Solvent‐ and interface‐induced surface segregation in blends of isotactic polypropylene with poly(ethylene‐co‐propylene) rubber

The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004     

Multiple Coverings of the Plane with Triangles

We prove that any 43-fold covering of the plane with translates of a triangle can be decomposed into two coverings.     

Looking at Fokker-Planck dynamics with a noisy instrument

We consider the class of experiments which can be characterized by a Fokker-PIanck dynamics corresponding to the overdamped motion of a state point in a suitable stochastic potential. We assume that the general form of the potential is known (or can be guessed with reasonable accuracy), but that its parameters are to be determined experimentally by measurements made with a noisy instrument. This possible method for determining the potential parameters, which exploits the system's own internal stochastic motion in order to explore rapidly its available parameter space, is substantially more efficient than traditional methods involving time averages of single point measurements, and yet does not appear to have been previously considered. The method could be important when, for example, the experiment must be completed in a limited time owing either to the expense of the experimental materials or to the temporary stationarity of the preparation, situations which are commonly encountered in experimental biochemistry and biology.     

Optimization for pattern classification using biased random search techniques

We demonstrate how optimization problems arise in the field of pattern classification, in particular in using piecewise-linear classification and classification based on an optimal linear separator. We motivate the need in this area for a general purpose optimization approach. We discuss ALOPEX, a biased random search approach, from the point of view of this need. While ALOPEX itself failed to fulfil our need, a newly-introduced generalization of it (iterated ALOPEX) was found to be appropriate for the optimization problems of our particular concern. We conclude the paper with a brief critical evaluation of this approach as compared to our original aims.     

Cyclolinear polysiloxanes. II. Crosslinking and characterization

The synthesis and characterization of two groups of novel networks prepared from cyclolinear polysiloxanes are described. The first group of networks from cyclolinear polysiloxanes (N‐CLPSs) was synthesized by the hydrosilation of vinyl‐terminated cyclolinear polyorganosiloxanes [prepared from diacetoxydiethyltetramethylcyclotetrasiloxane (D₄Et₂OAc₂) or diacetoxytriethylpentamethylcyclopentasiloxane (D₅Et₃OAc₂)] with a copolymer of dimethylsiloxane and methylhydrosiloxane as the crosslinking agent. Hydrosilation was effected with a platinum carbonyl catalyst with a cyclovinylsiloxane moderator. The second group of networks (N‐eCLPSs) was prepared similarly with extended cyclolinear polysiloxanes. The mechanical properties of the novel networks were comparable to those of polydimethylsiloxane networks (N‐PDMS). The oxygen permeabilities were similar to or slightly higher than that of N‐PDMS. The glass‐transition temperatures of D₄Et₂OAc₂‐ and D₅Et₃OAc₂‐based N‐CLPSs were ?67.8 and ?90.8 °C, respectively, whereas the incorporation of polydimethylsiloxane spacers into similar N‐eCLPSs lowered their glass‐transition temperatures to ?109.7 and ?115.0 °C. Upon heating to 800 °C in air, N‐CLPSs yielded more residue than N‐eCLPSs, which in turn yielded more residue than N‐PDMS. These results may have been due to the presence of T units in the cyclic siloxane units, which may have inhibited chain degradation or the formation of volatile products. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4053–4062, 2006     

Natural abundance 13C - 13C coupling constants observed via double quantum coherence. Structural elucidation by the one- and the two-dimensional NMR experiements of velloziolone,a new seco-diterpene.

With the help of Natural Abundance ¹³C - ¹³C Coupling Constants, observed via double quantum coherence, the structural determination of VELLOZIOLONE (1), a new diterpene, has been carried out.     

Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands

Exchange of one PCy3 unit of the classical Grubbs catalyst 1 by N-heterocyclic carbene (NHC) ligands leads to "second-generation" metathesis catalysts of superior reactivity and increased stability. Several complexes of this type have been prepared and fully characterized, six of them by X-ray crystallography. These include the unique chelate complexes 13 and 14 in which the NHC- and the Ru-CR entities are tethered to form a metallacycle. A particularly favorable design feature is that the reactivity of such catalysts can be easily adjusted by changing the electronic and steric properties of the NHC ligands. The catalytic activity also strongly depends on the solvent used; NMR investigations provide a tentative explanation of this effect. Applications of the "second-generation" catalysts to ring closing alkene metathesis and intramolecular enyne cycloisomerization reactions provide insights into their catalytic performance. From these comparative studies it is deduced that no single catalyst is optimal for different types of applications. The search for the most reactive catalyst for a specific transformation is facilitated by IR thermography allowing a rapid and semi-quantitative ranking among a given set of catalysts.     

S1P1-selective in vivo-active agonists from high-throughput screening: off-the-shelf chemical probes of receptor interactions, signaling, and fate

The essential role of the sphingosine 1-phosphate (S1P) receptor S1P(1) in regulating lymphocyte trafficking was demonstrated with the S1P(1)-selective nanomolar agonist, SEW2871. Despite its lack of charged headgroup, the tetraaromatic compound SEW2871 binds and activates S1P(1) through a combination of hydrophobic and ion-dipole interactions. Both S1P and SEW2871 activated ERK, Akt, and Rac signaling pathways and induced S1P(1) internalization and recycling, unlike FTY720-phosphate, which induces receptor degradation. Agonism with receptor recycling is sufficient for alteration of lymphocyte trafficking by S1P and SEW2871. S1P(1) modeling and mutagenesis studies revealed that residues binding the S1P headgroup are required for kinase activation by both S1P and SEW2871. Therefore, SEW2871 recapitulates the action of S1P in all the signaling pathways examined and overlaps in interactions with key headgroup binding receptor residues, presumably replacing salt-bridge interactions with ion-dipole interactions.