Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands : synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F8), diphenylaminofluorenyl (NPh2- F8), or naphthalimidylfluorenyl (NI-F8) motifs on the bipyridyl or acetylide ligands (Pt-4−Pt-8), (i.e., {4,4′-bis[7-R1-F8-(≡)n-]bpy}Pt(7- R2-F8- ≡ -)2, where F8 = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′- bipyridine, Pt-4: R1 = R2 = BTZ, n = 0; Pt-5: R1 = BTZ, R2 = NI, n = 0; Pt-6: R1 = R2 = BTZ, n = 1; Pt-7: R1 = BTZ, R2 = NPh2, n = 1; Pt- 8: R1 = NPh2, R2 = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly 1π,π* transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially 1MLCT (metal-to-ligand charge transfer)/ 1LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some 1ILCT (intraligand charge transfer) transition for Pt-4−Pt-7, and predominantly 1ILCT transition admixing with minor 1MLCT/1LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the 1π,π* and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized 1π,π* fluorescence and 3MLCT/3LLCT phosphorescence in CH2Cl2, while Pt-5 manifests 1ILCT fluorescence and 3ILCT phosphorescence. However, only 1LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4−Pt-8 in CH3CN. Except for Pt-7 that contains NPh2 at the acetylide ligands, Pt-4−Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh2 on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.

Autologous human kidney proximal tubule epithelial cells (PTEC) modulate dendritic cell (DC), T cell and B cell responses

This is a comprehensive study of human kidney proximal tubular epithelial cells (PTEC) which are known to respond to and mediate the pathological process of a range of kidney diseases. It identifies various molecules expressed by PTEC and how these molecules participate in down-regulating the inflammatory process, thereby highlighting the clinical potential of these molecules to treat various kidney diseases. In the disease state, PTEC gain the ability to regulate the immune cell responses present within the interstitium. This down-regulation is a complex interaction of contact dependent/independent mechanisms involving various immuno-regulatory molecules including PD-L1, sHLA-G and IDO. The overall outcome of this down-regulation is suppressed DC maturation, decreased number of antibody producing B cells and low T cell responses. These manifestations within a clinical setting are expected to dampen the ongoing inflammation, preventing the damage caused to the kidney tissue.

The ‘state of play’ in Australia: Early childhood educators and play-based learning

This article provides an overview of the Education Meets Play study that will investigate early childhood educators’ use of play-based learning, now mandatory under the National Quality Standard. By building on what can be gleaned about educators’ approaches to play-based learning prior to the implementation of the Early Years Learning Framework, the study will contribute to the evidence base concerning the implementation and effects of Australia’s early childhood education and care policy reform initiatives.

Cell type-dependent, infection-induced, aberrant DNA methylation in gastric cancer

Epigenetic changes correspond to heritable modifications of the chromatin structure, which do not involve any alteration of the DNA sequence but nonetheless affect gene expression. These mechanisms play an important role in cell differentiation, but aberrant occurrences are also associated with a number of diseases, including cancer and neural development disorders. In particular, aberrant DNA methylation induced by H. Pylori has been found to be a significant risk factor in gastric cancer. To investigate the sensitivity of different genes and cell types to this infection, a computational model of methylation in gastric crypts is developed. In this article, we review existing results from physical experiments and outline their limitations, before presenting the computational model and investigating the influence of its parameters.

Experimental and numerical investigation of strain-rate dependent mechanical properties of single living cells

The objective of this project is to investigate the strain-rate dependent mechanical behaviour of single living cells using both experimental and numerical techniques. The results revealed that living cells behave as porohyperlastic materials and that both solid and fluid phases within the cells play important roles in their mechanical responses. The research reported in this thesis provides a better understanding of the mechanisms underlying the cellular responses to external mechanical loadings and of the process of mechanical signal transduction in living cells. It would help us to enhance knowledge of and insight into the role of mechanical forces in supporting tissue regeneration or degeneration.

Secular and religious moral grounds resonating across state schools in Indonesia

This paper describes moral education in Indonesia, more particularly, how teachers have implemented the Character Education policy issued by the Ministry of Education and Culture (MOEC) in 2010. This policy required teachers to instil certain values in every lesson, including EFL lessons, to contribute towards building a shared national moral character. Drawing on Durkheim's distinction between secular and religious morality, this paper considers how state schools accommodated and promoted this ‘rational moral education' or secular morality (Durkheim, 1925) in government schools, and how it interacted with religious moral education. This paper uses Bernstein's concepts of pedagogic discourse, instructional and regulative discourses to analyse how teachers have recontextualised this policy in the micro pedagogic settings of their EFL classes. Three types of data were collected for this study: interviews, class observations and teachers' lesson plans. In this way, four EFL teachers working in state schools were interviewed on two occasions and three of their classes were observed. The first interview identified teachers' beliefs and perceptions regarding the Character Education policy. Their classroom and lesson plans were observed to augment this information. Then the final interview asked about the teacher's thinking behind their actions in the observed classes. Since character education was issued within the broader frame of school based curriculum that offered schools and teachers more choices to develop the local curriculum and its intent, the analysis will focus on what moral premises were evident in their school and classes, and how such morality was transmitted through the EFL lessons. The conclusion suggests that teachers' implementation of moral education in their classes was dominated by their school communities and the teachers' own preferred value of religiosity. Such value played out in the classes through both the regulative discourse and the instructional discourse.

Structural and electronic properties of layered arsenic and antimony arsenide

Layered materials exhibit intriguing electronic characteristics and the search for new types of two-dimensional (2D) structures is of importance for future device fabrication. Using state-of-art first principle calculations, we identify and characterize the structural and electronic properties of two 2D layered arsenic materials, namely, arsenic and its alloy AsSb. The stable 2D structural configuration of arsenic is confirmed to be the low-buckled two-dimensional hexagonal structure by phonon and binding energy calculations. The monolayer exhibits indirect semiconducting properties with gap around 1.5 eV (corrected to 2.2 eV by hybrid function), which can be modulated into a direct semiconductor within a small amount of tensile strain. These semiconducting properties are preserved when cutting into 1D nanoribbons, but the band gap is edge dependent. It is interesting to find that an indirect to direct gap transition can be achieved under strain modulation of the armchair ribbon. Essentially the same phenomena can be found in layered AsSb, except a weak Rashba induced band splitting is present in AsSb due to the nonsymmetric structure and spin orbit coupling. When an additional layer is added on the top, a semiconductor–metal transition will occur. The findings here broaden the family of 2D materials beyond graphene and transition metal dichalcogenides and provide useful information for experimental fabrication of new layered materials with possible application in optoelectronics.

Estimating link-dependent origin-destination matrices from sample trajectories and traffic counts

In transport networks, Origin-Destination matrices (ODM) are classically estimated from road traffic counts whereas recent technologies grant also access to sample car trajectories. One example is the deployment in cities of Bluetooth scanners that measure the trajectories of Bluetooth equipped cars. Exploiting such sample trajectory information, the classical ODM estimation problem is here extended into a link-dependent ODM (LODM) one. This much larger size estimation problem is formulated here in a variational form as an inverse problem. We develop a convex optimization resolution algorithm that incorporates network constraints. We study the result of the proposed algorithm on simulated network traffic.

Evaluation of ANPR trials for traffic policing in Queensland. Report to the Queensland Police Service, State Traffic Support Branch

In response to the Travelsafe Committee Report No. 51 – report on the inquiry into Automatic Plate Recognition Technology – it was recommended that the Queensland Police Service continue to trial the deployment of ANPR technology for traffic enforcement work and to evaluate the road safety impacts and operational effectiveness of the technology. As such, the purpose of this report is to provide an independent evaluation of a trial of ANPR that was conducted by a project team within the State Traffic Support Branch of the Queensland Police Service (QPS) and provide recommendations as to the applicability and usability of the technology for use throughout Queensland...

Amygdala-dependent learning increases the number of spinophilin-immunoreactive dendritic spines in the lateral amygdala

During Pavlovian auditory fear conditioning a previously neutral auditory stimulus (CS) gains emotional significance through pairing with a noxious unconditioned stimulus (US). These associations are believed to be formed by way of plasticity at auditory input synapses on principal neurons in the lateral nucleus of the amygdala (LA). One proposed form of cellular plasticity involves structural changes in the number and morphology of dendritic spines...

Emergency pre-hospital disaster response training. What's the state of play?

Study/Objective This study examines the current state of disaster response education for Australian paramedics from a national and international perspective and identifies both potential gaps in content and challenges to the sustainability of knowledge acquired through occasional training. Background As demands for domestic and international disaster response increase, experience in the field has begun to challenge traditional assumptions that response to mass casualty events requires little specialist training. The need for a “streamlined process of safe medical team deployment into disaster regions”1 is generally accepted and, in Australia, the emergence of national humanitarian aid training has begun to respond to this gap. However, calls for a national framework for disaster health education2 haven’t received much traction. Methods A critical analysis of the peer reviewed and grey literature on the core components/competencies and training methods required to prepare Australian paramedics to contribute to effective health disaster response has been conducted. Research from the past 10 years has been examined along with federal and state policy with regard to paramedic disaster education. Results The literature shows that education and training for disaster response is variable and that an evidence based study specifically designed to outline sets of core competencies for Australian health care professionals has never been undertaken. While such competencies in disaster response have been developed for the American paradigm it is suggested that disaster response within the Australian context is somewhat different to that of the US, and therefore a gap in the current knowledge base exists. Conclusion Further research is needed to develop core competencies specific to Australian paramedics in order to standardise teaching in the area of health disaster management. Until this occurs the task of evaluating or creating disaster curricula that adequately prepares and maintains paramedics for an effective all hazards disaster response is seen as largely unattainable.

Role of rainfall and catchment characteristics on urban stormwater quality

Urbanisation significantly changes the characteristics of a catchment as natural areas are transformed to impervious surfaces such as roads, roofs and parking lots. The increased fraction of impervious surfaces leads to changes to the stormwater runoff characteristics, whilst a variety of anthropogenic activities common to urban areas generate a range of pollutants such as nutrients, solids and organic matter. These pollutants accumulate on catchment surfaces and are removed and trans- ported by stormwater runoff and thereby contribute pollutant loads to receiving waters. In summary, urbanisation influences the stormwater characteristics of a catchment, including hydrology and water quality. Due to the growing recognition that stormwater pollution is a significant environmental problem, the implementation of mitigation strategies to improve the quality of stormwater runoff is becoming increasingly common in urban areas. A scientifically robust stormwater quality treatment strategy is an essential requirement for effective urban stormwater management. The efficient design of treatment systems is closely dependent on the state of knowledge in relation to the primary factors influencing stormwater quality. In this regard, stormwater modelling outcomes provide designers with important guidance and datasets which significantly underpin the design of effective stormwater treatment systems. Therefore, the accuracy of modelling approaches and the reliability modelling outcomes are of particular concern. This book discusses the inherent complexity and key characteristics in the areas of urban hydrology and stormwater quality, based on the influence exerted by a range of rainfall and catchment characteristics. A comprehensive field sampling and testing programme in relation to pollutant build-up, an urban catchment monitoring programme in relation to stormwater quality and the outcomes from advanced statistical analyses provided the platform for the knowledge creation. Two case studies and two real-world applications are discussed to illustrate the translation of the knowledge created to practical use in relation to the role of rainfall and catchment characteristics on urban stormwater quality. An innovative rainfall classification based on stormwater quality was developed to support the effective and scientifically robust design of stormwater treatment systems. Underpinned by the rainfall classification methodology, a reliable approach for design rainfall selection is proposed in order to optimise stormwater treatment based on both, stormwater quality and quantity. This is a paradigm shift from the common approach where stormwater treatment systems are designed based solely on stormwater quantity data. Additionally, how pollutant build-up and stormwater runoff quality vary with a range of catchment characteristics was also investigated. Based on the study out- comes, it can be concluded that the use of only a limited number of catchment parameters such as land use and impervious surface percentage, as it is the case in current modelling approaches, could result in appreciable error in water quality estimation. Influential factors which should be incorporated into modelling in relation to catchment characteristics, should also include urban form and impervious surface area distribution. The knowledge created through the research investigations discussed in this monograph is expected to make a significant contribution to engineering practice such as hydrologic and stormwater quality modelling, stormwater treatment design and urban planning, as the study outcomes provide practical approaches and recommendations for urban stormwater quality enhancement. Furthermore, this monograph also demonstrates how fundamental knowledge of stormwater quality processes can be translated to provide guidance on engineering practice, the comprehensive application of multivariate data analyses techniques and a paradigm on integrative use of computer models and mathematical models to derive practical outcomes.