Exploiting the labile site in dinuclear [Pd2L2]n+ metallo-cycles: multi-step control over binding affinity without alteration of core host structure

While Nature often controls supramolecular processes through regulation giving multiple levels of activity, synthetic metallosupramolecular systems have generally been binary (e.g. on/off) when they have control over molecular recognition events, and have often relied upon drastic chemical transformations or complete disassembly to enforce this control. We report here a new low symmetry ligand with a bidentate and a monodentate site (L). In combination with Pd2+, this ligand forms a [2 + 2] metallo-macrocycle, [Pd2L2L′2]n+, where L′ is the monodentate ancillary ligand that occupies the fourth and final coordination site of the metal ions. This assembly is structurally simple, but displays nuanced, multi-step binding affinity toward a neutral diplatinate guest employed for proof-of-concept. This complexity is introduced through varying the identity of L′, which can either be solvent (DMSO) or the halides chloride, bromide or iodide. The identity of L′ alters the cationic charge of the complex (neutral DMSO versus monoanionic halides) or otherwise influences the electron deficiency of the binding site of the host through varied strength of halide-ligand intra-molecular hydrogen bonding. Cycling between these different complexes was demonstrated, except for L′ = chloride which is non-reversible. This system therefore is able to interact with a platinate guest with four different graduations of affinity in response to stimuli, while still retaining the same simple core cationic structure. In addition to multi-setting binding affinity, we believe this is the first example of the use of variable intramolecular hydrogen bonding strength in switchable ancillary ligands to alter the electronic character and hence the π-π recognition characteristics of a metallosupramolecular host.DP would like to thank the ARC for a DECRA Fellowship, and the Royal Society of New Zealand for a Rutherford Postdoctoral Fellowship. BH would like to gratefully acknowledge the MBIE Catalyst Fund for a PhD scholarship. RV would like to thank the University of Otago for a PhD scholarship. The authors would like to thank the Australia National University, the University of Canterbury, the University of Otago, and the MacDiarmid Institute for additional funding. The authors acknowledge the contribution of the NeSI high performance computing facilities to the results of this research. New Zealand’s national facilities are provided by the New Zealand eScience Infrastructure and funded jointly by NeSI’s collaborator institutions and through the Ministry of Business, Innovation & Employment’s Research Infrastructure program. https://www.nesi.org.nz

Identification of Novel Single Nucleotide Polymorphisms in Inflammatory Genes as Risk Factors Associated with Trachomatous Trichiasis

infection, the primary cause of trachoma. Despite control programs that include mass antibiotic treatment, reinfection and recurrence of trachoma are common after treatment cessation. Furthermore, a subset of infected individuals develop inflammation and are at greater risk for developing the severe sequela of trachoma known as trachomatous trichiasis (TT). While there are a number of environmental and behavioral risk factors for trachoma, genetic factors that influence inflammation and TT risk remain ill defined. = 0.001] with the combination of TNFA (-308A), LTA (252A), VCAM1 (-1594C), SCYA 11 (23T) minor allele, and the combination of TNFA (-308A), IL9 (113M), IL1B (5′UTR-T), and VCAM1 (-1594C). However, TT risk increased 13.5 times [odds ratio = 13.5 (95% confidence interval 3.3–22), p = 0.001] with the combination of TNFA (-308G), VDR (intron G), IL4R (50V), and ICAM1 (56M) minor allele.Evaluating genetic risk factors for trachoma will advance our understanding of disease pathogenesis, and should be considered in the context of designing global control programs

Your people, your volunteers

Building sustainable Not-for-profit (NFP) organisations is critical to society due to the social value they create including in countries such as Australia. Over one million paid employees worked in Australian charities in 2014 while almost half of charities have both paid employees and volunteers. Almost half of these charities reported that they had at least one paid employee and one volunteer. The Australian Productivity Commission estimated that 4.5 million persons contributed volunteer labour. Almost half of all paid employees in Australia’s charities/not-for-profit sector were found in education (31.6) and aged care (15.3%). Social services and hospital services and rehabilitation accounted for a further 8.1% and 7.3% respectively. This sector breakdown indicates that not-for-profit employees include a large number of professional employees. In contrast, this survey showed that 44.3% of charities employed no paid staff. Added to this is the managing of the estimated 6.1 million people who at some time take part in formal volunteering in Australia

Work-shadowing and related processes

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A "New Institutional" perspective on women's position in architecture: considering the cases of Australia and Sweden

Surprisingly little research on the position of women in architecture has attended to how the regulatory framing and governance of the architecture profession, through institutional and professional bodies, serves to construct and constrain professional identity in gendered ways.1 This article attempts such an analysis, applying a new institutional approach to understanding the continuing under-representation of women in architecture. Focusing primarily on the Australian architecture profession, we draw a contrast with features of the profession in Sweden. Our focus is on the legal rational institutions that legitimise and consequently shape the profession, and we attempt to show how credentials and registration processes, along with professional associations, act as legitimising frames for professional practice