Structure and properties of the dendron-encapsulated polyoxometalate (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], a first generation dendrizyme

Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of [(Zn(H(2)O))(3)(SbW(9)O(33))(2)](12)(-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na(6)K(6)[(Zn(H(2)O))(3)(SbW(9)O(33))(2)].23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts ("dendrizymes"), which are structurally related to naturally occurring metalloproteins.     

A Polymer-Based All-Solid-State Internal Reference System for pH Glass Electrodes – Performance and Charge Transfer

An all-solid-state internal reference system for pH glass electrodes employing polypyrrole (PPy)-Nafion® composites is described. pH sensors based on this reference system are characterised at 23±3°C. The observed characteristics of the resulting all-solid-state sensors, i.e. slope and linearity of the calibration plot, response behaviour, and signal stability, are very promising, and the differences with respect to the parameters of conventional liquid filled sensors are negligible. The values of the zero potential point, which differ from those of conventional pH glass electrodes, could be controlled within limits via the composition of the PPy-Nafion composite.The excellent sensor performance observed seems to be the consequence of a reversible charge transfer between the ion-conducting membrane, the mixed conducting PPy-Nafion interlayer, and the metal wire. A first discussion of the mechanism of this charge transfer is given.     

Clustering of imbalanced high-dimensional media data

Media content in large repositories usually exhibits multiple groups of strongly varying sizes. Media of potential interest often form notably smaller groups. Such media groups differ so much from the remaining data that it may be worthy to look at them in more detail. In contrast, media with popular content appear in larger groups. Identifying groups of varying sizes is addressed by clustering of imbalanced data. Clustering highly imbalanced media groups is additionally challenged by the high dimensionality of the underlying features. In this paper, we present the imbalanced clustering (IClust) algorithm designed to reveal group structures in high-dimensional media data. IClust employs an existing clustering method in order to find an initial set of a large number of potentially highly pure clusters which are then successively merged. The main advantage of IClust is that the number of clusters does not have to be pre-specified and that no specific assumptions about the cluster or data characteristics need to be made. Experiments on real-world media data demonstrate that in comparison to existing methods, IClust is able to better identify media groups, especially groups of small sizes.     

Über eine auffällige Bildung des 1-Phenyl-5-methyl-3-pyrazolons

Ohne Zusammenfassung     

Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality

We report on novel chiral tridentate [NO₂]H₂ and tetradentate [N₂O₂]H₂ Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis involves diastereoselective metalation of chiral ferrocene or pentamethylferrocene acetals, followed by stereoconservative hydroxyalkylation and condensation with chiral hydroxyamines or diamines, respectively. In comparison to salen-type systems, an important advantage of these ligands is their tunable steric protection of the alkoxide donor site. A total of 18 different ligands varying in electronic and steric properties have been prepared and fully characterized by NMR, IR, mass spectroscopy and by single crystal structure analysis of nine precursors and representatives.     

Calcium phosphate colloids with hierarchical structure controlled by polyaspartates

 Precipitation of calcium phosphate in a double-jet experiment in the presence of sodium polyaspartic acid results in a structural evolution of stable colloidal objects with a variety of unconventional morphologies. This structural evolution is characterized by a combination of techniques, namely static and dynamic light scattering, small-angle and wide-angle X-ray scattering, and transmission electron microscopy. It is shown that after immediate formation of amorphous precursor nanoparticles with a “parachute architecture”, the system transfers into a hollow sphere morphology in the 500-nm region and is composed of plateletlike nanocrystals, and again is transferred into a final, “snowball-like” morphology of high structural definition and monodispersity. The kinetics depends on the amount and the molecular weight of the polymer, but similar structural elements are found in all the cases examined. When repeated in a triple-jet experiment, which also ensures a constant polymer concentration, it was possible to intercept a postulated intermediate structure in practically complete yield, namely crystalline hydroxyapatite nanofibres with extremely high axial ratios which form an interwoven gel. Received: 11 May 2001 Accepted: 14 September 2001     

p-Hydroxybenzylierung von Carbanionen mit Chinonmethid-liefernden Verbindungen

p-Hydroxybenzylation of Carbanions with Quinonemethide Precursors. 3,5-Dialkylated 4-hydroxy-benzyl derivatives 4, 5 and 6 are useful starting materials for the p-hydroxybenzlation of carbanions derived from activated methylene compounds 7 . The reaction presumably proceeds through intermediate formation of quinonemethides 2 . The scope of the reaction is discussed.     

δ(34)S values in recent sea sediments and their significance using several sediment profiles from the western Baltic Sea

The isotope ratios of various sulphur components (total sulphur content in the sediment, sulphate and H(2)S in the pore-water) were measured in a number of cores from recent marine sediments taken from the Kieler Bucht (Kiel Bay) region in the western Baltic Sea. Additionally, the quantitative contents of total sulphur, sulphate, sulphide, chloride, organic carbon, iron and water in the sediment and in the pore-water solutions, respectively, were determined. These investigations provided the following results: 1. The sulphur contained in the sediment (～ 0.3-2% of the dry sample) was for the most part introduced only after sedimentation. This confirms the deliberations of Kaplan et al. [The Distribution and Isotopic Abundance of Sulfur in Recent Marine Sediments off Southern California, Geochim. Cosmochim. Acta 27, 297 (1963)]. The organic substance contributes to the sulphur content of the sediment only to an insignificant degree (in our samples with ～5-10% of the total sulphur). 2. The sulphate in the pore-waters has been identified as a source for sulphur in the sediment. During normal sedimentation, the exchange of sulphate by diffusion significant for changes in the sulphur content goes down to a sediment depth of 4-6 cm. In this process, the sulphate consumed by reduction and formation of sulphide or pyrite is mostly replaced. The uppermost sediment layer thus represents a partially open system for the total sulphur. The diagenesis of the sulphur is allochemical. At depths below 4-6 cm, we are dealing with a closed system. The further diagenesis of sulphur here is isochemical. 3. The isotope values of the sediment sulphur are influenced primarily by sulphur which comes into the sediment by diffusion and which is bound by subsequent bacteriological reduction as either sulphide or pyrite. As a consequence of the prevailing reduction of (32)S and reverse-diffusion of sulphate into the open sea water, a (32)S enrichment takes place in the uppermost layer of the sediment. The δ(34)S values in the sediment range in general between-15 and-35‰, while seawater sulphate is+20‰. No relationship could be established between sedimentological or chemical changes and isotope ratios. In the cores, successive sandy and clayish layers showed no change in the δ(34)S values. However, the sedimentation rate seems to influence δ(34)S values. In one core with relatively low sedimentation rates, the δ(34)S values varied between-29 and-33‰, while cores with higher sedimentation rates showed values between-17 and-24‰. 4. As sediment depth increases, the pore-water sulphate shows, as expected, decreasing concentrations (in a depth of 30-40 cm, we found between 20 and 70% of the seawater values), and increasing δ(34)S values (in one case reaching more than+60‰). The concentration of sulphide in the pore-water increases, however, with sediment depth (to various extents, reaching 80 mg S per litre in one case). The δ(34)S values of the pore-water sulphide in all cores show increases paralleling the sulphate sulphur, with a nearly constant δ difference of 50-60‰ in all cores. This seems to confirm the genetic relationship between the two components.     

Maximal spanning trees,asset graphs and random matrix denoising in the analysis of dynamics of financial networks

We study the time dependence of maximal spanning trees and asset graphs based on correlation matrices of stock returns. In these networks the nodes represent companies and links are related to the correlation coefficients between them. Special emphasis is given to the comparison between ordinary and denoised correlation matrices. The analysis of single- and multi-step survival ratios of the corresponding networks reveals that the ordinary correlation matrices are more stable in time than the denoised ones. Our study also shows that some information about the cluster structure of the companies is lost in the denoising procedure. Cluster structure that makes sense from an economic point of view exists, and can easily be observed in networks based on denoised correlation matrices. However, this structure is somewhat clearer in the networks based on ordinary correlation matrices. Some technical aspects, such as the random matrix denoising procedure, are also presented.