957 resultados para NICKEL(II)-BASED CATALYSTS


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This paper is a continuation of the paper titled “Concurrent multi-scale modeling of civil infrastructure for analyses on structural deteriorating—Part I: Modeling methodology and strategy” with the emphasis on model updating and verification for the developed concurrent multi-scale model. The sensitivity-based parameter updating method was applied and some important issues such as selection of reference data and model parameters, and model updating procedures on the multi-scale model were investigated based on the sensitivity analysis of the selected model parameters. The experimental modal data as well as static response in terms of component nominal stresses and hot-spot stresses at the concerned locations were used for dynamic response- and static response-oriented model updating, respectively. The updated multi-scale model was further verified to act as the baseline model which is assumed to be finite-element model closest to the real situation of the structure available for the subsequent arbitrary numerical simulation. The comparison of dynamic and static responses between the calculated results by the final model and measured data indicated the updating and verification methods applied in this paper are reliable and accurate for the multi-scale model of frame-like structure. The general procedures of multi-scale model updating and verification were finally proposed for nonlinear physical-based modeling of large civil infrastructure, and it was applied to the model verification of a long-span bridge as an actual engineering practice of the proposed procedures.

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INTRODUCTION In their target article, Yuri Hanin and Muza Hanina outlined a novel multidisciplinary approach to performance optimisation for sport psychologists called the Identification-Control-Correction (ICC) programme. According to the authors, this empirically-verified, psycho-pedagogical strategy is designed to improve the quality of coaching and consistency of performance in highly skilled athletes and involves a number of steps including: (i) identifying and increasing self-awareness of ‘optimal’ and ‘non-optimal’ movement patterns for individual athletes; (ii) learning to deliberately control the process of task execution; and iii), correcting habitual and random errors and managing radical changes of movement patterns. Although no specific examples were provided, the ICC programme has apparently been successful in enhancing the performance of Olympic-level athletes. In this commentary, we address what we consider to be some important issues arising from the target article. We specifically focus attention on the contentious topic of optimization in neurobiological movement systems, the role of constraints in shaping emergent movement patterns and the functional role of movement variability in producing stable performance outcomes. In our view, the target article and, indeed, the proposed ICC programme, would benefit from a dynamical systems theoretical backdrop rather than the cognitive scientific approach that appears to be advocated. Although Hanin and Hanina made reference to, and attempted to integrate, constructs typically associated with dynamical systems theoretical accounts of motor control and learning (e.g., Bernstein’s problem, movement variability, etc.), these ideas required more detailed elaboration, which we provide in this commentary.

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The automatic extraction of road features from remote sensed images has been a topic of great interest within the photogrammetric and remote sensing communities for over 3 decades. Although various techniques have been reported in the literature, it is still challenging to efficiently extract the road details with the increasing of image resolution as well as the requirement for accurate and up-to-date road data. In this paper, we will focus on the automatic detection of road lane markings, which are crucial for many applications, including lane level navigation and lane departure warning. The approach consists of four steps: i) data preprocessing, ii) image segmentation and road surface detection, iii) road lane marking extraction based on the generated road surface, and iv) testing and system evaluation. The proposed approach utilized the unsupervised ISODATA image segmentation algorithm, which segments the image into vegetation regions, and road surface based only on the Cb component of YCbCr color space. A shadow detection method based on YCbCr color space is also employed to detect and recover the shadows from the road surface casted by the vehicles and trees. Finally, the lane marking features are detected from the road surface using the histogram clustering. The experiments of applying the proposed method to the aerial imagery dataset of Gympie, Queensland demonstrate the efficiency of the approach.

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Over the past decade, plants have been used as expression hosts for the production of pharmaceutically important and commercially valuable proteins. Plants offer many advantages over other expression systems such as lower production costs, rapid scale up of production, similar post-translational modification as animals and the low likelihood of contamination with animal pathogens, microbial toxins or oncogenic sequences. However, improving recombinant protein yield remains one of the greatest challenges to molecular farming. In-Plant Activation (InPAct) is a newly developed technology that offers activatable and high-level expression of heterologous proteins in plants. InPAct vectors contain the geminivirus cis elements essential for rolling circle replication (RCR) and are arranged such that the gene of interest is only expressed in the presence of the cognate viral replication-associated protein (Rep). The expression of Rep in planta may be controlled by a tissue-specific, developmentally regulated or chemically inducible promoter such that heterologous protein accumulation can be spatially and temporally controlled. One of the challenges for the successful exploitation of InPAct technology is the control of Rep expression as even very low levels of this protein can reduce transformation efficiency, cause abnormal phenotypes and premature activation of the InPAct vector in regenerated plants. Tight regulation over transgene expression is also essential if expressing cytotoxic products. Unfortunately, many tissue-specific and inducible promoters are unsuitable for controlling expression of Rep due to low basal activity in the absence of inducer or in tissues other than the target tissue. This PhD aimed to control Rep activity through the production of single chain variable fragments (scFvs) specific to the motif III of Tobacco yellow dwarf virus (TbYDV) Rep. Due to the important role played by the conserved motif III in the RCR, it was postulated that such scFvs can be used to neutralise the activity of the low amount of Rep expressed from a “leaky” inducible promoter, thus preventing activation of the TbYDV-based InPAct vector until intentional induction. Such scFvs could also offer the potential to confer partial or complete resistance to TbYDV, and possibly heterologous viruses as motif III is conserved between geminiviruses. Studies were first undertaken to determine the levels of TbYDV Rep and TbYDV replication-associated protein A (RepA) required for optimal transgene expression from a TbYDV-based InPAct vector. Transient assays in a non-regenerable Nicotiana tabacum (NT-1) cell line were undertaken using a TbYDV-based InPAct vector containing the uidA reporter gene (encoding GUS) in combination with TbYDV Rep and RepA under the control of promoters with high (CaMV 35S) or low (Banana bunchy top virus DNA-R, BT1) activity. The replication enhancer protein of Tomato leaf curl begomovirus (ToLCV), REn, was also used in some co-bombardment experiments to examine whether RepA could be substituted by a replication enhancer from another geminivirus genus. GUS expression was observed both quantitatively and qualitatively by fluorometric and histochemical assays, respectively. GUS expression from the TbYDV-based InPAct vector was found to be greater when Rep was expected to be expressed at low levels (BT1 promoter) rather than high levels (35S promoter). GUS expression was further enhanced when Rep and RepA were co-bombarded with a low ratio of Rep to RepA. Substituting TbYDV RepA with ToLCV REn also enhanced GUS expression but more importantly highest GUS expression was observed when cells were co-transformed with expression vectors directing low levels of Rep and high levels of RepA irrespective of the level of REn. In this case, GUS expression was approximately 74-fold higher than that from a non-replicating vector. The use of different terminators, namely CaMV 35S and Nos terminators, in InPAct vectors was found to influence GUS expression. In the presence of Rep, GUS expression was greater using pInPActGUS-Nos rather than pInPActGUS-35S. The only instance of GUS expression being greater from vectors containing the 35S terminator was when comparing expression from cells transformed with Rep, RepA and REnexpressing vectors and either non-replicating vectors, p35SGS-Nos or p35SGS-35S. This difference was most likely caused by an interaction of viral replication proteins with each other and the terminators. These results indicated that (i) the level of replication associated proteins is critical to high transgene expression, (ii) the choice of terminator within the InPAct vector may affect expression levels and (iii) very low levels of Rep can activate InPAct vectors hence controlling its activity is critical. Prior to generating recombinant scFvs, a recombinant TbYDV Rep was produced in E. coli to act as a control to enable the screening for Rep-specific antibodies. A bacterial expression vector was constructed to express recombinant TbYDV Rep with an Nterminal His-tag (N-His-Rep). Despite investigating several purification techniques including Ni-NTA, anion exchange, hydrophobic interaction and size exclusion chromatography, N-His-Rep could only be partially purified using a Ni-NTA column under native conditions. Although it was not certain that this recombinant N-His-Rep had the same conformation as the native TbYDV Rep and was functional, results from an electromobility shift assay (EMSA) showed that N-His-Rep was able to interact with the TbYDV LIR and was, therefore, possibly functional. Two hybridoma cell lines from mice, immunised with a synthetic peptide containing the TbYDV Rep motif III amino acid sequence, were generated by GenScript (USA). Monoclonal antibodies secreted by the two hybridoma cell lines were first screened against denatured N-His-Rep in Western analysis. After demonstrating their ability to bind N-His-Rep, two scFvs (scFv1 and scFv2) were generated using a PCR-based approach. Whereas the variable heavy chain (VH) from both cell lines could be amplified, only the variable light chain (VL) from cell line 2 was amplified. As a result, scFv1 contained VH and VL from cell line 1, whereas scFv2 contained VH from cell line 2 and VL from cell line 1. Both scFvs were first expressed in E. coli in order to evaluate their affinity to the recombinant TbYDV N-His-Rep. The preliminary results demonstrated that both scFvs were able to bind to the denatured N-His-Rep. However, EMSAs revealed that only scFv2 was able to bind to native N-His-Rep and prevent it from interacting with the TbYDV LIR. Each scFv was cloned into plant expression vectors and co-bombarded into NT-1 cells with the TbYDV-based InPAct GUS expression vector and pBT1-Rep to examine whether the scFvs could prevent Rep from mediating RCR. Although it was expected that the addition of the scFvs would result in decreased GUS expression, GUS expression was found to slightly increase. This increase was even more pronounced when the scFvs were targeted to the cell nucleus by the inclusion of the Simian virus 40 large T antigen (SV40) nuclear localisation signal (NLS). It was postulated that the scFvs were binding to a proportion of Rep, leaving a small amount available to mediate RCR. The outcomes of this project provide evidence that very high levels of recombinant protein can theoretically be expressed using InPAct vectors with judicious selection and control of viral replication proteins. However, the question of whether the scFvs generated in this project have sufficient affinity for TbYDV Rep to prevent its activity in a stably transformed plant remains unknown. It may be that other scFvs with different combinations of VH and VL may have greater affinity for TbYDV Rep. Such scFvs, when expressed at high levels in planta, might also confer resistance to TbYDV and possibly heterologous geminiviruses.

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The inquiry documented in this thesis is located at the nexus of technological innovation and traditional schooling. As we enter the second decade of a new century, few would argue against the increasingly urgent need to integrate digital literacies with traditional academic knowledge. Yet, despite substantial investments from governments and businesses, the adoption and diffusion of contemporary digital tools in formal schooling remain sluggish. To date, research on technology adoption in schools tends to take a deficit perspective of schools and teachers, with the lack of resources and teacher ‘technophobia’ most commonly cited as barriers to digital uptake. Corresponding interventions that focus on increasing funding and upskilling teachers, however, have made little difference to adoption trends in the last decade. Empirical evidence that explicates the cultural and pedagogical complexities of innovation diffusion within long-established conventions of mainstream schooling, particularly from the standpoint of students, is wanting. To address this knowledge gap, this thesis inquires into how students evaluate and account for the constraints and affordances of contemporary digital tools when they engage with them as part of their conventional schooling. It documents the attempted integration of a student-led Web 2.0 learning initiative, known as the Student Media Centre (SMC), into the schooling practices of a long-established, high-performing independent senior boys’ school in urban Australia. The study employed an ‘explanatory’ two-phase research design (Creswell, 2003) that combined complementary quantitative and qualitative methods to achieve both breadth of measurement and richness of characterisation. In the initial quantitative phase, a self-reported questionnaire was administered to the senior school student population to determine adoption trends and predictors of SMC usage (N=481). Measurement constructs included individual learning dispositions (learning and performance goals, cognitive playfulness and personal innovativeness), as well as social and technological variables (peer support, perceived usefulness and ease of use). Incremental predictive models of SMC usage were conducted using Classification and Regression Tree (CART) modelling: (i) individual-level predictors, (ii) individual and social predictors, and (iii) individual, social and technological predictors. Peer support emerged as the best predictor of SMC usage. Other salient predictors include perceived ease of use and usefulness, cognitive playfulness and learning goals. On the whole, an overwhelming proportion of students reported low usage levels, low perceived usefulness and a lack of peer support for engaging with the digital learning initiative. The small minority of frequent users reported having high levels of peer support and robust learning goal orientations, rather than being predominantly driven by performance goals. These findings indicate that tensions around social validation, digital learning and academic performance pressures influence students’ engagement with the Web 2.0 learning initiative. The qualitative phase that followed provided insights into these tensions by shifting the analytics from individual attitudes and behaviours to shared social and cultural reasoning practices that explain students’ engagement with the innovation. Six indepth focus groups, comprising 60 students with different levels of SMC usage, were conducted, audio-recorded and transcribed. Textual data were analysed using Membership Categorisation Analysis. Students’ accounts converged around a key proposition. The Web 2.0 learning initiative was useful-in-principle but useless-in-practice. While students endorsed the usefulness of the SMC for enhancing multimodal engagement, extending peer-topeer networks and acquiring real-world skills, they also called attention to a number of constraints that obfuscated the realisation of these design affordances in practice. These constraints were cast in terms of three binary formulations of social and cultural imperatives at play within the school: (i) ‘cool/uncool’, (ii) ‘dominant staff/compliant student’, and (iii) ‘digital learning/academic performance’. The first formulation foregrounds the social stigma of the SMC among peers and its resultant lack of positive network benefits. The second relates to students’ perception of the school culture as authoritarian and punitive with adverse effects on the very student agency required to drive the innovation. The third points to academic performance pressures in a crowded curriculum with tight timelines. Taken together, findings from both phases of the study provide the following key insights. First, students endorsed the learning affordances of contemporary digital tools such as the SMC for enhancing their current schooling practices. For the majority of students, however, these learning affordances were overshadowed by the performative demands of schooling, both social and academic. The student participants saw engagement with the SMC in-school as distinct from, even oppositional to, the conventional social and academic performance indicators of schooling, namely (i) being ‘cool’ (or at least ‘not uncool’), (ii) sufficiently ‘compliant’, and (iii) achieving good academic grades. Their reasoned response therefore, was simply to resist engagement with the digital learning innovation. Second, a small minority of students seemed dispositionally inclined to negotiate the learning affordances and performance constraints of digital learning and traditional schooling more effectively than others. These students were able to engage more frequently and meaningfully with the SMC in school. Their ability to adapt and traverse seemingly incommensurate social and institutional identities and norms is theorised as cultural agility – a dispositional construct that comprises personal innovativeness, cognitive playfulness and learning goals orientation. The logic then is ‘both and’ rather than ‘either or’ for these individuals with a capacity to accommodate both learning and performance in school, whether in terms of digital engagement and academic excellence, or successful brokerage across multiple social identities and institutional affiliations within the school. In sum, this study takes us beyond the familiar terrain of deficit discourses that tend to blame institutional conservatism, lack of resourcing and teacher resistance for low uptake of digital technologies in schools. It does so by providing an empirical base for the development of a ‘third way’ of theorising technological and pedagogical innovation in schools, one which is more informed by students as critical stakeholders and thus more relevant to the lived culture within the school, and its complex relationship to students’ lives outside of school. It is in this relationship that we find an explanation for how these individuals can, at the one time, be digital kids and analogue students.

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Road features extraction from remote sensed imagery has been a long-term topic of great interest within the photogrammetry and remote sensing communities for over three decades. The majority of the early work only focused on linear feature detection approaches, with restrictive assumption on image resolution and road appearance. The widely available of high resolution digital aerial images makes it possible to extract sub-road features, e.g. road pavement markings. In this paper, we will focus on the automatic extraction of road lane markings, which are required by various lane-based vehicle applications, such as, autonomous vehicle navigation, and lane departure warning. The proposed approach consists of three phases: i) road centerline extraction from low resolution image, ii) road surface detection in the original image, and iii) pavement marking extraction on the generated road surface. The proposed method was tested on the aerial imagery dataset of the Bruce Highway, Queensland, and the results demonstrate the efficiency of our approach.

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The unusual (1:1) complex ‘adduct’ salt of copper(II) with 4,5-dichlorophthalic acid (H2DCPA), having formula [Cu(H2O)4(C8H3Cl2O4) (C8H4Cl2O4)] . (C8H3Cl2O4) has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P21/c, with Z = 4 in a cell with dimensions a = 20.1376(7), b =12.8408(4) c = 12.1910(4) Å, β = 105.509(4)o. The complex is based on discrete tetragonally distorted octahedral [CuO6] coordination centres with the four water ligands occupying the square planar sites [Cu-O, 1.962(4)-1.987(4) Å] and the monodentate carboxyl-O donors of two DCPA ligand species in the axial sites. The first of these bonds [Cu-O, 2.341(4) Å] is with an oxygen of a HDCPA monoanion, the second with an oxygen of a H2DCPA acid species [Cu-O, 2.418(4) Å]. The un-coordinated ‘adduct’ molecule is a HDCPA counter anion which is strongly hydrogen-bonded to the coordinated H2DCPA ligand [O… O, 2.503(6) Å] while a number of peripheral intra- and intermolecular hydrogen-bonding interactions give a two-dimensional network structure.

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The notion of pedagogy for anyone in the teaching profession is innocuous. The term itself, is steeped in history but the details of the practice can be elusive. What does it mean for an academic to be embracing pedagogy? The problem is not limited to academics; most teachers baulk at the introduction of a pedagogic agenda and resist attempts to have them reflect on their classroom teaching practice, where ever that classroom might be constituted. This paper explores the application of a pedagogic model (Education Queensland, 2001) which was developed in the context of primary and secondary teaching and was part of a schooling agenda to improve pedagogy. As a teacher educator I introduced the model to classroom teachers (Hill, 2002) using an Appreciative Inquiry (Cooperrider and Srivastva 1987) model and at the same time applied the model to my own pedagogy as an academic. Despite being instigated as a model for classroom teachers, I found through my own practitioner investigation that the model was useful for exploring my own pedagogy as a university academic (Hill, 2007, 2008). Cooperrider, D.L. and Srivastva, S. (1987) Appreciative inquiry in organisational life, in Passmore, W. and Woodman, R. (Eds) Research in Organisational Changes and Development (Vol 1) Greenwich, CT: JAI Press. Pp 129-69 Education Queensland (2001) School Reform Longitudinal Study (QSRLS), Brisbane, Queensland Government. Hill, G. (2002, December ) Reflecting on professional practice with a cracked mirror: Productive Pedagogy experiences. Australian Association for Research in Education Conference. Brisbane, Australia. Hill, G. (2007) Making the assessment criteria explicit through writing feedback: A pedagogical approach to developing academic writing. International Journal of Pedagogies and Learning 3(1), 59-66. Hill, G. (2008) Supervising Practice Based Research. Studies in Learning, Evaluation, Innovation and Development, 5(4), 78-87

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Mesenchymal Stem Cells (MSC) are frequently incorporated into osteochondral implants and cell seeding is often facilitated with hydrogels which exert a profound influence on the chondrogenic differentiation of MSC. An attempt was made to elucidate this effect by comparing the chondrogenic differentiation of Bone Marrow Stromal Cells (BMSC) in fibrin and fibrin alginate composites. A biphasic osteochondral model which simulated the native in vivo environment was employed in the study. In the first stage of the experiment, BMSC was encapsulated in fibrin, Fibrin Alginate 0.3% (FA0.3) and 0.6% (FA0.6). Chondrogenic differentiation within these cell-hydrogel pellets was compared against that of standard cell pellets under inductive conditions and the matrices which supported chondrogenesis were used in the cartilage phase of biphasic constructs. Neo-cartilage growth was monitored in these cocultures. It was observed that hydrogel encapsulation influenced mesenchymal condensation which preceded chondrogenic differentiation. Early cell agglomeration was observed in fibrin as compared to fibrin alginate composites. These fibrin encapsulated cells differentiated into chondrocytes which secreted aggrecan and collagen II. When the alginate content rose from 0.3 to 0.6%, chondrogenic differentiation declined with a reduction in the expression of collagen II and aggrecan. Fibrin and FA0.3 were tested in the cartilage phase of the biphasic osteochondral constructs and the former supported superior cartilage growth with higher cellularity, total Glycosaminoglycan (GAG) and collagen II levels. The FA0.3 cartilage phase was found to be fragmented and partially calcified. The use of fibrin for cartilage repair was advocated as it facilitated BMSC chondrogenesis and cartilaginous growth in an osteochondral environment.

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The concept of sustainable urban development has been pushed to the forefront of policy-making and politics as the world wakes up to the impacts of climate change and the effects of modern urban lifestyles. Today, sustainable development has become a very prominent element in the day-to-day debate on urban policy and the expression of that policy in urban planning and development decisions. As a result of this, during the last few years, sustainable development automation applications such as sustainable urban development decision support systems have become popular tools as they offer new opportunities for local governments to realise their sustainable development agendas. This chapter explores a range of issues associated with the application of information and communication technologies and decision support systems in the process of underpinning sustainable urban development. The chapter considers how information and communication technologies can be applied to enhance urban planning, raise environmental awareness, share decisions and improve public participation. It introduces and explores three web-based geographical information systems projects as best practice. These systems are developed as support tools to include public opinion in the urban planning and development processes, and to provide planners with comprehensive tools for the analysis of sustainable urban development variants in order to prepare the best plans for constructing sustainable urban communities and futures.

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In this paper, we presented an automatic system for precise urban road model reconstruction based on aerial images with high spatial resolution. The proposed approach consists of two steps: i) road surface detection and ii) road pavement marking extraction. In the first step, support vector machine (SVM) was utilized to classify the images into two categories: road and non-road. In the second step, road lane markings are further extracted on the generated road surface based on 2D Gabor filters. The experiments using several pan-sharpened aerial images of Brisbane, Queensland have validated the proposed method.

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Dry powder inhaler (DPI) formulations is one of the most useful aerosol preparations in which drugs may be formulated as carrier-based interactive mixtures with micronised drug particles (<5 μm) adhered onto the surface of large inert carriers (lactose powders). The addition of magnesium stearate (MgSt) (1-3), was found to increase dispersion of various drugs from DPI formulations. Recently, some active compounds coated with 5% (wt/wt) MgSt using the mechanofusion method showed significant improvements in aerosolization behavior due to the reduction in intrinsic cohesion force (4). Application of MgSt in powder formulations is not new; however, no studies demonstrated the minimum threshold level for this excipient in efficient aerosolization of drug powders from the interactive mixtures. Therefore, this study investigated the role of MgSt concentration on the efficient dispersion of salbutamol sulphate (SS) from DPI formulations.

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This review collects and summarises the biological applications of the element cobalt. Small amounts of the ferromagnetic metal can be found in rock, soil, plants and animals, but is mainly obtained as a by-product of nickel and copper mining, and is separated from the ores (mainly cobaltite, erythrite, glaucodot and skutterudite) using a variety of methods. Compounds of cobalt include several oxides, including: green cobalt(II) (CoO), blue cobalt(II,III) (Co3O4), and black cobalt(III) (Co2O3); four halides including pink cobalt(II) fluoride (CoF2), blue cobalt(II) chloride (CoCl2), green cobalt(II) bromide (CoBr2), and blue-black cobalt(II) iodide (CoI2). The main application of cobalt is in its metal form in cobalt-based super alloys, though other uses include lithium cobalt oxide batteries, chemical reaction catalyst, pigments and colouring, and radioisotopes in medicine. It is known to mimic hypoxia on the cellular level by stabilizing the α subunit of hypoxia inducing factor (HIF), when chemically applied as cobalt chloride (CoCl2). This is seen in many biological research applications, where it has shown to promote angiogenesis, erythropoiesis and anaerobic metabolism through the transcriptional activation of genes such as vascular endothelial growth factor (VEGF) and erythropoietin (EPO), contributing significantly to the pathophysiology of major categories of disease, such as myocardial, renal and cerebral ischaemia, high altitude related maladies and bone defects. As a necessary constituent for the formation of vitamin B12, it is essential to all animals, including humans, however excessive exposure can lead to tissue and cellular toxicity. Cobalt has been shown to provide promising potential in clinical applications, however further studies are necessary to clarify its role in hypoxia-responsive genes and the applications of cobalt-chloride treated tissues.

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The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrite(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites studied have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations based upon CRTA measurements show that 7 moles of water is lost, proving the formula of hexacyanoferrite(II) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.5 .7 H2O and for the hexacyanoferrate(III) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.66 * 9 H2O. Dehydroxylation combined with CN unit loss occurs in three steps between a) 310 and 367°C b) 367 and 390°C and c) between 390 and 428°C for both the hexacyanoferrite(II) and hexacyanoferrate(III) intercalated hydrotalcite.

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For a series of six-coordinate Ru(II)(CO)L or Rh(III)(X–)L porphyrins which are facially differentiated by having a naphthoquinol- or hydroquinol-containing strap across one face, we show that ligand migration from one face to the other can occur under mild conditions, and that ligand site preference is dependent on the nature of L and X–. For bulky nitrogen-based ligands, the strap can be displaced sideways to accommodate the ligand on the same side as the strap. For the ligand pyrazine, we show 1 H NMR evidence for monodentate and bidentate binding modes on both faces, dependent on ligand concentration and metalloporphyrin structure, and that inter-facial migration is rapid under normal conditions. For monodentate substituted pyridine ligands there is a site dependence on structure, and we show clear evidence of dynamic ligand migration through a series of ligand exchange reactions.