Zeolite supported gold nanoparticles for selective photooxidation of aromatic alcohols under visible light irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99%) under visible light irradiation at ambient temperature. Au/zeolite photocatalysts were characterized by UV/Vis, XPS, TEM, XRD, EDS, BET, IR, and Raman techniques. The Surface Plasmon Resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports, and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range, and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterization data and the photocatalytic performances, we proposed a possible photooxidation mechanism.

The rest flies down the wind : complexities of late style in the work of Christina Stead

Examining the late style of a writer is like skirting around quicksand. End-of-career reflection can subvert long standing critical accounts; revisionist publishing histories or newly minted archival work can do likewise. And, as Nancy J. Troy suggests, an artist’s last thoughts are rarely planned as such (15). In the case of Christina Stead any consideration of late style is made more difficult because, chronologically speaking, her ‘late’ works were written some 20 years before her death in 1983. Thus chronology can be deceptive, as Nicholas Delbanco points out in Lastingness: The Art of Old Age. Stead’s last novel, I’m Dying Laughing The Humourist, was completed, at least in rough draft form in 1966, when Stead was 64, but friends and readers suggested many changes. The book was published posthumously in 1986. Stead’s work is receiving increasing critical attention so a discussion of her ‘late style’ is important, particularly given that her fiction seems to refuse so many attempts at category-making. This perspective reveals two interesting aspects of her late work: first her consistent engagement with the problems of age for women, and in particular women writers, and second, the consequence of a life-long attention to the representation of dialogic sound in her novels, a preoccupation that results in what can be termed an aural signature. My discussion refers to Edward Said’s and Nicholas Delbanco’s ideas about late style by way of a focus on selective biographical issues and Stead’s engagement with radical politics before moving to an examination of what can be called an aural signature in several novels. Her fiction demonstrates one of the agreed markers of late style: she was constantly looking forward and looking back through innovation in form and content.

'Dripping sweat: sub-tropical spaces in recent Brisbane fiction'

This paper considers the literary landscape of contemporary Brisbane and pays particular attention to the relationship between sub-tropical spaces (homes, streets, and clubs) and local writing. ‘Dripping Sweat’ proposes that within the new urban cool of Brisbane’s cultural life there is nostalgia for the sub-tropical environment that continues to intrude on contemporary fiction. The paper considers the architecture of both public and private spaces and discusses how the literary imagination re-designs contemporary Brisbane with a selective appropriation of environmental settings.

Perceiving and pursuing novelty : a grounded theory of adolescent creativity

Creativity plays an increasingly important role in our personal, social, educational, and community lives. For adolescents, creativity can enable self-expression, be a means of pushing boundaries, and assist learning, achievement, and completion of everyday tasks. Moreover, adolescents who demonstrate creativity can potentially enhance their capacity to face unknown future challenges, address mounting social and ecological issues in our global society, and improve their career opportunities and contribution to the economy. For these reasons, creativity is an essential capacity for young people in their present and future, and is highlighted as a priority in current educational policy nationally and internationally. Despite growing recognition of creativity’s importance and attention to creativity in research, the creative experience from the perspectives of the creators themselves and the creativity of adolescents are neglected fields of study. Hence, this research investigated adolescents’ self-reported experiences of creativity to improve understandings of their creative processes and manifestations, and how these can be supported or inhibited. Although some aspects of creativity have been extensively researched, there were no comprehensive, multidisciplinary theoretical frameworks of adolescent creativity to provide a foundation for this study. Therefore, a grounded theory methodology was adopted for the purpose of constructing a new theory to describe and explain adolescents’ creativity in a range of domains. The study’s constructivist-interpretivist perspective viewed the data and findings as interpretations of adolescents’ creative experiences, co-constructed by the participants and the researcher. The research was conducted in two academically selective high schools in Australia: one arts school, and one science, mathematics, and technology school. Twenty adolescent participants (10 from each school) were selected using theoretical sampling. Data were collected via focus groups, individual interviews, an online discussion forum, and email communications. Grounded theory methods informed a process of concurrent data collection and analysis; each iteration of analysis informed subsequent data collection. Findings portray creativity as it was perceived and experienced by participants, presented in a Grounded Theory of Adolescent Creativity. The Grounded Theory of Adolescent Creativity comprises a core category, Perceiving and Pursuing Novelty: Not the Norm, which linked all findings in the study. This core category explains how creativity involved adolescents perceiving stimuli and experiences differently, approaching tasks or life unconventionally, and pursuing novel ideas to create outcomes that are not the norm when compared with outcomes by peers. Elaboration of the core category is provided by the major categories of findings. That is, adolescent creativity entailed utilising a network of Sub-Processes of Creativity, using strategies for Managing Constraints and Challenges, and drawing on different Approaches to Creativity – adaptation, transfer, synthesis, and genesis – to apply the sub-processes and produce creative outcomes. Potentially, there were Effects of Creativity on Creators and Audiences, depending on the adolescent and the task. Three Types of Creativity were identified as the manifestations of the creative process: creative personal expression, creative boundary pushing, and creative task achievement. Interactions among adolescents’ dispositions and environments were influential in their creativity. Patterns and variations of these interactions revealed a framework of four Contexts for Creativity that offered different levels of support for creativity: high creative disposition–supportive environment; high creative disposition–inhibiting environment; low creative disposition–supportive environment; and low creative disposition–inhibiting environment. These contexts represent dimensional ranges of how dispositions and environments supported or inhibited creativity, and reveal that the optimal context for creativity differed depending on the adolescent, task, domain, and environment. This study makes four main contributions, which have methodological and theoretical implications for researchers, as well as practical implications for adolescents, parents, teachers, policy and curriculum developers, and other interested stakeholders who aim to foster the creativity of adolescents. First, this study contributes methodologically through its constructivist-interpretivist grounded theory methodology combining the grounded theory approaches of Corbin and Strauss (2008) and Charmaz (2006). Innovative data collection was also demonstrated through integration of data from online and face-to-face interactions with adolescents, within the grounded theory design. These methodological contributions have broad applicability to researchers examining complex constructs and processes, and with populations who integrate multimedia as a natural form of communication. Second, applicable to creativity in diverse domains, the Grounded Theory of Adolescent Creativity supports a hybrid view of creativity as both domain-general and domain-specific. A third major contribution was identification of a new form of creativity, educational creativity (ed-c), which categorises creativity for learning or achievement within the constraints of formal educational contexts. These theoretical contributions inform further research about creativity in different domains or multidisciplinary areas, and with populations engaged in formal education. However, the key contribution of this research is that it presents an original Theory and Model of Adolescent Creativity to explain the complex, multifaceted phenomenon of adolescents’ creative experiences.

Secondary curve behavior in Lenke Type 1C adolescent idiopathic scoliosis after thoracoscopic selective anterior thoracic fusion

Study Design. Analysis of a case series of 24 Lenke 1C adolescent idiopathic scoliosis (AIS) patients receiving selective thoracoscopic anterior scoliosis correction. Objective. To report the behaviour of the compensatory lumbar curve in a group of Lenke IC AIS patients following thoracoscopic anterior scoliosis correction, and to compare the results of this study with previously published data. Summary of Background Data. Several prior studies have reported spontaneous lumbar curve correction for both anterior and posterior selective fusion in Lenke 1C/King-Moe II patients; however to our knowledge no previous studies have reported outcomes of thoracoscopic anterior correction for this curve type. Methods. All AIS patients with a curve classification of Lenke 1C and a minimum of 24 months follow-up were retrieved from a consecutive series of 190 AIS patients who underwent thoracoscopic anterior instrumented fusion. Cobb angles of the major curve, instrumented levels, compensatory lumbar curve, and T5-T12 kyphosis were recorded, as well as coronal spinal balance, T1 tilt angle and shoulder balance. All radiographic parameters were measured before surgery and at 2, 6, 12 and 24 months after surgery. Results. Twenty-four female patients with right thoracic curves had a mean thoracic Cobb angle of 53.0° before surgery, decreasing to 24.9° two years after surgery. The mean lumbar compensatory Cobb angle was 43.5° before surgery, spontaneously correcting to 25.4° two years after surgery, indicating balance between the thoracic and lumbar scoliotic curves. The lumbar correction achieved (41.8%) compares favourably to previous studies. Conclusions. Selective thoracoscopic anterior fusion allows spontaneous lumbar curve correction and achieves coronal balance of main thoracic and compensatory lumbar curves, good cosmesis and patient satisfaction. Correction and balance are maintained 24 months after surgery.

Driving selective aerobic oxidation of alkyl aromatics by sunlight on alcohol grafted metal hydroxides

It is very difficult to selectively oxidise stable compounds such as toluene and xylenes to useful chemicals with molecular oxygen (O 2) under moderate conditions. To achieve high conversion and less over-oxidised products, a new class of photocatalysts, metal hydroxide nanoparticles grafted with alcohols, is devised. They can efficiently oxidise alkyl aromatic compounds with O 2 using visible or ultraviolet light or even sunlight to generate the corresponding aldehydes, alcohols and acids at ambient temperatures and give very little over-oxidation. For example toluene can be oxidised with a 23% conversion after a 48-hour exposure to sunlight with 85% of the product being benzaldehyde, and only a trace of CO 2.The surface complexes grafted onto metal hydroxides can absorb light, generating free radicals on the surface, which then initiate aerobic oxidation of the stable alkyl aromatic molecules with high product selectivity. This mechanism is distinctly different from those of any known catalysts. The use of the new photocatalysts as a controlled means to generate surface radicals through light excitation allows us to drive the production of fine organic chemicals at ambient temperatures with sunlight. The process with the new photocatalysts is especially valuable for temperature-sensitive syntheses and a greener process than many conventional thermal reactions. © 2012 The Royal Society of Chemistry.

Selective essays in competitive environments

This thesis is a collection of essays that utilises descriptive and empirical tools to examine competitive environments such as in academia, superrich and sport. The essays capture different aspects of the winner-take-all phenomenon by looking at citation and publication inequality in a top tier economics journal namely the American Economic Review. How globalisation and corruption influence the accumulation of extraordinary wealth and finally, how in a fairly equal competition, that is in the National Rugby League in Australia, wearing red shirts could lead to a comparative advantage and hence, tip the balance between winning and losing. The results within academia indicate that a highly unequal distribution exist, in which only a few top authors or institutions produce the majority of output. Furthermore, the results obtained in the superrich environment indicate that corruption and globalisation enhances the accumulation of extraordinary wealth. Finally, the results in the sport environment are mixed. While we find support for a positive effect of wearing red jerseys in our descriptive analysis, we find a negative effect when we control at the team level. However, when we investigate the relative difference in the degree of redness between home and away team, we find a quite strong positive effect of wearing red shirts even after controlling at the team level.

Managing distraction and attention in diverse cohorts : 21st century challenges to law student engagement

It is imperative that we consider the use of current and emerging technologies in terms of the nature of our learners, the physical environment of the lecture theatre, and how technology may help to support appropriate pedagogies that facilitate the capturing of student attention in active engaging learning experiences. It is argued that a re-evaluation of pedagogy is required to address the tech-savy traits of the 21st century learner and the extent to which their mobile devices are capable of not only distracting them from learning but also enhancing face-to-face learning experiences.

Selective reductions using visible light photocatalysts of supported gold nanoparticles

Photocatalytic synthesis using visible light is a desirable chemical process because of its potential to utilize sunlight. Supported gold nanoparticles (Au-NPs) were found to be efficient photocatalysts and the effects of the supports were identified including CeO2, TiO2, ZrO2, Al2O3, and zeolite Y. In particular Au/CeO2 exhibited the high catalytic activity to reduce nitroaromatics to azo compounds, hydrogenate azobenzene to hydroazobenzene, reduce ketones to alcohols, and deoxygenate epoxides to alkenes at ambient temperatures, under irradiation of visible light (or simulated sunlight). The reac-tive efficiency depends on two primary factors: one is the light adsorption of catalysts and another is the driving ability of catalysts corresponding to the reactants. The light absorption by Au-NPs is due to surface plasmon resonance effect or inter-band electron transition; this is related to the reduction ability of the photocatalysts. Irradiation with shorter wavelengths can excite the conduction electrons in Au-NPs to higher energy levels and as a result, induce reduction with more negative reduction potentials. It is known when irradiated with light the Au-NPs can abstract hydrogen from isopropanol forming Au-H species on the Au-NP surface. Hence, we proposed that the active Au-H species will react with the N=O, N=N, C=O double bonds or epoxide bonds, which are weakened by the interaction with the excited electrons in the Au-NPs, and yield the final reductive products. The reacting power of the Au-H species depends on the energy of the excited electrons in Au-NPs: the higher the electronic energy, the stronger the reduction ability of the Au-H species. This finding demonstrates that we can tune the reduction ability of the photocatalysts by manipulating the irradiation wavelength.

Future-proofing our community for natural disaster requires more attention on men

Response to the "2011 Brisbane floods affected residents' health"

Selective cleavage of human sex hormone-binding globulin by kallikrein-related peptidases and effects on androgen action in LNCaP prostate cancer cells

Stimulation of the androgen receptor via bioavailable androgens, including testosterone and testosterone metabolites, is a key driver of prostate development and the early stages of prostate cancer. Androgens are hydrophobic and as such require carrier proteins, including sex hormone-binding globulin (SHBG), to enable efficient distribution from sites of biosynthesis to target tissues. The similarly hydrophobic corticosteroids also require a carrier protein whose affinity for steroid is modulated by proteolysis. However, proteolytic mechanisms regulating the SHBG/androgen complex have not been reported. Here, we show that the cancer-associated serine proteases, kallikrein-related peptidase (KLK)4 and KLK14, bind strongly to SHBG in glutathione S-transferase interaction analyses. Further, we demonstrate that active KLK4 and KLK14 cleave human SHBG at unique sites and in an androgen-dependent manner. KLK4 separated androgen-free SHBG into its two laminin G-like (LG) domains that were subsequently proteolytically stable even after prolonged digestion, whereas a catalytically equivalent amount of KLK14 reduced SHBG to small peptide fragments over the same period. Conversely, proteolysis of 5α-dihydrotestosterone (DHT)-bound SHBG was similar for both KLKs and left the steroid binding LG4 domain intact. Characterization of this proteolysis fragment by [(3)H]-labeled DHT binding assays revealed that it retained identical affinity for androgen compared with full-length SHBG (dissociation constant = 1.92 nM). Consistent with this, both full-length SHBG and SHBG-LG4 significantly increased DHT-mediated transcriptional activity of the androgen receptor compared with DHT delivered without carrier protein. Collectively, these data provide the first evidence that SHBG is a target for proteolysis and demonstrate that a stable fragment derived from proteolysis of steroid-bound SHBG retains binding function in vitro.

Out of sight, out of mind/out of mind, out of site : Schooling and attention deficit hyperactivity disorder

Attention Deficit Hyperactivity Disorder is a diagnostic term now indelibly scored on the public psyche. In some quarters, a diagnosis of “ADHD” is regarded with derision. In others it is welcomed with relief. Despite intense multi-disciplinary research, the jury is still out with regards to the “truth” of ADHD. Not surprisingly, the rapid increase in diagnosis over the past fifteen years, coupled with an exponential rise in the prescription of restricted class psychopharmaceuticals has stirred virulent debate. Provoking the most interest, it seems, are questions regarding causality. Typically, these revolve around possible antecedents for “disorderly” behaviour – bad food, bad tv and bad parents. Very seldom is the institution of schooling ever in the line of sight. To investigate this gap, I draw on Foucault to question what might be happening in schools and how this may be contributing to the definition, recognition and classification of particular children as a particular kind of “disorderly”.

Enhanced hydrogen separation by vertically-aligned carbon nanotube membranes with zeolite imidazolate frameworks as a selective layer

Vertically-aligned carbon nanotube (VACNT) membranes show very high permeation fluxes due to the inherent smooth and frictionless nature of the interior of the nanotubes. However, the hydrogen selectivities are all in the Knudsen range and are quite low. In this study we grew molecular sieve zeolite imidazolate frameworks (ZIFs) via secondary seeded growth on the VACNT membranes as a gas selective layer. The ZIF layer has a thickness of 5–6 μm and shows good contact with the VACNT membrane surface. The VACNT supported ZIF membrane shows much higher H2 selectivity than Ar (7.0); O2 (13.6); N2 (15.1) and CH4 (9.8). We conclude that tailoring metal–organic frameworks on the membrane surface can be an effective route to improve the gas separation performance of the VACNT membrane.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.