Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Mechanisms of change in negative thinking and urinary monoamines in depressed patients during acute treatment with group cognitive behavior therapy and antidepressant medication

This naturalistic study investigated the mechanisms of change in measures of negative thinking and in 24-h urinary metabolites of noradrenaline (norepinephrine), dopamine and serotonin in a sample of 43 depressed hospital patients attending an eight-session group cognitive behavior therapy program. Most participants (91%) were taking antidepressant medication throughout the therapy period according to their treating Psychiatrists' prescriptions. The sample was divided into outcome categories (19 Responders and 24 Non-responders) on the basis of a clinically reliable change index [Jacobson, N.S., & Truax, P., 1991. Clinical significance: a statistical approach to defining meaningful change in psychotherapy research. Journal of Consulting and Clinical Psychology, 59, 12–19.] applied to the Beck Depression Inventory scores at the end of the therapy. Results of repeated measures analysis of variance [ANOVA] analyses of variance indicated that all measures of negative thinking improved significantly during therapy, and significantly more so in the Responders as expected. The treatment had a significant impact on urinary adrenaline and metadrenaline excretion however, these changes occurred in both Responders and Non-responders. Acute treatment did not significantly influence the six other monoamine metabolites. In summary, changes in urinary monoamine levels during combined treatment for depression were not associated with self-reported changes in mood symptoms.

The mechanism of maturation of insulin-like growth factor-1

This study, to elucidate the role of des(1-3)IGF-I in the maturation of IGF-I,used two strategies. The first was to detect the presence of enzymes in tissues, which would act on IGF-I to produce des(1-3)IGF-I, and the second was to detect the potential products of such enzymic activity, namely Gly-Pro-Glu(GPE), Gly-Pro(GP) and des(l- 3)IGF-I. No neutral tripeptidyl peptidase (TPP II), which would release the tripeptide GPE from IGF-I, was detected in brain, urine nor in red or white blood cells. The TPPlike activity which was detected, was attributed to a combined action of a dipeptidyl peptidase (DPP N) and an aminopeptidase (AP A). A true TPP II was, however, detected in platelets. Two purified TPP II enzymes were investigated but they did not release GPE from IGF-I under a variety of conditions. Consequently, TPP II seemed unlikely to participate in the formation of des(1-3)IGF-I. In contrast, an acidic tripeptidyl peptidase activity (TPP I) was detected in brain and colostrum, the former with a pH optimum of 4.5 and the latter 3.8. It seems likely that such an enzyme would participate in the formation of des( 1-3 )IGF-I in these tissues in vitro, ie. that des(1-3)IGF-I may have been produced as an artifact in the isolation of IGF-I from brain and colostrum in acidic conditions. This contrasts with suggestions of an in vivo role for des(1-3)IGF-I, as reported by others. The activity of a dipeptidyl peptidase N (DPP N) from urine, which should release the dipeptide GP from IGF-I, was assessed under a variety of conditions and with a variety of additives and potential enzyme stimulants, but there was no release of GP. The DPP N also exhibited a transferase activity with synthetic substrates in the presence of dipeptides, at lower concentrations than previously reported for other acceptors or other proteolytic enzymes. In addition, a low concentration of a product,possibly the tetrapeptide Gly-Pro-Gly-Leu, was detected with the action of the enzyme on IGF-I in the presence of the dipeptide Gly-Leu. As part of attempts to detect tissue production of des(1-3)IGF-I, a monoclonal antibody (MAb ), directed towards the GPE- end ofiGF-I was produced by immunisation with a 10-mer covalently attached to a carrier protein. By the use of indirect ELISA and inhibitor studies, the MAb was shown to selectively recognise peptides with anNterminal GPE- sequence, and applied to the indirect detection of des(1-3)IGF-I. The concentration of GPE in brain, measured by mass spectrometry ( MS), was low, and the concentration of total IGF-I (measured by ELISA with a commercial polyclonal antibody [P Ab]) was 40 times higher at 50 nmol/kg. This also, was not consistent with the action of a tripeptidyl peptidase in brain that converted all IGF-I to des(1-3)IGF-I plus GPE. Contrasting ELISA results, using the MAb prepared in this study, suggest an even higher concentration of intact IGF-I of 150 nmollkg. This would argue against the presence of any des( 1-3 )IGF-I in brain, but in turn, this indicates either the presence of other substances containing a GPE amino-terminus or other cross reacting epitope. Although the results of the specificity studies reported in Chapter 5 would make this latter possibility seem unlikely, it cannot be completely excluded. No GP was detected in brain by MS. No GPE was detected in colostrum by capillary electrophoresis (CE) but the interference from extraneous substances reduced the detectability of GPE by CE and this approach would require further, prior, purification and concentration steps. A molecule, with a migration time equal to that of the peptide GP, was detected in colostrum by CE, but the concentration (~ 10 11mo/L) was much higher than the IGF-I concentration measured by radio-immunoassay using a PAb (80 nmol/L) or using a Mab (300-400 nmolL). A DPP IV enzyme was detected in colostrum and this could account for the GP, derived from substrates other than IGF-1. Based on the differential results of the two antibody assays, there was no indication of the presence of des(1-3)IGF-I in brain or colostrum. In the absence of any enzyme activity directed towards the amino terminus of IGF-I and the absence any potential products, IGF-I, therefore, does not appear to "mature" via des(1-3)IGF-I in the brain, nor in the neutral colostrum. In spite of these results which indicate the absence of an enzymic attack on IGF-I and the absence of the expected products in tissues, the possibility that the conversion of IGF-I may occur in neutral conditions in limited amounts, cannot be ruled out. It remains possible that in the extracellular environment of the membrane, a complex interaction of IGF-I, binding protein, aminopeptidase(s) and receptor, produces des(1- 3)IGF-I as a transient product which is bound to the receptor and internalised.

A functional screen identifies lateral transfer of beta-glucuronidase (gus) from bacteria to fungi

Lateral gene transfer (LGT) from prokaryotes to microbial eukaryotes is usually detected by chance through genome-sequencing projects. Here, we explore a different, hypothesis-driven approach. We show that the fitness advantage associated with the transferred gene, typically invoked only in retrospect, can be used to design a functional screen capable of identifying postulated LGT cases. We hypothesized that beta-glucuronidase (gus) genes may be prone to LGT from bacteria to fungi (thought to lack gus) because this would enable fungi to utilize glucuronides in vertebrate urine as a carbon source. Using an enrichment procedure based on a glucose-releasing glucuronide analog (cellobiouronic acid), we isolated two gus(+) ascomycete fungi from soils (Penicillium canescens and Scopulariopsis sp.). A phylogenetic analysis suggested that their gus genes, as well as the gus genes identified in genomic sequences of the ascomycetes Aspergillus nidulans and Gibberella zeae, had been introgressed laterally from high-GC gram(+) bacteria. Two such bacteria (Arthrobacter spp.), isolated together with the gus(+) fungi, appeared to be the descendants of a bacterial donor organism from which gus had been transferred to fungi. This scenario was independently supported by similar substrate affinities of the encoded beta-glucuronidases, the absence of introns from fungal gus genes, and the similarity between the signal peptide-encoding 5' extensions of some fungal gus genes and the Arthrobacter sequences upstream of gus. Differences in the sequences of the fungal 5' extensions suggested at least two separate introgression events after the divergence of the two main Euascomycete classes. We suggest that deposition of glucuronides on soils as a result of the colonization of land by vertebrates may have favored LGT of gus from bacteria to fungi in soils.

Biological monitoring of occupational exposure to polycyclic aromatic hydrocarbons in prebake smelting

In 1984, the International Agency for Research on Cancer determined that working in the primary aluminium production process was associated with exposure to certain polycyclic aromatic hydrocarbons (PAHs) that are probably carcinogenic to humans. Key sources of PAH exposure within the occupational environment of a prebake aluminium smelter are processes associated with use of coal-tar pitch. Despite the potential for exposure via inhalation, ingestion and dermal adsorption, to date occupational exposure limits exist only for airborne contaminants. This study, based at a prebake aluminium smelter in Queensland, Australia, compares exposures of workers who came in contact with PAHs from coal-tar pitch in the smelter’s anode plant (n = 69) and cell-reconstruction area (n = 28), and a non-production control group (n = 17). Literature relevant to PAH exposures in industry and methods of monitoring and assessing occupational hazards associated with these compounds are reviewed, and methods relevant to PAH exposure are discussed in the context of the study site. The study utilises air monitoring of PAHs to quantify exposure via the inhalation route and biological monitoring of 1-hydroxypyrene (1-OHP) in urine of workers to assess total body burden from all routes of entry. Exposures determined for similar exposure groups, sampled over three years, are compared with published occupational PAH exposure limits and/or guidelines. Results of paired personal air monitoring samples and samples collected for 1-OHP in urine monitoring do not correlate. Predictive ability of the benzene-soluble fraction (BSF) in personal air monitoring in relation to the 1-OHP levels in urine is poor (adjusted R2 < 1%) even after adjustment for potential confounders of smoking status and use of personal protective equipment. For static air BSF levels in the anode plant, the median was 0.023 mg/m3 (range 0.002–0.250), almost twice as high as in the cell-reconstruction area (median = 0.013 mg/m3, range 0.003–0.154). In contrast, median BSF personal exposure in the anode plant was 0.036 mg/m3 (range 0.003–0.563), significantly lower than the median measured in the reconstruction area (0.054 mg/m3, range 0.003–0.371) (p = 0.041). The observation that median 1-OHP levels in urine were significantly higher in the anode plant than in the reconstruction area (6.62 µmol/mol creatinine, range 0.09–33.44 and 0.17 µmol/mol creatinine, range 0.001–2.47, respectively) parallels the static air measurements of BSF rather than the personal air monitoring results (p < 0.001). Results of air measurements and biological monitoring show that tasks associated with paste mixing and anode forming in the forming area of the anode plant resulted in higher PAH exposure than tasks in the non-forming areas; median 1-OHP levels in urine from workers in the forming area (14.20 µmol/mol creatinine, range 2.02–33.44) were almost four times higher than those obtained from workers in the non-forming area (4.11 µmol/mol creatinine, range 0.09–26.99; p < 0.001). Results justify use of biological monitoring as an important adjunct to existing measures of PAH exposure in the aluminium industry. Although monitoring of 1-OHP in urine may not be an accurate measure of biological effect on an individual, it is a better indicator of total PAH exposure than BSF in air. In January 2005, interim study results prompted a plant management decision to modify control measures to reduce skin exposure. Comparison of 1-OHP in urine from workers pre- and post-modifications showed substantial downward trends. Exposure via the dermal route was identified as a contributor to overall dose. Reduction in 1-OHP urine concentrations achieved by reducing skin exposure demonstrate the importance of exposure via this alternative pathway. Finally, control measures are recommended to ameliorate risk associated with PAH exposure in the primary aluminium production process, and suggestions for future research include development of methods capable of more specifically monitoring carcinogenic constituents of PAH mixtures, such as benzo[a]pyrene.

Fear and danger in nocturnal urban environments

At the centre of this research is an ethnographic study that saw the researcher embedded within the fabric of inner city life to better understand what characteristics of user activity and interaction could be enhanced by technology. The initial research indicated that the experience of traversing the city after dark unified an otherwise divergent user group through a shared concern for personal safety. Managing this fear and danger represented an important user need. We found that mobile social networking systems are not only integral for bringing people together, they can help in the process of users safely dispersing as well. We conclude, however, that at a time when the average iPhone staggers under the weight of a plethora of apps that do everything from acting as a carpenter’s level to a pregnancy predictor, we consider the potential for the functionality of a personal safety device to be embodied within a stand alone artifact.

Group segmentation during object tracking using optical flow discontinuities

Within a surveillance video, occlusions are commonplace, and accurately resolving these occlusions is key when seeking to accurately track objects. The challenge of accurately segmenting objects is further complicated by the fact that within many real-world surveillance environments, the objects appear very similar. For example, footage of pedestrians in a city environment will consist of many people wearing dark suits. In this paper, we propose a novel technique to segment groups and resolve occlusions using optical flow discontinuities. We demonstrate that the ratio of continuous to discontinuous pixels within a region can be used to locate the overlapping edges, and incorporate this into an object tracking framework. Results on a portion of the ETISEO database show that the proposed algorithm results in improved tracking performance overall, and improved tracking within occlusions.

Imperception? Dreamtime 2.0 Down Under

The Northern Hemisphere slumbers, dreaming that – one day – it is going to split up its empire, before the seas boil and the towers collapse. During this same dark night, Australia is wide awake, chirpy as a Canadian, strapping as a Bondi blonde, having an election...

The international search for ethics norms : which consumer behaviors do consumers consider (un)acceptable?

Purpose: Businesses cannot rely on their customers to always do the right thing. To help researchers and service providers better understand the dark (and light) side of customer behavior, this study aims to aggregate and investigate perceptions of consumer ethics from young consumers on five continents. The study seeks to present a profile of consumer behavioral norms, how ethical inclinations have evolved over time, and country differences. ---------- Design/methodology/approach: Data were collected from ten countries across five continents between 1997 and 2007. A self-administered questionnaire containing 14 consumer scenarios asked respondents to rate acceptability of questionable consumer actions. ---------- Findings: Overall, consumers found four of the 14 questionable consumer actions acceptable. Illegal activities were mostly viewed as unethical, while some legal actions that were against company policy were viewed less harshly. Differences across continents emerged, with Europeans being the least critical, while Asians and Africans shared duties as most critical of consumer actions. Over time, consumers have become less tolerant of questionable behaviors. ---------- Practical implications: Service providers should use the findings of this study to better understand the service customer. Knowing what customers in general believe is ethical or unethical can help service designers focus on the aspects of the technology or design most vulnerable to customer deviance. ---------- Multinationals already know they must adapt their business practices to the market in which they are operating, but they must also adapt their expectations as to the behavior of the corresponding consumer base. Originality/value: This investigation into consumer ethics helps businesses understand what their customer base believes is the right thing in their role as customer. This is a large-scale study of consumer ethics including 3,739 respondents on five continents offering an evolving view of the ethical inclinations of young consumers.

Lost children and imaginary mothers in Sonya Hartnett's Of A Boy

In Powers of Horror, Julia Kristeva writes about lost children. These are what she calls “dejects,” who, in the psychodrama of subject formation, fail to fully absent the body of the mother, to accept the Law of the Father and the Symbolic, and subsequently to establish “clear boundaries which constitute the object-world for normal subjects.” Dejects are “strays” looking for a place to belong, a place that is bound up with the Imaginary mother of the pre-Oedipal period. Kristeva’s sketch of the deject as one who is unable to negotiate a proper path to the Symbolicis useful to a reading of Hartnett’s Of A Boy (2002),a novel that also deals with lost children and imaginary mothers. However, in its portrayal of children who are doomed to never achieve adulthood, Of A Boy enacts a haunting retrieval of the pre-Oedipal from the dark side of phallocentric representation, privileging the semiotic (Kristeva’s concept) and the maternal as necessary disruptive checks on a patriarchal Symbolic Order.

A lesson in tension yet to be taut : a review

NOBEL prize-winning British writer Harold Pinter is best known for his social commentaries and for dark, sometimes violent "comedies of menace" that capture the cruelty at the heart of human relationships. It has been a while since a Pinter play was on the Brisbane stage, and it is exciting to see one of his lesser known early works, Betrayal, as part of Queensland Theatre Company's session. Betrayal moves backwards from a potentially scandalous moment. In a pub one night, Emma tells Jerry that his best friend Robert is divorcing her. Robert has been unfaithful. And, what's more, Robert now knows about their lengthy affair. What follows is a series of scenes that look back at the stages of that affair and the secrets that have lain unspoken at the heart of their comfortable middle-class lives for so long. Betrayal is characterised by the sparsity of action and language, dark humour, and sudden outbreaks of seemingly excessive cruelty that are a trademark of Pinter's writing for the theatre.

Tips for generating a media release and media coverage : how the media ate up my research on Aussie horror movies

The focus of this paper is preparing research for dissemination by mainstream print, broadcast, and online media. While the rise of the blogosphere and social media is proving an effective way of reaching niche audiences, my own research reached such an audience through traditional media. The first major study of Australian horror cinema, my PhD thesis A Dark New World: Anatomy of Australian Horror Films, generated strong interest from horror movie fans, film scholars, and filmmakers. I worked closely with the Queensland University of Technology’s (QUT) public relations unit to write two separate media releases circulated on October 13, 2008 and October 14, 2009. This chapter reflects upon the process of working with the media and provides tips for reaching audiences, particularly in terms of strategically planning outcomes. It delves into the background of my study which would later influence my approach to the media, the process of drafting media releases, and key outcomes and benefits from popularising research. A key lesson from this experience is that redeveloping research for the media requires a sharp writing style, letting go of academic justification, catchy quotes, and an ability to distil complex details into easy-to-understand concepts. Although my study received strong media coverage, and I have since become a media commentator, my experiences also revealed a number of pitfalls that are likely to arise for other researchers keen on targeting media coverage.

The role of vision in obese and normal-weight children's gait control

Previous research has suggested that perceptual-motor difficulties may account for obese children's lower motor competence; however, specific evidence is currently lacking. Therefore, this study examined the effect of altered visual conditions on spatiotemporal and kinematic gait parameters in obese versus normal-weight children. Thirty-two obese and normal-weight children (11.2 ± 1.5 years) walked barefoot on an instrumented walkway at constant self-selected speed during LIGHT and DARK conditions. Three-dimensional motion analysis was performed to calculate spatiotemporal parameters, as well as sagittal trunk segment and lower extremity joint angles at heel-strike and toe-off. Self-selected speed did not significantly differ between groups. In the DARK condition, all participants walked at a significantly slower speed, decreased stride length, and increased stride width. Without normal vision, obese children had a more pronounced increase in relative double support time compared to the normal-weight group, resulting in a significantly greater percentage of the gait cycle spent in stance. Walking in the DARK, both groups showed greater forward tilt of the trunk and restricted hip movement. All participants had increased knee flexion at heel-strike, as well as decreased knee extension and ankle plantarflexion at toe-off in the DARK condition. The removal of normal vision affected obese children's temporal gait pattern to a larger extent than that of normal-weight peers. Results suggest an increased dependency on vision in obese children to control locomotion. Next to the mechanical problem of moving excess mass, a different coupling between perception and action appears to be governing obese children's motor coordination and control.

Theoretical comparison of innovative window daylighting devices for a sub-tropical climate using radiance

Daylighting in tropical and sub-tropical climates presents a unique challenge that is generally not well understood by designers. In a sub-tropical region such as Brisbane, Australia the majority of the year comprises of sunny clear skies with few overcast days and as a consequence windows can easily become sources of overheating and glare. The main strategy in dealing with this issue is extensive shading on windows. However, this in turn prevents daylight penetration into buildings often causing an interior to appear gloomy and dark even though there is more than sufficient daylight available. As a result electric lighting is the main source of light, even during the day. Innovative daylight devices which redirect light from windows offer a potential solution to this issue. These devices can potentially improve daylighting in buildings by increasing the illumination within the environment decreasing the high contrast between the window and work regions and deflecting potentially glare causing sunlight away from the observer. However, the performance of such innovative daylighting devices are generally quantified under overcast skies (i.e. daylight factors) or skies without sun, which are typical of European climates and are misleading when considering these devices for tropical or sub-tropical climates. This study sought to compare four innovative window daylighting devices in RADIANCE; light shelves, laser cut panels, micro-light guides and light redirecting blinds. These devices were simulated in RADIANCE under sub-tropical skies (for Brisbane) within the test case of a typical CBD office space. For each device the quantity of light redirected and its distribution within the space was used as the basis for comparison. In addition, glare analysis on each device was conducted using Weinold and Christoffersons evalglare. The analysis was conducted for selected hours for a day in each season. The majority of buildings that humans will occupy in their lifetime are already constructed, and extensive remodelling of most of these buildings is unlikely. Therefore the most effective way to improve daylighting in the near future will be through the alteration existing window spaces. Thus it will be important to understand the performance of daylighting systems with respect to the climate it is to be used in. This type of analysis is important to determine the applicability of a daylighting strategy so that designers can achieve energy efficiency as well the health benefits of natural daylight.

Corrupt police networks : uncovering hidden relationship patterns, functions and roles

This article applies social network analysis techniques to a case study of police corruption in order to produce findings which will assist in corruption prevention and investigation. Police corruption is commonly studied but rarely are sophisticated tools of analyse engaged to add rigour to the field of study. This article analyses the ‘First Joke’ a systemic and long lasting corruption network in the Queensland Police Force, a state police agency in Australia. It uses the data obtained from a commission of inquiry which exposed the network and develops hypotheses as to the nature of the networks structure based on existing literature into dark networks and criminal networks. These hypotheses are tested by entering the data into UCINET and analysing the outcomes through social network analysis measures of average path distance, centrality and density. The conclusions reached show that the network has characteristics not predicted by the literature.