Recycled PMMA prepared directly from crude MMA obtained from thermal depolymerization of mixed PMMA waste.

Recycled PMMA was prepared by directly polymerizing crude pyrolysis oils from lab-scale pyrolysis of collected industrial waste PMMA. The pyrolysis oils consisted mainly of methyl methacrylate (MMA, >85%), while the type and number of by-products from the thermal process were assigned through GC-MS analysis showing a clear correlation to the pyrolysis temperature. By-products can be removed by distillation; however, directly employing the crude oils to prepare PMMA through solution, suspension, emulsion, or casting polymerization was investigated to assess the potential for omitting this costly step.

Dynamic dilution exponent in monodisperse entangled polymer solutions.

We study and model the linear viscoelastic properties of several entangled semi-dilute and concentrated solutions of linear chains of different molar masses and at different concentrations dissolved in their oligomers. We discuss the dilution effect of the oligomers on the entangled long chains. In particular, we investigate the influence of both concentration and molar mass on the value of the effective dynamic dilution exponent determined from the level of the storage plateau at low and intermediate frequencies.

Novel magnetic nanoparticles coated by benzene- and β-cyclodextrin-bearing dextran, and the sorption of polycyclic aromatic hydrocarbon.

We present the synthesis of novel magnetic nanoparticles functionalized by benzene- and β-cyclodextrin-derivatized dextran. The grafting strategy was based on the [alkynyl-iron] cluster in the modified dextrans, which were prepared by click reaction from alkyne-modified dextran and benzyl azide or mono-6-O-deoxy-monoazido β-cyclodextrin. Characterization was then carried out by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometry.

Structural study of four complexes of the M-N2S2 type derived from diethylphenylazothioformamide and the metals palladium, platinum, copper and nickel.

The four electron-transfer complexes trans-(di(N,N-diethyl-(2-phenyldiazenyl)thioformamide-kappaS,kappaN2))nickel, trans-(di(N,N-diethyl-(2-phenyldiazenyl)thioformamide-kappaS,kappaN2))copper, trans-(di(N,N-diethyl-(2-phenyldiazenyl)thioformamide-kappaS,kappaN2))palladium and trans-(di(N,N-diethyl-(2-phenyldiazenyl)thioformamide-kappaS,kappaN2))platinum have been crystallized, and their structures have been determined at low temperature. All the complexes are of the M-N2S2 type. The crystals of both the nickel and the copper complex belong to the tetragonal P4(1)2(1)2 system, in which the central metal ion lies on a twofold axis.

Isomerization of the protonated acetone dimer in the gas phase.

Mass spectrometry-based methods have been employed in order to study the reactions of non- (h(6)/h(6)), half (d(6)/h(6)), and fully (d(6)/d(6)) deuterium labeled protonated dimers of acetone in the gas phase. Neither kinetic nor thermodynamic isotope effects were found. From MIKES experiments (both spontaneous and collision-induced dissociations), it was found that the relative ion yield (m/z 65 vs m/z 59) from the dissociation reaction of half deuterium labeled (d(6)/h(6)) protonated dimer of acetone is dependent on the internal energy.

Ultrathin films of semiconducting polymers on water.

Ultrathin films of polythiophene derivatives spread on water were studied by means of synchrotron radiation, using grazing incidence diffraction and (specular) reflectometry to obtain the molecular orientation in the films. The semicrystalline films were anisotropic, showing a strong tendency of orienting the crystalline alpha-axis perpendicularly to the water subphase. The crystalline domains extend essentially through the entire sample thickness, found to be 10-15 nm.

Limitations of using Raman microscopy for the analysis of high-content-carbon-filled ethylene propylene diene monomer rubber.

The effects of laser irradiation on changes to the surface chemistry and structure of a commercially available ethylene propylene diene monomer (EPDM) rubber sample after Raman microscopy analysis was investigated. The Raman measurements were carried out with different levels of laser power on the sample, ranging from 4.55 mW to 0.

Nanoporous materials with spherical and gyroid cavities created by quantitative etching of polydimethylsiloxane in polystyrene-polydimethylsiloxane block copolymers.

A new method for quantitative etching of the poly(dimethylsiloxane) block in polystyrene-poly(dimethylsiloxane) (PS-PDMS) block copolymers is reported. Reacting the block copolymer with anhydrous hydrogen fluoride renders a nanoporous material (NPM) with the remaining glassy PS maintaining the original bulk morphology. 1H NMR, mass difference, size exclusion chromatography, and X-ray photoelectron spectroscopy were used to characterize the materials before and after etching.

Directional synthesis of a dye-linked conducting homopolymer.

We report a new synthesis of a 10,20-diphenyl-5,15-bis(4-cyanophenyl)porphyrin (1) and its reduction to give 10,20-diphenyl-5,15-bis(4-formylphenyl)porphyrin (2). When the conducting polymer poly(2',5'-dioctyl-4,4' '-terphenylenecyanovinylene) was prepared in the presence of 2, we obtained a three-domain structure, compound 3, consisting of two homopolymer blocks (J domains) with the porphyrin dye molecule (P domain) in the middle. The JPJ assembly was subjected to photophysical studies where we showed that the J domain could serve as a light-harvesting antenna for the P domain.

An exceptional red shift of emission maxima upon fluorine substitution.

The effect of perfluorination on photophysical properties was investigated through synthesis and photophysical characterization of two isostructural donor-acceptor-donor dye molecules. The synthesis of two versatile fluorinated benzene compounds, 1,4-difluoro-2,5-diperfluorooctylbenzene (1) and 1,4-dibromo-2,5-difluoro-3,6-diperfluorooctylbenzene (2), is presented. The X-ray structure of 2 has been determined and shows that the perfluorinated octyl chains segregate from the benzene rings in the solid state, giving rise to a layered structure.

A new versatile receptor platform.

We prepared a molecular receptor based on the molecular tweezer concept. Our system offers versatility, an extremely short synthetic route, good yield, large quantities, and finally having binding constants that equal the best known tweezer molecules when it comes to binding various nitroaromatics such as 1,3,5-trinitrotoluene (24 M(-1)), 1,3,5-trinitrobenzene (182 M(-1)), and 2,4,7-trinitrofluorenone (490 M(-1)) as determined using 1H NMR in CDCl3. It is notable that these binding constants are achieved although the molecular framework is not locked in a fixed and rigid conformation.

A Chiral Metal Surface.

Pronounced surface restructuring leads to the formation of chiral kink sites when a chiral molecular overlayer (2,5,8,11,14,17-hexa-(tert-butyl)decacyclene) is adsorbed onto an extended, flat metal surface (Cu{110}). The process is proposed to happen as a result of the adsorbed molecule inducing chirality in the achiral surface.

Structural properties of DNO investigated with pyrene excimer formation.

Four diamino acid-Nalpha-substituted oligopeptide (DNO) oligomers substituted with pyrenyl as photophysical probes were synthesized. The excimer formation and ground-state association of the pyrenyl groups were investigated by means of absorption and steady-state fluorescence spectroscopy together with time-resolved fluorescence techniques. The photophysical parameters obtained from the different derivatives reflect the secondary structural properties of the DNO backbones.