Synthesis, reactive mechanism and thermal stability of W1-xAlxC (x=0.33, 0.5, 0.75, 0.86) nanocrystalline

W1-xAlxC (x = 0.33, 0.50, 0.75, 0.86) solid solutions have been synthesized directly by ball-milling tungsten powder, aluminum powder and activated carbon. The structural development of W0.5Al0.5C phase with the milling times up to 160 h has been followed using X-ray diffraction. X-ray photoelectron spectra demonstrate that Al atom takes the place of W. High temperature annealing experiment reveals that Al is stable in hexagonal structure to 1873 K. Transmission electron microscopy image shows that the grain size of the prepared powders is about 5 nm.

Synthesis, structure and reactive mechanism of intermetallic W3Mg

Assisted by mechanical alloying and high-pressure technique, a new W3Mg intermetallic was formed. W3Mg amorphous mixture was obtained by mechanically alloying the pure metal powder mixtures at designated composition for 20 h. A new compound was found after the Subsequent high pressure and high temperature treatment. W3Mg intermetallic was identified as a tetragonal structure and the lattice parameter was a = 0.7880 nm, c = 0.7070 nm. The synthesis mechanism is also discussed in this paper.

Synthesis, structure and reactive mechanism of intermetallic W4Mg

Assisted by a mechanical alloying and high-pressure technique, a new W4Mg intermetallic was formed. W4Mg amorphous mixture was obtained by mechanically alloying the pure metal powder mixtures at designated composition for 20 h. A new compound was found after the subsequent high-pressure and high-temperature treatment. W4Mg intermetallic was identified as a cubic structure and the lattice parameter was a=0.4150 nm. The synthesis mechanism is also discussed in this paper.

Crystallization of mechanically alloyed amorphous W-Mg alloy under high pressure

Pure metal powder mixtures of W and Mg at the desired composition were milled in conventional high-energy ball mill, and amorphous alloy W50Mg50 was obtained after milling for 20 h. The structure evolution of elemental powder mixtures was studied following milling and subsequent high pressure and high temperature treatment. The amorphous alloy transform into a nanocrystalline material below 1050 degreesC at 4.0 GPa. On increasing the temperature, it transforms into a mixture of several new crystal phases under high-pressure condition. It also found that both mechanical alloying and high pressure treatment are the two necessary processes to form the nanocrystalline and the new phases.

Quantitative structure-toxicity relationships for chlorophenols to bioluminescent lux-marked bacteria using atom-based semi-empirical molecular-orbital descriptors

Literature data on the toxicity of chlorophenols for three luminescent bacteria (Vibrio fischeri, and the lux-marked Pseudomonas fluorescens 10586s pUCD607 and Burkholderia spp. RASC c2 (Tn4431)) have been analyzed in relation to a set of computed molecular physico-chemical properties. The quantitative structure-toxicity relationships of the compounds in each species showed marked differences when based upon semi-empirical molecular-orbital molecular and atom based properties. For mono-, di- and tri-chlorophenols multiple linear regression analysis of V. fischeri toxicity showed a good correlation with the solvent accessible surface area and the charge on the oxygen atom. This correlation successfully predicted the toxicity of the heavily chlorinated phenols, suggesting in V. fischeri only one overall mechanism is present for all chlorophenols. Good correlations were also found for RASC c2 with molecular properties, such as the surface area and the nucleophilic super-delocalizability of the oxygen. In contrast the best QSTR for P. fluorescens contained the 2nd order connectivity index and ELUMO suggesting a different, more reactive mechanism. Cross-species correlations were examined, and between V. fischeri and RASC c2 the inclusion of the minimum value of the nucleophilic susceptibility on the ring carbons produced good results. Poorer correlations were found with P. fluorescens highlighting the relative similarity of V. fischeri and RASC c2, in contrast to that of P. fluorescens.

QoS improvement in TCP/IP-based wireless sensor networks using cross-layer optimization

Dissertação de Mestrado, Engenharia Informática, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

Proyectando entre ruinas : lógicas de intervención continua en la arquitectura contemporánea

Los cambios percibidos hacia finales del siglo XX y a principios del nuevo milenio, nos ha mostrado que la crisis cultural de la que somos participes refleja también una crisis de los modelos universales. Nuestra situación contemporánea, parece indicar que ya no es posible formular un sistema estético para atribuirle una vigencia universal e intemporal más allá de su estricta eficacia puntual. La referencia organizada, delimitada, invariable y específica que ofrecía cualquier emplazamiento, en tanto preexistencia, reflejaba una jerarquía del sistema formal basado en lo extensivo: la medida, las normas, el movimiento, el tiempo, la modulación, los códigos y las reglas. Sin embargo, actualmente, algunos aspectos que permanecían latentes sobre lo construido, emergen bajo connotaciones intensivas, transgrediendo la simple manifestación visual y expresiva, para centrase en las propiedades del comportamiento de la materia y la energía como determinantes de un proceso de adaptación en el entorno. A lo largo del todo el siglo XX, el desarrollo de la relación del proyecto sobre lo construido ha sido abordado, casi en exclusiva, entre acciones de preservación o intervención. Ambas perspectivas, manifestaban esfuerzos por articular un pensamiento que diera una consistencia teórica, como soporte para la producción de la acción aditiva. No obstante, en las últimas décadas de finales de siglo, la teoría arquitectónica terminó por incluir pensamientos de otros campos que parecen contaminar la visión sesgada que nos refería lo construido. Todo este entramado conceptual previo, aglomeraba valiosos intentos por dar contenido a una teoría que pudiese ser entendida desde una sola posición argumental. Es así, que en 1979 Ignasi Solá-Morales integró todas las imprecisiones que referían una actuación sobre una arquitectura existente, bajo el termino de “intervención”, el cual fue argumentado en dos sentidos: El primero referido a cualquier tipo de actuación que se puede hacer en un edificio, desde la defensa, preservación, conservación, reutilización, y demás acciones. Se trata de un ámbito donde permanece latente el sentido de intensidad, como factor común de entendimiento de una misma acción. En segundo lugar, más restringido, la idea de intervención se erige como el acto crítico a las ideas anteriores. Ambos representan en definitiva, formas de interpretación de un nuevo discurso. “Una intervención, es tanto como intentar que el edificio vuelva a decir algo o lo diga en una determinada dirección”. A mediados de 1985, motivado por la corriente de revisión historiográfica y la preocupación del deterioro de los centros históricos que recorría toda Europa, Solá-Morales se propone reflexionar sobre “la relación” entre una intervención de nueva arquitectura y la arquitectura previamente existente. Relación condicionada estrictamente bajo consideraciones lingüísticas, a su entender, en sintonía con toda la producción arquitectónica de todo el siglo XX. Del Contraste a la Analogía, resumirá las transformaciones en la concepción discursiva de la intervención arquitectónica, como un fenómeno cambiante en función de los valores culturales, pero a su vez, mostrando una clara tendencia dialógica entres dos categorías formales: El Contraste, enfatizando las posibilidades de la novedad y la diferencia; y por otro lado la emergente Analogía, como una nueva sensibilidad de interpretación del edificio antiguo, donde la semejanza y la diversidad se manifiestan simultáneamente. El aporte reflexivo de los escritos de Solá-Morales podría ser definitivo, si en las últimas décadas antes del fin de siglo, no se hubiesen percibido ciertos cambios sobre la continuidad de la expresión lingüística que fomentaba la arquitectura, hacia una especie de hipertrofia figurativa. Entre muchos argumentos: La disolución de la consistencia compositiva y el estilo unitario, la incorporación volumétrica del proyecto como dispositivo reactivo, y el cambio de visión desde lo retrospectivo hacia lo prospectivo que sugiere la nueva conservación. En este contexto de desintegración, el proyecto, en tanto incorporación o añadido sobre un edificio construido, deja de ser considerado como un apéndice volumétrico subordinado por la reglas compositivas y formales de lo antiguo, para ser considerado como un organismo de orden reactivo, que produce en el soporte existente una alteración en su conformación estructural y sistémica. La extensión, antes espacial, se considera ahora una extensión sensorial y morfológica con la implementación de la tecnología y la hiper-información, pero a su vez, marcados por una fuerte tendencia de optimización energética en su rol operativo, ante el surgimiento del factor ecológico en la producción contemporánea. En una sociedad, como la nuestra, que se está modernizando intensamente, es difícil compartir una adecuada sintonía con las formas del pasado. Desde 1790, fecha de la primera convención francesa para la conservación de monumentos, la escala de lo que se pretende preservar es cada vez más ambiciosa, tanto es así, que al día de hoy el repertorio de lo que se conserva incluye prácticamente todas las tipologías del entorno construido. Para Koolhaas, el intervalo entre el objeto y el momento en el cual se decide su conservación se ha reducido, desde dos milenios en 1882 a unas décadas hoy en día. En breve este lapso desaparecerá, demostrando un cambio radical desde lo retrospectivo hacia lo prospectivo, es decir, que dentro de poco habrá que decidir que es lo que se conserva antes de construir. Solá-Morales, en su momento, distinguió la relación entre lo nuevo y lo antiguo, entre el contraste y la analogía. Hoy casi tres décadas después, el objetivo consiste en evaluar si el modelo de intervención arquitectónica sobre lo construido se ha mantenido desde entonces o si han aparecido nuevas formas de posicionamiento del proyecto sobre lo construido. Nuestro trabajo pretende demostrar el cambio de enfoque proyectual con la preexistencia y que éste tiene estrecha relación con la incorporación de nuevos conceptos, técnicas, herramientas y necesidades que imprimen el contexto cultural, producido por el cambio de siglo. Esta suposición nos orienta a establecer un paralelismo arquitectónico entre los modos de relación en que se manifiesta lo nuevo, entre una posición comúnmente asumida (Tópica), genérica y ortodoxa, fundamentada en lo visual y expresivo de las últimas décadas del siglo XX, y una realidad emergente (Heterotópica), extraordinaria y heterodoxa que estimula lo inmaterial y que parece emerger con creciente intensidad en el siglo XXI. Si a lo largo de todo el siglo XX, el proyecto de intervención arquitectónico, se debatía entre la continuidad y discontinuidad de las categorías formales marcadas por la expresión del edificio preexistente, la nueva intervención contemporánea, como dispositivo reactivo en el paisaje y en el territorio, demanda una absoluta continuidad, ya no visual, expresiva, ni funcional, sino una continuidad fisiológica de adaptación y cambio con la propia dinámica del territorio, bajo nuevas reglas de juego y desplegando planes y estrategias operativas (proyectivas) desde su propia lógica y contingencia. El objeto de esta investigación es determinar los nuevos modos de continuidad y las posibles lógicas de producción que se manifiestan dentro de la Intervención Arquitectónica, intentando superar lo aparente de su relación física y visual, como resultado de la incorporación del factor operativo desplegado por el nuevo dispositivo contemporáneo. Creemos que es acertado mantener la senda connotativa que marca la denominación intervención arquitectónica, por aglutinar conceptos y acercamientos teóricos previos que han ido evolucionando en el tiempo. Si bien el término adolece de mayor alcance operativo desde su formulación, una cualidad que infieren nuestras lógicas contemporáneas, podría ser la reformulación y consolidación de un concepto de intervención más idóneo con nuestros tiempos, anteponiendo un procedimiento lógico desde su propia necesidad y contingencia. Finalmente, nuestro planteamiento inicial aspira a constituir un nueva forma de reflexión que nos permita comprender las complejas implicaciones que infiere la nueva arquitectura sobre la preexistencia, motivada por las incorporación de factores externos al simple juicio formal y expresivo preponderante a finales del siglo XX. Del mismo modo, nuestro camino propuesto, como alternativa, permite proyectar posibles sendas de prospección, al considerar lo preexistente como un ámbito que abarca la totalidad del territorio con dinámicas emergentes de cambio, y con ellas, sus lógicas de intervención.Abstract The perceived changes towards the end of the XXth century and at the beginning of the new milennium have shown us that the cultural crisis in which we participate also reflects a crisis of the universal models. The difference between our contemporary situation and the typical situations of modern orthodoxy and post-modernistic fragmentation, seems to indicate that it is no longer possible to formulate a valid esthetic system, to assign a universal and eternal validity to it beyond its strictly punctual effectiveness; which is even subject to questioning because of the continuous transformations that take place in time and in the sensibility of the subject itself every time it takes over the place. The organised reference that any location offered, limited, invariable and specific, while pre-existing, reflected a hierarchy of the formal system based on the applicable: measure, standards, movement, time, modulation, codes and rules. Authors like Marshall Mc Luhan, Paul Virilio, or Marc Augé anticipated a reality where the conventional system already did not seem to respond to the new architectural requests in which information, speed, disappearance and the virtual had blurred the traditional limits of place; pre-existence did no longer possess a specific delimitation and, on the contrary, they expect to reach a global scale. Currently, some aspects that stayed latent relating to the constructed, surface from intensive connotations, transgressing the simple visual and expressive manifestation in order to focus on the traits of the behaviour of material and energy as determinants of a process of adaptation to the surroundings. Throughout the entire Century, the development of the relation of the project relating to the constructed has been addressed, almost exclusively, in preservational or interventianal actions. Both perspectives showed efforts in order to express a thought that would give a theoretical consistency as a base for the production of the additive action. Nevertheless, the last decades of the Century, architectural theory ended up including thoughts from other fields that seem to contaminate the biased vision 15 which the constructed related us. Ecology, planning, philosophy, global economy, etc, suggest new approaches to the construction of the contemporary city; but this time with a determined idea of change and continuous transformation, that enriches the panorama of thought and architectural practice, at the same time, according to some, it puts disciplinary specification at risk, given that there is no architecture without destruction, the constructed organism requires mutation in order to adjust to the change of shape. All of this previous conceptual framework gathered valuable intents to give importance to a theory that could be understood solely from an argumental position. Thusly, in 1979 Ignasi Solá-Morales integrated all of the imprecisions that referred to an action in existing architecture under the term of “Intervention”, which was explained in two ways: The first referring to any type of intervention that can be carried out in a building, regarding protection, conservation, reuse, etc. It is about a scope where the meaning of intensity stays latent as a common factor of the understanding of a single action. Secondly, more limitedly, the idea of intervention is established as the critical act to the other previous ideas such as restauration, conservation, reuse, etc. Both ultimately represent ways of interpretation of a new speech. “An intervention, is as much as trying to make the building say something again or that it be said in a certain direction”. Mid 1985, motivated by the current of historiographical revision and the concerns regarding the deterioration of historical centres that traversed Europe, Solá-Morales decides to reflect on “the relationship” between an intervention of the new architecture and the previously existing architecture. A relationship determined strictly by linguistic considerations, to his understanding, in harmony with all of the architectural production of the XXth century. From Contrast to Analogy would summarise transformations in the discursive perception of architectural intervention, as a changing phenomenon depending on cultural values, but at the same time, showing a clear dialogical tendency between two formal categories: Contrast, emphasising the possibilities of novelty and difference; and on the other hand the emerging Analogy, as a new awareness of interpretation of the ancient building, where the similarity and diversity are manifested simultaneously. For Solá-Morales the analogical procedure is not based on the visible simultaneity of formal orders, but on associations that the subject establishes throughout time. Through analogy it is tried to overcome the simple visual relationship with the antique, to focus on its spacial, physical and geographical nature. If the analogical attempt guides an opening towards a new continuity; it still persists in the connection of dimensional, typological and figurative factors, subordinate to the formal hierarchy of the preexisting subjects. 16 The reflexive contribution of Solá-Morales’ works could be final, if in the last decades before the end of the century there had not been certain changes regarding linguistic expression, encouraged by architecture, towards a kind of figurative hypertrophy, amongst many arguments we are in this case interested in three moments: The dissolution of the compositional consistency and the united style, the volumetric incorporation of the project as a reactive mechanism, and the change of the vision from retrospective towards prospective that the new conservation suggests. The recurrence to the history of architecture and its recognisable forms, as a way of perpetuating memory and establishing a reference, dissolved any instinct of compositive unity and style, provoking permanent relationships to tend to disappear. The composition and coherence lead to suppose a type of discontinuity of isolated objects in which only possible relationships could appear; no longer as an order of certain formal and compositive rules, but as a special way of setting elements in a specific work. The new globalised field required new forms of consistency between the project and the pre-existent subject, motivated amongst others by the higher pace of market evolution, increase of consumer tax and the level of information and competence between different locations; aspects which finally made stylistic consistence inefficient. In this context of disintegration, the project, in incorporation as well as added to a constructed building, stops being considered as a volumetric appendix subordinate to compositive and formal rules of old, to be considered as an organism of reactive order, that causes a change in the structural and systematic configuration of the existing foundation. The extension, previsouly spatial, is now considered a sensorial and morphological extension, with the implementation of technology and hyper-information, but at the same time, marked by a strong tendency of energetic optimization in its operational role, facing the emergence of the ecological factor in contemporary production. The technological world turns into a new nature, a nature that should be analysed from ecological terms; in other words, as an event of transition in the continuous redistribution of energy. In this area, effectiveness is not only determined by the capacity of adaptation to changing conditions, but also by its transforming capacity “expressly” in order to change an environment. In a society, like ours, that is modernising intensively, it is difficult to share an adecuate agreement with the forms of the past. From 1790, the date of the first French convention for the conservation of monuments, the scale of what is expexted to be preserved is more and more ambitious, so much so that nowadays the repertoire of that what is conserved includes practically all typologies of the constructed surroundings. For Koolhaas, the ínterval between the object and the moment when its conservation is decided has been reduced, from two 17 milennia in 1882 to a few decades nowadays. Shortly this lapse will disappear, showing a radical change of retrospective towards prospective, that is to say, that soon it will be necessary to decide what to conserve before constructing. The shapes of cities are the result of the continuous incorporation of architecture, and perhaps that only through architecture the response to the universe can be understood, the continuity of what has already been constructed. Our work is understood also within that system, modifying the field of action and leaving the road ready for the next movement of those that will follow after us. Continuity does not mean conservatism, continuity means being conscient of the transitory value of our answers to specific needs, accepting the change that we have received. That what has been constructed to remain and last, should cause future interventions to be integrated in it. It is necessary to accept continuity as a rule. Solá-Morales, in his time, distinguished between the relationship with new and old, between contrast and analogy. Today, almost three decades later, the objective consists of evaluating whether the model of architectural intervention in the constructed has been maintained since then or if new ways of positioning the project regarding the constructed have appeared. Our work claims to show the change of the approach of projects with pre-existing subjects and that this has got a close relation to the incorporation of new concepts, techniques, tools and necessities that impress the cultural context, caused by the change of centuries. This assumption guides us to establish a parallelism between the forms of connection where that what is new is manifested between a commonly assumed (topical), generic and orthodox position, based on that what is visual and expressive in the last decades of the XXth century, and an emerging (heterotopical), extraordinary and heterodox reality that stimulates the immaterial and that seems to emerge with growing intensity in the XXIst century. If throughout the XXth century the project of architectural intervention was considered from the continuity and discontinuity of formal categories, marked by the expression of the pre-existing building, the new contemporary intervention, as a reactive device in the landscape and territory, demands an absolute continuity. No longer a visual, expressive or functional one but a morphological continuity of adaptation and change with its own territorial dynamics, under new game rules and unfolding new operative (projective) strategies from its own logic and contingency. 18 The aim of this research is to determine new forms of continuity and the possible logic of production that are expressed in the Architectural Intervention, trying to overcome the obviousness of its physical and visual relationship, at the beginning of this new century, as a result of the incorporation of the operative factor that the new architectural device unfolds. We think it is correct to maintain the connotative path that marks the name architectural intervention by bringing previous concepts and theorical approaches that have been evolving through time together. If the name suffers from a wider operational range because of its formulation, a quality that our contemporary logic provokes, the reformulation and consolidation of an interventional concept could be more suitable for our times, giving preference to a logical method from its own necessity and contingency. It seems that now time shapes the topics, it is no longer about materialising a certain time but about expressing the changes that its new temporality generates. Finally, our initial approach aspires to form a new way of reflection that permits us to understand the complex implications that the new architecture submits the pre-existing subject to, motivated by the incorporation of factors external to simple formal and expressive judgement, prevailing at the end of the XXth century. In the same way, our set road, as an alternative, permits the contemplation of possible research paths, considering that what is pre-existing as an area that spans the whole territory with emerging changing dynamics and, with them, their interventional logics.

Growth mechanism of the Nb(X)Si-2 and [Nb(X)](5)Si-3 phases by reactive diffusion in Nb (X = Ti, Mo, or Zr)-Si systems

The effects of Mo, Ti, and Zr on the diffusion and growth of the Nb(X)Si-2 and Nb(X)(5)Si-3 phases in an Nb(X)-Si system are analyzed. The integrated diffusion coefficients are determined from diffusion couple experiments and compared with the data previously calculated in a binary Nb-Si system. The growth rates of both phases are affected by the addition of Mo and Zr, whereas the addition of Ti has no effect. The atomic mechanism of diffusion is also discussed based on the crystal structure and the possible changes in the defect concentrations due to alloying. Finally, the growth mechanism of the phases is discussed on the basis of a physico-chemical approach. (C) 2011 Elsevier Ltd. All rights reserved.

NADPH oxidase-mediated generation of reactive oxygen species: A new mechanism for X-ray-induced HeLa cell death

Oxidative damage is an important mechanism in X-ray-induced cell death. Radiolysis of water molecules is a source of reactive oxygen species (ROS) that contribute to X-ray-induced cell death. In this study, we showed by ROS detection and a cell survival assay that NADPH oxidase has a very important role in X-ray-induced cell death. Under X-ray irradiation, the upregulation of the expression of NADPH oxidase membrane Subunit gp91(phox) was dose-dependent. Meanwhile, the cytoplasmic subunit p47(phox) was translocated to the cell membrane and localized with p22(phox) and gp91(phox) to form reactive NADPH oxidase. Our data Suggest, for the first time, that NADPH oxidase-mediated generation of ROS is an important contributor to X-ray-induced cell death. This suggests a new target for combined gene transfer and radiotherapy.

Functionalization of isotactic polypropylene with maleic anhydride by reactive extrusion: mechanism of melt grafting

In this work, chemical structures and molecular parameters of grafted materials of PP-g-MAH prepared by melt reactive extrusion were studied by using electrospray ionization-mass spectrometer and gel permeation chromatography. It was found that the initial radicals, due to homolitic scission of dicumyl peroxide could be combined with maleic anhydride (MAH) monomers as well as polypropylene (PP) molecular chains. The homopolymerization of MAH cannot occur and the MAH radicals undergo a dismutational reaction under the processing condition (180-190 degreesC). A modified mechanism of melt grafting MAH onto PP has been proposed tentatively on the basis of our experimental results and other experimental findings published in the literature. (C) 2001 Elsevier Science Ltd. All rights reserved.

The application of a profluorescent nitroxide probe to detect reactive oxygen species derived from combustion-generated particulate matter

Particulate pollution has been widely recognised as an important risk factor to human health. In addition to increases in respiratory and cardiovascular morbidity associated with exposure to particulate matter (PM), WHO estimates that urban PM causes 0.8 million premature deaths globally and that 1.5 million people die prematurely from exposure to indoor smoke generated from the combustion of solid fuels. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. Oxidative stress caused by generation of free radicals and related reactive oxygen species (ROS) at the sites of deposition has been proposed as a mechanism for many of the adverse health outcomes associated with exposure to PM. In addition to particle-induced generation of ROS in lung tissue cells, several recent studies have shown that particles may also contain ROS. As such, they present a direct cause of oxidative stress and related adverse health effects. Cellular responses to oxidative stress have been widely investigated using various cell exposure assays. However, for a rapid screening of the oxidative potential of PM, less time-consuming and less expensive, cell-free assays are needed. The main aim of this research project was to investigate the application of a novel profluorescent nitroxide probe, synthesised at QUT, as a rapid screening assay in assessing the oxidative potential of PM. Considering that this was the first time that a profluorescent nitroxide probe was applied in investigating the oxidative stress potential of PM, the proof of concept regarding the detection of PM–derived ROS by using such probes needed to be demonstrated and a sampling methodology needed to be developed. Sampling through an impinger containing profluorescent nitroxide solution was chosen as a means of particle collection as it allowed particles to react with the profluorescent nitroxide probe during sampling, avoiding in that way any possible chemical changes resulting from delays between the sampling and the analysis of the PM. Among several profluorescent nitroxide probes available at QUT, bis(phenylethynyl)anthracene-nitroxide (BPEAnit) was found to be the most suitable probe, mainly due to relatively long excitation and emission wavelengths (λex= 430 nm; λem= 485 and 513 nm). These wavelengths are long enough to avoid overlap with the background fluorescence coming from light absorbing compounds which may be present in PM (e.g. polycyclic aromatic hydrocarbons and their derivatives). Given that combustion, in general, is one of the major sources of ambient PM, this project aimed at getting an insight into the oxidative stress potential of combustion-generated PM, namely cigarette smoke, diesel exhaust and wood smoke PM. During the course of this research project, it was demonstrated that the BPEAnit probe based assay is sufficiently sensitive and robust enough to be applied as a rapid screening test for PM-derived ROS detection. Considering that for all three aerosol sources (i.e. cigarette smoke, diesel exhaust and wood smoke) the same assay was applied, the results presented in this thesis allow direct comparison of the oxidative potential measured for all three sources of PM. In summary, it was found that there was a substantial difference between the amounts of ROS per unit of PM mass (ROS concentration) for particles emitted by different combustion sources. For example, particles from cigarette smoke were found to have up to 80 times less ROS per unit of mass than particles produced during logwood combustion. For both diesel and wood combustion it has been demonstrated that the type of fuel significantly affects the oxidative potential of the particles emitted. Similarly, the operating conditions of the combustion source were also found to affect the oxidative potential of particulate emissions. Moreover, this project has demonstrated a strong link between semivolatile (i.e. organic) species and ROS and therefore, clearly highlights the importance of semivolatile species in particle-induced toxicity.

Adsorption of reactive dye on seawater-neutralised bauxite refinery residue

This investigation has demonstrated the need for thermal treatment of seawater neutralised red mud (SWRM) in order to obtain reasonable adsorption of Reactive Blue dye 19 (RB 19). Thermal treatment results in a greater surface area, which results in an increased adsorption capacity due to more available adsorption sites. Adsorption of RB 19 has been found to be best achieved in acidic conditions using SWNRM400 (heated to 400 �C) with an adsorption capacity of 416.7 mg/g compared to 250.0 mg/g for untreated SWNRM. Kinetic studies indicate a pseudosecond-order reaction mechanism is responsible for the adsorption of RB 19 using SWNRM, which indicates adsorption occurs by electrostatic interactions.

Harnessing the influence of reactive edges and defects of graphene substrates for achieving complete cycle of room-temperature molecular sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene-nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water-based dispersions of single-layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p-type responses to NO2 and NH3) and the edges of graphene nanomesh structures (showing n-type responses to NO2 and NH3) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene-based materials.

Plasma-induced death of HepG2 cancer cells : intracellular effects of reactive species

Reports show that cold atmospheric-pressure plasmas can induce death of cancer cells in several minutes. However, very little is presently known about the mechanism of the plasma-induced death of cancer cells. In this paper, an atmospheric-pressure plasma plume is used to treat HepG2 cells. The experimental results show that the plasma can effectively control the intracellular concentrations of ROS, NO and lipid peroxide. It is shown that these concentrations are directly related to the mechanism of the HepG2 death, which involves several stages. First, the plasma generates NO species, which increases the NO concentration in the extracellular medium. Second, the intracellular NO concentration is increased due to the NO diffusion from the medium. Third, an increase in the intracellular NO concentration leads to the increase of the intracellular ROS concentration. Fourth, the increased oxidative stress results in more effective lipid peroxidation and consequently, cell injury. The combined action of NO, ROS and lipid peroxide species eventually results in the HepG2 cell death. The mechanism of death of human hepatocellular carcinoma cells (HepG2) induced by atmospheric-pressure room-temperature plasma, related to the plasma-controlled intracellular concentrations of reactive oxygen species (ROS), nitric oxide (NO) and lipid peroxide is revealed. Only 34.75 s are required to reduce the number of the viable HepG2 cells by 50%.

Enhanced fast handover triggering mechanism for fast proxy mobile IPv6

Handover performance is critical to support real-time traffic applications in wireless network communications. The longer the handover delay is, the longer an Mobile Node (MN) is prevented from sending and receiving any data packet. In real-time network communication applications, such as VoIP and video-conference, a long handover delay is often unacceptable. In order to achieve better handover performance, Fast Proxy Mobile IPv6 (FPMIPv6) has been standardised as an improvement to the original Proxy Mobile IPv6 (PMIPv6) in the Internet Engineering Task Force (IETF). The FPMIPv6 adopts a link layer triggering mechanism to perform two modes of operation: predictive and reactive modes. Using the link layer triggering, the handover performance of the FPMIPv6 can be improved in the predictive mode. However, an unsuccessful predictive handover operation will lead to activation of a reactive handover. In the reactive mode, MNs still experience long handover delays and a large amount of packet loss, which significantly degrade the handover performance of the FPMIPv6. Addressing this problem, this thesis presents an Enhanced Triggering Mechanism (ETM) in the FPMIPv6 to form an enhanced FPMIPv6 (eFPMIPv6). The ETM reduces the most time consuming processes in the reactive handover: the failed Handover Initiate (HO-Initiate) delay and bidirectional tunnel establishment delay. Consequently, the overall handover performance of the FPMIPv6 is enhanced in the eFPMIPv6. To show the advantages of the proposed eFPMIPv6, a theoretical analysis is carried out to mathematically model the performance of PMIPv6, FPMIPv6 and eFPMIPv6. Extensive case studies are conducted to validate the effectiveness of the presented eFPMIPv6 mechanism. They are carried out under various scenarios with changes in network link delay, traffic load, number of hops and MN moving velocity. The case studies show that the proposed mechanism ETM reduces the reactive handover delay, and the presented eFPMIPv6 outperforms the PMIPv6 and FPMIPv6 in terms of the overall handover performance.