From star-shaped to dendritic poly(ethylene oxide)s: Toward increasingly branched architectures by anionic polymerization

Polymers with dendritic structure are a category of macromolecular architectures that has received considerable attention in the last decade. These polymers, also referred to as dendrimers, exhibit a degree of branching equal to unity. Interest in dendrimers whose branching points are linked to each other by generations of macromolecular size is in contrast quite new. This paper describes a new synthetic strategy which allows access to poly(ethylene oxide) (PEO) with dendritic structure. PEO dendrimers with different degree of compactness have been synthesized upon modifying the size of successive generations.     

Modal characteristics of few-mode silica-based photonic crystal fibres

The modal characteristics of silica-based photonic crystal fibres (PCF) are examined through a scalar modal analysis combined with an effective V-parameter model using a finite-difference method. Cut off frequencies of the lowest-order modes and the normalised dispersion curves are given and are found to be quasi-independent of the hole-size-to-pitch ratio. A simple and accurate empirical relation for the cutoff wavelength is given for the first higher-order mode for fibres with hole-size-to-pitch ratio below 0.7. These results should be very useful in designing PCF's for various applications.     

Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers

One- and two-photon characterizations of a series of hetero- and homoleptic [RuL_3-n(bpy)_n]²⁺ (n = 0, 1, 2) complexes carrying bipyridine π-extended ligands (L), have been carried out. These π-extended D−π−A−A−π−D-type ligands (L), where the electron donor units (D) are based on diphenylamine, carbazolyl, or fluorenyl units, have been designed to modulate the conjugation extension and the donating effect. Density functional theory calculations were performed in order to rationalize the observed spectra. Calculations show that the electronic structure of the π-extended ligands has a pronounced effect on the composition of HOMO and LUMO and on the metallic contribution to frontier MOs, resulting in strikingly different nonlinear properties. This work demonstrates that ILCT transitions are the keystone of one- and two-photon absorption bands in the studied systems and reveals how much MLCT and LLCT charge transfers play a decisive role on the two-photon properties of both hetero- and homoleptic ruthenium complexes through cooperative or suppressive effects.     

Hydrogenation Size-Selective Pt/Hollow Beta Catalysts

The aim of the present work is to synthesize a zeolite-based catalyst with a hollow morphology and highly dispersed metal nanoparticles (NPs) encapsulated inside the zeolite micropores. For this purpose, we have studied a treatment using tetraalkylammonium (TAA) bromides for the selective removal of a large Pt particle from the outer surface of a hollow Beta zeolite. TEM analysis reveals that we succeeded in the synthesis of a hollow beta zeolite single crystal with encapsulated particles, with a high dispersion of 50–60 %. The molecular-sieve-type mechanism of the obtained catalysts was evaluated in the model reaction of toluene and mesitylene catalytic hydrogenation. Thanks to the high dispersion. a 10-fold activity enhancement has been obtained with respect to hollow beta zeolites with encapsulated NPs recently described in the literature.     

Influence of the microstructure on the photooxidative degradation of poly(3-hexylthiophene)

The influence of the microstructure of poly(3-hexylthiophene) (P3HT) on its photodegradation upon exposure to UV-visible light was studied. High-regioregular (>98%) and low-regioregular (<95%) P3HTs with different molecular weights, dispersities and purities were submitted to irradiation under accelerated artificial ageing conditions. While the molecular weight had no effect on the photodegradation rate, a linear relationship was observed between the photodegradation rate and the regioregularity. The higher photo-instability of low-regioregular P3HTs, which have low crystalline phase content, could be due to the fact that the radical chain oxidation occurs predominantly in the amorphous phase of the polymer. Low-regioregular P3HTs also have a higher number of impurities, especially Fe residues, which are well known for their photocatalytic effect. The results also show that, at low concentrations, oxidation products are able to quench the singlet state of P3HT by acting as electron traps, and that the shortest wavelengths of solar light are the most harmful. Finally, the photooxidation of P3HT leads to the formation of low-molecular-weight carboxylic acids that can easily diffuse and migrate out of low-regioregular P3HT thin films. These results are therefore relevant to the preparation, storage and lifetimes of P3HT-based organic solar cells.     

Carbon Nanoparticle Production by Inductively Coupled Thermal Plasmas: Controlling the Thermal History of Particle Nucleation

The process control for reproducibility, uniformity, and achievement of desired structures for carbon black generated in thermal plasma devices is studied in this paper through modeling, and correlated with experimental results. A numerical simulation of the flow and energy fields, stream function lines and the quench rates of the plasma gas in a conical shape reactor at different pressures was made. An argon plasma is used with highly diluted methane (0.6–7%) as the carbon precursor. The quench rates were studied in order to observe the flow development and hence the thermal history of particle nucleation. Three pressure cases of 20.7, 55.2 and 101.3 kPa and two plasma powers cases of 10 and 20 kW were studied. The modeling results enabled carbon nanoflakes production in the experimental tests performed on an inductively coupled thermal plasma system. Results indicate a robust process control enabling very little particle morphology variation over this wide range of reactor pressure values and varying plasma power, and a very high reproducibility of the particle morphologies obtained.