From single crystal surfaces to single atoms : investigating active sites in electrocatalysis

Electrocatalytic processes will undoubtedly be at the heart of energising future transportation and technology with the added importance of being able to create the necessary fuels required to do so in an environmentally friendly and cost effective manner. For this to be successful two almost mutually exclusive surface properties need to be reconciled, namely producing highly active/reactive surface sites that exhibit long term stability. This article reviews the various approaches which have been undertaken to study the elusive nature of these active sites on metal surfaces which are considered as adatoms or clusters of adatoms with low coordination number. This includes the pioneering studies at extended well defined stepped single crystal surfaces using cyclic voltammetry up to the highly sophisticated in situ electrochemical imaging techniques used to study chemically synthesised nanomaterials. By combining the information attained from single crystal surfaces, individual nanoparticles of defined size and shape, density functional theory calculations and new concepts such as mesoporous multimetallic thin films and single atom electrocatalysts new insights into the design and fabrication of materials with highly active but stable active sites can be achieved. The area of electrocatalysis is therefore not only a fascinating and exciting field in terms of realistic technological and economical benefits but also from the fundamental understanding that can be acquired by studying such an array of interesting materials.

Affective events theory as a framework for understanding third-party consumer complaints

Poor complaint management may result in organizations losing customers and revenue. Consumers exhibit negative emotional responses when dissatisfied and this may lead to a complaint to a third-party organization. Since little information is available on the role of emotion in the consumer complaint process or how to manage complaints effectively, we offer an emotions perspective by applying Affective Events Theory (AET) to complaint behavior. This study presents the first application of AET in a consumption context and advances a theoretical framework supported by qualitative research for emotional responses to complaints. In contrast to commonly held views on gender and emotion, men as well as women use emotion-focused coping to complain.

Stability of corneal topography and wavefront aberrations in young Singaporeans

Purpose To investigate the differences between and variations across time in corneal topography and ocular wavefront aberrations in young Singaporean myopes and emmetropes. Methods We used a videokeratoscope and wavefront sensor to measure the ocular surface topography and wavefront aberrations of the total eye optics in the morning, mid-day and late afternoon on two separate days. Topography data were used to derive the corneal surface wavefront aberrations. Both the corneal and total wavefronts were analysed up to the 4th radial order of the Zernike polynomial expansion, and were centred on the entrance pupil (5 mm). The participants included 12 young progressing myopes, 13 young stable myopes and 15 young age-matched emmetropes. Results For all subjects considered together there were significant changes in some of the aberrations terms across the day, such as spherical aberration ( ) and vertical coma ( ) (repeated measures ANOVA, p<0.05). The magnitude of positive spherical aberration ( ) was significantly lower in the progressing myope group than that of the stable myopes (p=0.04) and emmetrope group (p=0.02). There were also significant interactions between refractive group and time of day for with/against-the-rule astigmatism ( ). Significantly lower 4th order RMS of ocular wavefront aberrations were found in the progressing myope group compared with the stable myopes and emmetropes (p<0.01). Conclusions These differences and variations in the corneal and total aberrations may have significance for our understanding of refractive error development and for clinical applications requiring accurate wavefront measurements.

The Deleuze Spray, New York 1977 : an Interview with Sanford Kwinter, Professor of Architectural Theory and Criticism at the Harvard Graduate School of Design, on the Architectural Reception of Gilles Deleuze in America

So what do you want to know? I was in Paris between ‘75 and ‘78. But about half way through, Sylvère published the Anti-Oedipus issue of Semiotext(e) and, actually, that was for me one of the deciding events that made me decide to come to the United States, to come study at Columbia University. There appeared to be this little group working at Columbia working around these issues. In 1970, in Paris even, Deleuze was a cult – there was an incredibly small number of people following Deleuze... A transcript of my Interview with Kwinter about the Architectural Reception of Deleuze in America, which took place at Jerry’s,' Soho, New York, 15 January 2003. The transcript appeared as an Appendix at the back of my Masters Thesis undertaken at Yale School of Architecture, printed May 2003.

Recasting the theory of mosquito-borne pathogen transmission dynamics and control

Mosquito-borne diseases pose some of the greatest challenges in public health, especially in tropical and sub-tropical regions of theworld. Efforts to control these diseases have been underpinned by a theoretical framework developed for malaria by Ross and Macdonald, including models, metrics for measuring transmission, and theory of control that identifies key vulnerabilities in the transmission cycle. That framework, especially Macdonald’s formula for R0 and its entomological derivative, vectorial capacity, are nowused to study dynamics and design interventions for many mosquito-borne diseases. A systematic review of 388 models published between 1970 and 2010 found that the vast majority adopted the Ross–Macdonald assumption of homogeneous transmission in a well-mixed population. Studies comparing models and data question these assumptions and point to the capacity to model heterogeneous, focal transmission as the most important but relatively unexplored component in current theory. Fine-scale heterogeneity causes transmission dynamics to be nonlinear, and poses problems for modeling, epidemiology and measurement. Novel mathematical approaches show how heterogeneity arises from the biology and the landscape on which the processes of mosquito biting and pathogen transmission unfold. Emerging theory focuses attention on the ecological and social context formosquito blood feeding, themovement of both hosts and mosquitoes, and the relevant spatial scales for measuring transmission and for modeling dynamics and control.

The changing motivations of students’ use of lecture podcasts across a semester: An extended theory of planned behaviour approach

We extended the previous work of Moss, O’Connor and White, to include a measure of group norms within the theory of planned behaviour (TPB), to examine the influences on students’ decisions to use lecture podcasts as part of their learning. Participants (N = 90) completed the extended TPB predictors before semester began (Time 1) and mid-semester (Time 2) and reported on their podcast use at mid-semester (Time 2) and end of semester (Time 3). We found that attitudes and perceived social pressures were important in informing intentions at both time points. At Time 1, perceptions of control over performing the behaviour and, at Time 2, perceptions of whether podcast use was normative among fellow students (group norms) also predicted intended podcast use. Intentions to use podcasting predicted self-reported use at both Time 2 and Time 3. These results provide important applied information for educators to encourage student use of novel on-line educational tools.

Study protocol : a randomised controlled trial of a theory-based online intervention to improve sun safety among Australian adults

Background The effects of exposure to ultraviolet radiation are a significant concern in Australia which has one of the highest incidences of skin cancer in the world. Despite most skin cancers being preventable by encouraging consistent adoption of sun-protective behaviours, incidence rates are not decreasing. There is a dearth of research examining the factors involved in engaging in sun-protective behaviours. Further, online multi-behavioural theory-based interventions have yet to be explored fully as a medium for improving sun-protective behaviour in adults. This paper presents the study protocol of a randomised controlled trial of an online intervention based on the Theory of Planned Behaviour (TPB) that aims to improve sun safety among Australian adults. Methods/Design Approximately 420 adults aged 18 and over and predominantly from Queensland, Australia, will be recruited and randomised to the intervention (n = 200), information only (n = 200) or the control group (n = 20). The intervention focuses on encouraging supportive attitudes and beliefs toward sun-protective behaviour, fostering perceptions of normative support for sun protection, and increasing perceptions of control/self-efficacy over sun protection. The intervention will be delivered online over a single session. Data will be collected immediately prior to the intervention (Time 1), immediately following the intervention (Time 1b), and one week (Time 2) and one month (Time 3) post-intervention. Primary outcomes are intentions to sun protect and sun-protective behaviour. Secondary outcomes are the participants’ attitudes toward sun protection, perceptions of normative support for sun protection (i.e. subjective norms, group norms, personal norms and image norms) and perceptions of control/self-efficacy toward sun protection. Discussion The study will contribute to an understanding of the effectiveness of a TPB-based online intervention to improve Australian adults’ sun-protective behaviour. Trials registry Australian and New Zealand Trials Registry number ACTRN12613000470796

Investigation of the effects of various types of wind turbine generators on power-system stability

It has become more and more demanding to investigate the impacts of wind farms on power system operation as ever-increasing penetration levels of wind power have the potential to bring about a series of dynamic stability problems for power systems. This paper undertakes such an investigation through investigating the small signal and transient stabilities of power systems that are separately integrated with three types of wind turbine generators (WTGs), namely the squirrel cage induction generator (SCIG), the doubly fed induction generator (DFIG), and the permanent magnet generator (PMG). To examine the effects of these WTGs on a power system with regard to its stability under different operating conditions, a selected synchronous generator (SG) of the well-known Western Electricity Coordinating Council (WECC three-unit nine-bus system and an eight-unit 24-bus system is replaced in turn by each type of WTG with the same capacity. The performances of the power system in response to the disturbances are then systematically compared. Specifically, the following comparisons are undertaken: (1) performances of the power system before and after the integration of the WTGs; and (2) performances of the power system and the associated consequences when the SCIG, DFIG, or PMG are separately connected to the system. These stability case studies utilize both eigenvalue analysis and dynamic time-domain simulation methods.

Wide area controls for transient and dynamic stability enhancement

This paper presents a study done into the effectiveness of using local acceleration measurements vs. remote angle measurements in providing stabilising control via SVCs following large disturbances. The system studied was an analogue of the Queensland-New South Wales Interconnection (QNI) and involved the control of an existing Static Var Compensators (SVC) at Sydney West. This study is placed in the context of wide area controls for large systems using aggregated models for groups of machines.

Switching radical stability by pH-induced orbital conversion

In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

Desorption electrospray ionisation mass spectrometry of stabilised polyesters reveals activation of hindered amine light stabilisers

The use of hindered amine light stabilizers (HALS) to retard thermo- and photo-degradation of polymers has become increasingly common. Proposed mechanisms of polymer stabilisation involve significant changes to the HALS chemical structure; however, reports of the characterisation of these modified chemical species are limited. To better understand the fate of HALS and determine their in situ modifications, desorption electrospray ionisation mass spectrometry (DESI-MS) was employed to characterise ten commercially available HALS present in polyester-based coil coatings. TINUVIN® 770, 292, 144, 123, 152, and NOR371; HOSTAVIN® 3052, 3055, 3050, and 3058 were separately formulated with a pigmented, thermosetting polyester resin, cured on metal at 262 C and analysed directly by DESI-MS. High-level ab initio molecular orbital theory calculations were also undertaken to aid the mechanistic interpretation of the results. For HALS containing N-substituted piperidines (i.e., N-CH3, N-C(O)CH3, and N-OR) a secondary piperidine (N-H) analogue was detected in all cases. The formation of these intermediates can be explained either through hydrogen abstraction based mechanisms or direct N-OR homolysis with the former dominant under normal service temperatures (ca. 25-80 C), and the latter potentially becoming competitive under the high temperatures associated with curing (ca. 230-260 C). © 2013 Elsevier Ltd. All rights reserved.

The implementation of a guideline of care for patients with a Sengstaken-Blakemore tube in situ in a general intensive care unit using transitional change theory

The use of the Sengstaken–Blakemore tube as a life-saving treatment for bleeding oesophageal varices is slowly becoming the least preferred method possibly due to the potential complications associated with its placement. Nursing practice pertaining to the care of this patient group appears ad hoc and reliant on local knowledge and experience as opposed to recognised evidence of best practice. Therefore, this paper focuses on the application of Lewin's transitional change theory used to introduce a change in nursing practice with the application of a guideline to enhance the care of patients with a Sengstaken–Blakemore tube in situ within a general intensive care unit. This method identified some of the complexities surrounding the change process including the driving and restraining forces that must be harnessed and minimised in order for the adoption of change to be successful.

Cartographic Strategies of Postmodernity : the Figure of the Map in Contemporary Theory and Fiction

The last fifty years have witnessed the growing pervasiveness of the figure of the map in critical, theoretical, and fictional discourse. References to mapping and cartography are endemic in poststructuralist theory, and, similarly, geographically and culturally diverse authors of twentieth-century fiction seem fixated upon mapping. While the map metaphor has been employed for centuries to highlight issues of textual representation and epistemology, the map metaphor itself has undergone a transformation in the postmodern era. This metamorphosis draws together poststructuralist conceptualizations of epistemology, textuality, cartography, and metaphor, and signals a shift away from modernist preoccupations with temporality and objectivity to a postmodern pragmatics of spatiality and subjectivity. Cartographic Strategies of Postmodernity charts this metamorphosis of cartographic metaphor, and argues that the ongoing reworking of the map metaphor renders it a formative and performative metaphor of postmodernity.