Local Structure of ZnO Micro Flowers and Nanoparticles Obtained by Micro‐Segmented Flow Synthesis

The micro‐segmented flow technique was applied for continuous synthesis of ZnO micro‐ and nanoparticles with short residence times of 9.4 s and 21.4 s, respectively. The obtained particles were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Small angle X‐ray scattering (SAXS) and photoluminescence spectroscopy were used to determine the size and optical properties of ZnO nanoparticles. In addition, extended X‐ray absorption fine structure (EXAFS) spectroscopy was employed to investigate local structural properties. The EXAFS measurements reveal a larger degree of structural disorder in the nanoparticles than the microparticles. These structural changes should be taken into consideration while evaluating the size‐dependent visible emission of ZnO nanoparticles.     

Contributions of hydroxyethyl groups to the DNA binding affinities of anthracene probes

Contributions of hydroxyethyl functions to the DNA binding affinities of substituted anthracenes are evaluated by calorimetry and spectroscopy. Isothermal titration calorimetry indicated that binding of the ligands to calf thymus DNA (5 mM Tris buffer, 50 mM NaCl, pH 7.2, 25 degrees C) is exothermic. The binding constants increased from 1.5 x 10(4) to 1.7 x 10(6) M(-1) as a function of increase in the number of hydroxyethyl functions (0-4). DNA binding was accompanied by red-shifted absorption (approximately 630 cm(-1)), strong hypochromism (>65%), positive induced-circular dichroism bands, and negative linear dichroism signals. DNA binding, in general, increased the helix stabilities to a significant extent (DeltaT(m) approximately 7 degrees C, DeltaDeltaH approximately 3 kcal/mol, DeltaDeltaS approximately 6-20 cal/K.mol). The binding constants showed a strong correlation with the number of hydroxyethyl groups present on the anthracene ring system. Analysis of the binding data using the hydrophobicity parameter (Log P) showed a poor correlation between the binding affinity and hydrophobicity. This observation was also supported by a comparison of the affinities of probes carrying N-ethyl (Kb = 0.8 x 10(5) M(-1)) versus N-hydroxyethyl side chains (Kb = 5.5 x 10(5) M(-1)). These are the very first examples of a strong quantitative correlation between the DNA binding affinity of a probe and the number of hydroxyethyl groups present on the probe. These quantitative findings are useful in the rational design of new ligands for high-affinity binding to DNA.     

Thermostable biocatalytic films of enzymes and polylysine on electrodes and nanoparticles in microemulsions

Microemulsions of oil, water and surfactant were evaluated as media for biocatalysis at high temperatures employing films of polylysine (PLL) and the enzymes horseradish peroxidase (HRP), soybean peroxidase (SBP) and the protein myoglobin (Mb). PLL was covalently linked to oxidized pyrolytic graphite electrodes or carboxylated 500 nm diameter silica nanoparticles, then cross-linked by amidization to HRP, SBP and Mb. The resulting film systems were stable at 90 degrees C for >12 h in microemulsions. Characterization of the microemulsions by conductivity, viscosity and probe diffusion coefficients suggested that these media have bicontinuous microstructures from 25 to 90 degrees C. UV circular dichroism and visible spectroscopy confirmed that the enzymes retained near-native conformation in the films at temperatures as high as 90 degrees C. Oxidation of o-methoxyphenol to 3,3'-dimethoxy-4,4'-biphenoquinone by enzyme-PLL films on silica nanoparticles gave yields 3-5-fold larger in microemulsions at 90 degrees C compared to the same reaction at 25 degrees C. The best yields were in CTAB microemulsions and were 3-fold larger than in buffers at 90 degrees C.     

Radical polymerization of methyl methacrylate in the presence of stereoregular poly(methyl methacrylate). VI. Kinetic template effects at higher conversion

The kinetics of radical template polymerization of methyl methacrylate along isotactic poly(methyl methacrylate) as polymer template was studied. It appeared that in addition to a rate increase at low conversions, a second rate enhancement can take place at higher conversion, depending on the nature of the solvent and temperature. While the initial template effect was previously mainly ascribed to hindered segmental motion of propagation chain radicals, the second rate effect is thought to be caused by hindered translational motion of growing chains in a physical network built up during polymerization. The observed second effect is strong in the weakly complexing and network-promoting solvent toluene, but it is less pronounced in the strongly complexing solvent dimethylformamide. In acetone, also a strongly complexing solvent, the formed stereocomplexes crystallize at low conversions. Due to this crystallization the propagating chains become immobilized, which also results in a strong second rate enhancement. The observed effects are dependent on temperature, but hardly depend on template molecular weight. The influence of the template is further demonstrated by varying its concentration and by the disappearance of the rate enhancement at higher conversion, when the templates become fully covered.     

Oxidative phenol coupling catalyzed by polymer-bound copper-imidazole complexes

Polymer-bound imidazole-copper(II) complexes were investigated and applied as catalysts for oxidative coupling (polymerization) of 2,6-dialkylphenols. These polymeric catalysts were also immobilized on silica particles through adsorption, quaternization and grafting. Especially, the grafted catalysts showed interesting catalytic properties, e.g. good specificity for C-O coupling and very good stability during prolonged use in continuous processes. This stability furnished new information about the mechanism of the oxidative coupling polymerization. Finally, this reaction was optimized for the preparation of PPO-type telechelics.     

Some simplification in spin-free configuration interaction studies

A simplification has been attempted in the procedures for determining the matrix elements of the generators of the unitary group U(n) over a tensor basis spanning the irreducible representation 2 ^N/2–S , 1 ^2S for an N-electron system. It has been shown that these matrix elements require, for their determination, only the corresponding representation matrices of cyclic permutations of the group S _N . A viable algorithm has been obtained for determining these representation matrices.     

Kinetik der oxidativen Polymerisation von 1,8-Nonadiin

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