Unusual hydrate stabilization in the two-dimensional layered structure of quinacrinium bis(2-carboxy-4,5-dichlorobenzoate) tetrahydrate, a proton-transfer compound of the drug quinacrine

The crystal structure of the hydrated proton-transfer compound of the drug quinacrine [rac-N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] with 4,5-dichlorophthalic acid, C23H32ClN3O2+ . 2(C8H3Cl2O4-).4H2O (I), has been determined at 200 K. The four labile water molecules of solvation form discrete ...O--H...O--H... hydrogen-bonded chains parallel to the quinacrine side chain, the two N--H groups of which act as hydrogen-bond donors for two of the water acceptor molecules. The other water molecules, as well as the acridinium H atom, also form hydrogen bonds with the two anion species and extend the structure into two-dimensional sheets. Between these sheets there are also weak cation--anion and anion--anion pi-pi aromatic ring interactions. This structure represents only the third example of a simple quinacrine derivative for which structural data are available but differs from the other two in that it is unstable in the X-ray beam due to efflorescence, probably associated with the destruction of the unusual four-membered water chain structures.

Proton-transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl) aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic

The structures of two 1:1 proton-transfer red-black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+.C7H5O6S-.CH3OH (I), 2-(4-aminophenyl)-1-hydrazin-1-ium 4-(phenydiazinyl)anilinium bis(benzenesulfonate), 2C12H12N3+.2C6H5O3S-, (II) and 4-(phenyldiazenyl)aniline-3,5-dinitrobenzoic acid (1/2) C12H11N3.2C~7~H~4~N~2~O~6~, (III). In compound (I) the diaxenyl rather than the aniline group of aniline yellow is protonated and this group subsequently akes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation-anion association involving aromatic C--H...O hydrogen bonds, giving a conjoint R1/2(6)R1/2(7)R2/1(4)motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and thee, together with other associations give a one-dimensional chain structure. In compound (III), rather than proton-transfer, there is a preferential formation of a classic R2/2(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, result in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.

Synthesis of 4-arm star poly(L-Lactide) oligomers using an in situ-generated calcium-based initiator

Using an in situ-generated calcium-based initiating species derived from pentaerythritol, the bulk synthesis of well-defined 4-arm star poly(L-lactide) oligomers has been studied in detail. The substitution of the traditional initiator, stannous octoate with calcium hydride allowed the synthesis of oligomers that had both low PDIs and a comparable number of polymeric arms (3.7 – 3.9) to oligomers of similar molecular weight. Investigations into the degree of control observed during the course of the polymerization found that the insolubility of pentaerythritol in molten L-lactide resulted in an uncontrolled polymerization only when the feed mole ratio of L-lactide to pentaerythritol was 13. At feed ratios of 40 and greater, a pseudo-living polymerization was observed. As part of this study, in situ FT-Raman spectroscopy was demonstrated to be a suitable method to monitor the kinetics of the ring-opening polymerization (ROP) of lactide. The advantages of using this technique rather than FT-IR-ATR and 1H NMR for monitoring L-lactide consumption during polymerization are discussed.

4-(2-hydroxyethyl)anilinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate

In the structure of the title compound C8H12NO+ C7H5O6S- . H2O, from the reaction of 2-(4-aminophenyl)ethanol with 5-sulfosalicylic acid, the cations form head-to-tail hydrogen-bonded chains through C1/1(9) anilinium N+-H...O(hydroxyl} interactions while the anions also form similar but C1/1(8)-linked chains through carboxylic acid O-..O(sulfonate) interactions. The chains inter-associate through a number of N-H...O and O-H...O bridging interactions giving a two-dimensional array in the ab plane.

Report to the Government 2.0 Taskforce : Project 4 - Copyright Law and Intellectual Property

This report is the primary output of Project 4: Copyright and Intellectual Property, the aim of which was to produce a report considering how greater access to and use of government information could be achieved within the scope of the current copyright law. In our submission for Project 4, we undertook to address: •the policy rationales underlying copyright and how they apply in the context of materials owned, held and used by government; • the recommendations of the Copyright Law Review Committee (CLRC) in its 2005 report on Crown copyright; • the legislative and regulatory barriers to information sharing in key domains, including where legal impediments such as copyright have been relied upon (whether rightly or wrongly) to justify a refusal to provide access to government data; • copyright licensing models appropriate to government materials and examples of licensing initiatives in Australia and other relevant jurisdictions; and • issues specific to the galleries, libraries, archives and museums (“GLAM”) sector, including management of copyright in legacy materials and “orphan” works. In addressing these areas, we analysed the submissions received in response to the Government 2.0 Taskforce Issues Paper, consulted with members of the Task Force as well as several key stakeholders and considered the comments posted on the Task Force’s blog. This Project Report sets out our findings on the above issues. It puts forward recommendations for consideration by the Government 2.0 Task Force on steps that can be taken to ensure that copyright and intellectual property promote access to and use of government information.

Safeguarding rural Australia : addressing masculinity and violence in rural settings. Data report No. 4 - Risky behaviour - misuse of alcohol, illicit drugs, firearms use and abuse, other risky behaviour

This report focuses on our examination of extant data which have been sourced with respect to personally and socially risky behaviour associated with males living in regional and remote Australia . The AIHW (2008: PHE 97:89) defines personally risky behaviour, on the one hand, as working, swimming, boating, driving or operating hazardous machinery while intoxicated with alcohol or an illicit drug. Socially risky behaviour, on the other hand, is defined as creating a public disturbance, damaging property, stealing or verbally or physically abusing someone while intoxicated with alcohol or an illicit drug. Additional commentary resulting from exploration, examination and analyses of secondary data is published online in complementary reports in this series.

Kallikrein-related peptidase 4 activation of protease-activated receptor family members and association with prostate cancer

Two areas of particular importance in prostate cancer progression are primary tumour development and metastasis. These processes involve a number of physiological events, the mediators of which are still being discovered and characterised. Serine proteases have been shown to play a major role in cancer invasion and metastasis. The recently discovered phenomenon of their activation of a receptor family known as the protease activated receptors (PARs) has extended their physiological role to that of signaling molecule. Several serine proteases are expressed by malignant prostate cancer cells, including members of the kallikreinrelated peptidase (KLK) serine protease family, and increasingly these are being shown to be associated with prostate cancer progression. KLK4 is highly expressed in the prostate and expression levels increase during prostate cancer progression. Critically, recent studies have implicated KLK4 in processes associated with cancer. For example, the ectopic over-expression of KLK4 in prostate cancer cell lines results in an increased ability of these cells to form colonies, proliferate and migrate. In addition, it has been demonstrated that KLK4 is a potential mediator of cellular interactions between prostate cancer cells and osteoblasts (bone forming cells). The ability of KLK4 to influence cellular behaviour is believed to be through the selective cleavage of specific substrates. Identification of relevant in vivo substrates of KLK4 is critical to understanding the pathophysiological roles of this enzyme. Significantly, recent reports have demonstrated that several members of the KLK family are able to activate PARs. The PARs are relatively new members of the seven transmembrane domain containing G protein coupled receptor (GPCR) family. PARs are activated through proteolytic cleavage of their N-terminus by serine proteases, the resulting nascent N-terminal binds intramolecularly to initiate receptor activation. PARs are involved in a number of patho-physiological processes, including vascular repair and inflammation, and a growing body of evidence suggests roles in cancer. While expression of PAR family members has been documented in several types of cancers, including prostate, the role of these GPCRs in prostate cancer development and progression is yet to be examined. Interestingly, several studies have suggested potential roles in cellular invasion through the induction of cytoskeletal reorganisation and expression of basement membrane-degrading enzymes. Accordingly, this program of research focussed on the activation of the PARs by the prostate cancer associated enzyme KLK4, cellular processing of activated PARs and the expression pattern of receptor and agonist in prostate cancer. For these studies KLK4 was purified from the conditioned media of stably transfected Sf9 insect cells expressing a construct containing the complete human KLK4 coding sequence in frame with a V5 epitope and poly-histidine encoding sequences. The first aspect of this study was the further characterisation of this recombinant zymogen form of KLK4. The recombinant KLK4 zymogen was demonstrated to be activatable by the metalloendopeptidase thermolysin and amino terminal sequencing indicated that thermolysin activated KLK4 had the predicted N-terminus of mature active KLK4 (31IINED). Critically, removal of the pro-region successfully generated a catalytically active enzyme, with comparable activity to a previously published recombinant KLK4 produced from S2 insect cells. The second aspect of this study was the activation of the PARs by KLK4 and the initiation of signal transduction. This study demonstrated that KLK4 can activate PAR-1 and PAR-2 to mobilise intracellular Ca2+, but failed to activate PAR-4. Further, KLK4 activated PAR-1 and PAR-2 over distinct concentration ranges, with KLK4 activation and mobilisation of Ca2+ demonstrating higher efficacy through PAR-2. Thus, the remainder of this study focussed on PAR-2. KLK4 was demonstrated to directly cleave a synthetic peptide that mimicked the PAR-2 Nterminal activation sequence. Further, KLK4 mediated Ca2+ mobilisation through PAR-2 was accompanied by the initiation of the extra-cellular regulated kinase (ERK) cascade. The specificity of intracellular signaling mediated through PAR-2 by KLK4 activation was demonstrated by siRNA mediated protein depletion, with a reduction in PAR-2 protein levels correlating to a reduction in KLK4 mediated Ca2+mobilisation and ERK phosphorylation. The third aspect of this study examined cellular processing of KLK4 activated PAR- 2 in a prostate cancer cell line. PAR-2 was demonstrated to be expressed by five prostate derived cell lines including the prostate cancer cell line PC-3. It was also demonstrated by flow cytometry and confocal microscopy analyses that activation of PC-3 cell surface PAR-2 by KLK4 leads to internalisation of this receptor in a time dependent manner. Critically, in vivo relevance of the interaction between KLK4 and PAR-2 was established by the observation of the co-expression of receptor and agonist in primary prostate cancer and prostate cancer bone lesion samples by immunohistochemical analysis. Based on the results of this study a number of exciting future studies have been proposed, including, delineating differences in KLK4 cellular signaling via PAR-1 and PAR-2 and the role of PAR-1 and PAR-2 activation by KLK4 in prostate cancer cells and bone cells in prostate cancer progression.

How well are Australian infants and children aged 4 to 5 years doing? Findings from the Longitudinal Study of Australian Children Wave 1

This report presents an analysis of the data from the first wave of the Longitudinal Study of Australian Children (LSAC) to explore the wellbeing of 5,107 children in the infant cohort of the study and the 4,983 children, aged 4 to 5 years, in the child cohort. Wave 1 of LSAC includes measures of multiple aspects of children’s early development. These developmental measures are summarised in the LSAC Outcome Index, a composite measure which includes an overall index as well as three separate domain scores, tapping physical development, social and emotional functioning, and learning and cognitive development.

4-Hydroxy-4,4-diphenylbutan-2-one

The mol­ecules of the title compound, C16H16O2, display an intra­molecular O—HO hydrogen bond between the hydroxyl donor and the ketone acceptor. Inter­molecular C—Hπ inter­actions connect adjacent mol­ecules into chains that propagate parallel to the ac diagonal. The chains are arranged in sheets, and mol­ecules in adjacent sheets inter­act via inter­molecular O—HO hydrogen bonds.

Cosmopolitanism, the nation-state and imaginative realism

Contemporary writing on cosmopolitanism has asserted the need for a new sociological toolkit to deal with an emergent post-national social order. At the heart of this agenda is a misunderstanding about the role of the nation-state, which has led to some rather unhelpful theorizations. The state is assumed to be a dead hand in the development of post-national sentiments or an increasingly irrelevant social structure. We argue that the superseding of the nation-state is not necessary for the development of cosmopolitan sentiments of solidarity. In addition to classical sociology, it is work surrounding the concepts of cosmopolitan democracy and constitutional patriotism and the public sphere that can assist us in theorizing cosmopolitanism. What distinguishes this tradition is the utilization of social science concepts such as democracy, state, public sphere and law in an attempt to ground the idea of cosmopolitanism within the context of existing social structures.

Isopropylaminium 2-carboxy-4, 5-dichlorobenzoate

In the structure of the 1:1 proton-transfer compound of isopropylamine with 4,5-dichlorophthalic acid, C3H10N+·C8H3Cl2O4-, the three cation H-atom donors associate with three separate carboxyl O-atom anion acceptors, giving conjoint cyclic R44(12), R44(16) hydrogen-bonding cation-anion interactions in a one-dimensional ribbon structure. In the anions, the carboxyl groups lie slightly out of the plane of the benzene ring [maximum deviations = 0.439 (1) for a carboxylic acid O atom and 0.433 (1) Å for a carboxylate O atom]. However, the syn-related proton of the carboxylic acid group forms the common short intramolecular O-HOcarboxyl hydrogen bond.

Ethane-1,2-diaminium 4,5-dichlorophthalate

In the structure of the title compound, C2H10N22+·C8H2Cl2O42-, the dications and dianions form hydrogen-bonded ribbon substructures which enclose conjoint cyclic R21(7), R12(7) and R42(8) associations and extend down the c-axis direction. These ribbons inter-associate down b, giving a two-dimensional sheet structure. In the dianions, one of the carboxylate groups is essentially coplanar with the benzene ring, while the other is normal to it [C-C-C-O torsion angles = 177.67 (12) and 81.94 (17)°, respectively].

Voter behaviour and constitutional change in Australia since 1967

Australian Constitutional referendums have been part of the Australian political system since federation. Up to the year 1999 (the time of the last referendum in Australia), constitutional change in Australia does not have a good history of acceptance. Since 1901, there have been 44 proposed constitutional changes with eight gaining the required acceptance according to section 128 of the Australian Constitution. In the modern era since 1967, there have been 20 proposals over seven referendum votes for a total of four changes. Over this same period, there have been 13 federal general elections which have realised change in government just five times. This research examines the electoral behaviour of Australian voters from 1967 to 1999 for each referendum. Party identification has long been a key indicator in general election voting. This research considers whether the dominant theory of voter behaviour in general elections (the Michigan Model) provides a plausible explanation for voting in Australian referendums. In order to explain electoral behaviour in each referendum, this research has utilised available data from the Australian Electoral Commission, the 1996 Australian Bureau of Statistics Census data, and the 1999 Australian Constitutional Referendum Study. This data has provided the necessary variables required to measure the impact of the Michigan Model of voter behaviour. Measurements have been conducted using bivariate and multivariate analyses. Each referendum provides an overview of the events at the time of the referendum as well as the =yes‘ and =no‘ cases at the time each referendum was initiated. Results from this research provide support for the Michigan Model of voter behaviour in Australian referendum voting. This research concludes that party identification, as a key variable of the Michigan Model, shows that voters continue to take their cues for voting from the political party they identify with in Australian referendums. However, the outcome of Australian referendums clearly shows that partisanship is only one of a number of contributory factors in constitutional referendums.

The structure of the copper(II) complex with 4,5-dichlorophthalic acid: The 1:1 complex 'adduct' salt trans-tetraaqua(2-carboxy-4,5-dichlorobenzoato)(4,5-dichlorobenzene-1,2-dicarboxylic acid)copper(II) 2-carboxy-4,5-dichlorobenzoate

The unusual (1:1) complex ‘adduct’ salt of copper(II) with 4,5-dichlorophthalic acid (H2DCPA), having formula [Cu(H2O)4(C8H3Cl2O4) (C8H4Cl2O4)] . (C8H3Cl2O4) has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P21/c, with Z = 4 in a cell with dimensions a = 20.1376(7), b =12.8408(4) c = 12.1910(4) Å, β = 105.509(4)o. The complex is based on discrete tetragonally distorted octahedral [CuO6] coordination centres with the four water ligands occupying the square planar sites [Cu-O, 1.962(4)-1.987(4) Å] and the monodentate carboxyl-O donors of two DCPA ligand species in the axial sites. The first of these bonds [Cu-O, 2.341(4) Å] is with an oxygen of a HDCPA monoanion, the second with an oxygen of a H2DCPA acid species [Cu-O, 2.418(4) Å]. The un-coordinated ‘adduct’ molecule is a HDCPA counter anion which is strongly hydrogen-bonded to the coordinated H2DCPA ligand [O… O, 2.503(6) Å] while a number of peripheral intra- and intermolecular hydrogen-bonding interactions give a two-dimensional network structure.

Maintaining nutrition in aged care residents with a train-the-trainer intervention and nutrition coordinator

Objective: To investigate the impact of a train-the-trainer program on the nutritional status of older people in residential care. ----- Design: Prospective, randomized controlled study. Setting: Eight nursing homes in Southeast Queensland, Australia. ----- Participants: A total of 352 residents participated - 245 were female (69.6%). The mean age was 84.2 years and the majority (79.4%) were classified as high dependency. ----- Intervention: Residents from four nursing homes were randomly selected for a nutrition education program coordinated by Nutrition Coordinators. Residents from the other four nursing homes (control) received usual care. ----- Measurements: The Subjective Global Assessment was used to determine prevalence of malnutrition at baseline and six months post intervention. The Resident Classification Scale measured functional dependency. Prescribed diet, fluids, oral hygiene status and allied health referrals were obtained by chart audit. ----- Results: Approximately half the residents were well nourished with 49.4% moderately or severely malnourished. Residents in the intervention group were more likely to maintain or improve their nutritional status compared with the control group who were more likely to experience a deterioration (P=0.027). The odds of the control group being malnourished post test was 1.6 times more likely compared with the intervention group but this did not reach statistical significance (P=0.1). ----- Conclusion: The results of the study encourage the implementation of a Nutrition Coordinator program to maintain nutritional status of aged care residents. Nevertheless, malnutrition rates continue to be unacceptably high. In a rapidly aging society, the aged care sector needs to confront malnutrition and provide better resources for staff to take measures against this problem.