Low Temperature Photo-oxidation of Chloroperoxidase Compound II

Oxidation of the heme-thiolate enzyme chloroperoxidase (CPO) from Caldariomyces fumago with peroxynitrite (PN) gave the Compound II intermediate, which was photo-oxidized with 365 nm light to give a reactive oxidizing species. Cryo-solvents at pH ≈ 6 were employed, and reactions were conducted at temperatures as low as − 50 °C. The activity of CPO as evaluated by the chlorodimedone assay was unaltered by treatment with PN or by production of the oxidizing transient and subsequent reaction with styrene. EPR spectra at 77 K gave the amount of ferric protein at each stage in the reaction sequence. The PN oxidation step gave a 6:1 mixture of Compound II and ferric CPO, the photolysis step gave an approximate 1:1 mixture of active oxidant and ferric CPO, and the final mixture after reaction with excess styrene contained ferric CPO in 80% yield. In single turnover reactions at − 50 °C, styrene was oxidized to styrene oxide in high yield. Kinetic studies of styrene oxidation at − 50 °C displayed saturation kinetics with an equilibrium constant for formation of the complex of Kbind = 3.8 × 104 M− 1 and an oxidation rate constant of kox = 0.30 s− 1. UV–Visible spectra of mixtures formed in the photo-oxidation sequence at ca. − 50 °C did not contain the signature Q-band absorbance at 690 nm ascribed to CPO Compound I prepared by chemical oxidation of the enzyme, indicating that different species were formed in the chemical oxidation and the photo-oxidation sequence

Alternative catalysts for low-temperature CO-oxidation

MnO sub x, Ag/MnO sub x, Cu/MnO sub x, Pt/MnO sub x, Ru/MnO sub x, Au/CeO sub x, and Au/Fe2O3 were synthesized and tested for CO oxidation activity in low concentrations of stoichiometric CO and O2 at 30 to 75 C. Catalytic activity was measured for periods as long as 18000 minutes. At 75 deg Au/MnO sub x is most active sustaining nearly 100 percent CO conversion for 10000 minutes. It also retains high activity at 50 and 30 C with negligible decay in activity. A direct comparison between an unpretreated 10 percent Au/MnO sub x catalyst and an optimized 19.5 percent Pt/SnO sub 2 (pretreated) catalyst shows that the Au/MnO sub x catalyst exhibits much higher catalytic activity and far superior decay characteristics. Other catalysts including Au/CeO sub x and Au/Fe2O3 also perform well. The Cu/MnO sub x exhibits a high initial activity which decays rapidly. After the decay period the activity remains very stable making Cu/MnO sub x a potential candidate for long-term applications such as CO2 lasers in space

Al-Pt MOCVD coatings for the protection of Ti6242 alloy against oxidation at elevated temperature

Results on isothermal oxidation at 873K for 90 h of Al-Pt coatings on Ti6242 coupons are reported. These coatings were obtained by low temperature, low pressure metalorganic chemical vapor deposition using Me3(MeCp)Pt(VI) and dimethylethylamine alane. Three coating architectures were investigated, namely pure Al, Pt and Al sequential sublayers, and co-deposited Al and Pt. Oxidation kinetics revealed a strong transient oxidation regime followed by a diffusion driven parabolic one. Such coatings allow to decrease oxidation kinetics more than one order of magnitude compared with those of the bare Ti6242. Scanning electron microscopy, second ion mass spectrometry, X-ray diffraction and transmission electron microscopy revealed that these coatings present a rough surface morphology. They are dense, they develop scales composed of γ-Al2O3 and δ-Al2O3 and they prevent titanium diffusion from the alloy to the surface. It is concluded that coatings produced by this process show promise for use as effective protection against oxidation of Ti6242 alloys and consequently they may raise the maximum operating temperature tolerated by corresponding parts in helicopter turboengines

Improving oxidation resistance of carbon nanotube nanocomposites for aerospace applications

Carbon nanotubes (CNTs) based materials possess strong potential to substitute various functional materials developed exclusively for aerospace applications. However, because of the low oxidation temperature of CNTs (400-500 oC), using CNT based ceramic nanocomposites in high temperature applications can be problematic. Making ceramic-CNT nanocomposites by atomic layer deposition (ALD) method and field assisted sintering technology (FAST) is a good route to improve oxidative stability of CNTs. In this study, thermo-gravimetric analysis (TGA) of alumina coated CNTs (prepared by ALD) and alumina-CNT nanocomposites (prepared by FAST) were carried out. 16% improvements were observed in the oxidation resistance for alumina-CNT nanocompo-sites prepared by ALD and SPS techniques. Different strategies to improve oxidation resistance are discussed

Highly fluorinated polyurethanes

The reaction perfluorinated hydroxyl terminated polyether with diisocyanate to form polyurethane is discussed. Data are given on the resin's oxidation stability, chemical resistance, and low temperature flexibility

CO oxidation at low temperature on Au/CePO4: Mechanistic aspects

This work reports the synthesis and characterization of a cerium phosphate supported gold catalyst as well as its catalytic activity for the oxidation of CO. A precipitation method in the presence of an organic modifier followed by a hydrothermal treatment was used for the support synthesis, resulting in high surface area nanometric particles. Gold/cerium phosphate catalyst with a 1% (w/w) nominal gold content was characterized using XRF, XRD, N2 adsorption-desorption measurements, TEM and DRIFTS-MS. The catalyst shows good catalytic activity at low temperature. The activity is related to the generation of oxygen vacancies in the support caused by the elimination of structural oxygen. In situ studies revealed that the reaction of the oxygen vacancies with gaseous oxygen resulted in the formation of peroxo species. These species are responsible for the activity detected at room temperature in both the catalyst and the support. Moreover, the presence of carbonate and hydrogen carbonate acting as reaction intermediates have been observed

Literature survey on oxidations and fatigue lives at elevated temperatures

Nickel-base superalloys are the most complex and the most widely used for high temperature applications such as aircraft engine components. The desirable properties of nickel-base superalloys at high temperatures are tensile strength, thermomechanical fatigue resistance, low thermal expansion, as well as oxidation resistance. At elevated temperature, fatigue cracks are often initiated by grain boundary oxidation, and fatigue cracks often propagate along grain boundaries, where the oxidation rate is higher. Oxidation takes place at the interface between metal and gas. Properties of the metal substrate, the gaseous environment, as well as the oxides formed all interact to make the oxidation behavior of nickel-base superalloys extremely complicated. The important topics include general oxidation, selective oxidation, internal oxidation, grain boundary oxidation, multilayer oxide structure, accelerated oxidation under stress, stress-generation during oxidation, composition and substrate microstructural changes due to prolonged oxidation, fatigue crack initiation at oxidized grain boundaries and the oxidation accelerated fatigue crack propagation along grain boundaries

Low Temperature Oxidation of pure Iron : Growth kinetics and scale Morphologies

Isothermal oxidation of pure iron has been performed in air at atmospheric pressure between 260°C and 500°C. Growth kinetics are accurately analysed and scale morphologies are investigated by SEM and TEM observations. The calculation of the variations of the parabolic rate constant kp with scale thickness allows a better understanding of scale growth mechanisms involved at this intermediate temperature range, which have been poorly investigated up to now. These results are discussed with the objective of long term behaviour for long term interim storage of some nuclear waste containers

Beryllium thin films for resistor applications

Beryllium thin films have a protective oxidation resistant property at high temperature and high recrystallization temperature. However, the experimental film has very low temperature coefficient of resistance

Applications of low temperature CO-oxidation catalysts to breathable gases

Modifications of tin oxide/precious metal catalysts described for use in CO2 lasers have also been developed for use in other applications; namely, as low temperature CO oxidation components in fire escape hoods/masks for mines, aircrafts, hotels, and offices and in sealed environments, such as hyperbaric chambers and submarines. Tin oxide/precious metal catalysts have been prepared on a variety of high surface area cloth substrates for application in fire escape hoods. These show high and stable CO oxidation capability (10 to the 4th power ppm CO reduced to 10 to the 1st power ppm CO) at GHSV of 37,000 h(-1) with water saturated inlet gas at body heat (37 C) and below. Water vapor plays an important role in the surface state/performance of tin oxide catalyst. Water-resistant formulations have been produced by the introduction of transition metal promoters. Tin oxide/precious metal catalysts have also been developed for CO oxidation in the North Sea diving environment. These are currently in use in a variety of hyperbaric chambers and diving vehicles. Ambient temperature operation and resistance to atmospheric water vapor have been demonstrated, and as a result, they offer a viable alternative to hopcalite or heated catalyst systems. A new range of non-tin oxide based low temperature CO oxidation catalysts is described. They are based on reducible metal oxides promoted with previous metals. Preliminary data on selected materials in the form of both cloth artifacts and shaped pellets are presented. They are expected to be applicable both to the breathable gas application area and to CO2 lasers