The effect of mechanochemical activation upon the intercalation of a high-defect kaolinite with formamide

The effect of mechanochemical activation upon the intercalation of formamide into a high-defect kaolinite has been studied using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. X-ray diffraction shows that the intensity of the d(001) spacing decreases with grinding time and that the intercalated high-defect kaolinite expands to 10.2 A. The intensity of the peak of the expanded phase of the formamide-intercalated kaolinite decreases with grinding time. Thermal analysis reveals that the evolution temperature of the adsorbed formamide and loss of the inserting molecule increases with increased grinding time. The temperature of the dehydroxylation of the formamide-intercalated high-defect kaolinite decreases from 495 to 470oC with mechanochemical activation. Changes in the surface structure of the mechanochemically activated formamide-intercalated high-defect kaolinite were followed by DRIFT spectroscopy. Fundamentally the intensity of the high-defect kaolinite hydroxyl stretching bands decreases exponentially with grinding time and simultaneously the intensity of the bands attributed to the OH stretching vibrations of water increased. It is proposed that the mechanochemical activation of the high-defect kaolinite caused the conversion of the hydroxyls to water which coordinates the kaolinite surface. Significant changes in the infrared bands assigned to the hydroxyl deformation and amide stretching and bending modes were observed. The intensity decrease of these bands was exponentially related to the grinding time. The position of the amide C&unknown;O vibrational mode was found to be sensitive to grinding time. The effect of mechanochemical activation of the high-defect kaolinite reduces the capacity of the kaolinite to be intercalated with formamide.

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.

Multi-victim sexual assault : a case study in rural Australia

Objective: There is a paucity of information regarding cases of multi-victim sexual assault of children. The reported incidence suggests that these cases are rare. The aim of this paper is to provide practitioners with information about effective intervention strategies arising out of the direct experience of managing a case of multi-victim sexual assault in an Australian rural community. --------- Method: A descriptive, case-report methodology summarizing the investigation and intervention in a case of multi-victim sexual assault is reported. A community based intervention arising out of the disclosures of 21 male children is described. The intervention occurred at an individual, group, and community level using a coordinated multi-disciplinary team and natural helping networks. ---------- Results: The coordination of police and welfare services increased the communication flow to victims, their families, and the community. The case also demonstrated the utility in regularly briefing political and bureaucratic authorities as well as local officials about emergent issues. Coordinating political and bureaucratic responses was essential in obtaining ongoing support and sufficient researching to enable the effective delivery of services. ---------- Conclusions: Interventions were focused at an individual, group, and community level using a coordinated multi-disciplinary team and natural helping networks. This provided a choice of services which were sensitive to the case setting. Recommendations are offered for practitioners who are confronted with similar events. While this paper describes an approach for intervening in a case of multi-victim sexual assault, further empirical research is needed to enable service deliverers to efficaciously target interventions which offer choice to victims and their families.

Cyberbullying : the new face of workplace bullying?

While the subject of cyberbullying of children and adolescents has begun to be addressed, there has been less attention or research on cyberbullying in the workplace. Whilst male-dominated workplaces such as manufacturing settings have been found to have an increased risk of workplace bullying, the prevalence of cyberbullying in this sector is not known. This exploratory study investigated the prevalence and methods of face-to-face bullying and cyberbullying of males at work. One hundred and three surveys (a modified version of the NAQ-R1), were returned from randomly selected members of the Australian Manufacturing Worker’s Union (AMWU). The results showed that 34% of the respondents were bullied face-to-face, and 10.7% were cyberbullied. All victims of cyberbullying also experienced face-to-face bullying. The implications for organisations of their “duty of care” in regards to this new form of bullying are indicated.

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.