Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Directed Synthesis of Rocksalt AuCl Crystals

We report the first-time experimental realization of rocksalt AuCl crystals. Our approach involves Au(III) complexing and reduction to Au(I) using an amine-terminated surfactant in a low dielectric permittivity solvent. The low charge screening in nonpolar solvents promotes crystallization of rocksalt AuCl, in which the bonding is predominantly ionic, in preference over tetragonal AuCl. The rocksalt AuCl crystals obtained here will facilitate studies to unveil the nexus between electronic structure and crystal structure in AuCl polymorphs, and provide insights on these relationships in other polymorphic crystal systems. Our approach provides a new means for crystallizing selective polymorphs of inorganic compounds by subtly influencing the cation electronic structure by varying the dielectric permittivity of the synthesis medium. In addition, the AuCl crystals can serve as inexpensive Au(I) precursors for forming a variety of Au nanostructures.

Given and News : Media discourse and the construction of community on national days

National anniversaries such as independence days demand precise coordination in order to make citizens change their routines to forego work and spend the day at rest or at festivities that provide social focus and spectacle. The complex social construction of national days is taken for granted and operates as a given in the news media, which are the main agents responsible for coordinating these planned disruptions of normal routines. This study examines the language used in the news to construct the rather unnatural idea of national days and to align people in observing them. The data for the study consist of news stories about the Fourth of July in the New York Times, sampled over 150 years and are supplemented by material from other sources and other countries. The study is multidimensional, applying concepts from pragmatics (speech acts, politeness, information structure), systemic functional linguistics (the interpersonal metafunction and the Appraisal framework) and cognitive linguistics (frames, metaphor) as well as journalism and communications to arrive at an interdisciplinary understanding of how resources for meaning are used by writers and readers of the news stories. The analysis shows that on national anniversaries, nations tend to be metaphorized as persons having birthdays, to whom politeness should be shown. The face of the nation is to be respected in the sense of identifying the nation's interests as one's own (positive face) and speaking of citizen responsibilities rather than rights (negative face). Resources are available for both positive and negative evaluations of events and participants and the newspaper deftly changes footings (Goffman 1981) to demonstrate the required politeness while also heteroglossically allowing for a certain amount of disattention and even protest - within limits, for state holidays are almost never construed as Bakhtinian festivals, as they tend to reaffirm the hierarchy rather than invert it. Celebrations are evaluated mainly for impressiveness, and for the essentially contested quality of appropriateness, which covers norms of predictability, size, audience response, aesthetics, and explicit reference to the past. Events may also be negatively evaluated as dull ("banal") or inauthentic ("hoopla"). Audiences are evaluated chiefly in terms of their enthusiasm, or production of appropriate displays for emotional response, for national days are supposed to be occasions of flooding-out of nationalistic feeling. By making these evaluations, the newspaper reinforces its powerful position as an independent critic, while at the same time playing an active role in the construction and reproduction of emotional order embodied in "the nation's birthday." As an occasion for mobilization and demonstrations of power, national days may be seen to stand to war in the relation of play to fighting (Bateson 1955). Evidence from the newspaper's coverage of recent conflicts is adduced to support this analysis. In the course of the investigation, methods are developed for analyzing large collections of newspaper content, particularly topical soft news and feature materials that have hitherto been considered less influential and worthy of study than so-called hard news. In his work on evaluation in newspaper stories, White (1998) proposed that the classic hard news story is focused on an event that threatens the social order, but news of holidays and celebrations in general does not fit this pattern, in fact its central event is a reproduction of the social order. Thus in the system of news values (Galtung and Ruge 1965), national holiday news draws on "ground" news values such as continuity and predictability rather than "figure" news values such as negativity and surprise. It is argued that this ground helps form a necessary space for hard news to be seen as important, similar to the way in which the information structure of language is seen to rely on the regular alternation of given and new information (Chafe 1994).

Flood related loss and recovery of intertidal seagrass meadows in southern Queensland, Australia

The loss and recovery of intertidal seagrass meadows were assessed following the flood related catastrophic loss of seagrass meadows in February 1999 in the Sandy Strait, Queensland. Region wide recovery rates of intertidal meadows following the catastrophic disturbance were assessed by mapping seagrass abundance in the northern Great Sandy Strait region prior to and on 3 occasions after widespread loss of seagrass. Meadow-scale assessments of seagrass loss and recovery focussed on two existing Zostera capricorni monitoring meadows in the region. Mapping surveys showed that approximately 90% of intertidal seagrasses in the northern Great Sandy Strait disappeared after the February 1999 flooding of the Mary River. Full recovery of all seagrass meadows took 3 years. At the two study sites (Urangan and Wanggoolba Creek) the onset of Z. capricorni germination following the loss of seagrass occurred 14 months post-flood at Wanggoolba Creek, and at Urangan it took 20 months for germination to occur. By February 2001 (24 months post-flood) seagrass abundance at Wanggoolba Creek sites was comparable to pre-flood abundance levels and full recovery at Urangan sites was complete in August 2001 (31 months post-flood). Reduced water quality characterised by 2–3 fold increases in turbidity and nutrient concentrations during the 6 months following the flood was followed by a 95% loss of seagrass meadows in the region. Reductions in available light due to increased flood associated turbidity in February 1999 were the likely cause of seagrass loss in the Great Sandy Strait region, southern Queensland. Although seasonal cues influence the germination of Z. capricorni, the temporal variation in the onset of seed germination between sites suggests that germination following seagrass loss may be dependent on other factors (eg. physical and chemical characteristics of sediments and water). Elevated dissolved nitrogen concentrations during 1999 at Wanggoolba Creek suggest that this site received higher loads of sediments and nutrients from flood waters than Urangan. The germination of seeds at Wanggoolba Creek one year prior to Urangan coincides with relatively low suspended sediment concentrations in Wanggoolba Creek waters. The absence of organic rich sediments at Urangan for many months following their removal during the 1999 flood may also have inhibited seed germination. Data from population cohort analyses and population growth rates showed that rhizome weight and rhizome elongation rates increased over time, consistent with rapid growth during increases in temperature and light availability from May to October

Happily ever after: Romance, gender and the building blocks of domestic violence

My sister describes the state of something being a psychological or personal 'issue' - such as a trauma, compulsion, phobia, or obsession - as having 'brain spaghetti'. For example, apparently she has spaghetti about me pinning her down as a child and tickling her until she screamed for mercy. She knows this because when her spouse tried to do the same, the experience she had as a child came flooding back as a complex tangle of fears, feelings, and mental images. Notwithstanding the trauma inflicted on a sibling in my youth, the spaghetti metaphor is a simple but useful tool for explaining how complex our experiences are, and I bring it up here because I believe a lot of people have spaghetti about love. So much so, that often love becomes distorted, sometimes to the point of making one completely blind to manipulation and abuse. Part of the blame for 'love spaghetti' can be allotted to media depictions of romance and gender, which helps entrench and maintain our deeply held beliefs about what relationships should look like.

What drives plant biodiversity in the clay floodplain grasslands of NSW?

An assessment of the relative influences of management and environment on the composition of floodplain grasslands of north-western New South Wales was made using a regional vegetation survey sampling a range of land tenures (e. g. private property, travelling stock routes and nature reserves). A total of 364 taxa belonging to 55 different plant families was recorded. Partitioning of variance with redundancy analysis determined that environmental variables accounted for a greater proportion (61.3%) of the explained variance in species composition than disturbance-related variables (37.6%). Soil type (and fertility), sampling time and rainfall had a strong influence on species composition and there were also east-west variations in composition across the region. Of the disturbance-related variables, cultivation, stocking rate and flooding frequency were all influential. Total, native, forb, shrub and subshrub richness were positively correlated with increasing time since cultivation. Flood frequency was positively correlated with graminoid species richness and was negatively correlated with total and forb species richness. Site species richness was also influenced by environmental variables (e. g. soil type and rainfall). Despite the resilience of these grasslands, some forms of severe disturbance (e. g. several years of cultivation) can result in removal of some dominant perennial grasses (e. g. Astrebla spp.) and an increase in disturbance specialists. A simple heuristic transitional model is proposed that has conceptual thresholds for plant biodiversity status. This knowledge representation may be used to assist in the management of these grasslands by defining four broad levels of community richness and the drivers that change this status.

Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles

By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H-2 at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.

Insoluble anode of porous lead dioxide for electrosynthesis: preparation and characterization

Preparation of a novel type of titanium-substrate lead dioxide anode with enhanced electrocatalytic activity for electrosynthesis is described. It has been demonstrated that in the presence of a suitable surfactant in the coating solution, an adherent and mainly tetragonal form of lead dioxide is deposited on a platinized titanium surface such that the solution side of the coating is porous while the substrate side is compact. By an analysis of anodic charging curves and steady-state Tafel plots with such porous electrodes in contact with sodium sulphate solution, it has been proved that the electrochemically active area of these anodes is higher by more than an order of magnitude when compared to the area of conventional titanium-substrate lead dioxide anodes. The electrocatalytic activity is also thereby enhanced to a significant degree.

Efficacy of exclusion fencing to protect ephemeral floodplain lagoon habitats from feral pigs (Sus scrofa)

Foraging by feral pigs can strongly affect wetland vegetation assemblages and so too wider ecological processes, although their effects on freshwater ecosystems have seldom been tudied. We assessed the ecological effects of pig foraging in replicate fenced and unfenced ephemeral floodplain lagoons in tropical north-eastern Australia. Pig foraging activities in unfenced lagoons caused major changes to aquatic macrophyte communities and as a consequence, to the proportional amounts of open water and bare ground. The destruction of macrophyte communities and upheaval of wetland sediments significantly affected wetland turbidity, and caused prolonged anoxia and pH imbalances in the unfenced treatments. Whilst fencing of floodplain lagoons will protect against feral pig foraging activities, our repeated measures of many biological, physical and chemical parameters inferred that natural seasonal (i.e. temporal) effects had a greater influence on these variables than did pigs. To validate this observation requires measuring how these effects are influenced by the seemingly greater annual disturbance regime of variable flooding and drying in this tropical climate.

Resilience of a high-conservation-value, semi-arid grassland on fertile clay soils to burning, mowing and ploughing.

In grassland reserves, managed disturbance is often necessary to maintain plant species diversity. We carried out experiments to determine the impact of fire, kangaroo grazing, mowing and disc ploughing on grassland species richness and composition in a nature reserve in semi-arid eastern Australia. Vegetation response was influenced by winter-spring drought after establishment of the experiments, but moderate rainfall followed in late summer-autumn. Species composition varied greatly between sampling times, and the variability due to rainfall differences between seasons and years was greater than the effects of fire, kangaroo grazing, mowing or disc ploughing. In the fire experiment, species richness and composition recovered more rapidly after spring than autumn burning. Species richness and composition were similar to control sites within 12 months of burning and mowing, suggesting that removal of the dominant grass canopy is unnecessary to enhance plant diversity. Two fires (separated by 3 years) and post-fire kangaroo grazing had only minor influence on species richness and composition. Even disc ploughing caused only a small reduction in native richness. The minor impact of ploughing was explained by the small areas that were ploughed, the once-off nature of the treatment, and the high degree of natural movement and cracking in these shrink-swell soils. Recovery of the composition and richness of these grasslands was rapid because of the high proportion of perennial species that resprout vegetatively after fire and mowing. There appears to be little conservation benefit from fire, mowing or ploughing ungrazed areas, as we could identify no native plant species dependent on frequent disturbance for persistence in this grassland community. However, the ability of the Astrebla- and Dichanthium-dominated grasslands to recover quickly after disturbance, given favourable seasonal conditions, suggests that they are well adapted to natural disturbances (e.g. droughts, fire, flooding and native grazing).

Recovery of fish and crustacean communities during remediation of tidal wetlands affected by leachate from acid sulfate soils in north-eastern Australia.

In the 1970s, acid sulfate soils (ASS) distributed within about 720 ha of predominantly mangrove and salt pan wetlands at East Trinity in north Queensland were developed after the area was isolated from tidal flooding by a surrounding seawall and the installation of tidal gates on major drainage creeks. Following drainage and oxidation of these estuarine acidic sediments, resultant acid leachate caused considerable, ongoing environmental problems including regular fish kills. A rehabilitation program covering much of these former tidal wetlands commenced in 2000 using a lime-assisted tidal exchange management regime. Changes in the established populations of estuarine fish and crustaceans were monitored in the two creeks (Firewood and Hills Creeks) where tidal flows were reinstated. In Firewood Creek between 2001 and 2005, there was a progressive increase in fish species richness, diversity and abundance. The penaeid prawn Fenneropenaeus merguiensis was a major component of the cast net catches in the lower sections of both Firewood and Hills Creeks but its relative abundance decreased upstream of the tidal gates on the seawall. Well established stocks of predominantly juvenile, male Scylla serrata resident upstream of the tidal gates indicated suitable habitats with acceptable water and sediment quality and adequate availability of food. The regular fish kills that occurred prior to the management regime abated and, overall, the implementation of the rehabilitation program is yielding positive benefits for the local fisheries.

Permeation of gases through liquid films

Permeation of gases through single surfactant stabilized aqueous films has previously been studied in view of the potentiality of foam to separate gaseous mixtures. The earlier analysis assumed that the gas phase was well mixed and that the mass-transfer process was completely controlled by the liquid film. Permeabilities evaluated from single film data based on such analysis failed to predict the mass-transfer data obtained on permeation through two films. It is shown that the neglect of gas-phase resistance and the effect of film movement is the reason for the failure of the well-mixed gas models. An exact analysis of diffusion through two films is presented. It successfully predicts the experimental data on two films based on parameters evaluated from single film data.

Sustainable Grazing in the Channel Country Floodplains (phase 2) : A technical report on findings between March 2003 and June 2006

‘Sustainable Grazing in the Channel Country Floodplains’ was initiated by industry to redress the lack of objective information for sustainable management in the floodplains of Cooper Creek and the Diamantina and Georgina Rivers. The project has maintained links with the grazing community and has extensively drawn upon expert local experience and knowledge. The project has provided tools for managers to better anticipate the size of beneficial flooding arising from rains in the upper catchment and to more objectively assess the value of the pasture resulting from flooding. The latest information from the project has enabled customisation of the EDGENetwork™ Grazing Land Management training package for the Channel Country. In combination, these tools will assist in making earlier cattle stocking decisions, including when cattle may need to be mustered out of floodplain paddocks, how many additional cattle will be required to take advantage of the flood–grown pasture, and the timing of cattle turnoff. These will reduce costs by providing a greater lead time to plan cattle movements and purchases, and may enhance the sustainability of the resource base by better matching cattle numbers with the feed on offer.

VG07023 Driving better vegetable irrigation through profitable practice change

Despite recent flooding in eastern Australia, the availability/quality of irrigation water is a long-term issue for Australian vegetable growers. To survive, producers are told to implement new technologies. However, there is often little practical information investigating which improvements could make a real difference, and keep production profitable. In an Horticulture Australia Ltd three year project, scientists from the Department of Employment, Economic Development and Innovation (QLD), CSIRO, Department of Industry and Investment (NSW), and the National Centre for Engineering in Agriculture, evaluated practical irrigation improvements. We conducted experiments and case studies on farms in southern Queensland and Riverina vegetable districts, with over 100 extension events, including irrigation workshops, conferences, and field days.

On the functional ordering of biomembranes : Implications for drug binding

Cells are packed with membrane structures, defining the inside and outside, and the different subcellular compartments. These membranes consisting mainly of phospholipids have a variety of functions in addition to providing a permeability barrier for various compounds. These functions involve cellular signaling, where lipids can act as second messengers, or direct regulation of membrane associating proteins. The first part of this study focuses on relating some of the physicochemical properties of membrane lipids to the association of drug compounds to membranes. A fluorescence based method is described allowing for determination of the membrane association of drugs. This method was subsequently applied to a novel drug, siramesine, previously shown to have anti-cancer activity. Siramesine was found to associate with anionic lipids. Especially interesting is its strong affinity for a second messenger lipid phosphatidic acid. This is the first example of a small molecule drug compound specifically interacting with a cellular lipid. Phosphatidic acid in cells is required for the activation of many signaling pathways mediating growth and proliferation. This provides an intriguing possibility for a simple molecular mechanism of the observed anti-cancer activity of siramesine. In the second part the thermal behavior and self assembly of charged and uncharged membrane assemblies was studied. Strong inter-lamellar co-operativity was observed for multilamellar DPPC vesicles using fluorescence techniques together with calorimetry. The commonly used membrane models, large unilamellar vesicles (LUV) and multilamellar vesicles (MLV) were found to possess different biophysical properties as interlamellar interactions of MLVs drive segregation of a pyrene labeled lipid analogue into clusters. The effect of a counter-ion lattice on the self assembly of a cationic gemini surfactant was studied. The presence of NaCl strongly influenced the thermal phase behavior of M-1 vesicles, causing formation of giant vesicles upon exceeding a phase transition temperature, followed by a subsequent transition into a more homogenous dispersion. Understanding the underlying biophysical aspects of cellular membranes is of fundamental importance as the complex picture of the structure and function of cells is evolving. Many of the cellular reactions take place on membranes and membranes are known to regulate the activity of many peripheral and intergral membrane associating proteins. From the point of view of drug design and gene technology, membranes can provide an interesting target for future development of drugs, but also a vehicle sensitive for environmental changes allowing for encapsulating drugs and targeting them to the desired site of action.