The synthesis and application of novel profluorescent nitroxides as probes for polymer degradation

This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

Effective web service discovery using a combination of a semantic model and a data mining technique

With the advent of Service Oriented Architecture, Web Services have gained tremendous popularity. Due to the availability of a large number of Web services, finding an appropriate Web service according to the requirement of the user is a challenge. This warrants the need to establish an effective and reliable process of Web service discovery. A considerable body of research has emerged to develop methods to improve the accuracy of Web service discovery to match the best service. The process of Web service discovery results in suggesting many individual services that partially fulfil the user’s interest. By considering the semantic relationships of words used in describing the services as well as the use of input and output parameters can lead to accurate Web service discovery. Appropriate linking of individual matched services should fully satisfy the requirements which the user is looking for. This research proposes to integrate a semantic model and a data mining technique to enhance the accuracy of Web service discovery. A novel three-phase Web service discovery methodology has been proposed. The first phase performs match-making to find semantically similar Web services for a user query. In order to perform semantic analysis on the content present in the Web service description language document, the support-based latent semantic kernel is constructed using an innovative concept of binning and merging on the large quantity of text documents covering diverse areas of domain of knowledge. The use of a generic latent semantic kernel constructed with a large number of terms helps to find the hidden meaning of the query terms which otherwise could not be found. Sometimes a single Web service is unable to fully satisfy the requirement of the user. In such cases, a composition of multiple inter-related Web services is presented to the user. The task of checking the possibility of linking multiple Web services is done in the second phase. Once the feasibility of linking Web services is checked, the objective is to provide the user with the best composition of Web services. In the link analysis phase, the Web services are modelled as nodes of a graph and an allpair shortest-path algorithm is applied to find the optimum path at the minimum cost for traversal. The third phase which is the system integration, integrates the results from the preceding two phases by using an original fusion algorithm in the fusion engine. Finally, the recommendation engine which is an integral part of the system integration phase makes the final recommendations including individual and composite Web services to the user. In order to evaluate the performance of the proposed method, extensive experimentation has been performed. Results of the proposed support-based semantic kernel method of Web service discovery are compared with the results of the standard keyword-based information-retrieval method and a clustering-based machine-learning method of Web service discovery. The proposed method outperforms both information-retrieval and machine-learning based methods. Experimental results and statistical analysis also show that the best Web services compositions are obtained by considering 10 to 15 Web services that are found in phase-I for linking. Empirical results also ascertain that the fusion engine boosts the accuracy of Web service discovery by combining the inputs from both the semantic analysis (phase-I) and the link analysis (phase-II) in a systematic fashion. Overall, the accuracy of Web service discovery with the proposed method shows a significant improvement over traditional discovery methods.

Being ethical : how process drama assists pre-service drama teachers to reflect on professional ethics

This research thesis focuses on the experiences of pre-service drama teachers and considers how process drama may assist them to reflect on key aspects of professional ethics such as mandatory codes or standards, principled moral reasoning, moral character, moral agency, and moral literacy. Research from higher education provides evidence that current pedagogical approaches used to prepare pre –professionals for practice in medicine, engineering, accountancy, business, psychology, counselling, nursing and education, rarely address the more holistic or affective dimensions of professional ethics such as moral character. Process drama, a form of educational drama, is a complex improvisational group experience that invites participants to create and assume roles, and select and manage symbols in order to create a fictional world exploring human experience. Many practitioners claim that process drama offers an aesthetic space to develop a deeper understanding of self and situations, expanding the participant’s consciousness and ways of knowing. However, little research has been conducted into the potential efficacy of process drama in professional ethics education for pre-professionals. This study utilizes practitioner research and case study to explore how process drama may contribute to the development of professional ethics education and pedagogy.

Enriching relationships : community engagment toward sustainable coastal futures

Coastal communities face the social, cultural and environmental challenges of managing rapid urban and industrial development, expanding tourism, and sensitive ecological environments. Enriching relationships between communities and universities through a structured engagement process can deliver integrated options towards sustainable coastal futures. This process draws on the embedded knowledge and values of all participants in the relationship, and offers a wide and affordable range of options for the future. This paper reviews lessons learnt from two projects with coastal communities, and discusses their application in a third. Queensland University of Technology has formed collaborative partnerships with industry in Queensland's Wide Bay-Burnett region to undertake a series of planning and design projects with community engagement as a central process. Senior students worked with community and produced design and planning drawings and reports outlining future options for project areas. A reflective approach has been adopted by the authors to assess the engagement process and outcomes of each project to learn lessons to apply in the next. Methods include surveying community and student participants regarding the value they place on process and outcomes respectively in planning for a sustainable future. All project participants surveyed have placed high importance on the process of engagement, emphasising the value of developing relationships between all project partners. The quality of these relationships is central to planning for sustainable futures, and while the outcomes the students deliver are valued, it is as much for their catalytic role as for their contents. Design and planning projects through community engagement have been found to develop innovative responses to the challenges faced by coastal communities seeking direction toward sustainable futures. The enrichment of engagement relationships and processes has an important influence on the quality of these design and planning responses.

An innovative learning model for teaching architectural technology using building information modelling : a Queensland University of Technology perspective

In architecture courses, instilling a wider understanding of the industry specific representations practiced in the Building Industry is normally done under the auspices of Technology and Science subjects. Traditionally, building industry professionals communicated their design intentions using industry specific representations. Originally these mainly two dimensional representations such as plans, sections, elevations, schedules, etc. were produced manually, using a drawing board. Currently, this manual process has been digitised in the form of Computer Aided Design and Drafting (CADD) or ubiquitously simply CAD. While CAD has significant productivity and accuracy advantages over the earlier manual method, it still only produces industry specific representations of the design intent. Essentially, CAD is a digital version of the drawing board. The tool used for the production of these representations in industry is still mainly CAD. This is also the approach taken in most traditional university courses and mirrors the reality of the situation in the building industry. A successor to CAD, in the form of Building Information Modelling (BIM), is presently evolving in the Construction Industry. CAD is mostly a technical tool that conforms to existing industry practices. BIM on the other hand is revolutionary both as a technical tool and as an industry practice. Rather than producing representations of design intent, BIM produces an exact Virtual Prototype of any building that in an ideal situation is centrally stored and freely exchanged between the project team. Essentially, BIM builds any building twice: once in the virtual world, where any faults are resolved, and finally, in the real world. There is, however, no established model for learning through the use of this technology in Architecture courses. Queensland University of Technology (QUT), a tertiary institution that maintains close links with industry, recognises the importance of equipping their graduates with skills that are relevant to industry. BIM skills are currently in increasing demand throughout the construction industry through the evolution of construction industry practices. As such, during the second half of 2008, QUT 4th year architectural students were formally introduced for the first time to BIM, as both a technology and as an industry practice. This paper will outline the teaching team’s experiences and methodologies in offering a BIM unit (Architectural Technology and Science IV) at QUT for the first time and provide a description of the learning model. The paper will present the results of a survey on the learners’ perspectives of both BIM and their learning experiences as they learn about and through this technology.

Does venture opportunity variation matter? investigating systematic process differences between innovative and imitative new ventures

The central thesis in the article is that the venture creation process is different for innovative versus imitative ventures. This holds up; the pace of the process differs by type of venture as do, in line with theory-based hypotheses, the effects of certain human capital (HC) and social capital (SC) predictors. Importantly, and somewhat unexpectedly, the theoretically derived models using HC, SC, and certain controls are relatively successful explaining progress in the creation process for the minority of innovative ventures, but achieve very limited success for the imitative majority. This may be due to a rationalistic bias in conventional theorizing and suggests that there is need for considerable theoretical development regarding the important phenomenon of new venture creation processes. Another important result is that the building up of instrumental social capital, which we assess comprehensively and as a time variant construct, is important for making progress with both types of ventures, and increasingly, so as the process progresses. This result corroborates with stronger operationalization and more appropriate analysis method what previously published research has only been able to hint at.

Discovering, applying and integrating: The process of learning in coaching

Professional coaching is a rapidly expanding field with interdisciplinary roots and broad application. However, despite abundant prescriptive literature, research into the process of coaching is minimal. Similarly, although learning is inherently recognised in the process of coaching, the process of learning in coaching is little understood and learning theory makes up only a small part of the evidence-based coaching literature. In this grounded theory study of coaches and their clients, the process of learning in coaching across a range of coaching models is examined and discussed. The findings demonstrate how learning in coaching emerged as a process of discovering, applying and integrating new knowledge, which culminated in a process of developing. This process occurred through eight key coaching processes shared between coaches and clients and combined a multitude of learning theories.

Literature Review Value Alignment Process for Project Delivery

The objective of the project “Value Alignment Process for Project Delivery” is to provide a catalyst and tools for reform in the building and construction industry to transform business-as-usual performance into exceptional performance. The outcomes of this project will be beneficial to not only the construction industry, but to the community as a whole because a more sophisticated industry can deliver more effective use of assets, financing, operating and maintenance of facilities to suit the community’s needs. The research project consists of a study into best practice project delivery and the development of a suite of products, resources and services to guide project teams towards the best approach for a specific project. These resources will be focused on promoting the principles that underlie best practice project delivery, rather than on identifying a particular delivery system. The need for such tools and resources becomes more and more acute as the environment within which the construction industry operates becomes more and more complex, and as business and political imperatives shift to encompass or represent diverse stakeholder interests. To this end, this literature review looks at why it is essential to achieve transformation in the Australian construction industry in the context of its importance to the Australian economy. It seeks to investigate the concepts of ‘alignment’ and value’ as they pertain to construction industry processes and relationships. It comprehensively reviews drivers of project excellence and best practice project delivery principles and looks at how clients approach selection of project delivery systems. It critiques existing project delivery strategies and gives an overview of recent best practice initiatives. The literature review represents a milestone against the Project Agreement and forms a foundation document for this research project

Virtual design process : design validation tool schematic approach in car carrier

An important aspect of designing any product is validation. Virtual design process (VDP) is an alternative to hardware prototyping in which analysis of designs can be done without manufacturing physical samples. In recent years, VDP have been generated either for animation or filming applications. This paper proposes a virtual reality design process model on one of the applications when used as a validation tool. This technique is used to generate a complete design guideline and validation tool of product design. To support the design process of a product, a virtual environment and VDP method were developed that supports validation and an initial design cycle performed by a designer. The product model car carrier is used as illustration for which virtual design was generated. The loading and unloading sequence of the model for the prototype was generated using automated reasoning techniques and was completed by interactively animating the product in the virtual environment before complete design was built. By using the VDP process critical issues like loading, unloading, Australian Design rules (ADR) and clearance analysis were done. The process would save time, money in physical sampling and to large extent in complete math generation. Since only schematic models are required, it saves time in math modelling and handling of bigger size assemblies due to complexity of the models. This extension of VDP process for design evaluation is unique and was developed, implemented successfully. In this paper a Toll logistics and J Smith and Sons car carrier which is developed under author’s responsibility has been used to illustrate our approach of generating design validation via VDP.

Nation & internation practices in decision support tools in road asset management

This document provides a review of international and national practices in investment decision support tools in road asset management. Efforts were concentrated on identifying analytic frameworks, evaluation methodologies and criteria adopted by current tools. Emphasis was also given to how current approaches support Triple Bottom Line decision-making. Benefit Cost Analysis and Multiple Criteria Analysis are principle methodologies in supporting decision-making in Road Asset Management. The complexity of the applications shows significant differences in international practices. There is continuing discussion amongst practitioners and researchers regarding to which one is more appropriate in supporting decision-making. It is suggested that the two approaches should be regarded as complementary instead of competitive means. Multiple Criteria Analysis may be particularly helpful in early stages of project development, say strategic planning. Benefit Cost Analysis is used most widely for project prioritisation and selecting the final project from amongst a set of alternatives. Benefit Cost Analysis approach is useful tool for investment decision-making from an economic perspective. An extension of the approach, which includes social and environmental externalities, is currently used in supporting Triple Bottom Line decision-making in the road sector. However, efforts should be given to several issues in the applications. First of all, there is a need to reach a degree of commonality on considering social and environmental externalities, which may be achieved by aggregating the best practices. At different decision-making level, the detail of consideration of the externalities should be different. It is intended to develop a generic framework to coordinate the range of existing practices. The standard framework will also be helpful in reducing double counting, which appears in some current practices. Cautions should also be given to the methods of determining the value of social and environmental externalities. A number of methods, such as market price, resource costs and Willingness to Pay, are found in the review. The use of unreasonable monetisation methods in some cases has discredited Benefit Cost Analysis in the eyes of decision makers and the public. Some social externalities, such as employment and regional economic impacts, are generally omitted in current practices. This is due to the lack of information and credible models. It may be appropriate to consider these externalities in qualitative forms in a Multiple Criteria Analysis. Consensus has been reached in considering noise and air pollution in international practices. However, Australia practices generally omitted these externalities. Equity is an important consideration in Road Asset Management. The considerations are either between regions, or social groups, such as income, age, gender, disable, etc. In current practice, there is not a well developed quantitative measure for equity issues. More research is needed to target this issue. Although Multiple Criteria Analysis has been used for decades, there is not a generally accepted framework in the choice of modelling methods and various externalities. The result is that different analysts are unlikely to reach consistent conclusions about a policy measure. In current practices, some favour using methods which are able to prioritise alternatives, such as Goal Programming, Goal Achievement Matrix, Analytic Hierarchy Process. The others just present various impacts to decision-makers to characterise the projects. Weighting and scoring system are critical in most Multiple Criteria Analysis. However, the processes of assessing weights and scores were criticised as highly arbitrary and subjective. It is essential that the process should be as transparent as possible. Obtaining weights and scores by consulting local communities is a common practice, but is likely to result in bias towards local interests. Interactive approach has the advantage in helping decision-makers elaborating their preferences. However, computation burden may result in lose of interests of decision-makers during the solution process of a large-scale problem, say a large state road network. Current practices tend to use cardinal or ordinal scales in measure in non-monetised externalities. Distorted valuations can occur where variables measured in physical units, are converted to scales. For example, decibels of noise converts to a scale of -4 to +4 with a linear transformation, the difference between 3 and 4 represents a far greater increase in discomfort to people than the increase from 0 to 1. It is suggested to assign different weights to individual score. Due to overlapped goals, the problem of double counting also appears in some of Multiple Criteria Analysis. The situation can be improved by carefully selecting and defining investment goals and criteria. Other issues, such as the treatment of time effect, incorporating risk and uncertainty, have been given scant attention in current practices. This report suggested establishing a common analytic framework to deal with these issues.

Ethical behaviour in the construction procurement process

In construction, inter-organisational relationships are of the highest importance. Ethical practice and behaviour is a means for improving inter-organisational relationships by providing a clear understanding of the rights and obligations of all parties, improving productivity, affecting long-term business dealings, and influencing quality, time and costs. Therefore, the ability to build sustainable relationships grounded in ethical practice is important to the construction industry. Establishing ethical standards at the beginning of the procurement process provides an ethical platform for the project life cycle and the relationship between procurers and contractors. Therefore it is important to determine what the ethical issues are in the Australian construction industry from members of the industry themselves; including clients. This “bottom up” approach is not a particularly new concept. Ever since the Gyles Royal Commission in 1992 there has been a considerable effort by government agencies to develop policies to improve the ethical behaviour of the industry.

Is the sum more than the corporate entrepreneurship parts? the different effects of social capital on innovation, venturing, and renewal processes

Principal Topic Although corporate entrepreneurship is of vital importance for long-term firm survival and growth (Zahra and Covin, 1995), researchers still struggle with understanding how to manage corporate entrepreneurship activities. Corporate entrepreneurship consists of three parts: innovation, venturing, and renewal processes (Guth and Ginsberg, 1990). Innovation refers to the development of new products, venturing to the creation of new businesses, and renewal to redefining existing businesses (Sharma, and Chrisman, 1999; Verbeke et al., 2007). Although there are many studies focusing on one of these aspects (cf. Burgelman, 1985; Huff et al., 1992), it is very difficult to compare the outcomes of these studies due to differences in contexts, measures, and methodologies. This is a significant lack in our understanding of CE, as firms engage in all three aspects of CE, making it important to compare managerial and organizational antecedents of innovation, venturing and renewal processes. Because factors that may enhance venturing activities may simultaneously inhibit renewal activities. The limited studies that did empirically compare the individual dimensions (cf. Zahra, 1996; Zahra et al., 2000; Yiu and Lau, 2008; Yiu et al., 2007) generally failed to provide a systematic explanation for potential different effects of organizational antecedents on innovation, venturing, and renewal. With this study we aim to investigate the different effects of structural separation and social capital on corporate entrepreneurship activities. The access to existing and the development of new knowledge has been deemed of critical importance in CE-activities (Floyd and Wooldridge, 1999; Covin and Miles, 2007; Katila and Ahuja, 2002). Developing new knowledge can be facilitated by structurally separating corporate entrepreneurial units from mainstream units (cf. Burgelman, 1983; Hill and Rothaermel, 2003; O'Reilly and Tushman, 2004). Existing knowledge and resources are available through networks of social relationships, defined as social capital (Nahapiet and Ghoshal, 1998; Yiu and Lau, 2008). Although social capital has primarily been studied at the organizational level, it might be equally important at top management level (Belliveau et al., 1996). However, little is known about the joint effects of structural separation and integrative mechanisms to provide access to social capital on corporate entrepreneurship. Could these integrative mechanisms for example connect the separated units to facilitate both knowledge creation and sharing? Do these effects differ for innovation, venturing, and renewal processes? Are the effects different for organizational versus top management team integration mechanisms? Corporate entrepreneurship activities have for example been suggested to take place at different levels. Whereas innovation is suggested to be a more bottom-up process, strategic renewal is a more top-down process (Floyd and Lane, 2000; Volberda et al., 2001). Corporate venturing is also a more bottom-up process, but due to the greater required resource commitments relative to innovation, it ventures need to be approved by top management (Burgelman, 1983). As such we will explore the following key research question in this paper: How do social capital and structural separation on organizational and TMT level differentially influence innovation, venturing, and renewal processes? Methodology/Key Propositions We investigated our hypotheses on a final sample of 240 companies in a variety of industries in the Netherlands. All our measures were validated in previous studies. We targeted a second respondent in each firm to reduce problems with single-rater data (James et al., 1984). We separated the measurement of the independent and the dependent variables in two surveys to create a one-year time lag and reduce potential common method bias (Podsakoff et al., 2003). Results and Implications Consistent with our hypotheses, our results show that configurations of structural separation and integrative mechanisms have different effects on the three aspects of corporate entrepreneurship. Innovation was affected by organizational level mechanisms, renewal by integrative mechanisms on top management team level and venturing by mechanisms on both levels. Surprisingly, our results indicated that integrative mechanisms on top management team level had negative effects on corporate entrepreneurship activities. We believe this paper makes two significant contributions. First, we provide more insight in what the effects of ambidextrous organizational forms (i.e. combinations of differentiation and integration mechanisms) are on venturing, innovation and renewal processes. Our findings show that more valuable insights can be gained by comparing the individual parts of corporate entrepreneurship instead of focusing on the whole. Second, we deliver insights in how management can create a facilitative organizational context for these corporate entrepreneurship activities.

Union strategies in representing ‘new workers’ : the case of UK retail union

The purpose of this paper is to explore the changing nature of employee voice through trade union representation in the retail industry. The retail industry is a major employer in the UK and is one of the few private sector service industries with union representation (Griffin et al 2003). The requisite union: the Distributive and Allied Workers (USDAW) union is one of the biggest unions in the country. However, the characteristics of the industry provide unique challenges for employee voice and representation including: high labour turnover; high use of casual, female and student labour; and, variable levels of union recognition (Reynolds et al 2005). Irrespective of these challenges, any extension of representation and organisation by unions in the retail sector is inherently valuable, socially and politically, given that retail workers are often categorised as vulnerable, due to the fact that they are among the lowest paid in the economy, sourced from disadvantages labour markets and increasingly subject to atypical employment arrangements (Broadbridge 2002; Henley 2006; Lynch 2005; Roan 2003).