La jouissance est un des champs dont la psychanalyse fait usage pour rendre compte de ce qui pourrait expliquer le boitement structurel de la condition humaine, son paradoxe fondamental. Partant d'une épistémologie transcendantale, nous envisageons que, bien que le corps et la psyché ne revêtent pas les mêmes réalités, ils ont certains points d'accroche dont fait partie la jouissance et, bien que le corps ne détermine pas le psychisme, il le contraint. Il est alors proposé ici une hypothèse neuropsychanalytique de la jouissance, l'articulant autour du corps et de l'histoire. La jouissance serait la marque de ce qui a fait événement pour le sujet. Cette description permet de relier ce concept à la neurophysiologie des circuits dopaminergiques qui marquent physiologiquement tant la dimension pulsionnelle, que la dimension événementielle et donc historique.À partir de cette conceptualisation, un paradigme expérimental a été constitué afin d'investiguer cette possibilité d'une accroche entre le psychique et le biologique chez des sujets dépendants, lorsqu'ils sont confrontés à leur objet d'addiction. Concrètement, nous 'osons' l'hypothèse que plus un sujet manifeste d'indices repérables d'une mobilisation pulsionnelle dans son discours libre amorcé par l’objet addictif (dans ce cas-ci, la cigarette pour des fumeurs), plus il aura le geste rapide et sûr pour l’attraper ou des difficultés à inhiber son appétence vers cet objet. Ceci est investigué à travers un outil constitué à partir de la théorie psychanalytique d’une part, et à travers deux tâches de type Go-NoGo (évaluées par des mesures comportementales –temps de réaction et erreurs- et électrophysiologiques -la N2 et la P3, deux marqueurs considérés comme reflétant la signature des processus attentionnels et des biais d’inhibition-, d’autre part. La particularité du paradigme, outre cet usage d’outils issus de champs distincts, réside dans le fait que, à aucun moment, ce n’est le sens du discours des sujets, qui est investigué. L’outil psychanalytique évalue effectivement la façon dont les sujets s’expriment, et ce sont des juges naïfs (à l’égard de l’étude et de la psychanalyse) qui évaluent leur discours. Nos résultats mettent en évidence que les personnes dépendantes manifestent une tendance à l’impulsivité de façon générale. Mais, lorsque leur objet d’addiction est en place de support attentionnel, les sujets démontrent une augmentation significative de leurs performances et de l’amplitude de la P3, signe d’un investissement attentionnel. Les résultats des associations libres révèlent que la forme du discours des fumeurs est évaluée comme plus transgressive (comparativement aux non-fumeurs). Enfin, on retrouve une corrélation entre les indices psychiques (la transgression) et neurophysiologiques (la latence de la NoGo-N2). En conclusion, il semble que l’addiction dépasse la simple réalité pharmacologique de l’effet du toxique puisqu’il est repéré ici que l’effet de stimulant cognitif (manifeste par l’amélioration des performances) est induit par la simple représentation de la cigarette et non par la consommation de celle-ci. Ensuite, au regard de notre proposition épistémologique, nous semblons avoir réussi, sur base d’une lecture rapprochée des séminaires de Lacan, à construire un outil qui distingue de façon cohérente, consistante et valide une dimension pulsionnelle d’une dimension affective (valencée) dans ce qui peut s’entendre. Grâce à cet outil, nous avons trouvé des corrélations entre certains de ces marqueurs psychiques et certains paramètres physiologiques - les paramètres corrélant étant précisément des plus probants et la corrélation s’avérant être dans le sens prédit par notre construction hypothétique. Sur ce 'succès’, nous osons une conclusion épistémologique plus large qui propose que si l’univers du représentationnel, c'est-à-dire, du mental, est bien accroché au niveau de repères physiologiques, ceci n’est démontrable sur un plan mental que si l’on se borne à la forme des contenus mentaux – et, qui plus est, et de façon spéculative, en évitant toute hérméneutique au niveau des contenus mentaux. / Doctorat en Sciences psychologiques et de l'éducation / info:eu-repo/semantics/nonPublished

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Zeolite membranes are considered to be a promising alternative to polymeric membranes and they have the potential to separate gases under harsh conditions. Silicalite-1 membranes in particular are easy to prepare and suitable for several industrial applications. In this research project, silicalite-1/ceramic composite membranes were prepared using the pore plugging hydrothermal synthesis method and supports with zirconium oxide and/or titanium oxide as active layers. The effect of the support’s pore size on the morphology and permeation performance of the prepared membranes was investigated using five supports with different active layer pore sizes in the range of 0.14 – 1.4 m. The prepared membranes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), electron diffraction spectrometer (EDS), single gas and binary gas mixtures permeation tests. The results confirmed the presence of a typical silicalite-1 zeolite structure with a high internal crystalline order grown inside the pores of the active layer of the supports, with a dense film covering most of the supports active layers. Silicalite-1 crystals in the prepared membranes were preferably oriented with either a- or b-axes perpendicular to the support surface. Single gas permeation results illustrated that the observed permeances were not directly related to the kinetic diameter of permeants. Instead, the transport of the studied gases through the prepared membranes occurred by adsorption followed by surface diffusion mechanism. Binary gas tests performed with CO2 and N2 mixtures showed that the prepared membranes were selective and very permeable with CO2/N2 permselectivities up to 30 and a CO2 permeances in the order of 10-6 mol m-2 Pa-1 s-1. A model was developed, based on Maxwell−Stefan equations and Extended Langmuir adsorption isotherm, to describe the transport of binary CO2 and N2 mixtures through the prepared silicalite-1 membranes. The model results showed that the exchange diffusivities (D12 and D21) were less dependent on the feed pressure and feed composition compared to the permeances and the permselectivities. Hence, they are more appropriate to characterize the intrinsic transport properties of the prepared silicalite-1 membranes.

Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers is discussed. For (β-diket)Fe-N2 complexes, the additional influence of diketiminate donor atom (N(H) vs. S) is briefly addressed. The remainder of the chapter expands upon the treatment of β-diketiminate complexes. First, the activation and relative stabilities of side-bound and end-bound N2 isomers in monometallic ((β-diket)M-N2) and bimetallic ((β-diket)M-N2-M(β-diket)) first row transition metal complexes are addressed. Second, the thermodynamics of H/H+/H- addition to (β-diket)Fe-bound N2, followed by subsequent H additions up to release of ammonia, is discussed, for which two mechanisms (distal and alternating) are considered. Finally, the chapter concludes with partial distal and alternating mechanisms for H addition to N2 in bimetallic (β-diket)Fe-N2-Fe(β-diket) and (β-diket)M-N2-M(β-diket) (M = Ti,V,Fe), respectively.

Orientador: Sergio Persio Ravagnani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T19:00:28Z (GMT). No. of bitstreams: 1 Lavezo_AnaElisa_M.pdf: 1136570 bytes, checksum: e8e9754aa79e23bced02a8fa2d543e4c (MD5) Previous issue date: 2006 / Resumo: A separação de misturas gasosas é efetuada com o objetivo de obter um ou mais dos constituintes na forma altamente puros. Existem quatro métodos principais aplicados para a separação de gases: absorção, adsorção, destilação criogênia e membranas. A economia do processo determinará qual desses métodos é usado para alguma aplicação particular (Scott, 1995). A era moderna das membranas de separação de gases foi introduzída após 1980, quando as membranas poliméricas se tomaram economicamente viáveis (Robeson, 1999).Atualmente a separação baseada em membranas é utilizada largamente em escala industrial para produção de nitrogênio de alta pureza a partir do ar, tendo importante aplicação na inertização do ambiente para conservação de frutas e vegetais, reatores químicos e produção de NH3, assim como para segurança na operação com líquidos inflamáveis (Spillman, 1989). O objetivo deste trabalho é a otimização do custo total do processo de separação de misturas gasosas multicomponentes utilizando membrana de fibra oca. A otimização foi realizada utilizando o método "Constrained Rosenbrock (Hill AIgorithm)", para obter um produto final com alta qualidade e com um custo total minimizado. Para a otimização do custo total do processo são necessários os seguintes dados fornecidos pelo programa de Caramello (2002): pressão do permeado e da alimentação, taxa de fluxo do lado do alimentado, pureza e recuperação. A equação do custo total utilizada consiste em custo de instalação e custo operacional, ou seja, o custo total é o custo do módulo de permeação, custo de substituição da membrana (assumindo-se a vida útil da membrana a cada 3 anos), custo da energia elétrica e o custo de instalação do compressor.Otimizaram-se primeiramente dois parâmetros, número de cartuchos de membrana de fibra oca (QM) e pressão de alimentação (pt), em seguida fixou-se o número de cartuchos de membrana de fibra oca e foi otimizada a pressão de alimentação verificando se assim para cada análise o custo total otimizado para as seguintes purezas: 85%, 90%, 95% e 99% / Abstract: The separation of gas mixtures is made under the objective of obtaining one or more representatives in the highly pure form. Four methods can be used in gas separation: absorption, adsorption, distillation cryogenics and membranes. The economy of the process will determine which method will be used in a specific application (Scott, 1995). The modem era of gas-separation membrane was introduced in the early 1980s, when polymeric membranes became economically viable. (Robeson, 1999). Nowadays, membranes separation is used wide in industrial scale for the production of nitrogen in a high purity level from the air. This is an essential method for the inertization of the atmosphere air for fruits and vegetables storage, quimicos reactors and production of NH 3, as well as for safety when operating inflammable liquids (Spillman, 1989). The objective of this work is to optimization the cost related to the process of separation of multicomponents gas mixtures using membrane of hollow fiber. The optimization was made using "Constrained Rosenbrock (Hill Algorithm)", in order to obtain a high quality product with a reduced cost. For the process cost optimization the following data supplied for the program of Caramello (2002) is needed: feeding and permeated pressure, flow tax next to the feeder, purity and recovery. The equation of the cost used consists of: installation cost and operational cost. The total cost consists of the permeation module cost, the membrane substitution cost (assuming it useful life of the membrane to each 3 years), the electricity cost and finally the cost of the compressor installation. One first optimized two parameters: amount of membranes (QM) and pressure of feeding (P / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Philosophiae Doctor - PhD / Growth of symbiotic legume hosts is P limited, because of the high energetic requirements associated with N2 fixation. Attempts to overcome P deficiency in soils where legumes are grown involve addition of P-based fertilisers. However, these are produced from fmite, non-renewable resources that could be exhausted in the next 50-80 years. For this and other prudent reasons, viable alternatives are sought that include producing genetically enhanced plants with better P use efficiency (PUE). There exist some inter- and intraspecific genetic variation for associated traits of PUE in various legumes and these will have to be exploited to realize the development of P efficient cultivars. With the advent of sophisticated molecular tools, good progress has been made to understand the molecular response of some common physiological and morphological functions observed under LP. The research aims here were to investigate the energy costs and the alternative metabolic routes associated with C and N metabolism under LP in legumes, which is very scant in literature. We also investigated the recovery responses of nodulated roots upon P alleviation. Consequently, improvement strategies to produce legume varieties for better adaptation in poor P soils are envisaged. We have demonstrated varying degrees of sensitivity between the amide and ureide legume systems being investigated under short-term LP. The species-specific responses were ascribed to differences related to the agro-climatic origins, nodule morphologies and the type of N containing export product of the different legume types. These different responses also underscore possible different regulatory mechanisms under LP. Lupins were probed further, because of its apparent tolerance to P deficiency. Lupin nodules had between 3 to 5-fold higher Pj concentrations compared with soybeans under LP and HP, respectively. The maintenance of Pj levels, as oppose to a decline in the total P pool, is discussed in relation to its role in maintaining N2 fixation in lupins. Under LP, an effective Pj recycling mechanism in nodules is proposed to occur via the induction of the PEPc- MDH-ME route. This route also enhanced the capacity of root nodules to procure high malate concentrations that are used to fuel bacteroid respiration and N2 fixation. Two distinctly different cMDH proteins, one corresponding to HP and another corresponding to LP, were identified. The high malate concentrations reported here are speculated to have arisen through LP-induced cMDH. Metabolically available Pj decline developed gradually as P deficiency progressed. This coincided with a 15% decline in the %Ndfa. Moreover, under prolonged P deficiency the disproportionate synthesis of organic acids, most notably malate, that occurred at the expense of amino acids was proposed to account for this decline. The recovery in response to alleviation from LP involved alterations in the allocation of respiratory costs to growth and nutrient acquisition. Under LP, smaller nodules were formed and nodule metabolism revolved around accentuating PUE. Thus, there is considerable potential for improvement of P efficiency in legumes through manipulation of root: shoot partitioning.

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Philosophiae Doctor - PhD / The commercial need to improve the performance of low-cost organic solar cells has led to the idea for this research. The study discusses the synthesis of one dimensional TiO2 and ZnO nanowire arrays synthesised using a hydrothermal autoclave method and their application in bulk heterojunction inverted organic solar cells. Previous literature has shown that the precise manipulation, positioning and assembly of 1D nanostructures remain one of the greatest challenges in the field of nanotechnology, with much of the difficulty arising primarily from the lack of size and scale of the materials as well as the inability to visualise the nanostructures. In particular, one dimensional metal-oxides such as TiO2, ZnO and Fe2O3 have emerged as attractive alternatives to traditional semiconductor structures such as Si and GaAs as they are simple and inexpensive to manufacture, with research showing that application of ZnO nano-cones yield efficiencies of 8.4%, which is very attractive given the scope that exists in optimising the metal-oxide architecture. Much is still to be learned from the precise structural features of these materials and their influence on device performance. In this regard, this work largely focuses on this aspect of metal-oxide nanowires prior their application in organic solar cells.

Overweight and obesity are prevalent public health problems that impact physical, mental, and social health. Many studies have evaluated weight loss treatments, but most individuals are unsuccessful at maintaining weight loss long-term. Behavioral and cognitive interventions may be effective in promoting weight loss and weight loss maintenance. One cognitive intervention that has shown potential success in reducing weight and caloric intake is inhibitory control training (ICT). ICT involves trainings where individuals are asked to repeatedly withhold dominant responses to unhealthy or high-calorie food images in an effort to increase food-related inhibitory control abilities. Reductions in caloric intake or weight may occur after as little as one week of ICT; however, it is unclear how more frequent ICT sessions promote weight loss and reduce caloric intake. Further, studies on food-specific ICT are generally poorly powered and it is unclear how ICT affects underlying cognitive and neural mechanisms. One way to measure inhibitory control processes is through the N2 component of the scalp-recorded event-related potential (ERP). The amplitude of the N2 ERP component tends to be larger (i.e., more negative) when an individual inhibits a dominant response during go/no-go tasks compared to non-inhibition go trials. I conducted a quasi-randomized controlled trial where 100 individuals with overweight or obesity were assigned to either a generic (active control; n = 48) or food-specific ICT (experimental group; n = 52). ICTs were completed four times per week for four weeks. Weight and caloric intake were obtained at baseline, immediately after four-weeks of ICT, and at a 12-week follow-up. Participants also completed a high-calorie and a neutral go/no-go task while electroencephalogram (EEG) was recorded at each visit. Results from mixed model analyses suggest that neither weight, caloric intake, nor N2 ERP component amplitude towards high-calorie foods changed at post-testing or at the 12-week follow up for either group. Regression analyses suggest that individuals with lower baseline levels of inhibition may show greater weight loss and reductions in caloric intake after a generic ICT, while individuals with higher baseline levels of inhibition may show greater weight loss and reductions in caloric intake after a food-specific ICT. Self-report ratings indicated the appetitive drive towards food decreased over the course of the study, particularly for individuals with higher levels of baseline inhibition. Overall, generic- or food-specific ICT did not affect weight, caloric intake, or food-specific N2 ERP amplitude. Food-specific ICT may be more effective in reducing caloric intake and weight for individuals with larger inhibition responses to food stimuli, while generic ICT may be more effective in reducing caloric intake and weight for individuals with smaller inhibition responses to food stimuli. ICT may also be targeting other mediating processes, such as the appetitive value of food, as opposed to improving food-specific inhibitory control.