Biologically Inspired and Magnetically Recoverable Copper Porphyrinic Catalysts: A Greener Approach for Oxidation of Hydrocarbons with Molecular Oxygen

An efficient synthetic method for magnetically recoverable hybrid copper porphyrinic nanomaterials is reported. These functionalized magnetic materials prove to be efficient bioinspired oxidation catalysts of olefins and thiols, using molecular oxygen as oxidant, in total absence of reductants and solvents, with the highest TON (turnover number) yet achieved for this reaction (≈200 000). A comparative study between homogeneous and heterogeneous oxidation of cyclohexene is discussed, revealing the heterogeneous system to be the most promising concerning stability and reusability of the catalysts. The full characterization of the magnetic hybrid porphyrinic nanomaterials, by transmission electron microscopy, flame atomic absorption spectrometry, thermogravimetry, N₂ sorption, and infrared spectroscopy, is also described.     

Challenges in the Application of Stochastic Modal Identification Methods to a Cable-Stayed Bridge

This paper presents an analysis of the data collected in the ambient vibration test of the International Guadiana cable-stayed Bridge, which links Portugal and Spain, based on different output-only identification techniques: peak-picking, frequency domain decomposition, covariance-driven stochastic subspace identification, and data-driven stochastic subspace identification. The purpose of the analysis is to compare the performance of the four techniques and evaluate their efficiency in dealing with specific challenges involved in the modal identification of the tested cable-stayed bridge, namely the existence of closely spaced modes, the perturbation produced by the local vibration of stay-cables, and the variation of modal damping coefficients with wind velocity. The identified natural frequencies and mode shapes are compared with the corresponding modal parameters provided by a previously developed numerical model. Additionally, the variability of some modal damping coefficients is related with the variation of the wind characteristics and associated with a component of aerodynamic damping.     

Comparison of Fenton and sono-Fenton bisphenol A degradation

Degradation of bisphenol A (BPA) was carried out with the Fenton reagent with and without additional sonochemical treatment. The Fenton and the sono-Fenton decomposition of BPA showed that ultrasound irradiation of wastewater improved the wet oxidation process of 25 mg l(-1) BPA solutions. The sonochemical degradation of BPA was monitored using UV absorption and large volume injection packed capillary LC measurements.     

Association of indigo with zeolites for improved color stabilization

The durability of an organic color and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidizing conditions, using Raman and ultraviolet-visible (UV-Vis) spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In the absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high color stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.     

Electrical contact properties between the accumulation layer and metal electrodes in ultrathin poly(3-hexylthiophene)(P3HT) field effect transistors

Probing contact properties between an ultrathin conjugated polymer film and metal electrodes in field effect transistors (FETs) is crucial not only to understanding charge transport properties in the accumulation layer but also in building organic sensors with high sensitivity. We investigated the contact properties between gold electrodes and poly(3-hexylthiophene) (P3HT) as a function of film thickness using gated four-point sheet resistance measurements. In an FET with a 2 nm thick P3HT film, a large voltage drop of 1.9 V (V(D) = -3 V) corresponding to a contact resistance of 2.3 × 10(8) Ω was observed. An effective FET mobility of 1.4 × 10(-3) cm(2)/(V s) was calculated when the voltage drop at the contacts was factored out, which is approximately a factor of 3 greater than the two-contact FET mobility of 5.5 × 10(-4) cm(2)/(V s). A sharp decrease in the ratio of the contact resistance to the channel resistance was observed with increasing film thickness up to a thickness of approximately 6 nm, separating a contact limited regime from a charge transport limited regime. The origin of the large contact resistance observed in the device prepared with an ultrathin P3HT film is discussed in light of results from X-ray diffraction (XRD) and atomic force microscopy (AFM) studies.     

2D natural convection flows in tilted cavities: Porous media and homogeneous fluids

Natural convection flows are studied numerically for porous media and homogeneous fluids inside a rectangular cavity with inclination. These thermal fluid flows are considered under the respective two-dimensional unsteady Boussinesq approximation in stream function and vorticity variables. The study depends on the Rayleigh number, angle of inclination, and the aspect ratio of the cavity. At the validation stage our results are in good agreement with those reported by other authors. Results suppose to be new are presented either for angles of inclination not reported before or for high Rayleigh numbers with large aspect ratios. In rectangular porous cavities with Rayleigh number 10² multiple cells appear for some angles. In homogeneous fluids, for Rayleigh numbers of the order of 10⁵–10⁶ in large enough vertical cavities at most secondary cells appear for some angles and the flow becomes more complex and looks like to be oscillatory.