Synthesis,solid-state photophysical properties and electropolymerization of novel diazulenyl ethenes

The novel 1,2-di(azulen-1-yl)cyclopent-1-ene 3 was conveniently synthesized via a two-step procedure involving Vilsmeier–Haack acylation of azulene with N,N,N′,N′-tetraethylglutaramide (TEGA) and POCl₃, followed by an intramolecular McMurry coupling of the resulting diketone. In contrast with the previously reported (E)-1,2-di(azulen-1-yl)ethene that shows negligible fluorescence in the solid state, alkene 3 displays fluorescence emission from the S₂ excited state of the azulene moieties. This compound easily polymerizes upon electrochemical oxidation, leading to the formation of a conducting polymer film at the electrode surface.     

Influence of temperature and UV intensity on photo-polymerization reaction studied by photo-DSC

Photo-DSC was used to investigate the cure kinetics of a photo-initiated resin. The exothermal photo-polymerization reactions were performed in isothermal mode. The irradiation of photo-initiated resin was studied under different conditions of temperature, UV lamp intensity, and reaction atmosphere (nitrogen and air). The results obtained by photo-DSC allowed us to determine kinetic data of the photo-polymerized reactions: the global activation energy and reaction enthalpy, and the conversion as a function of time and temperature. Modulated temperature DSC measurements were carried out to verify whether vitrification occurs during polymerization. The conversion at the top and bottom of irradiated samples was obtained by FT-IR spectroscopy before and after photo-polymerization. A non-homogenous photo-polymerization into the material was observed, probably because of the light absorptions effects within the uppermost layers.     

Algorithm for preliminary evaluation of the correlation time of local dynamics in some polymeric materials

A method for preliminary evaluation of the correlation time of local dynamics of the polymeric chains, using the experimental nuclear magnetic resonance spin-lattice relaxation data, is proposed. The algorithm is based on the model of the passage of a particle over a potential energy barrier. This method was utilized for some molten polymers and concentrated polymeric solutions.     

Surface dipoles and work functions of alkylthiolates and fluorinated alkylthiolates on Au(111)

We study the dipole formation at the surface formed by -CH(3) and -CF(3) terminated short-chain alkylthiolate monolayers on Au(111). In particular, we monitor the change in work function upon chemisorption using density functional theory calculations. We separate the surface dipole into two contributions, resulting from the gold-adsorbate interaction and the intrinsic dipole of the adsorbate layer, respectively. The two contributions turn out to be approximately additive. Adsorbate dipoles are defined by calculating dipole densities of free-standing molecular monolayers. The gold-adsorbate interaction is, to a good degree, determined by the Au-S bond only. This bond is nearly apolar and its contribution to the surface dipole is relatively small. The surface dipole of the self-assembled monolayer is then dominated by the intrinsic dipole of the thiolate molecules. Alkylthiolates increase the work function of Au(111), whereas fluorinated alkylthiolates decrease it.     

Development and Application of Ultra Performance Liquid Chromatography Method to the Quantification of the Biotransformation of Methyl Paraben in Eisenia foetida

A simple and quick ultra performance liquid chromatography method (UPLC) has been developed for determination of methyl paraben (MP) and its major metabolites p‐hydroxybenzoic acid (pHBA) and phenol (Phe), following its biotransformations in Eisenia foetida. After different exposure time to paper contact test, the presence of methyl paraben and his biotransformation products in adult earthworms was monitored. Determination of its metabolites was achieved with a BEH (bridged ethane‐silicon hybrid) C₁₈ column (2.1×50 mm i.d., 1.7 µm particle size), using methanol/water/phosphoric acid as mobile phase, under a gradient elution program, and a PDA (photo‐diode array) detection (quantification with MaxPlot in the range 210–400 nm). The absorption of MP did not exceed 30% and in the first 4–6 h after exposure only minute amounts of pHBA and Phe were detected in the worm homogenates. After 48 h of exposures, almost 70% of absorbed MP was already metabolized to Phe and around 20% could be found as pHBA.     

Coherent frequency conversion in a superconducting artificial atom with two internal degrees of freedom

By adding a large inductance in a dc-SQUID phase qubit loop, one decouples the junctions' dynamics and creates a superconducting artificial atom with two internal degrees of freedom. In addition to the usual symmetric plasma mode (s mode) which gives rise to the phase qubit, an antisymmetric mode (a mode) appears. These two modes can be described by two anharmonic oscillators with eigenstates |ns> and |na> for the s and a mode, respectively. We show that a strong nonlinear coupling between the modes leads to a large energy splitting between states |0s,1a> and |2s,0a>. Finally, coherent frequency conversion is observed via free oscillations between the states |0s,1a> and |2s,0a>.     

Electrical DC conduction mechanism in some newly synthesized nylon 6/12 copolymers

The synthesis and the study of DC electrical transport properties (electrical conductivity, σ, and Seebeck coefficient, S) as a function of temperature of some recently synthesized nylon 6/12 copolymers with 0, 5, 10, 20, 30, and 50 wt % laurolactam (LL), respectively, are reported. Nylons were obtained by rotational molding via the anionic activated copolymerization of ε‐caprolactam and LL. As evidenced by XRD analyses, they are semicrystalline. The temperature dependences of σ and S are typical for polycrystalline semiconducting (p‐type) materials. The activation energy of electrical conduction lay in the range 0.79–1.22 eV, while the ratio of charge carrier mobilities ranged between 0.53 and 0.77. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 794–799, 2007