Synthesis and characterisation of hybrid gold/polymer nanoparticles for bioassay application

A bioassay technique, based on surface-enhanced Raman scattering (SERS) tagged gold nanoparticles encapsulated with a biotin functionalised polymer, has been demonstrated through the spectroscopic detection of a streptavidin binding event. A methodical series of steps preceded these results: synthesis of nanoparticles which were found to give a reproducible SERS signal; design and synthesis of polymers with RAFT-functional end groups able to encapsulate the gold nanoparticle. The polymer also enabled the attachment of a biotin molecule functionalised so that it could be attached to the hybrid nanoparticle through a modular process. Finally, the demonstrations of a positive bioassay for this model construct using streptavidin/biotin binding. The synthesis of silver and gold nanoparticles was performed by using tri-sodium citrate as the reducing agent. The shape of the silver nanoparticles was quite difficult to control. Gold nanoparticles were able to be prepared in more regular shapes (spherical) and therefore gave a more consistent and reproducible SERS signal. The synthesis of gold nanoparticles with a diameter of 30 nm was the most reproducible and these were also stable over the longest periods of time. From the SERS results the optimal size of gold nanoparticles was found to be approximately 30 nm. Obtaining a consistent SERS signal with nanoparticles smaller than this was particularly difficult. Nanoparticles more than 50 nm in diameter were too large to remain suspended for longer than a day or two and formed a precipitate, rendering the solutions useless for our desired application. Gold nanoparticles dispersed in water were able to be stabilised by the addition of as-synthesised polymers dissolved in a water miscible solvent. Polymer stabilised AuNPs could not be formed from polymers synthesised by conventional free radical polymerization, i.e. polymers that did not possess a sulphur containing end-group. This indicated that the sulphur-containing functionality present within the polymers was essential for the self assembly process to occur. Polymer stabilization of the gold colloid was evidenced by a range of techniques including, visible spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and Raman spectroscopy. After treatment of the hybrid nanoparticles with a series of SERS tags, focussing on 2-quinolinethiol the SERS signals were found to have comparable signal intensity to the citrate stabilised gold nanoparticles. This finding illustrates that the stabilization process does not interfere with the ability of gold nanoparticles to act as substrates for the SERS effect. Incorporation of a biotin moiety into the hybrid nanoparticles was achieved through a =click‘ reaction between an alkyne-functionalised polymer and an azido-functionalised biotin analogue. This functionalized biotin was prepared through a 4-step synthesis from biotin. Upon exposure of the surface-bound streptavidin to biotin-functionalised polymer hybrid gold nanoparticles, then washing, a SERS signal was obtained from the 2-quinolinethiol which was attached to the gold nanoparticles (positive assay). After exposure to functionalised polymer hybrid gold nanoparticles without biotin present then washing a SERS signal was not obtained as the nanoparticles did not bind to the streptavidin (negative assay). These results illustrate the applicability of the use of SERS active functional-polymer encapsulated gold nanoparticles for bioassay application.

Fourier active appearance models

Gaining invariance to camera and illumination variations has been a well investigated topic in Active Appearance Model (AAM) fitting literature. The major problem lies in the inability of the appearance parameters of the AAM to generalize to unseen conditions. An attractive approach for gaining invariance is to fit an AAM to a multiple filter response (e.g. Gabor) representation of the input image. Naively applying this concept with a traditional AAM is computationally prohibitive, especially as the number of filter responses increase. In this paper, we present a computationally efficient AAM fitting algorithm based on the Lucas-Kanade (LK) algorithm posed in the Fourier domain that affords invariance to both expression and illumination. We refer to this as a Fourier AAM (FAAM), and show that this method gives substantial improvement in person specific AAM fitting performance over traditional AAM fitting methods.

The impact of nonlinear exposure risk relationships on seasonal time series data: modelling danish neonatal birth anthropometric data

Background Birth weight and length have seasonal fluctuations. Previous analyses of birth weight by latitude effects identified seemingly contradictory results, showing both 6 and 12 monthly periodicities in weight. The aims of this paper are twofold: (a) to explore seasonal patterns in a large, Danish Medical Birth Register, and (b) to explore models based on seasonal exposures and a non-linear exposure-risk relationship. Methods Birth weight and birth lengths on over 1.5 million Danish singleton, live births were examined for seasonality. We modelled seasonal patterns based on linear, U- and J-shaped exposure-risk relationships. We then added an extra layer of complexity by modelling weighted population-based exposure patterns. Results The Danish data showed clear seasonal fluctuations for both birth weight and birth length. A bimodal model best fits the data, however the amplitude of the 6 and 12 month peaks changed over time. In the modelling exercises, U- and J-shaped exposure-risk relationships generate time series with both 6 and 12 month periodicities. Changing the weightings of the population exposure risks result in unexpected properties. A J-shaped exposure-risk relationship with a diminishing population exposure over time fitted the observed seasonal pattern in the Danish birth weight data. Conclusion In keeping with many other studies, Danish birth anthropometric data show complex and shifting seasonal patterns. We speculate that annual periodicities with non-linear exposure-risk models may underlie these findings. Understanding the nature of seasonal fluctuations can help generate candidate exposures.

A general procedure for the derivation of principal domains of higher-order spectra

A general procedure to determine the principal domain (i.e., nonredundant region of computation) of any higher-order spectrum is presented, using the bispectrum as an example. The procedure is then applied to derive the principal domain of the trispectrum of a real-valued, stationary time series. These results are easily extended to compute the principal domains of other higher-order spectra

Mean and variance of estimates of the bispectrum of a harmonic random process-an analysis including leakage effects

Analytical expressions are derived for the mean and variance, of estimates of the bispectrum of a real-time series assuming a cosinusoidal model. The effects of spectral leakage, inherent in discrete Fourier transform operation when the modes present in the signal have a nonintegral number of wavelengths in the record, are included in the analysis. A single phase-coupled triad of modes can cause the bispectrum to have a nonzero mean value over the entire region of computation owing to leakage. The variance of bispectral estimates in the presence of leakage has contributions from individual modes and from triads of phase-coupled modes. Time-domain windowing reduces the leakage. The theoretical expressions for the mean and variance of bispectral estimates are derived in terms of a function dependent on an arbitrary symmetric time-domain window applied to the record. the number of data, and the statistics of the phase coupling among triads of modes. The theoretical results are verified by numerical simulations for simple test cases and applied to laboratory data to examine phase coupling in a hypothesis testing framework

Higher order spectral analysis of Chua's circuit

Higher order spectral analysis is used to investigate nonlinearities in time series of voltages measured from a realization of Chua's circuit. For period-doubled limit cycles, quadratic and cubic nonlinear interactions result in phase coupling and energy exchange between increasing numbers of triads and quartets of Fourier components as the nonlinearity of the system is increased. For circuit parameters that result in a chaotic Rossler-type attractor, bicoherence and tricoherence spectra indicate that both quadratic and cubic nonlinear interactions are important to the dynamics. When the circuit exhibits a double-scroll chaotic attractor the bispectrum is zero, but the tricoherences are high, consistent with the importance of higher-than-second order nonlinear interactions during chaos associated with the double scroll.

Higher-Order spectra of nonlinear polynomial models for Chua's circuit

Polynomial models are shown to simulate accurately the quadratic and cubic nonlinear interactions (e.g. higher-order spectra) of time series of voltages measured in Chua's circuit. For circuit parameters resulting in a spiral attractor, bispectra and trispectra of the polynomial model are similar to those from the measured time series, suggesting that the individual interactions between triads and quartets of Fourier components that govern the process dynamics are modeled accurately. For parameters that produce the double-scroll attractor, both measured and modeled time series have small bispectra, but nonzero trispectra, consistent with higher-than-second order nonlinearities dominating the chaos.

Aggregate distance based clustering using Fibonacci Series -FIBCLUS

This paper proposes an innovative instance similarity based evaluation metric that reduces the search map for clustering to be performed. An aggregate global score is calculated for each instance using the novel idea of Fibonacci series. The use of Fibonacci numbers is able to separate the instances effectively and, in hence, the intra-cluster similarity is increased and the inter-cluster similarity is decreased during clustering. The proposed FIBCLUS algorithm is able to handle datasets with numerical, categorical and a mix of both types of attributes. Results obtained with FIBCLUS are compared with the results of existing algorithms such as k-means, x-means expected maximization and hierarchical algorithms that are widely used to cluster numeric, categorical and mix data types. Empirical analysis shows that FIBCLUS is able to produce better clustering solutions in terms of entropy, purity and F-score in comparison to the above described existing algorithms.

QUT Design Lecture Series

The QUT Design Lecture Series 2010 was a partnered event between QUT School of Design and the State Library of Queensland. The series, spanning from July to September 2010, involved 10 lectures delivered by international, national and local academics, researchers and practitioners. The QUT Design Lecture series 2010 was a public event which examined the cross over between design, digital technologies and artistic practices focusing upon research themes of intangible media, experimental eco-technologies and artistic-design production. Gold Medal Australian Institute of Architects, Clare Design opened the series, whilst internationally awarded and recognised Spanish design group Cloud 9 concluded the series, both focusing on new eco-technologies in the development of contemporary architecture.

Trends in policies, programs and practices in the Australasian First Year Experience literature 2000-2010. The First Year in Higher Education Research Series on Evidence-based Practice. Number 1

This publication is the first in a series of scholarly reports on research-based practice related to the First Year Experience in Higher Education. This report synthesises evidence about practice-based initiatives and pragmatic approaches in Aotearoa (New Zealand) and Australia that aim to enhance the experience of commencing students in the higher education sector. Trends in policies, programs and practices ... examines the first year experience literature from 2000-2010. It acknowledges the uniqueness of the Australasian socio-political context and its influence on the interests and output of researchers. The review surveyed almost 400 empirical reports and conceptual discussions produced over the decade that dealt with the stakeholders, institutions and the higher education sector in Australasia. The literature is examined through two theoretical constructs or “lenses”: first, a set of first year curriculum design principles and second, the generational approach to describing the maturation of initiatives. These outcomes and suggested directions for further research provide the challenges and the opportunities for FYE adherents, both scholars and practitioners, to grapple with in the next decade.

ArtConnexions series

The exhibition consists of a series of 9 large-scale cotton rag prints, printed from digital files, and a sound and picture animation on DVD composed of drawings, sound, analogue and digital photographs, and Super 8 footage. The exhibition represents the artist’s experience of Singapore during her residency. Source imagery was gathered from photographs taken at the Bukit Brown abandoned Chinese Cemetery in Singapore, and Australian native gardens in Parkville Melbourne. Historical sources include re-photographed Singapore 19th and early 20th century postcard images. The works use analogue, hand-drawn and digital imaging, still and animated, to explore the digital interface’s ability to combine mixed media. This practice stems from the digital imaging practice of layering, using various media editing software. The work is innovative in that it stretches the idea of the layer composition in a single image by setting each layer into motion using animation techniques. This creates a multitude of permutations and combinations as the two layers move in different rhythmic patterns. The work also represents an innovative collaboration between the photographic practitioner and a sound composer, Duncan King-Smith, who designed sound for the animation based on concepts of trance, repetition and abstraction. As part of the Art ConneXions program, the work travelled to numerous international venues including: Space 217 Singapore, RMIT Gallery Melbourne, National Museum Jakarta, Vietnam Fine Arts Museum Hanoi, and ifa (Institut fur Auslandsbeziehungen) Gallery in both Stuttgart and Berlin.

Synthesis of one-dimensional nanocomposites based on alumina nanofibres and their catalytic applications

Materials with one-dimensional (1D) nanostructure are important for catalysis. They are the preferred building blocks for catalytic nanoarchitecture, and can be used to fabricate designer catalysts. In this thesis, one such material, alumina nanofibre, was used as a precursor to prepare a range of nanocomposite catalysts. Utilising the specific properties of alumina nanofibres, a novel approach was developed to prepare macro-mesoporous nanocomposites, which consist of a stacked, fibrous nanocomposite with a core-shell structure. Two kinds of fibrous ZrO2/Al2O3 and TiO2/Al2O3 nanocomposites were successfully synthesised using boehmite nanofibers as a hard temperate and followed by a simple calcination. The alumina nanofibres provide the resultant nanocomposites with good thermal stability and mechanical stability. A series of one-dimensional (1D) zirconia/alumina nanocomposites were prepared by the deposition of zirconium species onto the 3D framework of boehmite nanofibres formed by dispersing boehmite nanofibres into a butanol solution, followed by calcination at 773 K. The materials were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and Fourier Transform Infrared spectroscopy (FT-IR). The results demonstrated that when the molar percentage, X, X=100*Zr/(Al+Zr), was > 30%, extremely long ZrO2/Al2O3 composite nanorods with evenly distributed ZrO2 nanocrystals formed on their surface. The stacking of such nanorods gave rise to a new kind of macroporous material without the use of any organic space filler\template or other specific drying techniques. The mechanism for the formation of these long ZrO2/Al2O3 composite nanorods is proposed in this work. A series of solid-superacid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid superacid counterparts were characterised by a variety of techniques including 27Al MAS-NMR, SEM, TEM, XPS, Nitrogen adsorption and Infrared Emission Spectroscopy. NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained superacids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia. Preparation of hierarchically macro-mesoporous catalyst by loading nanocrystallites on the framework of alumina bundles can provide an alternative system to design advanced nanocomposite catalyst with enhanced performance. A series of macro-mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesised. The materials were calcined at 723 K and were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and UV-visible spectroscopy (UV-visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100oC), which makes it possible to synthesize such materials on industrial scale. The performances of a series of resultant TiO2/Al2O3 nanocomposites with different morphologies were evaluated as a photocatalyst for the phenol degradation under UV irradiation. The photocatalyst (Ti/Al =2) with fibrous morphology exhibits higher activity than that of the photocatalyst with microspherical morphology which indeed has the highest Ti to Al molar ratio (Ti/Al =3) in the series of as-synthesised hierarchical TiO2/Al2O3 nanocomposites. Furthermore, the photocatalytic performances, for the fibrous nanocomposites with Ti/Al=2, were optimized by calcination at elevated temperatures. The nanocomposite prepared by calcination at 750oC exhibits the highest catalytic activity, and its performance per TiO2 unit is very close to that of the gold standard, Degussa P 25. This work also emphasizes two advantages of the nanocomposites with fibrous morphology: (1) the resistance to sintering, and (2) good catalyst recovery.