Enriching XML documents clustering by using concise structure and content

With the growing number of XML documents on theWeb it becomes essential to effectively organise these XML documents in order to retrieve useful information from them. A possible solution is to apply clustering on the XML documents to discover knowledge that promotes effective data management, information retrieval and query processing. However, many issues arise in discovering knowledge from these types of semi-structured documents due to their heterogeneity and structural irregularity. Most of the existing research on clustering techniques focuses only on one feature of the XML documents, this being either their structure or their content due to scalability and complexity problems. The knowledge gained in the form of clusters based on the structure or the content is not suitable for reallife datasets. It therefore becomes essential to include both the structure and content of XML documents in order to improve the accuracy and meaning of the clustering solution. However, the inclusion of both these kinds of information in the clustering process results in a huge overhead for the underlying clustering algorithm because of the high dimensionality of the data. The overall objective of this thesis is to address these issues by: (1) proposing methods to utilise frequent pattern mining techniques to reduce the dimension; (2) developing models to effectively combine the structure and content of XML documents; and (3) utilising the proposed models in clustering. This research first determines the structural similarity in the form of frequent subtrees and then uses these frequent subtrees to represent the constrained content of the XML documents in order to determine the content similarity. A clustering framework with two types of models, implicit and explicit, is developed. The implicit model uses a Vector Space Model (VSM) to combine the structure and the content information. The explicit model uses a higher order model, namely a 3- order Tensor Space Model (TSM), to explicitly combine the structure and the content information. This thesis also proposes a novel incremental technique to decompose largesized tensor models to utilise the decomposed solution for clustering the XML documents. The proposed framework and its components were extensively evaluated on several real-life datasets exhibiting extreme characteristics to understand the usefulness of the proposed framework in real-life situations. Additionally, this research evaluates the outcome of the clustering process on the collection selection problem in the information retrieval on the Wikipedia dataset. The experimental results demonstrate that the proposed frequent pattern mining and clustering methods outperform the related state-of-the-art approaches. In particular, the proposed framework of utilising frequent structures for constraining the content shows an improvement in accuracy over content-only and structure-only clustering results. The scalability evaluation experiments conducted on large scaled datasets clearly show the strengths of the proposed methods over state-of-the-art methods. In particular, this thesis work contributes to effectively combining the structure and the content of XML documents for clustering, in order to improve the accuracy of the clustering solution. In addition, it also contributes by addressing the research gaps in frequent pattern mining to generate efficient and concise frequent subtrees with various node relationships that could be used in clustering.

Plant programmed cell death : Can't live with it; Can't live without it

The decision of whether a cell should live or die is fundamental for the wellbeing of all organisms. Despite intense investigation into cell growth and proliferation, only recently has the essential and equally important idea that cells control/programme their own demise for proper maintenance of cellular homeostasis gained recognition. Furthermore, even though research into programmed cell death (PCD) has been an extremely active area of research there are significant gaps in our understanding of the process in plants. In this review, we discuss PCD during plant development and pathogenesis, and compare/contrast this with mammalian apoptosis. © 2008 Blackwell Publishing Ltd.

Using incomplete online metric maps for topological exploration with the Gap Navigation Tree

This paper presents a general, global approach to the problem of robot exploration, utilizing a topological data structure to guide an underlying Simultaneous Localization and Mapping (SLAM) process. A Gap Navigation Tree (GNT) is used to motivate global target selection and occluded regions of the environment (called “gaps”) are tracked probabilistically. The process of map construction and the motion of the vehicle alters both the shape and location of these regions. The use of online mapping is shown to reduce the difficulties in implementing the GNT.

Operations research for mining : a classification and literature review

In this paper, we describe the main processes and operations in mining industries and present a comprehensive survey of operations research methodologies that have been applied over the last several decades. The literature review is classified into four main categories: mine design; mine production; mine transportation; and mine evaluation. Mining design models are further separated according to two main mining methods: open-pit and underground. Moreover, mine production models are subcategorised into two groups: ore mining and coal mining. Mine transportation models are further partitioned in accordance with fleet management, truck haulage and train scheduling. Mine evaluation models are further subdivided into four clusters in terms of mining method selection, quality control, financial risks and environmental protection. The main characteristics of four Australian commercial mining software are addressed and compared. This paper bridges the gaps in the literature and motivates researchers to develop more applicable, realistic and comprehensive operations research models and solution techniques that are directly linked with mining industries.

"Silly hours" : facilitating more effective part-time work arrangements through job design

Part-time employment presents a conundrum in that it facilitates work-life priorities, while also, compared to equivalent full-time roles, attracting penalties such as diminished career prospects and lower commensurate remuneration. Recently, some promising theoretical developments in the job/work design literature suggest that consideration of work design may redress some of the penalties associated with part-time work. Adopting the framework of the Elaborated Model of Work Design by Parker and colleagues (2001), we examined this possibility through interviews with part-time professional service employees and their supervisors. The findings revealed that in organizations characterised by cultural norms of extended working hours and a singular-focused commitment to work, part-time roles were often inadequately re-designed when adapted from full-time arrangements. The findings also demonstrated that certain work design characteristics (e.g. predictability of work-flow, interdependencies with co-workers) render some roles more suitable for part-time arrangements than others. The research provides insights into gaps between policy objectives and outcomes associated with part-time work, challenges assumptions about the limitations of part-time roles, and suggests re-design strategies for more effective part-time arrangements.

What do we currently know about designing and evaluating road safety advertising?

Overview: What we currently know - content design and evaluation The direct role (persuasive effects) of advertising Review of some key findings within a conceptual framework of the persuasive process Definitional inconsistencies, methodological limitations, & gaps in existing knowledge Suggested issues/directions for future advertising research

The effect of exercise intensity on fat oxidation and non-exercise activity thermogenesis in overweight/obese men

It is frequently reported that the actual weight loss achieved through exercise interventions is less than theoretically expected. Amongst other compensatory adjustments that accompany exercise training (e.g., increases in resting metabolic rate and energy intake), a possible cause of the less than expected weight loss is a failure to produce a marked increase in total daily energy expenditure due to a compensatory reduction in non-exercise activity thermogenesis (NEAT). Therefore, there is a need to understand how behaviour is modified in response to exercise interventions. The proposed benefits of exercise training are numerous, including changes to fat oxidation. Given that a diminished capacity to oxidise fat could be a factor in the aetiology of obesity, an exercise training intensity that optimises fat oxidation in overweight/obese individuals would improve impaired fat oxidation, and potentially reduce health risks that are associated with obesity. To improve our understanding of the effectiveness of exercise for weight management, it is important to ensure exercise intensity is appropriately prescribed, and to identify and monitor potential compensatory behavioural changes consequent to exercise training. In line with the gaps in the literature, three studies were performed. The aim of Study 1 was to determine the effect of acute bouts of moderate- and high-intensity walking exercise on NEAT in overweight and obese men. Sixteen participants performed a single bout of either moderate-intensity walking exercise (MIE) or high-intensity walking exercise (HIE) on two separate occasions. The MIE consisted of walking for 60-min on a motorised treadmill at 6 km.h-1. The 60-min HIE session consisted of walking in 5-min intervals at 6 km.h-1 and 10% grade followed by 5-min at 0% grade. NEAT was assessed by accelerometer three days before, on the day of, and three days after the exercise sessions. There was no significant difference in NEAT vector magnitude (counts.min-1) between the pre-exercise period (days 1-3) and the exercise day (day 4) for either protocol. In addition, there was no change in NEAT during the three days following the MIE session, however NEAT increased by 16% on day 7 (post-exercise) compared with the exercise day (P = 0.32). During the post-exercise period following the HIE session, NEAT was increased by 25% on day 7 compared with the exercise day (P = 0.08), and by 30-33% compared with the pre-exercise period (day 1, day 2 and day 3); P = 0.03, 0.03, 0.02, respectively. To conclude, a single bout of either MIE or HIE did not alter NEAT on the exercise day or on the first two days following the exercise session. However, extending the monitoring of NEAT allowed the detection of a 48 hour delay in increased NEAT after performing HIE. A longer-term intervention is needed to determine the effect of accumulated exercise sessions over a week on NEAT. In Study 2, there were two primary aims. The first aim was to test the reliability of a discontinuous incremental exercise protocol (DISCON-FATmax) to identify the workload at which fat oxidation is maximised (FATmax). Ten overweight and obese sedentary male men (mean BMI of 29.5 ¡Ó 4.5 kg/m2 and mean age of 28.0 ¡Ó 5.3 y) participated in this study and performed two identical DISCON-FATmax tests one week apart. Each test consisted of alternate 4-min exercise and 2-min rest intervals on a cycle ergometer. The starting work load of 28 W was increased every 4-min using 14 W increments followed by 2-min rest intervals. When the respiratory exchange ratio was consistently >1.0, the workload was increased by 14 W every 2-min until volitional exhaustion. Fat oxidation was measured by indirect calorimetry. The mean FATmax, ƒtV O2peak, %ƒtV O2peak and %Wmax at which FATmax occurred during the two tests were 0.23 ¡Ó 0.09 and 0.18 ¡Ó 0.08 (g.min-1); 29.7 ¡Ó 7.8 and 28.3 ¡Ó 7.5 (ml.kg-1.min-1); 42.3 ¡Ó 7.2 and 42.6 ¡Ó 10.2 (%ƒtV O2max) and 36.4 ¡Ó 8.5 and 35.4 ¡Ó 10.9 (%), respectively. A paired-samples T-test revealed a significant difference in FATmax (g.min-1) between the tests (t = 2.65, P = 0.03). The mean difference in FATmax was 0.05 (g.min-1) with the 95% confidence interval ranging from 0.01 to 0.18. Paired-samples T-test, however, revealed no significant difference in the workloads (i.e. W) between the tests, t (9) = 0.70, P = 0.4. The intra-class correlation coefficient for FATmax (g.min-1) between the tests was 0.84 (95% confidence interval: 0.36-0.96, P < 0.01). However, Bland-Altman analysis revealed a large disagreement in FATmax (g.min-1) related to W between the two tests; 11 ¡Ó 14 (W) (4.1 ¡Ó 5.3 ƒtV O2peak (%)).These data demonstrate two important phenomena associated with exercise-induced substrate oxidation; firstly, that maximal fat oxidation derived from a discontinuous FATmax protocol differed statistically between repeated tests, and secondly, there was large variability in the workload corresponding with FATmax. The second aim of Study 2 was to test the validity of a DISCON-FATmax protocol by comparing maximal fat oxidation (g.min-1) determined by DISCON-FATmax with fat oxidation (g.min-1) during a continuous exercise protocol using a constant load (CONEX). Ten overweight and obese sedentary males (BMI = 29.5 ¡Ó 4.5 kg/m2; age = 28.0 ¡Ó 4.5 y) with a ƒtV O2max of 29.1 ¡Ó 7.5 ml.kg-1.min-1 performed a DISCON-FATmax test consisting of alternate 4-min exercise and 2-min rest intervals on a cycle ergometer. The 1-h CONEX protocol used the workload from the DISCON-FATmax to determine FATmax. The mean FATmax, ƒtV O2max, %ƒtV O2max and workload at which FATmax occurred during the DISCON-FATmax were 0.23 ¡Ó 0.09 (g.min-1); 29.1 ¡Ó 7.5 (ml.kg-1.min-1); 43.8 ¡Ó 7.3 (%ƒtV O2max) and 58.8 ¡Ó 19.6 (W), respectively. The mean fat oxidation during the 1-h CONEX protocol was 0.19 ¡Ó 0.07 (g.min-1). A paired-samples T-test revealed no significant difference in fat oxidation (g.min-1) between DISCON-FATmax and CONEX, t (9) = 1.85, P = 0.097 (two-tailed). There was also no significant correlation in fat oxidation between the DISCON-FATmax and CONEX (R=0.51, P = 0.14). Bland- Altman analysis revealed a large disagreement in fat oxidation between the DISCONFATmax and CONEX; the upper limit of agreement was 0.13 (g.min-1) and the lower limit of agreement was ¡V0.03 (g.min-1). These data suggest that the CONEX and DISCONFATmax protocols did not elicit different rates of fat oxidation (g.min-1). However, the individual variability in fat oxidation was large, particularly in the DISCON-FATmax test. Further research is needed to ascertain the validity of graded exercise tests for predicting fat oxidation during constant load exercise sessions. The aim of Study 3 was to compare the impact of two different intensities of four weeks of exercise training on fat oxidation, NEAT, and appetite in overweight and obese men. Using a cross-over design 11 participants (BMI = 29 ¡Ó 4 kg/m2; age = 27 ¡Ó 4 y) participated in a training study and were randomly assigned initially to: [1] a lowintensity (45%ƒtV O2max) exercise (LIT) or [2] a high-intensity interval (alternate 30 s at 90%ƒtV O2max followed by 30 s rest) exercise (HIIT) 40-min duration, three times a week. Participants completed four weeks of supervised training and between cross-over had a two week washout period. At baseline and the end of each exercise intervention,ƒtV O2max, fat oxidation, and NEAT were measured. Fat oxidation was determined during a standard 30-min continuous exercise bout at 45%ƒtV O2max. During the steady state exercise expired gases were measured intermittently for 5-min periods and HR was monitored continuously. In each training period, NEAT was measured for seven consecutive days using an accelerometer (RT3) the week before, at week 3 and the week after training. Subjective appetite sensations and food preferences were measured immediately before and after the first exercise session every week for four weeks during both LIT and HIIT. The mean fat oxidation rate during the standard continuous exercise bout at baseline for both LIT and HIIT was 0.14 ¡Ó 0.08 (g.min-1). After four weeks of exercise training, the mean fat oxidation was 0.178 ¡Ó 0.04 and 0.183 ¡Ó 0.04 g.min-1 for LIT and HIIT, respectively. The mean NEAT (counts.min-1) was 45 ¡Ó 18 at baseline, 55 ¡Ó 22 and 44 ¡Ó 16 during training, and 51 ¡Ó 14 and 50 ¡Ó 21 after training for LIT and HIIT, respectively. There was no significant difference in fat oxidation between LIT and HIIT. Moreover, although not statistically significant, there was some evidence to suggest that LIT and HIIT tend to increase fat oxidation during exercise at 45% ƒtV O2max (P = 0.14 and 0.08, respectively). The order of training treatment did not significantly influence changes in fat oxidation, NEAT, and appetite. NEAT (counts.min-1) was not significantly different in the week following training for either LIT or HIIT. Although not statistically significant (P = 0.08), NEAT was 20% lower during week 3 of exercise training in HIIT compared with LIT. Examination of appetite sensations revealed differences in the intensity of hunger, with higher ratings after LIT compared with HIIT. No differences were found in preferences for high-fat sweet foods between LIT and HIIT. In conclusion, the results of this thesis suggest that while fat oxidation during steady state exercise was not affected by the level of exercise intensity, there is strong evidence to suggest that intense exercise could have a debilitative effect on NEAT.

Is social entrepreneurship the way forward? The case of the livingin collective

Social entrepreneurship can be conceived generally as a creative force born to address emergent or longstanding unfulfilled community needs occurring within or across the non-profit, business or government sectors. In this paper, we consider the current case study of a collective comprising a non-profit community organisation, pro-bono design group and university researchers and its attempts to negotiate the tension between social innovation and social entrepreneurship in order to address the lack of suitable options for independent living for individuals with disabilities and their families. With much of the developed world coming to terms with a rapidly aging population, and increased survival rates for individuals with disabilities, there has never been a more opportune time to consider work such as this which attempts to address social and market gaps in a socially innovative and inclusive way.

Volume

In this video, words describing socially awkward conversations float around an animated cloud of gas. A cosmic stock music track accompanies the words. This work examines processes of signification. It emphasizes multiplicity and disconnection as fundamental and generative operations in making meaning. By playing with the simultaneity of internal monologues and external conversations, it draws attention to the seams, gaps and slippages that occur in signifying acts.

Current research in risk-aware business process management : overview, comparison, and gap analysis

The management of risks in business processes has been a subject of active research in the past few years. Many benefits can potentially be obtained by integrating the two traditionally-separated fields of risk management and business process management, including the ability to minimize risks in business processes (by design) and to mitigate risks at run time. In the past few years, an increasing amount of research aimed at delivering such an integrated system has been proposed. However, these research efforts vary in terms of their scope, goals, and functionality. Through systematic collection and evaluation of relevant literature, this paper compares and classifies current approaches in the area of risk-aware business process management in order to identify and explain relevant research gaps. The process through which relevant literature is collected, filtered, and evaluated is also detailed.

"Participation" in participatory design research

This thesis is about defining participation in the context of fostering research cohesion in the field of Participatory Design. The systematic and incremental building of new knowledge is the process by which science and research is advanced. This process requires a certain type of cohesion in the way research is undertaken for new knowledge to be built from the knowledge provided by previous projects and research. To support this process and to foster research cohesion three conditions are necessary. These conditions are: common ground between practitioners, problem-space positioning, and adherence to clear research criteria. The challenge of fostering research cohesion in Participatory Design is apparent in at least four themes raised in the literature: the role of politics within Participatory Design epistemology, the role of participation, design with users, and the ability to translate theory into practice. These four thematic challenges frame the context which the research gap is situated. These themes are also further investigated and the research gap – a general lack of research cohesion – along with one avenue for addressing this gap – a clear and operationalizable definition for participation – are identified. The intended contribution of this thesis is to develop a framework and visual tool to address this research gap. In particular, an initial approximation for a clear and operationalizable definition for participation will be proposed such that it can be used within the field of Participatory Design to run projects and foster research cohesion. In pursuit of this contribution, a critical lens is developed and used to analyse some of the principles and practices of Participatory Design that are regarded as foundational. This lens addresses how to define participation in a way that adheres to basic principles of scientific rigour – namely, ensuring that the elements of a theory are operationalizable, falsifiable, generalizable, and useful, and it also treats participation as a construct rather than treating the notion of participation as a variable. A systematic analysis is performed using this lens on the principles and practices that are considered foundational within the field. From this analysis, three components of the participation construct – impact, influence, and agency – are identified. These components are then broken down into two constituent variables each (six in all) and represented visually. Impact is described as the relationship between the quality and use of information. Influence is described as the relationship between the amount and scope of decision making. Agency is described as the relationship between the motivation of the participant and the solidarity of the group. Thus, as a construct, participation is described as the relationship between a participant’s impact, influence, and agency. In the concluding section, the value of this participation construct is explored for its utility in enhancing project work and fostering research cohesion. Three items of potential value that emerge are: the creation of a visual tool through the representation of these six constituent variables in one image; the elaboration of a common language for researchers based on the six constituent variables identified; and the ability to systematically identify and remedy participation gaps throughout the life of the project. While future research exploring the applicability of the participation construct in real world projects is necessary, it is intended that this initial approximation of a participation construct in the form of the visual tool will serve as the basis for a cohesive and rigorous discussion about participation in Participatory Design.

A tan in a test tube -in vitro models for investigating ultraviolet radiation-induced damage in skin

Presently, global rates of skin cancers induced by ultraviolet radiation (UVR) exposure are on the rise. In view of this, current knowledge gaps in the biology of photocarcinogenesis and skin cancer progression urgently need to be addressed. One factor that has limited skin cancer research has been the need for a reproducible and physiologically-relevant model able to represent the complexity of human skin. This review outlines the main currently-used in vitro models of UVR-induced skin damage. This includes the use of conventional two-dimensional cell culture techniques and the major animal models that have been employed in photobiology and photocarcinogenesis research. Additionally, the progression towards the use of cultured skin explants and tissue-engineered skin constructs, and their utility as models of native skin's responses to UVR are described. The inherent advantages and disadvantages of these in vitro systems are also discussed.

Developing a framework for planning healthy communities : the Logan Beaudesert health decision support system

In the last few decades, the focus on building healthy communities has grown significantly (Ashton, 2009). There is growing evidence that new approaches to planning are required to address the challenges faced by contemporary communities. These approaches need to be based on timely access to local information and collaborative planning processes (Murray, 2006; Scotch & Parmanto, 2006; Ashton, 2009; Kazda et al., 2009). However, there is little research to inform the methods that can support this type of responsive, local, collaborative and consultative health planning (Northridge et al., 2003). Some research justifies the use of decision support systems (DSS) as a tool to support planning for healthy communities. DSS have been found to increase collaboration between stakeholders and communities, improve the accuracy and quality of the decision-making process, and improve the availability of data and information for health decision-makers (Nobre et al., 1997; Cromley & McLafferty, 2002; Waring et al., 2005). Geographic information systems (GIS) have been suggested as an innovative method by which to implement DSS because they promote new ways of thinking about evidence and facilitate a broader understanding of communities. Furthermore, literature has indicated that online environments can have a positive impact on decision-making by enabling access to information by a broader audience (Kingston et al., 2001). However, only limited research has examined the implementation and impact of online DSS in the health planning field. Previous studies have emphasised the lack of effective information management systems and an absence of frameworks to guide the way in which information is used to promote informed decisions in health planning. It has become imperative to develop innovative approaches, frameworks and methods to support health planning. Thus, to address these identified gaps in the knowledge, this study aims to develop a conceptual planning framework for creating healthy communities and examine the impact of DSS in the Logan Beaudesert area. Specifically, the study aims to identify the key elements and domains of information that are needed to develop healthy communities, to develop a conceptual planning framework for creating healthy communities, to collaboratively develop and implement an online GIS-based Health DSS (i.e., HDSS), and to examine the impact of the HDSS on local decision-making processes. The study is based on a real-world case study of a community-based initiative that was established to improve public health outcomes and promote new ways of addressing chronic disease. The study involved the development of an online GIS-based health decision support system (HDSS), which was applied in the Logan Beaudesert region of Queensland, Australia. A planning framework was developed to account for the way in which information could be organised to contribute to a healthy community. The decision support system was developed within a unique settings-based initiative Logan Beaudesert Health Coalition (LBHC) designed to plan and improve the health capacity of Logan Beaudesert area in Queensland, Australia. This setting provided a suitable platform to apply a participatory research design to the development and implementation of the HDSS. Therefore, the HDSS was a pilot study examined the impact of this collaborative process, and the subsequent implementation of the HDSS on the way decision-making was perceived across the LBHC. As for the method, based on a systematic literature review, a comprehensive planning framework for creating healthy communities has been developed. This was followed by using a mixed method design, data were collected through both qualitative and quantitative methods. Specifically, data were collected by adopting a participatory action research (PAR) approach (i.e., PAR intervention) that informed the development and conceptualisation of the HDSS. A pre- and post-design was then used to determine the impact of the HDSS on decision-making. The findings of this study revealed a meaningful framework for organising information to guide planning for healthy communities. This conceptual framework provided a comprehensive system within which to organise existing data. The PAR process was useful in engaging stakeholders and decision-making in the development and implementation of the online GIS-based DSS. Through three PAR cycles, this study resulted in heightened awareness of online GIS-based DSS and openness to its implementation. It resulted in the development of a tailored system (i.e., HDSS) that addressed the local information and planning needs of the LBHC. In addition, the implementation of the DSS resulted in improved decision- making and greater satisfaction with decisions within the LBHC. For example, the study illustrated the culture in which decisions were made before and after the PAR intervention and what improvements have been observed after the application of the HDSS. In general, the findings indicated that decision-making processes are not merely informed (consequent of using the HDSS tool), but they also enhance the overall sense of ‗collaboration‘ in the health planning practice. For example, it was found that PAR intervention had a positive impact on the way decisions were made. The study revealed important features of the HDSS development and implementation process that will contribute to future research. Thus, the overall findings suggest that the HDSS is an effective tool, which would play an important role in the future for significantly improving the health planning practice.

A study of ionic liquids for dissolution of sugarcane bagasse

Over the last decade, Ionic Liquids (ILs) have been used for the dissolution and derivatization of isolated cellulose. This ability of ILs is now sought for their application in the selective dissolution of cellulose from lignocellulosic biomass, for the manufacture of cellulosic ethanol. However, there are significant knowledge gaps in the understanding of the chemistry of the interaction of biomass and ILs. While imidazolium ILs have been used successfully to dissolve both isolated crystalline cellulose and components of lignocellulosic biomass, phosphonium ILs have not been sufficiently explored for the use in dissolution of lignocellulosic biomass. This thesis reports on the study of the chemistry of sugarcane bagasse with phosphonium ILs. Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO4) are obtained using attenuated total reflectance-Fourier Transform Infra Red (FTIR). Absorption bands related to cellulose, hemicelluloses and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalysed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The quantitative measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm-1 has demonstrated utility and greater precision than the conventional Klason lignin method. The cleavage of lignin β-aryl ether bonds in sugarcane bagasse by the ionic liquid [P66614]Cl, in the presence of catalytic amounts of mineral acid. (ca. 0.4 %). The delignification process of bagasse is studied over a range of temperatures (120 °C to 150 °C) by monitoring the production of β-ketones (indicative of cleavage of β-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum delignification is obtained at 150 °C, with 52 % of lignin removed from the original lignin content of bagasse. No delignification is observed in the absence of acid which suggests that the reaction is acid catalysed with the IL solubilising the lignin fragments. The rate of delignification was significantly higher at 150 °C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of β-aryl ethers. An attempt has been made to propose a probable mechanism of delignifcation of bagasse with the phosphonuim IL. All polymeric components of bagasse, a lignocellulosic biomass, dissolve in the hydrophilic ionic liquid (IL) tributylmethylphosphonium methylsulfate ([P4441]MeSO4) with and without a catalytic amount of acid (H2SO4, ca. 0.4 %). The presence of acid significantly increases the extent of dissolution of bagasse in [P4441]MeSO4 (by ca. 2.5 times under conditions used here). The dissolved fractions can be partially recovered by the addition of an antisolvent (water) and are significantly enriched in lignin. Unlike acid catalysed dissolution in the hydrophobic IL tetradecyltrihexylphosphonium chloride there is little evidence of cleavage of β-aryl ether bonds of lignin dissolving in [P4441]MeSO4 (with and without acid), but this mechanism may play some role in the acid catalysed dissolution. The XRD of the undissolved fractions suggests that the IL may selectively dissolve the amorphous cellulose component, leaving behind crystalline material.

Comparative effectiveness of population interventions to improve access to reperfusion for ST-segment–elevation myocardial infarction in Australia

Background Improving timely access to reperfusion is a major goal of ST-segment–elevation myocardial infarction care. We sought to compare the population impact of interventions proposed to improve timely access to reperfusion therapy in Australia. Methods and Results Australian hospitals, population, and road network data were integrated using Geographical Information Systems. Hospitals were classified into those that provided primary percutaneous coronary intervention (PPCI) or fibrinolysis. Population impact of interventions proposed to improve timely access to reperfusion (PPCI, fibrinolysis, or both) were modeled and compared. Timely access to reperfusion was defined as the proportion of the population capable of reaching a fibrinolysis facility ≤60 minutes or a PPCI facility ≤120 minutes from emergency medical services activation. The majority (93.2%) of the Australian population has timely access to reperfusion, mainly (53%) through fibrinolysis. Only 40.2% of the population had timely access to PPCI, and access to PPCI services is particularly limited in regional and nonexistent in remote areas. Optimizing the emergency medical services’ response or increasing PPCI services resulted in marginal improvement in timely access (1.8% and 3.7%, respectively). Direct transport to PPCI facilities and interhospital transfer for PPCI improves timely access to PPCI for 19.4% and 23.5% of the population, respectively. Prehospital fibrinolysis markedly improved access to timely reperfusion in regional and remote Australia. Conclusions Significant gaps in timely provision of reperfusion remain in Australia. Systematic implementation of changes in service delivery has potential to improve timely access to PPCI for a majority of the population and improve access to fibrinolysis to those living in regional and remote areas.