489 resultados para pilaantunut maa


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Vita.

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Spine title.

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We developed an efficient, cost effective strategy for Fmoc-based solid phase synthesis of 'difficult' peptides and/or peptides containing Asp/Asn-Gly sequences, free of aspartimide and related products, using a peptoid methodology for the preparation of N-substituted glycines.

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The ultraviolet (UV) absorbance of the mucus of a Great Barrier Reef damselfish Pomacentrus amboinensis was investigated with regard to ontogeny and time spent in captivity. The UV absorbance of P. amboinensis mucus increased with fish size and decreased with time spent in captivity. The wavelength of maximum absorbance of the mucus did not change with fish size, but shifted towards shorter wavelengths with increasing time spent in captivity. The UV absorbance of the mucus of fish with 'fin rot' was compared to that of similar healthy individuals, and a significant decrease in UV absorbance of unhealthy fish mucus was detected; no wavelength shifting occurred. Pomacentrus amboinensis appears to sequester mycosporine-like amino acids from the diet in order to protect epithelial tissues from UV damage, and decreases in UV absorbance in captive fish were probably due to insufficient dietary availability.

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Modification of proteins by reactive ethanol metabolites has been known for some time to occur in the liver, the main site of ethanol metabolism. In more recent studies of laboratory animals, similar modifications have been detected in organs with lesser ability to metabolize ethanol, such as skeletal and cardiac muscle and brain. Such modification may alter protein function or form a neoantigen, making it a target for immune attack. We now report an analysis of protein modification derived from ethanol metabolites in human brain tissue by ELISA using adduct-specific antibodies. We obtained autopsy cerebellum samples from 10 alcoholic cerebellar degeneration cases and 10 matched controls under informed written consent from the next of kin and clearance from the UQ Human Ethics Committee. Elevated levels of protein modifications derived from acetaldehyde (unreduced-acetaldehyde and acetaldehyde-advanced glycation end-product adducts), from malondialdehyde (malondialdehyde adducts) and from combined adducts (malondialdehydeacetaldehyde (MAA) adducts) were detected in alcoholic cerebellar degeneration samples when compared to controls. Other adduct types found in liver samples, such as reduced-acetaldehyde and those derived from hydroxyethyl radicals, were not detected in brain samples. This may reflect the different routes of ethanol metabolism in the two tissues. This is the first report of elevated protein modification in alcoholic cerebellar degeneration, and suggests that such modification may play a role in the pathogenesis of brain injury. Supported by NIAAA under grant NIH AA12404 and the NHMRC (Australia) under grant #981723.

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This paper presents for the first time the concept of measurement assisted assembly (MAA) and outlines the research priorities of the realisation of this concept in the industry. MAA denotes a paradigm shift in assembly for high value and complex products and encompasses the development and use of novel metrology processes for the holistic integration and capability enhancement of key assembly and ancillary processes. A complete framework for MAA is detailed showing how this can facilitate a step change in assembly process capability and efficiency for large and complex products, such as airframes, where traditional assembly processes exhibit the requirement for rectification and rework, use inflexible tooling and are largely manual, resulting in cost and cycle time pressures. The concept of MAA encompasses a range of innovativemeasurement- assisted processes which enable rapid partto- part assembly, increased use of flexible automation, traceable quality assurance and control, reduced structure weight and improved levels of precision across the dimensional scales. A full scale industrial trial of MAA technologies has been carried out on an experimental aircraft wing demonstrating the viability of the approach while studies within 140 smaller companies have highlighted the need for better adoption of existing process capability and quality control standards. The identified research priorities for MAA include the development of both frameless and tooling embedded automated metrology networks. Other research priorities relate to the development of integrated dimensional variation management, thermal compensation algorithms as well as measurement planning and inspection of algorithms linking design to measurement and process planning. © Springer-Verlag London 2013.

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Measurement and variation control of geometrical Key Characteristics (KCs), such as flatness and gap of joint faces, coaxiality of cabin sections, is the crucial issue in large components assembly from the aerospace industry. Aiming to control geometrical KCs and to attain the best fit of posture, an optimization algorithm based on KCs for large components assembly is proposed. This approach regards the posture best fit, which is a key activity in Measurement Aided Assembly (MAA), as a two-phase optimal problem. In the first phase, the global measurement coordinate system of digital model and shop floor is unified with minimum error based on singular value decomposition, and the current posture of components being assembly is optimally solved in terms of minimum variation of all reference points. In the second phase, the best posture of the movable component is optimally determined by minimizing multiple KCs' variation with the constraints that every KC respectively conforms to its product specification. The optimal models and the process procedures for these two-phase optimal problems based on Particle Swarm Optimization (PSO) are proposed. In each model, every posture to be calculated is modeled as a 6 dimensional particle (three movement and three rotation parameters). Finally, an example that two cabin sections of satellite mainframe structure are being assembled is selected to verify the effectiveness of the proposed approach, models and algorithms. The experiment result shows the approach is promising and will provide a foundation for further study and application. © 2013 The Authors.

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Measurement assisted assembly (MAA) has the potential to facilitate a step change in assembly efficiency for large structures such as airframes through the reduction of rework, manually intensive processes and expensive monolithic assembly tooling. It is shown how MAA can enable rapid part-to-part assembly, increased use of flexible automation, traceable quality assurance and control, reduced structure weight and improved aerodynamic tolerances. These advances will require the development of automated networks of measurement instruments; model based thermal compensation, the automatic integration of 'live' measurement data into variation simulation and algorithms to generate cutting paths for predictive shimming and drilling processes. This paper sets out an architecture for digital systems which will enable this integrated approach to variation management. © 2013 The Authors.

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Liver cancer accounts for nearly 10% of all cancers in the US. Intrahepatic Arterial Radiomicrosphere Therapy (RMT), also known as Selective Internal Radiation Treatment (SIRT), is one of the evolving treatment modalities. Successful patient clinical outcomes require suitable treatment planning followed by delivery of the microspheres for therapy. The production and in vitro evaluation of various polymers (PGCD, CHS and CHSg) microspheres for a RMT and RMT planning are described. Microparticles with a 30±10 µm size distribution were prepared by emulsion method. The in vitro half-life of the particles was determined in PBS buffer and porcine plasma and their potential application (treatment or treatment planning) established. Further, the fast degrading microspheres (≤ 48 hours in vitro half-life) were labeled with 68Ga and/or 99mTc as they are suitable for the imaging component of treatment planning, which is the primary emphasis of this dissertation. Labeling kinetics demonstrated that 68Ga-PGCD, 68Ga-CHSg and 68Ga-NOTA-CHSg can be labeled with more than 95% yield in 15 minutes; 99mTc-PGCD and 99mTc-CHSg can also be labeled with high yield within 15-30 minutes. In vitro stability after four hours was more than 90% in saline and PBS buffer for all of them. Experiments in reconstituted hemoglobin lysate were also performed. Two successful imaging (RMT planning) agents were found: 99mTc-CHSg and 68Ga-NOTA-CHSg. For the 99mTc-PGCD a successful perfusion image was obtained after 10 minutes, however the in vivo degradation was very fast (half-life), releasing the 99mTc from the lungs. Slow degrading CHS microparticles (> 21 days half-life) were modified with p-SCN-b-DOTA and labeled with 90 Y for production of 90Y-DOTA-CHS. Radiochemical purity was evaluated in vitro and in vivo showing more than 90% stability after 72 and 24 hours respectively. All agents were compared to their respective gold standards (99mTc-MAA for 68Ga-NOTA-CHSg and 99m Tc-CHSg; 90Y-SirTEX for 90Y-DOTA-CHS) showing superior in vivo stability. RMT and RMT planning agents (Therapy, PET and SPECT imaging) were designed and successfully evaluated in vitro and in vivo.

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Acknowledgments This study was financed by FEDER funds through the Programa Operacional Factores de Competitividade— COMPETE, and National funds through the Portuguese Foundation for Science and Technology—FCT, within the scope of the projects PERSIST (PTDC/BIA-BEC/105110/2008), NETPERSIST (PTDC/ AAG-MAA/3227/2012), and MateFrag (PTDC/BIA-BIC/6582/2014). RP was supported by the FCT grant SFRH/BPD/73478/2010 and SFRH/BPD/109235/2015. PB was supported by EDP Biodiversity Chair. We thank Rita Brito and Marta Duarte for help during field work. We thank Chris Sutherland, Douglas Morris, William Morgan, and Richard Hassall for critical reviews of early versions of the paper. We also thank two anonymous reviewers for helpful comments to improve the paper.

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L’utilisation de lentilles cornéennes peut servir à améliorer le profil d’administration d’un principe actif dans les yeux. Avec une efficacité d’administration de 5% par l’utilisation de gouttes, on comprend rapidement que l’administration oculaire doit être améliorée. Cette faible administration a donné naissance à plusieurs tentatives visant à fabriquer des lentilles cornéennes médicamentées. Cependant, à cause de multiples raisons, aucune de ces tentatives n’a actuellement été mise sur le marché. Nous proposons dans cette étude, une possible amélioration des systèmes établis par le développement d’une lentille cornéenne à base de 2-(hydroxyéthyle)méthacrylate (HEMA), dans laquelle des microgels, à base de poly N-isopropylacrylamide (pNIPAM) thermosensible encapsulant un principe actif, seront incorporé. Nous avons donc débuté par développer une méthode analytique sensible par HPCL-MS/MS capable de quantifier plusieurs molécules à la fois. La méthode résultante a été validée selon les différents critères de la FDA et l’ICH en démontrant des limites de quantifications et de détections suffisamment basses, autant dans des fluides simulés que dans les tissus d’yeux de lapins. La méthode a été validée pour sept médicaments ophtalmiques : Pilocarpine, lidocaïne, proparacaïne, atropine, acétonide de triamcinolone, timolol et prednisolone. Nous avons ensuite fait la synthèse des microgels chargés négativement à base de NIPAM et d’acide méthacrylique (MAA). Nous avons encapsulé une molécule modèle dans des particules ayant une taille entre 200 et 600 nm dépendant de la composition ainsi qu’un potentiel zêta variant en fonction de la température. L’encapsulation de la rhodamine 6G (R6G) dans les microgels a été possible jusqu’à un chargement (DL%) de 38%. L’utilisation des isothermes de Langmuir a permis de montrer que l’encapsulation était principalement le résultat d’interactions électrostatiques entre les MAA et la R6G. Des cinétiques de libérations ont été effectuées à partir d’hydrogels d’acrylamide chargés en microgels encapsulant la R6G. Il a été trouvé que la libération des hydrogels chargés en microgels s’effectuait majoritairement selon l’affinité au microgel et sur une période d’environ 4-24 heures. La libération à partir de ces systèmes a été comparée à des formules d’hydrogels contenant des liposomes ou des nanogels de chitosan. Ces trois derniers (liposomes, microgels et nanogels) ont présenté des résultats prometteurs pour différentes applications avec différents profils de libérations. Enfin, nous avons transposé le modèle développé avec les gels d’acrylamide pour fabriquer des lentilles de contact de 260 à 340 µm d’épaisseur à base de pHEMA contenant les microgels avec une molécule encapsulée devant être administrée dans les yeux. Nous avons modifié la composition de l’hydrogel en incorporant un polymère linéaire, la polyvinylpyrrolidone (PVP). L’obtention d’hydrogels partiellement interpénétrés améliore la rétention d’eau dans les lentilles cornéennes. L’encapsulation dans les microgels chargés négativement a donné de meilleurs rendements avec la lidocaïne et cette dernière a été libérée de la lentille de pHEMA en totalité en approximativement 2 heures qu’elle soit ou non encapsulée dans des microgels. Ainsi dans cette étude pilote, l’impact des microgels n’a pas pu être déterminé et, de ce fait, nécessitera des études approfondies sur la structure et les propriétés de la lentille qui a été développée. En utilisant des modèles de libération plus représentatifs de la physiologie de l’œil, nous pourrions conclure avec plus de certitude concernant l’efficacité d’un tel système d’administration et s’il est possible de l’optimiser.

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Uusiutuvan energian käytön lisääntyminen lisää sähkön varastoinnin tarvetta. Litiumioniakku-jen on todettu olevan oivallisia keinoja varastoida sähköä esimerkiksi sähköautojen energian-lähteeksi. Tästä syystä akkujen kysyntä kasvaa nopeaa tahtia, jolloin nykyiset litiumlähteet ei-vät enää riitä tuottamaan tarpeeksi litiumia kasvavaan tarpeeseen. Tämän vuoksi litiumin tal-teenottoon tulee valjastaa uusia litiumin lähteitä, joiden hyödynnettävyys nykyisellä tekniikalla on pienen litiumkonsentraation ja muiden alkali- ja maa-alkalimetallien läsnäolon takia vaikeaa. Tällä hetkellä litiumia otetaan talteen eniten korkean litiumpitoisuuden luonnon suolajärvistä. Nykyisin käytössä oleva litiumin erotusprosessi on hidas ja sen käyttö pienten litiumkonsent-raatioiden suola-altailla on kannattamatonta. Tehokkaampana talteenottomenetelmänä luonnon suolajärvillä nähdään litiumin selektiivinen uutto ionisilla nesteillä. Menetelmä on todettu toi-mivaksi suolajärvillä, joilla on matala litiumkonsentraatio. Uusien suolajärvien käyttöönotto ei ratkaise kaikkia litiumin talteenottoon liittyviä ongelmia, sillä suolajärvet ovat alttiita ilmastonmuutokselle, eikä niiden litiumvarannot ole ehtymättömät. Merien litiumvarantoja sen sijaan pidetään lähes ehtymättöminä. Litiumin talteenotto meristä on mahdollista ionisia nesteitä ja membraaneja hyödyntävällä elektrodialyysilaitteistolla, jolla litiumia voidaan ottaa talteen myös hyvin pienistä pitoisuuksista. Lisäksi on mahdollista, että litiumin talteenottoon yhdistetään juomaveden valmistus. Tällainen vedenpuhdistusprosessi olisi myös hyvä kestävän kehityksen näkökulmasta.

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Abstract : Wastepaper sludge ash (WSA) is generated by a cogeneration station by burning wastepaper sludge. It mainly consists of amorphous aluminosilicate phase, anhydrite, gehlenite, calcite, lime, C2S, C3A, quartz, anorthite, traces of mayenite. Because of its free lime content (~10%), WSA suspension has a high pH (13). Previous researchers have found that the WSA composition has poor robustness and the variations lead to some unsoundness for Portland cement (PC) blended WSA concrete. This thesis focused on the use of WSA in different types of concrete mixes to avoid the deleterious effect of the expansion due to the WSA hydration. As a result, WSA were used in making alkali-activated materials (AAMs) as a precursor source and as a potential activator in consideration of its amorphous content and the high alkaline nature. Moreover, the autogenous shrinkage behavior of PC concrete at low w/b ratio was used in order to compensate the expansion effect due to WSA. The concrete properties as well as the volume change were investigated for the modified WSA blended concrete. The reaction mechanism and microstructure of newly formed binder were evaluated by X-ray diffraction (XRD), calorimetry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). When WSA was used as precursor, the results showed incompatible reaction between WSA and alkaline solution. The mixtures were not workable and provided very low compressive strength no matter what kinds of chemical activators were used. This was due to the metallic aluminum in WSA, which releases abundant hydrogen gas when WSA reacts with strong alkaline solution. Besides, the results of this thesis showed that WSA can activate the glassy phase contained in slag, glass powder (GP) and class F fly ash (FFA) with an optimum blended ratio of 50:50. The WSA/slag (mass ratio of 50:50) mortar (w/b of 0.47) attained 46 MPa at 28 days without heat curing assistance. A significant fast setting was noticed for the WSA-activated binder due to the C3A phase, free lime and metallic aluminum contained in the WSA. Adding 5% of gypsum can delay the fast setting, but this greatly increased the potential risk of intern sulfate attack. The XRD, TGA and calorimetry analyses demonstrated the formation of ettringite, C-S-H, portlandite, hydrogarnet and calcium carboaluminate in the hydrated binder. The mechanical performance of different binder was closely related to the microstructure of corresponding binder which was proved by the SEM observation. The hydrated WSA/slag and WSA/FFA binder formed a C-A-S-H type of gel with lower Ca/Si ratio (0.47~1.6). A hybrid gel (i.e. C-N-A-S-H) was observed for the WSA/GP binder with a very low Ca/Si ratio (0.26) and Na/Si ratio (0.03). The SEM/EDX analyses displayed the formation of expansive gel (ettringite and thaumasite) in the gypsum added WSA/slag concrete. The gradual emission of hydrogen gas due to the reaction of WSA with alkaline environment significantly increased the porosity and degraded the microstructure of hydrated matrix after the setting. In the last phase of this research WSA-PC blended binder was tailored to form a high autogenous shrinkage concrete in order to compensate the initial expansion. Different binders were proportioned with PC, WSA, silica fume or slag. The microstructure and mechanical properties of concrete can be improved by decreasing w/b ratios and by incorporating silica fume or slag. The 28-day compressive strength of WSA-blended concrete was above 22 MPa and reached 45 MPa when silica fume was added. The PC concrete incorporating silica fume or slag tended to develop higher autogenous shrinkage at low w/b ratios, and thus the ternary binder with the addition of WSA inhibited the long term shrinkage due to the initial expansion property to WSA. In the restrained shrinkage test, the concrete ring incorporating the ternary binder (PC/WSA/slag) revealed negligible potential to cracking up to 96 days as a result of the offset effect by WSA expansion. The WSA blended regular concrete could be produced for potential applications with reduced expansion, good mechanical property and lower permeability.