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.

Drama, storymaking and iPads in the early years

In this chapter we consider how the iPad and selected applications such as Draw and Tell (Duck Duck Moose, 2013), Popplet (Notion Inc., 2013) and Puppet Pals (Polished Play LLC, 2013) can assist children in collaborative storying, retelling and sequencing story moments that can assist young children in their acquisition of oracy and their understanding of the world, both real and imagined, and their personal relationships. The data gathered from the project will also analysed through the lense of “critical and creative thinking” (ACARA, 2013, p.20-21) skills articulated as one of the general capabilities required in all subject areas of the Australian national curriculum, but which has particular application to The Arts subject areas. In this chapter, we consider artefacts created by preschool children using iPads and selected apps and interviews conducted with preschool children and their caregivers during our research project. We then offer examples of practice to assist preschool teachers in supporting children in their storymaking using the iPad and discuss approaches for engagement that twins the live and mediatised representation of a story.

Gone Girl and the mediatization of crime

Gone Girl (David Fincher, 2014) will not be remembered for its representation of journalists, although both lead characters are, as the narrative opens in 2012, magazine writers made redundant in the wake of the 2008 global financial crisis. To this extent they personify the “death of journalism” narrative of recent years in the United States, but we never see them in a newsroom or doing journalistic work. The marriage of Nick and Amy Dunne (Ben Affleck and Rosamund Pike) is cast as a victim of, among other things, the downturn in the US economy which accompanied the credit crunch. But this is not the subject of Gone Girl, so much as a context for the marital dysfunctionality at the heart of its plot...

Working the iceberg : a staffroom morality play

This play comes from a research project about how teachers understand and sustain their work in challenging secondary school classrooms. The research asked “How DO teachers work in these classrooms?” not “How SHOULD they?” In the play you meet three teachers who speak candidly about their principles, priorities and vulnerabilities to a pre-service teacher as they move between classes and staffroom. These are real people, real quotes and real feelings taken from real interview data, not idealised guidelines for ‘best practice’. Rather than templates for practice, the play offers a variety of models, issues and food for thought to discuss in teacher education programs. The project was interested in the moral dynamics of classrooms created under the Council of Australian Governments’ 2009 Compact with Young Australians, a policy move that required students to be ‘earning or learning till 17’ across all Australian states. By removing the unemployment benefit for this age group, and tying school attendance to family welfare entitlements, these policies effectively raised the minimum school-leaving age. The risk in this well-intended policy move is that a lack of suitable job opportunities will keep young people at school longer than they want to be there. The effects of this ‘earning or learning’ policy will impact some communities, schools and classrooms much harder than others. The title uses the metaphor of an iceberg to refer to the complex community-school relations that lie below classroom interactions. The idea of a morality play in the play’s title refers back to a medieval form of popular play that used characters to instruct the audience in virtues and values. In the same way, this play seeks to bring to the surface and embody the different moral principles that can inform teacher’s work. The research involved classroom ethnographies of classes for 16 to 17 years olds in non-academic pathways. Eight different teacher/ class combinations were sampled across 2 high schools, 2 TAFE colleges and I hybrid TAFE/school program in three towns experiencing chronic youth unemployment. Their timetabled lessons were observed across 3 to 4 weeks and the teachers and some students were interviewed in each site. The project was funded by an ARC Discovery Early Career Award, 2012-214.

Black comedy : the ABC makes bold foray into race relations

ABC’s new Indigenous sketch show Black Comedy, which premiered last night, is touted as a “show by blackfellas … for everyone”. As a blackfella, I’m not sure I agree that it is for “everyone” but that’s precisely why I love it. It’s been over 40 years since Basically Black, the first Indigenous sketch show aired on our screens, and it’s been too long a wait to see our mob doing humour our way in our living rooms once again. The characters we met last night were, as promised, bigger and blacker than ever. When it comes to Australian television … well it’s about time.

News via Voldemort: Parody accounts in topical discussions on Twitter

Parody accounts are prevalent on Twitter, offering irreverent interpretations of public figures, fictional characters and more. These accounts post comments framed within the context of their fictional universes or stereotypes of their subjects, responding in-character to topical events. This article positions parody accounts as a ritualised social media practice, an extension of fan practices and irreverent Internet culture. By providing a typology of parody accounts and analysing the topicality of selected parody accounts’ tweets, the research examines how these accounts contribute to topical discussions. In-character framing of topical comments allows parody accounts to offer original interpretations of breaking news that receive more attention than their other tweets. The presence and longevity of parody accounts underline the importance of humour on social media, including within news and topical coverage.

Epigenetic modelling

The field of epigenetics looks at changes in the chromosomal structure that affect gene expression without altering DNA sequence. A large-scale modelling project to better understand these mechanisms is gaining momentum. Early advances in genetics led to the all-genetic paradigm: phenotype (an organism's characteristics/behaviour) is determined by genotype (its genetic make-up). This was later amended and expressed by the well-known formula P = G + E, encompassing the notion that the visible characteristics of a living organism (the phenotype, P) is a combination of hereditary genetic factors (the genotype, G) and environmental factors (E). However, this method fails to explain why in diseases such as schizophrenia we still observe differences between identical twins. Furthermore, the identification of environmental factors (such as smoking and air quality for lung cancer) is relatively rare. The formula also fails to explain cell differentiation from a single fertilized cell. In the wake of early work by Waddington, more recent results have emphasized that the expression of the genotype can be altered without any change in the DNA sequence. This phenomenon has been tagged as epigenetics. To form the chromosome, DNA strands roll over nucleosomes, which are a cluster of nine proteins (histones), as detailed in Figure 1. Epigenetic mechanisms involve inherited alterations in these two structures, eg through attachment of a functional group to the amino acids (methyl, acetyl and phosphate). These 'stable alterations' arise during development and cell proliferation and persist through cell division. While information within the genetic material is not changed, instructions for its assembly and interpretation may be. Modelling this new paradigm, P = G + E + EpiG, is the object of our study.

The Reef Cycle: Paradise; Paradise Plundered; Paradise Preserved by people Power

This is a musical theatre production with an environmental message addressing a Queensland, Australia tussle between the development of the Galilee Coal Basin and the potential threat to the health of the Great Barrier Reef along the Queensland coast. The drama is enacted by characters representing "goodies" and "baddies" and includes epic poetry, dance, orchestra and drama. The whole performance is enacted in the midst of a post graduate student art exhibition with a coral and coal theme.

The Ex/centric fixations project # 2 - Memory, language and polyvocal performative writing

In this paper, Bree Hadley discusses The Ex/centric Fixations Project, a practice-led research project which explores the inadequacy of language as a technology for expressing human experiences of difference, discrimination or marginalisation within mainstream cultures. The project asks questions about the way experience, memory and the public discourses available to express them are bound together, about the silences, failures and falsehoods embedded in any effort to convey human experience via public discourses, and about how these failures might form the basis of a performative writing method. It has, to date, focused on developing a method that expresses experience through improvised, intertextual and discontinous collages of language drawn from a variety of public discourses. Aesthetically, this method works with what Hans Theis Lehmann (Postdramatic Theatre p. 17) calls a “textual variant” of the postdramatic “in which language appears not as the speech of characters – if there are still definable characters at all – but as an autonomous theatricality” (Ibid. 18). It is defined by what Lehmann, following Julia Kristeva, calls a “polylogue”, which presents experience as a conflicted, discontinuous and circular phenomenon, akin to a musical fugue, to break away from “an order centred on one logos” (Ibid. 32). The texts function simultaneously as a series of parts, and as wholes, interwoven voices seeming almost to connect, almost to respond to each other, and almost to tell – or challenging each other’s telling – of a story. In this paper, Hadley offers a performative demonstration, together with descriptions of the way spectators respond, including the way their playful, polyvocal texture impacts on engagement, and the way the presence or non-presence of performing bodies to which the experiences depicted can be attached impacts on engagement. She suggests that the improvised, intertextual and experimental enactments of self embodied in the texts encourage spectators to engage at an emotional level, and make-meaning based primarily on memories they recall in the moment, and thus has the potential to counter the risk that people may read depictions of experiences radically different from their own in reductive, essentialised ways.

Social media, audiences, and audience co-creativity in contemporary performance: Restoring balance?

Producers, technicians, performers, audiences and critics are all critical components of the performing arts ecology – critical components of an ecosystem that have to come together into some sort of productive relationship if the performing arts are to be vital, viable and successful. Different performance practices developed in different times, spaces and places do, of course, connect these players in different ways as part of their attempt to achieve their own definition of success, be it based on entertainment, educational, expression, empowerment, or something else. In some contemporary performance practices, social media platforms, applications and processes are seen to have significant potential to restore balance to the relationship between performer and audience, providing audiences with more power to participate in a performance event. In this paper, I investigate prevailing assumptions about social media’s power to democratise performance practice, or, at least, develop more co-creative performance practices in which producers, performers and audiences participate actively before, during and after the event. I focus, in particular, on the use of social media as a means of developing a participatory aesthetic in which an audience member is asked to contribute to the cast of characters, plot or progression of a performance. Although diverse – from performances streamed online, to performances that offer transmedia components the audience can use to learn more about character, context and plot online, to performances that incorporate online voting, liking or linking, to performances that unfold fully online on websites, blogs, microblogs or other social media platforms – what a lot of uses of social media in contemporary performance today share is a desire to encourage audiences to reflect on their role in making, and making meaning, of the event. In this paper I interrogate if, and if so how, this democratises or develops deeper levels of co-creativity in the relationship between producers, performers and audiences.

Foliar micromorphology and anatomy of Ugni molinae Turcz. (Myrtaceae), with particular reference to schizogenous secretory cavities

Background Ugni molinae Turcz. is one of the most studied species of South American Myrtaceae due to its edible fruits and foliar medicinal compounds. However, there is no anatomical study of the leaves or secretory cavities. This paper seeks to describe the leaf micromorphology and anatomy of the species using standard protocols for light and scanning electron microscopy. Secretory cavities were anatomically characterized in young and mature leaves. Histochemical staining of the cavities was performed. Results The leaves of U. molinae are hypostomatic, have a wavy surface and possess scattered hairs. Leaf anatomical features include dorsiventral mesophyll, two to three layers of palisade parenchyma with abundant chloroplasts, calcium oxalate crystals and internal phloem in vascular bundles. Schizogenous secretory cavities are present on the abaxial surface and are mainly located on the margins of the leaves. Histochemical tests of these cavities suggest the presence of lipophilic substances. Conclusions This is the first study of secretory cavities in Chilean Myrtaceae. In general, micromorphological and anatomical characters are similar to other species of the family. The present findings could provide valuable anatomical information for future research in South American Myrtaceae.

The impact of simulated astigmatism on functional measures of visual performance

Uncorrected refractive error, including astigmatism, is a leading cause of reversible visual impairment. While the ability to perform vision-related daily activities is reduced when people are not optimally corrected, only limited research has investigated the impact of uncorrected astigmatism. Given the capacity to perform vision-related daily activities involves integration of a range of visual and cognitive cues, this research examined the impact of simulated astigmatism on visual tasks that also involved cognitive input. The research also examined whether the higher levels of complexity inherent in Chinese characters makes them more susceptible to the effects of astigmatism. The effects of different powers of astigmatism, as well as astigmatism at different axes were investigated in order to determine the minimum level of astigmatism that resulted in a decrement in visual performance.

Leaf micromorphology and anatomy of Myrceugenia rufa (Myrtaceae): An endemic coastal shrub of north-central Chile

Species of fleshy-fruited Myrtaceae are generally associated with humid environments and their vegetative anatomy is mainly mesophytic. Myrceugenia rufa is an endemic and rare species from arid zones of the coast of central Chile and there are no anatomical studies regarding its leaf anatomy and environmental adaptations. Here we describe the leaf micromorphology and anatomy of the species using standard protocols for light and scanning electron microscopy. The leaf anatomy of M. rufa matches that of other Myrtaceae, such as presence of druses, schizogenous secretory ducts and internal phloem. Leaves of M. rufa exhibit a double epidermis, thick cuticle, abundant unicellular hairs, large substomatal chambers covered by trichomes and a dense palisade parenchyma. Leaf characters of M. rufa confirm an anatomical adaptation to xerophytic environments.

Micromorphology and anatomy of leaves of Syzygium floribundum (Myrtaceae: Syzygieae), a rainforest tree endemic to eastern Australia

Although species of Syzygium are abundant components of the rainforests in Queensland and New South Wales, little is known about the anatomy of the Australian taxa. Here we describe the foliar anatomy and micromorphology of Syzygium floribundum (syn: Waterhousea floribunda) using standard protocols for scanning electron microscopy (SEM) and light microscopy. Syzygium floribundum possesses dorsiventral leaves with cyclo-staurocytic stomata, single epidermis, internal phloem, rhombus-shaped calcium oxalate crystals and complex-open midrib. In general, leaf anatomical and micromorphological characters are common with some species of the tribe Syzygieae. However, this particular combination of leaf characters has not been reported in a species of the genus. The anatomy of the species is typical of mesophytic taxa.

Free Sherlock: The copyright battle of Baker Street

Sherlock Holmes faces his greatest challenge – since his fight to the death with Professor James Moriarty at Reichenbach Falls. Who owns Sherlock Holmes, the world’s greatest detective? Is it the estate of Sir Arthur Conan Doyle? Or the mysterious socialite Andrea Plunket? Or does Sherlock Holmes belong to the public? This is the question currently being debated in copyright litigation in the United States courts, raising larger questions about copyright law and the public domain, the ownership of literary characters, and the role of sequels, adaptations, and mash-ups.