Influences of molecular structure on co-crystallization of polypyridyl metal complexes.

Heteroleptic complexes of the type \[RuL2L′](PF6)2 (L, L′ = combinations of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy)) were found to cocrystallize with \[Ni(phen)3](PF6)2 to produce cocrystals of \[Ni(phen)3]x\[RuL2L′]1–x(PF6)2. In this report we show that the ability of the complexes to cocrystallize is influenced by the number of common ligands between complexes in solution. Supramolecular selection is a phenomenon caused by molecular recognition through which cocrystals can grow from the same solution but contain different ratios of the molecular components. It was found that systems where L = phen displayed less supramolecular selection than systems where L = bipy. With increasing supramolecular selection, the composition of cocrystals was found to vary significantly from the initial relative concentration in the cocrystallizing solution, and therefore it was increasingly difficult to control the final composition of the resultant cocrystals. Consequently, modulation of concentration-dependent properties such as phase was also found to be less predictable with increasing supramolecular selection. Notwithstanding the complication afforded by the presence of supramolecular selection, our results reaffirm the robustness of the \[M(phen)3](PF6)2 structure because it was maintained even when ca. 90% of the complexes in the cocrystals were \[Ru(phen)(bipy)2](PF6)2, which in its pure form is not isomorphous with \[M(phen)3](PF6)2. Experiments between complexes without common ligands, i.e., \[Ru(bipy)3](PF6)2 cocrystallized with \[Ni(phen)3](PF6)2, were found to approach the limit to which molecular recognition processes can be confused into cocrystallizing different molecules to form single cocrystals. For these systems the result was the formation of block-shaped crystals skewered by a needle-shaped crystals.

Vision-based operations of a large industrial vehicle : autonomous hot metal carrier

Hot metal carriers (HMCs) are large forklift-type vehicles used to move molten metal in aluminum smelters. This paper reports on field experiments that demonstrate that HMCs can operate autonomously and in particular can use vision as a primary sensor to locate the load of aluminum. We present our complete system but focus on the vision system elements and also detail experiments demonstrating reliable operation of the materials handling task. Two key experiments are described, lasting 2 and 5 h, in which the HMC traveled 15 km in total and handled the load 80 times.

Liquid metal/metal oxide frameworks with incorporated Ga2O3 for photocatalysis

Solvothermally synthesized Ga2O3 nanoparticles are incorporated into liquid metal/metal oxide (LM/MO) frameworks in order to form enhanced photocatalytic systems. The LM/MO frameworks, both with and without incorporated Ga2O3 nanoparticles, show photocatalytic activitydue to a plasmonic effect where performance is related to the loading of Ga2O3 nanoparticles. Optimum photocatalytic efficiency is obtained with 1 wt% incorporation of Ga2O3 nanoparticles. This can be attributed to the sub-bandgap states of LM/MO frameworks, contributing to pseudo-ohmic contacts which reduce the free carrier injection barrier to Ga2O3.

Inside the ‘Hurt Locker’: The combined effects of explosive ordnance disposal and chemical protective clothing on physiological tolerance time in extreme environments

Background Explosive ordnance disposal (EOD) technicians are often required to wear specialised clothing combinations that not only protect against the risk of explosion but also potential chemical contamination. This heavy (>35kg) and encapsulating ensemble is likely to increase physiological strain by increasing metabolic heat production and impairing heat dissipation. This study investigated the physiological tolerance times of two different chemical protective undergarments, commonly worn with EOD personal protective clothing, in a range of simulated environmental extremes and work intensities Methods Seven males performed eighteen trials wearing two ensembles. The trials involved walking on a treadmill at 2.5, 4 and 5.5 km.h-1 at each of the following environmental conditions, 21, 30 and 37°C wet bulb globe temperature (WBGT). The trials were ceased if the participants’ core temperature reached 39°C, if heart rate exceeded 90% of maximum, if walking time reached 60 minutes or due to volitional fatigue. Results Physiological tolerance times ranged from 8 to 60 min and the duration (mean difference: 2.78 min, P>0.05) were similar in both ensembles. A significant effect for environment (21>30>37°C WBGT, P<0.05) and work intensity (2.5>4>5.5 km.h-1, P< 0.05) was observed in tolerance time. The majority of trials across both ensembles (101/126; 80.1%) were terminated due to participants achieving a heart rate equivalent to greater than 90% of their maximum. Conclusions Physiological tolerance times wearing these two chemical protective undergarments, worn underneath EOD personal protective clothing, were similar and predominantly limited by cardiovascular strain.

Autonomous hot metal carrier: Navigation and manipulation with a 20 tonne industrial vehicle

This paper reports work on the automation of a hot metal carrier, which is a 20 tonne forklift-type vehicle used to move molten metal in aluminium smelters. To achieve efficient vehicle operation, issues of autonomous navigation and materials handling must be addressed. We present our complete system and experiments demonstrating reliable operation. One of the most significant experiments was five-hours of continuous operation where the vehicle travelled over 8 km and conducted 60 load handling operations. Finally, an experiment where the vehicle and autonomous operation were supervised from the other side of the world via a satellite phone network are described.

Book Review: "Metal Rules the Globe: Heavy Metal Music around the World". Durham, NC: Duke University Press.

It is rare to find an anthology that realizes the possibilities of the form. We tend to regard our edited collections as lesser siblings, and forget their special value. But at times, a subject seems to require an edited collection much more than it does a classic monograph. So it is with the subject showcased here, which concerns the global circulation, performance and consumption of heavy metal. This is a relatively new and emerging body of work, hitherto scattered disparately in the broader popular music studies, but quickly gaining status as a “studies” with the establishment of a global conference, a journal, and publication of this anthology, all in recent years. Metal Rules the Globe took the editors’ a decade to compile. That they have thought deeply about how they want the collection to speak shows through in the book’s thoughtful arrangement and design, and in the way in which they draw on the contributions herein to develop for the field a research agenda that will take it forward...

Autonomous hot metal carrier

This paper reports work involved with the automation of a Hot Metal Carrier — a 20 tonne forklift-type vehicle used to move molten metal in aluminium smelters. To achieve efficient vehicle operation, issues of autonomous navigation and materials handling must be addressed. We present our complete system and experiments demontrating reliable operation. One of the most significant experiments was five-hours of continuous operation where the vehicle travelled over 8 km and conducted 60 load handling operations. We also describe an experiment where the vehicle and autonomous operation were supervised from the other side of the world via a satellite phone network.

Transition metal layered double hydroxides for energy storage

Various types of layered double hydroxides, a type of clay, were synthesised. They were then electrochemically tested to determine whether the samples would be suitable to store energy as supercapacitors. A manganese aluminium layered double hydroxide was electrochemically tested for the first time and found to have a large capacitance.

The structures of the isomorphous potassium and rubidium salts of 4-nitrobenzoic acid and an overview of the metal complex stereochemistries of the alkali metal salt series with this ligand

The structures of the isomorphous potassium and rubidium polymeric coordination complexes with 4-nitrobenzoic acid, poly[mu2-aqua-aqua-mu3-(4-nitrobenzoato)-potassium], [K(C7H4N2O2)(H2O)2]n, (I) and poly[mu3-aqua-aqua-mu5-(4-nitrobenzoato)-rubidium], [Rb(C7H4N2O2)(H2O)2]n, (II) have been determined. In (I) the very distorted KO6 coordination sphere about the K+ centres in the repeat unit comprise two bridging nitro O-atom donors, a single bridging carboxyl O-atom donor and two water molecules, one of which is bridging. In the the Rb complex (II), the same basic MO6 coordination is found in the repeat unit but is expanded to RbO9 through a slight increase in the accepted Rb-O bond length range and includes an additional Rb-O(carboxyl) bond, completing a bidentate O,O'-chelate interaction, and additional bridging Rb-Onitro) and Rb-O(water) bonds. The comparative K-O and Rb-O bond length ranges are 2.738(3)-3.002(3)Ang. (I) and 2.884(2)-3.182(2)Ang. (II). The structure of (II) is also isomorphous as well as isostructural with the known structure of the nine-coordinate caesium 4-nitrobenzoate analogue, [Cs(C7H4N2O~2~)(H~2~O)2]n, (III) in which the Cs---O range is 3.047(4)-3.338(4)Ang. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups as well as extensions along c through the p-related carboxyl group, giving a two-dimensional structure in (I). In (II) and (III), three-dimensional structures are generated through additional bridges through the nitro and water O-atoms. In all structures, both water molecules are involved in similar intra-polymer O-H...O hydrogen-bonding interactions to both carboxyl as well as water O-atom acceptors. A comparison of the varied coordination behaviour of the full set of Li-Cs salts with 4-nitrobenzoic acid is also made.

The influence of financial risk tolerance and risk perception on individual investment decision-making in a financial advice context

The aim of this thesis is to examine how risk tolerance and risk perception, two important but often misunderstood constructs, jointly influence client investment decisions in a financial advice context. By distinguishing the roles of these two risk constructs in client decision-making, in this thesis a new direction in studying financial/investment risks is provided while practice and regulation in the financial services industry is potentially informed. Based on the literature relating to risks and individual decision-making, a theoretical framework is developed and relevant hypotheses are tested in two studies with financial adviser clients in Australia. Results reveal that financial risk tolerance influences asset allocation both directly and indirectly through risk perception. The intervening role of risk perception suggests that risk tolerance affects how clients perceive the riskiness of an investment product which influences client decision-making.

An evaluation of potential candidate genes involved in salinity tolerance in striped catfish (Pangasianodon hypopthalmus) using an RNA-SEQ approach

The project investigated the molecular response of Tra catfish (Pangasianodon hypophthalmus) to elevated salinity conditions. We employed Next generation sequencing platform to evaluate differential gene expression profiles of key genes under two salinity conditions. Results of the current project can form the basis for further studies to confirm the functional roles of specific genes that influence salinity tolerance in the target species and more broadly in other freshwater teleost fishes. Ultimately, the approach can contribute to developing superior culture stocks of the target species.

Generation of catalytically active materials from a liquid metal precursor

A facile route to prepare catalystically active materials from a galinstan liquid metal alloy is introduced. Sonicating liquid galinstan in alkaline solution or treating it in reducing media results in the creation of solid In/Sn rich microspheres that show catalytic activity toward both potassium ferricyanide and 4-nitrophenol reduction.

Effects of metal ion concentration on electrodeposited CuZnSn film and its application in kesterite Cu2ZnSnS4solar cells

In this study, effects of concentrations of Cu(II), Zn(II) and Sn(II) ions in the electrolytic bath solution on the properties of electrochemically deposited CuZnSn (CZT) films were investigated. Study of the composition of a CZT film has shown that the metallic content (relative atomic ratio) in the film increased linearly with increase in the metal ion concentration. It is the first time that the relationship of the compositions of the alloy phases in the co-electrodeposited CZT film with the concentration of metal ions has been revealed. The results have confirmed that the formation and content of Cu6Sn5 and Cu5Zn8 alloy phases in the film were directly controlled by the concentration of Cu(II). SEM measurements have shown that Sn(II) has significant impact on film morphology, which became more porous as a result of the larger nucleation size of tin. The changes in the surface properties of the films was also confirmed by chronoamperometry characteristic (i–t) deposition curves. By optimization of metal ion concentrations in the electrolyte solution, a copper-poor and zinc-rich kesterite Cu2ZnSnS4 (CZTS) film was synthesized by the sulfurization of the deposited CZT film. The solar cell with the CZTS film showed an energy conversion efficiency of 2.15% under the illumination intensity of 100 mW cm 2.

Direct photocatalysis for organic synthesis by using plasmonic-metal nanoparticles irradiated with visible light

Recent advances in direct-use plasmonic-metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible-light irradiation have attracted great interest. Plasmonic-metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic-metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light-excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic-metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation.

Viable photocatalysts under solar-spectrum irradiation: Nonplasmonic metal nanoparticles

Supported nanoparticles (NPs) of nonplasmonic transition metals (Pd, Pt, Rh, and Ir) are widely used as thermally activated catalysts for the synthesis of important organic compounds, but little is known about their photocatalytic capabilities. We discovered that irradiation with light can significantly enhance the intrinsic catalytic performance of these metal NPs at ambient temperatures for several types of reactions. These metal NPs strongly absorb the light mainly through interband electronic transitions. The excited electrons interact with the reactant molecules on the particles to accelerate these reactions. The rate of the catalyzed reaction depends on the concentration and energy of the excited electrons, which can be increased by increasing the light intensity or by reducing the irradiation wavelength. The metal NPs can also effectively couple thermal and light energy sources to more efficiently drive chemical transformations.