Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Quantification of motor vehicle emission factors from on road measurements

Assessment and prediction of the impact of vehicular traffic emissions on air quality and exposure levels requires knowledge of vehicle emission factors. The aim of this study was quantification of emission factors from an on road, over twelve months measurement program conducted at two sites in Brisbane: 1) freeway type (free flowing traffic at about 100 km/h, fleet dominated by small passenger cars - Tora St); and 2) urban busy road with stop/start traffic mode, fleet comprising a significant fraction of heavy duty vehicles - Ipswich Rd. A physical model linking concentrations measured at the road for specific meteorological conditions with motor vehicle emission factors was applied for data analyses. The focus of the study was on submicrometer particles; however the measurements also included supermicrometer particles, PM2.5, carbon monoxide, sulfur dioxide, oxides of nitrogen. The results of the study are summarised in this paper. In particular, the emission factors for submicrometer particles were 6.08 x 1013 and 5.15 x 1013 particles per vehicle-1 km-1 for Tora St and Ipswich Rd respectively and for supermicrometer particles for Tora St, 1.48 x 109 particles per vehicle-1 km-1. Emission factors of diesel vehicles at both sites were about an order of magnitude higher than emissions from gasoline powered vehicles. For submicrometer particles and gasoline vehicles the emission factors were 6.08 x 1013 and 4.34 x 1013 particles per vehicle-1 km-1 for Tora St and Ipswich Rd, respectively, and for diesel vehicles were 5.35 x 1014 and 2.03 x 1014 particles per vehicle-1 km-1 for Tora St and Ipswich Rd, respectively. For supermicrometer particles at Tora St the emission factors were 2.59 x 109 and 1.53 x 1012 particles per vehicle-1 km-1, for gasoline and diesel vehicles, respectively.

The STRATIFY tool and clinical judgment were poor predictors of falling in an acute hospital setting

Objective: To compare the effectiveness of the STRATIFY falls tool with nurses’ clinical judgments in predicting patient falls. Study Design and Setting: A prospective cohort study was conducted among the inpatients of an acute tertiary hospital. Participants were patients over 65 years of age admitted to any hospital unit. Sensitivity, specificity, and positive predictive value (PPV) and negative predictive values (NPV) of the instrument and nurses’ clinical judgments in predicting falls were calculated. Results: Seven hundred and eighty-eight patients were screened and followed up during the study period. The fall prevalence was 9.2%. Of the 335 patients classified as being ‘‘at risk’’ for falling using the STRATIFY tool, 59 (17.6%) did sustain a fall (sensitivity50.82, specificity50.61, PPV50.18, NPV50.97). Nurses judged that 501 patients were at risk of falling and, of these, 60 (12.0%) fell (sensitivity50.84, specificity50.38, PPV50.12, NPV50.96). The STRATIFY tool correctly identified significantly more patients as either fallers or nonfallers than the nurses (P50.027). Conclusion: Considering the poor specificity and high rates of false-positive results for both the STRATIFY tool and nurses’ clinical judgments, we conclude that neither of these approaches are useful for screening of falls in acute hospital settings.

On medium specificity and discipline crossovers in modern art : An interview with Jacques Ranciére on Medium-Specificity and Discipline Crossovers in Modern Art

Jacques Ranciere's work on aesthetics has received a great deal of attention recently. Given his work has enormous range – taking in art and literature, political theory, historiography, pedagogy and worker's history – Andrew McNamara and Toni Ross (UNSW) seek to explore his wider project in this interview, while showing how it leads to his alternative insights into aesthetics. Rancière sets aside the core suppositions linking the medium to aesthetic judgment, which has informed many definitions of modernism. Rancière is emphatic in freeing aesthetic judgment from issues of medium-specificity. He argues that the idea of autonomy associated with medium-specificity – or 'truth to the medium' – was 'a very late one' in modernism, and that post-medium trends were already evident in early modernism. While not stressing a simple continuity between early modernism and contemporary art, Ranciere nonetheless emphasizes the ethical and political ramifications of maintaining an a-disciplinary stance.

Semi-active control for structural vibration based on predictive algorithm [Chinese title = 基于预测算法的结构振动半主动控制]

Based on Newmark-β method, a structural vibration response is predicted. Through finding the appropriate control force parameters within certain ranges to optimize the objective function, the predictive control of the structural vibration is achieved. At the same time, the numerical simulation analysis of a two-storey frame structure with magneto-rheological (MR) dampers under earthquake records is carried out, and the parameter influence on structural vibration reduction is discussed. The results demonstrate that the semi-active control based on Newmark-β predictive algorithm is better than the classical control strategy based on full-state feedback control and has remarkable advantages of structural vibration reduction and control robustness.

Learning, language and leadership : conduits to dynamic public service networks

Networks are having a profound impact on the way society is organised at the local, national and international level. Networks are not ‘business as usual’. The defining feature of networks and a key indicator for their success is the strength and quality of the interactions between members. This relational power of networks provides the mechanism to bring together previously dispersed and even competitive entities into a collective venture. Such an operating context demands the ability to work in a more horizontal, relational manner. In addition a social infrastructure must be formed that will support and encourage efforts to become more collaborative. This paper seeks to understand how network members come to know about working in networks, how they work on their relationships and create new meanings about the nature of their linked work. In doing so, it proposes that learning, language and leadership, herein defined as the ‘3Ls’ represent critical mediating aspects for networks.

The role of sensation seeking and need for cognition on web-site evaluations : a resource-matching perspective

The Internet theoretically enables marketers to personalize a Website to an individual consumer. This article examines optimal Website design from the perspective of personality trait theory and resource-matching theory. The influence of two traits relevant to Internet Web-site processing—sensation seeking and need for cognition— were studied in the context of resource matching and different levels of Web-site complexity. Data were collected at two points of time: personality-trait data and a laboratory experiment using constructed Web sites. Results reveal that (a) subjects prefer Web sites of a medium level of complexity, rather than high or low complexity; (b)high sensation seekers prefer complex visual designs, and low sensation seekers simple visual designs, both in Web sites of medium complexity; and (c) high need-for-cognition subjects evaluated Web sites with high verbal and low visual complexity more favourably.

Characterising anomalous events using change point correlation on unsolicited network traffic

Monitoring unused or dark IP addresses offers opportunities to extract useful information about both on-going and new attack patterns. In recent years, different techniques have been used to analyze such traffic including sequential analysis where a change in traffic behavior, for example change in mean, is used as an indication of malicious activity. Change points themselves say little about detected change; further data processing is necessary for the extraction of useful information and to identify the exact cause of the detected change which is limited due to the size and nature of observed traffic. In this paper, we address the problem of analyzing a large volume of such traffic by correlating change points identified in different traffic parameters. The significance of the proposed technique is two-fold. Firstly, automatic extraction of information related to change points by correlating change points detected across multiple traffic parameters. Secondly, validation of the detected change point by the simultaneous presence of another change point in a different parameter. Using a real network trace collected from unused IP addresses, we demonstrate that the proposed technique enables us to not only validate the change point but also extract useful information about the causes of change points.

Increasing the Information available to Coroners : the effect on autopsy decision making

This paper details research completed in 2007 which investigated autopsy decision making in a death investigation. The data was gathered during the first year of operation of a new Coroners Act in Queensland, Australia, which changed the process of death investigation in three ways which are important to this paper. First, it required a greater amount of information to be gathered at the scene by police, and this included a thorough investigation of the circumstances of the death, including statements from witnesses, friends and family, as well as evidence gathering at the scene. Second, it required Coroners, for the first time, to determine the level of invasiveness of the autopsy required to complete the death investigation. Third, it enabled the communication of a genuine family concern, to be communicated to the Coroner. The outcome of such information was threefold. First, a greater amount of information offered to the Coroner led to a decrease in the number of full internal autopsies ordered, but an increase in the number of partial internal autopsies ordered. Second, this shift in autopsy decision making by Coroners saw certain factors given greater importance than others in decisions to order full internal or external only autopsies. Third, a raised family concern had a significant impact on autopsy decision making and tended to decrease the invasiveness of the autopsy ordered by Coroners.

Simultaneous kinetic-spectrophotometric determination of maltol and ethyl maltol in food samples by using chemometrics

A fast and accurate procedure has been researched and developed for the simultaneous determination of maltol and ethyl maltol, based on their reaction with iron(III) in the presence of o-phenanthroline in sulfuric acid medium. This reaction was the basis for an indirect kinetic spectrophotometric method, which followed the development of the pink ferroin product (λmax = 524 nm). The kinetic data were collected in the 370–900 nm range over 0–30 s. The optimized method indicates that individual analytes followed Beer’s law in the concentration range of 4.0–76.0 mg L−1 for both maltol and ethyl maltol. The LOD values of 1.6 mg L−1 for maltol and 1.4 mg L−1 for ethyl maltol agree well with those obtained by the alternative high performance liquid chromatography with ultraviolet detection (HPLC-UV). Three chemometrics methods, principal component regression (PCR), partial least squares (PLS) and principal component analysis–radial basis function–artificial neural networks (PC–RBF–ANN), were used to resolve the measured data with small kinetic differences between the two analytes as reflected by the development of the pink ferroin product. All three performed satisfactorily in the case of the synthetic verification samples, and in their application for the prediction of the analytes in several food products. The figures of merit for the analytes based on the multivariate models agreed well with those from the alternative HPLC-UV method involving the same samples.

A 5 year review of information requests to QISU

The Queensland Injury Surveillance Unit (QISU) has been collecting and analysing injury data in Queensland since 1988. QISU data is collected from participating emergency departments (EDs) in urban, rural and remote areas of Queensland. Using this data, QISU produces several injury bulletins per year on selected topics, providing a picture of Queensland injury, and setting this in the context of relevant local, national and international research and policy. These bulletins are used by numerous government and non-government groups to inform injury prevention and practice throughout the state. QISU bulletins are also used by local and state media to inform the general public of injury risk and prevention strategies. In addition to producing the bulletins, QISU regularly responds to requests for information from a variety of sources. These requests often require additional analysis of QISU data to tailor the response to the needs of the end user. This edition of the bulletin reviews 5 years of information requests to QISU.