Identification of copper species present in Cu-ZSM-5 catalysts for NOx reduction

The structure of Cu-ZSM-5 catalysts that show activity for direct NO decomposition and selective catalytic reduction of NOx by hydrocarbons has been investigated by a multitude of modern surface analysis and spectroscopy techniques including X-ray photoelectron spectroscopy, thermogravimetric analysis, and in situ Fourier transform infrared spectroscopy. A series of four catalysts were prepared by exchange of Na-ZSM-5 with dilute copper acetate, and the copper loading was controlled by variation of the solution pH. Underexchanged catalysts contained isolated Cu2+OH-(H2O) species and as the copper loading was increased Cu2+ ions incorporated into the zeolite lattice appeared. The sites at which the latter two copper species were located were fundamentally different. The Cu2+OH-(H2O) moieties were bound to two lattice oxygen ions and associated with one aluminum framework species. In contrast, the Cu2+ ions were probably bound to four lattice oxygen ions and associated with two framework aluminum ions. Once the Cu-ZSM-5 samples attained high levels of exchange, the development of [Cu(μ-OH)2Cu]n2+OH-(H2O) species along with a small concentration of Cu(OH)2 was observed. On activation in helium to 500°C the Cu2+OH-(H2O) species transformed into Cu2+O- and Cu+ moieties, whereas the Cu2+ ions were apparently unaffected by this treatment (apart from the loss of ligated water molecules). Calcination of the precursors resulted in the formation of Cu2+O2- and a one-dimensional CuO species. Temperature-programmed desorption studies revealed that oxygen was removed from the latter two species at 407 and 575°C, respectively. © 1999 Academic Press.

The formation of YBa2Cu3O7-x in melt-texture heat treatments

A study of the bulk formation of YBa2Cu3O7-x from the Y2BaCuO5 plus liquid regime reveals that phase formation occurs at appreciable rates below 950°C in air. This result has been observed for phase-pure YBa2Cu3O7-x starting material given two types of heat treatment: held at 1100°C and slow-cooled from 1030°C at 6°C/h or heat-treated isothermally. Differential thermal analysis, with a cooling rate of 10°C/min indicates that the degree of undercooling for the peritectic formation of YBa2Cu3O7-x is greater than 100°C. © 1994.

Paclitaxel resistance and multicellular spheroid formation are induced by kallikrein-related peptidase 4 in serous ovarian cancer cells in an ascites mimicking microenvironment

High tumor kallikrein-related-peptidase 4 (KLK4) levels are associated with a poor outcome for women with serous epithelial ovarian cancer (EOC), for which peritoneal dissemination and chemoresistance are key events. To determine the role of KLK4 in these events, we examined KLK4-transfected SKOV-3 and endogenous KLK4 expressing OVCA432 cells in 3-dimensional (3D) suspension culture to mimic the ascites microenvironment. KLK4-SKOV-3 cells formed multicellular aggregates (MCAs) as seen in ascites, as did SKOV-3 cells treated with active KLK4. MCA formation was reduced by treatment with a KLK4 blocking antibody or the selective active site KLK4 sunflower trypsin inhibitor (SFTI-FCQR). KLK4-MCAs formed larger cancer cell foci in mesothelial cell monolayers than those formed by vector and native SKOV-3 cells, suggesting KLK4-MCAs are highly invasive in the peritoneal microenvironment. A high level of KLK4 is expressed by ascitic EOC cells compared to matched primary tumor cells, further supporting its role in the ascitic microenvironment. Interestingly, KLK4 transfected SKOV-3 cells expressed high levels of the KLK4 substrate, urokinase plasminogen activator (uPA), particularly in 3D-suspension, and high levels of both KLK4 and uPA were observed in patient cells taken from ascites. Importantly, the KLK4-MCAs were paclitaxel resistant which was reversed by SFTI-FCQR and to a lesser degree by the general serine protease inhibitor, Aprotinin, suggesting that in addition to uPA, other as yet unidentified substrates of KLK4 must be involved. Nonetheless, these data suggest that KLK4 inhibition, in conjunction with paclitaxel, may improve the outcome for women with serous epithelial ovarian cancer and high KLK4 levels in their tumors.

Nature and genesis of clay minerals of the Rustler Formation in the vicinity of the Waste Isolation Pilot Plant in Souteastern New Mexico

Detailed mineralogical studies of the matrix and fracture-fill materials of a large number of samples from the Rustler Formation have been carried out using x-ray diffraction, high-resolution transmission electron microscopy, electron microprobe analysis, x-ray fluorescence, and atomic absorption spectrophotometry. These analyses indicate the presence of four clay minerals: interstratified chlorite/saponite, illite, chlorite, and serpentine. Corrensite (regularly stratified chlorite/saponite) is the dominant clay mineral in samples from the Culebra dolomite and two shale layers of the lower unnamed member of the Rustler Formation. Within other layers of the Rustler Formation, disordered mixed chlorite/saponite is usually the most abundant clay mineral. Studies of the morphology and composition of clay crystallites suggest that the corrensite was formed by the alteration of detrital dioctahedral smectite in magnesium-rich pore fluids during early diagenesis of the Rustler Formation. This study provides initial estimates of the abundance and nature of the clay minerals in the Culebra dolomite in the vicinity of the Waste Isolation Pilot Plant.

ACE research vignette 024 : New firm formation and job creation by type of firm an type of region.

This series of research vignettes is aimed at sharing current and interesting research findings from our team of international Entrepreneurship researchers. This vignette, written by Mr. Darren Kavanagh and Professor Per Davidsson, takes a closer look at job creation by new firms.

Combustion products of bulk aluminum rods burning in high pressure oxygen

Characterization of the combustion products released during the burning of commonly used engineering metallic materials may aid in material selection and risk assessment for the design of oxygen systems. The characterization of combustion products in regards to size distribution and morphology gives useful information for systems addressing fire detection. Aluminum rods (3.2-mm diameter cylinders) were vertically mounted inside a combustion chamber and ignited in pressurized oxygen by resistively heating an aluminum/palladium igniter wire attached to the bottom of the test sample. This paper describes the experimental work conducted to establish the particle size distribution and morphology of the resultant combustion products collected after the burning was completed and subsequently analyzed. In general, the combustion products consisted of a re-solidified oxidized slag and many small hollow spheres of size ranging from about 500 nm to 1000 µm in diameter, surfaced with quenched dendritic and grain-like structures. The combustion products were characterized using optical and scanning electron microscopy.

Situational non-flammable control valves for oxygen service

Past work has clearly demonstrated that numerous commonly used metallic materials will support burning in oxygen, especially at higher pressures. An approach to rectify this significant safety problem has been successfully developed and implemented by applying the concept of Situational Non-Flammability. This approach essentially removes or breaks one leg of the conceptual fire triangle, a tool commonly used to define the three things that are required to support burning; a fuel, an ignition source and an oxidizer. Since an oxidiser is always present in an oxygen system as are ignition sources, the concept of Situational Non-Flammability essentially removes the fuel leg of the fire triangle by only utilising materials that will not burn at the maximum pressure, for example, that the control valve is to be used in. The utilisation of this approach has lead to the development of a range of oxygen components that are practically unable to burn while in service at their design pressure thus providing an unparalleled level of first safety while not compromising on the performance or endurance required in the function of these components. This paper describes the concept of Situational Non-Flammability, how it was used to theoretically evaluate designs of components for oxygen service and the outcomes of the actual development, fabrication and finally utilisation of these components in real oxygen systems in a range of flow control devices.

Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres : 13th Volume

"Seventeen peer-reviewed papers cover the latest research on the ignition and combustion of metals and non-metals, oxygen compatibility of components and systems, analysis of ignition and combustion, failure analysis and safety. It includes aerospace, military, scuba diving, and industrial oxygen applications. Topics cover: • Development of safe oxygen systems • Ignition mechanisms within oxygen systems and how to avoid them • Specific hazards that exist with the oxygen mixture breathed by divers in the scuba industry • Issues related to oxygen system level safety • Issues related to oxygen safety in breathing systems • Detailed investigations and discussions related to the burn curves that have been generated for metals that are burning in a standard test fixture This new publication is a valuable resource for professionals in the air separation industries, oxygen manufacturers, manufacturers of materials intended for oxygen service, and users of oxygen and oxygen-enriched atmospheres, including aerospace, medical, industrial gases, chemical processing, steel and metals refining, as well as to military, commercial or recreational diving."--- publisher website

Particle formation and interaction

A wide variety of experiments that involve the physics of small particles (μm to cm in size) of planetary significance can be conducted on the Space Station. Processes of interest include nucleation and condensation of particles from a gas, aggregation of small particles into larger ones, and low velocity collisions of particles. Only experiments relevant to planetary processes will be discussed in detail here.

Low temperature response of nanostructured tungsten oxide thin films toward hydrogen and ethanol

Semiconducting metal oxide based gas sensors usually operate in the temperature range 200–500 °C. In this paper, we present a new WO3 thin film based gas sensor for H2 and C2H5OH, operating at 150 °C. Nanostructured WO3 thin films were synthesized by thermal evaporation method. The properties of the as-deposited films were modified by annealing in air at 300 °C and 400 °C. Various analytical techniques such as AFM, TEM, XPS, XRD and Raman spectroscopy have been employed to characterize their properties. A clear indication from TEM and XRD analysis is that the as-deposited WO3 films are highly amorphous and no improvement is observed in the crystallinity of the films after annealing at 300 °C. Annealing at 400 °C significantly improved the crystalline properties of the films with the formation of about 5 nm grains. The films annealed at 300 °C show no response to C2H5OH (ethanol) and a little response to H2, with maximum response obtained at 280 °C. The films annealed at 400 °C show a very good response to H2 and a moderate response to C2H5OH (ethanol) at 150 °C. XPS analysis revealed that annealing of the WO3 thin films at 400 °C produces a significant change in stoichiometry, increasing the number of oxygen vacancies in the film, which is highly beneficial for gas sensing. Our results demonstrate that gas sensors with significant performance at low operating temperatures can be obtained by annealing the WO3 films at 400 °C and optimizing the crystallinity and nanostructure of the as-deposited films.

Nanoporous Graphitic-C3N4@Carbon Metal-Free Electrocatalysts for Highly Efficient Oxygen Reduction

Based on theoretical prediction, a g-C3N4@carbon metal-free oxygen reduction reaction (ORR) electrocatalyst was designed and synthesized by uniform incorporation of g-C3N4 into a mesoporous carbon to enhance the electron transfer efficiency of g-C3N4. The resulting g-C3N4@carbon composite exhibited competitive catalytic activity (11.3 mA cm–2 kinetic-limiting current density at −0.6 V) and superior methanol tolerance compared to a commercial Pt/C catalyst. Furthermore, it demonstrated significantly higher catalytic efficiency (nearly 100% of four-electron ORR process selectivity) than a Pt/C catalyst. The proposed synthesis route is facile and low-cost, providing a feasible method for the development of highly efficient electrocatalysts.

Formation of single-walled carbon nanotube via the interaction of graphene nanoribbons : ab initio density functional calculations

The interaction of bare graphene nanoribbons (GNRs) was investigated by ab initio density functional theory calculations with both the local density approximation (LDA) and the generalized gradient approximation (GGA). Remarkably, two bare 8-GNRs with zigzag-shaped edges are predicted to form an (8, 8) armchair single-wall carbon nanotube (SWCNT) without any obvious activation barrier. The formation of a (10, 0) zigzag SWCNT from two bare 10-GNRs with armchair-shaped edges has activation barriers of 0.23 and 0.61 eV for using the LDA and the revised PBE exchange correlation functional, respectively, Our results suggest a possible route to control the growth of specific types SWCNT via the interaction of GNRs.

Tipping the balance : sclerotinia sclerotiorum secreted oxalic acid suppresses host defenses by manipulating the host redox environment

Sclerotinia sclerotiorum is a necrotrophic ascomycete fungus with an extremely broad host range. This pathogen produces the non-specific phytotoxin and key pathogenicity factor, oxalic acid (OA). Our recent work indicated that this fungus and more specifically OA, can induce apoptotic-like programmed cell death (PCD) in plant hosts, this induction of PCD and disease requires generation of reactive oxygen species (ROS) in the host, a process triggered by fungal secreted OA. Conversely, during the initial stages of infection, OA also dampens the plant oxidative burst, an early host response generally associated with plant defense. This scenario presents a challenge regarding the mechanistic details of OA function; as OA both suppresses and induces host ROS during the compatible interaction. In the present study we generated transgenic plants expressing a redox-regulated GFP reporter. Results show that initially, Sclerotinia (via OA) generates a reducing environment in host cells that suppress host defense responses including the oxidative burst and callose deposition, akin to compatible biotrophic pathogens. Once infection is established however, this necrotroph induces the generation of plant ROS leading to PCD of host tissue, the result of which is of direct benefit to the pathogen. In contrast, a non-pathogenic OA-deficient mutant failed to alter host redox status. The mutant produced hypersensitive response-like features following host inoculation, including ROS induction, callose formation, restricted growth and cell death. These results indicate active recognition of the mutant and further point to suppression of defenses by the wild type necrotrophic fungus. Chemical reduction of host cells with dithiothreitol (DTT) or potassium oxalate (KOA) restored the ability of this mutant to cause disease. Thus, Sclerotinia uses a novel strategy involving regulation of host redox status to establish infection. These results address a long-standing issue involving the ability of OA to both inhibit and promote ROS to achieve pathogenic success.

Combined electrophoretic deposition–anodization method to fabricate reduced graphene oxide–TiO2 nanotube films

We directly constructed reduced graphene oxide–titanium oxide nanotube (RGO–TNT) film using a single-step, combined electrophoretic deposition–anodization (CEPDA) method. This method, based on the simultaneous anodic growth of tubular TiO2 and the electrophoretic-driven motion of RGO, allowed the formation of an effective interface between the two components, thus improving the electron transfer kinetics. Composites of these graphitic carbons with different levels of oxygen-containing groups, electron conductivity and interface reaction time were investigated; a fine balance of these parameters was achieved.

Study of new particle formation in subtropical urban environment in Brisbane, Australia

Atmospheric ultrafine particles play an important role in affecting human health, altering climate and degrading visibility. Numerous studies have been conducted to better understand the formation process of these particles, including field measurements, laboratory chamber studies and mathematical modeling approaches. Field studies on new particle formation found that formation processes were significantly affected by atmospheric conditions, such as the availability of particle precursors and meteorological conditions. However, those studies were mainly carried out in rural areas of the northern hemisphere and information on new particle formation in urban areas, especially those in subtropical regions, is limited. In general, subtropical regions display a higher level of solar radiation, along with stronger photochemical reactivity, than those regions investigated in previous studies. However, based on the results of these studies, the mechanisms involved in the new particle formation process remain unclear, particularly in the Southern Hemisphere. Therefore, in order to fill this gap in knowledge, a new particle formation study was conducted in a subtropical urban area in the Southern Hemisphere during 2009, which measured particle size distribution in different locations in Brisbane, Australia. Characterisation of nucleation events was conducted at the campus building of the Queensland University of Technology (QUT), located in an urban area of Brisbane. Overall, the annual average number concentrations of ultrafine, Aitken and nucleation mode particles were found to be 9.3 x 103, 3.7 x 103 and 5.6 x 103 cm-3, respectively. This was comparable to levels measured in urban areas of northern Europe, but lower than those from polluted urban areas such as the Yangtze River Delta, China and Huelva and Santa Cruz de Tenerife, Spain. Average particle number concentration (PNC) in the Brisbane region did not show significant seasonal variation, however a relatively large variation was observed during the warmer season. Diurnal variation of Aitken and nucleation mode particles displayed different patterns, which suggested that direct vehicle exhaust emissions were a major contributor of Aitken mode particles, while nucleation mode particles originated from vehicle exhaust emissions in the morning and photochemical production at around noon. A total of 65 nucleation events were observed during 2009, in which 40 events were classified as nucleation growth events and the remainder were nucleation burst events. An interesting observation in this study was that all nucleation growth events were associated with vehicle exhaust emission plumes, while the nucleation burst events were associated with industrial emission plumes from an industrial area. The average particle growth rate for nucleation events was found to be 4.6 nm hr-1 (ranging from 1.79-7.78 nm hr-1), which is comparable to other urban studies conducted in the United States, while monthly particle growth rates were found to be positively related to monthly solar radiation (r = 0.76, p <0.05). The particle growth rate values reported in this work are the first of their kind to be reported for the subtropical urban area of Australia. Furthermore, the influence of nucleation events on PNC within the urban airshed was also investigated. PNC was simultaneously measured at urban (QUT), roadside (Woolloongabba) and semi-urban (Rocklea) sites in Brisbane during 2009. Total PNC at these sites was found to be significantly affected by regional nucleation events. The relative fractions of PNC to total daily PNC observed at QUT, Woolloongabba and Rocklea were found to be 12%, 9% and 14%, respectively, during regional nucleation events. These values were higher than those observed as a result of vehicle exhaust emissions during weekday mornings, which ranged from 5.1-5.5% at QUT and Woolloongabba. In addition, PNC in the semi-urban area of Rocklea increased by a factor of 15.4 when it was upwind from urban pollution sources under the influence of nucleation burst events. Finally, we investigated the influence of sulfuric acid on new particle formation in the study region. A H2SO4 proxy was calculated by using [SO2], solar radiation and particle condensation sink data to represent the new particle production strength for the urban, roadside and semi-urban areas of Brisbane during the period June-July of 2009. The temporal variations of the H2SO4 proxies and the nucleation mode particle concentration were found to be in phase during nucleation events in the urban and roadside areas. In contrast, the peak of proxy concentration occurred 1-2 hr prior to the observed peak in nucleation mode particle concentration at the downwind semi-urban area of Brisbane. A moderate to strong linear relationship was found between the proxy and the freshly formed particles, with r2 values of 0.26-0.77 during the nucleation events. In addition, the log[H2SO4 proxy] required to produce new particles was found to be ~1.0 ppb Wm-2 s and below 0.5 ppb Wm-2 s for the urban and semi-urban areas, respectively. The particle growth rates were similar during nucleation events at the three study locations, with an average value of 2.7 ± 0.5 nm hr-1. This result suggested that a similar nucleation mechanism dominated in the study region, which was strongly related to sulphuric acid concentration, however the relationship between the proxy and PNC was poor in the semi-urban area of Rocklea. This can be explained by the fact that the nucleation process was initiated upwind of the site and the resultant particles were transported via the wind to Rocklea. This explanation is also supported by the higher geometric mean diameter value observed for particles during the nucleation event and the time lag relationship between the H2SO4 proxy and PNC observed at Rocklea. In summary, particle size distribution was continuously measured in a subtropical urban area of southern hemisphere during 2009, the findings from which formed the first particle size distribution dataset in the study region. The characteristics of nucleation events in the Brisbane region were quantified and the properties of the nucleation growth and burst events are discussed in detail using a case studies approach. To further investigate the influence of nucleation events on PNC in the study region, PNC was simultaneously measured at three locations to examine the spatial variation of PNC during the regional nucleation events. In addition, the impact of upwind urban pollution on the downwind semi-urban area was quantified during these nucleation events. Sulphuric acid was found to be an important factor influencing new particle formation in the urban and roadside areas of the study region, however, a direct relationship with nucleation events at the semi-urban site was not observed. This study provided an overview of new particle formation in the Brisbane region, and its influence on PNC in the surrounding area. The findings of this work are the first of their kind for an urban area in the southern hemisphere.