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.     

<Emphasis Type="Italic">FCC/BCC</Emphasis> competition and enhancement of saturation magnetization in nanocrystalline Co-Ni-Fe films

The structure, chemical composition, and magnetic properties of electrochemically deposited nanocrystalline Co-Ni-Fe films were investigated using a number of techniques. A high saturation magnetic induction up to B _s = 21 kG was attained. An enhancement of the saturation magnetization compared to the ideal anticipated one was revealed, which correlated with the nonlinear behavior of the structural phase composition and lattice parameters with the change of the composition. The text was submitted by the authors in English.     

Bounds for rectilinear crossing numbers

A rectilinear drawing of a graph is one where each edge is drawn as a straight-line segment, and the rectilinear crossing number of a graph is the minimum number of crossings over all rectilinear drawings. We describe, for every integer k ≥ 4, a class of graphs of crossing number k, but unbounded rectilinear crossing number. This is best possible since the rectilinear crossing number is equal to the crossing number whenever the latter is at most 3. Further, if we consider drawings where each edge is drawn as a polygonal line segment with at most one break point, then the resulting crossing number is at most quadratic in the regular crossing number. © 1993 John Wiley & Sons, Inc.     

Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

Large Water-Soluble Cyclophanes with Convergent Intracavity Functionality

New tricyclic spacers, readily available through fourfold Mannich reaction of substituted dibenzyl ketones, were introduced into a series of ten H₂O-soluble cyclophanes with spacious preorganized cavity binding sites. These spacers provide H₂O-solubility with amine or crown-ether functionality remote from the cyclophane cavity while directing functional groups such as keto or OH groups in a precise geometrical array inside the cavity. The cyclophanes were designed to include organic substrates via a combination of apolar and specific polar functional group interactions. The X-ray crystal-structure analysis of the tritopic receptor 18 with one potential neutral-molecule and two cation-binding sites showed a large rectangular open cavity with dimensions of roughly 9 × 14 Å and a spacing of 9.7 Å between the O-atoms of two convergent C?O groups. Despite the binding-site preorganization, cyclophanes incorporating two of the new spacers did not show any substrate binding in aqueous solutions. The failure of these systems to function as receptors is mainly due to steric hindrance to important cyclophane aromatic ring-guest interactions. Also, the favorable solvation of the intracavity functionality may prevent the formation of complexes. Hybrid receptors constructed from the novel spacers and diphenylmethane units were found to bind flat aromatic substrates as well as bulky [4.2]paracyclophanes. The observed large differences in stability (ΔΔG°> 2 kcal mol^?1) of the complexes formed by three structurally closely related hybrid receptors with convergent C?O, OH or CH₂ groups and 6-hydroxynaphthalene-2-carbonitrile as guest can be explained by a strong solvation effect of the convergent functional groups on apolar inclusion complexation.     

Forecasting call frequency at a financial services call centre

A forecasting model is developed for the number of daily applications for loans at a financial services telephone call centre. The purpose of the forecasts and the associated prediction intervals is to provide effective staffing policies within the call centre. The model building process is constrained by the availability of only 2 years and 7 months of data. The distinctive feature of the data is that demand is driven in the main by advertising. The analysis given focuses on applications stimulated by press advertising. Unlike previous analyses of broadly similar data, where ARIMA models were used, a model with a dynamic level, multiplicative calendar effects and a multiplicative advertising response is developed and shown to be effective.     

Issues in Managing Information Technology

This paper describes three case studies which investigated issues relating to the implementation and management of advanced information technology. The benefits derived from information technology were found to vary from one organization to another. These studies provide further evidence to support earlier research findings that senior management has an important role to play in the effective exploitation of information technology, and that the investment approach taken by an organization has a significant effect on the development of computer-based information systems. The effectiveness of a system depends not only on applying the appropriate technology, but also on how successfully technical and behavioural issues are resolved.