60 resultados para sterically hindered organotellurium


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Over the past 3 decades, the status of sea turtles and the need for their protection to aid population recovery have increasingly captured the interest of government agencies, non-governmental organisations (NGOs) and the general public worldwide. This interest has been matched by increased research attention, focusing on a wide variety of topics relating to sea turtle biology and ecology, together with the interrelations of sea turtles with the physical and natural environments. Although sea turtles have been better studied than most other marine fauna, management actions and their evaluation are often hindered by the lack of data on turtle biology, human–turtle interactions, turtle population status and threats. In an effort to inform effective sea turtle conservation a list of priority research questions was assembled based on the opinions of 35 sea turtle researchers from 13 nations working in fields related to turtle biology and/or conservation. The combined experience of the contributing researchers spanned the globe as well as many relevant disciplines involved in conservation research. An initial list of more than 200 questions gathered from respondents was condensed into 20 metaquestions and classified under 5 categories: reproductive biology, biogeography, population ecology, threats and conservation strategies.

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Polypyrrole is a material with immensely useful properties suitable for a wide range of electrochemical applications, but its development has been hindered by cumbersome manufacturing processes. Here we show that a simple modification to the standard electrochemical polymerization method produces polypyrrole films of equivalently high conductivity and superior mechanical properties in one-tenth of the polymerization time. Preparing the film as a series of electrodeposited layers with thorough solvent washing between layering was found to produce excellent quality films even when layer deposition was accelerated by high current. The washing step between the sequentially polymerized layers altered the deposition mechanism, eliminating the typical dendritic growth and generating nonporous deposits. Solvent washing was shown to reduce the concentration of oligomeric species in the near-electrode region and hinder the three-dimensional growth mechanism that occurs by deposition of secondary particles from solution. As artificial muscles, the high density sequentially polymerized films produced the highest mechanical work output yet reported for polypyrrole actuators.

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Coasts composed of resistant lithologies such as granite are generally highly resistant to erosion. They tend to evolve over multiple sea level cycles with highstands acting to remove subaerially weathered material. This often results in a landscape dominated by plunging cliffs with shore platforms rarely occurring. The long-term evolution of these landforms means that throughout the Quaternary these coasts have been variably exposed to different sea level elevations which means erosion may have been concentrated at different elevations from today. Investigations of the submarine landscape of granitic coasts have however been hindered by an inability to accurately image the nearshore morphology. Only with the advent of multibeam sonar and aerial laser surveying can topographic data now be seamlessly collected from above and below sea level. This study tests the utility of these techniques and finds that very accurate measurements can be made of the nearshore thereby allowing researchers to study the submarine profile with the same accuracy as the subaerial profile. From a combination of terrestrial and marine LiDAR data with multibeam sonar data, it is found that the morphology of granite domes is virtually unaffected by erosion at sea level. It appears that evolution of these landscapes on the coast is a very slow process with modern sea level acting only to remove subaerially weathered debris. The size and orientation of the joints determines the erosional potential of the granite. Where joints are densely spaced (<2 m apart) or the bedrock is highly weathered can semi-horizontal surfaces form.

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Stroke is a common neurological condition which is becoming increasingly common as the population ages. This entails healthcare monitoring systems suitable for home use, with remote access for medical professionals and emergency responders. The mobile phone is becoming the easy access tool for self-evaluation of health, but it is hindered by inherent problems including computational power and storage capacity. This research proposes a novel cloud based architecture of a biomedical system for a wearable motion kinematic analysis system which mitigates the above mentioned deficiencies of mobile devices. The system contains three subsystems: 1. Bio Kin WMS for measuring the acceleration and rotation of movement 2. Bio Kin Mobi for Mobile phone based data gathering and visualization 3. Bio Kin Cloud for data intensive computations and storage. The system is implemented as a web system and an android based mobile application. The web system communicates with the mobile application using an encrypted data structure containing sensor data and identifiable headings. The raw data, according to identifiable headings, is stored in the Amazon Relational Database Service which is automatically backed up daily. The system was deployed and tested in Amazon Web Services.

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The successful commercialization of smart wearable garments is hindered by the lack of fully integrated carbon-based energy storage devices into smart wearables. Since electrodes are the active components that determine the performance of energy storage systems, it is important to rationally design and engineer hierarchical architectures atboth the nano- and macroscale that can enjoy all of the necessary requirements for a perfect electrode. Here we demonstrate a large-scale flexible fabrication of highly porous high-performance multifunctional graphene oxide (GO) and rGO fibers and yarns by taking advantage of the intrinsic soft self-assembly behavior of ultralarge graphene oxide liquid crystalline dispersions. The produced yarns, which are the only practical form of these architectures for real-life device applications, were found to be mechanically robust (Young's modulus in excess of 29 GPa) and exhibited high native electrical conductivity (2508 ± 632 S m(-1)) and exceptionally high specific surface area (2605 m(2) g(-1) before reduction and 2210 m(2) g(-1) after reduction). Furthermore, the highly porous nature of these architectures enabled us to translate the superior electrochemical properties of individual graphene sheets into practical everyday use devices with complex geometrical architectures. The as-prepared final architectures exhibited an open network structure with a continuous ion transport network, resulting in unrivaled charge storage capacity (409 F g(-1) at 1 A g(-1)) and rate capability (56 F g(-1) at 100 A g(-1)) while maintaining their strong flexible nature.

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Issue addressed Social-ecological models of health behaviour acknowledge environmental influences, but research examining how the environment shapes physical activity in rural settings is limited. This study aimed to explore the environmental factors that act as barriers or facilitators to physical activity participation among rural adults. Methods Forty-nine adults from three regions of rural Tasmania, Australia, participated in semi-structured interviews that explored features of the environment that supported or hindered physical activity. Interviews were digitally recorded, transcribed verbatim and analysed thematically. Results Four key themes emerged: functionality, diversity, spaces and places for all and realistic expectations. 'Functionality' included connectivity with other destinations, distance, safety, continuity, supporting infrastructure and surfacing. While there was limited 'diversity' of structured activities and recreational facilities, the importance of easy and convenient access to a natural environment that accommodated physical activity was highlighted. 'Spaces and places for all' highlighted the importance of shared-use areas, particularly those that were family-and dog-friendly. Despite desires for more physical activity opportunities, many participants had 'realistic expectations' of what was feasible in rural settings. Conclusions Functionality, diversity, spaces and places for all and realistic expectations were identified as considerations important for physical activity among rural adults. Further research using quantitative approaches in larger samples is needed to confirm these findings. So what? Urban-centric views of environmental influences on physical activity are unlikely to be entirely appropriate for rural areas. Evidence-based recommendations are provided for creating new or modifying existing infrastructure to support active living in rural settings.

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PURPOSE: Despite increasing evidence that the physical environment impacts on physical activity among urban-dwellers, little attention has been devoted to understanding this relationship in rural populations. Work in this area is further hindered by a lack of environmental measures specifically designed for rural settings. This qualitative study aimed to explore the salience of urban physical activity environment constructs among rural adults. METHODS: In 2011, 49 rural men and women from three distinct areas (coastal, animal-based farming, forestry/plant-based farming) of rural Tasmania, Australia, were purposively recruited to participate in semi-structured interviews. Interviews explored features of the built and social environment commonly examined in studies of urban adults, including functional characteristics (eg, lighting, footpaths, roads/verges), road and personal safety, availability and accessibility of places to be active, destinations, and aesthetics. Interviews were recorded, transcribed verbatim and analysed using a content-thematic approach using QSR NVivo software. FINDINGS: While some urban environmental constructs were salient to these rural adults, such as availability of and accessibility to places to be active, some constructs were operationalised differently, such as road safety (where large trucks and winding roads rather than traffic density was of concern), or were not considered relevant (eg, personal safety related to crime, availability of walkable destinations, aesthetics). CONCLUSIONS: The measurement of the physical environment in rural populations may require reconsideration and/or modification to ensure salience and appropriate quantification of associations with physical activity in future studies.

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Tool condition monitoring is an important factor in ensuring manufacturing efficiency and product quality. Audio signal based methods are a promising technique for condition monitoring. However, the influence of interfering signals and background noise has hindered the use of this technique in production sites. Blind signal separation (BSS) has the potential to solve this problem by recovering the signal of interest out of the observed mixtures, given that the knowledge about the BSS model is available. In this paper, we discuss the development of the BSS model for sheet metal stamping with a mechanical press system, so that the BSS techniques based on this model can be developed in future. This involves conducting a set of specially designed machine operations and developing a novel signal extraction technique. Also, the link between stamping process conditions and the extracted audio signal associated with stamping was successfully demonstrated by conducting a series of trials with different lubrication conditions and levels of tool wear.

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Control of introduced predators to mitigate biodiversity impacts is a pressing conservation challenge. Across Australia feral cats (Felis catus) are a major threat to terrestrial biodiversity. Currently feral cat control is hindered by the limited utility of existing predator baiting methods. Further proposed control methods include use of the novel poison para-aminopropiophenone (PAPP) which may present a hazard to some native animal populations. Here we used experimental and predictive approaches to evaluate feral cat bait take by a large native Australian predatory reptile the Lace monitor (Varanus varius). These lizards would be expected to readily detect, ingest and consume a lethal dose (depending on toxin) from surface-laid baits intended for feral cat control if a precautionary approach was not adopted when baiting. We modelled V. varius bait take using experimental and predictive biophysical modelling approaches to evaluate temporal effects of climate variables on V. varius activity and hence potential for bait removal. Finally we conducted a pre-PAPP baiting site occupancy assessment of V. varius within Wilson Promontory National Park (WPNP) to provide a basis for monitoring any longer term population effects of cat baiting. V. varius removed 7 % of deployed baits from 73 % of bait stations across another study area in Far Eastern Victoria. Daily bait removal was positively correlated with maximum temperature and solar radiation. Biophysical modelling for Far Eastern Victoria predicted that maximum temperatures <19.5 °C prevented V. varius activity and hence opportunity for bait removal. V. varius in WPNP was undetectable suggesting aerial baiting posed limited hazard to this species at this location. Depending how climate influences annual activity patterns and the specific poison, surface-laid baits could pose a significant mortality risk to V. varius. However, use of biophysical models to predict periods of V. varius inactivity may provide a novel means to reduce non-target bait take by this predator.

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The reaction of tellurium tetrahalides, TeX4 (XCl. Br) with acetyltrimethylsilane in CCl4 at ambient temperature, unlike that of the aryltellurium trichlorides, ArTeCl3 that give the expected electrophilic substitution products, Ar(Me3SiCOCH2)TeCl2, (Ar = 1-C10H7, 2; 2,4,6-Me3C6H2, 3), afforded novel silylated heterocycles, 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium halides 1a and 1b. These Te(II) heterocyclic compounds undergo halide exchange with sodium iodide and also add dihalogens oxidatively to afford the corresponding iodide, 1c and the Te(IV) trihalides, 5a and 5b respectively. A large lowering of ν(CO) is indicative of strong Te⋯OC interactions among these heterocycles, and is also substantiated by single-crystal X-ray diffraction data for 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium chloride. The 125Te chemical shifts for the new 10-Te-3 telluranes and 12-Te-5 pertelluranes that involve tellurium bound to two highly electronegative atoms (O, X) are among the highest (downfield) reported for organotellurium(II) and (IV) compounds.

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This paper provides a review of the literature while contributing to academic understanding of the concepts of agility and flexibility within the supply chain. The research identified 83 peer-reviewed articles through a structured review technique, which is based on a three-stage refinement process. Data reduction procedures using codification, sentence strings and a review of keywords, title, abstract and conclusion were used in the search. The papers identified focused on organizational and supply chain agility and flexibility. The acknowledged gaps in understanding and development of agility and flexibility in supply chains were identified and categorized in terms of conceptual, contextual and methodological gaps. Subsequent to the gap analysis, this paper argues that effective relationship integration with key partners is a fundamental mechanism for mitigating the problem of control dissipation, which has hindered academic understanding with respect to development and application of agile and flexible capabilities in supply chains. The findings in this paper will help academics to gain a better understanding and to develop the concepts of supply chain agility and flexibility. In addition, the findings indicate that supply chain stakeholders need to address the issue of relationship integration when undertaking, or participating in agility and flexibility development programmes, so as to maximize supply chain performance. The paper concludes by highlighting implications for managers and researchers, and proposes a number of areas for future investigation.

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Prior to the amalgamation of Scotland’s eight police forces into Police Scotland in 2013 by the Scottish National Party government, Scottish policing generally enjoyed a ‘cool’ political climate, with low scrutiny and minimal political engagement. This paper argues these conditions hindered the critical interrogation of Scottish policing, allowing a policy of unregulated and unfettered stop and search to flourish unchallenged for two decades. We then show how this policy was swiftly dismantled in the ‘heated’ environment that followed centralization, a move that gave rise to the unprecedented scrutiny of Scottish policing by media and political commentators. The analysis suggests that the legitimacy and reputation of the police may owe a debt to political environments that encourage either ‘soft’ or ‘hard’ analysis. Also, that more heated political environments, often disparaged by academics and criminal justice practitioners, can drive accountability and contribute to more progressive outcomes.

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In this paper, we demonstrate that an amphiphilic block copolymer such as polyethylene glycol-b-polyethylene can be used as both dispersing and interfacial compatibilizing agent for the melt compounding of LLDPE with cellulose nano-fibers. A simple and effective spray drying methodology was first used for the first time for the preparation of a powdered cellulose nano-fibers extrusion feedstock. Surface adsorption of the amphiphilic PEG-b-PE was carried out directly in solution during this process. These various dry cellulosic feedstock were subsequently combined with LLDPE via extrusion to produce a range of nano-composites. The collective outcomes of this research are several folds. Firstly we show that presence of surface adsorbed PEG-b-PE effectively hindered the aggregation of the cellulose nano-fibers during the extrusion, affording clear homogenous materials with minimum aggregation even at the highest loading of cellulose nano-fibers (∼23 vol.%). Secondly, the tailored LLDPE/cellulose interface arising from intra- and inter-molecular hydrogen and Van der Waals bonds yielded significant levels of mechanical improvements in terms of storage and tensile modulus. We believe this study provides a simple technological template to produce high quality and performant polyolefins cellulose-based nano-composites.

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The heterogeneous phase reaction of Ru(η2-RL)(PPh3)2(CO)Cl, 1 with lithium acetylacetonate (Liacac) afforded the complexes of the type Ru(η1-RL)(PPh3)2(CO)(acac), 2 in excellent yield where η2-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5 and η1-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is H, Me, Cl. The chelation of acac is attended with the cleavage of Ru-O and Ru-Cl bonds and iminium-phenolato → imine-phenol prototropic shift. A sterically controlled change in rotational conformation is involved in the 12 conversion. The conversion is irreversible and the type 2 species are thermodynamically more stable than the carboxylate, nitrite and nitrate complexes of 1. The crystal structures of Ru(η1-MeL)(PPh3)2(CO)(acac), 2(Me) and Ru(η1-ClL)(PPh3)2(CO)(acac), 2(Cl) are reported. Spectral (UV-Vis, IR, 1H NMR) and electrochemical data of the complexes are also reported. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses. The complexes were also screened in vitro for their antiproliferative properties against the MCF-7 breast cancer cell lines by using the MTT assay. Flow cytometric analysis showed that the complexes arrested the cell cycle in the sub G0 phase.