Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Educational markets in space : gamekeeping professionals across Australian communities

This paper argues that the logic of neoliberal choice policy is typically blind to considerations of space and place, but inevitably impacts on rural and remote locations in the way that middle class professionals view the opportunities available in their local educational markets. The paper considers the value of middle class professionals’ educational capitals in regional communities and their problematic distribution, given that class fraction’s particular investment in choice strategies to ensure their children’s future. It then profiles the educational market in six communities along a transect between a major regional centre and a remote ‘outback’ town, using publicly available data from the Australian government’s ‘My School’ website. Comparison of the local markets shows how educational outcomes are distributed across the local markets and how dimensions of ‘choice’ thin out over the transect. Interview data offers insights into how professional families in these localities engage selectively with these local educational markets, or plan to transcend them. The discussion reflects on the growing importance of educational choices as a marker of place in the competition between localities to attract and retain professionals to staff vital human services in their communities.

Efficient safety information retrieval on construction sites: a preliminary methodology

IT-supported field data management benefits on-site construction management by improving accessibility to the information and promoting efficient communication between project team members. However, most of on-site safety inspections still heavily rely on subjective judgment and manual reporting processes and thus observers’ experiences often determine the quality of risk identification and control. This study aims to develop a methodology to efficiently retrieve safety-related information so that the safety inspectors can easily access to the relevant site safety information for safer decision making. The proposed methodology consists of three stages: (1) development of a comprehensive safety database which contains information of risk factors, accident types, impact of accidents and safety regulations; (2) identification of relationships among different risk factors based on statistical analysis methods; and (3) user-specified information retrieval using data mining techniques for safety management. This paper presents an overall methodology and preliminary results of the first stage research conducted with 101 accident investigation reports.

The Moral Economy of Everyday Crime: Markets, Consumers and Citizens

Between the crimes in the suites and the crimes in the streets lies the mostly unexplored terrain within which we find crimes of ‘everyday life’. Not all of these are formally illegal, but all are generally seen as morally dubious. Most of the crimes of everyday life are committed in the contemporary marketplace, and by those who think of themselves (and are mostly considered by others) as respectable citizens. We contextualize normative orientations that are conducive to such types of behaviour using a framework that links E. P. Thompson’s (1963) concept of the ‘moral economy’ with Institutional Anomie Theory (Messner and Rosenfeld 1994, 2007). Findings from a comparative survey study in three economic change regions (England and Wales, Western and Eastern Germany) show that a syndrome of market anomie comprising distrust, fear and cynical attitudes toward law increases the willingness of respectable citizens to engage in illegal and unfair practices in the marketplace.

Managing Work, Hedonism and 'the Borderline' Between the Legal and Illegal Markets: Two Case Studies of Recreational Heavy Drug Users

In the context of cultural and/or differential ‘normalisation’ of certain forms of drug use, this article describes two case-studies of heavy recreational drug users. The daily lives of these users blur the line between the legal and the illegal; their drug trading is generally as a consumer and ‘friend of a friend’ small dealer in the low-level market. In the first case, problems with management of employment, time and financial budgeting are described; in the second case, such management is accomplished. Discussion refers to: differences between the two in relation to resources and vulnerability to risks, and to leisure/pleasure cultures of hedonism. The research agenda should pay more attention to users who seek to maintain a legitimate lifestyle but who develop problems managing work and their drug-related leisure. Understanding the consumer demand and dealing activity of such users is important in trying to develop a fuller understanding of drug markets.

Mixed-dimensional consistent coupling by multi-point constraint equations for efficient multi-scale modeling

Finding an appropriate linking method to connect different dimensional element types in a single finite element model is a key issue in the multi-scale modeling. This paper presents a mixed dimensional coupling method using multi-point constraint equations derived by equating the work done on either side of interface connecting beam elements and shell elements for constructing a finite element multiscale model. A typical steel truss frame structure is selected as case example and the reduced scale specimen of this truss section is then studied in the laboratory to measure its dynamic and static behavior in global truss and local welded details while the different analytical models are developed for numerical simulation. Comparison of dynamic and static response of the calculated results among different numerical models as well as the good agreement with those from experimental results indicates that the proposed multi-scale model is efficient and accurate.

Developing an efficient and reliable dry powder inhaler for pulmonary drug delivery : a review for multidisciplinary researchers

Pulmonary drug delivery is the focus of much research and development because of its great potential to produce maximum therapeutic benefit. Among the available options the dry powder inhaler (DPI) is the preferred device for the treatment of an increasingly diverse number of diseases. However, as drug delivery from a DPI involves a complicated set of physical processes and the integration of drug formulations, device design and patient usage, the engineering development of this medical technology is proving to be a great challenge. Currently there is large range of devices that are either available on the market or under development, however, none exhibit superior clinical efficacy. A major concern is the inter- and intra-patient variability of the drug dosage delivered to the deep lungs. The extent of variability depends on the drug formulation, the device design and the patient’s inhalation profile. This article reviews recent advances in DPI technology and presents the key factors which motivate and constrain the successful engineering of a universal, patient-independent DPI that is capable of efficient, reliable and repeatable drug delivery. A strong emphasis is placed on the physical processes of drug powder aerosolisation, deagglomeration, and dispersion and on the engineering of formulations and inhalers that can optimise these processes.