Dynamic axial ligand-site exchange in facially discriminated ruthenium(II) carbonyl and rhodium(III) halide metalloporphyrins

For a series of six-coordinate Ru(II)(CO)L or Rh(III)(X–)L porphyrins which are facially differentiated by having a naphthoquinol- or hydroquinol-containing strap across one face, we show that ligand migration from one face to the other can occur under mild conditions, and that ligand site preference is dependent on the nature of L and X–. For bulky nitrogen-based ligands, the strap can be displaced sideways to accommodate the ligand on the same side as the strap. For the ligand pyrazine, we show 1 H NMR evidence for monodentate and bidentate binding modes on both faces, dependent on ligand concentration and metalloporphyrin structure, and that inter-facial migration is rapid under normal conditions. For monodentate substituted pyridine ligands there is a site dependence on structure, and we show clear evidence of dynamic ligand migration through a series of ligand exchange reactions.

Graphene-like nano-sheets for surface acoustic wave gas sensor applications

The gas sensing properties of graphene-like nano-sheets deposited on 36° YX lithium tantalate (LiTaO3) surface acoustic wave (SAW) transducers are reported. The thin graphene-like nano-sheets were produced via the reduction of graphite oxide which was deposited on SAW interdigitated transducers (IDTs). Their sensing performance was assessed towards hydrogen (H2) and carbon monoxide (CO) in a synthetic air carrier gas at room temperature (25 °C) and 40 °C. Raman and X-ray photoelectron spectroscopy (XPS) revealed that the deposited graphite oxide (GO) was not completely reduced creating small, graphitic nanocrystals ∼2.7 nm in size. © 2008 Elsevier B.V.

Exchange design patterns for electronic intermediairies

Intermediaries have introduced electronic services with varying success. One of the problems an intermediary faces is deciding what kind of exchange service it should offer to its customers and suppliers. For example, should it only provide a catalogue or should it also enable customers to order products? Developing the right exchange design is a complex undertaking because of the many design options on the one hand and the interests of multiple actors to be considered on the other. This is far more difficult than simple prescriptions like ‘creating a win-win situation’ suggest. We address this problem by developing design patterns for the exchanges between customers, intermediary, and suppliers related to role, linkage, transparency, and ovelty choices. For developing these design patterns, we studied four distinct electronic intermediaries and dentified exchange design choices that require trade-offs relating to the interests of customers, intermediary, and suppliers. The exchange design patterns contribute to the development of design theory for electronic intermediaries by filling a gap between basic business models and detailed business process designs.

A hydrogen gas sensor based on Pt/nanostructured WO3/SiC Schottky diode

Pt/nanostructured WO3/SiC Schottky diodes were fabricated and applied for hydrogen gas sensing applications. The nanostructured WO3 films were synthesized from tungsten coated SiC substrates via an acid-etching method using a 1.5 M HNO3 solution for 1 hr, 2 hrs and 3 hrs duration. Scanning electron microscopy of the developed films revealed platelet crystals with thicknesses in the order of 20-60 nm and lengths between 100-700 nm. X-ray diffraction analysis revealed that the rate of oxidation of tungsten increases as the duration of acid-etching increases. The devices were tested towards hydrogen gas balanced in air at different temperatures from 25°C to 200°C. At 200°C, voltage shifts of 0.45 V, 0.93 V and 2.37 V were recorded for devices acid-etched for 1 hr, 2 hrs and 3 hrs duration, respectively upon exposure to 1% hydrogen, under a constant forward bias current of 500 µA.

Strategic dalliances as an enabler for discontinuous innovation in slow clockspeed industries: evidence from the oil and gas industry

The concept of ‘strategic dalliances’– defined as non-committal relationships that companies can ‘dip in and out of,’ or dally with, while simultaneously maintaining longer-term strategic partnerships with other firms and suppliers – has emerged as a promising strategy by which organizations can create discontinuous innovations. But does this approach work equally well for every sector? Moreover, how can these links be effectively used to foster the process of discontinuous innovation? Toward assessing the role that industry clockspeed plays in the success or failure of strategic dalliances, we provide case study evidence from Twister BV, an upstream oil and gas technology provider, and show that strategic dalliances can be an enabler for the discontinuous innovation process in slow clockspeed industries. Implications for research and practice are discussed, and conclusions from our findings are drawn.

Regulating greenhouse gas emissions from coal mining activities in the context of climate change

Current approaches to the regulation of coal mining activities in Australia have facilitated the extraction of substantial amounts of coal and coal seam gas. The regulation of coal mining activities must now achieve the reduction or mitigation of greenhouse gas emissions in order to address the challenge of climate change and achieve ecologically sustainable development. Several legislative mechanisms currently exist which appear to offer the means to bring about the reduction or mitigation of greenhouse gas emissions from coal mining activities, yet Australia’s emissions from coal mining continue to rise. This article critiques these existing legislative mechanisms and presents recommendations for reform.

Iron biogeochemistry and associated greenhouse gas evolution in a forested subtropical Australian coastal catchment : Poona Creek, Southeast Queensland

Iron (Fe) is the fourth most abundant element in the Earth’s crust. Excess Fe mobilization from terrestrial into aquatic systems is of concern for deterioration of water quality via biofouling and nuisance algal blooms in coastal and marine systems. Substantial Fe dissolution and transport involve alternate Fe(II) oxidation followed by Fe(III) reduction, with a diversity of Bacteria and Archaea acting as the key catalyst. Microbially-mediated Fe cycling is of global significance with regard to cycles of carbon (C), sulfur (S) and manganese (Mn). However, knowledge regarding microbial Fe cycling in circumneutral-pH habitats that prevail on Earth has been lacking until recently. In particular, little is known regarding microbial function in Fe cycling and associated Fe mobilization and greenhouse (CO2 and CH4, GHG) evolution in subtropical Australian coastal systems where microbial response to ambient variations such as seasonal flooding and land use changes is of concern. Using the plantation-forested Poona Creek catchment on the Fraser Coast of Southeast Queensland (SEQ), this research aimed to 1) study Fe cycling-associated bacterial populations in diverse terrestrial and aquatic habitats of a representative subtropical coastal circumneutral-pH (4–7) ecosystem; and 2) assess potential impacts of Pinus plantation forestry practices on microbially-mediated Fe mobilization, organic C mineralization and associated GHG evolution in coastal SEQ. A combination of wet-chemical extraction, undisturbed core microcosm, laboratory bacterial cultivation, microscopy and 16S rRNA-based molecular phylogenetic techniques were employed. The study area consisted primarily of loamy sands, with low organic C and dissolved nutrients. Total reactive Fe was abundant and evenly distributed within soil 0–30 cm profiles. Organic complexation primarily controlled Fe bioavailability and forms in well-drained plantation soils and water-logged, native riparian soils, whereas tidal flushing exerted a strong “seawater effect” in estuarine locations and formed a large proportion of inorganic Fe(III) complexes. There was a lack of Fe(II) sources across the catchment terrestrial system. Mature, first-rotation plantation clear-felling and second-rotation replanting significantly decreased organic matter and poorly crystalline Fe in well-drained soils, although variations in labile soil organic C fractions (dissolved organic C, DOC; and microbial biomass C, MBC) were minor. Both well-drained plantation soils and water-logged, native-vegetation soils were inhabited by a variety of cultivable, chemotrophic bacterial populations capable of C, Fe, S and Mn metabolism via lithotrophic or heterotrophic, (micro)aerobic or anaerobic pathways. Neutrophilic Fe(III)-reducing bacteria (FeRB) were most abundant, followed by aerobic, heterotrophic bacteria (heterotrophic plate count, HPC). Despite an abundance of FeRB, cultivable Fe(II)-oxidizing bacteria (FeOB) were absent in associated soils. A lack of links between cultivable Fe, S or Mn bacterial densities and relevant chemical measurements (except for HPC correlated with DOC) was likely due to complex biogeochemical interactions. Neither did variations in cultivable bacterial densities correlate with plantation forestry practices, despite total cultivable bacterial densities being significantly lower in estuarine soils when compared with well-drained plantation soils and water-logged, riparian native-vegetation soils. Given that bacterial Fe(III) reduction is the primary mechanism of Fe oxide dissolution in soils upon saturation, associated Fe mobilization involved several abiotic and biological processes. Abiotic oxidation of dissolved Fe(II) by Mn appeared to control Fe transport and inhibit Fe dissolution from mature, first-rotation plantation soils post-saturation. Such an effect was not observed in clear-felled and replanted soils associated with low SOM and potentially low Mn reactivity. Associated GHG evolution post-saturation mainly involved variable CO2 emissions, with low, but consistently increasing CH4 effluxes in mature, first-rotation plantation soil only. In comparison, water-logged soils in the riparian native-vegetation buffer zone functioned as an important GHG source, with high potentials for Fe mobilization and GHG, particularly CH4 emissions in riparian loam soils associated with high clay and crystalline Fe fractions. Active Fe–C cycling was unlikely to occur in lower-catchment estuarine soils associated with low cultivable bacterial densities and GHG effluxes. As a key component of bacterial Fe cycling, neutrophilic FeOB widely occurred in diverse aquatic, but not terrestrial, habitats of the catchment study area. Stalked and sheathed FeOB resembling Gallionella and Leptothrix were limited to microbial mat material deposited in surface fresh waters associated with a circumneutral-pH seep, and clay-rich soil within riparian buffer zones. Unicellular, Sideroxydans-related FeOB (96% sequence identity) were ubiquitous in surface and subsurface freshwater environments, with highest abundance in estuary-adjacent shallow coastal groundwater water associated with redox transition. The abundance of dissolved C and Fe in the groundwater-dependent system was associated with high numbers of cultivable anaerobic, heterotrophic FeRB, microaerophilic, putatively lithotrophic FeOB and aerobic, heterotrophic bacteria. This research represents the first study of microbial Fe cycling in diverse circumneutral-pH environments (terrestrial–aquatic, freshwater–estuarine, surface–subsurface) of a subtropical coastal ecosystem. It also represents the first study of its kind in the southern hemisphere. This work highlights the significance of bacterial Fe(III) reduction in terrestrial, and bacterial Fe(II) oxidation in aquatic catchment Fe cycling. Results indicate the risk of promotion of Fe mobilization due to plantation clear-felling and replanting, and GHG emissions associated with seasonal water-logging. Additional significant outcomes were also achieved. The first direct evidence for multiple biomineralization patterns of neutrophilic, microaerophilic, unicellular FeOB was presented. A putatively pure culture, which represents the first cultivable neutrophilic FeOB from the southern hemisphere, was obtained as representative FeOB ubiquitous in diverse catchment aquatic habitats.

On forward secrecy in one-round key exchange

Most one-round key exchange protocols provide only weak forward secrecy at best. Furthermore, one-round protocols with strong forward secrecy often break badly when faced with an adversary who can obtain ephemeral keys. We provide a characterisation of how strong forward secrecy can be achieved in one-round key exchange. Moreover, we show that protocols exist which provide strong forward secrecy and remain secure with weak forward secrecy even when the adversary is allowed to obtain ephemeral keys. We provide a compiler to achieve this for any existing secure protocol with weak forward secrecy.

Volatile properties of particles emitted by compressed natural gas and diesel buses during steady state and transient driving modes

Volatile properties of particle emissions from four compressed natural gas (CNG) and four diesel buses were investigated under steady state and transient driving modes on a chassis dynamometer. The exhaust was diluted utilising a full-flow continuous volume sampling system and passed through a thermodenuder at controlled temperature. Particle number concentration and size distribution were measured with a condensation particle counter and a scanning mobility particle sizer, respectively. We show that, while almost all the particles emitted by the CNG buses were in the nanoparticle size range, at least 85% and 98% were removed at 100ºC and 250ºC, respectively. Closer analysis of the volatility of particles emitted during transient cycles showed that volatilisation began at around 40°C with the majority occurring by 80°C. Particles produced during hard acceleration from rest exhibited lower volatility than that produced during other times of the cycle. Based on our results and the observation of ash deposits on the walls of the tailpipes, we suggest that these non-volatile particles were composed mostly of ash from lubricating oil. Heating the diesel bus emissions to 100ºC removed ultrafine particle numbers by 69% to 82% when a nucleation mode was present and just 18% when it was not.

Hydrogen gas sensing properties of Pt/Ta2O5 Schottky diodes based on Si and SiC substrates

In this paper, we fabricated Pt/tantalum oxide (Ta2O5) Schottky diodes for hydrogen sensing applications. Thin (4 nm) layer of Ta2O5 was deposited on silicon (Si) and silicon carbide (SiC) substrates by radio frequency (RF) sputtering technique. We compared the performance of these sensors at different elevated temperatures of 100 ∘C and 150 ∘C. At these temperatures, the sensor based on SiC exhibited a larger sensitivity while the sensor based on Si exhibited a faster response toward hydrogen gas. We discussed herein, the responses exhibited by the Pt/Ta2O5 based Schottky diodes demonstrated a promising potential for hydrogen sensing applications.

The exchange: an experiment in environmentally sustainable urban practice for a subtropical climate

The exchange pavilion offers a dialogue between two Expositions: 1998 in Brisbane and 2010 in Shanghai; and a chance to examine the impact that climate change will have on urban best practice outcomes in cities of the future. The Exchange exhibits the proposition that environmentally sustainable buildings need to interact responsively with a range of technical innovations to enable communities (and hence cities) to control and better manage their immediate environment. The 'Exchange' pavilion is a design experiment that integrates 3 key research elements: * An interactive digital exchange * A living green system wall (vertical and temporal) * A public urban star (horizontal and spatial) The proposition argues that the environmentally sustainability of any city is reliant on harnessing the full spectrum of intellectual and creative capital of the winder community (from universities to Government bodies to citizens) - a true knowledge city.

Hydrogen gas sensing performance of a Pt/graphene/SiC device

In this work, we present the development of a Pt/graphene/SiC device for hydrogen gas sensing. A single layer of graphene was deposited on 6H-SiC via chemical vapor deposition. The presence of graphene C-C bonds was observed via X-ray photoelectron spectroscopy analysis. Current-voltage characteristics of the device were measured at the presence of hydrogen at different temperatures, from 25°C to 170°C. The dynamic response of the device was recorded towards hydrogen gas at an optimum temperature of 130°C. A voltage shift of 191 mV was recorded towards 1% hydrogen at −1 mA constant current.