Contributions to analytical chemistry

This collection of seventy-five publications represents the authors contribution to spectroscopy, separation science and flow analysis. Of particular note are the fundamental investigations into chemiluminescence and the innovative strategies for its utilisation as a sensitive and selective means of detection for several important and challenging problems in analytical chemistry.

Off-line two-dimensional liquid chromatography for metabolomics: an example using Agaricus bisporus mushrooms exposed to UV irradiation

It has previously been shown that irradiation with UV light increases the vitamin D content of certain mushroom species, but the effect on other nutrients is unknown, and is difficult to assess due to the complexity of the sample matrix. Here, an offline reversed phase × reversed phase two-dimensional liquid chromatography methodology was developed and applied to Agaricus bisporus mushrooms in order to demonstrate the potential of the technique and assess the effect of UV irradiation on the mushroom’s metabolic profile. The method allowed the detection of 158 peaks in a single analytical run. A total of 51 compounds including sugars, amino acids, organic and fatty acids and phenolic compounds were identified using certified reference standards. After irradiation of the mushrooms with UV for 30 s the number of peaks detected decreased from 158 to 150; 47 compounds increased in concentration while 72 substances decreased. This is the first time that two-dimensional liquid chromatography has been carried out for the metabolomic analysis of mushrooms. The data provide an overview of the gain/loss of nutritional value of the mushrooms following UV irradiation and demonstrate that the increased peak capacity and separation space of two-dimensional liquid chromatography has great potential in metabolomics.

Novel dielectrophoretic platforms for manipulation and separation of particles

This research presents the development of a microfluidic system which takes advantage of dielectrophoresis to manipulate particles. The system utilises curved microelectrodes to create strong dielectrophoretic forces within the microchannel, and exploits a novel operating strategy by patterning carbon nanotubes between the microelectrodes to trap low-conductive particles.

Underdetermined blind source separation by parallel factor analysis in time-frequency domain

This paper presents a new time-frequency approach to the underdetermined blind source separation using the parallel factor decomposition of third-order tensors. Without any constraint on the number of active sources at an auto-term time-frequency point, this approach can directly separate the sources as long as the uniqueness condition of parallel factor decomposition is satisfied. Compared with the existing two-stage methods where the mixing matrix should be estimated at first and then used to recover the sources, our approach yields better source separation performance in the presence of noise. Moreover, the mixing matrix can be estimated at the same time of the source separation process. Numerical simulations are presented to show the superior performance of the proposed approach to some of the existing two-stage blind source separation methods that use the time-frequency representation as well.

The determination of bioactives using multidimensional separation and detection systems

This project was focused on the development of platform technology for the separation and detection of complex samples. The samples investigated included roasted coffee beans, opiate alkaloids and amino acids.

Niche separation in burrowing seabirds in Bass Strait

Islands in north-central Bass Strait support significant populations of short-tailed shearwaters, little penguins, fairy prions and common diving-petrels. Dietary analyses showed that while penguins consume mainly fish, the other species primarily feed on krill. Together, these seabirds consume an estimated 1,270,200 tonnes of prey throughout Bass Strait during breeding.

Recycling textiles : The use of ionic liquids in the separation of cotton polyester blends

Textiles are commonly made from intimate blends of polyester and cotton, which makes recycling very difficult. We report for the first time the use of ionic liquid in the separation of polyester cotton blends. By selective dissolution of the cotton component, the polyester component can be separated and recovered in high yield. This finding presents an environmentally benign approach to recycling textile waste. © 2014 The Royal Society of Chemistry.

Does dynamic vulcanization induce phase separation?

Immiscible and miscible blends of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) were subjected to dynamic vulcanization to investigate the effect of crosslinking on phase separation. As a result of different processability, mixing torque behavior of miscible and immiscible blends was significantly different from one another. Scanning electron microscopy (SEM) was used to investigate the morphology of the system. After dynamic vulcanization, submicron ACM droplets were observed in the samples near the binodal curve of the system under mixing conditions. Small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of dynamic vulcanization on the lamellar structure of the system. It was shown that for samples near the boundary of phase separation, increasing the crosslink density led to a decrease in the lamellar long period (L) as a sign of increment of crosslink density induced phase decomposition. Effects of shear rate on the final morphology of the system were investigated by changing the mixing temperature and by comparing the results of dynamic vulcanization at one phase and two phase regions.

Hybrid high internal phase emulsion (HIPE) organogels with oil separation properties

Hybrid HIPE organogels were prepared from pre-formed hybrid organogels, which were formed from a triblock ionomer and Fe3O4 nanoparticles via charge-driven assembly. Magnetic materials can be obtained from these hybrid HIPE organogels simply by removal of solvents, and these materials have been confirmed to be excellent candidates for absorption of oil from water.

A superamphiphobic coating with an ammonia-triggered transition to superhydrophilic and superoleophobic for oil-water separation

Superhydrophilic and superoleophobic materials are very attractive for efficient and cost-effective oil-water separation, but also very challenging to prepare. Reported herein is a new superamphiphobic coating that turns superhydrophilic and superoleophobic upon ammonia exposure. The coating is prepared from a mixture of silica nanoparticles and heptadecafluorononanoic acid-modified TiO2 sol by a facile dip-coating method. Commonly used materials, including polyester fabric and polyurethane sponge, modified with this coating show unusual capabilities for controllable filtration of an oil-water mixture and selective removal of water from bulk oil. We anticipate that this novel coating may lead to the development of advanced oil-water separation techniques.

Fabrication of superhydrophobic surfaces by smoke deposition and application in oil-water separation

 Utilizing the smoke emitted by discarded silicone combustion, a simple method of smoke deposition is presented for fabricating a superhydrophobic surface with outstanding water repellence, which exhibited a water contact angle of 164 ± 0.8° and a sliding angle of lower than 1°. In addition, the as-prepared surface possesses favourable heat, water impact and water immersion stabilities. Oil leakages seriously endanger both the environment and the social economy. By this simple smoke deposition method, a selective-wettability copper mesh has been fabricated to separate oil-water mixtures. The smoke-deposited mesh achieved a high separation efficiency of over 93% for various oils, and showed excellent reusability, maintaining a high separation efficiency over 10 cycles. The water repellence of the used mesh can be refreshed by recoating with silicone and smoke deposition. This work provides a new strategy to utilize discarded silicone to fabricate superhydrophobic surfaces and oil-water separation meshes.

A convex geometry-based blind source separation method for separating nonnegative sources

This paper presents a convex geometry (CG)-based method for blind separation of nonnegative sources. First, the unaccessible source matrix is normalized to be column-sum-to-one by mapping the available observation matrix. Then, its zero-samples are found by searching the facets of the convex hull spanned by the mapped observations. Considering these zero-samples, a quadratic cost function with respect to each row of the unmixing matrix, together with a linear constraint in relation to the involved variables, is proposed. Upon which, an algorithm is presented to estimate the unmixing matrix by solving a classical convex optimization problem. Unlike the traditional blind source separation (BSS) methods, the CG-based method does not require the independence assumption, nor the uncorrelation assumption. Compared with the BSS methods that are specifically designed to distinguish between nonnegative sources, the proposed method requires a weaker sparsity condition. Provided simulation results illustrate the performance of our method.

Science into policy? Discourse, coastal management and knowledge

The world's coastal resources are under pressure, even more so under climate change with 90% of the world's population living near or along our coastal zone. Ecologically, this zone is also the most productive, and the mainstay of economic livelihoods on a global scale. Managing the coast effectively is crucial, but as an area it remains contested. Despite multiple efforts to manage the coast, it remains a contested space. This paper offers a reflection into the ways in which different discourses influence and impact on one specific dimension of coastal zone management-the transmission of science into the policy domain. Using historical and discourse analysis, we find that the science-policy interface is largely constructed within two knowledge discourses: (i) scientific knowledge and (ii) local knowledge. This arbitrary separation into a binary discursive landscape mitigates against science-policy integration in practice especially given each discourse in itself, encompasses multiple forms of knowledge. We argue that in order to better understand how to build scientific research outputs into policy, decision makers and researchers need to understand how knowledge works in practice, overcome this dichotomous construction of knowledge and specifically, re-construct or transition the notion of 'science as knowledge' into 'all knowledge types' into policy.

Hydrogen bonding interactions in poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone)/poly(hydroxyether of bisphenol A) triblock copolymer/homopolymer blends and the effect on crystallization, microphase separation and self-assembly

This study investigated the self-assembled microphase separated morphologies that are obtained in bulk, by the complexation of a semicrystalline poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer and a homopolymer, poly(hydroxyether of bisphenol A) (PH) in tetrahydrofuran (THF). In these blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically, the homopolymer interacts with PCL blocks through hydrogen bonding interactions. The crystallization, microphase separation and crystalline structures of a triblock copolymer/homopolymer blends were investigated. The phase behavior of the complexes was investigated using small-angle X-ray scattering and transmission electron microscopy. At low PH concentrations, PCL interacts relatively weakly with PH, whereas in complexes containing more than 50 wt% PH, the PCL block interacts significantly with PH, leading to the formation of composition-dependent nanostructures. SAXS and TEM results indicate that the lamellar morphology of neat PCL-PDMS-PCL triblock copolymer changes into disordered structures at 40-60 wt% PH. Spherical microdomains were obtained in the order of 40-50 nm in complexes with 80 wt% PH. At this concentration, the complexes show a completely homogenous phase of PH/PCL, with phase-separated spherical PDMS domains. The formation of these nanostructures and changes in morphology depends on the strength of hydrogen bonding between PH/PCL blocks and also the phase separated PDMS blocks.