Does chemometrics enhance the performance of electroanalysis?

This review explores the question whether chemometrics methods enhance the performance of electroanalytical methods. Electroanalysis has long benefited from the well-established techniques such as potentiometric titrations, polarography and voltammetry, and the more novel ones such as electronic tongues and noses, which have enlarged the scope of applications. The electroanalytical methods have been improved with the application of chemometrics for simultaneous quantitative prediction of analytes or qualitative resolution of complex overlapping responses. Typical methods include partial least squares (PLS), artificial neural networks (ANNs), and multiple curve resolution methods (MCR-ALS, N-PLS and PARAFAC). This review aims to provide the practising analyst with a broad guide to electroanalytical applications supported by chemometrics. In this context, after a general consideration of the use of a number of electroanalytical techniques with the aid of chemometrics methods, several overviews follow with each one focusing on an important field of application such as food, pharmaceuticals, pesticides and the environment. The growth of chemometrics in conjunction with electronic tongue and nose sensors is highlighted, and this is followed by an overview of the use of chemometrics for the resolution of complicated profiles for qualitative identification of analytes, especially with the use of the MCR-ALS methodology. Finally, the performance of electroanalytical methods is compared with that of some spectrophotometric procedures on the basis of figures-of-merit. This showed that electroanalytical methods can perform as well as the spectrophotometric ones. PLS-1 appears to be the method of practical choice if the %relative prediction error of not, vert, similar±10% is acceptable.

Fingerprinting of complex mixtures with the use of high performance liquid chromatography, inductively coupled plasma atomic emission spectroscopy and chemometrics

The molecular and metal profile fingerprints were obtained from a complex substance, Atractylis chinensis DC—a traditional Chinese medicine (TCM), with the use of the high performance liquid chromatography (HPLC) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) techniques. This substance was used in this work as an example of a complex biological material, which has found application as a TCM. Such TCM samples are traditionally processed by the Bran, Cut, Fried and Swill methods, and were collected from five provinces in China. The data matrices obtained from the two types of analysis produced two principal component biplots, which showed that the HPLC fingerprint data were discriminated on the basis of the methods for processing the raw TCM, while the metal analysis grouped according to the geographical origin. When the two data matrices were combined into a one two-way matrix, the resulting biplot showed a clear separation on the basis of the HPLC fingerprints. Importantly, within each different grouping the objects separated according to their geographical origin, and they ranked approximately in the same order in each group. This result suggested that by using such an approach, it is possible to derive improved characterisation of the complex TCM materials on the basis of the two kinds of analytical data. In addition, two supervised pattern recognition methods, K-nearest neighbors (KNNs) method, and linear discriminant analysis (LDA), were successfully applied to the individual data matrices—thus, supporting the PCA approach.

The development and evaluation of an innovative nursing practice model to improve undergraduate nursing students' competence in paediatric physical assessment

Introduction The purpose of this study was to develop, implement and evaluate the impact of an educational intervention, comprising an innovative model of clinical decisionmaking and educational delivery strategy for facilitating nursing students‘ learning and development of competence in paediatric physical assessment practices. Background of the study Nursing students have an undergraduate education that aims to produce graduates of a generalist nature who demonstrate entry level competence for providing nursing care in a variety of health settings. Consistent with population morbidity and health care roles, paediatric nursing concepts typically form a comparatively small part of undergraduate curricula and students‘ exposure to paediatric physical assessment concepts and principles are brief. However, the nursing shortage has changed traditional nursing employment patterns and new graduates form the majority of the recruitment pool for paediatric nursing speciality staff. Paediatric nursing is a popular career choice for graduates and anecdotal evidence suggests that nursing students who select a clinical placement in their final year intend to seek employment in paediatrics upon graduation. Although concepts of paediatric nursing are included within undergraduate curriculum, students‘ ability to develop the required habits of mind to practice in what is still regarded as a speciality area of practice is somewhat limited. One of the areas of practice where this particularly impacts is in paediatric nursing physical assessment. Physical assessment is a fundamental component of nursing practice and competence in this area of practice is central to nursing students‘ development of clinical capability for practice as a registered nurse. Timely recognition of physiologic deterioration of patients is a key outcome of nurses‘ competent use of physical assessment strategies, regardless of the practice context. In paediatric nursing contexts children‘s physical assessment practices must specifically accommodate the child‘s different physiological composition, function and pattern of clinical deterioration (Hockenberry & Barrera, 2007). Thus, to effectively manage physical assessment of patients within the paediatric practice setting nursing students need to integrate paediatric nursing theory into their practice. This requires significant information processing and it is in this process where students are frequently challenged. The provision of rules or models can guide practice and assist novice-level nurses to develop their capabilities (Benner, 1984; Benner, Hooper-Kyriakidis & Stannard, 1999). Nursing practice models are cognitive tools that represent simplified patterns of expert analysis employing concepts that suit the limited reasoning of the inexperienced, and can represent the =rules‘ referred to by Benner (1984). Without a practice model of physical assessment students are likely to be uncertain about how to proceed with data collection, the interpretation of paediatric clinical findings and the appraisal of findings. These circumstances can result in ad hoc and unreliable nursing physical assessment that forms a poor basis for nursing decisions. The educational intervention developed as part of this study sought to resolve this problem and support nursing students‘ development of competence in paediatric physical assessment. Methods This study utilised the Context Input Process Product (CIPP) Model by Stufflebeam (2004) as the theoretical framework that underpinned the research design and evaluation methodology. Each of the four elements in the CIPP model were utilised to guide discrete stages of this study. The Context element informed design of the clinical decision-making process, the Paediatric Nursing Physical Assessment model. The Input element was utilised in appraising relevant literature, identifying an appropriate instructional methodology to facilitate learning and educational intervention delivery to undergraduate nursing students, and development of program content (the CD-ROM kit). Study One employed the Process element and used expert panel approaches to review and refine instructional methods, identifying potential barriers to obtaining an effective evaluation outcome. The Product element guided design and implementation of Study Two, which was conducted in two phases. Phase One employed a quasiexperimental between-subjects methodology to evaluate the impact of the educational intervention on nursing students‘ clinical performance and selfappraisal of practices in paediatric physical assessment. Phase Two employed a thematic analysis and explored the experiences and perspectives of a sample subgroup of nursing students who used the PNPA CD-ROM kit as preparation for paediatric clinical placement. Results Results from the Process review in Study One indicated that the prototype CDROM kit containing the PNPA model met the predetermined benchmarks for face validity and the impact evaluation instrumentation had adequate content validity in comparison with predetermined benchmarks. In the first phase of Study Two the educational intervention did not result in statistically significant differences in measures of student performance or self-appraisal of practice. However, in Phase Two qualitative commentary from students, and from the expert panel who reviewed the prototype CD-ROM kit (Study One, Phase One), strongly endorsed the quality of the intervention and its potential for supporting learning. This raises questions regarding transfer of learning and it is likely that, within this study, several factors have influenced students‘ transfer of learning from the educational intervention to the clinical practice environment, where outcomes were measured. Conclusion In summary, the educational intervention employed in this study provides insights into the potential e-learning approaches offer for delivering authentic learning experiences to undergraduate nursing students. Findings in this study raise important questions regarding possible pedagogical influences on learning outcomes, issues within the transfer of theory to practice and factors that may have influenced findings within the context of this study. This study makes a unique contribution to nursing education, specifically with respect to progressing an understanding of the challenges faced in employing instructive methods to impact upon nursing students‘ development of competence. The important contribution transfer of learning processes make to students‘ transition into the professional practice context and to their development of competence within the context of speciality practice is also highlighted. This study contributes to a greater awareness of the complexity of translating theoretical learning at undergraduate level into clinical practice, particularly within speciality contexts.

A constraints-led perspective to understanding skill acquisition and game play: A basis for integration of motor learning theory and physical education praxis?

Background: In order to design appropriate environments for performance and learning of movement skills, physical educators need a sound theoretical model of the learner and of processes of learning. In physical education, this type of modelling informs the organization of learning environments and effective and efficient use of practice time. An emerging theoretical framework in motor learning, relevant to physical education, advocates a constraints-led perspective for acquisition of movement skills and game play knowledge. This framework shows how physical educators could use task, performer and environmental constraints to channel acquisition of movement skills and decision making behaviours in learners. From this viewpoint, learners generate specific movement solutions to satisfy the unique combination of constraints imposed on them, a process which can be harnessed during physical education lessons. Purpose: In this paper the aim is to provide an overview of the motor learning approach emanating from the constraints-led perspective, and examine how it can substantiate a platform for a new pedagogical framework in physical education: nonlinear pedagogy. We aim to demonstrate that it is only through theoretically valid and objective empirical work of an applied nature that a conceptually sound nonlinear pedagogy model can continue to evolve and support research in physical education. We present some important implications for designing practices in games lessons, showing how a constraints-led perspective on motor learning could assist physical educators in understanding how to structure learning experiences for learners at different stages, with specific focus on understanding the design of games teaching programmes in physical education, using exemplars from Rugby Union and Cricket. Findings: Research evidence from recent studies examining movement models demonstrates that physical education teachers need a strong understanding of sport performance so that task constraints can be manipulated so that information-movement couplings are maintained in a learning environment that is representative of real performance situations. Physical educators should also understand that movement variability may not necessarily be detrimental to learning and could be an important phenomenon prior to the acquisition of a stable and functional movement pattern. We highlight how the nonlinear pedagogical approach is student-centred and empowers individuals to become active learners via a more hands-off approach to learning. Summary: A constraints-based perspective has the potential to provide physical educators with a framework for understanding how performer, task and environmental constraints shape each individual‟s physical education. Understanding the underlying neurobiological processes present in a constraints-led perspective to skill acquisition and game play can raise awareness of physical educators that teaching is a dynamic 'art' interwoven with the 'science' of motor learning theories.

Expert performance in sport and the dynamics of talent development

Research on expertise, talent identification and development has tended to be mono-disciplinary, typically adopting adopting neurogenetic deterministic or environmentalist positions, with an over-riding focus on operational issues. In this paper the validity of dualist positions on sport expertise is evaluated. It is argued that, to advance understanding of expertise and talent development, a shift towards a multi-disciplinary and integrative science focus is necessary, along with the development of a comprehensive multi-disciplinary theoretical rationale. Here we elucidate dynamical systems theory as a multi-disciplinary theoretical rationale for capturing how multiple interacting constraints can shape the development of expert performers. This approach suggests that talent development programmes should eschew the notion of common optimal performance models, emphasise the individual nature of pathways to expertise, and identify the range of interacting constraints that impinge on performance potential of individual athletes, rather than evaluating current performance on physical tests referenced to group norms.

Parental physical activity : exploring the role of social support

Objectives: To explore the influence of social support on parental physical activity (PA). Methods: Forty parents (21 mothers, 19 fathers) participated in semistructured individual or group interviews. Data were analyzed using thematic content analysis.---------- Results: Instrumental (eg, providing child care, taking over chores), emotional (eg, encouragement, companionship), and informational support (eg, ideas and advice) as well as reciprocal support (eg, giving as well as receiving support) and autonomy support (eg, respecting one’s choices) are important for parents’ PA behavior. However, having support for being active is not straightforward in that many parents discussed issues that inhibited the facilitative nature of social support for PA performance (eg, guilt in getting help). Conclusions: Results highlight the complex nature of social support in facilitating parental PA.

Paediatric obesity, physical activity and the musculoskeletal system

The current epidemic of paediatric obesity is consistent with a myriad of health-related comorbid conditions. Despite the higher prevalence of orthopaedic conditions in overweight children, a paucity of published research has considered the influence of these conditions on the ability to undertake physical activity. As physical activity participation is directly related to improvements in physical fitness, skeletal health and metabolic conditions, higher levels of physical activity are encouraged, and exercise is commonly prescribed in the treatment and management of childhood obesity. However, research has not correlated orthopaedic conditions, including the increased joint pain and discomfort that is commonly reported by overweight children, with decreases in physical activity. Research has confirmed that overweight children typically display a slower, more tentative walking pattern with increased forces to the hip, knee and ankle during 'normal' gait. This research, combined with anthropometric data indicating a higher prevalence of musculoskeletal malalignment in overweight children, suggests that such individuals are poorly equipped to undertake certain forms of physical activity. Concomitant increases in obesity and decreases in physical activity level strongly support the need to better understand the musculoskeletal factors associated with the performance of motor tasks by overweight and obese children.

Understanding parental physical activity : meanings, habits, and social role influence

Objectives: The research aimed to explore parents’ understandings of physical activity (PA), patterns of PA-related behaviour, and how constructions of social role expectations might influence their PA behaviour. Design and Method: Using a qualitative descriptive design and adopting a social constructionism approach to broaden interpretations of parents’ understandings, 40 adults (21 mothers, 19 fathers; aged 23 to 49 years) living in South East Queensland, Australia participated in semi-structured individual and group interviews. The interviews were analysed using thematic analysis. Results: Parents had clear understandings of what constitutes PA and engaged in various activities which were integrated with or independent of the children. Being active with children, however, was not always constructed favourably in which many parents described the difficulties of being active with their children. All individuals experienced changes in their PA behaviours after having children. For most, a decline in PA level, intensity, and structure was experienced; however, some did experience parenthood as a time to be active. A level of acceptance for the lack of activity performed was also expressed as were feelings of resentment and envy for those who maintained previous activity habits. Parenting and partner roles were considered most influential on PA-related behaviour and were constructed in ways that had both positive and negative influences on activity performance. Parents, however, were empowered to construct strategies to resolve conflicts between social role performance and being active. Conclusion: Results show that parents experience unique difficulties that intervention work should consider when designing programs aimed at increasing parental PA.

Piezoelectric PVDF materials performance and operation limits in space environments

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films are achieved via charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to suffer due to strong vacuum UV, gamma, X-ray, energetic particles and atomic oxygen under low earth orbit exposure conditions. The degradation of PVDF and its copolymers under various stress environments has been investigated. Initial radiation aging studies using gamma- and e-beam irradiation have shown complex material changes with significant crosslinking, lowered melting and Curie points (where observable), effects on crystallinity, but little influence on overall piezoelectric properties. Surprisingly, complex aging processes have also been observed in elevated temperature environments with annealing phenomena and cyclic stresses resulting in thermal depoling of domains. Overall materials performance appears to be governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and AO exposure is evident as depoling and surface erosion. Major differences between individual copolymers have been observed providing feedback on material selection strategies.

Fixing the volatile : studio vocal performance techniques

The process of compiling a studio vocal performance from many takes can often result in the performer producing a new complete performance once this new "best of" assemblage is heard back. This paper investigates the ways that the physical process of recording can alter vocal performance techniques, and in particular, the establishing of a definitive melodic and rhythmic structure. Drawing on his many years of experience as a commercially successful producer, including the attainment of a Grammy award, the author will analyse the process of producing a “credible” vocal performance in depth, with specific case studies and examples. The question of authenticity in rock and pop will also be discussed and, in this context, the uniqueness of the producer’s role as critical arbiter – what gives the producer the authority to make such performance evaluations? Techniques for creating conditions in the studio that are conducive to vocal performances, in many ways a very unnatural performance environment, will be discussed, touching on areas such as the psycho-acoustic properties of headphone mixes, the avoidance of intimidatory practices, and a methodology for inducing the perception of a “familiar” acoustic environment.

Effect of physical activity and other stressors on appetite: Overcoming underconsumption of military operational rations revisited.

Recognizing the importance of good nutrition for physical and mental status, the Department of Defense asked the Institute of Medicine to guide the design of the nutritional composition of a ration for soldiers on short-term, high-stress missions. Nutrient Composition of Rations for Short-Term, High-Intensity Combat Operations considers military performance, health concerns, food intake, energy expenditure, physical exercise, and food technology issues. The success of military operations depends to a large extent on the physical and mental status of the individuals involved.

Directing for the 360 degree frame : developing a directorial approach to performance capture

What happens when the traditional framing mechanisms of our performance environments are removed and we are forced as directors to work with actors in digital environments that capture performance in 360 degrees? As directors contend with the challenges of interactive performance, the emergence of the online audience and the powerful influence of the games industry, how can we approach the challenges of directing work that is performance captured and presented in real time using motion capture and associated 3D imaging software? The 360 degree real time capture of performance, while allowing for an unlimited amount of framing potential, demands a unique and uncompromisingly disciplined style of direction and performance that has thus far remained unstudied and unquantified. By a close analysis of the groundbreaking work of artists like Robert Zemeckis and the Wetta Digital studio it is possible to begin to quantify what the technical requirements and challenges of 360 degree direction might be, but little has been discovered about the challenges of communicating the unlimited potential of framing and focus to the actors who work with these directors within these systems. It cannot be argued that the potential of theatrical space has evolved beyond the physical and moved into a more accessible virtual and digitised form, so how then can we direct for this unlimited potential and where do we place the focus of our directed (and captured) performance?

A process for the management of physical infrastructure

Physical infrastructure assets are important components of our society and our economy. They are usually designed to last for many years, are expected to be heavily used during their lifetime, carry considerable load, and are exposed to the natural environment. They are also normally major structures, and therefore present a heavy investment, requiring constant management over their life cycle to ensure that they perform as required by their owners and users. Given a complex and varied infrastructure life cycle, constraints on available resources, and continuing requirements for effectiveness and efficiency, good management of infrastructure is important. While there is often no one best management approach, the choice of options is improved by better identification and analysis of the issues, by the ability to prioritise objectives, and by a scientific approach to the analysis process. The abilities to better understand the effect of inputs in the infrastructure life cycle on results, to minimise uncertainty, and to better evaluate the effect of decisions in a complex environment, are important in allocating scarce resources and making sound decisions. Through the development of an infrastructure management modelling and analysis methodology, this thesis provides a process that assists the infrastructure manager in the analysis, prioritisation and decision making process. This is achieved through the use of practical, relatively simple tools, integrated in a modular flexible framework that aims to provide an understanding of the interactions and issues in the infrastructure management process. The methodology uses a combination of flowcharting and analysis techniques. It first charts the infrastructure management process and its underlying infrastructure life cycle through the time interaction diagram, a graphical flowcharting methodology that is an extension of methodologies for modelling data flows in information systems. This process divides the infrastructure management process over time into self contained modules that are based on a particular set of activities, the information flows between which are defined by the interfaces and relationships between them. The modular approach also permits more detailed analysis, or aggregation, as the case may be. It also forms the basis of ext~nding the infrastructure modelling and analysis process to infrastructure networks, through using individual infrastructure assets and their related projects as the basis of the network analysis process. It is recognised that the infrastructure manager is required to meet, and balance, a number of different objectives, and therefore a number of high level outcome goals for the infrastructure management process have been developed, based on common purpose or measurement scales. These goals form the basis of classifYing the larger set of multiple objectives for analysis purposes. A two stage approach that rationalises then weights objectives, using a paired comparison process, ensures that the objectives required to be met are both kept to the minimum number required and are fairly weighted. Qualitative variables are incorporated into the weighting and scoring process, utility functions being proposed where there is risk, or a trade-off situation applies. Variability is considered important in the infrastructure life cycle, the approach used being based on analytical principles but incorporating randomness in variables where required. The modular design of the process permits alternative processes to be used within particular modules, if this is considered a more appropriate way of analysis, provided boundary conditions and requirements for linkages to other modules, are met. Development and use of the methodology has highlighted a number of infrastructure life cycle issues, including data and information aspects, and consequences of change over the life cycle, as well as variability and the other matters discussed above. It has also highlighted the requirement to use judgment where required, and for organisations that own and manage infrastructure to retain intellectual knowledge regarding that infrastructure. It is considered that the methodology discussed in this thesis, which to the author's knowledge has not been developed elsewhere, may be used for the analysis of alternatives, planning, prioritisation of a number of projects, and identification of the principal issues in the infrastructure life cycle.

The design and testing of a daylighting device : optimising the energy and optical performance of Australian commercial buildings

The effective daylighting of multistorey commercial building interiors poses an interesting problem for designers in Australia’s tropical and subtropical context. Given that a building exterior receives adequate sun and skylight as dictated by location-specific factors such as weather, siting and external obstructions; then the availability of daylight throughout its interior is dependant on certain building characteristics: the distance from a window façade (room depth), ceiling or window head height, window size and the visible transmittance of daylighting apertures. The daylighting of general stock, multistorey commercial buildings is made difficult by their design limitations with respect to some of these characteristics. The admission of daylight to these interiors is usually exclusively by vertical windows. Using conventional glazing, such windows can only admit sun and skylight to a depth of approximately 2 times the window height. This penetration depth is typically much less than the depth of the office interiors, so that core areas of these buildings receive little or no daylight. This issue is particularly relevant where deep, open plan office layouts prevail. The resulting interior daylight pattern is a relatively narrow perimeter zone bathed in (sometimes too intense) light, contrasted with a poorly daylit core zone. The broad luminance range this may present to a building occupant’s visual field can be a source of discomfort glare. Furthermore, the need in most tropical and subtropical regions to restrict solar heat gains to building interiors for much of the year has resulted in the widespread use of heavily tinted or reflective glazing on commercial building façades. This strategy reduces the amount of solar radiation admitted to the interior, thereby decreasing daylight levels proportionately throughout. However this technique does little to improve the way light is distributed throughout the office space. Where clear skies dominate weather conditions, at different times of day or year direct sunlight may pass unobstructed through vertical windows causing disability or discomfort glare for building occupants and as such, its admission to an interior must be appropriately controlled. Any daylighting system to be applied to multistorey commercial buildings must consider these design obstacles, and attempt to improve the distribution of daylight throughout these deep, sidelit office spaces without causing glare conditions. The research described in this thesis delineates first the design optimisation and then the actual prototyping and manufacture process of a daylighting device to be applied to such multistorey buildings in tropical and subtropical environments.