Electrochromic films undergo a colour change when small ions and electrons are inserted into them, under the influence of an applied electric field. These films are also known as ion-intercalation electrodes, and may be incorporated into glazing structures more commonly known as 'smart windows'. Smart windows are that which may be used to control the amount of heat and light entering a building and may therefore be used to minimise the energy consumption associated with heating, cooling and lighting. The commercial success of smart windows, requires that they operate reproducibly at temperatures up to approximately 70ºC, for many tens of thousands of colouring and bleaching cycles. An understanding of the underlying kinetic processes over a wide temperature range is therefore needed, in order to determine suitable control strategies and switching conditions capable of fulfilling these requirements. The research detailed in this thesis has involved an investigation into the kinetic behaviour of ion-intercalation electrodes, and simulation of the electrical response as a means of developing a tool for predicting and then optimising electrochromic switching. More specifically, the electrical and optical properties of electrochromic thin films of WO3/TiO2 have been studied over a wide temperature range, appropriate for the operation of electrochromic windows. The magnitude of the voltages required for coloration and bleaching significantly reduces as temperature increases. Some irreversibility was observed at high temperature, as well as a reduction in coloration efficiency. Further investigation revealed that self-bleaching and irreversibility effects were caused by the presence of water, and this problem was exacerbated at high temperature. Post-experiment chemical analysis of a film sample revealed that some trapping of the inserted ions had occurred, however the amount of ions remaining in the film was much smaller than expected. The results suggested that a large quantity of the lithium ions injected into the film were lost to the electrolyte after many cycles, possibly accompanied by some film dissolution. Experimental work carried out in a dry-box showed that films may be cycled reversibly in a very dry environment, and the optical properties were independent of temperature under these conditions. Unfortunately, the conditions which led to reversible cycling and good electrochromic memory, also resulted in very long response times for film bleaching. This result implies that a good electrochromic memory and a fast response are mutually competitive aims. Data from high temperature experiments was simulated with a mathematical model and the mobility of lithium ions inside the electrochromic films was estimated in the process. The estimated diffusion coefficients agreed well with published values, and exhibited an Arrhenius dependence on temperature. Activation energies for diffusion were calculated and the results were very reasonable. Some deviation from ideal Arrhenius behaviour was observed for the estimated diffusion coefficients at high temperature. It is likely that the rate limiting mechanism changes from diffusive motion of ions at low temperature, to charge transfer at high temperature.

The resistance perceived by guest molecules upon entering or leaving a microporous host material (the “surface barrier”) is known to often surpass the influence of diffusion in its interior on the overall rate of molecular uptake and release [1, 2]. Our knowledge of the relevant mechanisms of surface permeation, however, is still rather limited. This is related to the difficulties in its direct measurement which, given the “nanoscopic” extension of the relevant space scale, notably exceed the difficulties which do exist with already the diffusion measurement. A question discussed in this context refers to the possibility that the resistance perceived by the molecules on entering the pore space may differ from that perceived upon leaving [3-5].

Le concept de réversibilité est ancien, mais il soulève de nos jours beaucoup d'intérêt. Il est en effet exploité dans de nombreux domaines tels que la conception de circuits, le débogage et le test de programmes, la simulation et l'informatique quantique. L'idée d'un modèle de programmation réversible peut se montrer particulièrement intéressante pour la construction de systèmes sûrs de fonctionnement, ne serait-ce que parce que plusieurs techniques connues pour la construction de tels systèmes exploitent une forme ou une autre de retour en arrière ou de reprise. Nous poursuivons dans cette thèse l'étude entreprise avec CCS réversible par Vincent Danos et Jean Krivine, en définissant un pi-calcul d'ordre supérieur réversible (rhopi). Nous prouvons que le modèle obtenu est causalement cohérent, et que l'on peut encoder fidèlement rhopi dans une variante du pi-calcul d'ordre supérieur. Nous définissons également une primitive de reprise à grain fin qui permet de contrôler le retour en arrière dans une exécution concurrente. Nous spécifions formellement la sémantique de cette primitive, et nous montrons qu'elle possède de bonnes propriétés, y compris en présence d'opérations de reprise concurrentes. Enfin nous définissons un algorithme concurrent implantant cette primitive de reprise et ous montrons que cet algorithme respecte la sémantique définie. / Reversible computing has a long history. Nowadays, reversible computing is attracting increasing interest because of its potential applications in diverse fields, including hardware design, biological modelling, program debugging and testing and quantum computing. Of particular interest is the application of reversible computation notions to the study of programming abstractions for dependable systems, because several techniques used to build dependable systems rely on some forms of undo or rollback. We continue, in this thesis, the study undertaken on reversible CCS by Vincent Danos and Jean Krivine, by defining a reversible higher-order pi-calculus (rhopi). We prove that reversibility in our calculus is causally consistent and that one can encode faithfully rhopi into a variant of HOpi. Moreover we design a fine-grained rollback primitive able to control the rollback of a concurrent execution. We give a formal specification of this primitive and show that it enjoys good properties, even in presence of concurrent conflicting rollbacks. We then devise a concurrent algorithm implementing such primitive and show that the algorithm respects the defined semantics.

This thesis explores the phenomenon of touch and describes its meaning in the healthcare context. Caring science theory based on a lifeworld approach forms the theoretical perspective of the dissertation and consequently the patient perspective is guiding the research. The ontological, epistemological and methodological framework of the thesis is phenomenology. The overall aim was to describe the phenomenon of touch in the healthcare context. Touch showed to be a phenomenon with several diverse aspects being differentially explicit in different contexts. Four empirical studies were therefore conducted in different contexts. Further, a synthesis of the empirical results was carried out to show the invariant meanings and structure of the phenomenon. Furthermore, a philosophical illumination of the results was carried out to further deepen and expand the understanding of touch related to healthcare. The phenomenon of touch is described as a complex caring movement, as an interplay between lived bodies forming a foundation to understand health, suffering, well-being, and care. The results show how touch has the power to both alleviate the patients’ suffering and to experience joy and deep connectedness, as well as how touch can frighten and cause or worsen suffering. In order to take advantage of the caring potential, the person who touches must be fully present in all senses of the word. Caring touch of different kinds can never be reduced to a “method”. It is much more than a mechanical and static act or a treatment. Moreover, touch that is objectifying may be understood as an obstacle or detrimental for the caring relationship and well-being since it lacks the necessary pliable interpersonal room. Such touch creates distance and alienation rather than closeness, trust and togetherness. If the potential of touch for caring is to be used and the threat of non-caring warded off, then the intentionality of touch must be balanced visavi the existential vulnerability of the individual. Therefore carers need to be open and attentive to the lifeworld of the patients to enhance their health-processes and avoid hurting them.

A questão dos direitos humanos sempre teve como principal embasamento a noção de pessoa humana e sua dignidade. Corolário lógico dessa acepção é a formalização de tais direitos como previsões obrigatórias a todas as Constituições, de forma a garantir a limitação do poder do Estado e o pleno desenvolvimento da personalidade humana. Daí a noção de direitos fundamentais. O objetivo do presente estudo é analisar a questão do direito fundamental à Previdência Social no Brasil sob o prisma de sua importância como direito humano, e consequentemente, direito fundamental, e à luz do princípio da proibição do retrocesso social. Suporta-se na necessidade de observância dos princípios humanistas para uma efetiva e eficiente proteção dos direitos sociais no Brasil, sem os quais se deflagra retrocesso social. Tem sua relevância baseada em uma temática constantemente atualizada, consequência das várias mudanças enfrentadas pelo sistema de proteção social no Brasil, em especial o previdenciário, atualmente conduzidas muitas vezes sem qualquer preocupação do princípio basilar da dignidade da pessoa humana. Este trabalho é iniciado com a verificação da definição de direitos humanos e as questões a eles correlatas, tais como sua convolação em direitos fundamentais e a possibilidade de restrição ou limitação dos mesmos. Em seguida, é abordada a temática da proteção dos direitos humanos a partir da concepção de retrocesso social e o momento de sua efetivação, a partir da identificação do aspecto nuclear do direito a ser protegido. Na sequência, o direito fundamental à previdência social é avaliado desde sua percepção até sua fundamentação, em cada uma de suas nuances, sob os preceitos da proibição do retrocesso social. Por fim, à luz de tudo o quanto foi apurado, passa-se a uma análise concreta das hipóteses em que houve ameaça ou efetivação de retrocesso social na previdência social brasileira, bem como a possibilidade de sua permissão em determinadas situações, sem que isso se configure prejuízo à justiça social e à dignidade humana. / The issue of human rights has always had as its main foundation the notion of the human person and his dignity. A logical corollary of this interpretation is the formalization of such rights as mandatory provisions in all Constitutions, as a way to insure the limitation of the power of the State and the full development of the human personality. Thence the notion of fundamental rights. The objective of the present study is to analyze the issue of fundamental rights to Social Security in Brazil under the angle of its relevance as a human right, and consequently, a fundamental right, and in the light of the principle of prohibition of a social regression. This is supported by the need to observe humanist principles for an effective and efficient protection of social rights in Brazil, which, if not present, a social regression is triggered. It has its relevance based on a theme that is being constantly updated, which is a consequence of several changes confronted by the system for social protection in Brazil, especially the social security segment, handled sometimes without any concern for the cardinal principle of dignity of the human person nowadays. This work begins with the verification of the definition of human rights and the issues correlated to it, such as its conversion to fundamental rights and the possibility for their restriction or limitation. Afterwards, it is addressed the thematic for the protection of human rights based on the conception of social regression and the moment it becomes effective, based on the identification of the core aspect of the right to be protected. In the sequence, the fundamental right to social security is evaluated from its perception to its institution, in each one of its nuances, under the precepts of the prohibition of social regression. Finally, in the light of everything that has been assessed, begins a concrete analysis of the hypotheses where there was a threat to or a materialization of social regression at the Brazilian social security, as well as the possibility to allow it in particular situations, without any damage to social justice and to human dignity.

O formoterol é um fármaco beta-agonista de ação prolongada com rápido início de ação e eficácia broncodilatadora que podem determinar melhora significativa e imediata da função pulmonar. Pacientes com DPOC apresentam pouca ou nenhuma resposta ao broncodilatador (BD) no volume expiratório forçado no primeiro segundo (VEF1), podendo apresentar reversibilidade em outras variáveis se avaliados por pletismografia. O objetivo do estudo é avaliar por pletismografia a eficácia broncodilatadora do formoterol após 30 minutos de sua aplicação em portadores de DPOC. Foram estudados 40 pacientes portadores de DPOC com pobre resposta ao BD de curta ação. Encontravam-se no estágio II ou III da DPOC (SBPT/GOLD) e apresentavam VEF1 menor que 70% do valor previsto. Foram randomizados em dois grupos de 20 pacientes, com características clínicas semelhantes, recebendo cada um formoterol ou placebo, através de inalador de pó seco (aerolizer) com repetição das provas funcionais após 30 minutos. Foram observados aumentos significativos do VEF1 (12,4%) grupo formoterol (F) em relação ao grupo placebo (P) que foi de 0,1% (p=0,00065), da capacidade inspiratória (7,4% X 2,7%;p=0,05) e capacidade vital forçada (12,8% X 5,1%; p=0,017), redução importante da resistência das vias aéreas (-14% X 2,6% ; p=0,010). Foram ainda detectadas no grupo F modificações não expressivas do volume residual, da condutância das vias aéreas e da capacidade vital. Concluindo, em portadores de DPOC com pobre reversibilidade ao BD no teste espirométrico simples, o formoterol levou a uma melhora significativa da função pulmonar por pletismografia após 30 minutos de sua administração. / Formoterol is a long-acting ß2 agonist drug with rapid onset of action and the bronchodilator efficacy determine a prompt improvement in lung function. Patients with COPD may show minimal improvement after bronchodilator (BD) on volume in first second (FEV1), but they can show reversibility in other parameters if plethysmography was realized. The objective of this study was to evaluate, by plethysmography, the effectiveness of formoterol as a bronchodilator after 30 minutes of administration to patients with COPD. Forty COPD patients with poorly reversible obstruction confirmed by shortacting bronchodilator use at the spirometric test were prospectively evaluated. All patients were classified as having stage II or III SBPT/GOLD, presenting FEV1 lower than 70% of predict. The patients were randomized in two groups of 20, both with similar clinical characteristics, each group receiving either formoterol or placebo by dry powder device (aerolizer) and the lung function tests were repeated in 30 minutes after the drug administration. Significant increases in FEV1 (12,4%) in formoterol group (F) and 0,1% in placebo group (P) (P=0,00065), in inspiratory capacity (7,4% X 2,7% ; p=0,05) and in forced vital capacity (12,8% X 5,1%; p=0,017) and decrease in airway resistence (p=0,010) were observed in the F= -14% when compared with P= 2,6%. Residual volume decreased while specific airways condutance and vital capacity increased less important. In conclusion COPD patients with poor reversibility, formoterol promoted significant improvement in lung function by plethysmography after 30 minutes of its administration.

A questão dos direitos humanos sempre teve como principal embasamento a noção de pessoa humana e sua dignidade. Corolário lógico dessa acepção é a formalização de tais direitos como previsões obrigatórias a todas as Constituições, de forma a garantir a limitação do poder do Estado e o pleno desenvolvimento da personalidade humana. Daí a noção de direitos fundamentais. O objetivo do presente estudo é analisar a questão do direito fundamental à Previdência Social no Brasil sob o prisma de sua importância como direito humano, e consequentemente, direito fundamental, e à luz do princípio da proibição do retrocesso social. Suporta-se na necessidade de observância dos princípios humanistas para uma efetiva e eficiente proteção dos direitos sociais no Brasil, sem os quais se deflagra retrocesso social. Tem sua relevância baseada em uma temática constantemente atualizada, consequência das várias mudanças enfrentadas pelo sistema de proteção social no Brasil, em especial o previdenciário, atualmente conduzidas muitas vezes sem qualquer preocupação do princípio basilar da dignidade da pessoa humana. Este trabalho é iniciado com a verificação da definição de direitos humanos e as questões a eles correlatas, tais como sua convolação em direitos fundamentais e a possibilidade de restrição ou limitação dos mesmos. Em seguida, é abordada a temática da proteção dos direitos humanos a partir da concepção de retrocesso social e o momento de sua efetivação, a partir da identificação do aspecto nuclear do direito a ser protegido. Na sequência, o direito fundamental à previdência social é avaliado desde sua percepção até sua fundamentação, em cada uma de suas nuances, sob os preceitos da proibição do retrocesso social. Por fim, à luz de tudo o quanto foi apurado, passa-se a uma análise concreta das hipóteses em que houve ameaça ou efetivação de retrocesso social na previdência social brasileira, bem como a possibilidade de sua permissão em determinadas situações, sem que isso se configure prejuízo à justiça social e à dignidade humana. / The issue of human rights has always had as its main foundation the notion of the human person and his dignity. A logical corollary of this interpretation is the formalization of such rights as mandatory provisions in all Constitutions, as a way to insure the limitation of the power of the State and the full development of the human personality. Thence the notion of fundamental rights. The objective of the present study is to analyze the issue of fundamental rights to Social Security in Brazil under the angle of its relevance as a human right, and consequently, a fundamental right, and in the light of the principle of prohibition of a social regression. This is supported by the need to observe humanist principles for an effective and efficient protection of social rights in Brazil, which, if not present, a social regression is triggered. It has its relevance based on a theme that is being constantly updated, which is a consequence of several changes confronted by the system for social protection in Brazil, especially the social security segment, handled sometimes without any concern for the cardinal principle of dignity of the human person nowadays. This work begins with the verification of the definition of human rights and the issues correlated to it, such as its conversion to fundamental rights and the possibility for their restriction or limitation. Afterwards, it is addressed the thematic for the protection of human rights based on the conception of social regression and the moment it becomes effective, based on the identification of the core aspect of the right to be protected. In the sequence, the fundamental right to social security is evaluated from its perception to its institution, in each one of its nuances, under the precepts of the prohibition of social regression. Finally, in the light of everything that has been assessed, begins a concrete analysis of the hypotheses where there was a threat to or a materialization of social regression at the Brazilian social security, as well as the possibility to allow it in particular situations, without any damage to social justice and to human dignity.

We study the cause of the signature over finite fields of integrability in two dimensional discrete dynamical systems by using theory from algebraic geometry. In particular the theory of elliptic curves is used to prove the major result of the thesis: that all birational maps that preserve an elliptic curve necessarily act on that elliptic curve as addition under the associated group law. Our result generalises special cases previously given in the literature. We apply this theorem to the specific cases when the ground fields are finite fields of prime order and the function field $mathbb{C}(t)$. In the former case, this yields an explanation of the aforementioned signature over finite fields of integrability. In the latter case we arrive at an analogue of the Arnol'd-Liouville theorem. Other results that are related to this approach to integrability are also proven and their consequences considered in examples. Of particular importance are two separate items: (i) we define a generalization of integrability called mixing and examine its relation to integrability; and (ii) we use the concept of rotation number to study differences and similarities between birational integrable maps that preserve the same foliation. The final chapter is given over to considering the existence of the signature of reversibility in higher (three and four) dimensional maps. A conjecture regarding the distribution of periodic orbits generated by such maps when considered over finite fields is given along with numerical evidence to support the conjecture.

Motor proteins are microscopic biological machines that convert chemical energy into mechanical motion and work. They power a diverse range of biological processes, for example the swimming and crawling motion of bacteria, intracellular transport, and muscle contraction. Understanding the physical basis of these processes is interesting in its own right, but also has an interesting potential for applications in medicine and nanotechnology. The ongoing rapid developments in single molecule experimental techniques make it possible to probe these systems on the single molecule level, with increasing temporal and spatial resolution. The work presented in this thesis is concerned with physical modeling of motor proteins on the molecular scale, and with theoretical challenges in the interpretation of single molecule experiments. First, we have investigated how a small groups of elastically coupled motors collaborate, or fail to do so, when producing strong forces. Using a simple model inspired by the motor protein PilT, we find that the motors counteract each other if the density becomes higher than a certain threshold, which depends on the asymmetry of the system. Second, we have contributed to the interpretation of experiments in which the stepwise motion of a motor protein is followed in real time. Such data is naturally interpreted in terms of first passage processes. Our main conclusions are (1) Contrary to some earlier suggestions, the stepping events do not correspond to the cycle completion events associated with the work of Hill and co-workers. We have given a correct formulation. (2) Simple kinetic models predict a generic mechanism that gives rise to correlations in step directions and waiting times. Analysis of stepping data from a chimaeric flagellar motor was consistent with this prediction. (3) In the special case of a reversible motor, the chemical driving force can be extracted from statistical analysis of stepping trajectories. / QC 20100820

Silylated amines, also known as reversible ionic liquids (RevILs), have been designed and structurally modified by our group for potential use as solvents for CO₂ capture from flue gas. An ideal CO₂ capture ionic liquid should be able to selectively and reversibly capture CO₂ and have tolerance for other components in flue gas, including SO₂, NO₂, and O₂. In this project, we study the reactivity, selectivity, uptake capacity, and reversibility of RevILs in the presence of pure SO₂ and mixed gas streams tosimulate flue gas compositions. Tripropylsilylamine (TPSA), a candidate CO₂ capture RevIL, reacts with pure SO₂ to form an ionic liquid consisting of an ammonium group and a salfamate group, supported by IR and NMR results. The resulting IL with pure SO₂ partially reverses when heated to temperatures of upto 500 C in the TGA. TGA analysis of the ionic liquid formed from a 4 vol% SO₂ in CO₂ mixture indicates a possible reversal temperature in the 86-163 C range.