262 resultados para Reversible Addition Fragmentation Chain Transfer (raft)


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Climate change, resource depletion and increasing urbanization are converging global issues that are challenging the way we design, construct and operate buildings. The housing sector is a significant contributor to these global issues through consumption of limited resources, waste generation and disposal (solid, liquid and atmospheric waste) and negative human health impacts (Senick 2006). Although the design and construction of ‘sustainable housing’ would appear to be an obvious and technically feasible solution, there remains multi-faceted issues affecting the delivery of sustainable housing (Holloway and Bunker 2006). Two fundamental issues - what makes a house sustainable, and to what extent regulation should be used to deliver sustainability - have been, and continue to be, debated at multiple levels in society. Despite personal, professional and political views on these issues, three key characteristics of the whole housing supply chain require fundamental change if we are to successfully address sustainability challenges (Birkeland 2008). These include: fragmentation; established methods, practices and processes, and the relationships between players. A more in-depth understanding of the role of ethics (values, beliefs and standards) and potential ethical conflicts within the supply chain will assist in better defining the nature of the fundamental changes required...

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Waitrose has a strong commitment to organic farming but also uses products from 'conventional' farms. At the production stage, Waitrose own-label products are fully traceable, GM-free and all suppliers undergo a detailed assessment programme based on current best practice. Crop suppliers to Waitrose operate an authenticity programme to certify that each assignment is GM-free and produce is screened for pesticide residues. Waitrose sources conventional crops grown from 'Integrated Crop Management Systems' (ICMS) using best horticultural practices. The 'Assured Product' scheme regulates all UK produce to ICMS standards and these audits are being extended worldwide. Business is withdrawn from suppliers who fail the audit. In relation to this, Waitrose has increased its Fairtrade range as in its view 'Buying these products provides direct additional benefit to workers in the developing countries where they are produced and assists marginal producers by giving them access to markets they would not otherwise have'. Currently, Waitrose is developing its own sustainable timber assessment criteria. For livestock, protocols are in place to ensure that animals are reared under the 'most natural conditions possible' and free range produce is offered where animals have access to open space although some produce is not from free-range animals. Waitrose also use a 'Hazards Analysis Critical Points' system to identify food safety hazards that occur at any stage from production to point of sale and to ensure that full measures are in place to control them. In addition, mechanisms have been implemented to reduce fuel use and hence reduce CO2 emissions in the transport of products and staff, and to increase the energy use efficiency of refrigeration systems which account for approximately 60% of Waitrose energy use.

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Organizations adopt a Supply Chain Management System (SCMS) expecting benefits to the organization and its functions. However, organizations are facing mounting challenges to realizing benefits through SCMS. Studies suggest a growing dissatisfaction among client organizations due to an increasing gap between expectations and realization of SCMS benefits. Further, reflecting the Enterprise System studies such as Seddon et al. (2010), SCMS benefits are also expected to flow to the organization throughout its lifecycle rather than being realized all at once. This research therefore proposes to derive a lifecycle-wide understanding of SCMS benefits and realization to derive a benefit expectation management framework to attain the full potential of an SCMS. The primary research question of this study is: How can client organizations better manage their benefit expectations of SCM systems? The specific research goals of the current study include: (1) to better understand the misalignment of received and expected benefits of SCM systems; (2) to identify the key factors influencing SCM system expectations and to develop a framework to manage SCMS benefits; (3) to explore how organizational satisfaction is influenced by the lack of SCMS benefit confirmation; and (4) to explore how to improve the realization of SCM system benefits. Expectation-Confirmation Theory (ECT) provides the theoretical underpinning for this study. ECT has been widely used in the consumer behavior literature to study customer satisfaction, post-purchase behavior and service marketing in general. Recently, ECT has been extended into Information Systems (IS) research focusing on individual user satisfaction and IS continuance. However, only a handful of studies have employed ECT to study organizational satisfaction on large-scale IS. The current study will enrich the research stream by extending ECT into organizational-level analysis and verifying the preliminary findings of relevant works by Staples et al. (2002), Nevo and Chan (2007) and Nevo and Wade (2007). Moreover, this study will go further trying to operationalize the constructs of ECT into the context of SCMS. The empirical findings of the study commence with a content analysis, through which 41 vendor reports and academic reports are analyzed yielding sixty expected benefits of SCMS. Then, the expected benefits are compared with the benefits realized at a case organization in the Fast Moving Consumer Goods industry sector that had implemented a SAP Supply Chain Management System seven years earlier. The study develops an SCMS Benefit Expectation Management (SCMS-BEM) Framework. The comparison of benefit expectations and confirmations highlights that, while certain benefits are realized earlier in the lifecycle, other benefits could take almost a decade to realize. Further analysis and discussion on how the developed SCMS-BEM Framework influences ECT when applied in SCMS was also conducted. It is recommended that when establishing their expectations of the SCMS, clients should remember that confirmation of these expectations will have a long lifecycle, as shown in the different time periods in the SCMS-BEM Framework. Moreover, the SCMS-BEM Framework will allow organizations to maintain high levels of satisfaction through careful mitigation and confirming expectations based on the lifecycle phase. In addition, the study reveals that different stakeholder groups have different expectations of the same SCMS. The perspective of multiple stakeholders has significant implications for the application of ECT in the SCMS context. When forming expectations of the SCMS, the collection of organizational benefits of SCMS should represent the perceptions of all stakeholder groups. The same mechanism should be employed in the measurements of received SCMS benefits. Moreover, for SCMS, there exists interdependence of the satisfaction among the various stakeholders. The satisfaction of decision-makers or the authorized staff is not only driven by their own expectation confirmation level, it is also influenced by the confirmation level of other stakeholders‘ expectations in the organization. Satisfaction from any one particular stakeholder group can not reflect the true satisfaction of the client organization. Furthermore, it is inferred from the SCMS-BEM Framework that organizations should place emphasis on the viewpoints of the operational and management staff when evaluating the benefits of SCMS in the short and middle term. At the same time, organizations should be placing more attention on the perspectives of strategic staff when evaluating the performance of the SCMS in the long term.

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Background WSUD implementation in the Gold Coast City Council area commenced more than a decade ago. As a result, Council is expected to be in possession of WSUD assets valued at over tens of million dollars. The Gold Coast City Council is responsible for the maintenance and long-term management of these WSUD assets. Any shortcoming in implementation of best WSUD practices can potentially result in substantial liabilities and ineffective expenditure for the Council in addition to reduced efficiencies and outcomes. This highlights the importance of periodic auditing of WSUD implementation. Project scope The overall study entailed the following tasks: * A state-of-the-art literature review of the conceptual hydraulic and water quality treatment principles, current state of knowledge in relation to industry standards, best practice and identification of knowledge gaps in relation to maintenance and management practices and potential barriers to the implementation of WSUD. * Council stakeholder interviews to understand current practical issues in relation to the implementation of WSUD and the process of WSUD application from development application approval to asset management. * Field auditing of selected WSUD systems for condition assessment and identification of possible strengths and weaknesses in implementation. * Review of the Land Development Guidelines in order to identify any gaps and to propose recommendations for improvement. Conclusions Given below is a consolidated summary of the findings of the study undertaken. State-of-the-art literature review Though the conceptual framework for WSUD implementation is well established, the underlying theoretical knowledge underpinning the treatment processes and maintenance regimes and life cycle costing are still not well understood. Essentially, these are the recurring themes in the literature, namely, the inadequate understanding of treatment processes and lack of guidance to ensure specificity of maintenance regimes and life cycle costing of WSUDs. The fundamental barriers to successful WSUD implementation are: * Lack of knowledge transfer – This essentially relates to the lack of appropriate dissemination of research outcomes and the common absence of protocols for knowledge transfer within the same organisation. * Cultural barriers – These relate to social and institutional factors, including institutional inertia and the lack of clear understanding of the benefits. * Fragmented responsibilities – This results from poor administrative integration within local councils in relation to WSUDs. * Technical barriers – These relate to lack of knowledge on operational and maintenance practices which is compounded by model limitations and the lack of long-term quantitative performance evaluation data. * Lack of engineering standards – Despite the availability of numerous guidelines which are non-enforceable and can sometimes be confusing, there is a need for stringent engineering standards. The knowledge gaps in relation to WSUDs are only closing very slowly. Some of the common knowledge gaps identified in recent publications have been recognised almost a decade ago. The key knowledge gaps identified in the published literature are: * lack of knowledge on operational and maintenance practices; * lack of reliable methodology for identifying life cycle issues including costs; * lack of technical knowledge on system performance; * lack of guidance on retrofitting in existing developments. Based on the review of barriers to WSUD implementation and current knowledge gaps, the following were identified as core areas for further investigation: * performance evaluation of WSUD devices to enhance model development and to assess their viability in the context of environmental, economic and social drivers; establishing realistic life cycle costs to strengthen maintenance and asset management practices; * development of guidelines specific to retrofitting in view of the unique challenges posed by existing urban precincts together with guidance to ensure site specificity; establishment of a process for knowledge translation for enhancing currently available best practice guidelines; * identification of drivers and overcoming of barriers in the areas of institutional fragmentation, knowledge gaps and awareness of WSUD practices. GCCC stakeholder interviews Fourteen staff members involved in WSUD systems management in the Gold Coast City Council, representing four Directorates were interviewed using a standard questionnaire. The primary issues identified by the stakeholders were: * standardisation of WSUD terminology; * clear protocols for safeguarding devices during the construction phase; * engagement of all council stakeholders in the WSUD process from the initial phase; * limitations in the Land Development Guidelines; * ensuring public safety through design; * system siting to avoid conflicts with environmental and public use of open space; * provision of adequate access for maintenance; * integration of social and ecosystem issues to ensure long-term viability of systems in relation to both, vandalism and visual recreation; * lack of performance monitoring and inadequacy of the maintenance budget; * lack of technical training for staff involved in WSUD design approvals and maintenance; incentives for developers for acting responsibly in stormwater management. Field auditing of WSUD systems A representative cross section of WSUD systems in the Gold Coast were audited in the field. The following strengths and weaknesses in WSUD implementation were noted: * The implementation of WSUD systems in the field is not consistent. * The concerns raised by the stakeholders during the interviews in relation to WSUD implementation was validated from the observations from the field auditing, particularly in relation to the following: * safeguarding of devices during the construction phase * public safety * accessibility for maintenance * lack of performance monitoring by Council to assess system performance * inadequate maintenance of existing systems to suit site specific requirements. * A treatment train approach is not being consistently adopted. * Most of the systems audited have satisfactorily catered for public safety. Accessibility for maintenance has been satisfactorily catered for in most of the systems that were audited. * Systems are being commissioned prior to construction activities being substantially completed. * The hydraulic design of most systems appears to be satisfactory. * The design intent of the systems is not always clear. Review of Land Development Guidelines The Land Development Guidelines (TDG) was extensively reviewed and the following primary issues were noted in relation to WSUD implementation: * the LDG appears to have been prepared primarily to provide guidance to developers. It is not clear to what extent the guidelines are applicable to Council staff involved in WSUD maintenance and management; * Section 13 is very voluminous and appears to be a compilation of a series of individual documents resulting in difficulties in locating specific information, a lack of integration and duplication of information; * the LDG has been developed with a primary focus on new urban precinct development and the retrofitting of systems in existing developments has not been specifically discussed; * WSUDs are discussed in two different sections in the LDG and it is not clear which section takes precedence as there are inconsistencies between the two sections; there is inconsistent terminology being used; * there is a need for consolidation of information provided in different sections in the LDG; * there are inconsistencies in the design criteria provided; * there is a need for regular updating of the LDG to ensure that the information provided encompasses the state-of-the-art; * there is limited guidance provided for the preparation of maintenance plans and life cycle costing to assist developers in asset handover and to assist Council staff in assessment. * Based on these observations, eleven recommendations have been provided which are discussed below. Additionally, the stakeholder provided the following specific comments during the interviews in relation to the LDG: * lack of flexibility to cover the different stages of the life cycle of the systems; * no differentiation in projects undertaken by developers and Council; * inadequate information with regards to safety issues such as maximum standing water depth, fencing and safety barriers and public access; * lack of detailed design criteria in relation to Crime Prevention through Environmental Design, safety, amenity, environment, surrounding uses and impacts on surroundings; * inadequate information regarding maintenance requirements specific to the assessment and compliance phases; * recommendations for plantings are based primarily on landscape requirements rather than pollutant uptake capability. Recommendations With regards to the Land Development Guidelines, the following specific recommendations are provided: 1. the relevant sections and their extent of applicability to Council should be clearly identified; 2. integration of the different subsections within Section 13 and re-formatting the document for easy reference; 3. the maintenance guidelines provided in Section 13 should be translated to a maintenance manual for guidance of Council staff; 4. should consider extending the Guidelines to specifically encompass retrofitting of WSUD systems to existing urban precincts; 5. Section 3 needs to be revised to be made consistent with Section 13, to ensure priority for WSUD practices in urban precincts and to move away from conventional stormwater drainage design such as kerb and channelling; 6. it would also be good to specify as to which Section takes predominance in relation to stormwater drainage. It is expected that Section 13 would take predominance over the other sections in the LDG; 7. terminology needs to be made consistent to avoid confusion among developers and Council staff. Water Sensitive Urban Design is the term commonly used in Australia for stormwater quality treatment, rather than Stormwater Quality Improvement Devices. This once again underlines the need for ensuring consistency between Section 3 and Section 13; 8. it would also be good if there is a glossary of commonly used terms in relation to WSUD for use by all stakeholders and which should also be reflected in the LDG; 9. consolidation of all WSUD information into one section should be considered together with appropriate indicators in other LDG Sections regarding the availability of WSUD information. Ensuring consistency in the information provided is implied; 10. Section 13 should be updated at regular intervals to ensure the incorporation of the latest in research outcomes and incorporating criteria and guidance based on the state-of-the-art knowledge. The updating could be undertaken, say, in five year cycles. This would help to overcome the current lack of knowledge transfer; 11. the Council should consider commissioning specialised studies to extend the current knowledge base in relation to WSUD maintenance and life cycle costing. Additionally, Recommendation 10 is also applicable in this instance. The following additional recommendations are made based on the state-of-the-art literature review, stakeholder interviews and field auditing of WSUD systems: 1. Performance monitoring of existing systems to assess improvements to water quality, identify modifications and enhancements to improve performance; 2. Appropriate and monitored maintenance during different phases of development of built assets over time is needed to investigate the most appropriate time/phase of development to commission the final WSUD asset. 3. Undertake focussed investigations in the areas of WSUD maintenance and asset management in order to establish more realistic life cycle costs of systems and maintenance schedules; 4. the engagement of all relevant Council stakeholders from the initial stage of concept planning through to asset handover, and ongoing monitoring. This close engagement of internal stakeholders will assist in building a greater understanding of responsibilities and contribute to overcoming constraints imposed by fragmented responsibilities; 5. the undertaking of a public education program to inform the community of the benefits and ecosystem functions of WSUD systems; 6. technical training to impart state-of-the-art knowledge to staff involved in the approval of designs and maintenance and management of WSUD projects; 7. during the construction phase, it is important to ensure that appropriate measures to safeguard WSUD devices are implemented; 8. risks associated with potential public access to open water zones should be minimised with the application of appropriate safety measures; 9. system siting should ensure that potential conflicts are avoided with respect to public and ecosystem needs; 10. integration of social and ecosystem issues to ensure long-term viability of systems; provide incentives to developers who are proactive and responsible in the area of stormwater management.

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In the electricity market environment, coordination of system reliability and economics of a power system is of great significance in determining the available transfer capability (ATC). In addition, the risks associated with uncertainties should be properly addressed in the ATC determination process for risk-benefit maximization. Against this background, it is necessary that the ATC be optimally allocated and utilized within relative security constraints. First of all, the non-sequential Monte Carlo stimulation is employed to derive the probability density distribution of ATC of designated areas incorporating uncertainty factors. Second, on the basis of that, a multi-objective optimization model is formulated to determine the multi-area ATC so as to maximize the risk-benefits. Then, the solution to the developed model is achieved by the fast non-dominated sorting (NSGA-II) algorithm, which could decrease the risk caused by uncertainties while coordinating the ATCs of different areas. Finally, the IEEE 118-bus test system is served for demonstrating the essential features of the developed model and employed algorithm.

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The chemically reversible solid−solid phase transformation of a TCNQ-modified glassy carbon, indium tin oxide, or metal electrode into Co\[TCNQ]2(H2O)2 material in the presence of Co2+(aq) containing electrolytes has been induced and monitored electrochemically. Voltammetric data reveal that the TCNQ/Co\[TCNQ]2(H2O)2 interconversion process is independent of electrode material and identity of cobalt electrolyte anion. However, a marked dependence on electrolyte concentration, scan rate, and method of electrode modification (drop casting or mechanical attachment) is found. Cyclic voltammetric and double potential step chronoamperometric measurements confirm that formation of Co\[TCNQ]2(H2O)2 occurs through a rate-determining nucleation and growth process that initially involves incorporation of Co2+(aq) ions into the reduced TCNQ crystal lattice at the TCNQ|electrode|electrolyte interface. Similarly, the reverse (oxidation) process, which involves transformation of solid Co\[TCNQ]2(H2O)2 back to parent TCNQ crystals, also is controlled by nucleation−growth kinetics. The overall chemically reversible process that represents this transformation is described by the reaction:  2TCNQ0(s) + 2e- + Co2+(aq) + 2H2O \[Co(TCNQ)2(H2O)2](s). Ex situ SEM images illustrated that this reversible TCNQ/Co\[TCNQ]2(H2O)2 conversion process is accompanied by drastic size and morphology changes in the parent solid TCNQ. In addition, different sizes of needle-shaped nanorod/nanowire crystals of Co\[TCNQ]2(H2O)2 are formed depending on the method of surface immobilization.

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Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an \[M + NO2](+) adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro-(RNO2) or nitrosoxy-(RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized \[M + NO2](+) adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro-and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized \[M + NO2](+) adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

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RATIONALE Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required. METHODS Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M+Na]+ ions that can be mass-selected and subjected to laser irradiation (=266nm) on a modified linear ion-trap mass spectrometer. RESULTS Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carboncarbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M+NaI]center dot+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carboncarbon bond dissociation without scrambling of molecular information. CONCLUSIONS Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box. Copyright (c) 2013 John Wiley & Sons, Ltd.

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Gas-phase transformation of synthetic phosphatidylcholine (PC) monocations to structurally informative anions is demonstrated via ion/ion reactions with doubly deprotonated 1,4-phenylenedipropionic acid (PDPA). Two synthetic PC isomers, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (PC16:0/18:1) and 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (PC18:1/16:0), were subjected to this ion/ion chemistry. The product of the ion/ion reaction is a negatively charged complex, \[PC + PDPA - H](-). Collisional activation of the long-lived complex causes transfer of a proton and methyl cation to PDPA, generating \[PC - CH3](-). Subsequent collisional activation of the demethylated PC anions produces abundant fatty acid carboxylate anions and low-abundance acyl neutral losses as free acids and ketenes. Product ion spectra of \[PC - CH3](-) suggest favorable cleavage at the sn-2 position over the sn-1 due to distinct differences in the relative abundances. In contrast, collisional activation of PC cations is absent of abundant fatty acid chain-related product ions and typically indicates only the lipid class via formation of the phosphocholine cation. A solution phase method to produce the gas-phase adducted PC anion is also demonstrated. Product ion spectra derived from the solution phase method are similar to the results generated via ion/ion chemistry. This work demonstrates a gas-phase means to increase structural characterization of phosphatidylcholines via ion/ion chemistry. Grant Number ARC/CE0561607, ARC/DP120102922

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Landscape change is an ongoing process even within established urban landscapes. Yet, analyses of fragmentation and deforestation have focused primarily on the conversion of non-urban to urban landscapes in rural landscapes and ignored urban landscapes. To determine the ecological effects of continued urbanization in urban landscapes, tree-covered patches were mapped in the Gwynns Falls watershed (17158.6 ha) in Maryland for 1994 and 1999 to document fragmentation, deforestation, and reforestation. The watershed was divided into lower (urban core), middle (older suburbs), and upper (recent suburbs) subsections. Over the entire watershed a net of 264.5 of 4855.5 ha of tree-covered patches were converted to urban land use-125 new tree-covered patches were added through fragmentation, 4 were added through reforestation, 43 were lost through deforestation, and 7 were combined with an adjacent patch. In addition, 180 patches were reduced in size. In the urban core, deforestation continued with conversion to commercial land use. Because of the lack of vegetation, commercial land uses are problematic for both species conservation and derived ecosystem benefits. In the lower subsection, shape complexity increased for tree-covered patches less than 10 ha. Changes in shape resulted from canopy expansion, planted materials, and reforestation of vacant sites. In the middle and upper subsections, the shape index value for tree-covered patches decreased, indicating simplification. Density analyses of the subsections showed no change with respect to patch densities but pointed out the importance of small patches (≤5 ha) as "stepping stone" to link large patches (e. g., ≥100 ha). Using an urban forest effect model, we estimated, for the entire watershed, total carbon loss and pollution removal, from 1994 to 1999, to be 14,235,889.2 kg and 13,011.4 kg, respectively due to urban land-use conversions.

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Objectives: To examine factors associated with the uptake of i) long-acting reversible, ii) permanent and iii) traditional contraceptive methods among Australian women. Methods: Participants in the Australian Longitudinal Study on Women's Health born in 1973–78 reported on their contraceptive use at three surveys: 2003, 2006 and 2009. The participants were 5,849 women aged 25–30 in 2003 randomly sampled from Medicare. The main outcome measure was current contraceptive method at age 28–33 years categorised as long-acting reversible methods (implant, IUD, injection), permanent (tubal ligation, vasectomy), and traditional methods (oral contraceptive pills, condoms, withdrawal, safe period). Results: Compared to women living in major cities, women in inner regional areas were more likely to use long-acting (OR=1.26, 95%CI 1.03–1.55) or permanent methods (OR=1.43, 95%CI 1.17–1.76). Women living in outer regional/remote areas were more likely than women living in cities to use long-acting (OR=1.65, 95%CI 1.31–2.08) or permanent methods (OR=1.69, 95%CI 1.43–2.14). Conclusions: Location of residence is an important factor in women's choices about long-acting and permanent contraception in addition to the number and age of their children. Implications: Further research is needed to understand the role of geographical location in women's access to contraceptive options in Australia.

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Radiative and total heat transfer at the flow stagnation point of a 1:40.8 binary scaled model of the Titan Explorer vehicle were measured in the X3 expansion tube. Results from the current study illustrated that with the addition of CH4 into a N2 test gas radiative heat transfer could be detected. For a test gas of 5% CH4 and 95% N2, simulating an atmospheric model for Titanic aerocapture, approximately 4% of the experimentally measured total stagnation point heat transfer was found to be due to radiation. This was in comparison to < 1% measured for a test gas of pure nitrogen. When scaled to the flight vehicle, experimental results indicate a 64% contribution of radiation (test gas 5% CH4/95% N2). Previous numerical results however have predicted this contribution to be between 80-92%. Thus, experimental results from the current study suggest that numerical analyses are over-predicting the radiative heat transfer on the flight vehicle.

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The structures of the 1:1 hydrated proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with oxalic acid, 4-carbamoylpiperidinium hydrogen oxalate dihydrate, C6H13N2O+·C2HO4-·2H2O, (I), and with adipic acid, bis­(4-car­bam­oylpiperidinium) adipate dihydrate, 2C6H13N2O+·C6H8O42-·2H2O, (II), are three-dimensional hydrogen-bonded constructs involving several different types of enlarged water-bridged cyclic associations. In the structure of (I), the oxalate monoanions give head-to-tail carb­oxy­lic acid O-HOcarboxyl hydrogen-bonding inter­actions, forming C(5) chain substructures which extend along a. The isonipecotamide cations also give parallel chain substructures through amide N-HO hydrogen bonds, the chains being linked across b and down c by alternating water bridges involving both carboxyl and amide O-atom acceptors and amide and piperidinium N-HOcarboxyl hydrogen bonds, generating cyclic R43(10) and R32(11) motifs. In the structure of (II), the asymmetric unit comprises a piperidinium cation, half an adipate dianion, which lies across a crystallographic inversion centre, and a solvent water mol­ecule. In the crystal structure, the two inversion-related cations are inter­linked through the two water mol­ecules, which act as acceptors in dual amide N-HOwater hydrogen bonds, to give a cyclic R42(8) association which is conjoined with an R44(12) motif. Further N-HOwater, water O-HOamide and piperidinium N-HOcarbox­yl hydrogen bonds give the overall three-dimensional structure. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. The presence of solvent water mol­ecules in these structures is largely responsible for the non-occurrence of the common hydrogen-bonded amide-amide dimer, promoting instead various expanded cyclic hydrogen-bonding motifs.

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Numeric sets can be used to store and distribute important information such as currency exchange rates and stock forecasts. It is useful to watermark such data for proving ownership in case of illegal distribution by someone. This paper analyzes the numerical set watermarking model presented by Sion et. al in “On watermarking numeric sets”, identifies it’s weaknesses, and proposes a novel scheme that overcomes these problems. One of the weaknesses of Sion’s watermarking scheme is the requirement to have a normally-distributed set, which is not true for many numeric sets such as forecast figures. Experiments indicate that the scheme is also susceptible to subset addition and secondary watermarking attacks. The watermarking model we propose can be used for numeric sets with arbitrary distribution. Theoretical analysis and experimental results show that the scheme is strongly resilient against sorting, subset selection, subset addition, distortion, and secondary watermarking attacks.

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The last two decades have witnessed a fragmentation of previously integrated systems of production and service delivery with the advent of boundary-less, networked and porous organisational forms. This trend has been associated with the growth of outsourcing and increased use of contingent workers. One consequence of these changes is the development of production/service delivery systems based on complex national and international networks of multi-tiered subcontracting increasingly labelled as supply chains. A growing body of research indicates that subcontracting and contingent work arrangements affect design and decision-making processes in ways that can seriously undermine occupational health and safety (OHS). Elaborate supply chains also present a regulatory challenge because legal responsibility for OHS is diffused amongst a wider array of parties, targeting key decision-makers is more difficult, and government agencies encounter greater logistical difficulties trying to safeguard contingent workers. In a number of industries these problems have prompted new forms of regulatory intervention, including mechanisms for sheeting legal responsibility to the top of supply chains, contractual tracking devices and increasing industry, union and community involvement in enforcement. After describing the problems just alluded to this paper examines recent efforts to regulate supply chains to safeguard OHS in the United Kingdom and Australia.