Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

The role of nature-based experiences in the development and maintenance of wellness

Wellness is now seen as central to redefining the National Health agenda. There is growing evidence that contact with nature and physical activity in nature has considerable positive effects on human health. At the most basic level humanity is reliant on the natural world for resources such as air and water. However, a growing body of research is finding that beyond this fundamental relationship exposure to the non-human natural world can also positively enhance perceptions of physiological, emotional, psychological and spiritual health in ways that cannot be satisfied by alternate means. Theoretical explanations for this have posited that non-human nature might 1) restore mental fatigue, 2) trigger deep reflections, 3) provide an opportunity for nurturing and 4) rekindle innate connections. In this paper the authors show how human wellness is strongly connected to their relationship with the natural world. This paper points to how non-human nature could be better utilised for enhancing human health and wellness.

Getting lost in the field : the unpredictable nature of fieldwork with young people

This chapter focuses on the unpredictable nature of fieldwork with young offenders, specifically with those in a marginalised context. We begin by recounting our experiences working with young people who have had contact with criminal justice processes, particularly those who are the subject of extreme levels of official social control. We then turn to a discussion of the challenges associated with the unpredictable nature of fieldwork, specifically the difficulties associated with negotiating access with gatekeepers and negotiating with young people. We also discuss specific challenges with the research ethics governance of ethically sensitive research in this context (e.g. interviewing young people about offending behaviour). Finally, we recount our experiences in working these young people, with a focus on ‘the grunt’: that is, drawing out young peoples’ stories in interviews. We conclude with some reflections on the need to develop systematic instruction in qualitative work in this specific context.

The nature and prevalence of inter-organizational project ventures : evidence from a large scale field study in the Netherlands 2006-2009

There has recently been noted a rapid increase in research attention to projects that involve outside partners. Our knowledge of such inter-organizational projects, however, is limited. This paper reports large scale data from a repeated trend survey amongst 2000 SMEs in 2006 and 2009 that focused on inter-organizational project ventures. Our major findings indicate that the overall prevalence of inter-organizational project ventures remained significant and stable over time, even despite the economic crisis. Moreover, we find that these ventures predominantly solve repetitive rather than unique tasks and are embedded in prior relations between the partnering organizations. These findings provide empirical support for the recent claims that project management should pay more attention to inter-organizational forms of project organization, and suggest that the archetypical view of projects as being unique in every respect should be reconsidered. Both have important implications for project management, especially in the area of project-based learning.

Molecular phylogeny supports the paraphyletic nature of the genus Trogoderma (Coleoptera: Dermestidae) collected in the Australasian ecozone

To date, a molecular phylogenetic approach has not been used to investigate the evolutionary structure of Trogoderma and closely related genera. Using two mitochondrial genes, Cytochrome Oxidase I and Cytochrome B, and the nuclear gene, 18S, the reported polyphyletic positioning of Trogoderma was examined. Paraphyly in Trogoderma was observed, with one Australian Trogoderma species reconciled as sister to all Dermestidae and the Anthrenocerus genus deeply nested within the Australian Trogoderma clade. In addition, time to most recent common ancestor for a number of Dermestidae was calculated. Based on these estimations, the Dermestidae origin exceeded 175 million years, placing the origins of this family in Pangaea.

Nature and genesis of clay minerals of the Rustler Formation in the vicinity of the Waste Isolation Pilot Plant in Souteastern New Mexico

Detailed mineralogical studies of the matrix and fracture-fill materials of a large number of samples from the Rustler Formation have been carried out using x-ray diffraction, high-resolution transmission electron microscopy, electron microprobe analysis, x-ray fluorescence, and atomic absorption spectrophotometry. These analyses indicate the presence of four clay minerals: interstratified chlorite/saponite, illite, chlorite, and serpentine. Corrensite (regularly stratified chlorite/saponite) is the dominant clay mineral in samples from the Culebra dolomite and two shale layers of the lower unnamed member of the Rustler Formation. Within other layers of the Rustler Formation, disordered mixed chlorite/saponite is usually the most abundant clay mineral. Studies of the morphology and composition of clay crystallites suggest that the corrensite was formed by the alteration of detrital dioctahedral smectite in magnesium-rich pore fluids during early diagenesis of the Rustler Formation. This study provides initial estimates of the abundance and nature of the clay minerals in the Culebra dolomite in the vicinity of the Waste Isolation Pilot Plant.

An analysis of the timeliness and nature of profit warnings in the aftermath of the Global Financial Crisis

The global financial crisis (GFC) has severely impacted the financial position and performance of many companies internationally. Because of its severity and associated increase in uncertainty it challenges the effectiveness of existing disclosure regulation. Australia provides a unique environment in which to test the effects of the GFC on corporate disclosure because statutory rules mandate the timely disclosure of ‘price-sensitive’ information (ASX Rule 3.1) by listed entities. Exploiting this institutional setting we investigate the determinants and timeliness of profit warnings issued by the top 500 ASX-listed firms with profit declines in the 2009 fiscal year. Our findings show that firms behave differently with regard to the issuance of profit warnings: larger and more indebted firms are more likely to issue a profit warning and tend to be timelier; surprisingly, poorer performing firms tend to release the news more quickly and this might be attributed to an increasing threat of litigation. Our analysis of profit warning determinants shows interesting results with the presence of asset impairments hindering the early disclosure of profit warnings. Our findings are novel for two main reasons: first, we provide insights into the impact of global financial crisis on profit warning behaviour; second, we are the first to examine the differential impact of alternative features of profit warnings on disclosure timeliness. The findings have implications for regulators in determining compliance with continuous disclosure rules and more broadly, for market participants in interpreting profit warnings.

Emotions in the Experiential Consumption of Mobile Phones

Although marketers have a strong interest in finding ways to engage with consumers through mobile phones, the everyday experiential, or affective consumption practices surrounding this technology have received limited attention in the literature. To address this limitation, we used appraisal theory, which specifies it is the way individuals appraise situations or events that elicit emotions. We conducted an experience sampling method study to explore the emotions that individuals experience during their interactions with and through their mobile phones and what situations or events elicit these emotions. The preliminary findings show a number of significant relationships between emotions and specfic clusters of situations and events. Additionally, age and gender were also important indicators. The research contributes to a deeper understanding of the experiential nature of mobile information technologies through consumers’ everyday-consumption-related emotions and the situations and events that elicit them.

A natural model for architecture : the nature of the evolutionary model 1995

John Frazer's architectural work is inspired by living and generative processes. Both evolutionary and revolutionary, it explores informatin ecologies and the dynamics of the spaces between objects. Fuelled by an interest in the cybernetic work of Gordon Pask and Norbert Wiener, and the possibilities of the computer and the "new science" it has facilitated, Frazer and his team of collaborators have conducted a series of experiments that utilize genetic algorithms, cellular automata, emergent behaviour, complexity and feedback loops to create a truly dynamic architecture. Frazer studied at the Architectural Association (AA) in London from 1963 to 1969, and later became unit master of Diploma Unit 11 there. He was subsequently Director of Computer-Aided Design at the University of Ulter - a post he held while writing An Evolutionary Architecture in 1995 - and a lecturer at the University of Cambridge. In 1983 he co-founded Autographics Software Ltd, which pioneered microprocessor graphics. Frazer was awarded a person chair at the University of Ulster in 1984. In Frazer's hands, architecture becomes machine-readable, formally open-ended and responsive. His work as computer consultant to Cedric Price's Generator Project of 1976 (see P84)led to the development of a series of tools and processes; these have resulted in projects such as the Calbuild Kit (1985) and the Universal Constructor (1990). These subsequent computer-orientated architectural machines are makers of architectural form beyond the full control of the architect-programmer. Frazer makes much reference to the multi-celled relationships found in nature, and their ongoing morphosis in response to continually changing contextual criteria. He defines the elements that describe his evolutionary architectural model thus: "A genetic code script, rules for the development of the code, mapping of the code to a virtual model, the nature of the environment for the development of the model and, most importantly, the criteria for selection. In setting out these parameters for designing evolutionary architectures, Frazer goes beyond the usual notions of architectural beauty and aesthetics. Nevertheless his work is not without an aesthetic: some pieces are a frenzy of mad wire, while others have a modularity that is reminiscent of biological form. Algorithms form the basis of Frazer's designs. These algorithms determine a variety of formal results dependent on the nature of the information they are given. His work, therefore, is always dynamic, always evolving and always different. Designing with algorithms is also critical to other architects featured in this book, such as Marcos Novak (see p150). Frazer has made an unparalleled contribution to defining architectural possibilities for the twenty-first century, and remains an inspiration to architects seeking to create responsive environments. Architects were initially slow to pick up on the opportunities that the computer provides. These opportunities are both representational and spatial: computers can help architects draw buildings and, more importantly, they can help architects create varied spaces, both virtual and actual. Frazer's work was groundbreaking in this respect, and well before its time.

Research Monograph: The role of community and lifestyle in the making of a knowledge city

Our brief is to investigate the role of community and lifestyle in the making of a globally successful knowledge city region. Our approach is essentially pragmatic. We start by broadly examining knowledge-based urban development from a number of different perspectives. The first view is historical. In this context knowledge work and knowledge workers are seen as vital parts of a new emergent mode of production reliant on the continual production of abstract knowledge. We briefly develop this perspective to encompass the work of Richard Florida who has, notedly, claimed: “Wherever talent goes, innovation, creativity, and economic growth are sure to follow.” Our next perspective examines concepts of knowledge and modes of its production to discover knowledge is not an unchanging object but a human activity that changes in form and content through history. The suggestion emerges that not only is the production of contemporary ‘knowledge’ organised in a specific (and new) manner but also the output of this networked production is a particular type of knowledge (i.e. techné). The third perspective locates knowledge production and its workers in the contemporary urban context. As such, it co-ordinates the knowledge city in the increasingly global structure of cities and develops a typology of different groups of knowledge workers in their preferred urban environment(s). We see emerging here a distinctive geography of knowledge production. It is an urban phenomenon. There is, in short, something about the nature of cities that knowledge workers find particularly attractive. In the next, essentially anthropological, perspective we start to explore the needs and desires of the individual knowledge worker. Beyond the needs basic to any modern human household an attempt is made to deduce, from a base understanding of knowledge work as mental labour, the compensatory cultural needs of the knowledge worker when not at work - and the expression of these needs in the urban fabric. Our final perspective consists of two case studies. In a review of the experiences of Austin, Texas and Singapore’s one-north precinct we collect empirical data on, respectively, a knowledge city that has sustained itself for over 50 years and an urban precinct newly launched into the global market for knowledge work and knowledge workers. Interwoven The Role of Community and Lifestyle in the Making of a Knowledge City Urban Research Program 8 through all perspectives, in the form of apposite citation, is that of ‘expert opinion’ gathered in a rudimentary poll of academic and industry sources. This opinion appears in text boxes while details of the survey can be found in Appendix A. In the conclusion of the report we interpret the wide range of evidence gathered above in a policy frame. It is our hope this report will leave the reader with a clearer picture of the decisive organisational, infrastructural, aesthetic and social dimensions of a knowledge precinct.

Issues in the development of pitch labelling skill

Pitch discrimination skills are important for general musicianship. The ability to name musical notes or produce orally any named note without the benefit of a known reference is called Absolute Pitch (AP) and is comparatively rare. Relative Pitch (RP) is the ability to name notes when a known reference is available. AP has historically been regarded as being innate. This paper will examine the notion that pitch discrimination skill is based on knowledge constructed through a suite of experiences. That is, it is learnt. In particular, it will be argued that early experiences promote the development of AP. Second it will argue that AP and RP represent different types of knowledge, and that this knowledge emerges from different experiences. AP is a unique research phenomenon because it spans the fields of cognition and perception, in that it links verbal labels with physiological sensations, and because of its rarity. It may provide a vantage for investigating the nature/nurture of musicianship; expertise; knowledge structure development; and the role of knowledge in perception. The study of AP may inform educational practice and curriculum design both in music and cross-curriculur. This paper will report an initial investigation into the similarities and differences between the musical experiences of AP possessors and the manifestation of their AP skill. Interview and questionnaire data will be used for the development and proposal of a preliminary model for AP development.