Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

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.

Formation of nanoporous materials via mild retro-Diels–Alder chemistry

Poly(styrene)-block-poly(ethylene oxide) copolymers synthesized via the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and hetero Diels–Alder (HDA) cycloaddition can be cleaved in the solid state by a retro-HDA reaction occurring at 90 °C. Nanoporous films can be prepared from these polymers using a simple heating and washing procedure.

Aircraft emission reduction through multi-disciplinary flight path optimisation

There is worldwide interest in reducing aircraft emissions. The difficulty of reducing emissions including water vapour, carbon dioxide (CO2) and oxides of nitrogen (NOx) is mainly due from the fact that a commercial aircraft is usually designed for a particular optimal cruise altitude but may be requested or required to operate and deviate at different altitude and speeds to archive a desired or commanded flight plan, resulting in increased emissions. This is a multi- disciplinary problem with multiple trade-offs such as optimising engine efficiency, minimising fuel burnt, minimise emissions while maintaining aircraft separation and air safety. This project presents the coupling of an advanced optimisation technique with mathematical models and algorithms for aircraft emission reduction through flight optimisation. Numerical results show that the method is able to capture a set of useful trade-offs between aircraft range and NOx, and mission fuel consumption and NOx. In addition, alternative cruise operating conditions including Mach and altitude that produce minimum NOx and CO2 (minimum mission fuel weight) are suggested.

Assessing students in senior science: an analysis of questions in contextualised chemistry exams

This study explores the development of a coding system for analysing test questions in two context-based chemistry exams. We describe our unique analytical procedures before contrasting the data from both tests. Our findings indicate that when a new curriculum is developed such as a context-based curriculum, teachers are required to combine the previously separate domains of context and concept to develop contextualised assessment. We argue that constructing contextualised assessment items requires teachers to view concepts and context as interconnected rather than as separate entities that may polarise scientific endeavour. Implications for practice, curriculum and assessment-development in context-based courses are proposed.

Order of instruction effects - do they make a difference when teaching senior chemistry with computer based visualizations?

This study investigated whether conceptual development is greater if students learning senior chemistry hear teacher explanations and other traditional teaching approaches first then see computer based visualizations or vice versa. Five Canadian chemistry classes, taught by three different teachers, studied the topics of Le Chatelier’s Principle and dynamic chemical equilibria using scientific visualizations with the explanation and visualizations in different orders. Conceptual development was measured using a 12 item test based on the Chemistry Concepts Inventory. Data was obtained about the students’ abilities, learning styles (auditory, visual or kinesthetic) and sex, and the relationships between these factors and conceptual development due to the teaching sequences were investigated. It was found that teaching sequence is not important in terms of students’ conceptual learning gains, across the whole cohort or for any of the three subgroups.

But does it work? Effectiveness of scientific visualisations in high school chemistry and physics instruction.

Scientific visualisations such as computer-based animations and simulations are increasingly a feature of high school science instruction. Visualisations are adopted enthusiastically by teachers and embraced by students, and there is good evidence that they are popular and well received. There is limited evidence, however, of how effective they are in enabling students to learn key scientific concepts. This paper reports the results of a quantitative study conducted in Australian physics and chemistry classrooms. In general there was no statistically significant difference between teaching with and without visualisations, however there were intriguing differences around student sex and academic ability.

Measuring the effectiveness of computer-based scientific visualisations for conceptual development in Australian chemistry classrooms

Visual modes of representation have always been very important in science and science education. Interactive computer-based animations and simulations offer new visual resources for chemistry education. Many studies have shown that students enjoy learning with visualisations but few have explored how learning outcomes compare when teaching with or without visualisations. This study employs a quasi-experimental crossover research design and quantitative methods to measure the educational effectiveness - defined as level of conceptual development on the part of students - of using computer-based scientific visualisations versus teaching without visualisations in teaching chemistry. In addition to finding that teaching with visualisations offered outcomes that were not significantly different from teaching without visualisations, the study also explored differences in outcomes for male and female students, students with different learning styles (visual, aural, kinesthetic) and students of differing levels of academic ability.

One approach to finding evidence for the effectiveness of scientific visualisations in high school physics and chemistry education

Enormous amounts of money and energy are being devoted to the development, use and organisation of computer-based scientific visualisations (e.g. animations and simulations) in science education. It seems plausible that visualisations that enable students to gain visual access to scientific phenomena that are too large, too small or occur too quickly or too slowly to be seen by the naked eye, or to scientific concepts and models, would yield enhanced conceptual learning. When the literature is searched, however, it quickly becomes apparent that there is a dearth of quantitative evidence for the effectiveness of scientific visualisations in enhancing students’ learning of science concepts. This paper outlines an Australian project that is using innovative research methodology to gather evidence on this question in physics and chemistry classrooms.

Properties of lignin and poly(hydroxybutyrate) blends

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

Speckle reduction in optical coherence tomography imaging by affine-motion image registration

Signal-degrading speckle is one factor that can reduce the quality of optical coherence tomography images. We demonstrate the use of a hierarchical model-based motion estimation processing scheme based on an affine-motion model to reduce speckle in optical coherence tomography imaging, by image registration and the averaging of multiple B-scans. The proposed technique is evaluated against other methods available in the literature. The results from a set of retinal images show the benefit of the proposed technique, which provides an improvement in signal-to-noise ratio of the square root of the number of averaged images, leading to clearer visual information in the averaged image. The benefits of the proposed technique are also explored in the case of ocular anterior segment imaging.

Nanostructures for sensors, electronics, energy and environment

Nanoscale science is growing evermore important on a global scale and is widely seen as playing an integral part in the growth of future world economies. The daunting energy crisis we are facing could be solved not only by new and improved ways of getting energy directly from the sun, but also by saving power thanks to advancements in electronics and sensors. New, cheap dye-sensitized and polymer solar cells hold the promise of environmentally friendly and simple production methods, along with mechanical flexibility and low weight, matching the conditions for a widespread deployment of this technology. Cheap sensors based on nanomaterials can make a fundamental contribution to the reduction of greenhouse gas emissions, allowing the creation of large sensor networks to monitor countries and cities, improving our quality of life. Nanowires and nano-platelets of metal oxides are at the forefront of the research to improve sensitivity and reduce the power consumption in gas sensors. Nanoelectronics is the next step in the electronic roadmap, with many devices currently in production already containing components smaller than 100 nm. Molecules and conducting polymers are at the forefront of this research with the goal of reducing component size through the use of cheap and environmentally friendly production methods. This, and the coming steps that will eventually bring the individual circuit element close to the ultimate limit of the atomic level, are expected to deliver better devices with reduced power consumption.

Estimation of energy saving of commercial building by living wall and green facade in sub-tropical climate of Australia

This paper investigates energy saving potential of commercial building by living wall and green façade system using Envelope Thermal Transfer Value (ETTV) equation in Sub-tropical climate of Australia. Energy saving of four commercial buildings was quantified by applying living wall and green façade system to the west facing wall. A field experimental facility, from which temperature data of living wall system was collected, was used to quantify wall temperatures and heat gain under controlled conditions. The experimental parameters were accumulated with extensive data of existing commercial building to quantify energy saving. Based on temperature data of living wall system comprised of Australian native plants, equivalent temperature of living wall system has been computed. Then, shading coefficient of plants in green façade system has been included in mathematical equation and in graphical analysis. To minimize the air-conditioned load of commercial building, therefore to minimize the heat gain of commercial building, an analysis of building heat gain reduction by living wall and green façade system has been performed. Overall, cooling energy performance of commercial building before and after living wall and green façade system application has been examined. The quantified energy saving showed that only living wall system on opaque part of west facing wall can save 8-13 % of cooling energy consumption where as only green façade system on opaque part of west facing wall can save 9.5-18% cooling energy consumption of commercial building. Again, green façade system on fenestration system on west facing wall can save 28-35 % of cooling energy consumption where as combination of both living wall on opaque part of west facing wall and green façade on fenestration system on west facing wall can save 35-40% cooling energy consumption of commercial building in sub-tropical climate of Australia.

New perspectives on context-based chemistry education : using a dialectical sociocultural approach to view teaching and learning

Context-based chemistry education aims to improve student interest and motivation in chemistry by connecting canonical chemistry concepts with real-world contexts. Implementation of context-based chemistry programmes began 20 years ago in an attempt to make the learning of chemistry meaningful for students. This paper reviews such programmes through empirical studies on six international courses, ChemCom (USA), Salters (UK), Industrial Science (Israel), Chemie im Kontext (Germany), Chemistry in Practice (The Netherlands) and PLON (The Netherlands). These studies are categorised through emergent characteristics of: relevance, interest/attitudes motivation and deeper understanding. These characteristics can be found to an extent in a number of other curricular initiatives, such as science-technology-society approaches and problem-based learning or project based science, the latter of which often incorporates an inquiry-based approach to science education. These initiatives in science education are also considered with a focus on the characteristics of these approaches that are emphasised in context-based education. While such curricular studies provide a starting point for discussing context-based approaches in chemistry, to advance our understanding of how students connect canonical science concepts with the real-world context, a new theoretical framework is required. A dialectical sociocultural framework originating in the work of Vygotsky is used as a referent for analysing the complex human interactions that occur in context-based classrooms, providing teachers with recent information about the pedagogical structures and resources that afford students the agency to learn.

An investigation of building physical properties selection to combat global warming

Global warming can have a significant impact on building energy performance and indoor thermal environment, as well as the health and productivity of people living and working inside them. Through the building simulation technique, this paper investigates the adaptation potential of different selections of building physical properties to increased outdoor temperature in Australia. It is found that overall, an office building with lower insulation level, smaller window to wall ratio and/or a glass type with lower shading coefficient, and lower internal load density will have the effect of lowering building cooling load and total energy use, and therefore have a better potential to adapt to the warming external climate. Compared with clear glass, it is shown that the use of reflective glass for the sample building with WWR being 0.5 reduces the building cooling load by more than 12%. A lower internal load can also have a significant impact on the reduction of building cooling load, as well as the building energy use. Through the comparison of results between current and future weather scenarios, it is found that the patterns found in the current weather scenario also exist in the future weather scenarios, but to a smaller extent.