elliptical polarization of waves. The measurement of the phase velocities of shear waves as functions of the wave polarization is suggested as a method for the determination of the fiber orientation in a composite material.     

Migration order of dipeptide and tripeptide enantiomers in the presence of single isomer and randomly sulfated cyclodextrins as a function of pH

The present study was conducted in order to evaluate the cyclodextrin (CD)-mediated chiral separation of peptide enantiomers as uncharged analytes at pH 5.3 using randomly sulfated beta-cyclodextrin, heptakis-6-sulfato-beta-CD and heptakis-(2,3-diacetyl-6-sulfato)-beta-CD as chiral selectors. Although less effective compared to stronger acidic conditions, the CDs proved to be suitable chiral selectors for the present set of peptides at pH 5.3. The carrier ability of the negatively charged CDs upon reversal of the applied voltage may also be exploited leading to a reversal of the migration order. In addition, reversal of the enantiomer migration order upon increasing the buffer pH from 2.5 to 5.3 was also observed for Ala-Tyr in the presence of randomly sulfated beta-CD, for Ala-Phe, Ala-Tyr, Phe-Phe, Asp-PheNH(2) and Gly-Ala-Phe in the presence of heptakis-6-sulfato-beta-CD, and for Phe-Phe and Ala-Leu in the presence of heptakis-(2,3-diacetyl-6-sulfato)-beta-CD. The migration behavior could be explained on the basis of the complexation constants and the mobilities of the peptide-CD complexes. While a change in the affinity pattern of the CDs upon increasing the pH was observed for some peptides, complex mobility was the primary factor for other peptide-CD combinations affecting the enantiomer migration order at the two pH values studied.     

Untersuchungen zur Bildung von Doppelringsilicationen in Trimethyl-(2-hydroxyethyl)ammoniumsilicatlösungen

Investigation on the Formation of Double-ring Silicate Ions in Trimethyl-(2-hydroxyethyl) Ammoniumsilicate Solutions The formation of double-four ring silicate ions have been investigated after the mixing of Tetramethoxysilan with Trimethyl-(2-hydroxyethyl)ammoniumhydroxide in the molar ratio 1:1 (c_SiO2 = 1.53 mol · kg^?1) in dependence of the time. About 20–30% of the rapid hydrolysing esters has reacted to double-three- and double-four ring ions after a short time, whereas 70–80% first condense to oligomers and polymers. In the further course of reaction also the oligomers, the polymers and the intermediate formed double-three-ring species changes to double-four-ring ions. After three hours about 90% of the silicon dioxide is in the double-four-ring constitution.     

Epitaxial growth of sexiphenyl on Al(111): from monolayer to crystalline films

A combination of in situ surface sensitive-techniques, UV photoemission and low energy electron diffraction, with ex situ bulk sensitive X-ray diffraction reveals the formation of epitaxial thin films of sexiphenyl on Al(111) starting from the first monolayer. For room temperature growth, highly ordered films are formed with a unique alignment of the sexiphenyl molecules with the long axes of all molecules aligned parallel to both the surface and the <10> azimuthal directions of Al(111). This is related to a densely packed highly commensurate first monolayer, which acts as a template for the unique (21) crystallite orientation observed.     

Kinetics of the adsorptional deformation of zeolites

Adsorptional deformation in the Xe-CaA system has been studied at 303 K; the kinetics of adsorption and deformation has been investigated. A kinetic model of deformation is proposed based on the principle of the instantaneous establishment of local deformational equilibrium. Kinetic deformation curves based on this model are plotted that have local extrema above equilibrium values or in the negative region. It is shown that when Xe is adsorbed by CaA zeolite and trans-2-butene is adsorbed by NaA zeolite, the time required for deformational equilibrium to be established is negligibly small, and that deformation at any point of time at any point in the crystal is in equilibrium with respect to adsorption and temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1948–1951, September, 1990.