Suspension polymerization of thermotropic monomer: Formation of droplets or beads

Ordered beads were obtained by the suspension copolymerization of amesogenic methacrylate-based monomer and methacrylic acid. The stability of these particles and the liquid crystal organization inside the particles depend mainly on the time of polymerization and on the crosslinking. Suspended droplets of monomers or polymers can be obtained as well as solid spheres. The solid particles exhibit ordered microstructures with a liquid crystal configuration that has a variable form depending on polymerization time and observation temperature. Bead characteristics such as morphology, size and polydispersity, and porosity are discussed and compared with those of non-mesomorphic beads. The mesomorphic beads are smaller and their porosity lower. The presence of a crosslinker during the polymerization process leads to more mechanically stable particles with retention of polymorphism.     

Aldolic Condensations on Inorganic Solid Support: Application to the Synthesis of O-Ethyl Esters of 3-Phenyl-2-propenethioic Acids

Aldolic condensations with 0-ethyl thioesters are performed on basic alumina to give 2,3-unsaturated thioates. The stereochemistry of the reaction is discussed and compared with Knoevenagel's, Pinner's and Wittig-Horner's reactions.     

Thermoresponsive poly(N-vinyl caprolactam)-coated gold nanoparticles: sharp reversible response and easy tunability

Narrowly distributed poly(N-vinyl caprolactam) obtained by the MADIX/RAFT process was used for the preparation of novel thermoresponsive gold nanoparticles presenting a sharp reversible response to temperature, which can be easily modulated near the physiological temperature by simply changing the polymer molecular weight or concentration.     

Regiocontrol of the palladium-catalyzed tin hydride addition to Z-enynols: remarkable Z-directing effects

Palladium-catalyzed hydrostannation of substituted Z- and E-enynols is discussed and compared. The regioselectivity of the H-Sn bond addition was found to be controlled by the geometry of the double bond (Z- or syn-directing effect) rather than the nature of its substituents. Exclusively alpha-vinyl stannanes were obtained from Z-enynols having various substituents on the double bond regardless of their electronic, steric, or chelating natures.     

Natural neighbor coordinates of points on a surface

Natural neighbor coordinates and natural neighbor interpolation have been introduced by Sibson for interpolating multivariate scattered data. In this paper, we consider the case where the data points belong to a smooth surface , i.e., a (d−1)-manifold of . We show that the natural neighbor coordinates of a point X belonging to tends to behave as a local system of coordinates on the surface when the density of points increases. Our result does not assume any knowledge about the ordering, connectivity or topology of the data points or of the surface. An important ingredient in our proof is the fact that a subset of the vertices of the Voronoi diagram of the data points converges towards the medial axis of when the sampling density increases.     

Room-Temperature Photoinduced Electron Transfer in a Prussian Blue Analogue under Hydrostatic Pressure

In from the cold: The Co(III) Fe(II) state of a CoFe Prussian blue analogue undergoes a Co(III) ?Fe(II) →(Co(II) ?Fe(III) )* electron transfer at room temperature when irradiated by visible light (532?nm; see scheme). This property was confirmed using energy-dispersive X-ray absorption spectroscopy at the Co and Fe K-edges of the piezo-induced Co(III) Fe(II) state.     

Synthesis of 1,1-diarylethylenes via efficient iron/copper co-catalyzed coupling of 1-arylvinyl halides with Grignard reagents

An efficient access to 1,1-diarylethylenes of biological interest by coupling functionalized aryl Grignard reagents and 1-arylvinyl halides in the presence of FeCl(3)/CuTC is described. This bimetallic system proved to be superior to the use of Fe or Cu catalyst alone. The synthetic utility of this protocol is illustrated in the field of steroid chemistry.     

Strong Constraints on Models that Explain the Violation of Bell Inequalities with Hidden Superluminal Influences

We discuss models that attempt to provide an explanation for the violation of Bell inequalities at a distance in terms of hidden influences. These models reproduce the quantum correlations in most situations, but are restricted to produce local correlations in some configurations. The argument presented in (Bancal et al. Nat Phys 8:867, 2012) applies to all of these models, which can thus be proved to allow for faster-than-light communication. In other words, the signalling character of these models cannot remain hidden.     

Platinum oxide catalyzed hydrosilylation of unsymmetrical internal aryl alkynes under ortho-substituent regiocontrol

[chemical reaction: see text]. PtO2- and H2PtCl6-catalyzed hydrosilylation of internal aryl alkynes having a para or an ortho substituent with triethylsilane are discussed and compared. The regioselectivity of the H-Si bond addition was found to be controlled by the ortho substituent rather than the nature of the platinum catalyst. Arylalkynes with an ortho substituent, regardless of its electronic nature, directed the silyl substituent mainly to the alpha-position. PtO2 proved to be a versatile and powerful catalyst compared to H2PtCl6 since it prevents the alkyne reduction.