A study of the chemistry of some polyfluoroaromatic prop-2-ynyl ethers and prop-2-enyl thioethers

This work involves vapour phase and solution-phase studies of several polyfluoroaromatic prop-2-ynyl ethers and prop-2-enyl thio- ethers. When the prop-2-enyl thioether has a hydrogen ortho to the sulphur then a conventional thio-Claisen rearrangement occurs. However, if there are fluorine substitutents ortho to the sulphur then rearrangement to an ortho-dienethione is followed by hemolysis of the carbon to fluorine bond of the carbon to which the prop-2-enyl group has migrated. Claisen rearrangement followed by homolytic cleavage of the carbon to fluorine bond of the carbon to which the prop-2-ynyl group migrates occurs for the prop-2-ynyl ethers, which have fluorine substitutents ortho to the oxygen. The thesis is divided into six main parts. Chapter one deals with the literature on the Claisen and thio-Claisen rearrangements including the mechanistic development of the Claisen rearrangement. Chapters two and three are concerned with the thermal reactions of pentafluorophenyl, 2,3,4,5-tetrafluorophenyl, and 2,3,5,6-tetra- fluorophenyl prop-2-enyl thioethers. Chapter four describes attempted syntheses of the compounds arising out of the reaction of pentafluorophenyl prop-2-enyl thioether in N,N-diethylani1ine .Chapters five and six discuss the thermal chemistry of pentafluorophenyl and 1,3,4,5,6,7,8-heptafluoro-2-naphthyl prop-2-ynyl ethers.The thesis ends with a general conclusion tying together the work on the prop-2-enyl thioethers with that on the prop-2-ynyl ethers

Competitive Tendering for Bus Services: The Improved Adelaide Model

In 1994 the Government of South Australia initiated a process to contract out scheduled bus services in metropolitan Adelaide. The services, which currently involve use of about 760 buses that carry 47 million passengers per year in a service area of 880 square kilometres, had been operated by a Government organisation. Services were contracted out primarily on an areas basis, with ten area and four route contracts. By 1996 two contracts had been awarded to a private operator and three to the Government operator following two rounds of competitive tendering. Remaining services were provided by the Government operator through negotiated contracts. A review of the bus contracting system was undertaken in 1998, and features of the system modified, including a reduction in the number of contracts to six area and one route contract. All seven contracts were subsequently competitively tendered and won by private operators: the new contracts commenced in April 2000. The refinements to the Adelaide M odel secured greater interest from industry and keener pricing, which resulted in substantial cost savings. In developing the revised model, particular attention was paid to supplier market considerations. This included the division of responsibilities for service planning between the tendering authority and operators, and incentive structures to align operator objectives with Government goals in relation to service level, service quality and patronage. A number of other aspects of the former model were also revised. The paper also summarises the impacts of the overall competitive tendering process on costs, services and patronage. It draws out lessons learned that may be applicable to other authorities contemplating competitive tendering of public transport services

Economic Incentives to Increase Public Transport Patronage – The Theory and the Practice

This paper reports on an innovative policy for central government funding to local passenger transport services in New Zealand, that ties funding directly to performance. The new policy, known as Patronage Funding, was developed and implemented by Transfund New Zealand, with assistance from consultants. Under the policy, government funding to the regions for public transport services is based directly on the patronage generated. This leaves responsibility for service planning with regional government, but encourages them to improve services in such a way as to generate additional patronage. The payment rates are based on estimates of both the user benefits and externality benefits of improving services and hence attracting additional passengers. The externality component comprises benefits associated with reduced road congestion, safety and environmental benefits. Hence, the payment rates vary by city, time period (peak/off-peak) and distance travelled. The paper describes the economic theory and the analyses underlying the new policy, key aspects of its implementation, and experience in the first six months since its introduction in November 2000

Effective ways to grow urban bus markets – a synthesis of evidence

Institute of Transport and Logistics Studies. Faculty of Economics and Business. The University of Sydne

Effect Of AlN Spacer In The Layer Structure On High Rf Performance GaN-Based HEMTs On Low Resistivity Silicon At K-Band Application

AlGaN/GaN High Electron Mobility Transistors (HEMTs) grown on Si substrate are emerging as an attractive devices for many RF applications. This is due to lower circuits realization cost and multifunction chips integration. In this study we investigate the effect of AlN spacer between AlGaN and GaN of a sub-micron gate (0.3 μm) AlGaN/GaN and AlGaN/AlN/GaN HEMTs on a Low Resistivity LR Si substrates on RF performance. We have observed an enhancement in RF performance fT and fMAX in the HEMT with of AlN spacer; (fT) was increased from 47 GHz to 55 GHz and (fMAX) was increased from 79 GHz to 121 GHz. This enhancement in performance is mainly due to the increase in the mobility in the channel and confinement of the carriers reducing Cgs, and delay τ under the gate. We believe this is the first RF study of this type as previous studies were based on the effects of the DC characteristic of the devices [1]

Competitive tendering as a contracting mechanism for subsidising transportation: The bus experience

Competitive tendering (CT) is a popular mechanism for the provision of transport services where a major objective is the containment of the cost to government of service provision. Although the primary focus is recognised as cost efficiency, whereby the cost outcome should be conditional on a given level of service, difficulties in establishing appropriate tests for service level compliance has become a cause of concern about the effectiveness of the CT paradigm as a value for money initiative. While recognizing the growing evidence that competitive tendering can reduce levels of subsidy, typically in the 20-30% range, what is lacking in the support is an explicit statement that such gains are usually a windfall gain when first introducing CT, and especially when the incumbent is a public supplier (or a public operator almost exclusively dependent on government funding), and that financial gains through retendering are notably absent. Furthermore the risk of discouraging investment back into the provision of services because of uncertainty of continuity is starting to show up as incentive-incompatible and a discouragement to quality operators who would in the normal course of business reinvest much more. This has led to a growing interest in and support for performance based contracts (PBCs) in which the incentive structure is more conducive to the growing the business (under a trusting partnership between the regulator and the operator) and where CT is a last resort noncompliance strategy. This paper reviews the international successes and failure of CT as a subsidy reduction strategy within the bus sector, and promotes the idea of PBCs as a way of recognizing the real role of subsidy under the umbrella of a value for money objective

Seeing the world through others’ minds: inferring social context from behaviour

Past research tells us that individuals can infer information about a target’s emotional state and intentions from their facial expressions (Frith & Frith, 2012), a process known as mentalising. This extends to inferring the events that caused the facial reaction (e.g. Pillai, Sheppard, & Mitchell, 2012; Pillai et al., 2014), an ability known as retrodictive mindreading. Here, we enter new territory by investigating whether or not people (perceivers) can guess a target’s social context by observing their response to stimuli. In Experiment 1, perceivers viewed targets’ responses and were able to determine whether these targets were alone or observed by another person. In Experiment 2, another group of perceivers, without any knowledge of the social context or what the targets were watching, judged whether targets were hiding or exaggerating their facial expressions; and their judgments discriminated between conditions in which targets were observed and alone. Experiment 3 established that another group of perceivers’ judgments of social context were associated with estimations of target expressivity to some degree. In Experiments 1 and 2, the eye movements of perceivers also varied between conditions in which targets were observed and alone. Perceivers were thus able to infer a target’s social context from their visible response. The results demonstrate an ability to use other minds as a window onto a social context that could not be seen directly

Identifying quality indicators for prehospital emergency care services in the low to middle income setting: The South African perspective

Introduction Historically, performance within the Prehospital Emergency Care (PEC) setting has been assessed primarily based on response times. While easy to measure and valued by the public, overall, response time targets are a poor predictor of quality of care and clinical outcomes. Over the last two decades however, significant progress has been made towards improving the assessment of PEC performance, largely in the form of the development of PEC-specific quality indicators (QIs). Despite this progress, there has been little to no development of similar systems within the low- to middle-income country setting. As a result, the aim of this study was to identify a set of QIs appropriate for use in the South African PEC setting. Methods A three-round modified online Delphi study design was conducted to identify, refine and review a list of QIs for potential use in the South African PEC setting. Operational definitions, data components and criteria for use were developed for 210 QIs for inclusion into the study. Results In total, 104 QIs reached consensus agreement including, 90 clinical QIs, across 15 subcategories, and 14 non-clinical QIs across two subcategories. Amongst the clinical category, airway management (n = 13 QIs; 14%); out-of-hospital cardiac arrest (n = 13 QIs; 14%); and acute coronary syndromes (n = 11 QIs; 12%) made up the majority. Within the non-clinical category, adverse events made up the significant majority with nine QIs (64%). Conclusion Within the South Africa setting, there are a multitude of QIs that are relevant and appropriate for use in PEC. This was evident in the number, variety and type of QIs reaching consensus agreement in our study. Furthermore, both the methodology employed, and findings of this study may be used to inform the development of PEC specific QIs within other LMIC settings.Peer reviewe

Experimental insights into the airtightness measurement of a house-sized chamber in a sheltered environment using blower door and pulse methods

This paper introduces a comparison study of measuring the airtightness of a house-sized test chamber using the novel pulse technique and a low range blower door method in a sheltered environment. Eight different testing plates were prepared and applied to the improvised envelope of the chamber to establish different leakage characteristics. Each testing plate has a unique opening in its centre, achieved by obtaining different combinations of shape and thickness of the opening. By using the sheltered environment, the vagaries of the natural condition when testing within buildings have been reduced providing a more robust testing environment. This investigation focuses on how the air leakage rate calculated from the measurements made by both techniques compare with each other. Comparable results (0-5.3%) under most scenarios have been obtained. Larger discrepancies (14.6% and 21.8%) were observed in the two airtight scenarios due to insufficient pressure range achieved in a standard pulse test. This finding guided further improvement on the testing performance. Further pulse tests under different scenarios, involving the use of an internal barrier and various location of the pulse unit were also performed to investigate the uniform pressure distribution and resilience to external interferences. It showed the internal barrier and location had minor impact (1.62% to 4.65%) on the test results