342 resultados para analytical approaches


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An analytical evaluation of the higher ac harmonic components derived from large amplitude Fourier transformed voltammetry is provided for the reversible oxidation of ferrocenemethanol (FcMeOH) and oxidation of uric acid by an EEC mechanism in a pH 7.4 phosphate buffer at a glassy carbon (GC) electrode. The small background current in the analytically optimal fifth harmonic is predominantly attributed to faradaic current associated with the presence of electroactive functional groups on the GC electrode surface, rather than to capacitive current which dominates the background in the dc, and the initial three ac harmonics. The detection limits for the dc and the first to fifth harmonic ac components are 1.9, 5.89, 2.1, 2.5, 0.8, and 0.5 µM for FcMeOH, respectively, using a sine wave modulation of 100 mV at 21.46 Hz and a dc sweep rate of 111.76 mV s−1. Analytical performance then progressively deteriorates in the sixth and higher harmonics. For the determination of uric acid, the capacitive background current was enhanced and the reproducibility lowered by the presence of surface active uric acid, but the rapid overall 2e− rather than 1e– electron transfer process gives rise to a significantly enhanced fifth harmonic faradaic current which enabled a detection limit of 0.3 µM to be achieved which is similar to that reported using chemically modified electrodes. Resolution of overlapping voltammetric signals for a mixture of uric acid and dopamine is also achieved using higher fourth or fifth harmonic components, under very low background current conditions. The use of higher fourth and fifth harmonics exhibiting highly favorable faradaic to background (noise) current ratios should therefore be considered in analytical applications under circumstances where the electron transfer rate is fast.

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This study was conducted within the context of a flexible education institution where conventional educational assessment practices and tests fail to recognise and assess the creativity and cultural capital of a cohort of marginalised young people. A new assessment model which included an electronic-portfolio-social-networking system (EPS) was developed and trialled to identify and exhibit evidence of students' learning. The study aimed to discern unique forms of cultural capital (Bourdieu, 1986) possessed by students who attend the Edmund Rice Education Australia Flexible Learning Centre Network (EREAFLCN). The EPS was trialled at the case study schools in an intervention and developed a space where students could make evident culturally specific forms of capital and funds of knowledge (Gonzalez, Moll, & Amanti, 2005). These resources were evaluated, modified and developed through dialogic processes utilising assessment for learning approaches (Qualifications and Curriculum Development Agency, 2009) in online and classroom settings. Students, peers and staff engaged in the recognition, judgement, revision and evaluation of students' cultural capital in a subfield of exchange (Bourdieu, 1990). The study developed the theory of assessment for learning as a field of exchange incorporating an online system as a teaching and assessment model. The term efield has been coined to describe this particular capital exchange model. A quasi-ethnographic approach was used to develop a collective case study (Stake, 1995). This case study involved an in-depth exploration of five students' forms of cultural capital and the ways in which this capital could be assessed and exchanged using the efield model. A comparative analysis of the five cases was conducted to identify the emergent issues of students' recognisable cultural capital resources and the processes of exchange that can be facilitated to acquire legitimate credentials for these students in the Australian field of education. The participants in the study were young people at two EREAFLC schools aged between 12 and 18 years. Data was collected through interviews, observations and examination of documents made available by the EREAFLCN. The data was coded and analysed using a theoretical framework based on Bourdieu's analytical tools and a sociocultural psychology theoretical perspective. Findings suggest that processes based on dialogic relationships can identify and recognise students' forms of cultural capital that are frequently misrecognised in mainstream school environments. The theory of assessment for learning as a field of exchange was developed into praxis and integrated in an intervention. The efield model was found to be an effective sociocultural tool in converting and exchanging students' capital resources for legitimated cultural and symbolic capital in the field of education.

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The recent advances in the understanding of the pathogenesis of ovarian cancer have been helpful in addressing issues in diagnosis, prognosis and management. The study of ovarian tumours by novel techniques such as immunohistochemistry, fluorescent in situ hybridisation, comparative genomic hybridisation, polymerase chain reaction and new tumour markers have aided the evaluation and application of new concepts into clinical practice. The correlation of novel surrogate tumour specific features with response to treatment and outcome in patients has defined prognostic factors which may allow the future design of tailored therapy based on a molecular profile of the tumour. These have also been used to design new approaches to therapy such as antibody targeting and gene therapy. The delineation of roles of c-erbB2, c-fms and other novel receptor kinases in the pathogenesis of ovarian cancer has led initially to the development of anti-c-erbB2 monoclonal antibody therapy. The discovery of BRCA1 and BRCA2 genes will have an impact in the diagnosis and the prevention of familial ovarian cancer. The important role played by recessive genes such as p53 in cancer has raised the possibility of restoration of gene function by gene therapy. Although the pathological diagnosis of ovarian cancer is still confirmed principally on morphological features, addition of newer investigations will increasingly be useful in addressing difficult diagnostic problems. The increasingly rapid pace of discovery of genes important in disease, makes it imperative that the evaluation of their contribution in the pathogenesis of ovarian cancer is undertaken swiftly, thus improving the overall management of patients and their outcome.

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Fossils and sediments preserved in caves are an excellent source of information for investigating impacts of past environmental changes on biodiversity. Until recently studies have relied on morphology-based palaeontological approaches, but recent advances in molecular analytical methods offer excellent potential for extracting a greater array of biological information from these sites. This study presents a thorough assessment of DNA preservation from late Pleistocene–Holocene vertebrate fossils and sediments from Kelly Hill Cave Kangaroo Island, South Australia. Using a combination of extraction techniques and sequencing technologies, ancient DNA was characterised from over 70 bones and 20 sediment samples from 15 stratigraphic layers ranging in age from >20 ka to ∼6.8 ka. A combination of primers targeting marsupial and placental mammals, reptiles and two universal plant primers were used to reveal genetic biodiversity for comparison with the mainland and with the morphological fossil record for Kelly Hill Cave. We demonstrate that Kelly Hill Cave has excellent long-term DNA preservation, back to at least 20 ka. This contrasts with the majority of Australian cave sites thus far explored for ancient DNA preservation, and highlights the great promise Kangaroo Island caves hold for yielding the hitherto-elusive DNA of extinct Australian Pleistocene species.

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Learning science through the process of inquiry is advocated in curriculum documents across many jurisdictions. However, a number of studies suggest that teachers struggle to help students engage in inquiry practices. This is not surprising as many teachers of science have not engaged in scientific inquiry and possibly hold naïve ideas about what constitutes scientific inquiry. This study investigates teachers’ self-reported approaches to teaching science through inquiry. Phenomenographic interviews undertaken with 20 elementary teachers revealed teachers identified six approaches to teaching for inquiry, clustered within three categories. These approaches were categorized as Free and Illustrated Inquiry as part of experience-centered category, Solution and Method Inquiry as part of problem-centered category, and Topic and Chaperoned Inquiry as part of a question-centered category. This study contributes to our theoretical understanding of how teachers approach Inquiry Teaching, and suggests fertile areas of future research into this valued and influential phenomenon broadly known as “Inquiry Teaching”.

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Forming peer alliances to share and build knowledge is an important aspect of community arts practice, and these co-creation processes are increasingly being mediated by the internet. This paper offers guidance for practitioners who are interested in better utilising the internet to connect, share, and make new knowledge. It argues that new approaches are required to foster the organising activities that underpin online co-creation, building from the premise that people have become increasingly networked as individuals rather than in groups (Rainie and Wellman 2012: 6), and that these new ways of connecting enable new modes of peer-to-peer production and exchange. This position advocates that practitioners move beyond situating the internet as a platform for dissemination and a tool for co-creating media, to embrace its knowledge collaboration potential. Drawing on a design experiment I developed to promote online knowledge co-creation, this paper suggests three development phases – developing connections, developing ideas, and developing agility – to ground six methods. They are: switching and routing, engaging in small trades of ideas with networked individuals; organising, co-ordinating networked individuals and their data; beta-release, offering ‘beta’ artifacts as knowledge trades; beta-testing, trialing and modifying other peoples ‘beta’ ideas; adapting, responding to technological disruption; and, reconfiguring, embracing opportunities offered by technological disruption. These approaches position knowledge co-creation as another capability of the community artist, along with co-creating art and media.

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The studies presented in this review explore three distinct areas with potential for inhibiting HIV infection in women. Based on emerging information from the physiology, endocrinology and immunology of the female reproductive tract (FRT), we propose unique 'works in progress' for protecting women from HIV. Various aspects of FRT immunity are suppressed by estradiol during the menstrual cycle, making women more susceptible to HIV infection. By engineering commensal Lactobacillus to secrete the anti-HIV molecule Elafin as estradiol levels increase, women could be protected from HIV infection. Selective estrogen response modifiers enhance barrier integrity and enhance secretion of protective anti-HIV molecules. Finally, understanding the interactions and regulation of FRT endogenous antimicrobials, proteases, antiproteases, etc., all of which are under hormonal control, will open new avenues to therapeutic manipulation of the FRT mucosal microenvironment. By seeking new alternatives to preventing HIV infection in women, we may finally disrupt the HIV pandemic.

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There are a number of pressing issues facing contemporary online environments that are causing disputes among participants and platform operators and increasing the likelihood of external regulation. A number of solutions have been proposed, including industry self-governance, top-down regulation and emergent self-governance such as EVE Online’s “Council of Stellar Management”. However, none of these solutions seem entirely satisfying; facing challenges from developers who fear regulators will not understand their platforms, or players who feel they are not sufficiently empowered to influence the platform, while many authors have raised concerns over the implementation of top-down regulation, and why the industry may be well-served to pre-empt such action. This paper considers case studies of EVE Online and the offshore gambling industry, and whether a version of self-governance may be suitable for the future of the industry.

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There is currently a wide range of research into the recent introduction of student response systems in higher education and tertiary settings (Banks 2006; Kay and Le Sange, 2009; Beatty and Gerace 2009; Lantz 2010; Sprague and Dahl 2009). However, most of this pedagogical literature has generated ‘how to’ approaches regarding the use of ‘clickers’, keypads, and similar response technologies. There are currently no systematic reviews on the effectiveness of ‘GoSoapBox’ – a more recent, and increasingly popular student response system – for its capacity to enhance critical thinking, and achieve sustained learning outcomes. With rapid developments in teaching and learning technologies across all undergraduate disciplines, there is a need to obtain comprehensive, evidence-based advice on these types of technologies, their uses, and overall efficacy. This paper addresses this current gap in knowledge. Our teaching team, in an undergraduate Sociology and Public Health unit at the Queensland University of Technology (QUT), introduced GoSoapBox as a mechanism for discussing controversial topics, such as sexuality, gender, economics, religion, and politics during lectures, and to take opinion polls on social and cultural issues affecting human health. We also used this new teaching technology to allow students to interact with each other during class – both on both social and academic topics – and to generate discussions and debates during lectures. The paper reports on a data-driven study into how this interactive online tool worked to improve engagement and the quality of academic work produced by students. This paper will firstly, cover the recent literature reviewing student response systems in tertiary settings. Secondly, it will outline the theoretical framework used to generate this pedagogical research. In keeping with the social and collaborative features of Web 2.0 technologies, Bandura’s Social Learning Theory (SLT) will be applied here to investigate the effectiveness of GoSoapBox as an online tool for improving learning experiences and the quality of academic output by students. Bandura has emphasised the Internet as a tool for ‘self-controlled learning’ (Bandura 2001), as it provides the education sector with an opportunity to reconceptualise the relationship between learning and thinking (Glassman & Kang 2011). Thirdly, we describe the methods used to implement the use of GoSoapBox in our lectures and tutorials, and which aspects of the technology we drew on for learning purposes, as well as the methods for obtaining feedback from the students about the effectiveness or otherwise of this tool. Fourthly, we report cover findings from an examination of all student/staff activity on GoSoapBox as well as reports from students about the benefits and limitations of it as a learning aid. We then display a theoretical model that is produced via an iterative analytical process between SLT and our data analysis for use by academics and teachers across the undergraduate curriculum. The model has implications for all teachers considering the use of student response systems to improve the learning experiences of their students. Finally, we consider some of the negative aspects of GoSoapBox as a learning aid.

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In the 21st century, it has become apparent that ‘knowledge’ is a major factor of postmodern production (Yigitcanlar et al., 2007). Beyond this, in today’s rapidly globalizing world, knowledge, along with the social and technological settings, is seen as a key to secure economic prosperity and quality of life (Yigitcanlar et al., 2008a). However, limiting the benefits of a ‘knowledge-based development’ to only economic gains—and to a degree to social ones—is quite a narrow sighted view (Yigitcanlar et al., 2008b). Thus, the concept of ‘knowledge-based urban development’ is coined to bring economic prosperity, environmental sustainability, a just socio-spatial order and good governance to cities, and as a result producing a purposefully designed city—i.e., ‘knowledge city’—generating positive environmental and governance outcomes as well as economic and societal ones (Yigitcanlar, 2011; Carrillo et al., 2014).

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How to live sustainably is a topic of local, national and international importance. The Australian National Curriculum (ACARA, 2011) identifies sustainability as a cross-disciplinary strand, obligating teachers to build sustainability into their pedagogical practices. In early childhood education, the Early Years Learning Framework (2009) and more recently, the National Quality Framework (2011) provide impetus for early childhood education for sustainably (ECEfS). This article discusses ECEfS, but first, it addresses climate change putting this into a sustainability perspective.

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Arachidonic acid metabolism through cyclooxygenase (COX), lipoxygenase (LOX) and cytochrome P-450 epoxygenase (EPOX) pathways is responsible for the formation of biologically active eicosanoids, including prostanoids, leukotrienes, hydroxyeicosatetraenoic acid, epoxyeicosatrienoic acid and hydroperoxyeicosatetraenoic acids. Altered eicosanoid expression levels are commonly observed during tumour development and progression of a range of malignancies, including non-small cell lung cancer (NSCLC). Arachidonic acid-derived eicosanoids affect a range of biological phenomena to modulate tumour processes such as cell growth, survival, angiogenesis, cell adhesion, invasion and migration and metastatic potential. Numerous studies have demonstrated that eicosanoids modulate NSCLC development and progression, while targeting these pathways has generally been shown to inhibit tumour growth/progression. Modulation of these arachidonic acid-derived pathways for the prevention and/or treatment of NSCLC has been the subject of significant interest over the past number of years, with a number of clinical trials examining the potential of COX and LOX inhibitors in combination with traditional and novel molecular approaches. However, results from these trials have been largely disappointing. Furthermore, enthusiasm for the use of selective COX-2 inhibitors for cancer prevention/treatment waned, due to their association with adverse cardiovascular events in chemoprevention trials. While COX and LOX targeting may both retain promise for NSCLC prevention and/or treatment, there is an urgent need to understand the downstream signalling mechanisms through which these and other arachidonic acid-derived signalling pathways mediate their effects on tumourigenesis. This will allow for development of safer and potentially more effective strategies for NSCLC prevention and/or treatment. Chemoprevention studies with PGI2 analogues have demonstrated considerable promise, while binding to/signalling through PGE2 receptors have also been the subject of interest for NSCLC treatment. In this chapter, the role of the eicosanoid signalling pathways in non-small cell lung cancer will be discussed. In particular, the effect of the eicosanoids on tumour cell proliferation, their roles in induction of cell death, effects on angiogenesis, migration, invasion and their regulation of the immune response will be assessed, with signal transduction pathways involved in these processes also discussed. Finally, novel approaches targeting these arachidonic acid-derived eicosanoids (using pharmacological or natural agents) for chemoprevention and/or treatment of NSCLC will be outlined. Elucidating the molecular mechanisms underlying the effects of specific or general arachidonic acid pathway modulators may lead to the design of biologically and pharmacologically targeted therapeutic strategies for NSCLC prevention/treatment, which may be used alone or in combination with conventional therapies.

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This thesis considers and evaluates different approaches to regulating online gaming communities, including traditional top-down regulation, as well as bottom-up and hybrid forms led by participants. I examine the regulatory environment in both the video game and gambling industries through case studies of the science fiction, massively multiplayer game Eve Online and offshore gambling platforms and their community sites. I identify that the participant driven approach to regulation sometimes used in the offshore gambling industry was dependent on a number of factors, notably the strength of the community and the risks to platform operators of negative publicity. By subsequently comparing this to the video gaming industry, I suggest that participant driven processes may be an appropriate way to resolve disputes in the games industry, and show how these are – to a limited extent – already being applied.

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Recent expansion in research in the field of lipidomics has been driven by the development of new mass spectrometric tools and protocols for the identification and quantification of molecular lipids in complex matrices. Although there are similarities between the field of lipidomics and the allied field of mass spectrometry (e.g., proteomics), lipids present some unique advantages and challenges for mass spectrometric analysis. The application of electrospray ionization to crude lipid extracts without prior fractionation-the so-called shotgun approach-is one such example, as it has perhaps been more successfully applied in lipidomics than in any other discipline. Conversely, the diverse molecular structure of lipids means that collision-induced dissociation alone may be limited in providing unique descriptions of complex lipid structures, and the development of additional, complementary tools for ion activation and analysis is required to overcome these challenges. In this article, we discuss the state of the art in lipid mass spectrometry and highlight several areas in which current approaches are deficient and further innovation is required.

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Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl] benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation. © 2014 the Owner Societies.