Time-resolved spectroscopy of the metal-to-metal charge transfer excited state in dinuclear cyano-bridged mixed-valence complexes

Visible pump-probe spectroscopy has been used to identify and characterize short-lived metal-to-metal charge transfer (MMCT) excited states in a group of cyano-bridged mixed-valence complexes of the formula [(LCoNCMII)-N-III(CN)(5)](-), where L is a pentadentate macrocyclic pentaamine (L-14) or triamine-dithiaether (L-14S) and M is Fe or Ru. Nanosecond pump-probe spectroscopy on frozen solutions of [(LCoNCFeII)-Co-14-N-III(CN)(5)](-) and [(LCoNCFeII)-Co-14S-N-III(CN)(5)](-) at 11 K enabled the construction of difference transient absorption spectra that featured a rise in absorbance in the region of 350-400 nm consistent with the generation of the ferricyanide chromophore of the photoexcited complex. The MMCT excited state of the Ru analogue [(LCoNCRuII)-Co-14-N-III(CN)(5)](-) was too short-lived to allow its detection. Femtosecond pump-probe spectroscopy on aqueous solutions of [(LCoNCFeII)-Co-14-N-III(CN)(5)](-) and [(LCoNCFeII)-Co-14S-N-III(CN)(5)](-) at room temperature enabled the lifetimes of their Co-II-Fe-III MMCT excited states to be determined as 0.8 and 1.3 ps, respectively.

Clinical supervision in school counselling and career counselling: Is it time to develop a new story?

Supervision provides benefits for school counsellors and career counsellors such as support, an opportunity to gain new ideas and strategies, and personal and professional development. Despite this, studies have also shown that school counsellors perceive that the amount of time they participate in supervision is inadequate. In career counselling, there is little evidence that supervision has even been established as a mainstream professional practice. The reasons for this curious situation, whereby little time is spent on a potentially beneficial activity, are uncertain. The present study investigated the supervisory experiences of a group of school counsellors and career counsellors for a six month period following their completion of an intensive supervision training program. Participants recorded their supervisory experiences in a structured diary. Even though the participants were well informed about supervision, the findings of the present study are consistent with those of previous studies. This history of repeatedly similar findings suggests that it may be timely to ask some fundamental questions about supervision in these two professions. Such questions in turn suggest possible new research directions.

Motorcycle accident risk could be inflated by a time to arrival illusion

Purpose. Drivers adopt smaller safety margins when pulling out in front of motorcycles compared with cars. This could partly account for why the most common motorcycle/car accident involves a car violating a motorcyclist's right of way. One possible explanation is the size-arrival effect in which smaller objects are perceived to arrive later than larger objects. That is, drivers may estimate the time to arrival of motorcycles to be later than cars because motorcycles are smaller. Methods. We investigated arrival time judgments using a temporal occlusion paradigm. Drivers recruited from the student population (n = 28 and n = 33) saw video footage of oncoming vehicles and had to press a response button when they judged that vehicles would reach them. Results. In experiment 1, the time to arrival of motorcycles was estimated to be significantly later than larger vehicles (a car and a van) for different approach speeds and viewing times. In experiment 2, we investigated an alternative explanation to the size-arrival effect: that the smaller size of motorcycles places them below the threshold needed for observers to make an accurate time to arrival judgment using tau. We found that the motorcycle/car difference in arrival time estimates was maintained for very short occlusion durations when tau could be estimated for both motorcycles and cars. Conclusions. Results are consistent with the size-arrival effect and are inconsistent with the tau threshold explanation. Drivers estimate motorcycles will reach them later than cars across a range of conditions. This could have safety implications.

Optimal periodic preventive maintenance policy for leased equipment

For leased equipment the lessor incurs penalty costs for failures occurring over the lease period and for not rectifying such failures within a specified time limit. Through preventive maintenance actions the penalty costs can be reduced but this is achieved at the expense of increased maintenance costs. The paper looks at a periodic preventive maintenance policy which achieves a tradeoff between the penalty and maintenance costs. (c) 2005 Elsevier Ltd. All rights reserved.

Prevalence, severity, and heritability of Stephanofilaria lesions on cattle in central and southern Queensland, Australia

Observations of cattle in central and southern Queensland are collated to de. ne the prevalence and area of Stephanofilaria lesions associated with infestations of the buffalo fly, Haematobia irritans exigua. The observations were made on herds that were being used for other purposes. In a survey of similar to 1500 animals at Belmont in central Queensland in 1982, 98% of cows and 70% of calves had lesions. Most lesions were on the neck and dewlap and 10% were raw and weeping at the time of sampling. The total area of lesions per animal was strongly related to cattle breed and age. Old Bos taurus animals had the greatest area of lesions, whereas young Bos indicus had the least. Heritability estimates were low, averaging 0.01 for calves and 0.18 for cows. A smaller survey of cows and steers at Craighoyle in central Queensland in 1986 showed a higher numbers of lesions and positive correlations between the total lesion area and animal size. The lesion area increased with tick survival, suggesting that tick-resistant animals are also resistant to Stephanofilaria infection. Steers had smaller areas of lesions than cows, as found previously with cattle ticks. Long-term monitoring observations in central and southern Queensland between 1981 and 1986 showed that the total area of lesions was seasonal with a peak in late summer, consistent with the seasonal incidence of buffalo fly. Animals segregated into Low and High lesion herds maintained their differences over time. The lesions penetrated the dermis of the cattle hides and rendered the affected area unusable, but few lesions occurred on valuable parts of the hide so such economic effects are likely to be insignificant. One animal nearly died of a haemorrhage from a lesion on the dewlap and had to be treated. The results can inform policy on buffalo fly control, and biosecurity preparations in relation to the potential establishment of the OldWorld screw-worm fly, Chrysomyia bezziana, in Australia, which will be facilitated by the lesions. The results emphasise the significant animal welfare and biosecurity risks posed by the lesions in northern Australia.

A survey of regular ecstasy users' knowledge and practices around determining pill content and purity: Implications for policy and practice.

Objective: To examine the methods used by a sample of regular ecstasy users to determine the content and purity of ecstasy pills, their knowledge of the limitations of available pill testing methods, and how pill test results would influence their drug use behaviour. Method: Data were collected from regular ecstasy users (n = 810) recruited from all eight capital cities of Australia. Data were analysed using multiple logistic regression and chi-square (chi(2)) tests of association. Open-ended responses were coded for themes. Results: The majority of the sample(84%) reported attempting to find out the content and purity of ecstasy at least some of the time, most commonly asking friends or dealers. Less than one quarter (22%) reported personal use of testing kits. There was a moderate level of awareness of the limitations of testing kits among those who reported having used them. Over half (57%) of those reporting personal use of testing kits reported that they would not take a pill if test results indicated that it contained ketamine and over three quarters (76%) reported that they would not take an "unknown" pill (producing no reaction in a reagent test). Finally, a considerable majority (63%) expressed interest in pill testing should it be more widely available. Conclusions: The majority of regular ecstasy users sampled in this Australian study report previous attempts to determine the content and purity of pills sold as ecstasy. Although only a small proportion have used testing kits, many report that they would do so if they were more widely available. The results of pill tests may influence drug use if they indicate that pills contain substances which ecstasy users do not want to ingest or are of unknown content. More detailed research examining ways in which pill testing may influence drug use is required to inform evidence-based policy. (c) 2006 Elsevier B.V. All rights reserved.

The risk premium for equity: implications for resource allocation, welfare and policy

Analysis of the equity premium puzzle has focused on private sector capital markets. The object of this paper is to consider the welfare and policy implications of each of the broad classes of explanations of the equity premium puzzle. As would be expected, the greater the deviation from the first-best outcome implied by a given explanation of the equity premium puzzle, the more interventionist are the implied policy conclusions. Nevertheless, even explanations of the equity premium puzzle consistent with a general consumption-based asset pricing model have important welfare and policy implications.

Doom and gloom or a time for optimism: Potential aspirants' views about school leadership - now and for the future

Principal recruitment has attracted national and international attention in recent years (eg. Barty et al, 2005 in Australia; Earley et al, 2002 in the UK; Brooking et al, 2003 in New Zealand; Williams, 2003 in Canada). Importantly, Australian research in both state and non-state schools suggests that potential principal aspirants are less enthusiastic than might be expected in their desire to become principals (D’Arbon et al, 2002; Cranston et al, 2004; Lacey, 2002). Given the importance of ensuring we have quality leaders for our schools in the future, the research reported here (which is on-going) examined the views of potential aspirants (primary and secondary deputy principals) from one large government education system in Australia about the principalship and their intentions in seeking promotion (or otherwise) to such positions and the reasons driving these intentions. Data were collected via the Aspiring Principals Questionnaire (APQ) – especially developed for the study – comprising 38 closed items mainly of a Likert-type format, 5 open-ended items linked to particular closed items allowing participants to add their own suggestions/ideas, expand/elaborate on responses; and 4 further more general open-ended items. A number of system-level policy and practice recommendations have been developed from the findings.

Methods for conflict resolution in policy-based management systems

While developments in distributed object computing environments, such as the Common Object Request Broker Architecture (CORBA) [17] and the Telecommunication Intelligent Network Architecture (TINA) [16], have enabled interoperability between domains in large open distributed systems, managing the resources within such systems has become an increasingly complex task. This challenge has been considered for several years within the distributed systems management research community and policy-based management has recently emerged as a promising solution. Large evolving enterprises present a significant challenge for policy-based management partly due to the requirement to support both mutual transparency and individual autonomy between domains [2], but also because the fluidity and complexity of interactions occurring within such environments requires an ability to cope with the coexistence of multiple, potentially inconsistent policies. This paper discusses the need of providing both dynamic (run-time) and static (compile-time) conflict detection and resolution for policies in such systems and builds on our earlier conflict detection work [7, 8] to introduce the methods for conflict resolution in large open distributed systems.

Bernstein's theory of pedagogic discourse: linguistics, educational policy and practice in the UK English/literacy classroom

In “The English Patient: English Grammar and teaching in the Twentieth Century”, Hudson and Walmsley (2005) contens that the decline of grammar in schools was linked to a similar decline in English universities, where no serious research or teaching on English grammar took place. This article argues that such a decline was due not only to a lack of research, but also because it suited educational policies of the time. It applies Bernstein’s theory of pedagogic discourse (1990 & 1996) to the case study of the debate surrounding the introduction of a national curriculum in English in England in the late 1980s and the National Literacy Strategy in the 1990s, to demonstrate the links between academic theory and educational policy.

Policy into practice:a study of public policy implementation and the role of learning

Public policy becomes managerial practice through a process of implementation. There is an established literature within Implementation Studies which explains the variables and some of the processes involved in implementation, but less attention has been focused upon how public service managers convert new policy initiatives into practice. The research proposes that managers and their organisations have to go through a process of learning in order to achieve the implementation of public policy. Data was collected over a five year period from four case studies of capital investment appraisal in the British National Health Service. Further data was collected from taped interviews by key actors within the case studies. The findings suggest that managers do learn to implement policy and four factors are important in this learning process. These are; (i) the nature of bureaucratic responsibility; (ii) the motivation of actors towards learning; (iii) the passage of time which allows for the development of competence and (iv) the use of project team structures. The research has demonstrated that the conversion of policy into practice occurs through the operationalisation of solutions to policy problems via job tasks. As such it suggests that in understanding how policy is implemented, technical learning is more important than cultural learning, in this context. In conclusion, a "Model of Learned Implementation" is presented, together with a discussion of some of the implications of the research. These are the possible use of more pilot projects for new policy initiatives and the more systematic diffusion of knowledge about implementation solutions.

Implicit leadership theories in applied settings:factor structure, generalizability, and stability over time

The present empirical investigation had a 3-fold purpose: (a) to cross-validate L. R. Offermann, J. K. Kennedy, and P. W. Wirtz's (1994) scale of Implicit Leadership Theories (ILTs) in several organizational settings and to further provide a shorter scale of ILTs in organizations; (b) to assess the generalizability of ILTs across different employee groups, and (c) to evaluate ILTs' change over time. Two independent samples were used for the scale validation (N 1 = 500 and N 2 = 439). A 6-factor structure (Sensitivity, Intelligence, Dedication, Dynamism, Tyranny, and Masculinity) was found to most accurately represent ILTs in organizational settings. Regarding the generalizability of ILTs, although the 6-factor structure was consistent across different employee groups, there was only partial support for total factorial invariance. Finally, evaluation of gamma, beta, and alpha change provided support for ILTs' stability over time.

The development of hard real-time systems using a formal approach

Hard real-time systems are a class of computer control systems that must react to demands of their environment by providing `correct' and timely responses. Since these systems are increasingly being used in systems with safety implications, it is crucial that they are designed and developed to operate in a correct manner. This thesis is concerned with developing formal techniques that allow the specification, verification and design of hard real-time systems. Formal techniques for hard real-time systems must be capable of capturing the system's functional and performance requirements, and previous work has proposed a number of techniques which range from the mathematically intensive to those with some mathematical content. This thesis develops formal techniques that contain both an informal and a formal component because it is considered that the informality provides ease of understanding and the formality allows precise specification and verification. Specifically, the combination of Petri nets and temporal logic is considered for the specification and verification of hard real-time systems. Approaches that combine Petri nets and temporal logic by allowing a consistent translation between each formalism are examined. Previously, such techniques have been applied to the formal analysis of concurrent systems. This thesis adapts these techniques for use in the modelling, design and formal analysis of hard real-time systems. The techniques are applied to the problem of specifying a controller for a high-speed manufacturing system. It is shown that they can be used to prove liveness and safety properties, including qualitative aspects of system performance. The problem of verifying quantitative real-time properties is addressed by developing a further technique which combines the formalisms of timed Petri nets and real-time temporal logic. A unifying feature of these techniques is the common temporal description of the Petri net. A common problem with Petri net based techniques is the complexity problems associated with generating the reachability graph. This thesis addresses this problem by using concurrency sets to generate a partial reachability graph pertaining to a particular state. These sets also allows each state to be checked for the presence of inconsistencies and hazards. The problem of designing a controller for the high-speed manufacturing system is also considered. The approach adopted mvolves the use of a model-based controller: This type of controller uses the Petri net models developed, thus preservIng the properties already proven of the controller. It. also contains a model of the physical system which is synchronised to the real application to provide timely responses. The various way of forming the synchronization between these processes is considered and the resulting nets are analysed using concurrency sets.

'Urine testing is a waste of time': newly diagnosed Type 2 diabetes patients' perceptions of self-monitoring

Aims To date, there is no convincing evidence that non-insulin treated patients who undertake self-blood glucose monitoring (SBGM) have better glycaemic control than those who test their urine. This has led to a recommendation that non-insulin dependent patients undertake urine testing, which is the cheaper option. This recommendation does not take account of patients' experiences and views. This study explores the respective merits of urine testing and SBGM from the perspectives of newly diagnosed patients with Type 2 diabetes. Methods Qualitative study using repeat in-depth interviews with 40 patients. Patients were interviewed three times at 6-monthly intervals over 1 year. Patients were recruited from hospital clinics and general practices in Lothian, Scotland. The study was informed by grounded theory, which involves concurrent data collection and analysis. Results Patients reported strongly negative views of urine testing, particularly when they compared it with SBGM. Patients perceived urine testing as less convenient, less hygienic and less accurate than SBGM. Most patients assumed that blood glucose meters were given to those with a more advanced or serious form of diabetes. This could have implications for how they thought about their own disease. Patients often interpreted negative urine results as indicating that they could not have diabetes. Conclusions Professionals should be aware of the meanings and understandings patients attach to the receipt and use of different types of self-monitoring equipment. Guidelines that promote the use of consistent criteria for equipment allocation are required. The manner in which negative urine results are conveyed needs to be reconsidered.

Social policy in the UK

Social policy is a very complex area, and this chapter has only offered a brief summary of the most significant recent changes to the UK welfare state. Social policy expenditure has fluctuated over time, with considerable increases through the late 1990s and 2000s, but reductions planned in many areas by the current Coalition Government. The UK welfare state has slowly come to terms with women’s engagement in the labour market, but failed to overcome the persistent inequality between male and female incomes. While competition and choice have been introduced in many areas of the welfare state, their impacts have been varied and contested. Aside from health and education, UK social policy has become increasingly ‘residualised’, with many transfers now means-tested and services like social housing becoming less widely available. At the same time, however, different patterns can be observed across the UK, particularly in the fields of social care and education, where different arrangements apply in different nations. Future developments in social policy are likely to be shaped by the challenge of an ageing population, and the recently hardened public attitude towards particular groups of social policy beneficiaries.