Raman study of the polybenzimidazole-phosphoric acid interactions in membranes for fuel cells

Poly(2,5-benzimidazole) (AB-PBI) membranes are investigated by studying the FT-Raman signals due to the benzimidazole ring vibration together with the C-C and C-H out-of- and in-plane ring deformations. By immersion in aqueous ortho-phosphoric acid for different time periods, membranes with various doping degrees, i.e. different molar fractions of acid, are prepared. The chemical-physical interactions between polymer and acid are studied through band shifting and intensity change of diagnostic peaks in the 500-2000 cm(-1) spectral range. The formation of hydrogen bonding networks surrounding the polymer seems to be the main reason for the observed interactions. Only if the AB-PBI polymer is highly doped, the Raman spectra show an additional signal, which can be attributed to the presence of free phosphoric acid molecules in the polymer network. For low and intermediate doping degrees no evidence for free phosphoric acid molecules can be seen in the spectra. The extent of the polymer-phosphoric acid interactions in the doped membrane material is reinvestigated after a period of one month and the stability discussed. Our results provide insight into the role of phosphoric acid as a medium in the conductivity mechanism in polybenzimidazole.     

Impedance matching in photonic crystal microcavities for second-harmonic generation

By numerically integrating the three-dimensional Maxwell equations in the time domain with reference to a dispersive quadratically nonlinear material, we study second-harmonic generation in planar photonic crystal microresonators. The proposed scheme allows efficient coupling of the pump radiation to the defect resonant mode. The outcoupled generated second harmonic is maximized by impedance matching the photonic crystal cavity to the output waveguide.     

Antimony‐Doped Tin Oxide Nanocrystals: Synthesis and Solubility Behavior in Organic Solvents

The right mix : SnO₂:Sb nanocrystals (NCs) can be solubilized into organic solvents with a suitable solvent/surfactant combination to achieve a stable colloid (see picture). A single synthesis route and different solvent/amphiphilic molecule pairs are used to obtain soluble NC colloids, instead of requiring several syntheses to obtain soluble NCs in different solvents.

     

3‐D viscous Cahn–Hilliard equation with memory

We deal with the memory relaxation of the viscous Cahn–Hilliard equation in 3‐D, covering the well‐known hyperbolic version of the model. We study the long‐term dynamic of the system in dependence of the scaling parameter of the memory kernel ε and of the viscosity coefficient δ. In particular we construct a family of exponential attractors, which is robust as both ε and δ go to zero, provided that ε is linearly controlled by δ. Copyright © 2008 John Wiley & Sons, Ltd.     

Beam instabilities in the scale-free regime

The instabilities arising in a one-dimensional beam sustained by the diffusive photorefractive nonlinearity in out-of-equilibrium ferroelectrics are theoretically and numerically investigated. In the "scale-free model," in striking contrast with the well-known spatial modulational instability, two different beam instabilities dominate: a defocusing and a fragmenting process. Both are independent of the beam power and are not associated with any specific periodic pattern.     

Media containing aromatic compounds induce peculiar proteins in Acinetobacter radioresistens, as revealed by proteome analysis.

An Acinetobacter radioresistens strain able to grow on phenol or benzoate as sole carbon and energy source through the beta-ketoadipate pathway was isolated in our laboratories. In previous research, we found a different expression of catechol-1,2-dioxygenase isoenzymes (C-1,2-O) depending on the growth substrate (phenol or benzoate). In the present study, we used proteome techniques to extend our investigation to other enzymes involved in the aromatic degradation pathway. Since the first nontoxic metabolite in this route is cis,cis-muconic acid, we focused our attention on the enzymes leading to this compound, chiefly phenol hydroxylase (PH), benzoate dioxygenase (BD), cis-1,2-dihydroxycyclohexa-3,5-diene-1-carboxylate dehydrogenase (D) and C-1,2-O. In particular, the A. radioresistens proteome was monitored under different growth substrate conditions, using acetate, benzoate, or phenol as sole carbon source. We compared the protein maps by software image analysis and detected marked differences, suggesting the inducibility of most enzymes. This research also sought to evaluate the conditions allowing the best expression of enzymes to be used in immobilized systems suitable for bioremediation. The experimental data indicate that benzoate is the best carbon source to gain the highest amount of C-1,2-O and D, while phenol is the best growth substrate to obtain PH.     

The topological degree theory for a class of noncompact multimaps

In questo lavoro viene definito il grado topologico per mappe multivoche di Vietoris fondamentalmente restrittibili. Tale grado è ad un sol valore, contrariamente a costruzioni precedenti. Le tecniche sono sostanzialmente di tipo analitico ed evitano le complicazioni tecniche della topologia algebrica. Entrata in Redazione il 30 Novembre 1998. The work of G. Conti and P. Zecca is partially supported by a National Grant 40% MURST. The work of V. Obukhovski is partially supported by the Russian Foundation for Basic Research Grant 96-01-00360. The work of the second author was carried out during his tenure at the University of Florence under a fellowship from the Italian Ministery of Forign Affairs through Landau Network-Centro Volta and the Italian CNR.     

Organocatalyzed Phospha-Michael Addition: A Highly Efficient Synthesis of Customized Bis(acyl)phosphane Oxide Photoinitiators

Addition of the P−H bond in bis(mesitoyl)phosphine, HP(COMes)₂ (BAPH), to a wide variety of activated carbon–carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R−P(COMes)₂, under very mild conditions in excellent yields after only a short time. All phosphines RP(COMes)₂ can subsequently be oxidized to the corresponding bis(acyl)phosphane oxides, RPO(COMes)₂, a substance class belonging to the most potent photoinitiators for radical polymerizations known to date. Thus, a simple and highly atom economic method has been found that allows the preparation of a broad range of photoinitiators adapted to their specific field of application even on a large scale.