Spectrometric and voltammetric studies of the interaction between quercetin and bovine serum albumin using warfarin as site marker with the aid of chemometrics

The interaction of quercetin, which is a bioflavonoid, with bovine serum albumin (BSA) was investigated under pseudo-physiological conditions by the application of UV–vis spectrometry, spectrofluorimetry and cyclic voltammetry (CV). These studies indicated a cooperative interaction between the quercetin–BSA complex and warfarin, which produced a ternary complex, quercetin–BSA–warfarin. It was found that both quercetin and warfarin were located in site I. However, the spectra of these three components overlapped and the chemometrics method – multivariate curve resolution-alternating least squares (MCR-ALS) was applied to resolve the spectra. The resolved spectra of quercetin–BSA and warfarin agreed well with their measured spectra, and importantly, the spectrum of the quercetin–BSA–warfarin complex was extracted. These results allowed the rationalization of the behaviour of the overlapping spectra. At lower concentrations ([warfarin] < 1 × 10−5 mol L−1), most of the site marker reacted with the quercetin–BSA, but free warfarin was present at higher concentrations. Interestingly, the ratio between quercetin–BSA and warfarin was found to be 1:2, suggesting a quercetin–BSA–(warfarin)2 complex, and the estimated equilibrium constant was 1.4 × 1011 M−2. The results suggest that at low concentrations, warfarin binds at the high-affinity sites (HAS), while low-affinity binding sites (LAS) are occupied at higher concentrations.

Fluorescence spectrometric study on the interactions of isoprocarb and sodium 2-isopropylphenate with bovine serum albumin

The binding interaction of the pesticide Isoprocarb and its degradation product, sodium 2-isopropylphenate, with bovine serum albumin (BSA) was studied by spectrofluorimetry under simulated physiological conditions. Both Isoprocarb and sodium 2-isopropylphenate quenched the intrinsic fluorescence of BSA. This quenching proceeded via a static mechanism. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) obtained from the fluorescence data measured at two different temperatures showed that the binding of Isoprocarb to BSA involved hydrogen bonds and that of sodium 2-isopropylphenate to BSA involved hydrophobic and electrostatic interactions. Synchronous fluorescence spectroscopy of the interaction of BSA with either Isoprocarb or sodium 2-isopropylphenate showed that the molecular structure of the BSA was changed significantly, which is consistent with the known toxicity of the pesticide, i.e., the protein is denatured. The sodium 2-isopropylphenate, was estimated to be about 4–5 times more toxic than its parent, Isoprocarb. Synchronous fluorescence spectroscopy and the resolution of the three-way excitation–emission fluorescence spectra by the PARAFAC method extracted the relative concentration profiles of BSA, Isoprocab and sodium 2-isopropylphenate as a function of the added sodium 2-isopropylphenate. These profiles showed that the degradation product, sodium 2-isopropylphenate, displaced the pesticide in a competitive reaction with the BSA protein.

Biotribological assessment for artificial synovial joints : the role of boundary lubrication

Biotribology, the study of lubrication, wear and friction within the body, has become a topic of high importance in recent times as we continue to encounter debilitating diseases and trauma that destroy function of the joints. A highly successful surgical procedure to replace the joint with an artificial equivalent alleviates dysfunction and pain. However, the wear of the bearing surfaces in prosthetic joints is a significant clinical problem and more patients are surviving longer than the life expectancy of the joint replacement. Revision surgery is associated with increased morbidity and mortality and has a far less successful outcome than primary joint replacement. As such, it is essential to ensure that everything possible is done to limit the rate of revision surgery. Past experience indicates that the survival rate of the implant will be influenced by many parameters, of primary importance, the material properties of the implant, the composition of the synovial fluid and the method of lubrication. In prosthetic joints, effective boundary lubrication is known to take place. The interaction of the boundary lubricant and the bearing material is of utmost importance. The identity of the vital active ingredient within synovial fluid (SF) to which we owe the near frictionless performance of our articulating joints has been the quest of researchers for many years. Once identified, tribo tests can determine what materials and more importantly what surfaces this fraction of SF can function most optimally with. Surface-Active Phospholipids (SAPL) have been implicated as the body’s natural load bearing lubricant. Studies in this thesis are the first to fully characterise the adsorbed SAPL detected on the surface of retrieved prostheses and the first to verify the presence of SAPL on knee prostheses. Rinsings from the bearing surfaces of both hip and knee prostheses removed from revision operations were analysed using High Performance Liquid Chromatography (HPLC) to determine the presence and profile of SAPL. Several common prosthetic materials along with a novel biomaterial were investigated to determine their tribological interaction with various SAPLs. A pin-on-flat tribometer was used to make comparative friction measurements between the various tribo-pairs. A novel material, Pyrolytic Carbon (PyC) was screened as a potential candidate as a load bearing prosthetic material. Friction measurements were also performed on explanted prostheses. SAPL was detected on all retrieved implant bearing surfaces. As a result of the study eight different species of phosphatidylcholines were identified. The relative concentrations of each species were also determined indicating that the unsaturated species are dominant. Initial tribo tests employed a saturated phosphatidylcholine (SPC) and the subsequent tests adopted the addition of the newly identified major constituents of SAPL, unsaturated phosphatidylcholine (USPC), as the test lubricant. All tribo tests showed a dramatic reduction in friction when synthetic SAPL was used as the lubricant under boundary lubrication conditions. Some tribopairs showed more of an affinity to SAPL than others. PyC performed superior to the other prosthetic materials. Friction measurements with explanted prostheses verified the presence and performance of SAPL. SAPL, in particular phosphatidylcholine, plays an essential role in the lubrication of prosthetic joints. Of particular interest was the ability of SAPLs to reduce friction and ultimately wear of the bearing materials. The identification and knowledge of the lubricating constituents of SF is invaluable for not only the future development of artificial joints but also in developing effective cures for several disease processes where lubrication may play a role. The tribological interaction of the various tribo-pairs and SAPL is extremely favourable in the context of reducing friction at the bearing interface. PyC is highly recommended as a future candidate material for use in load bearing prosthetic joints considering its impressive tribological performance.

Groundwater flow model of the Logan river alluvial aquifer system Josephville, South East Queensland

The study focuses on an alluvial plain situated within a large meander of the Logan River at Josephville near Beaudesert which supports a factory that processes gelatine. The plant draws water from on site bores, as well as the Logan River, for its production processes and produces approximately 1.5 ML per day (Douglas Partners, 2004) of waste water containing high levels of dissolved ions. At present a series of treatment ponds are used to aerate the waste water reducing the level of organic matter; the water is then used to irrigate grazing land around the site. Within the study the hydrogeology is investigated, a conceptual groundwater model is produced and a numerical groundwater flow model is developed from this. On the site are several bores that access groundwater, plus a network of monitoring bores. Assessment of drilling logs shows the area is formed from a mixture of poorly sorted Quaternary alluvial sediments with a laterally continuous aquifer comprised of coarse sands and fine gravels that is in contact with the river. This aquifer occurs at a depth of between 11 and 15 metres and is overlain by a heterogeneous mixture of silts, sands and clays. The study investigates the degree of interaction between the river and the groundwater within the fluvially derived sediments for reasons of both environmental monitoring and sustainability of the potential local groundwater resource. A conceptual hydrogeological model of the site proposes two hydrostratigraphic units, a basal aquifer of coarse-grained materials overlain by a thick semi-confining unit of finer materials. From this, a two-layer groundwater flow model and hydraulic conductivity distribution was developed based on bore monitoring and rainfall data using MODFLOW (McDonald and Harbaugh, 1988) and PEST (Doherty, 2004) based on GMS 6.5 software (EMSI, 2008). A second model was also considered with the alluvium represented as a single hydrogeological unit. Both models were calibrated to steady state conditions and sensitivity analyses of the parameters has demonstrated that both models are very stable for changes in the range of ± 10% for all parameters and still reasonably stable for changes up to ± 20% with RMS errors in the model always less that 10%. The preferred two-layer model was found to give the more realistic representation of the site, where water level variations and the numerical modeling showed that the basal layer of coarse sands and fine gravels is hydraulically connected to the river and the upper layer comprising a poorly sorted mixture of silt-rich clays and sands of very low permeability limits infiltration from the surface to the lower layer. The paucity of historical data has limited the numerical modelling to a steady state one based on groundwater levels during a drought period and forecasts for varying hydrological conditions (e.g. short term as well as prolonged dry and wet conditions) cannot reasonably be made from such a model. If future modelling is to be undertaken it is necessary to establish a regular program of groundwater monitoring and maintain a long term database of water levels to enable a transient model to be developed at a later stage. This will require a valid monitoring network to be designed with additional bores required for adequate coverage of the hydrogeological conditions at the Josephville site. Further investigations would also be enhanced by undertaking pump testing to investigate hydrogeological properties in the aquifer.

Vibrational spectroscopic studies of laboratory scale polymer melt processing : application to a thermoplastic polyurethane nanocomposite

A laboratory scale twin screw extruder has been interfaced with a near infrared (NIR) spectrometer via a fibre optic link so that NIR spectra can be collected continuously during the small scale experimental melt state processing of polymeric materials. This system can be used to investigate melt state processes such as reactive extrusion, in real time, in order to explore the kinetics and mechanism of the reaction. A further advantage of the system is that it has the capability to measure apparent viscosity simultaneously which gives important additional information about molecular weight changes and polymer degradation during processing. The system was used to study the melt processing of a nanocomposite consisting of a thermoplastic polyurethane and an organically modified layered silicate.

Interaction between visual status, driver age and distracters on daytime driving performance

This study investigated the effects of visual status, driver age and the presence of secondary distracter tasks on driving performance. Twenty young (M = 26.8 years) and 19 old (M = 70.2 years) participants drove around a closed-road circuit under three visual (normal, simulated cataracts, blur) and three distracter conditions (none, visual, auditory). Simulated visual impairment, increased driver age and the presence of a distracter task detrimentally affected all measures of driving performance except gap judgments and lane keeping. Significant interaction effects were evident between visual status, age and distracters; simulated cataracts had the most negative impact on performance in the presence of visual distracters and a more negative impact for older drivers. The implications of these findings for driving behaviour and acquisition of driving-related information for people with common visual impairments are discussed

Same-sex intimate partner violence : exploring the parameters

Intimate partner violence (IPV) is not only a problem for heterosexual couples. Although research in the area is beset by methodological and definitional problems, studies generally demonstrate that IPV also affects those who identify as non-heterosexual; that is, those sexualities that are typically categorized as lesbian, gay, bisexual, transgender, or intersex (LGBTI). IPV appears to be at least as prevalent in LGBTI relationships as it is in heterosexual couples, and follows similar patterns (e.g. Australian Research Centre on Sex, Health and Society 2006; Donovan et al. 2006; Chan 2005; Craft and Serovich 2005; Burke et al. 2002; Jeffries and Ball 2008; Kelly and Warshafsky 1987; Letellier 1994; Turrell 2000; Ristock 2003; Vickers 1996). There is, however, little in the way of specific community or social services support available to either victims or perpetrators of violence in same-sex relationships (see Vickers 1996). In addition, there are important differences in the experience of IPV between LGBTI and non-LGBTI victims, and even among LGBTI individuals; for example, among transgender populations (Chan 2005), and those who are HIV sero-positive (Craft and Serovich 2005). These different experiences of IPV include the use of HIV and the threat of “outing” a partner as tools of control, as just two examples (Jeffries and Ball 2008; Salyer 1999; WA Government 2008b). Such differences impact on how LGBTI victims respond to the violence, including whether or not and how they seek help, what services they are able to avail themselves of, and how likely they are to remain with, or return to, their violent partners (Burke et al. 2002). This chapter explores the prevalent heteronormative discourses that surround IPV, both within the academic literature, and in general social and government discourses. It seeks to understand how same-sex IPV remains largely invisible, and suggests that these dominant discourses play a major role in maintaining this invisibility. In many respects, it builds on work by a number of scholars who have begun to interrogate the criminal justice and social discourses surrounding violent crime, primarily sexual violence, and who problematize these discourses (see for example Carmody 2003; Carmody and Carrington 2000; Marcus 1992). It will begin by outlining these dominant discourses, and then problematize these by identifying some of the important differences between LGBTI IPV and IPV in heterosexual relationships. In doing so, this chapter will suggest some possible reasons for the silence regarding IPV in LGBTI relationships, and the effects that this can have on victims. Although an equally important area of research, and another point at which the limitations of dominant social discourses surrounding IPV can be brought to light, this chapter will not examine violence experienced by heterosexual men at the hands of their intimate female partners. Instead, it will restrict itself to IPV perpetrated within same-sex relationships.

Дизайнът на взаимодействията, масовата комуникация и предизвикателствата на споделеното експертно знание (Interaction Design, Mass Communication And the Challenge of Distributed Expertise)

This paper considers some of the implications of the rise of design as a master-metaphor of the information age. It compares the terms 'interaction design' and 'mass communication', suggesting that both can be seen as a contradiction in terms, inappropriately preserving an industrial-age division between producers and consumers. With the shift from mass media to interactive media, semiotic and political power seems to be shifting too - from media producers to designers. This paper argues that it is important for the new discipline of 'interactive design' not to fall into habits of thought inherited from the 'mass' industrial era. Instead it argues for the significance, for designers and producers alike, of what I call 'distributed expertise' -including social network markets, a DIY-culture, user-led innovation, consumer co-created content, and the use of Web 2.0 affordances for social, scientific and creative purposes as well as for entertainment. It considers the importance of the growth of 'distributed expertise' as part of a new paradigm in the growth of knowledge, which has 'evolved' through a number of phases, from 'abstraction' to 'representation', to 'productivity'. In the context of technologically mediated popular participation in the growth of knowledge and social relationships, the paper argues that design and media-production professions need to cross rather than to maintain the gap between experts and everyone else, enabling all the agents in the system to navigate the shift into the paradigm of mass productivity.

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.

Remote interaction and user research : anaesthetic preadmission activity

In the absence of telehealth technology, rural patients must travel to a regional or metropolitan hospital for a preadmission consultation one week before their surgery. Currently, examination of the patient’s chest using a stethoscope (auscultation) is not possible over a telehealth network as existing digital stethoscopes have been designed for in-person auscultation. We report on the initial phase of research which ultimately aims to design a digital stethoscope for use in the telehealth context. This initial research phase describes the complexity of the activity of preadmission clinics and the implications for the design of the stethoscope. The research is conducted through field studies of existing face-to-face and remote consultations.

Utilisation of seed resources by small mammals : a two-way interaction

Within the Australian wet tropics bioregion, only 900 000 hectares of once continuous rainforest habitat between Townsville and Cooktown now remains. While on the Atherton Tableland, only 4% of the rainforest that once occurred there remains today with remnant vegetation now forming a matrix of rainforest dispersed within agricultural land (sugarcane, banana, orchard crops, townships and pastoral land). Some biologists have suggested that remnants often support both faunal and floral communities that differ significantly from remaining continuous forest. Australian tropical forests possess a relatively high diversity of native small mammal species particularly rodents, which unlike larger mammalian and avian frugivores elsewhere, have been shown to be resilient to the effects of fragmentation, patch isolation and reduction in patch size. While small mammals often become the dominant mammalian frugivores, in terms of their relative abundance, the relationship that exists between habitat diversity and structure, and the impacts of small mammal foraging within fragmented habitat patches in Australia, is still poorly understood. The relationship between foraging behaviour and demography of two small mammal species, Rattus fuscipes and Melomys cervinipes, and food resources in fragmented rainforest sites, were investigated in the current study. Population densities of both species were strongly related with overall density of seed resources in all rainforest fragments. The distribution of both mammal species however, was found to be independent of the distribution of seed resources. Seed utilisation trials indicated that M.cervinipes and R.fuscipes had less impact on seed resources (extent of seed harvesting) than did other rainforest frugivores. Experimental feeding trials demonstrated that in 85% of fruit species tested, rodent feeding increased seed germination by a factor of 3.5 suggesting that in Australian tropical rainforest remnants, small mammals may play a significant role in enhancing germination of large seeded fruits. This study has emphasised the role of small mammals in tropical rainforest systems in north eastern Australia, in particular, the role that they play within isolated forest fragments where larger frugivorous species may be absent.

User-centered video quality assessment for scalable video coding of H.264/AVC standard

Scalable video coding of H.264/AVC standard enables adaptive and flexible delivery for multiple devices and various network conditions. Only a few works have addressed the influence of different scalability parameters (frame rate, spatial resolution, and SNR) on the user perceived quality within a limited scope. In this paper, we have conducted an experiment of subjective quality assessment for video sequences encoded with H.264/SVC to gain a better understanding of the correlation between video content and UPQ at all scalable layers and the impact of rate-distortion method and different scalabilities on bitrate and UPQ. Findings from this experiment will contribute to a user-centered design of adaptive delivery of scalable video stream.

Determining a set of surrogate parameters to evaluate urban stormwater quality

This thesis details methodology to estimate urban stormwater quality based on a set of easy to measure physico-chemical parameters. These parameters can be used as surrogate parameters to estimate other key water quality parameters. The key pollutants considered in this study are nitrogen compounds, phosphorus compounds and solids. The use of surrogate parameter relationships to evaluate urban stormwater quality will reduce the cost of monitoring and so that scientists will have added capability to generate a large amount of data for more rigorous analysis of key urban stormwater quality processes, namely, pollutant build-up and wash-off. This in turn will assist in the development of more stringent stormwater quality mitigation strategies. The research methodology was based on a series of field investigations, laboratory testing and data analysis. Field investigations were conducted to collect pollutant build-up and wash-off samples from residential roads and roof surfaces. Past research has identified that these impervious surfaces are the primary pollutant sources to urban stormwater runoff. A specially designed vacuum system and rainfall simulator were used in the collection of pollutant build-up and wash-off samples. The collected samples were tested for a range of physico-chemical parameters. Data analysis was conducted using both univariate and multivariate data analysis techniques. Analysis of build-up samples showed that pollutant loads accumulated on road surfaces are higher compared to the pollutant loads on roof surfaces. Furthermore, it was found that the fraction of solids smaller than 150 ìm is the most polluted particle size fraction in solids build-up on both roads and roof surfaces. The analysis of wash-off data confirmed that the simulated wash-off process adopted for this research agrees well with the general understanding of the wash-off process on urban impervious surfaces. The observed pollutant concentrations in wash-off from road surfaces were different to pollutant concentrations in wash-off from roof surfaces. Therefore, firstly, the identification of surrogate parameters was undertaken separately for roads and roof surfaces. Secondly, a common set of surrogate parameter relationships were identified for both surfaces together to evaluate urban stormwater quality. Surrogate parameters were identified for nitrogen, phosphorus and solids separately. Electrical conductivity (EC), total organic carbon (TOC), dissolved organic carbon (DOC), total suspended solids (TSS), total dissolved solids (TDS), total solids (TS) and turbidity (TTU) were selected as the relatively easy to measure parameters. Consequently, surrogate parameters for nitrogen and phosphorus were identified from the set of easy to measure parameters for both road surfaces and roof surfaces. Additionally, surrogate parameters for TSS, TDS and TS which are key indicators of solids were obtained from EC and TTU which can be direct field measurements. The regression relationships which were developed for surrogate parameters and key parameter of interest were of a similar format for road and roof surfaces, namely it was in the form of simple linear regression equations. The identified relationships for road surfaces were DTN-TDS:DOC, TP-TS:TOC, TSS-TTU, TDS-EC and TSTTU: EC. The identified relationships for roof surfaces were DTN-TDS and TSTTU: EC. Some of the relationships developed had a higher confidence interval whilst others had a relatively low confidence interval. The relationships obtained for DTN-TDS, DTN-DOC, TP-TS and TS-EC for road surfaces demonstrated good near site portability potential. Currently, best management practices are focussed on providing treatment measures for stormwater runoff at catchment outlets where separation of road and roof runoff is not found. In this context, it is important to find a common set of surrogate parameter relationships for road surfaces and roof surfaces to evaluate urban stormwater quality. Consequently DTN-TDS, TS-EC and TS-TTU relationships were identified as the common relationships which are capable of providing measurements of DTN and TS irrespective of the surface type.