999 resultados para BRIDGING LIGANDS


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In the structure of title compound [Rb2(C7H4NO2)2(H2O)2]n the centrosymmetric cyclic dimeric repeating unit comprises two irregular RbO4 complex centres bridged by the carboxylate groups of the 5-nitrosalicylate ligands. The coordination about each Rb is completed by a monodentate water molecule and a phenolic O donor which gives a bridging extension [Rb-O range 3.116(7)-3.135(5)A]. The two-dimensional polymeric structure is stabilized by intermolecular water O-H...O(carboxyl) hydrogen bonds and weak inter-ring pi--pi interactions [minimum ring centroid separation, 3.620(4)A].

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The increasing capability of mobile devices and social networks to gather contextual and social data has led to increased interest in context-aware computing for mobile applications. This paper explores ways of reconciling two different viewpoints of context, representational and interactional, that have arisen respectively from technical and social science perspectives on context-aware computing. Through a case study in agile ridesharing, the importance of dynamic context control, historical context and broader context is discussed. We build upon earlier work that has sought to address the divide by further explicating the problem in the mobile context and expanding on the design approaches.

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Evidence supporting the benefits of exercise following the diagnosis of breast cancer is overwhelming and compelling. Exercise reduces the severity and number of treatment-related side effects, optimizes quality of life during and following treatment, and may optimize survival. Yet, exercise does not uniformly form part of the standards of care provided to women following a breast cancer diagnosis. This commentary summarizes the evidence in support of exercise as a form of adjuvant treatment and identifies and discusses potential issues preventing the formal integration of exercise into breast cancer care. Proposed within the commentary is a model of breast cancer care that incorporates exercise prescription as a key component but also integrates the need for surveillance and management for common breast cancer treatment-related morbidities, as well as education. While future research evaluating the potential cost savings through implementation of such amodel is required, a committed, collaborative approach by clinicians, allied health professionals, and researchers will be instrumental in bridging the gap between research and practice.

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The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR′2 is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-η3-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)2]+[B(3,5-(CF3)2C6H3)4]−, while the complex [(dtbpm κ2P)Ni(η3-CH(CH2Ph)Ph]+[B(3,5-(CF3)2C6H3)4]−is obtained from protonation of the Ni(0) olefin complex (dtbpm-κ2P)N(η2-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic η3-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the η3-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R′ on the phosphine ligand has been examined, and a clear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial η3 to η3 haptotropic shift processes of the[(R2PCH2PR′2)Ni] fragment and the η3−η1 change of the coordination mode of the benzyl group required for polymerization in those cations.

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The crystal structures of the rubidium and caesium complexes with 2-aminobenzenesulfonic acid (orthanilic acid), [Rb4(C6H6NO3S)4(H2O)]n (1) and [Cs(C6H6NO3S)]n (2) and have been determined at 200 K. Complex 1 has a repeating unit comprising four independent and different Rb coordination centres, (RbO8), (RbO7), (RbN2O4) and (RbO10), each having irregular stereochemistry and involving a number of bidentate chelate sulfonate-O,O’-metal and bridging interactions, giving a two-dimensional polymeric layered structure. Anhydrous complex 2 is also polymeric with the irregular (CsO7) coordination polyhedron comprising six sulfonate oxygen donors from three separate bidentate chelate sulfonate ligands and one monodentate bridging sulfonate oxygen, giving a two-dimensional layered structure.

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In 1997, the Australian government introduced regulations restricting work rights, income and Medicare access to asylum seekers living in the community on Bridging Visa E (BVE). These visa conditions have resulted in unacceptable hardship for asylum seekers. In response, a variety of community-based agencies have been established across Australia. This study documents and collates the experiences of some of these agencies working in Victoria. These organizations maintain a high degree of inter-agency communication and liaison, have an extensive community support network by way of volunteer work and financial assistance from philanthropic organizations and the public, and have developed successful alternative models of care for asylum seekers. However, many of the agencies have been unprepared and under-resourced for the specific legal, cultural, and health concerns common to asylum seekers on BVE. A discussion of the issues faced by the community sector in the current asylum seeker/refugee political context is presented

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This paper reports on some findings from the first year of a three-year longitudinal study, in which seventh to ninth-graders were introduced to engineering education. Specifically, the paper addresses students’ responses to an initial design activity involving bridge construction, which was implemented at the end of seventh grade. This paper also addresses how students created their bridge designs and applied these in their bridge constructions; their reflections on their designs; their reflections on why the bridge failed to support increased weights during the testing process; and their suggestions on ways in which they would improve their bridge designs. The present findings include identification of six, increasingly sophisticated levels of illustrated bridge designs, with designs improving between the classroom and homework activities of two focus groups of students. Students’ responses to the classroom activity revealed a number of iterative design processes, where the problem goals, including constraints, served as monitoring factors for students’ generation of ideas, design thinking and construction of an effective bridge.

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Fourteen new complexes of the form cis-\[RuIIX2(R2qpy2+)2]4+ (R2qpy2+ = a 4,4′:2′,2″:4″,4‴-quaterpyridinium ligand, X = Cl− or NCS−) have been prepared and isolated as their PF6− salts. Characterisation involved various techniques including 1H NMR spectroscopy and +electrospray or MALDI mass spectrometry. The UV–Vis spectra display intense intraligand π → π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-withdrawing strength of the pyridinium groups increases, while replacing Cl− with NCS− causes blue-shifts. Cyclic voltammograms show quasi-reversible or reversible RuIII/II oxidation waves, and several ligand-based reductions that are irreversible. The variations in the redox potentials correlate with changes in the MLCT energies. A single-crystal X-ray structure has been obtained for a protonated form of a proligand salt, \[(4-(CO2H)Ph)2qpyH3+]\[HSO4]3·3H2O. Time-dependent density functional theory calculations give adequate correlations with the experimental UV–Vis spectra for the two carboxylic acid-functionalised complexes in DMSO. Despite their attractive electronic absorption spectra, these dyes are relatively inefficient photosensitisers on electrodes coated with TiO2 or ZnO. These observations are attributed primarily to weak electronic coupling with the surfaces, since the DFT-derived LUMOs include no electron density near the carboxylic acid anchors.

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Learning Objective: To describe a collaborative system of clinical allocations using a dedicated, discipline specific administrative coordinator. Methods: The Clinical Placement Coordinator is the liaison person between the student, the academic staff and the clinical sites, and fills an important role in bridging the gap to enhance the student learning experience. With this in mind the Coordinator is very discipline focused and works closely with the academic staff who coordinate the clinical units within the program. This person is the ‘‘face’’ of QUT to the external stakeholders, and ensures that all parties experience a smooth process. This no mean feat given that there are over 350 students to be placed annually, across 14 separate clinical blocks ranging from 1 to 6 weeks in length at various sites. The processes involved in clinical placement allocation will be presented, and the roles of the staff in facilitating students’ placement preferences and matching with clinical site offers will be described. In many allied health programs in Australia, the clinical placement activity is carried out by an academic member of staff. However, this can result in delays in communications due to other workload requirements such as lecture, tutorial and practical class commitments. Having a dedicated knowledgeable administration officer has resulted in a person being available to take calls from clinical staff, meet with students to discuss allocation needs and ensure that academic staff are consulted if and when necessary. The Clinical Placement Coordinator is very much a part of the course team and attends professional meetings and conferences as an avenue of networking and meeting clinical staff. Results: The success in having a dedicated administrative officer as the Clinical Placement Coordinator acting as the conduit between academic staff and students, and the university and clinical staff has been highly successful to date. This was noted in commendations from the 2010 Course Accreditation Panel Report which stated: ‘‘The very positive perception in the professional community of Ms Margaret McBurney’s effective and efficient organization of student clinical placements. Students and clinical professionals commented favourably on the approachability of staff. There is confidence that program staff will follow up on issues raised urgently in clinical centres.’’

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Aims Wellness assessments can determine adolescent lifestyle behaviors. A better understanding of wellness differences between high and low SES adolescents could assist policy makers to develop improved strategies to bridge the gap between these two groups. The aim of this investigation was to explore wellness differences between high and low SES adolescents. Methods In total, 241 (125 high and 116 low SES) adolescents completed the 5-Factor Wellness Inventory (5F-Wel). The 5F-Wel comprises 97 items contributing to 17 subscales, 5 dimensions, 4 contexts, total wellness, and a life satisfaction index, with scores ranging from 0-100. Independent sample t-tests were performed with Levene’s test of equality for variances, which checked the assumption of homogeneity of variances. Results Overall, 117 (94%) and 112 (97 %) high and low SES participants had complete data and were included in the analysis. The high SES group scored higher for total wellness (M = 81.09, SE = .61) than the low SES group (M = 75.73, SE = .99). This difference was significant t (186) = 4.635, p < .05, with a medium effect size r = .32. The high SES group scored higher on 23 of 27 scales (21 scales, p < .05), while the low SES group scored higher on the remaining 3 scales (all non-significant). Conclusion These results contribute empirical data to the body of literature, indicating a large wellness discrepancy between high and low SES youth. Deficient areas can be targeted by policymakers to assist in bridging the gap between these groups.

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Current approaches to airport development and land use sit at odds with the tradition of airports as spaces for aviation (Stevens et a/. 2010). While airports remain the primary interface between air transport and society, the functions they include within their boundaries have expanded well beyond the provision of infrastructure for aviation and logistics. Shopping malls, commercial office space, hotels, golf courses and conference facilities arc increasingly normal uses of land within airport boundaries (Kasarda 2008), and enhance the role of airports from transport infrastructure to a new form of economic infrastructure (Freestone 2009). However, the expanding role of airports, and the resulting diversification in airport land uses, has not been without opposition.

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Background Transfusion-related acute lung injury (TRALI) is a serious and potentially fatal consequence of transfusion. A two-event TRALI model demonstrated date-of-expiry - day (D) 5 platelet (PLT) and D42 packed red blood cell (PRBC) supernatants (SN) induced TRALI in LPS-treated sheep. We have adapted a whole blood transfusion culture model as an investigative bridge between the ovine TRALI model human responses to transfusion. Methods A whole blood transfusion model was adapted to replicate the ovine model - specifically +/- 0.23μg/mL LPS as the first event and 10% SN volume (transfusion) as the second event. Four pooled SN from blood products, previously used in the TRALI ovine model, were investigated: D1-PLT, D5-PLT, D1-PRBC, and D42-PRBC. Fresh human whole blood (recipient) was mixed with combinations of LPS and BP-SN stimuli and incubated in vitro for 6 hrs. Addition of golgi plug enabled measurement of monocyte cytokine production (IL-6, IL-8, IL-10, IL-12, TNF-α, IL-1α, CXCL-5, IP-10, MIP-1α, MCP-1) using multi-colour flow cytometry. Responses for 6 recipients were assessed. Results In the presence of LPS, D42-PRBC-SN significantly increased monocyte IL-6 (P=0.031), IL-8 (P=0.016) and IL-1α (P=0.008) production compared to D1-PRBC-SN. This response to D42-PRBC-SN was LPS-dependent, and was not evident in non-LPSstimulated controls. This response was also specific to D42-PRBC-SN, as similar changes were not evident for the D5-PLT-SN, compared to the D1-PLT-SN, regardless of the presence of LPS. D5-PLT-SN significantly increased IL-12 production (P=0.024) compared to D1-PLT-SN. This response was again LPS-dependent. Conclusions These data demonstrate a novel two-event mechanism of monocyte inflammatory response that was dependent upon both the presence of date-of-expiry blood product SN and LPS. Further, these results demonstrate different cytokines responses induced by date-of-expiry PLT-SN and PRBC-SN. These data are consistent with the evidence from the ovine TRALI model, and enhancing its relevance to transfusion related changes in humans.