Nuclear Magnetic Resonance Spectroscopic and Computational Investigations of Chloroperoxidase Catalyzed Regio- and Enantio-Selective Transformations

Chloroperoxidase (CPO) is the most versatile heme-containing enzyme that catalyzes a broad spectrum of reactions. The remarkable feature of this enzyme is the high regio- and enantio-selectivity exhibited in CPO-catalyzed oxidation reactions. The aim of this dissertation is to elucidate the structural basis for regio- and enantio-selective transformations and investigate the application of CPO in biodegradation of synthetic dyes. To unravel the mechanism of CPO-catalyzed regioselective oxidation of indole, the dissertation explored the structure of CPO-indole complex using paramagnetic relaxation and molecular modeling. The distances between the protons of indole and the heme iron revealed that the pyrrole ring of indole is oriented toward the heme with its 2-H pointing directly at the heme iron. This provides the first experimental and theoretical explanation for the "unexpected" regioselectivity of CPO-catalyzed indole oxidation. Furthermore, the residues including Leu 70, Phe 103, Ile 179, Val 182, Glu 183, and Phe 186 were found essential to the substrate binding to CPO. These results will serve as a lighthouse in guiding the design of CPO mutants with tailor-made activities for biotechnological applications. To understand the origin of the enantioselectivity of CPO-catalyzed oxidation reactions, the interactions of CPO with substrates such as 2-(methylthio)thiophene were investigated by nuclear magnetic resonance spectroscopy (NMR) and computational techniques. In particular, the enantioselectivity is partly explained by the binding orientation of substrates. In third facet of this dissertation, a green and efficient system for degradation of synthetic dyes was developed. Several commercial dyes such as orange G were tested in the CPO-H2O2-Cl- system, where degradation of these dyes was found very efficient. The presence of halide ions and acidic pH were found necessary to the decomposition of dyes. Significantly, the results revealed that this degradation of azo dyes involves a ferric hypochlorite intermediate of CPO (Fe-OCl), compound X.

Mass assembly and morphological transformations since z ∼ 3 from CANDELS

We quantify the evolution of the stellar mass functions (SMFs) of star-forming and quiescent galaxies as a function of morphology from z ∼ 3 to the present. Our sample consists of ∼50 000 galaxies in the CANDELS fields (∼880 arcmin^2), which we divide into four main morphological types, i.e. pure bulge-dominated systems, pure spiral disc-dominated, intermediate two-component bulge+disc systems and irregular disturbed galaxies. At z ∼ 2, 80 per cent of the stellar mass density of star-forming galaxies is in irregular systems. However, by z ∼ 0.5, irregular objects only dominate at stellar masses below 10^9 M_⊙. A majority of the star-forming irregulars present at z ∼ 2 undergo a gradual transformation from disturbed to normal spiral disc morphologies by z ∼ 1 without significant interruption to their star formation. Rejuvenation after a quenching event does not seem to be common except perhaps for the most massive objects, because the fraction of bulge-dominated star-forming galaxies with M^*/M_⊙ > 10^10.7 reaches 40 per cent at z < 1. Quenching implies the presence of a bulge: the abundance of massive red discs is negligible at all redshifts over 2 dex in stellar mass. However, the dominant quenching mechanism evolves. At z > 2, the SMF of quiescent galaxies above M^* is dominated by compact spheroids. Quenching at this early epoch destroys the disc and produces a compact remnant unless the star-forming progenitors at even higher redshifts are significantly more dense. At 1 < z < 2, the majority of newly quenched galaxies are discs with a significant central bulge. This suggests that mass quenching at this epoch starts from the inner parts and preserves the disc. At z < 1, the high-mass end of the passive SMF is globally in place and the evolution mostly happens at stellar masses below 10^10 M_⊙. These low-mass galaxies are compact, bulge-dominated systems, which were environmentally quenched: destruction of the disc through ram-pressure stripping is the likely process.

Thermal treatment of weddellite—a Raman and infrared emission spectroscopic study

Thermal transformations of natural calcium oxalate dihydrate known in mineralogy as weddellite have been undertaken using a combination of Raman microscopy and infrared emission spectroscopy. The vibrational spectroscopic data was complimented with high resolution thermogravimetric analysis combined with evolved gas mass spectrometry. TG–MS identified three mass loss steps at 114, 422 and 592 °C. In the first mass loss step water is evolved only, in the second and third steps carbon dioxide is evolved. The combination of Raman microscopy and a thermal stage clearly identifies the changes in the molecular structure with thermal treatment. Weddellite is the phase in the temperature range up to the pre-dehydration temperature of 97 °C. At this temperature, the phase formed is whewellite (calcium oxalate monohydrate) and above 114 °C the phase is the anhydrous calcium oxalate. Above 422 °C, calcium carbonate is formed. Infrared emission spectroscopy shows that this mineral decomposes at around 650 °C. Changes in the position and intensity of the C=O and C---C stretching vibrations in the Raman spectra indicate the temperature range at which these phase changes occur.

Urban sustainability and growth management in south-east Asian city-regions : the case of Kuala Lumpur and Hong Kong

Major South-East Asian city-regions have experienced considerable physical, economic and social transformations during the past three decades. The rapid pace of globalisation and economic restructuring has resulted in these city-regions receiving the full impact of urbanisation pressures. In an attempt to ease these pressures, city-regions such as Bangkok, Seoul, Tokyo, Taipei, Hong Kong, Singapore and Kuala Lumpur have advocate growth management approaches giving particular interest to urban sustainability. These approaches promote efforts to achieve the triple bottom line sustainability by balancing economic and social development, and environmental protection, and putting more emphasis on compact and optimum development of urban forms. This paper evaluates the case of two South-East Asian city-regions, Kuala Lumpur and Hong Kong, and assesses their experiences in managing their urban forms whilst promoting sustainable patterns of urban development. The findings show that sustainable urban development initiatives employing a top down approach has yielded encouraging results in these case study city-regions. However the need for a more concerted effort towards the overall sustainability agenda still remains vital.

Towards model round-trip engineering : an abductive approach

Providing support for reversible transformations as a basis for round-trip engineering is a significant challenge in model transformation research. While there are a number of current approaches, they require the underlying transformation to exhibit an injective behaviour when reversing changes. This however, does not serve all practical transformations well. In this paper, we present a novel approach to round-trip engineering that does not place restrictions on the nature of the underlying transformation. Based on abductive logic programming, it allows us to compute a set of legitimate source changes that equate to a given change to the target model. Encouraging results are derived from an initial prototype that supports most concepts of the Tefkat transformation language

Australian Media and Culture

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Urban growth management for sustainable urbanization : examples from Asia-Pacific city regions

During the past three decades cities in the Asia-Pacific region have undergone massive transformations, characterised by rapid population growth and urbanisation. The rapid pace of globalisation and economic restructuring has resulted in these cities receiving the full impact of urbanisation pressures. In attempting to ease these pressures, major cities have advocated growth management approaches that give particular interest to sustainable urbanization and emphasise compact and optimum development of urban forms. This paper seeks to provide an insight into sustainable urbanisation practice, particularly on the promotion of compact urbanisation within Asia-Pacific’s fastest growing regions. The finding shows that within the context of resource constraints, sustainable urbanisation has been a key factor in the adoption of urban growth management initiatives promoting viable use of scarce resources for urban expansion.

The role of extreme sports in lifestyle enhancement and wellness

Alternative sports are fast becoming the physical activity of choice. Participation rates are even outstripping more traditional activities such as golf. At their most extreme there is no second chance, the most likely outcome of a mismanaged error or accident is death. At this level participants enjoy activities such as B.A.S.E. (Buildings, Antennae, Space, Earth) jumping, big wave surfing, waterfall kayaking, extreme skiing, rope-free climbing and extreme mountaineering. Probably the most common explanation for participation in extreme sports is the notion that participation is just a matter of some people‟s need to take unnecessary risks. This study reports on findings that indicate a more positive experience. A phenomenological method was used via unstructured interviews with 15 extreme sports participants (ages 30 – 72 years) and other firsthand accounts. Extreme sport participants directly related their experience to personal transformations that spill over to life in general. Athletes report feelings of deep psychological wellbeing and meaningfulness. The extreme sport experience enables a participant to break through personal barriers and develop an understanding of their own resourcefulness and emotional, cognitive, physical and spiritual capabilities. Furthermore such a breakthrough also seems to trigger a change in personal philosophy or view on life. The extreme sport experience transforms a participant though not in terms of working towards an external (social or cultural) perception of identity or towards some constructed perception of an ideal self, but by touching something within.

TraSe algorithm : automatic evolutionary morphing of electronic dance music

The TraSe (Transform-Select) algorithm has been developed to investigate the morphing of electronic music through automatically applying a series of deterministic compositional transformations to the source, guided towards a target by similarity metrics. This is in contrast to other morphing techniques such as interpolation or parameters or probabilistic variation. TraSe allows control over stylistic elements of the music through user-defined weighting of numerous compositional transformations. The formal evaluation of TraSe was mostly qualitative and occurred through nine participants completing an online questionnaire. The music generated by TraSe was generally felt to be less coherent than a human composed benchmark but in some cases judged as more creative.

Motivation, development and validation of a new spectral greenness index : a spectral dimension related to foliage projective cover

A method is presented for the development of a regional Landsat-5 Thematic Mapper (TM) and Landsat-7 Enhanced Thematic Mapper plus (ETM+) spectral greenness index, coherent with a six-dimensional index set, based on a single ETM+ spectral image of a reference landscape. The first three indices of the set are determined by a polar transformation of the first three principal components of the reference image and relate to scene brightness, percent foliage projective cover (FPC) and water related features. The remaining three principal components, of diminishing significance with respect to the reference image, complete the set. The reference landscape, a 2200 km2 area containing a mix of cattle pasture, native woodland and forest, is located near Injune in South East Queensland, Australia. The indices developed from the reference image were tested using TM spectral images from 19 regionally dispersed areas in Queensland, representative of dissimilar landscapes containing woody vegetation ranging from tall closed forest to low open woodland. Examples of image transformations and two-dimensional feature space plots are used to demonstrate image interpretations related to the first three indices. Coherent, sensible, interpretations of landscape features in images composed of the first three indices can be made in terms of brightness (red), foliage cover (green) and water (blue). A limited comparison is made with similar existing indices. The proposed greenness index was found to be very strongly related to FPC and insensitive to smoke. A novel Bayesian, bounded space, modelling method, was used to validate the greenness index as a good predictor of FPC. Airborne LiDAR (Light Detection and Ranging) estimates of FPC along transects of the 19 sites provided the training and validation data. Other spectral indices from the set were found to be useful as model covariates that could improve FPC predictions. They act to adjust the greenness/FPC relationship to suit different spectral backgrounds. The inclusion of an external meteorological covariate showed that further improvements to regional-scale predictions of FPC could be gained over those based on spectral indices alone.

“Filming in Progress”: New spaces for multimodal designing

Global trends call for new research to investigate multimodal designing mediated by new technologies and the implications for classroom spaces. This article addresses the relationship between new technologies, students’ multimodal designing, and the social production of classroom spaces. Multimodal semiotics and sociological principles are applied to a series of claymation movie-making lessons in an upper primary school in Australia. The analysis focuses on the social meanings embedded in the multimodal spaces of the classroom—dialogic, bodily, embodied, architectonic, and screen spaces. The findings demonstrate how the uses of new technologies and the students’ multimodal learning were tied to important transformations of space.

Model round-trip engineering

In the quest for shorter time-to-market, higher quality and reduced cost, model-driven software development has emerged as a promising approach to software engineering. The central idea is to promote models to first-class citizens in the development process. Starting from a set of very abstract models in the early stage of the development, they are refined into more concrete models and finally, as a last step, into code. As early phases of development focus on different concepts compared to later stages, various modelling languages are employed to most accurately capture the concepts and relations under discussion. In light of this refinement process, translating between modelling languages becomes a time-consuming and error-prone necessity. This is remedied by model transformations providing support for reusing and automating recurring translation efforts. These transformations typically can only be used to translate a source model into a target model, but not vice versa. This poses a problem if the target model is subject to change. In this case the models get out of sync and therefore do not constitute a coherent description of the software system anymore, leading to erroneous results in later stages. This is a serious threat to the promised benefits of quality, cost-saving, and time-to-market. Therefore, providing a means to restore synchronisation after changes to models is crucial if the model-driven vision is to be realised. This process of reflecting changes made to a target model back to the source model is commonly known as Round-Trip Engineering (RTE). While there are a number of approaches to this problem, they impose restrictions on the nature of the model transformation. Typically, in order for a transformation to be reversed, for every change to the target model there must be exactly one change to the source model. While this makes synchronisation relatively “easy”, it is ill-suited for many practically relevant transformations as they do not have this one-to-one character. To overcome these issues and to provide a more general approach to RTE, this thesis puts forward an approach in two stages. First, a formal understanding of model synchronisation on the basis of non-injective transformations (where a number of different source models can correspond to the same target model) is established. Second, detailed techniques are devised that allow the implementation of this understanding of synchronisation. A formal underpinning for these techniques is drawn from abductive logic reasoning, which allows the inference of explanations from an observation in the context of a background theory. As non-injective transformations are the subject of this research, there might be a number of changes to the source model that all equally reflect a certain target model change. To help guide the procedure in finding “good” source changes, model metrics and heuristics are investigated. Combining abductive reasoning with best-first search and a “suitable” heuristic enables efficient computation of a number of “good” source changes. With this procedure Round-Trip Engineering of non-injective transformations can be supported.

Selection and optimization of piezoelectric polyvinylidene fluoride polymers for adaptive optics in space environments

Various piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films depend on charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to deteriorate owing to strong vacuum UV, � -, X-ray, energetic particles and atomic oxygen exposure. We have investigated the degradation of PVDF and its copolymers under various stress environments detrimental to reliable operation in space. Initial radiation aging studies have shown complex material changes with lowered Curie temperatures, complex material changes with lowered melting points, morphological transformations and significant crosslinking, but little influence on piezoelectric d33 constants. Complex aging processes have also been observed in accelerated temperature environments inducing annealing phenomena and cyclic stresses. The results suggest that poling and chain orientation are negatively affected by radiation and temperature exposure. A framework for dealing with these complex material qualification issues and overall system survivability predictions in low earth orbit conditions has been established. It allows for improved material selection, feedback for manufacturing and processing, material optimization/stabilization strategies and provides guidance on any alternative materials.

Robust image hashing using higher order spectral features

Robust image hashing seeks to transform a given input image into a shorter hashed version using a key-dependent non-invertible transform. These image hashes can be used for watermarking, image integrity authentication or image indexing for fast retrieval. This paper introduces a new method of generating image hashes based on extracting Higher Order Spectral features from the Radon projection of an input image. The feature extraction process is non-invertible, non-linear and different hashes can be produced from the same image through the use of random permutations of the input. We show that the transform is robust to typical image transformations such as JPEG compression, noise, scaling, rotation, smoothing and cropping. We evaluate our system using a verification-style framework based on calculating false match, false non-match likelihoods using the publicly available Uncompressed Colour Image database (UCID) of 1320 images. We also compare our results to Swaminathan’s Fourier-Mellin based hashing method with at least 1% EER improvement under noise, scaling and sharpening.