Topics in the Chemistry of Main-Group and Transitional-Metal Fluorides

Phosphnylamines, Cl2P(O)NHR (R = Me, Et and Ph) , were obtained by the reaction of amine hydrochlorides, RNH2. HCl,, with phosphoryl chloride, P(O)Cl3. Fluorination of these derivatives by sodium fluoride produced the compounds F2P(O)NHR. Bis(dichlorophosphinyl)amines, [Cl2P(O)]2NR, and their fluoro- derivatives were synthesised by the condensation of the phosphinylamines with phosphoryl halides, P(O)FnCl3-n, in the presence of a tertiary amine. The difluoro- derivative. [FClP(O)]2Me, was obtained as a mixture of diastereoisomers from the reaction of heptamethyldisilazane, (Me3Si)2NMe, with P(O)FCl2. Attempts to synthesise the difluoro-compounds, Cl2P(O)NRP(O)F2, from F2P(O)NHR and P(O)Cl3 resulted in the formation of impure products. Possible reasons for this are discussed. The trifluoro- compounds, F2 P(O)NRP(O)FCl, were not prepared. 1H, 19F and 31P n. m. r. data are given for the diphosphinylamines synthesised, together with their infrared and mass spectra. The spectra are compared with those obtained from the phosphinylamines. Heptamethyldisilazane, (Me3Si)2NMe, and tungsten hexafluoride, WF6, reacted in the absence of a solvent to produce a white solid formulated as WF4 NMe and in the presence of MeCN to produce the complex WF4NMe.HeCN. The coordinated MeCN could be displaced by C5H5N (py) forming the complex WF4NMe. py. The adducts were characterised by elemental analyses and by n. m. r. and mass spectroscopy. Their spectra, together with those of WF4NMe.CD3CN and WF4NMe.C5D5N, are presented and discussed. Possible structures for both WF4NMe and WF4NMe. MeCN are suggested. A preliminary investigation into the chemistry of WF4NMe.MeCM showed that the fluorine atoms could be replaced but that the compound did not react with SF5Cl, SO2 or CS2. Hexamethyldisilazane, (Me3Si)2NH, and WF6 reacted in the presence of MeCN to produce a solid whose elemental analysis, infrared and n. m. r. spectra suggest that it has the composition NH4+WOF5- .MeCN. A reaction carried out between MoF6 and (Me3Si)2NMe in MeCN suggests that NoF6 reacts in a manner similar to that described for WF6 but that the reaction products are more susceptible to hydrolysis. Sulphur chloride pentafluoride, SF5-Cl, reacted exothermically with the chlorophosphines PhPCl2 and Ph2PCl to produce the corresponding fluorophosphoranes PhPF4 and Ph2PF3 along with SCl2 and Cl2. When SF5Cl reacted with MePCI2, although the phosphorane MePF4 was formed, the major product was a white solid which analysed as CH2 3Cl5 FP but which was not further characterised. The reactions between SF5Cl and the halogen free derivatives P(NMe2)3 and P(OMe)3 produced SF4, Cl2 and other products which were not completely identified but for which structures are suggested. SF5Cl did not react with either PPh3 or PCl3. Reaction schemes for these oxidative fluorinations by SF5Cl are presented and discussed. A detailed analysis of the vibrational spectra of CF3SF4Cl was carried out. This confirmed the evidence from n. m. r. spectroscopy that only the trans isomer of the compound is obtained from the synthesis involving CF3SF3, Cl2 and CsF. The infrared and Raman spectra of other substituted derivatives of SF6, CF3,SF4, CF2CF2Cl, SF5CF2CF2Cl and SF5CH=CH are presented and discussed

The Development of a Student Focused Model for Transition to University

The transition to university is a well recognised challenge, especially for non-traditional students. This paper presents a student-focused model for the transition to university, developed through an extensive literature review, discussions with a range of professionals nationally and internationally, and first year teaching practice. The model was applied to the development of a range of strategies to be implemented at one institution. The use of the model may facilitate the development of a university-wide approach to the issues of student transition to university and the first year in higher education experience. The model will allow a balanced approach to be developed

First year experience (FYE): International students’ experiences

International students confront a range of challenges during their transition to living and studying in Australia. Despite these challenges over 80% of international students reported high satisfaction with their life and study within Australia. This qualitative study reports on the experiences of 53 first year international students at ECU. Participants were students from across a range of study areas who responded to an online or face to face survey. Participants were required to respond to four questions which were analysed thematically to provide a summary of their experiences. Survey questions included their positive and negative experiences of being a first year student at ECU and changes that they suggested be considered by the university. Thematic analysis revealed a range of issues, most of which were reflected in previous research, however a range of ECU specific issues were also revealed, for example, resources and timetabling. This introductory research has provided initial data for developing future research. The cognitive nature of the survey may have limited the responses of participants. It is recommended that future research consider interviews with international students to review social and emotional issues

Short-term losses and long-term gains: the non-native species Austrominius modestus in Lough Hyne Marine Nature Reserve

The non-native barnacle species Austrominius modestus was first recorded in Ireland, close to Lough Hyne marine nature reserve in 1957. This species was not recorded inside the Lough until 1980, but by 2001 was the dominant intertidal barnacle within the reserve. It has been suggested that increases in the abundance of this species at other locations in Europe may be linked to increasing sea surface temperatures, and that A. modestus is an “ecological sleeper”. Despite an overall trend for increasing sea surface temperatures, this long term warming is punctuated by extreme events such as severely cold winters. A. modestus is warm water adapted, and has been recorded to decrease in abundance following cold winters. The winters of 2009/2010 and 2010/2011 were amongst the coldest recorded in Ireland in past decades. In the present study, higher levels of mortality were recorded for A. modestus than native barnacle species in Lough Hyne following these cold winters. Additionally, this species was recorded at lower abundances at the majority of sites surveyed in Lough Hyne in 2011 compared with 2009. Despite this, A. modestus remains the dominant barnacle species in the Lough and monitoring the recruitment of intertidal barnacles within Lough Hyne during 2014e2015 revealed that A. modestus was the most abundant recruit at study sites, both in removal plots and in the pre-existing community. The year-round breeding of A. modestus in addition to the closed nature of the Lough promotes A. modestus within the reserve. Despite this, native barnacle species continue to persist in Lough Hyne, though generally at low abundances, with the exception of exposed locations such as the Rapids and Bullock Island where natives outnumber A. modestus. The future intertidal barnacle community within the Lough is likely to be dominated by A. modestus with Chthamalus montagui and C. stellatus being abundant at sites which are not suitable for A. modestus. While the consequences of this are unknown, it is possible that the presence of A. modestus may alter trophic interactions and energy flow within the reserve

“A very orderly retreat”: Democratic transition in East Germany, 1989-90

East Germany's 1989-90 democratisation is among the best known of East European transitions, but does not lend itself to comparative analysis, due to the singular way in which political reform and democratic consolidation were subsumed by Germany's unification process. Yet aspects of East Germany's democratisation have proved amenable to comparative approaches. This article reviews the comparative literature that refers to East Germany, and finds a schism between those who designate East Germany's transition “regime collapse” and others who contend that it exemplifies “transition through extrication”. It inquires into the merits of each position and finds in favour of the latter. Drawing on primary and secondary literature, as well as archival and interview sources, it portrays a communist elite that was, to a large extent, prepared to adapt to changing circumstances and capable of learning from “reference states” such as Poland. Although East Germany was the Soviet state in which the positions of existing elites were most threatened by democratic transition, here too a surprising number succeeded in maintaining their position while filing across the bridge to market society. A concluding section outlines the alchemy through which their bureaucratic power was transmuted into property and influence in the “new Germany”

Cases before Australian Courts and Tribunals concerning Questions of Public International Law 2022

The Sydney Centre for International Law (SCIL), within the University of Sydney Law School, was established in 2003 as a centre of excellence in research and teaching in international law. Each year, the Centre’s interns prepare an article for the Australian Year Book of International Law about the role of international law in Australian courts, under supervision of SCIL staff. This year's article reviews decisions made in 2022 by select federal courts (the High Court of Australia, Federal Court of Australia, and newly created Federal Circuit and Family Court of Australia), along with the state and territory supreme and appeal courts, in which international law played a part

Pan-Cancer Analysis of lncRNA Regulation Supports Their Targeting of Cancer Genes in Each Tumor Context

Long noncoding RNAs (lncRNAs) are commonly dys-regulated in tumors, but only a handful are known toplay pathophysiological roles in cancer. We inferredlncRNAs that dysregulate cancer pathways, onco-genes, and tumor suppressors (cancer genes) bymodeling their effects on the activity of transcriptionfactors, RNA-binding proteins, and microRNAs in5,185 TCGA tumors and 1,019 ENCODE assays.Our predictions included hundreds of candidateonco- and tumor-suppressor lncRNAs (cancerlncRNAs) whose somatic alterations account for thedysregulation of dozens of cancer genes and path-ways in each of 14 tumor contexts. To demonstrateproof of concept, we showed that perturbations tar-geting OIP5-AS1 (an inferred tumor suppressor) andTUG1 and WT1-AS (inferred onco-lncRNAs) dysre-gulated cancer genes and altered proliferation ofbreast and gynecologic cancer cells. Our analysis in-dicates that, although most lncRNAs are dysregu-lated in a tumor-specific manner, some, includingOIP5-AS1, TUG1, NEAT1, MEG3, and TSIX, synergis-tically dysregulate cancer pathways in multiple tumorcontexts

Pan-cancer Alterations of the MYC Oncogene and Its Proximal Network across the Cancer Genome Atlas

Although theMYConcogene has been implicated incancer, a systematic assessment of alterations ofMYC, related transcription factors, and co-regulatoryproteins, forming the proximal MYC network (PMN),across human cancers is lacking. Using computa-tional approaches, we define genomic and proteo-mic features associated with MYC and the PMNacross the 33 cancers of The Cancer Genome Atlas.Pan-cancer, 28% of all samples had at least one ofthe MYC paralogs amplified. In contrast, the MYCantagonists MGA and MNT were the most frequentlymutated or deleted members, proposing a roleas tumor suppressors.MYCalterations were mutu-ally exclusive withPIK3CA,PTEN,APC,orBRAFalterations, suggesting that MYC is a distinct onco-genic driver. Expression analysis revealed MYC-associated pathways in tumor subtypes, such asimmune response and growth factor signaling; chro-matin, translation, and DNA replication/repair wereconserved pan-cancer. This analysis reveals insightsinto MYC biology and is a reference for biomarkersand therapeutics for cancers with alterations ofMYC or the PMN

Genomic, Pathway Network, and Immunologic Features Distinguishing Squamous Carcinomas

This integrated, multiplatform PanCancer Atlas study co-mapped and identified distinguishing molecular features of squamous cell carcinomas (SCCs) from five sites associated with smokin