Catalytic epoxidation of olefins in the presence of a vanadyl porphyrin complex

It was found that vanadyl porphyrin complexes synthesized from petroleum metal porphyrin concentrates stimulated epoxidation during the olefin oxygenation process. The yields of obtained oxiranes turned out to be 38–75%, depending on the olefin structure. An epoxidation mechanism that suggests the formation of a protonated dioxygen adduct as an intermediate during oxygenation of olefins in the presence of vanadyl porphyrin complexes was proposed. An analogy is drawn between the epoxide formation reaction upon the catalytic oxygenation of olefins and the Prilezhaev reaction.     

Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

State of polarization changes: Classification and measurement

We propose a standardization procedure that provides a convenient, quantitative and reproducible laboratory-based method for measuring the state of polarization (SOP) fluctuations produced by polarization varying devices. This method is based on the SOP distributions generated by commercial polarization scramblers. We show that these devices generate distributions of the maximum change of the SOP (in a given sample time) that follow Rayleigh statistics, which scale linearly with scrambling frequency and the sample time. We use this procedure to measure the SOP fluctuations in a short length of coiled fiber subject to mechanical perturbations.     

Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

Effects of surface charge, micro-bubble size and particle size on removal efficiency of electro-flotation.

Flotation is a water treatment alternative to sedimentation, and uses small bubbles to remove low-density particles from potable water and wastewater. The effect of zeta potential, bubble size and particle size on removal efficiency of the electro-flotation process was investigated because previous model-simulations indicated that these attributes are critical for high collision efficiency between micro-bubbles and particles. Solutions containing Al3+ as the metal ion were subjected to various conditions. The zeta potentials of bubbles and particles were similar under identical conditions, and their charges were influenced by metal ion concentration and pH. Maximum removal efficiency was 98 and 12% in the presence and absence of flocculation, respectively. Removal efficiency was higher when particle size was similar to bubble size. These results agree with modelling simulations and indicate that collision efficiency is greater when the zeta potential of one is negative and that of the other is positive and when their sizes are similar.     

On the linear correlation between microhardness and mechanical properties in polar polymers and blends

The tensile elastic modulus (E), yield stress (σ_Y) and microhardness (MH) of neat and binary and ternary blends of glassy semicrystalline ethylene–vinyl alcohol copolymer (EVOH), a glassy amorphous polyamide and a semicrystalline nylon‐containing ionomer covering a broad range of properties were examined. The tests were carried out on dry and water‐equilibrated samples to produce stiffer and softer materials, respectively. From the results, more accurate linear correlations were found to describe adequately the microhardness, modulus and yield stress of these strongly self‐associated polymers through hydrogen bonding. Copyright © 2003 Society of Chemical Industry     

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.     

Performance of thermostatic and electronic valves controlling the compressor capacity

The performance of the energy consumption of an electronic valve and a classical thermostatic valve has been compared when these expansion valves are adopted in a vapour compression plant subjected to a cold store. The main aim is to verify experimentally which type of expansion valve would be preferable from energy point of view when a classical thermostat or a fuzzy logic algorithm are used as the control system for the refrigeration capacity. The fuzzy logic‐based control is able to modulate continuously the compressor speed through an inverter. The results show that with a fuzzy algorithm, the thermostatic expansion valve allows an energy saving of about 8% in comparison with the electronic valve. When on–off control is used, the electric energy consumption obtained both with the electronic valve and with the thermostatic valve is comparable. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of surface waxes on the persistence of chlorpyrifos-methyl in apples, strawberries and grapefruits

The effects of the cuticle and epicuticular waxes of grapefruit, strawberry and apple on the photodegradation and penetration of chlorpyrifos-methyl were studied. Photodegradation experiments were conducted by exposing the insecticide to the light of a xenon lamp in the presence of a film of wax extracted from the fruit surface. The half-life of chlorpyrifos-methyl irradiated in absence of waxes was 9.6 min. The half-lives of pesticide irradiated in the presence of wax extracts of apple, grapefruit and strawberry were 83, 34 and 26 min, respectively. In penetration studies, fruit with and without wax layers were treated with an aqueous suspension of pesticide. The penetration of the pesticide from the cuticle to the pulp was measured after 24 h. Samples without wax contained a higher total amount of insecticide than those with wax. No pesticide was detected in samples of apple and grapefruit pulp. Residues were detected in all fractions of strawberry. The waxes and cuticle appear to have some effect on the photodegradation and penetration of chlorpyrifos-methyl in fruit samples.