PROLINE-BASED CHIRAL STATIONARY PHASES: INSIGHTS INTO THE MECHANISM OF CHIRAL SELECTIVITY

Proline (Pro) is a unique amino acid that has been examined previously as a potential chiral selector for high-performance liquid chromatography. In recent years, a new class of promising Pro based enantioselective stationary phases has been studied and the longer peptides were found to be competitive with commercial chiral stationary phases (CSPs). Here, we aim to perform a comprehensive examination of a t-butoxycarbonyl- (t-Boc-) terminated monoproline selector. This selector was grafted through an amide linkage to an aminopropyl siloxane-terminated Si (111) wafer and to a silicon atomic force microscopy tip. To ensure a flat, homogeneous overlayer of selectors suitable for force spectrometric measurements, the prepared surfaces were characterized using XPS, AFM and contact angle measurements. Chemical force spectrometry (CFS) has been used to examine the chiral discrimination in our monoproline CSP by measuring the interaction forces between two D- or L-monoproline monolayers in water and in the presence of a series of amino acids in solution to explore the degree to which binding of amino acids impacts self-selectivity. Chemical force titration (CFT) has been used to observe the influence of variations in pH on the binding interaction of proline modified chiral surfaces. Here we aim to explore the connection between side-chain hydrophobicity and differences in the nature of the binding between different ionic forms of amino acids and the t-Boc-Pro interface, and thereby to gain insight into the mechanism of chiral selectivity. The CFS results show several trends for different proline selector/amino acid combinations and indicate that the binding characteristics of amino acid to the proline surface is strongly dependent on the amino acid side chain where hydrophilic side chain amino acids exhibit a selectivity opposite to that seen for those with hydrophobic side chains. The CFT studies also provide valuable insights into interactions between the proline selector and the amino acids under a wide range of pH conditions, indicating that protonated amine groups of alanine and serine are closely involved in the binding mechanism to proline surfaces. On the other hand, the presence of the second carboxylic group in aspartic acid plays an important role while interacting with proline.

Analysis of Non-Stationary Flows Using Eulerian and Lagrangian Frameworks

Recent developments have made researchers to reconsider Lagrangian measurement techniques as an alternative to their Eulerian counterpart when investigating non-stationary flows. This thesis advances the state-of-the-art of Lagrangian measurement techniques by pursuing three different objectives: (i) developing new Lagrangian measurement techniques for difficult-to-measure, in situ flow environments; (ii) developing new post-processing strategies designed for unstructured Lagrangian data, as well as providing guidelines towards their use; and (iii) presenting the advantages that the Lagrangian framework has over their Eulerian counterpart in various non-stationary flow problems. Towards the first objective, a large-scale particle tracking velocimetry apparatus is designed for atmospheric surface layer measurements. Towards the second objective, two techniques, one for identifying Lagrangian Coherent Structures (LCS) and the other for characterizing entrainment directly from unstructured Lagrangian data, are developed. Finally, towards the third objective, the advantages of Lagrangian-based measurements are showcased in two unsteady flow problems: the atmospheric surface layer, and entrainment in a non-stationary turbulent flow. Through developing new experimental and post-processing strategies for Lagrangian data, and through showcasing the advantages of Lagrangian data in various non-stationary flows, the thesis works to help investigators to more easily adopt Lagrangian-based measurement techniques.

An application of two techniques for the analysis of short, multivariate non-stationary time-series of Mauritanian trawl survey data

Min/max autocorrelation factor analysis (MAFA) and dynamic factor analysis (DFA) are complementary techniques for analysing short (> 15-25 y), non-stationary, multivariate data sets. We illustrate the two techniques using catch rate (cpue) time-series (1982-2001) for 17 species caught during trawl surveys off Mauritania, with the NAO index, an upwelling index, sea surface temperature, and an index of fishing effort as explanatory variables. Both techniques gave coherent results, the most important common trend being a decrease in cpue during the latter half of the time-series, and the next important being an increase during the first half. A DFA model with SST and UPW as explanatory variables and two common trends gave good fits to most of the cpue time-series. (c) 2004 International Council for the Exploration of the Sea. Published by Elsevier Ltd. All rights reserved.

Estimation of the Traffic Intensity in a Piecewise-stationary Mt/Gt/1 Queue with Probing

We use a probing strategy to estimate the time dependent traffic intensity in an Mt/Gt/1 queue, where the arrival rate and the general service-time distribution change from one time interval to another, and derive statistical properties of the proposed estimator. We present a method to detect a switch from a stationary interval to another using a sequence of probes to improve the estimation. At the end, we compare our results with two estimators proposed in the literature for the M/G/1 queue.

Weather variability, tides, and Barmah Forest Virus Disease in the Gladstone region, Australia

In this study we examined the impact of weather variability and tides on the transmission of Barmah Forest virus (BFV) disease and developed a weather-based forecasting model for BFV disease in the Gladstone region, Australia. We used seasonal autoregressive integrated moving-average (SARIMA) models to determine the contribution of weather variables to BFV transmission after the time-series data of response and explanatory variables were made stationary through seasonal differencing. We obtained data on the monthly counts of BFV cases, weather variables (e.g., mean minimum and maximum temperature, total rainfall, and mean relative humidity), high and low tides, and the population size in the Gladstone region between January 1992 and December 2001 from the Queensland Department of Health, Australian Bureau of Meteorology, Queensland Department of Transport, and Australian Bureau of Statistics, respectively. The SARIMA model shows that the 5-month moving average of minimum temperature (β = 0.15, p-value < 0.001) was statistically significantly and positively associated with BFV disease, whereas high tide in the current month (β = −1.03, p-value = 0.04) was statistically significantly and inversely associated with it. However, no significant association was found for other variables. These results may be applied to forecast the occurrence of BFV disease and to use public health resources in BFV control and prevention.

An effective approach to verbose queries using a limited dependencies language model

Intuitively, any `bag of words' approach in IR should benefit from taking term dependencies into account. Unfortunately, for years the results of exploiting such dependencies have been mixed or inconclusive. To improve the situation, this paper shows how the natural language properties of the target documents can be used to transform and enrich the term dependencies to more useful statistics. This is done in three steps. The term co-occurrence statistics of queries and documents are each represented by a Markov chain. The paper proves that such a chain is ergodic, and therefore its asymptotic behavior is unique, stationary, and independent of the initial state. Next, the stationary distribution is taken to model queries and documents, rather than their initial distri- butions. Finally, ranking is achieved following the customary language modeling paradigm. The main contribution of this paper is to argue why the asymptotic behavior of the document model is a better representation then just the document's initial distribution. A secondary contribution is to investigate the practical application of this representation in case the queries become increasingly verbose. In the experiments (based on Lemur's search engine substrate) the default query model was replaced by the stable distribution of the query. Just modeling the query this way already resulted in significant improvements over a standard language model baseline. The results were on a par or better than more sophisticated algorithms that use fine-tuned parameters or extensive training. Moreover, the more verbose the query, the more effective the approach seems to become.

Robot path planning in dynamic environments using a simulated annealing based approach

Mobile robots are widely used in many industrial fields. Research on path planning for mobile robots is one of the most important aspects in mobile robots research. Path planning for a mobile robot is to find a collision-free route, through the robot’s environment with obstacles, from a specified start location to a desired goal destination while satisfying certain optimization criteria. Most of the existing path planning methods, such as the visibility graph, the cell decomposition, and the potential field are designed with the focus on static environments, in which there are only stationary obstacles. However, in practical systems such as Marine Science Research, Robots in Mining Industry, and RoboCup games, robots usually face dynamic environments, in which both moving and stationary obstacles exist. Because of the complexity of the dynamic environments, research on path planning in the environments with dynamic obstacles is limited. Limited numbers of papers have been published in this area in comparison with hundreds of reports on path planning in stationary environments in the open literature. Recently, a genetic algorithm based approach has been introduced to plan the optimal path for a mobile robot in a dynamic environment with moving obstacles. However, with the increase of the number of the obstacles in the environment, and the changes of the moving speed and direction of the robot and obstacles, the size of the problem to be solved increases sharply. Consequently, the performance of the genetic algorithm based approach deteriorates significantly. This motivates the research of this work. This research develops and implements a simulated annealing algorithm based approach to find the optimal path for a mobile robot in a dynamic environment with moving obstacles. The simulated annealing algorithm is an optimization algorithm similar to the genetic algorithm in principle. However, our investigation and simulations have indicated that the simulated annealing algorithm based approach is simpler and easier to implement. Its performance is also shown to be superior to that of the genetic algorithm based approach in both online and offline processing times as well as in obtaining the optimal solution for path planning of the robot in the dynamic environment. The first step of many path planning methods is to search an initial feasible path for the robot. A commonly used method for searching the initial path is to randomly pick up some vertices of the obstacles in the search space. This is time consuming in both static and dynamic path planning, and has an important impact on the efficiency of the dynamic path planning. This research proposes a heuristic method to search the feasible initial path efficiently. Then, the heuristic method is incorporated into the proposed simulated annealing algorithm based approach for dynamic robot path planning. Simulation experiments have shown that with the incorporation of the heuristic method, the developed simulated annealing algorithm based approach requires much shorter processing time to get the optimal solutions in the dynamic path planning problem. Furthermore, the quality of the solution, as characterized by the length of the planned path, is also improved with the incorporated heuristic method in the simulated annealing based approach for both online and offline path planning.

Communication infrastructure study for precise positioning services in regional Queensland

Providing precise positioning services in regional areas to support agriculture, mining, and construction sectors depends on the availability of ground continuously operating GNSS reference stations and communications linking these stations to central computers and users. With the support of CRC for Spatial Information, a more comprehensive review has been completed recently to examine various wired and wireless communication links available for precise positioning services, in particular in the Queensland regional areas. The study covers a wide range of communication technologies that are currently available, including fixed, mobile wireless, and Geo-stationary and or low earth orbiting satellites. These technologies are compared in terms of bandwidth, typical latency, reliability, coverage, and costs. Additionally, some tests were also conducted to determine the performances of different systems in the real environment. Finally, based on user application requirements, the paper discusses the suitability of different communication links.

Object tracking using multiple motion modalities

This paper presents an object tracking system that utilises a hybrid multi-layer motion segmentation and optical flow algorithm. While many tracking systems seek to combine multiple modalities such as motion and depth or multiple inputs within a fusion system to improve tracking robustness, current systems have avoided the combination of motion and optical flow. This combination allows the use of multiple modes within the object detection stage. Consequently, different categories of objects, within motion or stationary, can be effectively detected utilising either optical flow, static foreground or active foreground information. The proposed system is evaluated using the ETISEO database and evaluation metrics and compared to a baseline system utilising a single mode foreground segmentation technique. Results demonstrate a significant improvement in tracking results can be made through the incorporation of the additional motion information.

Optimal mission path planning (MPP) for an air sampling unmanned aerial system

This paper presents advanced optimization techniques for Mission Path Planning (MPP) of a UAS fitted with a spore trap to detect and monitor spores and plant pathogens. The UAV MPP aims to optimise the mission path planning search and monitoring of spores and plant pathogens that may allow the agricultural sector to be more competitive and more reliable. The UAV will be fitted with an air sampling or spore trap to detect and monitor spores and plant pathogens in remote areas not accessible to current stationary monitor methods. The optimal paths are computed using a Multi-Objective Evolutionary Algorithms (MOEAs). Two types of multi-objective optimisers are compared; the MOEA Non-dominated Sorting Genetic Algorithms II (NSGA-II) and Hybrid Game are implemented to produce a set of optimal collision-free trajectories in three-dimensional environment. The trajectories on a three-dimension terrain, which are generated off-line, are collision-free and are represented by using Bézier spline curves from start position to target and then target to start position or different position with altitude constraints. The efficiency of the two optimization methods is compared in terms of computational cost and design quality. Numerical results show the benefits of coupling a Hybrid-Game strategy to a MOEA for MPP tasks. The reduction of numerical cost is an important point as the faster the algorithm converges the better the algorithms is for an off-line design and for future on-line decisions of the UAV.

Safety implications of increased moped and scooter use in an Australian city

Drawing on two studies within a larger program of research into scooter and moped safety in Queensland, Australia, some key safety concerns specific to the use of these vehicles are discussed. A five phase observational study is used to identify distribution of powered two-wheeler (PTW) types in the city centre of Brisbane, Australia’s third largest city. Data were first collected in August 2008, and thereafter at six-monthly intervals. Stationary PTWs were directly observed in designated parking areas. Four focus groups involving 23 Brisbane riders were held in March 2009, aiming to explore perspectives on safety and transport planning in a semi-structured format. Information gathered in the focus groups informed development of a questionnaire targeting a larger sample of scooter and moped riders. The observations made to date indicate that 36% of all PTWs parked in Brisbane’s inner city are either mopeds or larger scooters, with the remaining 64% accounted for by motorcycles (n = 2037). These data suggest that mopeds and scooters are a significant transport mode in Brisbane, yet little is known about their safety relative to that of motorcycles. In focus groups, main motivating factors for scooter or moped use included parking availability, traffic congestion, cost, time-efficiency and enjoyment. Moped riders were generally younger and less experienced than other scooter riders, less likely to wear protective clothing, and less likely to have undertaken rider training. The focus groups have helped to identify some particular safety concerns regarding moped use in a jurisdiction requiring no motorcycle licence or rider training.

Performance analysis of adaptive lattice filters for FM signals and alpha-stable processes

The performance of an adaptive filter may be studied through the behaviour of the optimal and adaptive coefficients in a given environment. This thesis investigates the performance of finite impulse response adaptive lattice filters for two classes of input signals: (a) frequency modulated signals with polynomial phases of order p in complex Gaussian white noise (as nonstationary signals), and (b) the impulsive autoregressive processes with alpha-stable distributions (as non-Gaussian signals). Initially, an overview is given for linear prediction and adaptive filtering. The convergence and tracking properties of the stochastic gradient algorithms are discussed for stationary and nonstationary input signals. It is explained that the stochastic gradient lattice algorithm has many advantages over the least-mean square algorithm. Some of these advantages are having a modular structure, easy-guaranteed stability, less sensitivity to the eigenvalue spread of the input autocorrelation matrix, and easy quantization of filter coefficients (normally called reflection coefficients). We then characterize the performance of the stochastic gradient lattice algorithm for the frequency modulated signals through the optimal and adaptive lattice reflection coefficients. This is a difficult task due to the nonlinear dependence of the adaptive reflection coefficients on the preceding stages and the input signal. To ease the derivations, we assume that reflection coefficients of each stage are independent of the inputs to that stage. Then the optimal lattice filter is derived for the frequency modulated signals. This is performed by computing the optimal values of residual errors, reflection coefficients, and recovery errors. Next, we show the tracking behaviour of adaptive reflection coefficients for frequency modulated signals. This is carried out by computing the tracking model of these coefficients for the stochastic gradient lattice algorithm in average. The second-order convergence of the adaptive coefficients is investigated by modeling the theoretical asymptotic variance of the gradient noise at each stage. The accuracy of the analytical results is verified by computer simulations. Using the previous analytical results, we show a new property, the polynomial order reducing property of adaptive lattice filters. This property may be used to reduce the order of the polynomial phase of input frequency modulated signals. Considering two examples, we show how this property may be used in processing frequency modulated signals. In the first example, a detection procedure in carried out on a frequency modulated signal with a second-order polynomial phase in complex Gaussian white noise. We showed that using this technique a better probability of detection is obtained for the reduced-order phase signals compared to that of the traditional energy detector. Also, it is empirically shown that the distribution of the gradient noise in the first adaptive reflection coefficients approximates the Gaussian law. In the second example, the instantaneous frequency of the same observed signal is estimated. We show that by using this technique a lower mean square error is achieved for the estimated frequencies at high signal-to-noise ratios in comparison to that of the adaptive line enhancer. The performance of adaptive lattice filters is then investigated for the second type of input signals, i.e., impulsive autoregressive processes with alpha-stable distributions . The concept of alpha-stable distributions is first introduced. We discuss that the stochastic gradient algorithm which performs desirable results for finite variance input signals (like frequency modulated signals in noise) does not perform a fast convergence for infinite variance stable processes (due to using the minimum mean-square error criterion). To deal with such problems, the concept of minimum dispersion criterion, fractional lower order moments, and recently-developed algorithms for stable processes are introduced. We then study the possibility of using the lattice structure for impulsive stable processes. Accordingly, two new algorithms including the least-mean P-norm lattice algorithm and its normalized version are proposed for lattice filters based on the fractional lower order moments. Simulation results show that using the proposed algorithms, faster convergence speeds are achieved for parameters estimation of autoregressive stable processes with low to moderate degrees of impulsiveness in comparison to many other algorithms. Also, we discuss the effect of impulsiveness of stable processes on generating some misalignment between the estimated parameters and the true values. Due to the infinite variance of stable processes, the performance of the proposed algorithms is only investigated using extensive computer simulations.

Adaptive instantaneous frequency estimation: Techniques and algorithms

This thesis deals with the problem of the instantaneous frequency (IF) estimation of sinusoidal signals. This topic plays significant role in signal processing and communications. Depending on the type of the signal, two major approaches are considered. For IF estimation of single-tone or digitally-modulated sinusoidal signals (like frequency shift keying signals) the approach of digital phase-locked loops (DPLLs) is considered, and this is Part-I of this thesis. For FM signals the approach of time-frequency analysis is considered, and this is Part-II of the thesis. In part-I we have utilized sinusoidal DPLLs with non-uniform sampling scheme as this type is widely used in communication systems. The digital tanlock loop (DTL) has introduced significant advantages over other existing DPLLs. In the last 10 years many efforts have been made to improve DTL performance. However, this loop and all of its modifications utilizes Hilbert transformer (HT) to produce a signal-independent 90-degree phase-shifted version of the input signal. Hilbert transformer can be realized approximately using a finite impulse response (FIR) digital filter. This realization introduces further complexity in the loop in addition to approximations and frequency limitations on the input signal. We have tried to avoid practical difficulties associated with the conventional tanlock scheme while keeping its advantages. A time-delay is utilized in the tanlock scheme of DTL to produce a signal-dependent phase shift. This gave rise to the time-delay digital tanlock loop (TDTL). Fixed point theorems are used to analyze the behavior of the new loop. As such TDTL combines the two major approaches in DPLLs: the non-linear approach of sinusoidal DPLL based on fixed point analysis, and the linear tanlock approach based on the arctan phase detection. TDTL preserves the main advantages of the DTL despite its reduced structure. An application of TDTL in FSK demodulation is also considered. This idea of replacing HT by a time-delay may be of interest in other signal processing systems. Hence we have analyzed and compared the behaviors of the HT and the time-delay in the presence of additive Gaussian noise. Based on the above analysis, the behavior of the first and second-order TDTLs has been analyzed in additive Gaussian noise. Since DPLLs need time for locking, they are normally not efficient in tracking the continuously changing frequencies of non-stationary signals, i.e. signals with time-varying spectra. Nonstationary signals are of importance in synthetic and real life applications. An example is the frequency-modulated (FM) signals widely used in communication systems. Part-II of this thesis is dedicated for the IF estimation of non-stationary signals. For such signals the classical spectral techniques break down, due to the time-varying nature of their spectra, and more advanced techniques should be utilized. For the purpose of instantaneous frequency estimation of non-stationary signals there are two major approaches: parametric and non-parametric. We chose the non-parametric approach which is based on time-frequency analysis. This approach is computationally less expensive and more effective in dealing with multicomponent signals, which are the main aim of this part of the thesis. A time-frequency distribution (TFD) of a signal is a two-dimensional transformation of the signal to the time-frequency domain. Multicomponent signals can be identified by multiple energy peaks in the time-frequency domain. Many real life and synthetic signals are of multicomponent nature and there is little in the literature concerning IF estimation of such signals. This is why we have concentrated on multicomponent signals in Part-H. An adaptive algorithm for IF estimation using the quadratic time-frequency distributions has been analyzed. A class of time-frequency distributions that are more suitable for this purpose has been proposed. The kernels of this class are time-only or one-dimensional, rather than the time-lag (two-dimensional) kernels. Hence this class has been named as the T -class. If the parameters of these TFDs are properly chosen, they are more efficient than the existing fixed-kernel TFDs in terms of resolution (energy concentration around the IF) and artifacts reduction. The T-distributions has been used in the IF adaptive algorithm and proved to be efficient in tracking rapidly changing frequencies. They also enables direct amplitude estimation for the components of a multicomponent