A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Use of electronic portal imaging devices for electron treatment verification

This study aims to help broaden the use of electronic portal imaging devices (EPIDs) for pre-treatment patient positioning verification, from photon-beam radiotherapy to photon- and electron-beam radiotherapy, by proposing and testing a method for acquiring clinicallyuseful EPID images of patient anatomy using electron beams, with a view to enabling and encouraging further research in this area. EPID images used in this study were acquired using all available beams from a linac configured to deliver electron beams with nominal energies of 6, 9, 12, 16 and 20 MeV, as well as photon beams with nominal energies of 6 and 10 MV. A widely-available heterogeneous, approximately-humanoid, thorax phantom was used, to provide an indication of the contrast and noise produced when imaging different types of tissue with comparatively realistic thicknesses. The acquired images were automatically calibrated, corrected for the effects of variations in the sensitivity of individual photodiodes, using a flood field image. For electron beam imaging, flood field EPID calibration images were acquired with and without the placement of blocks of water-equivalent plastic (with thicknesses approximately equal to the practical range of electrons in the plastic) placed upstream of the EPID, to filter out the primary electron beam, leaving only the bremsstrahlung photon signal. While the electron beam images acquired using a standard (unfiltered) flood field calibration were observed to be noisy and difficult to interpret, the electron beam images acquired using the filtered flood field calibration showed tissues and bony anatomy with levels of contrast and noise that were similar to the contrast and noise levels seen in the clinically acceptable photon beam EPID images. The best electron beam imaging results (highest contrast, signal-to-noise and contrast-to-noise ratios) were achieved when the images were acquired using the higher energy electron beams (16 and 20 MeV) when the EPID was calibrated using an intermediate (12 MeV) electron beam energy. These results demonstrate the feasibility of acquiring clinically-useful EPID images of patient anatomy using electron beams and suggest important avenues for future investigation, thus enabling and encouraging further research in this area. There is manifest potential for the EPID imaging method proposed in this work to lead to the clinical use of electron beam imaging for geometric verification of electron treatments in the future.

The process for implementation of a Quality Management System within a multi-functional cereal laboratory

The intent of this study was to design, document and implement a Quality Management System (QMS) into a laboratory that incorporated both research and development (R&D) and routine analytical activities. In addition, it was necessary for the QMS to be easily and efficiently maintained to: (a) provide documented evidence that would validate the system's compliance with a certifiable standard, (b) fit the purpose of the laboratory, (c) accommodate prevailing government policies and standards, and (d) promote positive outcomes for the laboratory through documentation and verification of the procedures and methodologies implemented. Initially, a matrix was developed that documented the standards' requirements and the necessary steps to be made to meet those requirements. The matrix provided a check mechanism on the progression of the system's development. In addition, it was later utilised in the Quality Manual as a reference tool for the location of full procedures documented elsewhere in the system. The necessary documentation to build and monitor the system consisted of a series of manuals along with forms that provided auditable evidence of the workings of the QMS. Quality Management (QM), in one form or another, has been in existence since the early 1900's. However, the question still remains: is it a good thing or just a bugbear? Many of the older style systems failed because they were designed by non-users, fiercely regulatory, restrictive and generally deemed to be an imposition. It is now considered important to foster a sense of ownership of the system by the people who use the system. The system's design must be tailored to best fit the purpose of the operations of the facility if maximum benefits to the organisation are to be gained.

Context-sensitive evaluation: Determining the context surrounding the implementation of a government policy

This article explains the essence of the context-sensitive parameters and dimensions in play at the time of an intervention, through the application of Rog’s (2012) model of contextual parameters. Rog’s model offers evaluators a structured approach to examine an intervention. The initial study provided a systematic way to clarify the scope, variables, timing, and appropriate evaluation methodology to evaluate the implementation of a government policy. Given that the government implementation of an educational intervention under study did not follow the experimental research approach, nor the double cycle of action research approach, the application of Rog’s model provided an in-depth understanding of the context-sensitive environment; it is from this clear purpose that the broader evaluation was conducted. Overall, when governments or institutions implement policy to invoke educational change (and this intervention is not guided by an appropriate evaluation approach), then program evaluation is achievable post-implementation. In this situation, Rog’s (2012) model of contextual parameters is a useful way to achieve clarity of purpose to guide the program evaluation.

Implementation of an interactive relational graphics database

The benefits that accrue from the use of design database include (i) reduced costs of preparing data for application programs and of producing the final specification, and (ii) possibility of later usage of data stored in the database for other applications related to Computer Aided Engineering (CAE). An INTEractive Relational GRAphics Database (INTERGRAD) based on relational models has been developed to create, store, retrieve and update the data related to two dimensional drawings. INTERGRAD provides two languages, Picture Definition Language (PDL) and Picture Manipulation Language (PML). The software package has been implemented on a PDP 11/35 system under the RSX-11M version 3.1 operating system and uses the graphics facility consisting of a VT-11 graphics terminal, the DECgraphic 11 software and an input device, a lightpen.

Ultrasonic attenuation in strongly disordered electronic systems

The attenuation of long-wavelength phonons due to their interaction with electronic excitations in disordered systems is investigated here. Lattice strain couples to electronic stress, and thus ultrasonic attenuation measures electronic viscosity. The enhancement and critical divergence of electronic viscosity due to localization effects is calculated for the first time. Experimental consequences for the anomalous increase of ultrasonic attenuation in disordered metals close to the metal-insulator transition are discussed. In the localized regime, the appropriate model is one of electronic two-level systems (TLS’s) coupled to phonons. The TLS consists of a pair of states with one localized state occupied and the other unoccupied. The density of such low-excitation-energy TLS’s is nonzero due to long-range Coulomb interactions. The question of whether these could be significant low-energy excitations in glasses is touched upon.

Cresols - An investigation into their electronic structure and spectra

The three isomeric cresols were subjected to the all-valence-electron CNDO/2 andPPP-CI calculations. Results from this study were used: (i) to compare the electronic structures of these isomers vis-Ã-vis parent compounds-phenol and toluene, (ii) to obtain a quantitative picture of their chemical reactivities and electronic absorption spectra. Using the sgr-core charges derived from CNDO/2 calculations and subsequently revising the valence-state ionisation potential and one-center-two-electron repulsion integrals, thePPP-CI calculations were performed on the title compounds according toNishimoto andForster scheme. In these calculations the pseudo-unsaturated nature of the methyl group has been given due consideration. In spectral assignment, compared to the conventionalPPP approach, the CNDO/2-basedPPP-CI method gave a better agreement with the experimental data.

Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Understanding the determinants of Australian hospital nurses' hand hygiene decisions following the implementation of a national hand hygiene initiative

Hand hygiene is the primary measure in hospitals to reduce the spread of infections, with nurses experiencing the greatest frequency of patient contact. The ‘5 critical moments’ of hand hygiene initiative has been implemented in hospitals across Australia, accompanied by awareness-raising, staff training and auditing. The aim of this study was to understand the determinants of nurses’ hand hygiene decisions, using an extension of a common health decision-making model, the theory of planned behaviour (TPB), to inform future health education strategies to increase compliance. Nurses from 50 Australian hospitals (n = 2378) completed standard TPB measures (attitude, subjective norm, perceived behavioural control [PBC], intention) and the extended variables of group norm, risk perceptions (susceptibility, severity) and knowledge (subjective, objective) at Time 1, while a sub-sample (n = 797) reported their hand hygiene behaviour 2 weeks later. Regression analyses identified subjective norm, PBC, group norm, subjective knowledge and risk susceptibility as the significant predictors of nurses’ hand hygiene intentions, with intention and PBC predicting their compliance behaviour. Rather than targeting attitudes which are already very favourable among nurses, health education strategies should focus on normative influences and perceptions of control and risk in efforts to encourage hand hygiene adherence.

A Comparison of the Implementation of the Employment Provisions of the Americans with Disabilities Act of 1990 (ADA) in the United States and the Disability Discrimination Act (DDA) 1995 in the United Kingdom

This summarizes the results of recently conducted surveys in the United States and Britain to assess employer response in each of these countries to their respective employment disability nondiscrimination legislation.

Evaluation of the implementation of the prostate cancer specialist nurse role

A national prostate cancer specialist nursing pilot program, supported by Prostate Cancer Foundation of Australia, was launched in May 2012 with funding support from The Movember Foundation. The pilot program aimed to trial a best practice model for providing specialist nursing care to those affected by prostate cancer. Prostate cancer specialist nurses were allocated to 12 hospitals across all Australian states and territories to work in the context of multidisciplinary care. The Prostate Cancer Foundation provided professional development support for nurses through a structured program. This article presents key outcomes from the research commissioned by the Prostate Cancer Foundation to evaluate the prostate cancer specialist nurse role. Specifically, the paper reports evaluation data relating to the roles and functions of the prostate cancer specialist nurse to explore the influence of the role on outcomes for patients, carers and services.

Uzbekistan Supplementary NGO Report on the Implementation of the Convention on the Rights of the Child in the Republic of Uzbekistan

[Excerpt] The Convention on the Rights of the Child (CRC) was one of the first international instruments to which the Republic of Uzbekistan acceded, and with parliamentary ratification on 9 December 1992, the Republic of Uzbekistan entered into a commitment to observe all the provisions of the CRC and to shoulder its responsibility before the international community. As a result various legislative, administrative and other steps have been taken by the government of the Republic of Uzbekistan with a view to bringing the State policy and legislation on children to be in line with the provisions as enshrined in the Convention on the Rights of the Child. The Constitution incorporates the fundamental provisions of the Universal Declaration of Human Rights. At the current stage in the restructuring of the country’s social and economic development, solid foundations have been laid for the conduct of significant democratic reforms based on a recognition of the innate worth of the individual (including the child) and of the unconditional respect of his or her rights and freedoms. Until recently, the State acted as the main guarantor of the provision of all social services, however the process of the transition (political/economic) to a market economy has entailed the development of new economic relations with a reduction in the allocation of state resources for the provision of social services to children. The efforts of the government made so far to bring the state policy and legislation on the child to be in line with the provisions enshrined in the convention on the rights of the child are commendable; never the less, the implementations of all these policies and laws into practice needs a lot to desire as there are a number of ongoing child rights violations. The National Report has fundamentally overlooked a number of child rights privileges enshrined in the CRC that have not yet been realised, or those rights that have been eroded since the independence. These shortcomings need to be noted for consideration so that the state steps up its efforts to enact new laws and/or to enforce the existing rules and regulations required for the protection and implementation of these child rights, and to improve the overall situation for children in the Republic of Uzbekistan.

EMS in the pastoral industries of western Queensland: From customisation to implementation

This paper outlines the customisation of Environmental Management Systems (EMS) for the pastoral industry of western Queensland, the recruitment and training of pastoral producers, and their development and implementation of EMS. EMS was simplified to a 7-step process and producers were recruited to trial this customised EMS. Producers from 40 properties received EMS training, either as groups or individually. Of these, 37 commenced Pastoral EMS development through a facilitated approach that allowed them to learn about EMS while developing an EMS for their property. EMS implementation has been more effective with producers who were trained in groups. At this stage, however, most producers do not see value in EMS as there are currently no strong drivers to warrant continued development and implementation. Key findings resulting from this work were that personal contact and assistance is vital to encourage producers to trial EMS, and that a staged approach to EMS implementation, commencing with a self-assessment, is recommended. EMS training is most successful in a group situation; however, an alternative method of delivery should be provided for those producers who, either by choice or isolation, have to work alone. A support network is also necessary to encourage and maintain progress with EMS development and implementation, particularly where no strong drivers exist.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Implementation of a modified CVSD coder

This paper describes the implementation of the modified continuously variable slope delta modulator (MCVSD), in which the basic step size δ0 is made to vary as a function of input signal level. The information needed to carry out this is extracted at the local decoder output so that the coder and the decoder track each other. The result is a significant improvement in the dynamic range (about 15dB) as compared to CVSD coder without degrading the peak signal to noise ratio.