Synthesis of 3-stannyl and 3-silyl propargyl phosphanes and the formation of a phosphinoallene

The group 14 chloropropargyls R3ECCCH2Cl (R3E = Bu3Sn, Ph3Sn, Me2PhSi, iPr3Si, nPr3Si, nBu3Si), obtained by a modified literature procedure, react with LiPPh2 to afford the novel propargyl phosphanes Ph2PCH2CCER3 in high yield, as viscous oils; (Me3Si)2PCH2CCSiPhMe2 is similarly obtained from LiP(SiMe3)2. In contrast, the reaction of PhCCCH2MgCl with ClP(NEt2)2 fails to produce a comparable propargyl phosphane, but generates preferentially (>70%) the novel phosphinoallene (Et2N)2PC(Ph)=C=CH2, which is characterised spectroscopically, and through its reaction with HCl. The coordination chemistry of representative phosphanes is explored with respect to platinum and palladium for the first time

The development and chemistry of novel phosphacarbons and their derivatives

The exploration of low-coordinate phosphorus chemistry resulted in the synthesis of a range of novel phosphorus species which were duly characterised and subjected to extensive reactivity studies; potential applications and implications for the field are outlined. The group 14 chloropropargyls R3EC≡CCH2Cl (E = Si, Sn; R = nBu, Ph, Me2Ph, nPr, iPr) were prepared from HC≡CCH2Cl and the respective R3ECl. While attempts to convert R3EC≡CCH2Cl to R3EC≡CCH2PX2 (X = Cl, NEt2) via the Grignard reaction and addition of ClPX2 were unsuccessful, reactions with LiPR’2 effected conversion to group 14 propargylphosphines R3EC≡CCH2PR’2 (E = Si, Sn; R3 = nBu3, Ph3, Me2Ph, nPr3, iPr3; R’ = Ph, SiMe3). The addition of neat I2 to R3SiC≡CCH2P(SiMe3)2 afforded impure samples of R3SiC≡CCH2PI2 (R3 = Me2Ph, nPr3, nBu3) that could not be isolated from pentane solutions; attempts to convert R3SiC≡CCH2P(SiMe3)2 to R3SiC≡CC≡P with AgOTf and DABCO were unsuccessful. The synthesis of PhC≡CCH2PR’2 (R’ = Ph, SiMe3) was achieved by reaction with LiPR’2, while the Grignard reaction followed by addition to ClP(NEt2)2 afforded the novel allene Ph((NEt2)2P)C=C=CH2; reactions with HCl and MeI occurred exclusively at phosphorus. The syntheses of phosphaalkenes C6H4(1-C(OSiMe3)=PR’)(R) (R = 2-Me, 3-Me, 3-CN, 4-CN, 4-CO2Me, 4-COCl; R’ = H, SiMe3) were attempted by Becker condensation of C6H4(1- COCl)(R) and R’P(SiMe3)2. These reactions were studied in some detail in order to ascertain the principle reaction products, for which tentative identities were assigned. Phosphaalkenes E-/ZC6H4(1-C(OSiMe3)=PSiMe3)(2-Me) and E-/Z-C6H4(1-C(OSiMe3)=PSiMe3)(3-Me) were isolated and characterised spectroscopically. A library of meta- and para-substituted phosphomides C6H4(R)C(O)PPh2 (R = 3-Me, 3-CN, 3-CH2Cl, 4-CN, 4-CO2Me) was synthesised by reaction of HPPh2 with the respective acyl chlorides C6H4(R)COCl. Following standard literature methods for assessing electronic characteristics, IR data evidenced extensive delocalisation of the phosphorus lone pair into the carbonyl region in all cases, though coordination chemistry evidenced coordination exclusively via the phosphorus lone pair, indicative of little delocalisation. Novel di-phosphomides C5H3E(2,6-C(O)PPh2)2 (E = CH, N) were generated by addition of C5H3E(COCl)2 to HPPh2 and their behaviour as tridentate pincer ligands assessed by reaction with transition metals. The reaction of MeP(SiMe3)2 with C5H3E(2,6-C(O)PPh2)2 (E = CH, N) generated unprecedented diphosphametacyclophanes {3-CO-C6H4-C(O)PMe}2 and {2-CO-C5H3N-C(O)PMe}2; {3-COC6H4-C(O)PMe}2 is the first example of a metacyclophane that incorporates multiple phosphorus centres within the ligand skeleton, and was characterised crystallographically

Yarning with Minjungbal women: testimonial narratives of transgenerational trauma and healing explored through relationships with country and culture, community and family

Yarning with Minjungbal women incorporates the testimonial narratives of five women from the Minjungbal community of Tweed Heads in far northern New South Wales. Our combined metanarrative explores how we have been able to interrupt transgenerational trauma, which is the process that explains how the impacts of historical suffering are inherited by successive generations. Minjungbal women’s experiences of transgenerational trauma are discussed firstly through our ties to country and culture, secondly within the relationships in our community, and finally inside the dynamics of our families. Minjungbal women explain how we have experienced transgressions, resisted oppression, engendered healing and spread strength within each of these spheres. Minjungbal women’s relationships to country and culture, community and family have been influenced by the legacies of the past, and Minjungbal women still experience ongoing injustices from government policies and the attitudes of the dominant society. Nevertheless, this thesis contends that Minjungbal women have always been actors in resisting oppression, agents in interrupting the cycle of transgenerational trauma and instrumental in facilitating positive changes. Yarning with Minjungbal Women proposes that the key to resistance, resilience and healing lies within the teaching and learning that occurs within the context of relationships. Yarning with Minjungbal Women is therefore an embodiment of activism research as it is informed by the sharing of stories and the strengthening of relationships. Yarning with Minjungbal Women is a contribution to the field of research about the history of Minjungbal country. It contributes to existing research that explains the mechanisms by which the transgenerational transfer of trauma is inherited and passed on. This research is focussed though an Indigenous feminist heuristic perspective as the most culturally appropriate and immersive methodology for me to employ as a Minjungbal woman who has been shaped by transgenerational trauma, as I am perfectly suited to elucidate sensitive information from women in my community. The testimonial narratives were recorded using yarning as a communication method. Yarning facilitated the release of information in a way that Minjungbal women were comfortable with, giving them agency in the research process, as well as retaining the integrity of Minjungbal communication practises

The Afterlife of Christina of Sweden: Gender and Sexuality in Heritage and Fiction

From her reign until today, Christina of Sweden (1626-1689) has been the object of intrigue and scandal, appearing in seventeenth century political writings, commemorative prints, biographies, films, plays, and even a children’s book. The monarch has been described at best as ‘unconventional’ and at worst as an impulsive, over-emotional murderer. Christina’s sexuality and gender have been constantly reconstructed, re-examined, and re-interpreted. Christina’s actions, full of political and religious significance for seventeenth century Europe, have been immortalised in writing, images, and objects now found in museum collections. Within heritage Christina’s sexuality and gender are largely ignored and LGBTQ+ histories in general restricted to specific events, limiting the reach of these narratives. This article examines how Christina’s sexuality and gender is presented in film and literature. It compares these representations to museum interpretation text that accompanies objects related to Christina. Exploring Christina’s presence in these different environments, this article argues that her royal status gives her a ‘legitimate’ space within fictional representations and heritage that can be used to integrate LGBTQ+ narratives into the general historic and popular environments

Reading women in the medieval information age: the life of Elizabeth of Spalbeek and the book of Margery Kempe

In fifteenth-century England, information about the natural and supernatural worlds came to be broadly distributed in texts that circulated well beyond the institutional contexts in which this knowledge was first produced. Vernacular texts that deal with natural philosophy, medicine, and science, alongside a range of religious topics, were created in record numbers for a widening audience. Many of these testify to intensified interest in all aspects of the human body. Religious works written by, about, and for women participate in this ferment of ideas and information, crossing the boundaries between secular and transcendent themes and concerns. Because religious women were understood to have a special relationship to forms of physical piety, their vitae served as important vehicles for the production and dissemination of thinking about corporeality. The radical asceticism of the thirteenth-century Low Countries visionary Elizabeth of Spalbeek, as detailed in an important Middle English collection from the 1420s, Oxford, Bodleian Library, MS Douce 114, can be read as an investigation of the possibilities of the fleshly, this-worldly human body to materialize divine truth, and thus by extension as participating in local and intimate ways in the distribution and deinstitutionalization of knowledge. The Book of Margery Kempe, a work often seen as taking up the conventions of affective piety, [End Page 253] similarly participates in a current discourse concerning the materiality of the divine. As the work's complex treatment of the spirit as breath, fire, inspiration, or pneuma suggests, the Book is at once a contributor to and a product of the late medieval information era.Published versio

The Suv39H1 methyltransferase inhibitor chaetocin causes induction of integrated HIV-1 without producing a T cell response

AbstractLatent HIV-1 (human immunodeficiency virus-1) provirus is unaffected by current AIDS (acquired immunodeficiency syndrome) therapies. We show here that chaetocin, an SUV39H1 histone methyltransferase inhibitor, causes 25-fold induction of latent HIV-1 expression, while producing minimal toxicity and without causing T cell activation. Induction is associated with loss of histone H3 lysine 9 (H3K9) trimethylation at the long terminal repeat (LTR) promoter, and a corresponding increase in H3K9 acetylation. The effect of chaetocin is amplified synergistically in combination with histone deacetylase (HDAC) inhibitors. These results indicate that chaetocin may provide a therapy to purge cells of latent HIV-1, possibly in combination with other chromatin remodeling drugs

Exploring Flood Response Challenges, Training Needs, and the Impact of Online Flood Training for Lifeguards and Water Safety Professionals in South Africa

Flooding is a significant cause of human and economic loss in the African region, including in South Africa. Flood mitigation and response in South Africa is challenging due to a range of environmental, infrastructure, and policy constraints. Lifeguards represent a potential additional workforce to bolster flood mitigation and response. This study aimed to explore the feasibility and acceptability of online flood safety training for water safety professionals in South Africa, as well as assess the current flood response capacity and future needs of this group. Online surveys were completed by a convenience sample of South African water safety professionals (including lifeguards) pre-and post a series of four online flood training workshops. Free text responses were thematically coded and flood knowledge was compared between the pre-and post-workshop survey respondents. Sixty-eight responses were analysed (64.7% pre-workshop phase; 63.2% male, 29.4% aged 50–59 years). A range of challenges in flood mitigation and response were identified including equipment, training, and a lack of government support. However, positives were also identified including respondents’ willingness to assist in flood emergencies and good cooperation with neighbouring countries and across the region. Opportunities for better cross-municipal and government communication were discussed. In times of crisis, or in resource poor settings, water safety professionals can bolster traditional flood mitigation and response capacity. Opportunities exist to harness this willingness, but also improve cross-governmental and municipal knowledge sharing to improve future flood mitigation and response efforts in South Africa

The Heart of the Matter: The Coaching Model in America's Choice Schools

The Consortium for Policy Research in Education (CPRE) at the University of Pennsylvania was contracted by the National Center on Education and the Economy (NCEE) in 1998 to conduct the external evaluation of the America's Choice school design. CPRE designed and conducted a series of targeted studies on the implementation and impacts of the America's Choice design. This report coincides with the publication of three separate studies by CPRE on the impact of America's Choice in a number of districts across the country using a variety of quantitative and analytic approaches. Those impact analyses and a stand-alone piece on classroom observations conducted in Cohort 4 schools can be viewed as separate pieces or as complements to the information presented in this report. Another recent CPRE publication from fall 2001 is a widely distributed report entitled, Instructional Leadership in a Standards-based Reform, a companion piece to both the impact reports and this report

Detecting bipolar depression from geographic location data

Objective: This work aims to identify periods of depression using geolocation movements recorded from mobile phones in a prospective community study of individuals with bipolar disorder (BD). Methods: Anonymised geographic location recordings from 22 BD participants and 14 healthy controls (HC) were collected over 3 months. Participants reported their depressive symptomatology using a weekly questionnaire (QIDS-SR16). Recorded location data were pre-processed by detecting and removing imprecise data points and features were extracted to assess the level and regularity of geographic movements of the participant. A subset of features were selected using a wrapper feature selection method and presented to (a) a linear regression model and a quadratic generalised linear model with a logistic link function for questionnaire score estimation; and (b) a quadratic discriminant analysis classifier for depression detection in BD participants based on their questionnaire responses. Results: HC participants did not report depressive symptoms and their features showed similar distributions to nondepressed BD participants. Questionnaire score estimation using geolocation-derived features from BD participants demonstrated an optimal mean absolute error rate of 3.73 while depression detection demonstrated an optimal (median±IQR) F1 score of 0.857±0.022 using 5 features (classification accuracy: 0.849±0.016; sensitivity: 0.839±0.014; specificity: 0.872±0.047). Conclusion: These results demonstrate a strong link between geographic movements and depression in bipolar disorder. Significance: To our knowledge this is the first community study of passively recorded objective markers of depression in bipolar disorder of this scale. The techniques could help individuals monitor their depression and enable healthcare providers to detect those in need of care or treatment