Reaction of cytochrome P450 with cumene hydroperoxide: ESR spin-trapping evidence for the homolytic scission of the peroxide O-O bond by ferric cytochrome P450 1A2

ESR spin trapping was used to investigate the reaction of rabbit cytochrome P450 (P450) 1A2 with cumene hydroperoxide. Cumene hydroperoxide-derived peroxyl, alkoxyl, and carbon-centered radicals were formed and trapped during the reaction. The relative contributions of each radical adduct to the composite ESR spectrum were influenced by the concentration of the spin trap. Computer simulation of the experimental data obtained at various 5,5-dimethyl-1-pyrroline N-oxide (DMPO) concentrations was used to quantitate the contributions of each radical adduct to the composite ESR spectrum. The alkoxyl radical was the initial radical produced during the reaction. Experiments with 2-methyl-2-nitrosopropane identified the carbon-centered adducts as those of the methyl radical, hydroxymethyl radical, and a secondary carbon-centered radical. The reaction did not require NADPH-cytochrome P450 reductase or NADPH. It is concluded that the reaction involves the initial homolytic scission of the peroxide O-O bond to produce the cumoxyl radical. Methyl radicals were produced from the beta-scission of the cumoxyl radical. The peroxyl adduct was not observed in the absence of molecular oxygen. We conclude that the DMPO peroxyl radical adduct detected in the presence of oxygen was due to the methylperoxyl radical formed by the reaction of the methyl radical with oxygen. At a higher P450 concentration, a protein-derived radical adduct was also detected.     

Anfangsvorgänge bei Lichtenbergschen Figuren

Zusammenfassung Aufnahmen von Lichtenbergschen Figuren mit kurzen Spannungsstößen zeigen, daß bisher bekanntgewordene Bilder solcher Entladungsfiguren bereits ein verhältnismäßig weit vorgeschrittenes Stadium darstellen. Es gelingt mittels kurzer Stöße erste lawinenartige Anfänge der Figuren festzuhalten und einiges über Vorgänge im Anfangsstadium herauszulesen. Die negative Figur beginnt lawinenförmig an bevorzugten Stellen der Kathode. Bei nebeneinander entstandenen Lawinen ist sehr gut die gegenseitige Abstoßung infolge gleicher Ladung zu beobachten. Die Entladung hat einen geschichteten Aufbau. Die positiven Figuren bilden sich später aus. Es sprechen jedoch bisher keinerlei Anzeichen für ein Hinwachsen der Fäden zur Anode. Die Kanäle verjüngen sich zur Anode hin und selbst bei kurzen Stoßzeiten endet kein einziger vor der Anode. Auch die Art der gegenseitigen Abstoßung der positiven Fäden spricht mehr für ein Vorwachsen von der Anode aus. Aus den Farbaufnahmen ergibt sich für die filmschwärzende Strahlung eine Wellenlänge unter 450 m.     

Experimental abatement data of underflow baffles for removal of floatables in the CSOs of the Greater Montréal (Canada) area.

Underflow baffles have gained in popularity over the years as a viable mean to intercept floatables in Combined Sewer Overflows (CSOs). This choice was mainly justified by the extremely low capital cost (CAPEX) and operational cost (OPEX) of this solution, although the efficiency of underflow baffles has never been clearly proven. The only similar application to underflow baffles are scum boards in grit chambers and clarifier. However, the flow conditions at CSOs vary considerably from those in grit chambers and clarifier. For this reason, review of the behavior of floatables in a rapid flow is paramount. Only then can comprehensive design criteria for underflow baffles and overflow chambers be suggested. Pilot scale tests, performed in a 17 metres long basin at various flowrates, had already shown that a critical horizontal velocity for floatables (Vcr) may develop in the overflow chambers. In this follow up study, the fate of intercepted floatables was investigated. It appears from this latest data that permanent capture of floatables decreases rapidly with an increase in the horizontal velocity of the flow, no matter what the baffle depth. Baffle depth increases capture at lower velocities (0.17 m/s) but become irrelevant at higher velocities (0.61 m/s). This data suggests that capture efficiency of existing underflow baffles in overflow chambers can be, at best, very low whenever the horizontal velocity increases above 0.30 m/s or 1 ft/s.     

Development of catalysts for hydrogen generation from hydride compounds

Catalytic hydrolysis of NaBH₄ and NH₃BH₃ has been studied. It was shown that the nature of the support and the active component of the catalyst affect the H₂ generation rate. Despite similar sizes of rhodium particles formed on the surface of different supports (γ-Al₂O₃, TiO₂, carbon), their reactivity is different. Rh/TiO₂ with low rhodium concentration (1 wt.%) is the most active catalyst both in the hydrolysis of NaBH₄ and NH₃BH₃. The obtained results show that the rhodium chloride interaction with titania determines the reactivity of rhodium particles formed under action of NaBH₄ medium. TEM, DRS UV–vis and XPS were used to characterize the catalysts.     

Results of a User Study on 2D Hurricane Visualization

We present the results from a user study looking at the ability of observers to mentally integrate wind direction and magnitude over a vector field. The data set chosen for the study is an MM5 (PSU/NCAR Mesoscale Model) simulation of Hurricane Lili over the Gulf of Mexico as it approaches the southeastern United States. Nine observers participated in the study. This study investigates the effect of layering on the observer's ability to determine the magnitude and direction of a vector field. We found a tendency for observers to underestimate the magnitude of the vectors and a counter‐clockwise bias when determining the average direction of a vector field. We completed an additional study with two observers to try to uncover the source of the counter‐clockwise bias. These results have direct implications to atmospheric scientists, but may also be able to be applied to other fields that use 2D vector fields.     

Comparison between photocatalytic ozonation and other oxidation processes for the removal of phenols from water

Photocatalytic ozonation (1O₃ + VUV + TiO₂), ozonation (O₃), catalytic ozonation (O₃ + TiO₂), ozone photolysis (O₃ + VUV), photocatalysis (TiO₂ + VUV) and photolysis (VUV) have been compared in terms of formation of intermediates, extent of, mineralization (TOC, COD, chloride, nitrate) and kinetics in the aqueous treatment of three phenols (phenol, p‐chlorophenol and p‐nitrophenol). In all cases, photocatalytic ozonation led to lower degradation times for chemical oxygen demand and total organic carbon removal. Intermediates formed were similar in the different oxidation systems with some exceptions. They can be classified into three different types: polyphenols (resorcinol, catechol, hydroquinone), unsaturated carboxylic acids (maleic and fumaric acids) and saturated carboxylic acids (glyoxylic, formic and oxalic acids). First order kinetic equations have been checked for the oxidation processes studied in the case of the parent compound. Rate constants of these systems have also been calculated. Copyright © 2005 Society of Chemical Industry     

Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.     

Simplified 0.35-μm flash EEPROM process using high-temperatureoxide (HTO) deposited by LPCVD as interpoly dielectrics and peripheraltransistors gate oxide

A simplified flash EEPROM process was developed using high-temperature LPCVD oxide both as flash cells interpoly dielectrics and as peripheral transistors gate oxide (decoding logic). An O₂ anneal at 850°C lowers charge trapping and interface trap density induced by Fowler-Nordheim injection. However, electron trapping remains slightly higher than with dry thermal oxide. Similar memory charge loss and write-erase endurance are obtained as for ONO-insulated cells. HTO thus proves to have the required quality and reliability to be used in flash EEPROMs     

IPv6 delay and loss performance evolution

Although packet delay and loss are two important parameters of the Internet performance, to the best of our knowledge, the evolution of large‐scale IPv6 delay and loss performance has previously not been studied. In this paper, we analyze more than 600 end‐to‐end IPv6 paths between about 26 testboxes of RIPE Network Coordination Centre over two years, and compare the delay and loss performance over time with their IPv4 counterparts. We present and discuss the measurement methodologies and show that IPv6 paths have a higher delay and loss than their IPv4 counterparts. The main reason for the worse performance stems from IPv6‐in‐IPv4 tunnels rather than from native IPv6 paths and such tunnels are still widely used today. Copyright © 2007 John Wiley & Sons, Ltd.