Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

Four cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.

Experimental and theoretical investigation of compression of a cylinder using a rotating platen

A rig was constructed to carry out compression of an aluminum cylinder with a monotonically rotating platen. The tests carried out showed that the compression load decreased and the side wall bulge severity reduced when the die was rotated. Not all the work supplied by the rotating dies was transferred to the work-piece; circumferential slippage was frequently observed at the die/material interface. This slippage was quantified by comparing measurements made during interrupted testing with the angular velocity of the die. A compound velocity field based on an exponential cusp description of the barreling was employed in an upper bound analysis. An approximate analytical solution was obtained for the degree of barreling and the compression pressure. The model is able to reproduce the decrease in barreling and compression loads with increasing die rotation.

The role and theoretical evolution of knowledge translation and exchange in public health

Background There is an increased emphasis in public health research on effective models and strategies to support knowledge translation (KT), the exchange, synthesis and ethically sound application of research findings within a complex set of interactions among researchers and knowledge users. In other words, KT can be seen as an acceleration of the knowledge cycle—an acceleration of the natural transformation of knowledge into use (Canadian Institutes of Health Services Research. Knowledge Translation Strategy, 2004). The most recent conceptualizations consider the complexities of public health decision-making. The role of practitioners and communities is increasingly considered.

Methods We identify, describe and discuss the theoretical underpinnings of KT and recommend a way forward to build the evidence for more effective practice.

Results Theoretical perspectives increasingly influence research on KT in public health. A range of innovative work is being conducted to explore methods for KT using practical tools, often with the support of government.

Conclusions KT describes a crucial and to date under-developed element of the research process. There is an important gap in theoretically informed empirical studies of effectiveness of proposed approaches in public health, health promotion and preventive medicine, and thus much of the debate remains abstract. There is clearly an urgent policy need to establish the effectiveness of KT models in a range of contexts. This must include both the consideration of development and the utilization of knowledge.

Pursuit of the muscular ideal: Physical and psychological consequences and putative risk factors

Developing a lean muscular figure for the purposes of sports and/or appearance has become a central issue for males. Concern has been raised because the desire to develop such a body build may lead to the adoption of numerous health-threatening behaviors. Consequently, this review presents a comprehensive analysis of the physical and psychological consequences that result from the use of steroids (legal and illegal), ephedrine, and deleterious dieting strategies specific to males. Putative risk factors for these behaviors will be identified, and the clinical disorder associated with the extreme abuse of these behaviors, muscle dysmorphia, will be examined.

Associations of neighbourhood greenness with physical and mental health : do walking, social coherence and local social interaction explain the relationships?

Background: Studies have shown associations between health indices and access to “green” environments but the underlying mechanisms of this association are not clear.

Objectives: To examine associations of perceived neighbourhood “greenness” with perceived physical and mental health and to investigate whether walking and social factors account for the relationships.

Methods: A mailed survey collected the following data from adults (n  =  1895) in Adelaide, Australia: physical and mental health scores (12-item short-form health survey); perceived neighbourhood greenness; walking for recreation and for transport; social coherence; local social interaction and sociodemographic variables.

Results: After adjusting for sociodemographic variables, those who perceived their neighbourhood as highly green had 1.37 and 1.60 times higher odds of better physical and mental health, respectively, compared with those who perceived the lowest greenness. Perceived greenness was also correlated with recreational walking and social factors. When walking for recreation and social factors were added to the regression models, recreational walking was a significant predictor of physical health; however, the association between greenness and physical health became non-significant. Recreational walking and social coherence were associated with mental health and the relationship between greenness and mental health remained significant.

Conclusions: Perceived neighbourhood greenness was more strongly associated with mental health than it was with physical health. Recreational walking seemed to explain the link between greenness and physical health, whereas the relationship between greenness and mental health was only partly accounted for by recreational walking and social coherence. The restorative effects of natural environments may be involved in the residual association of this latter relationship.

Are perceptions of the physical and social environment associated with mothers' walking for leisure and for transport? A longitudinal study

Objective
The role local neighbourhood environments play in influencing purpose-specific walking behaviors has not been well-explored in prospective studies. This study aimed to cross-sectionally and prospectively examine whether local physical and social environments were associated with mothers' walking for leisure and for transport.

Methods
In 2004, 357 mothers from Melbourne, Australia, provided information on their local physical and social neighbourhood environments, and in 2004 and 2006 reported weekly time spent walking for leisure and for transport. Environmental predictors of high levels of walking and increases in walking were examined using log binomial regression.

Results
Public transport accessibility and trusting many people in the neighbourhood were predictive of increases in walking for leisure, while connectivity, pedestrian crossings, a local traffic speed were predictive of increases in transport-related walking. Satisfaction with local facilities was associated with increasing both types of walking, and the social environment was important for maintaining high levels of both leisure- and transport-related walking.

Conclusion
The findings provide evidence of a longitudinal relationship between physical and social environments and walking behaviors amongst mothers. Enhancing satisfaction with local facilities and giving consideration to ‘walkability’, safety and public transport accessibility during environment planning processes may help mothers to increase walking.

Longitudinal examination of physical and relational aggression as precursors to later problem behaviors in adolescents

Research has addressed the consequences of being a victim of physical and relational aggression but less so the consequences of being an aggressor during adolescence. Consequently, relatively little is known about the extent to which aggression in early adolescence increases the risk of later aggression and other psychosocial problems. This study involves a representative sample of seventh- and ninth-grade students from Washington State ( N = 1,942). Students were surveyed on recruitment and then again 1 and 2 years later to learn about ongoing behavior problems, substance use, depression, and self-harm behaviors. Surveys also included measures of several hypothesized promotive factors: attachment to family, school commitment, and academic achievement. Findings suggest that being physically and/or relationally aggressive in grades 7 to 9 increases the risk of aggression and possibly other problem behaviors after accounting for age, gender, race, and a prior measure of each outcome. Independent promotive effects were observed in most analyses, although family attachment appeared a less robust predictor overall. Implications for prevention include acting on the behavior itself and enhancing promotive influences to lessen the risk of agression and other related problems.

Associations between the physical and social environment and depressive symptomology among Australian adolescents

Depression is a significant public health issue among Australian adolescents. A number of family, school and community level factors have been identified as important determinants of adolescent's health and well-being, including depression. This study examines associations between measures of the social and physical environment and adolescent mental health, specifically depressive symptomotology using data from the Healthy Neighbourhoods study, a large observational study carried out in 231 Australian schools stratified by socioeconomic quartiles and urban/non-urban geography, which focuses on adolescent health and well-being. Participants were 8256 year 6 and 8
students (48% male), aged 11-16 years (M = 11.6, SD = 0.8 years) from schools across Victoria,Queensland and Western Australia who completed a comprehensive on-line survey. Data collected included the Short Mood and Feeling Questionnaire (SMFQL a tool for assessing depressive symptomotology in adolescents. Results showed that the mean total depression score (possible range 0-26 with total scores;:: 8 used as the cutoff for depression symptomotology) was 6.4 (SD = 5.9), with scores for females (M = 6.8, SD = 6.3) higher than those for males (M = 5.9, SD = 5.5), and scores for year 8 students (M = 6.7,SD = 6.1) higher than those for year 6 students (M = 6.2, SD = 5.8) (p < .001). Greater access to sporting and play equipment, local parks, and more functional neighbourhoods for walking and jogging reduced the odds for depressive symptomotology (p < .05L while increased levels of abandoned homes, and higher levels of fighting within the neighbourhood, and fewer scout/guide clubs, local teams to play sport, and adults in the neighbourhood to talk with, as well as reduced neighbourhood safety increased the odds for depressive symptomotology (p < .05). These findings support the important role of physical and social environments in influencing adolescent health and well-being. Modifications to particular aspects of these environments at the community level may assist in providing adolescents some protection from depression.

Readiness for anger management : clinical and theoretical issues

Anger management methods are a common and successful feature of contemporary cognitive behavioral therapy. Meta-analyses and narrative reviews of the outcome of anger management have been broadly supportive of the view that it is an effective approach. We argue in this paper that an important impediment to the future success of anger management is the failure to fully address the issue of treatment readiness. We discuss distinctive features of anger that make readiness a more important issue than it is for other problem emotions and affects. Relevant theoretical models of readiness are discussed and we review the components of a lack of readiness, including difficulties in establishing a therapeutic alliance. Progress in this area requires greater attention to the measurement and analysis of readiness, to its inclusion as an independent variable in outcome studies and to its clinical modification when readiness is low.

Investigations into the analytical applications and fundamental chemistry of the chemiluminescent reactions of Tris(2,2'-bipyridyl)ruthenium(III) with certain Papaver Somniferum alkaloids and other related compounds

The reaction of tris(2,2’-bipyridyl)ruthenium(III) (Ru(bipy) ₃³⁺) with various analytes to generate chemiluminescence has been well documented. This investigation sought to undertake a chemiluminometic study of the reactions of Ru(bipy) ₃³⁺ with selected Papaver Somniferum alkaloids and specifically synthesised phenethylamines. The investigation, based on a kinetic study, primarily addressed the effect of varying reaction conditions (pH) on Ru(bipy) ₃³⁺ chemiluminescence production. To monitor these reactions, a batch chemiluminometer was specifically designed, fabricated and automated to conduct an extensive study on the selected compounds of interest. The instrumentation incorporated a custom built reaction cell and comprised an ‘on-line’ sample preparation system with which calibration standards could be automatically prepared. The instrumentation provided both time-independent (peak area) and time-dependent (kinetic profile) information. A novel approach to the stabilisation of Ru(bipy) ₃³⁺ as a chemiluminescencent reagent was also investigated and a recirculating system was employed with the batch chemiluminometer to provide a stable supply of Ru(bipy) ₃³⁺. Codeine, thebaine and 6-methoxy-codeine were the Papaver Somniferum alkaloids selected for this study and several N-methylated and N,N-dimethylated phenethylamines and methoxy-substituted phenetheylamines were also synthesised to investigate the affect of pH on the chemiluminescence emission efficiency. The versatility of the batch chemiluminometer facilitated the kinetic study of numerous analytes over a broad pH range. The exemplary performance of the chemiluminometer as an analytical instrument, was demonstrated by the calibration functions, based on peak area data, which exhibited excellent linearity and sensitivity. The estimated detection limits (3s) for the selected alkaloids were in the range 2 x 10^-9 M to 7 x 10^-9 at pH 5.0 and above, which compared favourably to detection limits for the same compounds determined using FIA. Relative standard deviations (n=5) for peak areas ranged between 1% to 5% with a mean of 3.1% for all calibration standards above 2.5 x 10^-8 M. Correlation between concentration and peak area, irrespective of pH and analyte was excellent, with all but two calibration functions having r-squared values greater than 0.990. The analytical figures of merit exemplified the precision and robustness of the reagent delivery and ‘on-line’ sample preparation, as well as the sensitivity of the system. The employment of the chemiluminometer for the measurement of total chemiluminescence emission (peak area) was in itself a feasible analytical technique, which generated highly reproducible and consistent data. Excellent analytical figures of merit, based on peak area, were similarly achieved for the phenethylamines. The effects of analyte structure on chemiluminescence activity was also investigated for the alkaloids and the phenethylamines. Subtle structural variations between the three alkaloids resulted in either a moderately reduced or enhanced total emission that was two or three fold difference only. A significant difference in reaction kinetics was observed between thebaine and codeine/6-methoxy-codeine, which was dependent upon pH. The time-dependent data, namely the observed rate constants for the initial rise in intensity and for the subsequent decay rate, were obtained by fitting a mathematical function (based on the postulated reaction mechanism) to the raw data. The determination of these rate constants for chemiluminescence reactions highlighted the feasibility for utilising such measurements for quantitative analytical applications. The kinetic data were used to discriminate between analyte responses in order to determine the concentrations of individual analytes in a binary mixture. A preliminary, multi-component investigation performed on a binary mixture of codeine and 6-methoxy-codeine (1:1) successfully determined the concentrations of these individual components using such rate constant measurements. Consequently, variations in kinetics resulted in a significant difference between the relative chemiluminescence response based on peak area measurements and the relative response base on peak height measurements obtained using FIA. With regards to the observed reactivity of secondary amines and tertiary amines, chemiluminescence peak area determinations confirmed the vital role of pH on reaction efficiency, which was governed by structural features and kinetics. The tertiary amines investigated generally produced a greater emission under acidic conditions than the corresponding secondary amines. However, the measured chemiluminescence responses were highly dependent upon pH, with similar peak areas obtained for both amine groups under slightly alkaline conditions.