Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Spectroscopic investigation of the polymerisation of pyrrole and thiophene within zeolite channels

The reaction of pyrrole and thiophene monomers with copper- or nickel-exchanged mordenite has been investigated using X-ray photoelectron (XPS) and photoacoustic infrared (PAIRS) spectroscopies. Because of the differing oxidising powers of the cations studied, polymerisation occurred only with copper-exchanged mordenite. PAIRS and XPS data indicated that both polypyrrole and polythiophene were partially oxidised when synthesised within the zeolite structure. IR spectra of polythiophene and polythiophene and polypyrrole showed intense bands typical of ring vibrations which could couple to the large dipole change induced by charges moving along the polythiophene chain. In addition it was noted that only vibrations typical of oxidised polymer structures were recorded, suggesting that the charge carrier was located within these segments. Furthermore, N 1s spectra contained a high binding energy peak at 402.5 eV which was attributed to a positively charged nitrogen species, in agreement with IR data. Significantly, C 1s spectra confirmed that molecular wires were formed within the confines of the zeolite lattice. Depth-profiling experiments suggested that polypyrrole was distributed throughout the entire zeolite host. By contrast, polythiophene may have been restricted to the uppermost zeolite channels owing to the ability of sulfur species to bond to CuI sites [produced by reduction of copper(II) ions during the polymerisation process], thus obstructing movement along the channels.

Development of an integrated metabolomic profiling approach for infectious diseases research

Metabolomic profiling offers direct insights into the chemical environment and metabolic pathway activities at sites of human disease. During infection, this environment may receive important contributions from both host and pathogen. Here we apply an untargeted metabolomics approach to identify compounds associated with an E. coli urinary tract infection population. Correlative and structural data from minimally processed samples were obtained using an optimized LC-MS platform capable of resolving ~2300 molecular features. Principal component analysis readily distinguished patient groups and multiple supervised chemometric analyses resolved robust metabolomic shifts between groups. These analyses revealed nine compounds whose provisional structures suggest candidate infection-associated endocrine, catabolic, and lipid pathways. Several of these metabolite signatures may derive from microbial processing of host metabolites. Overall, this study highlights the ability of metabolomic approaches to directly identify compounds encountered by, and produced from, bacterial pathogens within human hosts.

In vitro functional characterisation of IGF-I : VN-induced breast cancer progression

Members of the insulin-like growth factor (IGF) family have been shown to play critical roles in normal growth and development, as well as in tumour biology. The IGF system is complex and the biological effects of the IGFs are determined by their diverse interactions between many molecules, including their interactions with extracellular matrix (ECM) proteins. Recent studies have demonstrated that IGFs associate with the ECM protein vitronectin (VN) through IGF-binding proteins (IGFBP) and that this interaction modulates IGF-stimulated biological functions, namely cell migration and cell survival through the cooperative involvement of the type-I IGF receptor (IGF-1R) and VN-binding integrins. Since IGFs play important roles in the transformation and progression of breast cancer and VN has been found to be over-expressed at the leading edge of breast tumours, this project aimed to describe the effects of IGF-I:VN interactions on breast cell function. This was undertaken to dissect the molecular mechanisms underlying IGF-I:VN-induced responses and to design inhibitors to block the effects of such interactions. The studies described herein demonstrate that the increase in migration of MCF-7 breast cancer cells in response to the IGF-I:IGFBP-5:VN complex is accompanied by differential expression of genes known to be involved in migration, invasion and/or survival, including Tissue-factor (TF), Stratifin (SFN), Ephrin-B2, Sharp-2 and PAI-1. This „migration gene signature‟ was confirmed using real-time PCR analysis. Substitution of the native IGF-I within the IGF-I:IGFBP:VN complex with the IGF-I analogue, \[L24]\[A31]-IGF-I, which has a reduced affinity for the IGF-1R, failed to stimulate cell migration and interestingly, also failed to induce the differential gene expression. This supports the involvement of the IGF-1R in mediating these changes in gene expression. Furthermore, lentiviral shRNA-mediated stable knockdown of TF and SFN completely abrogated the increased cell migration induced by IGF-I:IGFBP:VN complexes in MCF-7 cells. Indeed, when these cells were grown in 3D Matrigel™ cultures a decrease in the overall size of the 3D spheroids in response to the IGF-I:IGFBP:VN complexes was observed compared to the parental MCF-7 cells. This suggests that TF and SFN have a role in complex-stimulated cell survival. Moreover, signalling studies performed on cells with the reduced expression of either TF or SFN had a decreased IGF-1R activation, suggesting the involvement of signalling pathways downstream of IGF-1R in TF- and/or SFN-mediated cell migration and cell survival. Taken together, these studies provide evidence for a common mechanism activated downstream of the IGF-1R that induces the expression of the „migration gene signature‟ in response to the IGF-I:IGFBP:VN complex that confers breast cancer cells the propensity to migrate and survive. Given the functional significance of the interdependence of ECM and growth factor (GF) interactions in stimulating processes key to breast cancer progression, this project aimed at developing strategies to prevent such growth factor:ECM interactions in an effort to inhibit the downstream functional effects. This may result in the reduction in the levels of ECM-bound IGF-I present in close proximity to the cells, thereby leading to a reduction in the stimulation of IGF-1R present on the cell surface. Indeed, the inhibition of IGF-I-mediated effects through the disruption of its association with ECM would not alter the physiological levels of IGF-I and potentially only exert effects in situations where abnormal over expression of ECM proteins are found; namely carcinomas and hyperproliferative diseases. In summary, this PhD project has identified novel, innovative and realistic strategies that can be used in vitro to inhibit the functions exerted by the IGF-I:IGFBP:VN multiprotein complexes critical for cancer progression, with a potential to be translated into in vivo investigations. Furthermore, TF and SFN were found to mediate IGF-I:IGFBP:VN-induced effects, thereby revealing their potential to be used as therapeutic targets or as predictive biomarkers for the efficacy of IGF-1R targeting therapies in breast cancer patients. In addition to its therapeutic and clinical scope, this PhD project has significantly contributed to the understanding of the role of the IGF system in breast tumour biology by providing valuable new information on the mechanistic events underpinning IGF-I:VN-mediated effects on breast cell functions. Furthermore, this is the first instance where favourable binding sites for IGF-II, IGFBP-3 and IGFBP-5 on VN have been identified. Taken together, this study has functionally characterised the interactions between IGF-I and VN and through innovative strategies has provided a platform for the development of novel therapies targeting these interactions and their downstream effects.

New labour and the environment : too little too late.

New Labour and the environment: too little too late – symbolic success but real failure Achievements: Introduction of the Climate Change Act 2008, Low Carbon Transition Plan, the creation of the Department of Energy and Climate Change, establishment of several ‘green’ quangos and Green Investment Bank, Warm Front Scheme, international leadership on Kyoto and the European Directive for Landfill and Renewable Energy. Disappointments: Increased green house gas emissions that failto meet domestic UK targets, let alone Kyoto; significant increasesin energy and transport emissions; EU air pollution violations; failure to regulate the importation of illegally logged timber and wildlife; increase in chemical agriculture; unwillingness to tackle corporate environmental crime; road expansions and runway projects at the expense of low emission alternative public transport. Biggest broken promises: Global warming, low carbon transport; protection of biodiversity.

Consumer engagement with eHealth information through smartphones and tablets : an Australian perspective

This paper is a work in progress that examines current consumer engagement with eHealth information through Smartphones or tablets. We focus on three activity types: seeking, posting and ‘other’ engagement activity and compare two age groups, 25-40s and over 40-55s. Findings show that around 30% of the younger age group is engaging with Government and other Health providers’ websites, receiving eHealth emails, and reading other people’s comments about health related issues in online discussion groups/websites/blog. Approximately 20% engage with Government and other Health providers’ social media and watch or listen to audio or video podcasts. For the older age group, their most active engagement with eHealth information is in the seeking category through Government or other health websites (approximately 15%), and less than 10% for social media sites. Their posting activity is less than 5%. Other activities show that less than 15% of the older age group engages through receiving emails and reading blogs, less than 10% watch or listen to podcasts, and their online consulting activity is less than 7%. We note that scores are low for both groups in terms of engaging with eHealth information through Twitter.

Spectroscopic characterization of manganese minerals

Manganese minerals ardenite, alleghanyite and leucopoenicite originated from Madhya Pradesh, India, Nagano prefecture Japan, Sussex Country and Parker Shaft Franklin, Sussex Country, New Jersey respectively are used in the present work. In these minerals manganese is the major constituent and iron if present is in traces only. An EPR study of on all of the above samples confirms the presence of Mn(II) with g around 2.0. Optical absorption spectrum of the mineral alleghanyite indicates that Mn(II) is present in two different octahedral sites and in leucophoenicite Mn(II) is also in octahedral geometry. Ardenite mineral gives only a few Mn(II) bands. NIR results of the minerals ardenite, leucophoenicite and alleghanyite are due to hydroxyl and silicate anions which confirming the formulae of the minerals.

'I want to educate school age children' : producing early childhood teacher professional identities

The Australian Government’s current workforce reforms in early childhood education and care (ECEC) include a major shift in qualification requirements. The new requirement is that university four-year degree-qualified teachers are employed in before-school contexts, including child care. Ironically, recent research studies show that, in Australia, the very preservice teachers who are enrolled in these degree programs have a reluctance to work in childcare. This article reports on part of a larger study which is inquiring into how early childhood teacher professional identities are discursively produced, and provides a partial mapping of the literature. One preservice teacher’s comment provides the starting point, and the paper locates some the discourses that are accessible to preservice teachers as they prepare for the early years workforce. An awareness of the discursive field provides a sound background for preparing early childhood teachers. A challenge for the field is to consider which discourses are dominant, and how they potentially work to privilege work in some ECEC contexts over others.

Producing and maintaining professional identities in early childhood

This study is an inquiry into early childhood teacher professional identities. In Australia, workforce reforms in early childhood include major shifts in qualification requirements that call for a university four-year degree-qualified teacher to be employed in child care. This marks a shift in the early years workforce, where previously there was no such requirement. At the same time as these reforms to quality measures are being implemented, and requiring a substantive up skilling of the workforce, there is a growing body of evidence through recent studies that suggests these same four-year degree-qualified early childhood teachers have an aversion to working in child care. Their preferred employment option is to work in the early years of more formal schooling, not in before-school contexts. This collision of agendas warrants investigation. This inquiry is designed to investigate the site at which advocacy for higher qualification requirements meets early childhood teachers who are reluctant to choose child care as a possible career pathway. The key research question for this study is: How are early childhood teachers’ professional identities currently produced? The work of this thesis is to problematise the early childhood teacher in child care through a particular method of discourse analysis. There are two sets of data. The first was a key early childhood political document that read as a "moment of arising" (Foucault, 1984a, p. 83). It is a political document which was selected for its current influence on the early childhood field, and in particular, workforce reforms that call for four-year degree-qualified teachers to work in before-school contexts, including child care. The second data set was generated through four focus group discussions conducted with preservice early childhood teachers. The document and transcripts of the focus groups were both analysed as text, as conceptualised by Foucault (1981). Foucault’s work spans a number of years and a range of philosophical matters. This thesis draws particularly on Foucault’s writings on discourse, power/knowledge, regimes of truth and resistance. In order to consider the production of early childhood teachers’ professional identities, the study is also informed by identity theorists, who have worked on gender, performativity and investment (Davies, 2004/2006; McNay, 1992; Osgood, 2012; Walkerdine, 1990; Weedon, 1997). The ways in which discourses intersect, compete and collide produce the subject (Foucault, 1981) and, in the case of this inquiry, there are a number of competing discourses at play, which produce the early childhood teacher. These particular theories turn particular lenses on the question of professional identities in early childhood, and such a study calls for the application of particular methodologies. Discourse analysis was used as the methodological framework, and the analysis was informed by Foucauldian concepts of discourse. While Foucault did not prescribe a form of discourse analysis as a method, his writings nonetheless provide a valuable framework for illuminating discursive practices and, in turn, how people are affected, through the shifts and distribution of power (Foucault, 1980a). The treatment used with both data sets involved redescription. For the policy document, a technique for reading document-as-text applied a genealogical approach (Foucault, 1984a). For the focus groups, the process of redescription (Rorty, 1989) involved reading talk-as-text. As a method, redescription involves describing "lots and lots of things in new ways until you have created a pattern of linguistic behaviour which will tempt the new generation to adopt it" (Rorty, 1989, p. 9). The development and application of categories (Davies, 2004/2006) built on a poststructuralist theoretical framework and the literature review informed the data analysis method of discourse analysis. Irony provided a rhetorical and playful tool (Haraway, 1991; Rorty, 1989), to look to how seemingly opposing discourses are held together. This opens a space to collapse binary thinking and consider seemingly contradictory terms in a way in which both terms are possible and both are true. Irony resists the choice of one or the other being right, and holds the opposites together in tension. The thesis concludes with proposals for new, ironic categories, which work to bring together seemingly opposing terms, located at sites in the field of early childhood where discourses compete, collide and intersect to produce and maintain early childhood teacher professional identities. The process of mapping these discourses goes some way to investigating the complexities about identities and career choices of early childhood teachers. The category of "the cost of loving" captures the collision between care/love, inherent in child care, and new discourses of investment/economics. Investment/economics has not completely replaced care/love, and these apparent opposites were not read as a binary because both are necessary and both are true (Haraway, 1991). They are held together in tension to produce early childhood teacher professional identities. The policy document under scrutiny was New Directions, released in 2007 by the then opposition ALP leader, Kevin Rudd. The claim was made strongly that the "economic prosperity" of Australia relies on investment in early childhood. The arguments to invest are compelling and the neuroscience/brain research/child development together with economic/investment discourses demand that early childhood is funding is increased. The intersection of these discourses produces professional identities of early childhood teachers as a necessary part of the country’s economy, and thus, worthy of high status. The child care sector and work in child care settings are necessary, with children and the early childhood teacher playing key roles in the economy of the nation. Through New Directions it becomes sayable (Foucault, 1972/1989) that the work the early childhood teacher performs is legitimated and valued. The children are produced as "economic units". A focus on what children are able to contribute to the future economy of the nation re-positions children and produces these "smart productive citizens", making future economic contribution. The early childhood teacher is produced through this image of a child and "the cost of loving" is emphasised. A number of these categories were produced through the readings of the document-as text and the talk-as-text. Two ironic categories were read in the analysis of the transcripts of the focus group discussions, when treated as talk-as-text data: the early childhood teacher as a "heroic victim"; and the early childhood teacher as a "glorified babysitter". This thesis raises new questions about professional identities in early childhood. These new questions might go some way to prompt re-thinking of some government policy, as well as some aspects of early childhood teacher education course design. The images of children and images of child care provide provocations to consider preservice teacher education course design. In particular, how child care, as one of the early childhood contexts, is located, conceptualised and spoken throughout the course. Consideration by course designers and teacher educators of what discourses are privileged in course content —what discourses are diminished or silenced—would go some way to reconceptualising child care within preservice teacher education and challenging dominant ways of speaking child care, and work in child care. This inquiry into early childhood teachers’ professional identities has gone some way to exploring the complexities around the early childhood teacher in child care. It is anticipated that the significance of this study will thus have immediate applicably and relevance for the Australian early childhood policy landscape. The early childhood field is in a state of rapid change, and this inquiry has examined some of the disconnects between policy and practice. Awareness of the discourses that are in play in the field will continue to allow space for conversations that challenge dominant assumptions about child care, work in child care and ways of being an early childhood teacher in child care.

Opportunities and challenges : school guidance counsellors’ perceptions of counselling students online

School guidance counsellors world-wide seek ways of providing appropriate professional assistance to all students. While young people integrate online technology into their daily lives and go online for information and to communicate with each other, school counsellors in Australia are not offering online support to students. This cross-sectional study reported on the reluctance of school counsellors to offer online counselling and the reasons for this. A survey of 210 school guidance counsellors found that there is conditional support for the introduction of online counselling into the school setting. Counsellors indicated that they would use online counselling if students accepted its use in the school setting though they question how genuine students would be in its use. Most respondents reported a lack of confidence in understanding the ethical and legal implications of online counselling. However, the majority of participants were prepared to undertake further professional development in this mode of counselling. Additionally, they sought confirmation of the effectiveness of counselling students online before committing themselves to it. The implications for school guidance practice are discussed.

A case study of pedagogical responses to internationalisation at a faith-based secondary school in Australia

This case study investigated pedagogical responses to internationalisation by a faith-based secondary school in Australia. Using social constructivism as the theoretical framework the study examined teaching and learning for culturally and linguistically diverse students. Data generated through questionnaires, focus groups, individual interviews and document archives were analysed and interpreted using thematic analysis. The findings showed that teachers believed themselves to be ill-equipped to teach international students. Their concerns centred on a lack of explicit pedagogical, cultural and linguistic knowledge to help the students acculturate and learn. Recommendations include the dissemination of school policies to teachers, intentional staff collaboration and professional development to address the teachers’ needs for internationalisation.

Inventory procedures for smallholder and community woodlots in the Philippines : methods, initial findings and insights

This paper details the processes and challenges involved in collecting inventory data from smallholder and community woodlots on Leyte Island, Philippines. Over the period from 2005 through to 2012, 253 woodlots at 170 sites were sampled as part of a large multidisciplinary project, resulting in a substantial timber inventory database. The inventory was undertaken to provide information for three separate but interrelated studies, namely (1) tree growth, performance and timber availability from private smallholder woodlots on Leyte Island; (2) tree growth and performance of mixed-species plantings of native species; and (3) the assessment of reforestation outcomes from various forms of reforestation. A common procedure for establishing plots within each site was developed and applied in each study, although the basis of site selection varied. A two-stage probability proportion to size sampling framework was developed to select smallholder woodlots for inclusion in the inventory. In contrast, community-based forestry woodlots were selected using stratified random sampling. Challenges encountered in undertaking the inventory were mostly associated with the need to consult widely before the commencement of the inventory and problems in identifying woodlots for inclusion. Most smallholder woodlots were only capable of producing merchantable volumes of less than 44 % of the site potential due to a lack of appropriate silviculture. There was a clear bimodal distribution of proportion that the woodlots comprised of the total smallholding area. This bimodality reflects two major motivations for smallholders to establish woodlots, namely timber production and to secure land tenure.

An ontology-based method for sparsity problem in tag recommendation

Tags or personal metadata for annotating web resources have been widely adopted in Web 2.0 sites. However, as tags are freely chosen by users, the vocabularies are diverse, ambiguous and sometimes only meaningful to individuals. Tag recommenders may assist users during tagging process. Its objective is to suggest relevant tags to use as well as to help consolidating vocabulary in the systems. In this paper we discuss our approach for providing personalized tag recommendation by making use of existing domain ontology generated from folksonomy. Specifically we evaluated the approach in sparse situation. The evaluation shows that the proposed ontology-based method has improved the accuracy of tag recommendation in this situation.

Lysine residues of IGF-I are substrates for transglutaminases and modulate downstream IGF-I signalling

Numerous studies have reported associations between IGF-I and other extra cellular matrix (ECM) proteins, including fibronectin (FN), integrins, IGF-binding proteins (IGFBPs) and through IGFBPs, with vitronectin (VN). Nevertheless, the precise nature and mechanisms of these interactions are still being characterised. In this paper, we discuss transglutaminases (TGases) as a constituent of the ECM and provide evidence for the first time that IGF-I is a lysine (K)-donor substrate to TGases. When IGF-I was incubated with an alpha-2 plasmin inhibitor-derived Q peptide in the presence of tissue transglutaminase (TG2), an IGF-I:Q peptide cross-linked species was detected using Western immunoblotting and confirmed by mass spectrometry. Similar findings were observed in the presence of Factor XIIIa (FXIIIa) TGase. To identify the precise location of this K-donor TGase site/s on IGF-I, all the three IGF-I K-sites, individually and collectively (K27, K65 and K68), were substituted to arginine (R) using site-directed mutagenesis. Incubation of these K→R IGF-I analogues with Q peptide in the presence of TG2 or FXIIIa resulted in the absence of cross-linking in IGF-I analogues bearing arginine substitution at site 68. This established that K68 within the IGF-I D-domain was the principal K-donor site to TGases. We further annotated the functional significance of these K→R IGF-I analogues on IGF-I mediated actions. IGF-I analogues with K→R substitution within the D-domain at K65 and K68 hindered migration of MCF-7 breast carcinoma cells and correspondingly reduced PI3-K/AKT activation. Therefore, this study also provides first insights into a possible functional role of the previously uncharacterised IGF-I D-domain.

PEGylation of lysine residues reduces the pro-migratory activity of IGF-I

Background: The insulin-like growth factor (IGF) system is composed of ligands and receptors which regulate cell proliferation, survival, differentiation and migration. Some functions are regulated via intracellular signaling cascades, others by involvement of the extracellular milieu, including binding proteins and other extracellular matrix proteins. However, understanding of their functions and the exact nature of these interactions remains incomplete. Methods: IGF-I was PEGylated at its lysine sites - K27, K65 and K68. Binding of PEG-IGF-I to the IGFBPs was analyzed using BIAcore and its ability to activate the IGF-IR was assessed using IGF-IR phosphorylation assay. Furthermore, functional consequences of PEGylating the lysine residues of IGF-I was investigated using cell viability and cell migration assays. In addition, particular downstream signaling pathways regularly implicated in these mechanisms were also dissected using phospho-AKT and phospho-ERK1/2 assays. Results: In this study, IGF-I specifically PEGylated at lysine 27 (PEG-K27), 65 (PEG-K65) or 68 (PEG-K68) were employed. Receptor phosphorylation was only reduced by 2-fold with PEG-K65 and PEG-K68 over all the time points tested, and as observed in two cell types, 3T3 fibroblasts and MCF-7 breast cancer cells. PEGylation at K27 resulted in a much larger effect, with more than 10-fold lower activation for 3T3 fibroblasts and a ~3 fold reduced IGF-IR activation for MCF-7 breast cancer cells over 15 minutes. In addition, all PEG-IGF-I variants demonstrated a ten-fold reduction in the association rate to IGF binding proteins (IGFBPs). Functionally, all PEG variants completely lost their ability to induce cell migration in the presence of IGFBP-3/vitronectin (VN) complexes as compared to IGF-I; in contrast, cell viability was fully preserved. Further investigations into the downstream signaling pathways revealed that the PI3-K/AKT pathway was preferentially affected upon treatment with the PEG-IGF-I variants compared to the MAPK/ERK pathway. Conclusion: PEGylation of IGF-I has an impact on cell migration but not cell viability. General significance: PEG-IGF-I may differentially modulate IGF-I mediated functions that are dependent on its interaction with its receptor as well as key extracellular proteins such as VN and IGFBPs.