953 resultados para supported intermediates


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La0.8Sr0.2Mn1.1O3 (LSM1.1)-10 mol% Sc2O3-Stabilized ZrO2 co-doped with CeO2 (ScSZ) composite cathodes were investigated for anode-supported solid oxide fuel cells (SOFCs) with thin 8 mol% Y2O3-stabilized ZrO2 (YSZ) electrolyte. X-ray diffraction (XRD) results indicated that the ScSZ electrolytes displayed good chemical compatibility with the nonstoichiometric LSM1.1 against co-firing at 1300 degrees C. Increasing the CeO2 content in the ScSZ electrolytes dramatically suppressed the electrode polarization resistance, which may be related to the improved surface oxygen exchange or the enlarged active area of cathode. The 5Ce10ScZr was the best electrolyte for the composite cathodes, which caused a small ohmic resistance decrease and the reduced polarization resistance and brought about the highest cell performance. The cell performances at lower temperatures seemed to rely on the electrode polarization resistance more seriously, than the ohmic resistance. Compared with the cell impedance at higher temperatures, the higher the 5Ce10ScZr proportion in the composite cathodes, the smaller the increment of the charge transfer resistance at lower temperatures. The anode-supported SOFC with the LSM1.1-5Ce10ScZr (60:40) composite cathode achieved the maximum power densities of 0.82 W/cm(2) at 650 degrees C and 2.24 W/cm(2) at 800 degrees C, respectively. (c) 2005 Elsevier B.V. All rights reserved.

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This study describes relocation experiences of older people moving to supported housing in Scotland focusing on the nature of support. Using mixed methods, Phase one involved a Scottish cross-sectional survey of all people aged 65 and over moving into Coburg (Scotland) Housing Association supported accommodation during the first six months of 2008. A total of 122 respondents were included in the survey (59% response rate). People moved locally at advanced ages with moderate disability levels to achieve more manageable housing and support, suggesting ‘assistance migration’. Expectations were high, with many seeing it as a new start in life and generally positive views of moving were reported. In Phase two, five in-depth multiple-perspective longitudinal case studies were conducted to explore the experience of relocation into supported housing. In each case an older person, primary carer and the housing manager - all women – were interviewed over six months following relocation. Analysis was undertaken using a thematic framework approach (Ritchie et al., 2003). Findings suggested older women acted with agency to adapt to their new lives; recreating ‘normality’ through organising space and routines. It is argued that returning to normality formed the overarching objective of the older women as they sought to feel ‘in place’. Responsibilities for meeting assistance needs were often implicit, contested and shifting, leading to fragile, uncertain and transitory arrangements. Drawing on recent advances in developmental psychology it is argued ‘longings’ of older people, and others, to achieve an optimal life can relate and motivate towards actions such as relocation. Yet, personal ‘longings’ can be prioritised differently and may result in disputes over goal setting and ways needs are met. Further, utopian ideals must be reconciled with the reality of daily life. Policy and practitioners could adopt broader, dignity based objectives to assist older people to identify ways of aiding such reconciliation.

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Offshore wind turbines supported on monopile foundations are dynamically sensitive because the overall natural frequencies of these structures are close to the different forcing frequencies imposed upon them. The structures are designed for an intended life of 25 to 30 years, but little is known about their long term behaviour. To study their long term behaviour, a series of laboratory tests were conducted in which a scaled model wind turbine supported on a monopile in kaolin clay was subjected to between 32,000 and 172,000 cycles of horizontal loading and the changes in natural frequency and damping of the model were monitored. The experimental results are presented using a non-dimensional framework based on an interpretation of the governing mechanics. The change in natural frequency was found to be strongly dependent on the shear strain level in the soil next to the pile. Practical guidance for choosing the diameter of monopile is suggested based on element test results using the concept of volumetric threshold shear strain.

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This paper presents experimental results that aimed to investigate the effects of soil liquefaction on the modal parameters (i.e. frequency and damping ratio) of pile-supported structures. The tests were carried out using the shaking table facility of the Bristol Laboratory for Advanced Dynamics Engineering (BLADE) at the University of Bristol (UK) whereby four pile-supported structures (two single piles and two pile groups) with and without superstructure mass were tested. The experimental investigation aimed to monitor the variation in natural frequency and damping of the four physical models at different degrees of excess pore water pressure generation and in full-liquefaction condition. The experimental results showed that the natural frequency of pile-supported structures may decrease considerably owing to the loss of lateral support offered by the soil to the pile. On the other hand, the damping ratio of structure may increase to values in excess of 20%. These findings have important design consequences: (a) for low-period structures, substantial reduction of spectral acceleration is expected; (b) during and after liquefaction, the response of the system may be dictated by the interactions of multiple loadings, that is, horizontal, axial and overturning moment, which were negligible prior to liquefaction; and (c) with the onset of liquefaction due to increased flexibility of pile-supported structure, larger spectral displacement may be expected, which in turn may enhance Pdelta effects and consequently amplification of overturning moment. Practical implications for pile design are discussed.

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Supported housing for individuals with severe mental illness strives to provide the services necessary to place and keep individuals in independent housing that is integrated into the community and in which the consumer has choice and control over his or her services and supports. Supported housing can be contrasted to an earlier model called the “linear residential approach” in which individuals are moved from the most restrictive settings (e.g., inpatient settings) through a series of more independent settings (e.g., group homes, supervised apartments) and then finally to independent housing. This approach has been criticized as punishing the client due to frequent moves, and as being less likely to result in independent housing. In the supported housing model (Anthony & Blanch, 1988) consumers have choice and control over their living environment, their treatment, and supports (e.g., case management, mental health and substance abuse services). Supports are flexible and faded in and out depending on needs. Results of this systematic review of supported housing suggest that there are several well-controlled studies of supported housing and several studies conducted with less rigorous designs. Overall, our synthesis suggests that supported housing can improve the living situation of individuals who are psychiatrically disabled, homeless and with substance abuse problems. Results show that supported housing can help people stay in apartments or homes up to about 80% of the time over an extended period. These results are contrary to concerns expressed by proponents of the linear residential model and housing models that espoused more restrictive environments. Results also show that housing subsidies or vouchers are helpful in getting and keeping individuals housed. Housing services appear to be cost effective and to reduce the costs of other social and clinical services. In order to be most effective, intensive case management services (rather than traditional case management) are needed and will generally lead to better housing outcomes. Having access to affordable housing and having a service system that is well-integrated is also important. Providing a person with supported housing reduces the likelihood that they will be re-hospitalized, although supported housing does not always lead to reduced psychiatric symptoms. Supported housing can improve clients’ quality of life and satisfaction with their living situation. Providing supported housing options that are of decent quality is important in order to keep people housed and satisfied with their housing. In addition, rapid entry into housing, with the provision of choices is critical. Program and clinical supports may be able to mitigate the social isolation that has sometimes been associated with supported housing.

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Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO2 clusters, Ti2O4, Ti3O6 and Ti4O8 supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO2, demonstrating the usefulness of this composite system for redox catalysis.

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Several lines of evidence point strongly toward the importance of highly alpha-helical intermediates in the folding of all globular proteins, regardless of their native structure. However, experimental refolding studies demonstrate no observable alpha-helical intermediate during refolding of some beta-sheet proteins and have dampened enthusiasm for this model of protein folding. In this study, beta-sheet proteins were hypothesized to have potential to form amphiphilic helices at a period of <3.6 residues/turn that matches or exceeds the potential at 3.6 residues/turn. Hypothetically, such potential is the basis for an effective and unidirectional mechanism by which highly alpha-helical intermediates might be rapidly disassembled during folding and potentially accounts for the difficulty in detecting highly alpha-helical intermediates during the folding of some proteins. The presence of this potential was confirmed, indicating that a model entailing ubiquitous formation of alpha-helical intermediates during the folding of globular proteins predicts previously unrecognized features of primary structure. Further, the folding of fatty acid binding protein, a predominantly beta-sheet protein that exhibits no apparent highly alpha-helical intermediate during folding, was dramatically accelerated by 2,2,2-trifluoroethanol, a solvent that stabilizes alpha-helical structure. This observation suggests that formation of an alpha-helix can be a rate-limiting step during folding of a predominantly beta-sheet protein and further supports the role of highly alpha-helical intermediates in the folding of all globular proteins.

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Two 17-mer oligodeoxynucleotide-5'-linked-(6,7-diphenylpterin) conjugates, 2 and 3, were prepared as photosensitisers for targeting photooxidative damage to a 34-mer DNA oligodeoxynucleotide (ODN) fragment 1 representing the chimeric bcr-abl gene that is implicated in the pathogenesis of chronic myeloid leukaemia (CML). The base sequence in the 17-mer was 3'G G T A G T T A T T C C T T C T T5'. In the first of these ODN conjugates (2) the pterin was attached at its N3 atom, via a -(CH2)3OPO(OH)- linker, to the 5'-OH group of the ODN. Conjugate 2 was prepared from 2-amino-3-(3-hydroxypropyl)-6,7-diphenyl-4(3H)-pteridinone 10, using phosphoramidite methodology. Starting material 10 was prepared from 5-amino-7-methylthiofurazano[3,4-d]pyrimidine 4 via an unusual highly resonance stabilised cation 8, incorporating the rare 2H,6H-pyrimido[6,1-b][1,3]oxazine ring system. In the characterisation of 10 two pteridine phosphazenes, 15 and 29, were obtained, as well as new products containing two uncommon tricyclic ring systems, namely pyrimido[2,1-b]pteridine (20 and 24) and pyrimido[1,2-c]pteridine (27). In the second ODN conjugate the linker was -(CH2)5CONH(CH2)6OPO(OH)- and was attached to the 2-amino group of the pterin. In the preparation of 3, the N-hydroxysuccinimide ester 37 of 2-(5-carboxypentylamino)-6,7-diphenyl-4(3H)-pteridinone was condensed with the hexylamino-modified 17-mer. Excitation of 36 with near UV light in the presence of the single-stranded target 34-mer, 5'T G A C C A T C A A T A A G14 G A A G18 A A G21 C C C T T C A G C G G C C3' 1 caused oxidative damage at guanine bases, leading to alkali-labile sites which were monitored by polyacrylamide gel electrophoresis. Cleavage was observed at all guanine sites with a marked preference for cleavage at G14. In contrast, excitation of ODN-pteridine conjugate 2 in the presence of 1 caused oxidation of the latter predominantly at G18, with a smaller extent of cleavage at G15 and G14 (in the double-stranded portion) and G21. These results contrast with our previous observation of specific cleavage at G21 with ruthenium polypyridyl sensitisers, and suggest that a different mechanism, probably one involving Type 1 photochemical electron transfer, is operative. Much lower yields were found with the ODN-pteridine conjugate 3, perhaps as a consequence of the longer linker between the ODN and the pteridine in this case.

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Can learning quality be maintained in the face of increasing class size by the use of Computer Supported Co-operative Learning (CSCL) technologies? In particular, can Computer-Mediated Communication promote critical thinking in addition to surface information transfer? We compared face-to-face seminars with asynchronous computer conferencing in the same Information Management class. From Garrison's theory of critical thinking and Henri's critical reasoning skills, we developed two ways of evaluating critical thinking: a student questionnaire and a content analysis technique. We found evidence for critical thinking in both situations, with some subtle differences in learning style. This paper provides an overview of this work.

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Can learning quality be maintained in the face of increasing class size by the use of Computer Supported Co-operative Learning (CSCL) technologies? In particular, can Computer-Mediated Communication promote critical thinking in addition to surface information transfer? We compared face-to-face seminars with asynchronous computer conferencing in the same Information Management class. From Garrison's theory of critical thinking and Henri's critical reasoning skills, we developed two ways of evaluating critical thinking: a student questionnaire and a content analysis technique. We found evidence for critical thinking in both situations, with some subtle differences in learning style. This paper provides an overview of this work.

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This paper gives a detailed account of the content analysis method developed at Queen's University Belfast to measure critical thinking during group learning, as used in our controlled comparisons between learning in face-to-face and computer conference seminars. From Garrison's 5 stages of critical thinking, and Henri's cognitive skills needed in CMC, we have developed two research instruments: a student questionnaire and this content analysis method. The content analysis relies on identifying, within transcripts, examples of indicators of obviously critical and obviously uncritical thinking, from which several critical thinking ratios can be calculated.