Photochemistry and chemometrics : an overview

Photochemistry has made significant contributions to our understanding of many important natural processes as well as the scientific discoveries of the man-made world. The measurements from such studies are often complex and may require advanced data interpretation with the use of multivariate or chemometrics methods. In general, such methods have been applied successfully for data display, classification, multivariate curve resolution and prediction in analytical chemistry, environmental chemistry, engineering, medical research and industry. However, in photochemistry, by comparison, applications of such multivariate approaches were found to be less frequent although a variety of methods have been used, especially with spectroscopic photochemical applications. The methods include Principal Component Analysis (PCA; data display), Partial Least Squares (PLS; prediction), Artificial Neural Networks (ANN; prediction) and several models for multivariate curve resolution related to Parallel Factor Analysis (PARAFAC; decomposition of complex responses). Applications of such methods are discussed in this overview and typical examples include photodegradation of herbicides, prediction of antibiotics in human fluids (fluorescence spectroscopy), non-destructive in- and on-line monitoring (near infrared spectroscopy) and fast-time resolution of spectroscopic signals from photochemical reactions. It is also quite clear from the literature that the scope of spectroscopic photochemistry was enhanced by the application of chemometrics. To highlight and encourage further applications of chemometrics in photochemistry, several additional chemometrics approaches are discussed using data collected by the authors. The use of a PCA biplot is illustrated with an analysis of a matrix containing data on the performance of photocatalysts developed for water splitting and hydrogen production. In addition, the applications of the Multi-Criteria Decision Making (MCDM) ranking methods and Fuzzy Clustering are demonstrated with an analysis of water quality data matrix. Other examples of topics include the application of simultaneous kinetic spectroscopic methods for prediction of pesticides, and the use of response fingerprinting approach for classification of medicinal preparations. In general, the overview endeavours to emphasise the advantages of chemometrics' interpretation of multivariate photochemical data, and an Appendix of references and summaries of common and less usual chemometrics methods noted in this work, is provided. Crown Copyright © 2010.

Performance control of distributed generation using digital estimation of signal parameters

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of seven published/submitted papers, of which one has been published, three accepted for publication and the other three are under review. This project is financially supported by an Australian Research Council (ARC) Discovery Grant with the aim of proposing strategies for the performance control of Distributed Generation (DG) system with digital estimation of power system signal parameters. Distributed Generation (DG) has been recently introduced as a new concept for the generation of power and the enhancement of conventionally produced electricity. Global warming issue calls for renewable energy resources in electricity production. Distributed generation based on solar energy (photovoltaic and solar thermal), wind, biomass, mini-hydro along with use of fuel cell and micro turbine will gain substantial momentum in the near future. Technically, DG can be a viable solution for the issue of the integration of renewable or non-conventional energy resources. Basically, DG sources can be connected to local power system through power electronic devices, i.e. inverters or ac-ac converters. The interconnection of DG systems to power system as a compensator or a power source with high quality performance is the main aim of this study. Source and load unbalance, load non-linearity, interharmonic distortion, supply voltage distortion, distortion at the point of common coupling in weak source cases, source current power factor, and synchronism of generated currents or voltages are the issues of concern. The interconnection of DG sources shall be carried out by using power electronics switching devices that inject high frequency components rather than the desired current. Also, noise and harmonic distortions can impact the performance of the control strategies. To be able to mitigate the negative effect of high frequency and harmonic as well as noise distortion to achieve satisfactory performance of DG systems, new methods of signal parameter estimation have been proposed in this thesis. These methods are based on processing the digital samples of power system signals. Thus, proposing advanced techniques for the digital estimation of signal parameters and methods for the generation of DG reference currents using the estimates provided is the targeted scope of this thesis. An introduction to this research – including a description of the research problem, the literature review and an account of the research progress linking the research papers – is presented in Chapter 1. One of the main parameters of a power system signal is its frequency. Phasor Measurement (PM) technique is one of the renowned and advanced techniques used for the estimation of power system frequency. Chapter 2 focuses on an in-depth analysis conducted on the PM technique to reveal its strengths and drawbacks. The analysis will be followed by a new technique proposed to enhance the speed of the PM technique while the input signal is free of even-order harmonics. The other techniques proposed in this thesis as the novel ones will be compared with the PM technique comprehensively studied in Chapter 2. An algorithm based on the concept of Kalman filtering is proposed in Chapter 3. The algorithm is intended to estimate signal parameters like amplitude, frequency and phase angle in the online mode. The Kalman filter is modified to operate on the output signal of a Finite Impulse Response (FIR) filter designed by a plain summation. The frequency estimation unit is independent from the Kalman filter and uses the samples refined by the FIR filter. The frequency estimated is given to the Kalman filter to be used in building the transition matrices. The initial settings for the modified Kalman filter are obtained through a trial and error exercise. Another algorithm again based on the concept of Kalman filtering is proposed in Chapter 4 for the estimation of signal parameters. The Kalman filter is also modified to operate on the output signal of the same FIR filter explained above. Nevertheless, the frequency estimation unit, unlike the one proposed in Chapter 3, is not segregated and it interacts with the Kalman filter. The frequency estimated is given to the Kalman filter and other parameters such as the amplitudes and phase angles estimated by the Kalman filter is taken to the frequency estimation unit. Chapter 5 proposes another algorithm based on the concept of Kalman filtering. This time, the state parameters are obtained through matrix arrangements where the noise level is reduced on the sample vector. The purified state vector is used to obtain a new measurement vector for a basic Kalman filter applied. The Kalman filter used has similar structure to a basic Kalman filter except the initial settings are computed through an extensive math-work with regards to the matrix arrangement utilized. Chapter 6 proposes another algorithm based on the concept of Kalman filtering similar to that of Chapter 3. However, this time the initial settings required for the better performance of the modified Kalman filter are calculated instead of being guessed by trial and error exercises. The simulations results for the parameters of signal estimated are enhanced due to the correct settings applied. Moreover, an enhanced Least Error Square (LES) technique is proposed to take on the estimation when a critical transient is detected in the input signal. In fact, some large, sudden changes in the parameters of the signal at these critical transients are not very well tracked by Kalman filtering. However, the proposed LES technique is found to be much faster in tracking these changes. Therefore, an appropriate combination of the LES and modified Kalman filtering is proposed in Chapter 6. Also, this time the ability of the proposed algorithm is verified on the real data obtained from a prototype test object. Chapter 7 proposes the other algorithm based on the concept of Kalman filtering similar to those of Chapter 3 and 6. However, this time an optimal digital filter is designed instead of the simple summation FIR filter. New initial settings for the modified Kalman filter are calculated based on the coefficients of the digital filter applied. Also, the ability of the proposed algorithm is verified on the real data obtained from a prototype test object. Chapter 8 uses the estimation algorithm proposed in Chapter 7 for the interconnection scheme of a DG to power network. Robust estimates of the signal amplitudes and phase angles obtained by the estimation approach are used in the reference generation of the compensation scheme. Several simulation tests provided in this chapter show that the proposed scheme can very well handle the source and load unbalance, load non-linearity, interharmonic distortion, supply voltage distortion, and synchronism of generated currents or voltages. The purposed compensation scheme also prevents distortion in voltage at the point of common coupling in weak source cases, balances the source currents, and makes the supply side power factor a desired value.

Rethinking regulatory design : The Australian National Classification Scheme review

This paper considers issues of methodological innovation in communication, media and cultural studies, that arise out of the extent to which we now live in a media environment characterised by an digital media abundance, the convergence of media platforms, content and services, and the globalisation of media content through ubiquitous computing and high-speed broadband networks. These developments have also entailed a shift in the producer-consumer relationships that characterised the 20th century mass communications paradigm, with the rapid proliferation of user-created content, accelerated innovation, the growing empowerment of media users themselves, and the blurring of distinctions between public and private, as well as age-based distinctions in terms of what media can be accessed by whom and for what purpose. It considers these issues through a case study of the Australian Law Reform Commission's National Classification Scheme Review.

‘Spotty Dick’ : a research experiment to test design suitability for the use of jewelled spot matrix patterns for UV aware men’s swimwear

The great male Aussie cossie is growing spots. The ‘dick’ tog, as it is colloquially referred to, is linked to Australia’s national identify with overtly masculine bronzed Aussie bodies clothed in this iconic apparel. Yet the reality is our hunger for worshiping the sun and the addiction to a beach lifestyle is tempered by the pragmatic need for neck-to-knee, or more apt head-to-toe, swimwear. Spotty Dick is an irreverent play on male swimwear – it experiments with alternate modes to sheath the body with Lyrca in order to protect it from searing UV’s and at the same time light-heartedly fools around with texture and pattern; to be specific, black Scharovsky crystals, jewelled in spot patterns - jewelled clothing is not characteristically aligned to menswear and even less so to the great Aussie cossie. The crystals form a matrix of spots that attempt to provoke a sense of mischievousness aligned to the Aussie beach larrikin. Ironically, spot patterns are in itself a form of a parody, as prolonged sun exposure ages the skin and sun spots can occur if appropriate sun protection is not used. ‘Spotty Dick’ – a research experiment to test design suitability for the use of jewelled spot matrix patterns for UV aware men’s swimwear. The creative work was paraded at 56 shows, over a 2 week period, and an estimated 50,000 people viewed the work.

Integrating electrical vehicles to demand side response scheme in Queensland Australia

Depleting fossil fuel resources and increased accumulation of greenhouse gas emissions are increasingly making electrical vehicles (EV) attractive option for the transportation sector. However uncontrolled random charging and discharging of EVs may aggravate the problems of an already stressed system during the peak demand and cause voltage problems during low demand. This paper develops a demand side response scheme for properly integrating EVs in the Electrical Network. The scheme enacted upon information on electricity market conditions regularly released by the Australian Energy Market Operator (AEMO) on the internet. The scheme adopts Internet relays and solid state switches to cycle charging and discharging of EVs. Due to the pending time-of-use and real-price programs, financial benefits will represent driving incentives to consumers to implement the scheme. A wide-scale dissemination of the scheme is expected to mitigate excessive peaks on the electrical network with all associated technical, economic and social benefits.

Restart : reflections on the British scheme of the 80s for the long term unemployed

The chapter reflects on the first two years of the Restart Scheme introduced by the Manpower Services Commission for Long term unemployed people in the UK from a facilitator's perspective ten years later. It examines the actual weekly program for participants with some case examples from one of the pilot centres, Crawley College, West Sussex, an area of low unemployment. The observations suggested that even in a place where there are many job vacancies, there will be a 3-4% of the population who are unable to compete for jobs and participate in the work force unless sheltered workshops and specialized training initiatives are established.

Globalization, media policy and regulatory design : rethinking the Australian media classification scheme

This paper considers the debate about the relationship between globalization and media policy from the perspective provided by a current review of the Australian media classification scheme. Drawing upon the author’s recent experience in being ‘inside’ the policy process, as Lead Commissioner on the Australian National Classification Scheme Review, it is argued that theories of globalization – including theories of neoliberal globalization – fail to adequately capture the complexities of the reform process, particularly around the relationship between regulation and markets. The paper considers the pressure points for media content policies arising from media globalization, and the wider questions surrounding media content policies in an age of media convergence.

Computationally efficient methods for solving time-variable-order time-space fractional reaction-diffusion equation

Fractional differential equations are becoming more widely accepted as a powerful tool in modelling anomalous diffusion, which is exhibited by various materials and processes. Recently, researchers have suggested that rather than using constant order fractional operators, some processes are more accurately modelled using fractional orders that vary with time and/or space. In this paper we develop computationally efficient techniques for solving time-variable-order time-space fractional reaction-diffusion equations (tsfrde) using the finite difference scheme. We adopt the Coimbra variable order time fractional operator and variable order fractional Laplacian operator in space where both orders are functions of time. Because the fractional operator is nonlocal, it is challenging to efficiently deal with its long range dependence when using classical numerical techniques to solve such equations. The novelty of our method is that the numerical solution of the time-variable-order tsfrde is written in terms of a matrix function vector product at each time step. This product is approximated efficiently by the Lanczos method, which is a powerful iterative technique for approximating the action of a matrix function by projecting onto a Krylov subspace. Furthermore an adaptive preconditioner is constructed that dramatically reduces the size of the required Krylov subspaces and hence the overall computational cost. Numerical examples, including the variable-order fractional Fisher equation, are presented to demonstrate the accuracy and efficiency of the approach.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Revising the scope of the copyright "Safe Harbour Scheme"

Submission to the Australian Government Attorney General’s Department consultation paper on Revising the Scope of the Copyright ‘Safe Harbour Scheme’

Sensitivity of the NMR density matrix to pulse sequence parameters : a simplified analytic approach

We present a formalism for the analysis of sensitivity of nuclear magnetic resonance pulse sequences to variations of pulse sequence parameters, such as radiofrequency pulses, gradient pulses or evolution delays. The formalism enables the calculation of compact, analytic expressions for the derivatives of the density matrix and the observed signal with respect to the parameters varied. The analysis is based on two constructs computed in the course of modified density-matrix simulations: the error interrogation operators and error commutators. The approach presented is consequently named the Error Commutator Formalism (ECF). It is used to evaluate the sensitivity of the density matrix to parameter variation based on the simulations carried out for the ideal parameters, obviating the need for finite-difference calculations of signal errors. The ECF analysis therefore carries a computational cost comparable to a single density-matrix or product-operator simulation. Its application is illustrated using a number of examples from basic NMR spectroscopy. We show that the strength of the ECF is its ability to provide analytic insights into the propagation of errors through pulse sequences and the behaviour of signal errors under phase cycling. Furthermore, the approach is algorithmic and easily amenable to implementation in the form of a programming code. It is envisaged that it could be incorporated into standard NMR product-operator simulation packages.