Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

INFO2009 2012-13 Resource Group 28 Animation on Green IT

Animation on Green IT Container EdShare to be used to assemble resources developed by team for coursework 2. The metadata will be updated by the group, and description modified when the resource set has been completed. The resource has been set up with an instructional readme file. This will be replaced by each group with a new readme file. Each group needs to update this description. Further instructions in readme.txt

What happens to precocious readers’ performance by the age of 11 years?

This paper reports on the progress made by a group of fourteen 11-year-old children who had been originally identified as being precocious readers before they started primary school at the age of 5-years. The data enable comparisons to be made with the performance of the children when they were younger so that a six year longitudinal analysis can be made. The children who began school as precocious readers continued to make progress in reading accuracy, rate and comprehension, thereby maintaining their superior performance relative to a comparison group. However, their progress appeared to follow the same developmental trajectory as that of the comparison group. Measures of phonological awareness showed that there are long term, stable individual differences which correlated with all measures of reading. The children who were reading precociously early showed significantly higher levels of phonological awareness than the comparison children. In addition, they showed the same levels of performance on this task as a further group of high achieving young adults. A positive effect of being able to read at precociously early age was identified in the significantly higher levels of receptive vocabulary found amongst the these children. The analyses indicated that rises in receptive vocabulary resulted from reading performance rather than the other way round

CONTRA: Improving the performance of dynamic investigations in natural abundance organic solids by mirror-symmetric constant-time CODEX

We present a minor but essential modification to the CODEX 1D-MAS exchange experiment. The new CONTRA method, which requires minor changes of the original sequence only, has advantages over the previously introduced S-CODEX, since it is less sensitive to artefacts caused by finite pulse lengths. The performance of this variant, including the finite pulse effect, was confirmed by SIMPSON calculations and demonstrated on a number of dynamic systems. (C) 2007 Elsevier Inc. All rights reserved.

The Borsuk-Ulam theorem for homotopy spherical space forms

In this work, we show for which odd-dimensional homotopy spherical space forms the Borsuk-Ulam theorem holds. These spaces are the quotient of a homotopy odd-dimensional sphere by a free action of a finite group. Also, the types of these spaces which admit a free involution are characterized. The case of even-dimensional homotopy spherical space forms is basically known.

Characterization of Polyurethane Resins by FTIR, TGA, and XRD

Fourier Transformed Infrared Spectroscopy, Thermogravimetric Analysis, and X-ray Diffractometry have been used to investigate the rigid, semi rigid, and soft polyurethane (PU) forms, which were developed by the Group of Analytic Chemistry and Technology of Polymers - USF - Sao Carlos. The -NCO/-OH ratios were 0.6, 0.5, and 0.3% for rigid, semi rigid, and soft PUs, respectively, showing that different ratios cause differences in thermal behaviors and crystalline structures of the synthesized PU resins. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 263-268, 2010

Mark-aided distributed filtering by using neural network for DDoS defense

Currently Distributed Denial of Service (DDoS) attacks have been identified as one of the most serious problems on the Internet. The aim of DDoS attacks is to prevent legitimate users from accessing desired resources, such as network bandwidth. Hence the immediate task of DDoS defense is to provide as much resources as possible to legitimate users when there is an attack. Unfortunately most current defense approaches can not efficiently detect and filter out attack traffic. Our approach is to find the network anomalies by using neural network, deploy the system at distributed routers, identify the attack packets, and then filter them. The marks in the IP header that are generated by a group of IP traceback schemes, Deterministic Packet Marking (DPM)/Flexible Deterministic Packet Marking (FDPM), assist this process of identifying attack packets. The experimental results show that this approach can be used to defend against both intensive and subtle DDoS attacks, and can catch DDoS attacks’ characteristic of starting from multiple sources to a single victim. According to results, we find the marks in IP headers can enhance the sensitivity and accuracy of detection, thus improve the legitimate traffic throughput and reduce attack traffic throughput. Therefore, it can perform well in filtering DDoS attack traffic precisely and effectively.

Short term reoffending by child victim sex offenders in New Zealand : a comparison of those with and without extended supervision

Sexual offenders with child victims in New Zealand who are considered at high risk for reoffending are subject to an Extended Supervision Order. This allows for a period of supervision of up to ten years following release to the community. The present study examined 89 offenders given Extended Supervision Orders over the 33 month period since the legislation was enacted. All types of reoffending resulting in criminal convictions by this group were included. A matched sample of sexual offenders with child victims released prior to this legislation and a sample of offenders judged to be lower risk were compared to those under extended supervision. Offenders under extended supervision reoffended faster and at a higher rate for both sexual and general offences than those deemed lower risk, but at a lower rate than pre-extended supervision high risk offenders. The relationship between specialist treatment programme attendance and completion, actuarial risk level, and recidivism in the extended supervision sample were also investigated. These variables were found not to be significant predictors of sexual recidivism.

Modelling income group differences in the health and economic impacts of targeted food taxes and subsidies

Objective : To examine the effects, by income group, of targeted food taxes and subsidies on nutrition, health and expenditure in the UK.

Methods : A model based on consumption data and demand elasticity was constructed to predict the effects of four food taxation-subsidy regimens. Resulting changes in demand, expenditure, nutrition, cardiovascular disease (CVD) and cancer mortality were estimated.

Data : Expenditure data were taken from the Expenditure and Food Survey; estimates of price elasticities of demand for food were taken from a report based on the National Food Survey 1988–2000. Estimates of effect on CVD and cancer mortality of changing fat, salt, fruit and vegetable intake were taken from previous meta-analyses.

Results : (i) Taxing principal sources of dietary saturated fat is unlikely to reduce cardiovascular disease (CVD) or cancer mortality. (ii) Taxing ‘less healthy’ foods (defined by the WXYfm nutrient profiling model) could increase CVD and cancer deaths by 35–1300 yearly. (iii) Taxing ‘less healthy’ foods and subsidising fruits and vegetables by 17.5% could avert up to 2900 CVD and cancer deaths yearly. (iv) Taxing ‘less healthy’ foods and using all tax revenue to subsidize fruits and vegetables could avert up to 6400 CVD and cancer deaths yearly. Few obesity-related CVD deaths are averted by any of the regimens. All four regimens would be economically regressive and positive health effects will not necessarily be greater in lower-income groups where the need for dietary improvement is higher.

Conclusions : A targeted food tax combined with the appropriate subsidy on fruits and vegetables could reduce deaths from CVD and cancer.

Assessing the strain experienced by managers and professional Australian footballers using an augmented job strain model

Generic models of job stress, such as the Job Strain Model (JSM), have recently been criticised for focusing on a small number of general work characteristics while ignoring those that are occupation-specific (Sparks & Cooper, 1999). However this criticism is based on limited research that has not examined the relative influence of all three dimensions of the JSM - job demand, job control and social support - and job-specific stressors. The JSM is the most commonly used model underpinning large-scale occupational stress research (Fox, Dwyer, & Ganster, 1993) and is regarded as the most influential model in the research on the psycho-social work environment, stress and disease in recent times (Kristensen, 1995). This thesis addresses the lack of information on the relative influence of the JSM and job-specific stressors by assessing the capacity of an augmented JSM to predict the strain experienced by managers and professional Australian footballers. The augmented JSM consisted of job-specific stressors in addition to the generic components of the model. Managers and professional Australian footballers represent two very different occupational groups. While the day-today roles of a manager include planning, organising, monitoring and controlling (Carroll & Gillen, 1987), the working life of a professional Australian footballer revolves around preparing for and playing football (Shanahan, 1998). It was expected that the large differences in the work undertaken by managers and professional Australian footballers would maximise the opportunities for identifying job-specific stressors and measuring the extent that these vary from one group to the next. The large disparity between managers and professional footballers was also used to assess the cross-occupational versatility of the JSM when it had been augmented by job-specific stressors. This thesis consisted of three major studies. Study One involved a survey of Australian managers, while studies Two and Three focused on professional Australian footballers. The latter group was under-represented in the literature, and as a result of the lack of information on the stressors commonly experienced by this group, an in-depth qualitative study was undertaken in Study Two. The results from Study Two then informed the survey of professional footballers that was conducted in Study Three. Contrary to previous research examining the relative influence of generic and job-specific stressors, the results only provided moderate support for augmenting the JSM with job-specific stressors. Instead of supporting the versatility of the augmented JSM, the overall findings reinforced the broad relevance of the original JSM. Of the four health outcomes measured in Studies One and Three, there was only one - the psychological health of professional Australian footballers - where the proportion of total variance explained by job-specific stressors exceeded 13%. Despite the generally strong performance of the JSM across the two occupational groups, the importance of demand, control and support diminished when examining the less conventional occupation of professional football. The generic model was too narrow to capture the highly specific work characteristics that are important for this occupational group and, as a result, the job-specific stressors explained significantly more of the strain over and above that already provided by the generic model. These findings indicate that when investigating the stressors experienced by conventional occupational groups such as managers, the large amount resources required to identify job-specific stressors are unlikely to be cost-effective. In contrast, the influence of the more situation specific stressors is significantly greater in unconventional occupations and thus the benefits of identifying these non-generic stressors are more likely to outweigh the costs. Studies One and Three identified strong connections between job-specific stressors and important characteristics of the occupation being studied. These connections were consistent with previous research and suggest that before attempting to identify job-specific stressors, researchers need to first become familiar with the nature and context of the occupation. The final issue addressed in this thesis was the role of work and non-work support. The findings indicate that the support provided by supervisors and colleagues was a significant predictor of wellbeing for both managers and professional footballers. In contrast, the level of explained strain accounted for by non-work support was not significant. These results indicate that when developing strategies to protect and enhance employee well-being, particular attention should be given to monitoring and, where necessary, boosting the effectiveness of work-based support. The findings from this thesis have been fed back to the management and sporting communities via conference presentations and peer-reviewed journals (refer pp 220-221). All three studies have been presented at national and international conferences and, overall, were well received by participants. Similarly, the methods, results and major findings arising from Studies One and Two have been critiqued by anonymous reviewers from two international journals. These papers have been accepted for publication in 2001 and 2002 and feedback from the reviewers indicates that the findings represent a significant and unique contribution to the literature. The results of Study Three are currently under review by a sports psychology journal.

Duration of unemployment and suicide in Australia over the period 1985–2006: an ecological investigation by sex and age during rising versus declining national unemployment rates

Background The relationship between unemployment and suicide may be sensitive to demographic factors, national unemployment rates, and length of time without employment. This study investigated these factors in relation to suicide in Australia for the period 1985–2006, in an ecological study. Methods The outcome variable was annual suicide rate by age group, sex and the eight states and territories over 22 years of observation (total observations=1760). The main predictor variable was the average duration of unemployment in the population, categorised into three time periods (<2 weeks, 2–4 weeks, >4 weeks). Poisson regression models were used to investigate the relationship between duration of unemployment and suicide over the years 1985–2006 in a series of cross-sectional analyses. Interaction analyses indicated significant differences during periods of declining or increasing labour market opportunity and by age group. Results During periods of declining unemployment rates in the country, longer durations of unemployment were associated with higher male suicide rates. During periods of increasing unemployment in the country, longer unemployment duration was associated with lower male suicide rates. Effect modification was also apparent by age-group, with stronger associations between unemployment duration and male suicide evident in those aged 25–34 and 55–64, and weaker associations in those aged 15–24 and 44–54 years. Longer length of unemployment was not associated with an increase in female suicide rates. Conclusions The labour market opportunities in Australia modified the effect of duration of unemployment on suicide, and the effect was more prominent in men and older age groups. This may reflect social norms and acceptability about unemployment, as well as life-stage influences associated with transitions into and out of the labour market.

Gradient structure produced by three roll planetary milling: numerical simulation and microstructural observations

In this study a gradient grain structure was produced by processing rod billets through three roll planetary milling (also known as PSW process). This kind of gradient structure is reported to provide an excellent combination of strength and ductility owing to an ultrafine-grained surface layer and a coarse-grained interior of the billet. Specifically, copper rod samples were subjected to up to six passes of PSW at room temperature. To study the evolution of the microstructure during the deformation, microhardness measurements and Electron Backscatter Diffraction (EBSD) analysis were performed after one, three and six passes. Additionally, the distributions of the equivalent stress during PSW and the equivalent strain after processing were studied by finite element analysis using the commercial software QFORM. The results showed the efficacy of PSW as a means of imparting a gradient ultrafine-grained structure to copper rods. A good correlation between the simulated equivalent strain distribution and the measured microhardness distribution was demonstrated.

Neuroethologic differences in sleep deprivation induced by the single- and multiple-platform methods

It has been proposed that the multiple-platform method (MP) for desynchronized sleep (DS) deprivation eliminates the stress induced by social isolation and by the restriction of locomotion in the single-platform (SP) method. MP, however, induces a higher increase in plasma corticosterone and ACTH levels than SP. Since deprivation is of heuristic value to identify the functional role of this state of sleep, the objective of the present study was to determine the behavioral differences exhibited by rats during sleep deprivation induced by these two methods. All behavioral patterns exhibited by a group of 7 albino male Wistar rats submitted to 4 days of sleep deprivation by the MP method (15 platforms, spaced 150 mm apart) and by 7 other rats submitted to sleep deprivation by the SP method were recorded in order to elaborate an ethogram. The behavioral patterns were quantitated in 10 replications by naive observers using other groups of 7 rats each submitted to the same deprivation schedule. Each quantification session lasted 35 min and the behavioral patterns presented by each rat over a period of 5 min were counted. The results obtained were: a) rats submitted to the MP method changed platforms at a mean rate of 2.62 ± 1.17 platforms h-1 animal-1; b) the number of episodes of noninteractive waking patterns for the MP animals was significantly higher than that for SP animals (1077 vs 768); c) additional episodes of waking patterns (26.9 ± 18.9 episodes/session) were promoted by social interaction in MP animals; d) the cumulative number of sleep episodes observed in the MP test (311) was significantly lower (chi-square test, 1 d.f., P<0.05) than that observed in the SP test (534); e) rats submitted to the MP test did not show the well-known increase in ambulatory activity observed after the end of the SP test; f) comparison of 6 MP and 6 SP rats showed a significantly shorter latency to the onset of DS in MP rats (7.8 ± 4.3 and 29.0 ± 25.0 min, respectively; Student t-test, P<0.05). We conclude that the social interaction occurring in the MP test generates additional stress since it increases the time of forced wakefulness and reduces the time of rest promoted by synchronized sleep.

Closed expressions for Lie algebra invariants and finite transformations

A simple procedure to obtain complete, closed expressions for Lie algebra invariants is presented. The invariants are ultimately polynomials in the group parameters. The construction of finite group elements requires the use of projectors, whose coefficients are invariant polynomials. The detailed general forms of these projectors are given. Closed expressions for finite Lorentz transformations, both homogeneous and inhomogeneous, as well as for Galilei transformations, are found as examples.

Potentially inappropriate medications used by the elderly: Prevalence and risk factors in Brazilian care homes

Abstract. Background: The use of potentially inappropriate medications (PIM) among the elderly is a serious public health problem because it is intrinsically linked to increased morbidity and mortality, causing high costs to public health systems. This study's objective was to verify the prevalence of and the factors associated with the use of PIMs by elderly Brazilians in institutional settings. Methods. We performed a transversal study, by consulting the case files of elderly people living in Long Term Care for the Elderly (LTC) in towns in the State of São Paulo, Brazil, as well as structured interviews with the nurses responsible for them.We identified PIMs using the list of recently updated Beers criteria developed by a group of specialists from the American Geriatrics Society (AGS), who reviewed the criteria based on studies with high scientific evidence levels. We defined the factors studied to evaluate the association with PIM use prior to the statistical analyses, which were the chi-square test and multiple logistic regression. Results: Among the elderly who used drugs daily, 82.6% were taking at least one PIM, with antipsychotics (26.5%) and analgesics (15.1%) being the most commonly used. Out of all the medications used, 32.4% were PIMs, with 29.7% of these being PIMs that the elderly should avoid independent of their condition, 1.1% being inappropriate medication for older adults with certain illnesses or syndromes, and 1.6% being medications that older adults should use with caution. In the multivariate analysis, the factors associated with PIM use were: polypharmacy (p = 0.0187), cerebrovascular disease (p = 0.0036), psychiatric disorders (p < 0.0001) and dependency (p = 0.0404). Conclusions: The results of this study showed a high prevalence of PIM use in institutionalized elderly Brazilian patients. and the associated factors were polypharmacy, psychiatric disorders, cerebrovascular diseases and dependency. © 2013 Lima et al.; licensee BioMed Central Ltd.