Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

Pedagogies of inclusive transition to school

Teachers in inclusive early education classrooms face competing pressures that are highlighted as children transition from play-based settings into formal school. Their challenge is to engage in pedagogical practice that caters for the complex range of school entrants. Yet the existing literature reports on transition challenges for separate groups of children rather than on shared needs or processes within diverse class populations. This study addressed this gap by investigating practices that supported transition in three Australian sites in which the populations represented different types of pedagogic challenge. Four themes regarding inclusion and transition were identified from a synthesis of the literature and applied to three cases. Results indicated that teachers adopted a range of approaches framed by the visibility of diversity, by classroom and school context and by the teachers’ professional transition in enacting changing policies. The results suggest that competing demands are balanced through dynamic, contextually framed strategies of relevance to both ECEC and schools.

Getting there, being there, staying and belonging: a case study of two indigenous Australian children’s transition to school

Indigenous Australians are among the most unhealthy populations in the world and yet they reside in a country where the non-Indigenous population enjoys high standards of well-being. Education has been identified as the key mechanism for closing this equity gap. At school commencement many Indigenous children are already at risk of disengagement. This four-year longitudinal study of two Indigenous boys from a socially marginalised community examined key factors affecting transitional trajectories into school. While child characteristics affected level of achievement the critical factors in sustaining positive educational engagement were social support, school practices, inclusion of family and positive expectation.

Bonding and bridging : transition to school and social capital formation among a community of Indigenous Australian children

This study reports on an intervention program designed to facilitate transition to school of a whole community of Indigenous Australian children who had previously not been attending. The children were from families displaced from their traditional lands and experienced on-going social marginalisation and transience. A social capital framework was employed to track change in the children’s social inclusion and family-school engagement for two years, from school entry. Sociometric measurement and interview techniques were applied to assess the children’s social connectedness and peer relationship quality. Using these data, analyses examined whether bonding within the group supported or inhibited formation of new social relationships. Although transience disrupted attendance, there was a group trend towards increased social inclusion with some evidence that group bonds supported bridging to new social relationships. Change in family-school engagement was tracked using multi-informant interviews. Limited engagement between school and families presented an on-going challenge to sustained educational engagement.

The importance of agency in facilitating the transition to a multifunctional countryside

We appreciate Holmes' body of work relating to transitions within the Australian landscape, and welcome the opportunity to engage in a discussion on this topic. The paper to which Holmes refers (Bjørkhaug and Richards, 2008) examined the application of agricultural (rather than landscape) multifunctionality in both Norway and Australia. Of specific focus was how non-tradeable concerns, such as environmental sustainability, faired under these divergent systems. We argued that Norway's multifunctionality was strong, due to it being embraced at both the policy and actor level, whereas Australia's could be described as weak. This ‘weak multifunctionality’ that we observed in Australia was due to an emerging bi-lateral (state and federal) policy framework that advocated the importance of environmental values which was rarely embraced by landholders who found themselves trapped on the ‘agricultural treadmill’. The nature of the treadmill is that alternative forms of land use are unthinkable when on-farm investments have been made that support the status quo – to get bigger and/or more efficient. For many of the Australian landholders interviewed in relation to this study, efficiency in production was at odds with the values necessary to effect a transition toward multifunctionality. For instance, graziers in Central Queensland were unconvinced of the value of conserving native flora and fauna when economic viability can be better assured through clear felling native forests to increase the productive capacity of the land.

A discussion of “Estimating the historical and future probabilities of large terrorist events'' by Aaron Clauset and Ryan Woodard

The terrorist attacks in the United States on September 11, 2001 appeared to be a harbinger of increased terrorism and violence in the 21st century, bringing terrorism and political violence to the forefront of public discussion. Questions about these events abound, and “Estimating the Historical and Future Probabilities of Large Scale Terrorist Event” [Clauset and Woodard (2013)] asks specifically, “how rare are large scale terrorist events?” and, in general, encourages discussion on the role of quantitative methods in terrorism research and policy and decision-making. Answering the primary question raises two challenges. The first is identify- ing terrorist events. The second is finding a simple yet robust model for rare events that has good explanatory and predictive capabilities. The challenges of identifying terrorist events is acknowledged and addressed by reviewing and using data from two well-known and reputable sources: the Memorial Institute for the Prevention of Terrorism-RAND database (MIPT-RAND) [Memorial Institute for the Prevention of Terrorism] and the Global Terror- ism Database (GTD) [National Consortium for the Study of Terrorism and Responses to Terrorism (START) (2012), LaFree and Dugan (2007)]. Clauset and Woodard (2013) provide a detailed discussion of the limitations of the data and the models used, in the context of the larger issues surrounding terrorism and policy.

Pockets of Change : Adaptation and Cultural Transition

Pockets of Change collects fourteen essays that address issues of cultural adaptation and transition in the Arts. Based on insights into a range of primary texts and cultural practices—from visual art to film, from literature to theatre—these essays investigate the ways in which traditions, art-forms, cultures and ethics adapt to challenge established boundaries.

Document ranking with quantum probabilities

In this thesis we investigate the use of quantum probability theory for ranking documents. Quantum probability theory is used to estimate the probability of relevance of a document given a user's query. We posit that quantum probability theory can lead to a better estimation of the probability of a document being relevant to a user's query than the common approach, i. e. the Probability Ranking Principle (PRP), which is based upon Kolmogorovian probability theory. Following our hypothesis, we formulate an analogy between the document retrieval scenario and a physical scenario, that of the double slit experiment. Through the analogy, we propose a novel ranking approach, the quantum probability ranking principle (qPRP). Key to our proposal is the presence of quantum interference. Mathematically, this is the statistical deviation between empirical observations and expected values predicted by the Kolmogorovian rule of additivity of probabilities of disjoint events in configurations such that of the double slit experiment. We propose an interpretation of quantum interference in the document ranking scenario, and examine how quantum interference can be effectively estimated for document retrieval. To validate our proposal and to gain more insights about approaches for document ranking, we (1) analyse PRP, qPRP and other ranking approaches, exposing the assumptions underlying their ranking criteria and formulating the conditions for the optimality of the two ranking principles, (2) empirically compare three ranking principles (i. e. PRP, interactive PRP, and qPRP) and two state-of-the-art ranking strategies in two retrieval scenarios, those of ad-hoc retrieval and diversity retrieval, (3) analytically contrast the ranking criteria of the examined approaches, exposing similarities and differences, (4) study the ranking behaviours of approaches alternative to PRP in terms of the kinematics they impose on relevant documents, i. e. by considering the extent and direction of the movements of relevant documents across the ranking recorded when comparing PRP against its alternatives. Our findings show that the effectiveness of the examined ranking approaches strongly depends upon the evaluation context. In the traditional evaluation context of ad-hoc retrieval, PRP is empirically shown to be better or comparable to alternative ranking approaches. However, when we turn to examine evaluation contexts that account for interdependent document relevance (i. e. when the relevance of a document is assessed also with respect to other retrieved documents, as it is the case in the diversity retrieval scenario) then the use of quantum probability theory and thus of qPRP is shown to improve retrieval and ranking effectiveness over the traditional PRP and alternative ranking strategies, such as Maximal Marginal Relevance, Portfolio theory, and Interactive PRP. This work represents a significant step forward regarding the use of quantum theory in information retrieval. It demonstrates in fact that the application of quantum theory to problems within information retrieval can lead to improvements both in modelling power and retrieval effectiveness, allowing the constructions of models that capture the complexity of information retrieval situations. Furthermore, the thesis opens up a number of lines for future research. These include: (1) investigating estimations and approximations of quantum interference in qPRP; (2) exploiting complex numbers for the representation of documents and queries, and; (3) applying the concepts underlying qPRP to tasks other than document ranking.

Mentoring : improving transition to practice

Nurse graduates indicate the transition from student of nursing to registered nurse (RN) is a difficult conversion. This impending change of role and accompanying higher expectations placed upon newly graduating RNs causes concern for students as their Bachelor of Nursing program nears completion. A career mentor scheme is suggested as a way to better prepare final year students for this transition. Evaluations indicate the positive impact the scheme has made on both mentors and mentees as it has enhanced their career development.

Career mentoring : a career development-enhancing strategy for university students in transition to employment

In 1992 the Queensland University of Technology (QUT) Convocation initiated the Mentor Scheme to assist students to better prepare for the transition to employment. The scheme has developed over the past six years and in 1998 more than 130 pairs of employers and students from 12 different disciplines participated in it. Evaluations indicate the positive impact the scheme has made on both mentors and mentees, particularly in enhancing mentees' career development.

Radiative and total heat transfer measurements to a Titan Explorer model

Radiative and total heat transfer at the flow stagnation point of a 1:40.8 binary scaled model of the Titan Explorer vehicle were measured in the X3 expansion tube. Results from the current study illustrated that with the addition of CH4 into a N2 test gas radiative heat transfer could be detected. For a test gas of 5% CH4 and 95% N2, simulating an atmospheric model for Titanic aerocapture, approximately 4% of the experimentally measured total stagnation point heat transfer was found to be due to radiation. This was in comparison to < 1% measured for a test gas of pure nitrogen. When scaled to the flight vehicle, experimental results indicate a 64% contribution of radiation (test gas 5% CH4/95% N2). Previous numerical results however have predicted this contribution to be between 80-92%. Thus, experimental results from the current study suggest that numerical analyses are over-predicting the radiative heat transfer on the flight vehicle.

Estimating present day extreme water level exceedance probabilities around the coastline of Australia : tides, extra-tropical storm surges and mean sea level

The occurrence of extreme water levels along low-lying, highly populated and/or developed coastlines can lead to considerable loss of life and billions of dollars of damage to coastal infrastructure. Therefore it is vitally important that the exceedance probabilities of extreme water levels are accurately evaluated to inform risk-based flood management, engineering and future land-use planning. This ensures the risk of catastrophic structural failures due to under-design or expensive wastes due to over-design are minimised. This paper estimates for the first time present day extreme water level exceedence probabilities around the whole coastline of Australia. A high-resolution depth averaged hydrodynamic model has been configured for the Australian continental shelf region and has been forced with tidal levels from a global tidal model and meteorological fields from a global reanalysis to generate a 61-year hindcast of water levels. Output from this model has been successfully validated against measurements from 30 tide gauge sites. At each numeric coastal grid point, extreme value distributions have been fitted to the derived time series of annual maxima and the several largest water levels each year to estimate exceedence probabilities. This provides a reliable estimate of water level probabilities around southern Australia; a region mainly impacted by extra-tropical cyclones. However, as the meteorological forcing used only weakly includes the effects of tropical cyclones, extreme water level probabilities are underestimated around the western, northern and north-eastern Australian coastline. In a companion paper we build on the work presented here and more accurately include tropical cyclone-induced surges in the estimation of extreme water level. The multi-decadal hindcast generated here has been used primarily to estimate extreme water level exceedance probabilities but could be used more widely in the future for a variety of other research and practical applications.