Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

An infinite level atom coupled to a heat bath

Wir untersuchen die Mathematik endlicher, an ein Wärmebad gekoppelter Teilchensysteme. Das Standard-Modell der Quantenelektrodynamik für Temperatur Null liefert einen Hamilton-Operator H, der die Energie von Teilchen beschreibt, welche mit Photonen wechselwirken. Im Heisenbergbild ist die Zeitevolution des physikalischen Systems durch die Wirkung einer Ein-Parameter-Gruppe auf eine Menge von Observablen A gegeben: Diese steht im Zusammenhang mit der Lösung der Schrödinger-Gleichung für H. Um Zustände von A, welche das physikalische System in der Nähe des thermischen Gleichgewichts zur Temperatur T darstellen, zu beschreiben, folgen wir dem Ansatz von Jaksic und Pillet, eine Darstellung von A zu konstruieren. Die Vektoren in dieser Darstellung definieren die Zustände, die Zeitentwicklung wird mit Hilfe des Standard Liouville-Operators L beschrieben. In dieser Doktorarbeit werden folgende Resultate bewiesen bzw. hergeleitet: - die Konstuktion einer Darstellung - die Selbstadjungiertheit des Standard Liouville-Operators - die Existenz eines Gleichgewichtszustandes in dieser Darstellung - der Limes des physikalischen Systems für große Zeiten.

A structured return to the 'Fourth Estate': interviews and inquiry that challenge entrenched authorities' 'knowledge'

Contemporary debates on the role of journalism in society are continuing the tradition of downplaying the role of proactive journalism - generally situated under the catchphrase of the Fourth Estate - in public policy making. This paper puts the case for the retention of a notion of a proactive form of journalism which can be broadly described as "investigative ", because it is important to the public policy process in modern democracies. It argues that critiques that downplay the potential of this form of journalism are flawed and overly deterministic. Finally. it seeks to illustrate how journalists can proactively inquire in ways that are relevant to the lives ofpeople in a range of settings, and that question elite sources in the interests ofthose people.

Optimal-stopping control for airborne collision avoidance and return-to-course flight

This paper considers an aircraft collision avoidance design problem that also incorporates design of the aircraft’s return-to-course flight. This control design problem is formulated as a non-linear optimal-stopping control problem; a formulation that does not require a prior knowledge of time taken to perform the avoidance and return-to-course manoeuvre. A dynamic programming solution to the avoidance and return-to-course problem is presented, before a Markov chain numerical approximation technique is described. Simulation results are presented that illustrate the proposed collision avoidance and return-to-course flight approach.

Should athletes return to sport after applying Ice? A systematic review of the effect of local 3 cooling on functional performance

Applying ice or other forms of topical cooling is a popular method of treating sports injuries. It is commonplace for athletes to return to competitive activity, shortly or immediately after the application of a cold treatment. In this article, we examine the effect of local tissue cooling on outcomes relating to functional performance and to discuss their relevance to the sporting environment. A computerized literature search, citation tracking and hand search was performed up to April, 2011. Eligible studies were trials involving healthy human participants, describing the effects of cooling on outcomes relating to functional performance. Two reviewers independently assessed the validity of included trials and calculated effect sizes. Thirty five trials met the inclusion criteria; all had a high risk of bias. The mean sample size was 19. Meta-analyses were not undertaken due to clinical heterogeneity. The majority of studies used cooling durations >20 minutes. Strength (peak torque/force) was reported by 25 studies with approximately 75% recording a decrease in strength immediately following cooling. There was evidence from six studies that cooling adversely affected speed, power and agility-based running tasks; two studies found this was negated with a short rewarming period. There was conflicting evidence on the effect of cooling on isolated muscular endurance. A small number of studies found that cooling decreased upper limb dexterity and accuracy. The current evidence base suggests that athletes will probably be at a performance disadvantage if they return to activity immediately after cooling. This is based on cooling for longer than 20 minutes, which may exceed the durations employed in some sporting environments. In addition, some of the reported changes were clinically small and may only be relevant in elite sport. Until better evidence is available, practitioners should use short cooling applications and/or undertake a progressive warm up prior to returning to play.

Choosing work and care : four Australian women negotiating return to paid work in the first year of motherhood

Australian women make decisions about return to paid work and care for their child within a policy environment that presents mixed messages about maternal employment and child care standards. Against this background an investigation of first-time mothers’ decision-making about workforce participation and child care was undertaken. Four women were studied from pregnancy through the first postnatal year using interview and diary methods. Inductive analyses identified three themes, all focused on dimensions of family security: financial security relating to family income, emotional security relating to child care quality, and pragmatic security relating to child care access. The current policy changes that aim to increase child care quality standards in Australia present a positive step toward alleviating family insecurities but are insufficient to alleviate the evidently high levels of tension between workforce participation and family life experienced by women transitioning back into the workforce in Australia.

The Working After Cancer Study (WACS): a population-based study of middle-aged workers diagnosed with colorectal cancer and their return to work experiences

Background The number of middle-aged working individuals being diagnosed with cancer is increasing and so too will disruptions to their employment. The aim of the Working After Cancer Study is to examine the changes to work participation in the 12 months following a diagnosis of primary colorectal cancer. The study will identify barriers to work resumption, describe limitations on workforce participation, and evaluate the influence of these factors on health-related quality of life. Methods/Design An observational population-based study has been designed involving 260 adults newly-diagnosed with colorectal cancer between January 2010 and September 2011 and who were in paid employment at the time they were diagnosed. These cancer cases will be compared to a nationally representative comparison group of 520 adults with no history of cancer from the general population. Eligible cases will have a histologically confirmed diagnosis of colorectal cancer and will be identified through the Queensland Cancer Registry. Data on the comparison group will be drawn from the Household, Income and Labour Dynamics in Australia (HILDA) Survey. Data collection for the cancer group will occur at 6 and 12 months after diagnosis, with work questions also asked about the time of diagnosis, while retrospective data on the comparison group will be come from HILDA Waves 2009 and 2010. Using validated instruments administered via telephone and postal surveys, data will be collected on socio-demographic factors, work status and circumstances, and health-related quality of life (HRQoL) for both groups while the cases will have additional data collected on cancer treatment and symptoms, work productivity and cancer-related HRQoL. Primary outcomes include change in work participation at 12 months, time to work re-entry, work limitations and change in HRQoL status. Discussion This study will address the reasons for work cessation after cancer, the mechanisms people use to remain working and existing workplace support structures and the implications for individuals, families and workplaces. It may also provide key information for governments on productivity losses.

Can a “Blue Sky” return to Indian megacities?

Deterioration of air quality in Indian megacities (Delhi, Mumbai or Kolkata) is much more significant than that observed in the megacities of developed countries. Densely packed high-rise buildings restrict the self-cleaning capabilities of Indian megacities. Also, the ever growing number of on-road vehicles, resuspension of the dust, and anthropogenic activities exacerbate the levels of ambient air pollution, which is in turn breathed by urban dwellers. Pollution levels exceeding the standards on a regular basis often result in a notable increase in morbidity and mortality. This article discusses the challenges faced by Indian megacities in their quest for sustainable growth, without compromising the air quality and urban way of life.

Keeping our nursing and midwifery workforce : factors that support non-practising clinicians to return to practice

BACKGROUND: Within Australia and internationally (Health Workforce Australia, 2012) an increasing and on-going nursing workforce shortage is documented. Recent international estimates indicate that there will be ongoing and significant gaps in the supply of a nursing workforce; the United Kingdom is predicted to have a reduction of 12.12% nurses over the coming eight years if a current 'steady state' is maintained (Buchan and Seacombe, 2011); Canada is predicted to have a shortage of 60,000 nurses by 2022 (Tomblin et al., 2012) with Australia's anticipated nursing shortage reported as over 90,000 by the year 2025 (Health Workforce Australia, 2012). Queensland Health in response to their tracked emerging nursing and midwifery workforce shortages developed a nursing and midwifery refresher programme to return registered staff back to the workforce. A study was undertaken between 2008 and 2010 to provide an understanding of how non-practising nurses and midwives maybe supported back into the workforce. METHODS: Programme applicants (444) were invited to respond to an on-line survey designed to understand what aspects of the programme supported their learning and ability to return to the workforce. This number represents those who applied but not all completed or commenced the programme. Descriptive statistics (Polit and Beck, 2008) were used to collate quantifiable survey responses and free text and unsolicited responses were themed. RESULTS: The survey received a 35.5% response rate (n=158) with a return of 20% of unsolicited comments in the form of e-mail responses which were included in the themed results. Key themes supporting participants' learning and ability to return to the workforce were: Respondents were 94% female and 6% male, with 37.7% >51 years of age. Child rearing was the foremost reason for female staff relinquishing workforce roles (36.6%). The primary reason for returning to the workforce was maintenance of registration (40.5%). Both theory and clinical placement components were seen by participants as contributing to their confidence to return to the health workforce. CONCLUSION: The Queensland Nursing and Midwifery Refresher Programs provided a structured programme for registered, non-practising nurses and midwives to return to the Queensland Health workforce. Responses indicated that clinical supervision and contract learning should be central to a return to workforce induction programme for registered but non-practising nurses and midwives. The majority of nurses and midwives returning to the workforce were approaching retirement age in 10-15 years.

A thermal expulsion approach to homogeneous large-volume methacrylate monolith preparation; enabling large-scale rapid purification of biomolecules

Numerous efforts have been dedicated to the synthesis of large-volume methacrylate monoliths for large-scale biomolecules purification but most were obstructed by the enormous release of exotherms during preparation, thereby introducing structural heterogeneity in the monolith pore system. A significant radial temperature gradient develops along the monolith thickness, reaching a terminal temperature that supersedes the maximum temperature required for structurally homogenous monoliths preparation. The enormous heat build-up is perceived to encompass the heat associated with initiator decomposition and the heat released from free radical-monomer and monomer-monomer interactions. The heat resulting from the initiator decomposition was expelled along with some gaseous fumes before commencing polymerization in a gradual addition fashion. Characteristics of 80 mL monolith prepared using this technique was compared with that of a similar monolith synthesized in a bulk polymerization mode. An extra similarity in the radial temperature profiles was observed for the monolith synthesized via the heat expulsion technique. A maximum radial temperature gradient of only 4.3°C was recorded at the center and 2.1°C at the monolith peripheral for the combined heat expulsion and gradual addition technique. The comparable radial temperature distributions obtained birthed identical pore size distributions at different radial points along the monolith thickness.

Equal shared parental responsibility and shared care post-return to Australia under the Hague Child Abduction Convention

This article explores the outcomes experienced by abducting primary carer mothers and their children post-return to Australia under the Hague Convention on Civil Aspects of International Child Abduction.1 The circumstances faced by families that experience international parental child abduction are examined by considering how part VII of the Australian Family Law Act 1975 (Cth) is applied to resolve parenting disputes post-return. At present, the statutory criteria found in part VII encourage an equal shared parental responsibility and shared care parenting approach.2 This emphasis aligns children’s best interests with collaborative parenting3 and their parents living within close geographical proximity of each other to facilitate the practicalities of the approach.4 Arguably, these statutory criteria guide the exercise of judicial discretion to determine a child’s best interests towards a parenting arrangement that is incompatible with the lifestyle and functional characteristics of these families.

A study of outcomes post-return to Australia under the Hague Child Abduction Convention for abducting primary-carer mothers and their children

This article reports the findings of an empirical study of outcomes experienced by abducting primary-carer mothers and their children post-return to Australia under the Hague Child Abduction Convention. The study specifically focused on legal and factual outcomes post-return to Australia as the child's habitual residence. The study contributes an original critique of the Convention's operation by examining the collective operation of Convention return proceedings and Pt VII proceedings under the Family Law Act 1975 (Cth) post-return. Convention return proceedings, and the resolution of the substantive parenting dispute post-return to Australia, are not distinct stages operating in isolation. Viewing them as such is a purely theoretical exercise divorced from the reality of the lives of transnational families. Arguably, a better measure of the Convention's success is the outcomes it produces as part of the entire system designed to address the contemporary problem of international parental child abduction. When a child is returned to Australia this system includes the operation of Australian family law.

Matter and movement: Expression as topological continuity or a return to Butades' wall

This paper aims to address the ways in which drawing can be understood as the becoming-expressive of materials, site, and body, over time. The discussion pivots around a series of studies that replace linear or causal relationships – in history, drawing and expression – with topological movement. My approach is largely through a speculative case study. In a rereading of the familiar Butades myth, I examine how a shadow tracing can variously be taken as the first mimetic art with its origins in the urge to “capture”, and, antithetically, as the originary expressive folding of matter, site and body. The paper is divided into five sections. The first presents the Butades myth, identifying the representational problem that lies at the roots of its traditional telling. The next three sections outline a series of topologies that facilitate a discussion of the Butades myth from historical, disciplinary, and expressive perspectives. The final section aims to show the relevance of this discussion to a contemporary drawing practice, using my own drawing research as a case study. The field of inquiry is that of representational critique. The fold, an image associated with a topological geometry, replaces the relational or signifying disjuncture of representational structures, and suggests a becoming- expressive of subject and object, form and matter.