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.     

Applications of random sampling to on-line algorithms in computational geometry

This paper presents a general framework for the design and randomized analysis of geometric algorithms. These algorithms are on-line and the framework provides general bounds for their expected space and time complexities when averaging over all permutations of the input data. The method is general and can be applied to various geometric problems. The power of the technique is illustrated by new efficient on-line algorithms for constructing convex hulls and Voronoi diagrams in any dimension, Voronoi diagrams of line segments in the plane, arrangements of curves in the plane, and others. This work has been supported in part by the ESPRIT Basic Research Action Nr. 3075 (ALCOM).     

Smooth surface reconstruction via natural neighbour interpolation of distance functions

We present an algorithm to reconstruct smooth surfaces of arbitrary topology from unorganised sample points and normals. The method uses natural neighbour interpolation, works in any dimension and accommodates non-uniform samples. The reconstructed surface interpolates the data points and is implicitly represented as the zero set of some pseudo-distance function. It can be meshed so as to satisfy a user-defined error bound, which makes the method especially relevant for small point sets. Experimental results are presented for surfaces in .     

DMSO-PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

PdI₂ in DMSO promoted the oxidation of functionalized diarylalkynes into benzil derivatives in excellent yields. This new oxidation reaction was achieved with short reaction times and low loading of palladium catalyst. This efficient catalytic process has been applied successfully to the one-pot construction of a series of nitrogen-containing heterocycles of biological interest according to a tandem oxidation-nitrogen nucleophiles condensation-cyclization.     

Front Cover: In Situ Generated DBU⋅HF Acts as a Fluorinating Agent in a Hexafluoroisobutylation Tandem Reaction: An Effective Route to 5,5,5,5’,5’,5’-Hexafluoroleucine (Eur. J. Org. Chem. 10/2023)

We report the direct incorporation of the hexafluoroisobutyl group on a chiral glycine Schiff base complex mediated by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The fluoroalkylation involves 2-(bromomethyl)-1,1,1,3,3,3-hexafluoropropane reagent, which generates in situ hexafluoroisobutylene (HFIB), and reacts then with the enolate through a tandem allylic shift/hydrofluorination process. We showed that the use of neutral organic base DBU generates in situ an original DBU⋅HF salt, which preserves the fluoride nucleophilicity and acts as a fluorinating agent. This fluoride salt promotes the hydrofluorination of the pentafluorinated alkene overcoming the usual fluoride β-elimination observed with α-CF₃-vinyl reagents. With alkali metal bases, by contrast, the hydrofluorination is disfavored and the pentafluorinated alkene intermediate is obtained predominantly. This study highlights the critical role of the fluoride counter ion to preserve its nucleophilicity. The protocol is amenable to multidecagram scale synthesis of enantiopure (S)- and (R)-5,5,5,5’,5’,5’-hexafluoroleucine and their N-Fmoc or N-Boc derivatives in good overall yield.     

Hyperbranched polyamidoamine as stabilizer for catalytically active nanoparticles in water

Poly(amidoamine) hyperbranched polymers (HYPAM) were successfully used to synthesize platinum nanoparticles of ca. 1.8 nm and to stabilize these particles in water. Furthermore these hyperbranched-stabilized platinum nanoparticles proved to be effective and robust for hydrogenation reaction in water.     

A method to estimate turbulence intensity and transverse Taylor microscale in turbulent flows from spatially averaged hot-wire data

A new approach to evaluate turbulence intensity and transverse Taylor microscale in turbulent flows is presented. The method is based on a correction scheme that compensates for probe resolution effects and is applied by combining the response of two single hot-wire sensors with different wire lengths. Even though the technique, when compared to other correction schemes, requires two independent measurements, it provides, for the same data, an estimate of the spanwise Taylor microscale. The method is here applied to streamwise turbulence intensity distributions of turbulent boundary layer flows but it is applicable generally in any turbulent flow. The technique has been firstly validated against spatially averaged DNS data of a zero pressure-gradient turbulent boundary layer showing a good capacity to reconstruct the actual profiles and to predict a qualitatively correct and quantitatively agreeing transverse Taylor microscale over the entire height of the boundary layer. Finally, the proposed method has been applied to available higher Reynolds number data from recent boundary layer experiments where an estimation of the turbulence intensity and of the Taylor microscale has been performed.     

Non-targeted analysis of wastewater treatment plant effluents by high performance liquid chromatography-time slice-solid phase extraction-nuclear magnetic resonance/time-of-flight-mass spectrometry

Extracts of effluents from two different wastewater treatment plants (WWTP) in Switzerland taken during the application period of pesticides were examined by coupling an HPLC-MS system to a nuclear magnetic resonance spectrometer using a post column peak trapping device. By trapping 1 min portions of the chromatogram onto post column solid phase extraction cartridges (time slice-SPE-NMR) a comprehensive overview of proton carrying constituents could be achieved. Non-supervised statistical analysis of the NMR spectra obtained by this approach revealed NMR resonances pointing to contaminants present in decreasing proton concentration in the extracts. Comparison of exact mass data acquired during the trapping process to these NMR resonances enabled the identification of the pesticides Linuron, Metazachlor, Ethofumesate, Isoproturon, Metamitron, Propazine and Chloridazon. Desaminometamitron, a known transformation product of Metamitron could also be identified together with unexpected highly concentrated C8, C10 and C12 fatty acids and their glycerol mono- and di esters. Other compounds identified were a drug metabolite (3-Carboxymefenamic acid), a sun screen agent (Ensulizole: 2-Phenyl-1H-1,3-benzodiazole-6-sulfonic acid) and industrial chemicals (Benzotriazole, N-Benzyl-indole). In addition, a number of well-resolved proton spectra cannot be attributed to a mass response showing the need of further investigations using 2D-NMR and different ionization techniques.