137 resultados para Grafting compatibility

em Queensland University of Technology - ePrints Archive


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Written by the surgeons of the Exeter Hip Team and their colleagues from around the world, this book describes 40 years of innovation and development with cemented hip replacement. Topics covered include the basic science behind successful cemented hip replacement, modern surgical techniques and recent advances. There is also extensive coverage of the revision techniques developed at Exeter and elsewhere, focussing on femoral and acetabular impaction grafting. Each chapter is a self-contained article with an emphasis, where appropriate, on practical techniques and surgical tips, supported by line drawings and intra-operative photographs.

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The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

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Between 1987 and 1999, 540 revision total hip replacements in 487 patients were performed at our institution with the femoral impaction grafting technique with a cemented femoral stem. All patients were prospectively followed for 2-15years post-operatively with no loss to follow-up. 494 hips remained successfully in situ at an average 6.7years. The ten year survival rate was 98.0% (95% CI 96.2 to 99.8) with aseptic loosening as the endpoint and 84.2% (95% CI 78.5 to 89.9) for re-operation for any reason. Indication for surgery and the use of any kind of reinforcement significantly influenced outcome (p<0.001). This is the largest known series of revision THR with femoral impaction grafting and the results support continued use of this technique.

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Background and purpose: Acetabular impaction grafting has been shown to have excellent results, but concerns regarding its suitability for larger defects have been highlighted. We report the use of this technique in a large cohort of patients with the aim of better understanding the limitations of the technique. Methods: We investigated a consecutive group of 339 cases of impaction grafting of the cup with morcellised impacted allograft bone for survivorship and mechanisms for early failure. Results: Kaplan Meier survival was 89.1% (95% CI 83.2 to 95.0%) at 5.8 years for revision for any reason, and 91.6% (95% CI 85.9 to 97.3%) for revision for aseptic loosening of the cup. Of the 15 cases revised for aseptic cup loosening, nine were large rim mesh reconstructions, two were fractured Kerboull-Postel plates, two were migrating cages, one medial wall mesh failure and one impaction alone failed. Interpretation: In our series, results were disappointing where a large rim mesh or significant reconstruction was required. In light of these results, our technique has changed in that we now use predominantly larger chips of purely cancellous bone, 8-10 mm3 in size, to fill the cavity and larger diameter cups to better fill the mouth of the reconstructed acetabulum. In addition we now make greater use of i) implants made of a highly porous in-growth surface to constrain allograft chips and ii) bulk allografts combined with cages and morcellised chips in cases with very large segmental and cavitary defects.

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Mandatory data breach notification laws are a novel and potentially important legal instrument regarding organisational protection of personal information. These laws require organisations that have suffered a data breach involving personal information to notify those persons that may be affected, and potentially government authorities, about the breach. The Australian Law Reform Commission (ALRC) has proposed the creation of a mandatory data breach notification scheme, implemented via amendments to the Privacy Act 1988 (Cth). However, the conceptual differences between data breach notification law and information privacy law are such that it is questionable whether a data breach notification scheme can be solely implemented via an information privacy law. Accordingly, this thesis by publications investigated, through six journal articles, the extent to which data breach notification law was conceptually and operationally compatible with information privacy law. The assessment of compatibility began with the identification of key issues related to data breach notification law. The first article, Stakeholder Perspectives Regarding the Mandatory Notification of Australian Data Breaches started this stage of the research which concluded in the second article, The Mandatory Notification of Data Breaches: Issues Arising for Australian and EU Legal Developments (‘Mandatory Notification‘). A key issue that emerged was whether data breach notification was itself an information privacy issue. This notion guided the remaining research and focused attention towards the next stage of research, an examination of the conceptual and operational foundations of both laws. The second article, Mandatory Notification and the third article, Encryption Safe Harbours and Data Breach Notification Laws did so from the perspective of data breach notification law. The fourth article, The Conceptual Basis of Personal Information in Australian Privacy Law and the fifth article, Privacy Invasive Geo-Mashups: Privacy 2.0 and the Limits of First Generation Information Privacy Laws did so for information privacy law. The final article, Contextualizing the Tensions and Weaknesses of Information Privacy and Data Breach Notification Laws synthesised previous research findings within the framework of contextualisation, principally developed by Nissenbaum. The examination of conceptual and operational foundations revealed tensions between both laws and shared weaknesses within both laws. First, the distinction between sectoral and comprehensive information privacy legal regimes was important as it shaped the development of US data breach notification laws and their subsequent implementable scope in other jurisdictions. Second, the sectoral versus comprehensive distinction produced different emphases in relation to data breach notification thus leading to different forms of remedy. The prime example is the distinction between market-based initiatives found in US data breach notification laws compared to rights-based protections found in the EU and Australia. Third, both laws are predicated on the regulation of personal information exchange processes even though both laws regulate this process from different perspectives, namely, a context independent or context dependent approach. Fourth, both laws have limited notions of harm that is further constrained by restrictive accountability frameworks. The findings of the research suggest that data breach notification is more compatible with information privacy law in some respects than others. Apparent compatibilities clearly exist as both laws have an interest in the protection of personal information. However, this thesis revealed that ostensible similarities are founded on some significant differences. Data breach notification law is either a comprehensive facet to a sectoral approach or a sectoral adjunct to a comprehensive regime. However, whilst there are fundamental differences between both laws they are not so great to make them incompatible with each other. The similarities between both laws are sufficient to forge compatibilities but it is likely that the distinctions between them will produce anomalies particularly if both laws are applied from a perspective that negates contextualisation.

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Introduction In 1952 the Nathan report stated that: Some of the most valuable activities of voluntary societies consist, however, in the fact that they may be able to stand aside from and criticize State action or inaction, in the interests of the inarticulate man in the street. Some 60 years later it remained the case that if a voluntary society wanted to gain or retain charitable status then, contrary to the Nathan report, the one thing it could not do was set itself up with the purpose of criticizing State action or inaction. This legal position was adopted by the authorities in Australia with the Australian Taxation Office (ATO) noting in Taxation Ruling TR2005/21: 102. An institution or fund is not charitable if its purpose is advocating a political party or cause, attempting to change the law or government policy, or propagating or promoting a particular point of view. So, why, if it is such a valuable activity, have governments steadfastly refused to allow charities to have as their purpose the freedom to advocate in this way and how has this situation been affected by the recent High Court of Australia decision in Aid/Watch v Commissioner of Taxation? This article proposes to address such questions. Beginning with some background history, it explains that, initially, the current constraints did not apply. Then it looks at the nature of these constraints: how does the law define what constitutes the type of political activity that a charity must not undertake? What is the rationale for prohibition? How has the judiciary contributed to the development of the law in this area in recent years? This will lead into a consideration of the Aid/Watch case and the implications arising from the recent final decision. The article concludes by reflecting on what has changed and why the view on this contentious matter now looks different from Australia.