Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Investigation of mechanisms governing emission of odorants

The literature identifies several models that describe inter-phase mass transfer, key to the emission process. While the emission process is complex and these models may be more or less successful at predicting mass transfer rates, they identify three key variables for a system involving a liquid and an air phase in contact with it: • A concentration (or partial pressure) gradient driving force; • The fluid dynamic characteristics within the liquid and air phases, and • The chemical properties of the individual components within the system. In three applied research projects conducted prior to this study, samples collected with two well-known sampling devices resulted in very different odour emission rates. It was not possible to adequately explain the differences observed. It appeared likely, however, that the sample collection device might have artefact effects on the emission of odorants, i.e. the sampling device appeared to have altered the mass transfer process. This raised the obvious question: Where two different emission rates are reported for a single source (differing only in the selection of sampling device), and a credible explanation for the difference in emission rate cannot be provided, which emission rate is correct? This research project aimed to identify the factors that determine odour emission rates, the impact that the characteristics of a sampling device may exert on the key mass transfer variables, and ultimately, the impact of the sampling device on the emission rate itself. To meet these objectives, a series of targeted reviews, and laboratory and field investigations, were conducted. Two widely-used, representative devices were chosen to investigate the influence of various parameters on the emission process. These investigations provided insight into the odour emission process generally, and the influence of the sampling device specifically.

Mechanisms of change in negative thinking and urinary monoamines in depressed patients during acute treatment with group cognitive behavior therapy and antidepressant medication

This naturalistic study investigated the mechanisms of change in measures of negative thinking and in 24-h urinary metabolites of noradrenaline (norepinephrine), dopamine and serotonin in a sample of 43 depressed hospital patients attending an eight-session group cognitive behavior therapy program. Most participants (91%) were taking antidepressant medication throughout the therapy period according to their treating Psychiatrists' prescriptions. The sample was divided into outcome categories (19 Responders and 24 Non-responders) on the basis of a clinically reliable change index [Jacobson, N.S., & Truax, P., 1991. Clinical significance: a statistical approach to defining meaningful change in psychotherapy research. Journal of Consulting and Clinical Psychology, 59, 12–19.] applied to the Beck Depression Inventory scores at the end of the therapy. Results of repeated measures analysis of variance [ANOVA] analyses of variance indicated that all measures of negative thinking improved significantly during therapy, and significantly more so in the Responders as expected. The treatment had a significant impact on urinary adrenaline and metadrenaline excretion however, these changes occurred in both Responders and Non-responders. Acute treatment did not significantly influence the six other monoamine metabolites. In summary, changes in urinary monoamine levels during combined treatment for depression were not associated with self-reported changes in mood symptoms.

Venture creation and resource processes : using Bricolage sustainability ventures

Principal Topic: Resource decisions are critical to the venture creation process, which has important subsequent impacts on venture creation and performance (Boeker, 1989). Most entrepreneurs however, suffer substantial resource constraints in venture creation and during venture growth (Shepherd et al., 2000). Little is known about how high potential, sustainability ventures (the ventures of interest in this research), despite resource constraints, achieve continued venture persistence and venture success. One promising theory that explicitly links to resource constraints is a concept developed by Levi Strauss (1967) termed bricolage. Bricolage aligns with notions of resourcefulness: using what's on hand, through making do, and recombining resources for new or novel purposes (Baker & Nelson 2005). To the best of our knowledge, previous studies have not systematically investigated internal and external constraints, their combinations, and subsequent bricolage patterns. The majority of bricolage literature focuses on external environmental constraints (e.g. Wieck 1989; Baker & Nelson 2005), thereby paying less attention to in evaluating internal constraints (e.g. skills and capabilities) or constraint combinations. In this paper we focus on ventures that typically face resource-poor environments. High potential, nascent and young sustainability ventures are often created and developed with resource constraints and in some cases, have greater resource requirements owing to higher levels of technical sophistication of their products (Rothaermel & Deeds 2006). These ventures usually have high aspirations and potential for growth who ''seeks to meet the needs and aspirations without compromising the ability to meet those of the future'' (Brundtland Commission 1983). High potential ventures are increasingly attributed with a central role in the development of innovation, and employment in developed economies (Acs 2008). Further, increasing awareness of environmental and sustainability issues has fostered demand for business processes that reduce detrimental environmental impacts of global development (Dean & McMullen 2007) and more environmentally sensitive products and services: representing an opportunity for the development of ventures that seek to satisfy this demand through entrepreneurial action. These ventures may choose to ''make do'' with existing resources in developing resource combinations that produce the least impact on the environment. The continuous conflict between the greater requirements for resources and limited resource availability in high potential sustainable ventures, with the added complexity of balancing this with an uncompromising focus on using ''what's on hand'' to lessen environment impacts may make bricolage behaviours critical for these ventures. Research into bricolage behaviour is however, the exception rather than the rule (Cunha 2005). More research is therefore needed to further develop and extend this emerging concept, especially in the context of sustainability ventures who are committed to personal and social goals of resourcefulness. To date, however, bricolage has not been studied specifically among high potential sustainable ventures. This research seeks to develop an in depth understanding of the impact of internal and external constraints and their combinations on the mechanisms employed in bricolage behaviours in differing dynamic environments. The following research question was developed to investigate this: How do internal, external resource constraints (or their combinations) impact bricolage resource decisions in high potential sustainability ventures? ---------- Methodology/Key Propositions: 6 case studies will be developed utilizing survey data from the Comprehensive Australian Study of Entrepreneurial Emergence (CAUSEE) large-scale longitudinal study of new venture start-ups in Australia. Prior to commencing case studies, 6 scoping interviews were conducted with key stakeholders including industry members, established businesses and government to ensure practical relevance in case development. The venture is considered the unit of analysis with the key informant being the entrepreneur and other management team members where appropriate. Triangulation techniques are used in this research including semi-structured interviews, survey data, onsite visits and secondary documentation website analysis, resumes, and business plans. These 6 sustainability ventures have been selected based on different environmental dynamism conditions including a traditionally mature market (building industry) and a more dynamic, evolving industry (renewable energy/solar ventures). In evaluating multidisciplinary literature, we expect the following external constraints are critical including: technology constraints (seen through lock-in of incumbents existing technology), institutional regulation and standards, access to markets, knowledge and training to nascent and young venture bricolage processes. The case studies will investigate internal constraints including resource fungability, resource combination capabilities, translating complex science/engineering knowledge into salient, valuable market propositions, i.e. appropriate market outcomes, and leveraging relationships may further influence bricolage decisions. ---------- Results and Implications: Intended ventures have been identified within the CAUSEE sample and have agreed to participate and secondary data collection for triangulation purposes has already commenced. Data collection of the case studies commenced 27th of May 2009. Analysis is expected to be completed finalised by 25th September 2009. This paper will report on the pattern of resource constraints and its impact on bricolage behaviours: its subsequent impact on resource deployment within venture creation and venture growth. As such, this research extends the theory of bricolage through the systematic analysis of constraints on resource management processes in sustainability ventures. For practice, this research may assist in providing a better understanding of the resource requirements and processes needed for continued venture persistence and growth in sustainability ventures. In these times of economic uncertainty, a better understanding of the influence on constraints and bricolage: the interplay of behaviours, processes and outcomes may enable greater venture continuance and success.

Early childhood education for sustainability : why it matters, what it is, and how whole centre action research and systems thinking can help

The global financial crisis, global pandemics, global warming and peak oil are indicative of a world facing major environmental, social and economic problems. At the same time, world population continues to rise and global inequalities deepen. Children are the most vulnerable to the impacts of unsustainable living with specific harms arising because of their physical and cognitive vulnerabilities. Nevertheless, children do not have to be victims in the face of these challenges. Education, including early childhood education, has an important role to in building resilience and capabilities in children that equip them as active and informed citizens now and in the future and who are capable of contributing to healthy and sustainable ways of living. Drawing on educational change literature, action research, education for sustainability, health promotion and systems theory, this paper outlines three strategies that can help reorient early childhood education towards sustainability. One strategy is the adoption of whole centre approaches to sustainability and education for sustainability. This means working across the whole of a centre’s operations – curriculum and pedagogy, physical and social environments, its partnerships and community connections. The second strategy – applied in conjunction with the first – is the use of action research to investigate the early childhood setting and to create the desired changes. The third strategy is the adoption of systems thinking as a way of leveraging support and momentum for change so that education for sustainability goes beyond the initiatives of individual teachers and centres, and becomes a systems-wide imperative.

“Filling out the forms was a nightmare” : project evaluation and the reflective practitioner in community theatre in contemporary Northern Ireland

Since the Good Friday Agreement of 1998, large sums have been invested in community theatre projects in Northern Ireland, in the interests of conflict transformation and peace building. While this injection of funds has resulted in an unprecedented level of applied theatre activity, opportunities to maximise learning from this activity are being missed. It is generally assumed that project evaluation is undertaken at least partly to assess the degree of success of projects against important social objectives, with a view to learning what works, what does not, and what might work in the future. However, three ethnographic case studies of organisations delivering applied theatre projects in Northern Ireland indicate that current processes used to evaluate such projects are both flawed and inadequate for this purpose. Practitioners report that the administrative work involved in applying for and justifying funding is onerous, burdensome, and occurs at the expense of artistic activity. This is a very real concern when the time and effort devoted to ‘filling out the forms’ does not ultimately result in useful evaluative information. There are strong disincentives for organisations to report honestly on their experiences of difficulties, or undesirable impacts of projects, and this problem is not transcended by the use of external evaluators. Current evaluation processes provide little opportunity to capture unexpected benefits of projects, and small but significant successes which occur in the context of over-ambitious objectives. Little or no attempt is made to assess long-term impacts of projects on communities. Finally, official evaluation mechanisms fail to capture the reflective practice and dialogic analysis of practitioners, which would richly inform future projects. The authors argue that there is a need for clearer lines of communication, and more opportunities for mutual learning, among stakeholders involved in community development. In particular, greater involvement of the higher education sector in partnership with government and non-government agencies could yield significant benefits in terms of optimizing learning from applied theatre project evaluations.

TCP-DR an effective protocol for infrastructure based wireless networks

TCP is a dominant protocol for consistent communication over the internet. It provides flow, congestion and error control mechanisms while using wired reliable networks. Its congestion control mechanism is not suitable for wireless links where data corruption and its lost rate are higher. The physical links are transparent from TCP that takes packet losses due to congestion only and initiates congestion handling mechanisms by reducing transmission speed. This results in wasting already limited available bandwidth on the wireless links. Therefore, there is no use to carry out research on increasing bandwidth of the wireless links until the available bandwidth is not optimally utilized. This paper proposed a hybrid scheme called TCP Detection and Recovery (TCP-DR) to distinguish congestion, corruption and mobility related losses and then instructs the data sending host to take appropriate action. Therefore, the link utilization is optimal while losses are either due to high bit error rate or mobility.

Prandial subcutaneous injections of glucagon-like peptide-1 cause weight loss in obese human subjects

Recombinant glucagon-like peptide-1 (7–36)amide (rGLP-1) was recently shown to cause significant weight loss in type 2 diabetics when administered for 6 weeks as a continuous subcutaneous infusion. The mechanisms responsible for the weight loss are not clarified. In the present study, rGLP-1 was given for 5d by prandial subcutaneous injections (PSI) (76nmol 30min before meals, four times daily; a total of 302·4nmol/24h) or by continuous subcutaneous infusion (CSI) (12·7nmol/h; a total of 304·8nmol/24h). This was performed in nineteen healthy obese subjects (mean age 44·2 (sem 2·5) years; BMI 39·0 (sem 1·2)kg/m2) in a prospective randomised, double-blind, placebo-controlled, cross-over study. Compared with the placebo, rGLP-1 administered as PSI and by CSI generated a 15% reduction in mean food intake per meal (P=0·02) after 5d treatment. A weight loss of 0·55 (sem 0·2) kg (P<0·05) was registered after 5d with PSI of rGLP-1. Gastric emptying rate was reduced during both PSI (P<0·001) and CSI (P<0·05) treatment, but more rapidly and to a greater extent with PSI of rGLP-1. To conclude, a 5d treatment of rGLP-1 at high doses by PSI, but not CSI, promptly slowed gastric emptying as a probable mechanism of action of increased satiety, decreased hunger and, hence, reduced food intake with an ensuing weight loss.

On PAR : Using Participatory Action Research to Improve Early Intervention

This manual is designed to assist human service practitioners and agencies, and the communities they work with, to enhance their skills in undertaking Participatory Action Research, and, in so doing improve the situations of people who are vulnerable. It utilises insights derived from a number of Australian Government funded programs, most notably Reconnect, NAYSS and Household Organisational Management Expenses (HOME) Advice.

Community voices, votes and action

The diversity of community voices in the SEQ ‘bellwether region’ has grown from a muted murmur in the mid twentieth century supporting provision of urban services, rural conservation and green belts, to the current clamour against over-development, and in favour of protecting local and regional open space, wetlands and natural habitats. This in turn has often resulted in vigorous campaigns against unpopular roads, dams, dumps and tall buildings. In the last twenty years community issues have played a major part in local government elections throughout the region and have even helped unseat (in 1995-1996) a state government which discounted their authenticity and community resolve.

Molecular markers of obesity and diabetes

Recently it has been shown that the consumption of a diet high in saturated fat is associated with impaired insulin sensitivity and increased incidence of type 2 diabetes. In contrast, diets that are high in monounsaturated fatty acids (MUFAs) or polyunsaturated fatty acids (PUFAs), especially very long chain n-3 fatty acids (FAs), are protective against disease. However, the molecular mechanisms by which saturated FAs induce the insulin resistance and hyperglycaemia associated with metabolic syndrome and type 2 diabetes are not clearly defined. It is possible that saturated FAs may act through alternative mechanisms compared to MUFA and PUFA to regulate of hepatic gene expression and metabolism. It is proposed that, like MUFA and PUFA, saturated FAs regulate the transcription of target genes. To test this hypothesis, hepatic gene expression analysis was undertaken in a human hepatoma cell line, Huh-7, after exposure to the saturated FA, palmitate. These experiments showed that palmitate is an effective regulator of gene expression for a wide variety of genes. A total of 162 genes were differentially expressed in response to palmitate. These changes not only affected the expression of genes related to nutrient transport and metabolism, they also extend to other cellular functions including, cytoskeletal architecture, cell growth, protein synthesis and oxidative stress response. In addition, this thesis has shown that palmitate exposure altered the expression patterns of several genes that have previously been identified in the literature as markers of risk of disease development, including CVD, hypertension, obesity and type 2 diabetes. The altered gene expression patterns associated with an increased risk of disease include apolipoprotein-B100 (apo-B100), apo-CIII, plasminogen activator inhibitor 1, insulin-like growth factor-I and insulin-like growth factor binding protein 3. This thesis reports the first observation that palmitate directly signals in cultured human hepatocytes to regulate expression of genes involved in energy metabolism as well as other important genes. Prolonged exposure to long-chain saturated FAs reduces glucose phosphorylation and glycogen synthesis in the liver. Decreased glucose metabolism leads to elevated rates of lipolysis, resulting in increased release of free FAs. Free FAs have a negative effect on insulin action on the liver, which in turn results in increased gluconeogenesis and systemic dyslipidaemia. It has been postulated that disruption of glucose transport and insulin secretion by prolonged excessive FA availability might be a non-genetic factor that has contributed to the staggering rise in prevalence of type 2 diabetes. As glucokinase (GK) is a key regulatory enzyme of hepatic glucose metabolism, changes in its activity may alter flux through the glycolytic and de novo lipogenic pathways and result in hyperglycaemia and ultimately insulin resistance. This thesis investigated the effects of saturated FA on the promoter activity of the glycolytic enzyme, GK, and various transcription factors that may influence the regulation of GK gene expression. These experiments have shown that the saturated FA, palmitate, is capable of decreasing GK promoter activity. In addition, quantitative real-time PCR has shown that palmitate incubation may also regulate GK gene expression through a known FA sensitive transcription factor, sterol regulatory element binding protein-1c (SREBP-1c), which upregulates GK transcription. To parallel the investigations into the mechanisms of FA molecular signalling, further studies of the effect of FAs on metabolic pathway flux were performed. Although certain FAs reduce SREBP-1c transcription in vitro, it is unclear whether this will result in decreased GK activity in vivo where positive effectors of SREBP-1c such as insulin are also present. Under these conditions, it is uncertain if the inhibitory effects of FAs would be overcome by insulin. The effects of a combination of FAs, insulin and glucose on glucose phosphorylation and metabolism in cultured primary rat hepatocytes at concentrations that mimic those in the portal circulation after a meal was examined. It was found that total GK activity was unaffected by an increased concentration of insulin, but palmitate and eicosapentaenoic acid significantly lowered total GK activity in the presence of insulin. Despite the fact that total GK enzyme activity was reduced in response to FA incubation, GK enzyme translocation from the inactive, nuclear bound, to active, cytoplasmic state was unaffected. Interestingly, none of the FAs tested inhibited glucose phosphorylation or the rate of glycolysis when insulin is present. These results suggest that in the presence of insulin the levels of the active, unbound cytoplasmic GK are sufficient to buffer a slight decrease in GK enzyme activity and decreased promoter activity caused by FA exposure. Although a high fat diet has been associated with impaired hepatic glucose metabolism, there is no evidence from this thesis that FAs themselves directly modulate flux through the glycolytic pathway in isolated primary hepatocytes when insulin is also present. Therefore, although FA affected expression of a wide range of genes, including GK, this did not affect glycolytic flux in the presence of insulin. However, it may be possible that a saturated FA-induced decrease in GK enzyme activity when combined with the onset of insulin resistance may promote the dys-regulation of glucose homeostasis and the subsequent development of hyperglycaemia, metabolic syndrome and type 2 diabetes.