Ruthenium(II) dichloro or dithiocyanato complexes with 4,4′:2′,2″:4″,4‴-quaterpyridinium ligands : towards photosensitisers with enhanced low-energy absorption properties

Fourteen new complexes of the form cis-\[RuIIX2(R2qpy2+)2]4+ (R2qpy2+ = a 4,4′:2′,2″:4″,4‴-quaterpyridinium ligand, X = Cl− or NCS−) have been prepared and isolated as their PF6− salts. Characterisation involved various techniques including 1H NMR spectroscopy and +electrospray or MALDI mass spectrometry. The UV–Vis spectra display intense intraligand π → π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-withdrawing strength of the pyridinium groups increases, while replacing Cl− with NCS− causes blue-shifts. Cyclic voltammograms show quasi-reversible or reversible RuIII/II oxidation waves, and several ligand-based reductions that are irreversible. The variations in the redox potentials correlate with changes in the MLCT energies. A single-crystal X-ray structure has been obtained for a protonated form of a proligand salt, \[(4-(CO2H)Ph)2qpyH3+]\[HSO4]3·3H2O. Time-dependent density functional theory calculations give adequate correlations with the experimental UV–Vis spectra for the two carboxylic acid-functionalised complexes in DMSO. Despite their attractive electronic absorption spectra, these dyes are relatively inefficient photosensitisers on electrodes coated with TiO2 or ZnO. These observations are attributed primarily to weak electronic coupling with the surfaces, since the DFT-derived LUMOs include no electron density near the carboxylic acid anchors.

Knowledge sharing leveraging new product development activities to derive enhanced business performance : mixed method study

Knowledge has been widely recognised as a determinant of business performance. Business capabilities require an effective share of resource and knowledge. Specifically, knowledge sharing (KS) between different companies and departments can improve manufacturing processes since intangible knowledge plays an enssential role in achieving competitive advantage. This paper presents a mixed method research study into the impact of KS on the effectiveness of new product development (NPD) in achieving desired business performance (BP). Firstly, an empirical study utilising moderated regression analysis was conducted to test whether and to what extent KS has leveraging power on the relationship between NPD and BP constructs and variables. Secondly, this empirically verified hypothesis was validated through explanatory case studies involving two Taiwanese manufacturing companies using a qualitative interaction term pattern matching technique. The study provides evidence that knowledge sharing and management activities are essential for deriving competitive advantage in the manufacturing industry.

Enhanced photocatalytic activity of titanium oxide nanotubes after heating treatment

Titanium oxide nanotubes were obtained by an electrochemical anodization method. Scanning electron microscope results demonstrate that the diameter of the tubes is about 120 nm and the length of the tubes is around 13 μm. Transmission electron microscope results indicate that the nanotubes are assembled by numerous nanoparticles and tube-like structure remains well after heat treatment at 400-600 °C. The photocatalysis performance of the nanotubes was evaluated in terms of the decomposition rate of methyl orange under UV irradiation. The results show that the photocatalytic activity was enhanced through the heating treatment of the nanotubes, and the nanotubes heated at 600 °C exhibits the best photocatalytic activity. X-ray diffraction patterns indicate that there is no phase transformation during the heat treatment. Therefore, the enhanced activity can be attributed to the improvement of nanotubes crystallinity, which may provide more insights about the effect of the crystallinity on the photocatalytic performance.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Fire safety of steel wall systems using enhanced plasterboards

Fire safety design is important to eliminate the loss of property and lives during fire events. Gypsum plasterboard is widely used as a fire safety material in the building industry all over the world. It contains gypsum (CaSO4.2H2O) and Calcium Carbonate (CaCO3) and most importantly free and chemically bound water in its crystal structure. The dehydration of the gypsum and the decomposition of Calcium Carbonate absorb heat, which gives the gypsum plasterboard fire resistant qualities. Currently plasterboard manufacturers use additives such as vermiculite to overcome shrinkage of gypsum core and glass fibre to bridge shrinkage cracks and enhance the integrity of board during calcination and after the loss of paper facings in fires. Past research has also attempted to reduce the thermal conductivity of plasterboards using fillers. However, no research has been undertaken to enhance the specific heat of plasterboard and the points of dehydration using chemical additives and fillers. Hence detailed experimental studies of powdered samples of plasterboard mixed with chemical additives and fillers in varying proportions were conducted. These tests showed the enhancement of specific heat of plasterboard. Numerical models were also developed to investigate the thermal performance of enhanced plasterboards under standard fire conditions. The results showed that the use of these enhanced plasterboards in steel wall systems can significantly improve their fire performance. This paper presents the details of this research and the results that can be used to enhance the fire safety of steel wall systems commonly used in buildings.

Enhanced hydrogen separation by vertically-aligned carbon nanotube membranes with zeolite imidazolate frameworks as a selective layer

Vertically-aligned carbon nanotube (VACNT) membranes show very high permeation fluxes due to the inherent smooth and frictionless nature of the interior of the nanotubes. However, the hydrogen selectivities are all in the Knudsen range and are quite low. In this study we grew molecular sieve zeolite imidazolate frameworks (ZIFs) via secondary seeded growth on the VACNT membranes as a gas selective layer. The ZIF layer has a thickness of 5–6 μm and shows good contact with the VACNT membrane surface. The VACNT supported ZIF membrane shows much higher H2 selectivity than Ar (7.0); O2 (13.6); N2 (15.1) and CH4 (9.8). We conclude that tailoring metal–organic frameworks on the membrane surface can be an effective route to improve the gas separation performance of the VACNT membrane.

Analysis of regionally enhanced GPS orbit and clock solutions and contribution to improvement of real-time precise point positioning

This work experimentally examines the performance benefits of a regional CORS network to the GPS orbit and clock solutions for supporting real-time Precise Point Positioning (PPP). The regionally enhanced GPS precise orbit solutions are derived from a global evenly distributed CORS network added with a densely distributed network in Australia and New Zealand. A series of computational schemes for different network configurations are adopted in the GAMIT-GLOBK and PANDA data processing. The precise GPS orbit results show that the regionally enhanced solutions achieve the overall orbit improvements with respect to the solutions derived from the global network only. Additionally, the orbital differences over GPS satellite arcs that are visible by any of the five Australia-wide CORS stations show a higher percentage of overall improvements compared to the satellite arcs that are not visible from these stations. The regional GPS clock and Uncalibrated Phase Delay (UPD) products are derived using the PANDA real time processing module from Australian CORS networks of 35 and 79 stations respectively. Analysis of PANDA kinematic PPP and kinematic PPP-AR solutions show certain overall improvements in the positioning performance from a denser network configuration after solution convergence. However, the clock and UPD enhancement on kinematic PPP solutions is marginal. It is suggested that other factors, such as effects of ionosphere, incorrectly fixed ambiguities, may be the more dominating, deserving further research attentions.

Ultra-trace detection of diagnostically important biomarkers using functionalised-Surface Enhanced Raman Spectroscopy (SERS)

Here we report an ultrasensitive method for detecting bio-active compounds in biological samples by means of functionalised nanoparticles interrogated by surface enhanced Raman spectroscopy (SERS). This method is applicable to the recovery and detection of many diagnostically important peptidyl analytes such as insulin, human growth hormone, growth factors (IGFs) and erythropoietin (EPO), as well as many small molecule analytes and metabolites. Our method, developed to detect EPO, demonstrates its utility in a complex yet well defined biological system. Recombinant human EPO (rhEPO) and EPO analogues have successfully been used to treat anaemia in end-stage renal failure, chronic disorders and infections, cancer and AIDS. Current methods for EPO testing are lengthy, laborious and relatively insensitive to low concentrations. In our rapid screening methodology, gold nanoparticles were functionalised with anti-EPO antibodies to provide very high selectivity towards the EPO protein in urine. These “smart sensor” nanoparticles interact with and trap EPO. Subsequent SERS screening allows for the detection and quantisation of ultra trace amounts (<<10-15 M) of EPO in urine samples with minimal sample preparation. We present data showing that the SERS spectrum differentiates between human endogenous EPO and rhEPO in unpurified urine, and potentially distinguishes between purified EPO isoforms. The elimination of sample preparation and direct screening in biological fluids significantly reduces the time required by current methods. Antibody recognition against a variety of biological targets and the availability of portable commercial SERS analysers for rapid onsite testing suggest broad diagnostic applicability in a flexible analytical platform.

Enhanced skin self-examination : a novel approach to skin cancer monitoring and follow-up

Advances in mobile telephone technology and available dermoscopic attachments for mobile telephones have created a unique opportunity for consumer-initiated mobile teledermoscopy. At least 2 companies market a dermoscope attachment for an iPhone (Apple), forming a mobile teledermoscope. These devices and the corresponding software applications (apps) enable (1) lesion magnification (at least ×20) and visualization with polarized light; (2) photographic documentation using the telephone camera; (3) lesion measurement (ruler); (4) adding of image and lesion details; and (5) e-mail data to a teledermatologist for review. For lesion assessment, the asymmetry-color (AC) rule has 94% sensitivity and 62 specificity for melanoma identification by consumers [1]. Thus, consumers can be educated to recognize asymmetry and color patterns in suspect lesions. However, we know little about consumers' use of mobile teledermoscopy for lesion assessment.

Investigation of ultra trace detection in functionalised-surface enhanced Raman spectroscopy (SERS)

We have developed an explanation for ultra trace detection found when using Au/Ag SERS nanoparticles linked to biochemical affinity tags, e.g. antibodies. The nanoparticle structure is not as usually assumed and the aggregated nanoparticles constitute hot spots that are indispensable for these very low levels of analyte detection, even more so when using a direct detection method.

Collaborative learning and critical thinking in technology-enhanced environments : an instructional design framework

The nature and characteristics of how learners learn today are changing. As technology use in learning and teaching continues to grow, its integration to facilitate deep learning and critical thinking becomes a primary consideration. The implications for learner use, implementation strategies, design of integration frameworks and evaluation of their effectiveness in learning environments cannot be overlooked. This study specifically looked at the impact that technology-enhanced learning environments have on different learners’ critical thinking in relation to eductive ability, technological self-efficacy, and approaches to learning and motivation in collaborative groups. These were explored within an instructional design framework called CoLeCTTE (collaborative learning and critical thinking in technology-enhanced environments) which was proposed, revised and used across three cases. The field of investigation was restricted to three key questions: 1) Do learner skill bases (learning approach and eductive ability) influence critical thinking within the proposed CoLeCTTE framework? If so, how?; 2) Do learning technologies influence the facilitation of deep learning and critical thinking within the proposed CoLeCTTE framework? If so, how?; and 3) How might learning be designed to facilitate the acquisition of deep learning and critical thinking within a technology-enabled collaborative environment? The rationale, assumptions and method of research for using a mixed method and naturalistic case study approach are discussed; and three cases are explored and analysed. The study was conducted at the tertiary level (undergraduate and postgraduate) where participants were engaged in critical technical discourse within their own disciplines. Group behaviour was observed and coded, attributes or skill bases were measured, and participants interviewed to acquire deeper insights into their experiences. A progressive case study approach was used, allowing case investigation to be implemented in a "ladder-like" manner. Cases 1 and 2 used the proposed CoLeCTTE framework with more in-depth analysis conducted for Case 2 resulting in a revision of the CoLeCTTE framework. Case 3 used the revised CoLeCTTE framework and in-depth analysis was conducted. The findings led to the final version of the framework. In Cases 1, 2 and 3, content analysis of group work was conducted to determine critical thinking performance. Thus, the researcher used three small groups where learner skill bases of eductive ability, technological self-efficacy, and approaches to learning and motivation were measured. Cases 2 and 3 participants were interviewed and observations provided more in-depth analysis. The main outcome of this study is analysis of the nature of critical thinking within collaborative groups and technology-enhanced environments positioned in a theoretical instructional design framework called CoLeCTTE. The findings of the study revealed the importance of the Achieving Motive dimension of a student’s learning approach and how direct intervention and strategies can positively influence critical thinking performance. The findings also identified factors that can adversely affect critical thinking performance and include poor learning skills, frustration, stress and poor self-confidence, prioritisations over learning; and inadequate appropriation of group role and tasks. These findings are set out as instructional design guidelines for the judicious integration of learning technologies into learning and teaching practice for higher education that will support deep learning and critical thinking in collaborative groups. These guidelines are presented in two key areas: technology and tools; and activity design, monitoring, control and feedback.

Dynamic robot path planning using an enhanced simulated annealing approach

Evolutionary computation is an effective tool for solving optimization problems. However, its significant computational demand has limited its real-time and on-line applications, especially in embedded systems with limited computing resources, e.g., mobile robots. Heuristic methods such as the genetic algorithm (GA) based approaches have been investigated for robot path planning in dynamic environments. However, research on the simulated annealing (SA) algorithm, another popular evolutionary computation algorithm, for dynamic path planning is still limited mainly due to its high computational demand. An enhanced SA approach, which integrates two additional mathematical operators and initial path selection heuristics into the standard SA, is developed in this work for robot path planning in dynamic environments with both static and dynamic obstacles. It improves the computing performance of the standard SA significantly while giving an optimal or near-optimal robot path solution, making its real-time and on-line applications possible. Using the classic and deterministic Dijkstra algorithm as a benchmark, comprehensive case studies are carried out to demonstrate the performance of the enhanced SA and other SA algorithms in various dynamic path planning scenarios.

Improving level crossing safety through enhanced data recording and reporting : The CRC for Rail Innovation’s Baseline Rail Level Crossing Video project

This paper describes the work being conducted in the baseline rail level crossing project, supported by the Australian rail industry and the Cooperative Research Centre for Rail Innovation. The paper discusses the limitations of near-miss data for analysis obtained using current level crossing occurrence reporting practices. The project is addressing these limitations through the development of a data collection and analysis system with an underlying level crossing accident causation model. An overview of the methodology and improved data recording process are described. The paper concludes with a brief discussion of benefits this project is expected to provide the Australian rail industry.

A sensitive assay for creatine kinase in serum samples dried on paper : enhanced thermal stability of the dried enzyme

A new bioluminescent creatine kinase (CK) assay using purified luciferase was used to analyse CK activity in serum samples dried on filter paper. Enzyme activity was preserved for over 1 wk on paper stored at room temperature. At 60°C, CK activity in liquid serum samples was rapidly inactivated, but the activity of enzyme stored on paper was preserved for at least 2 days.