Synthesis of profluorescent isoindoline nitroxides via palladium-catalysed Heck alkenylation

The synthesis of a new structural class of isoindoline nitroxides (aminoxyls), accessible via the palladium-catalysed Heck reaction, is presented. Reaction of the aryl bromoamine, 5-bromo-1,1,3,3-tetramethylisoindoline (4) or dibromoamine, 5,6-dibromo-1,1,3,3-tetramethylisoindoline (5) or the analogous bromonitroxides 6 and 7 with methyl acrylate gives the acrylate substituted tetramethylisoindoline amines 8 and 10 and nitroxides 12 and 14. Similarly, the reaction of the aryl bromides and dibromides 4–7 with methyl 4-vinylbenzoate gives the carboxystyryl substituted tetramethylisoindoline amines 9 and 11 and the analogous nitroxides 13 and 15. The carboxystyryl tetramethylisoindoline nitroxides demonstrate strongly suppressed fluorescence, which is revealed upon removal of the free radical by reduction or radical coupling.

Synthesis of a heparan sulfate mimetic disaccharide with a conformationally locked residue from a common intermediate

A simple mimetic of a heparan sulfate disaccharide sequence that binds to the growth factors FGF-1 and FGF-2 was synthesized by coupling a 2-azido-2-deoxy-D-glucosyl trichloroacetimidate donor with a 1,6-anhydro-2-azido-2-deoxy--D-glucose acceptor. Both the donor and acceptor were obtained from a common intermediate readily obtained from D-glucal. Molecular docking calculations showed that the predicted locations of the disaccharide sulfo groups in the binding site of FGF-1 and FGF-2 are similar to the positions observed for co-crystallized heparin-derived oligosaccharides obtained from published crystal structures.

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.

Synthesis of orchestrators from service choreographies

With service interaction modelling, it is customary to distinguish between two types of models: choreographies and orchestrations. A choreography describes interactions within a collection of services from a global perspective, where no service plays a privileged role. Instead, services interact in a peer-to-peer manner. In contrast, an orchestration describes the interactions between one particular service, the orchestrator, and a number of partner services. The main proposition of this work is an approach to bridge these two modelling viewpoints by synthesising orchestrators from choreographies. To start with, choreographies are defined using a simple behaviour description language based on communicating finite state machines. From such a model, orchestrators are initially synthesised in the form of state machines. It turns out that state machines are not suitable for orchestration modelling, because orchestrators generally need to engage in concurrent interactions. To address this issue, a technique is proposed to transform state machines into process models in the Business Process Modelling Notation (BPMN). Orchestrations represented in BPMN can then be augmented with additional business logic to achieve value-adding mediation. In addition, techniques exist for refining BPMN models into executable process definitions. The transformation from state machines to BPMN relies on Petri nets as an intermediary representation and leverages techniques from theory of regions to identify concurrency in the initial Petri net. Once concurrency has been identified, the resulting Petri net is transformed into a BPMN model. The original contributions of this work are: an algorithm to synthesise orchestrators from choreographies and a rules-based transformation from Petri nets into BPMN.

The synthesis of novel isoindoline nitroxides bearing water-solubilising functionality

A range of novel tetramethyl- and tetraethylisoindolinenitroxides, possessing aryl-linked carboxylic acids, amines, alcohols and phosphonic acids were prepared. Notably, the chemistry established for the aromatic dibromination of the tetramethylisoindolines was not easily transferred to the corresponding tetraethylisoindoline system. Instead, various tetraethylisoindoline analogues were accessed by the oxidation of methyl groups attached to the aromatic ring to give the carboxylic acids. The increased steric bulk of the tetraethyl structures should limit bio-reduction and these compounds may have potential as antioxidants.

Implications of precursor chemistry on the alkaline hydrothermal synthesis of titania/titanate nanostructures

A systematic study of four parameters within the alkaline hydrothermal treatment of three commercial titania powders—anatase, rutile, and Degussa P25—was made. These powders were treated with 5, 7.5, 9, and 10 M NaOH between 100 and 220 °C for 20 h. The effects of alkaline concentration, hydrothermal temperature, and precursor phase and crystallite size on the resultant nanostructure formation have been studied through X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and nitrogen adsorption. Through the correlation of these data, morphological phase diagrams were constructed for each commercial powder. Interpretation of the resultant morphological phase diagrams indicates that alkaline concentration and hydrothermal temperature affect nanostructure formation independently, where nanoribbon formation is significantly influenced by temperature for initial formation. The phase and crystallite size of the precursor also significantly influenced nanostructure formation, with rutile displaying a slower rate of precursor consumption compared with anatase. Small crystallite titania precursors formed nanostructures at reduced hydrothermal temperatures.

A Theoretical and Analytical Synthesis of Autopoiesis and Sociolinguistics for the Study of Organisational Communication

The purpose of this paper is threefold. First, we propose a systemic view of communication based in autopoiesis, the theory of living systems formulated by Maturana & Varela (1980, 1987). Second, we show the links between the underpinning assumptions of autopoiesis and the sociolinguistic approaches of Halliday (1978), Fairclough (1989, 1992, 1995) and Lemke (1995, 1994). Third, we propose a theoretical and analytical synthesis of autopoiesis and sociolinguistics for the study of organisational communication. In proposing a systemic theory for organisational communication, we argue that traditional approaches to communication, information, and the role of language in human organisations have, to date, been placed in teleological constraints because of an inverted focus on organisational purpose-the generally perceived role of an organisation within society-that obscure, rather than clarify, the role of language within human organisations. We argue that human social systems are, according to the criteria defined by Maturana and Varela, third-order, non-organismic living systems constituted in language. We further propose that sociolinguistics provides an appropriate analytical tool which is both compatible and penetrating in synthesis with the systemic framework provided by an autopoietic understanding of social organisation.

Carbodiimide-mediated synthesis of poly(L-lactide)-based networks

Poly(L-lactide-co-succinic anhydride) networks were synthesised via the carbodiimide-mediated coupling of poly(L-lactide) (PLLA) star polymers. When 4-(dimethylamino)pyridine (DMAP) alone was used as the catalyst gelation did not occur. However, when 4-(dimethylamino)pyridinium p-toluenesulfonate (DPTS), the salt of DMAP and p-toluenesulfonic acid (PTSA), was the catalyst, the networks obtained had gel fractions comparable to those which were reported for networks synthesised by conventional methods. Greater gel fractions and conversion of the prepolymer terminal hydroxyl groups were observed when the hydroxyl-terminated star prepolymers reacted with succinic anhydride in a one-pot procedure than when the hydroxyl-terminated star prepolymers reacted with presynthesised succinic-terminated star prepolymers. The thermal properties of the networks, glass transition temperature (Tg), melting temperature (Tm) and crystallinity (Xc) were all strongly influenced by the average molecular weights between the crosslinks ((M_c). The network with the smallest (M_c )(1400 g/mol) was amorphous and had a Tg of 59 °C while the network with the largest (M_c ) (7800 g/mol) was 15 % crystalline and had a Tg of 56 °C.

Low temperature synthesis of zeolite N from kaolinites and montmorillonites

Zeolite N was produced from a variety of kaolinites and montmorillonites at low temperature (b100 °C) in a constantly stirred reactor using potassic and potassic+sodic mother liquors with chloride or hydroxyl anions. Reactions were complete (N95% product) in less than 20 h depending on initial batch composition and type of clay minerals. Zeolite N with 1.0bSi/Alb2.2 was produced under these conditions using KOH in the presence of KCl, NaCl, KCl+NaCl and KCl+NaOH. Zeolite N was also formed under high potassium molarities in the absence of KCl. Zeolite synthesis was more sensitive to water content and temperature when sodium was used in initial batch compositions. Syntheses of zeolite N by these methods were undertaken at bench, pilot and industrial scales.

Indigenous men's support groups and social and emotional wellbeing : a meta-synthesis of the evidence

Indigenous men’s support groups are designed to empower men to take greater control and responsibility for their health and wellbeing. They provide health education sessions, counselling, men’s health clinics, diversionary programs for men facing criminal charges, cultural activities, drug- and alcohol-free social events, and advocacy for resources. Despite there being ~100 such groups across Australia, there is a dearth of literature on their strategies and outcomes. This paper is based on participatory action research involving two north Queensland groups which were the subject of a series of five ‘phased’ evaluative reports between 2002 and 2007. By applying ‘meta-ethnography’ to the five studies, we identified four themes which provide new interpretations of the data. Self-reported benefits included improved social and emotional wellbeing, modest lifestyle modifications and willingness to change current notions of ‘gendered’ roles within the home, such as sharing housework. Our qualitative research to date suggests that through promoting empowerment, wellbeing and social cohesion for men and their families, men’s support groups may be saving costs through reduced expenditure on health care, welfare, and criminal justice costs, and higher earnings. Future research needs to demonstrate this empirically.