New catalysts for organic synthesis driven by light and efficient sorbents for removal of radioactive ions from water

The body of the thesis contained two separate elements which made an original contribution to fundamental understanding in the areas of photocatalysis, chemical synthesis and water treatment. Research on chemical reactions catalyzed by noble metal nanoparticles (such as gold) or surface complex grafted metal oxides which can be driven by sunlight at ambient temperature and the second element on radioactive cesium (137Cs+) cations and iodine (125I-) anions recovery by the unique structural features of titanate nanostructures for firmly capture and safe storage; the works has been all published in journals that are rated at the top of their respective fields.

High energy states of gold and their importance in electrocatalytic processes at surfaces and interfaces

The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes

The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

Visible light photocatalysts for synthesis of fine organic chemicals on supported nanostructures

This thesis is focus on developing new photocatalysts for synthesis of fine organic chemicals on supported nanostructures. These photocatalysts can facilitate reactions by using visible light, moderate temperature and atmospheric pressure which is suitable for a sustainable, green and eco-friendly modern chemical industry. Both Semiconductor Photocatalyst and Noble Metal Photocatalysts are designed to facilitate the homocouplings reaction of imine generation by amines.

Genome-wide DNA methylation analysis of human brain tissue from schizophrenia patients

Recent studies suggest that genetic and environmental factors do not account for all the schizophrenia risk and epigenetics also plays a role in disease susceptibility. DNA methylation is a heritable epigenetic modification that can regulate gene expression. Genome-Wide DNA methylation analysis was performed on post-mortem human brain tissue from 24 patients with schizophrenia and 24 unaffected controls. DNA methylation was assessed at over 485 000 CpG sites using the Illumina Infinium Human Methylation450 Bead Chip. After adjusting for age and post-mortem interval (PMI), 4 641 probes corresponding to 2 929 unique genes were found to be differentially methylated. Of those genes, 1 291 were located in a CpG island and 817 were in a promoter region. These include NOS1, AKT1, DTNBP1, DNMT1, PPP3CC and SOX10 which have previously been associated with schizophrenia. More than 100 of these genes overlap with a previous DNA methylation study of peripheral blood from schizophrenia patients in which 27 000 CpG sites were analysed. Unsupervised clustering analysis of the top 3 000 most variable probes revealed two distinct groups with significantly more people with schizophrenia in cluster one compared to controls (p = 1.74x10-4). The first cluster was composed of 88% of patients with schizophrenia and only 12% controls while the second cluster was composed of 27% of patients with schizophrenia and 73% controls. These results strongly suggest that differential DNA methylation is important in schizophrenia etiology and add support for the use of DNA methylation profiles as a future prognostic indicator of schizophrenia.

Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Becoming a pharmacist : the role of curriculum in professional identity formation

Objective To understand how the formal curriculum experience of an Australian undergraduate pharmacy program supports students’ professional identity formation. Methods A qualitative ethnographic study was conducted over four weeks using participant observation and examined the ‘typical’ student experience from the perspective of a pharmacist. A one-week period of observation was undertaken with each of the four year groups (that is, for years one to four) comprising the undergraduate curriculum. Data were collected through observation of the formal curriculum experience using field notes, a reflective journal and informal interviews with 38 pharmacy students. Data were analyzed thematically using an a priori analytical framework. Results Our findings showed that the observed curriculum was a conventional curricular experience which focused on the provision of technical knowledge and provided some opportunities for practical engagement. There were some opportunities for students to imagine themselves as pharmacists, for example, when the lecture content related to practice or teaching staff described their approach to practice problems. However, there were limited opportunities for students to observe pharmacist role models, experiment with being a pharmacist or evaluate their professional identities. While curricular learning activities were available for students to develop as pharmacists e.g. patient counseling, there was no contact with patients and pharmacist academic staff tended to role model as educators with little evidence of their pharmacist selves. Conclusion These findings suggest that the current conventional approach to the curriculum design may not be fully enabling learning experiences which support students in successfully negotiating their professional identities. Instead it appeared to reinforce their identities as students with a naïve understanding of professional practice, making their future transition to professional practice challenging.

In pursuit of an architecture realism

The noble idea of studying seminal works to ‘see what we can learn’ has turned in the 1990s into ‘let’s see what we can take’ and in the last decade a more toxic derivative ‘what else can’t we take’. That is my observation as a student of architecture in the 1990s, and as a practitioner in the 2000s. In 2010, the sense that something is ending is clear. The next generation is rising and their gaze has shifted. The idea of classification (as a means of separation) was previously rejected by a generation of Postmodernists; the usefulness of difference declined. It’s there in the presence of plurality in the resulting architecture, a decision to mine history and seize in a willful manner. This is a process of looking back but never forward. It has been a mono-culture of absorption. The mono-culture rejected the pursuit of the realistic. It is a blanket suffocating all practice of architecture in this country from the mercantile to the intellectual. Independent reviews of Australia’s recent contributions to the Venice Architecture Biennales confirm the malaise. The next generation is beginning to reconsider classification as a means of unification. By acknowledging the characteristics of competing forces it is possible to bring them into a state of tension. Seeking a beautiful contrast is a means to a new end. In the political setting, this is described by Noel Pearson as the radical centre[1]. The concept transcends the political and in its most essential form is a cultural phenomenon. It resists the compromised position and suggests that we can look back while looking forward. The radical centre is the only demonstrated opportunity where it is possible to pursue a realistic architecture. A realistic architecture in Australia may be partially resolved by addressing our anxiety of permanence. Farrelly’s built desires[2] and Markham’s ritual demonstrations[3] are two ways into understanding the broader spectrum of permanence. But I think they are downstream of our core problem. Our problem, as architects, is that we are yet to come to terms with this place. Some call it landscape others call it country. Australian cities were laid out on what was mistaken for a blank canvas. On some occasions there was the consideration of the landscape when it presented insurmountable physical obstacles. The architecture since has continued to work on its piece of a constantly blank canvas. Even more ironic is the commercial awards programs that represent a claim within this framework but at best can only establish a dialogue within itself. This is a closed system unable to look forward. It is said that Melbourne is the most European city in the southern hemisphere but what is really being described there is the limitation of a senseless grid. After all, if Dutch landscape informs Dutch architecture why can’t the Australian landscape inform Australian architecture? To do that, we would have to acknowledge our moribund grasp of the meaning of the Australian landscape. Or more precisely what Indigenes call Country[4]. This is a complex notion and there are different ways into it. Country is experienced and understood through the senses and seared into memory. If one begins design at that starting point it is not unreasonable to think we can arrive at an end point that is a counter trajectory to where we have taken ourselves. A recent studio with Masters students confirmed this. Start by finding Country and it would be impossible to end up with a building looking like an Aboriginal man’s face. To date architecture in Australia has overwhelmingly ignored Country on the back of terra nullius. It can’t seem to get past the picturesque. Why is it so hard? The art world came to terms with this challenge, so too did the legal establishment, even the political scene headed into new waters. It would be easy to blame the budgets of commerce or the constraints of program or even the pressure of success. But that is too easy. Those factors are in fact the kind of limitations that opportunities grow out of. The past decade of economic plenty has, for the most part, smothered the idea that our capitals might enable civic settings or an architecture that is able to looks past lot line boundaries in a dignified manner. The denied opportunities of these settings to be prompted by the Country they occupy is criminal. The public realm is arrested in its development because we refuse to accept Country as a spatial condition. What we seem to be able to embrace is literal and symbolic gestures usually taking the form of a trumped up art installations. All talk – no action. To continue to leave the public realm to the stewardship of mercantile interests is like embracing derivative lending after the global financial crisis.Herein rests an argument for why we need a resourced Government Architect’s office operating not as an isolated lobbyist for business but as a steward of the public realm for both the past and the future. New South Wales is the leading model with Queensland close behind. That is not to say both do not have flaws but current calls for their cessation on the grounds of design parity poorly mask commercial self interest. In Queensland, lobbyists are heavily regulated now with an aim to ensure integrity and accountability. In essence, what I am speaking of will not be found in Reconciliation Action Plans that double as business plans, or the mining of Aboriginal culture for the next marketing gimmick, or even discussions around how to make buildings more ‘Aboriginal’. It will come from the next generation who reject the noxious mono-culture of absorption and embrace a counter trajectory to pursue an architecture of realism.

Becoming a pharmacist : students' perceptions of their curricular experience and professional identity formation

Introduction Student professional identity formation is important for enabling the successful transition between academic education and professional practice. Recognition of this has resulted in significant changes in professional education (e.g., the inclusion of experiential placements and authentic learning experiences). There is limited research that examines how the curricular experience influences pharmacy studentsʼ professional identity formation. Methods Using focus groups, comprising 82 students from all levels of a four-year Australian undergraduate pharmacy course, this study examined studentsʼ perceptions of their overall curricular experience and examined how these experiences influenced the construction of their professional identities. Results Our analysis found that the pharmacy students struggled with their professional identity formation. Many were entering the degree with little understanding of what being a pharmacist entailed. Once in the educational context, the nature of the role became both apparent and idealistic but not enacted. Students experienced dissonance between the idealistic notion of pharmacy practice and the realities of placements, and this may have been enhanced by a lack of patient-centered care role models. This struggle left them concluding that the role of the pharmacist was constrained and limited. Conclusions We argue that professional identity formation needs to be in the foreground from commencement of the degree and throughout the curriculum.

Pharmacy educators' intention for the curriculum : an Australian pilot study

Background: Pharmacy educators play an important role in supporting the professional identity formation of students, particularly in relation to their perceptions and strategies for the curriculum and subsequent learning experiences. Aim: To explore pharmacy educators’ perceptions of the purpose of the pharmacy curriculum and how they contribute to students’ development as pharmacists. Methods: A one-off survey using a 20-item questionnaire distributed to all pharmacy educators at a single school of pharmacy who contributed to an Australian undergraduate pharmacy degree program. Results: Most educators viewed the curriculum and their role from a traditional perspective. The educators felt the key purpose of the curriculum was to develop competent pharmacists by providing students with knowledge and skills. There was a limited emphasis on patient-centredness. Conclusion: Whilst educators were focused on developing competent pharmacists through the provision of knowledge and skills, important learning opportunities supporting identity formation may be missed.

Commercial friendships between gay salesmen and straight female customers

Perhaps it is now sacrosanct in marketing to contemplate that many service encounters, especially those in retail settings, are social encounters in which bonds between and among customers and employees are critical drivers of consumption (Beatty et al., 1996; Rosenbaum, 2006). Indeed, within retail settings, it is often possible for salespeople and customers to form so-called “commercial friendships” (Price and Arnould, 1999). These friendships result in both salespeople and their customers having social interactions that are close to those experienced in personal friendships (Swan et al., 2001), and which are extremely satisfying for all parties. Outside of marketing, the social science literature (Grigoriou, 2004; Rumens, 2008; Russell, DelPriore, Butterfield, and Hill, 2013) and popular press (de la Cruz and Dolby, 2007; Hopcke and Rafaty, 1999; Tilmann-Healy, 2001, Whitney, 1990) is replete with knowledge regarding the “absolutely fabulous” friendships (Hopcke and Rafaty, 1999) that often form between gay men and straight women. In fact, Western culture regularly highlights the compatibility of gay men and straight women in film, television, and writing, to the extent that they have now influenced popular thinking on the topic, so that gay men and straight females are viewed as sharing common plights and interests (Rumens, 2008). Yet, thus far, marketing researchers have looked askance at the effect of friendships between gay male employees and heterosexual female customers in consumption settings, such as retail stores and boutiques. Indeed, with the exception of Peretz’s (1995) participant observation regarding how young and outwardly gay salesmen use their ambiguous gender to sell women’s clothing, in a Paris-based luxury boutique, any theoretical explorations regarding retail-based commercial friendships between gay salesmen and female customers are non-existent—until now. This research addresses this apparent chasm in the literature by putting forth an original framework that shows how the emotional closeness between gay salesmen and female customers, due to the absence of sexual interest and inter-female competition, results in an intense emotional closeness, that facilitates pleasurable retail transactions, customer satisfaction, loyalty, and positive word-of-mouth. In doing so, this work extends the commercial friendship paradigm by considering retail-based, commercial friendships between an under-researched marketplace dyad; gay men and straight females. It is worth noting here that some straight women may find the idea of commercial friendships with gay salesmen as undesirable, due to the very notion of having relationships with retail organizations or employees (Noble and Phillips, 2004), or a personal disdain for homosexuality.

Making the transition from pharmacy student to pharmacist: Australian interns' perceptions of professional identity formation

Objectives The experience of transitioning from university to practice influences professional identity formation. It is unclear how this transitioning experience influences pharmacy interns' professional identities. This study aims to examine pharmacy interns' perceptions of their transition from university to the workplace and the influence this had on their pharmacist identities. Methods A qualitative approach using in-depth interviews was adopted for this study. Fifteen interns (community and hospital) from one school of pharmacy in Australia were interviewed. Questions were asked about the nature of their current intern role, their university experiences, how they saw themselves as pharmacists and their perceptions of the transition to practice. Key findings The interns interviewed entered the workplace valuing patient-focused aspects of practice and contributing to patient care. The nature of work meant there were limited opportunities to enact these aspects of their professional identities. The interns were challenged by interactions with patients and doctors, and experienced difficulties reconciling this with their university-derived professional identities. Also, the interns lacked the confidence and strategies to overcome these challenges. Some were exploring alternative ways of being pharmacists. Conclusions This paper argues that graduates' experience of the transition to practice was challenging. This was due to nascent professional identities formed in university and a lack of workplace experiences enabling patient-centred practices. The interns' formation of professional identities was highly responsive to the context of work. To facilitate the development of Australian patient-centred pharmacy practice, supporting professional identity formation should be a focus within pharmacy education.

An international comparison of the continuing professional development process (CPD) in Australia, New Zealand and the United Kingdom

Background: The Pharmacy Board of Australia stipulated that for renewal of registration, pharmacists must have accrued a minimum of 20 CPD credits over the 2010-11 registration years (1). Mandatory CPD is not new in Pharmacy. The UK and New Zealand have both established systems of CPD in recent years. The purpose of this study is to investigate established CPD processes in the UK and New Zealand with the view to making recommendations for the implementation of the CPD process in Australia. Objectives: To compare the acquisition and guidance on documentation of CPD credit points in Australia, New Zealand and the United Kingdom. Methodology: A comparative online search of the websites of each of the registering authorities was undertaken. Any practice standards or guidelines which relate to registration or continuing professional development were analysed and compared. Results: In New Zealand the Pharmacy Council require Pharmacists to have a minimum of 12 outcome credits over a 3-year period for recertification (2, 3). The outcome credit related to each CPD action and is based on relevance to the pharmacist and their practice. It is graded between one, for CPD which has occasional relevance to practice and three which have considerable relevance to practice. There are examples of completed CPD recording sheets on their website (8). In the UK, The General Pharmaceutical Council require Pharmacists to make a minimum of nine CPD entries per year (4) and detailed guidance on how to record CPD activities is provided (5,7). The Pharmacy Board of Australia divides CPD activities into three groups (6). Of the 20 credits required annually only 10 can be gained from group one activities, which is information accessed without assessment. There is only brief guidance on the recording of CPD. Discussion: The GPhC in the UK provided the most comprehensive guidance on acquisition of CPD credit points and documentation (5,7) The Pharmacy Council of New Zealand made CPD points relevant to practice.(2,8) The Pharmacy Board of Australia provided limited information for pharmacists on CPD activities, which may impede pharmacist participation. Information may assist in increasing pharmacists’ engagement in CPD activities. In conclusion, there is variation between the three countries in the amount and type of information provided about CPD requirements.

Extending genetic linkage analysis to diffusion tensor images to map single gene effects on brain fiber architecture

We extended genetic linkage analysis - an analysis widely used in quantitative genetics - to 3D images to analyze single gene effects on brain fiber architecture. We collected 4 Tesla diffusion tensor images (DTI) and genotype data from 258 healthy adult twins and their non-twin siblings. After high-dimensional fluid registration, at each voxel we estimated the genetic linkage between the single nucleotide polymorphism (SNP), Val66Met (dbSNP number rs6265), of the BDNF gene (brain-derived neurotrophic factor) with fractional anisotropy (FA) derived from each subject's DTI scan, by fitting structural equation models (SEM) from quantitative genetics. We also examined how image filtering affects the effect sizes for genetic linkage by examining how the overall significance of voxelwise effects varied with respect to full width at half maximum (FWHM) of the Gaussian smoothing applied to the FA images. Raw FA maps with no smoothing yielded the greatest sensitivity to detect gene effects, when corrected for multiple comparisons using the false discovery rate (FDR) procedure. The BDNF polymorphism significantly contributed to the variation in FA in the posterior cingulate gyrus, where it accounted for around 90-95% of the total variance in FA. Our study generated the first maps to visualize the effect of the BDNF gene on brain fiber integrity, suggesting that common genetic variants may strongly determine white matter integrity.