La present tesi doctoral tracta la modelitzacio de diferents estats de la materia: clusters o agregats, superficies i cristalls d'oxids metal.lics. Els metodes disponibles per abordar cada sistema han estat breument descrits, per justificar la seua utilitzacio en diverses aplicacions a materials. Primer, s'han proposat geometries per als agregats de V2O5 cations i neutres en fase gas, i s'han caracteritzat els estats electronics, estructura, espectre de vibracio i enllac quimic. Segon, s'han simulat superficies d'oxids metal.lics i processos d'adsorcio de molecules o atoms metal.lics: CH3OH i O2 sobre SnO2, Cu sobre ZnO. La interaccio adsorbat-superficie te lloc per un mecanisme acid/base, i s'ha caracteritzat la geometria i energia de cada supersistema (mode d'adsorcio, paper dels defectes de superficie). Finalment, s'ha estudiat el cristall de TiO2 en fase anatasa des de multiples punts de vista: descripcio de l'estructura en poliedres, estructura electronica (bandes i densitat d'estats), termodinamic (equacio d'estat) i d'enllac quimic ("Atoms In Molecules"). Les superficies mes estables han estat construides i els efectes de relaxacio avaluats.

Made available in DSpace on 2015-07-22T20:49:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-31 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Introdução: Os pacientes com Miopatia Mitocondrial (MM) e Oftalmoplegia Externa Progressiva (OEP) apresentam disfunção na cadeia respiratória com incapacidade de aumentar a extração de oxigênio muscular e sintetizar ATP aerobicamente, levando à intolerância ao esforço e lentificação da cinética do O2. Quando a extração de oxigênio é comprometida, na tentativa de se manter o consumo de oxigênio muscular, uma hipótese é que estes pacientes poderiam aumentar compensatoriamente a oferta de oxigênio, apresentando, assim, uma resposta hipercinética cardiovascular e ventilatória. Por outro lado, alguns indícios de menor oferta de oxigênio foram encontrados em pacientes com MM, como um menor fluxo sanguíneo muscular no antebraço e uma maior capacidade de produção de ATP após a suplementação de oxigênio. A cinética do O2 na fase de recuperação (REC) nos fornece, assim, subsídios quanto ao pagamento do débito de oxigênio tecidual e ao reabastecimento do estoque de oxigênio sanguíneo após o exercício. Ao nosso conhecimento, a cinética do O2 REC nunca foi avaliada nos pacientes com MM, assim como a integração desta variável com as respostas não-invasivas cardiovasculares e de extração de oxigênio muscular. Objetivo: contrastar as dinâmicas da oferta e da utilização de oxigênio na recuperação do exercício em pacientes com MM; e identificar os principais mecanismos fisiopatológicos da intolerância ao esforço nestes indivíduos. Métodos: Foram avaliadas em 12 pacientes com MM e 12 controles saudáveis, as cinéticas de recuperação: (i) do O2 pulmonar, (ii) da variação na concentração da deoxiemoglobina ([HHb], mensurada pela espectroscopia de raios quasi infravermelhos - NIRS) no vasto lateral, (iii) do débito cardíaco (DC) por bioimpedância transtorácica, após um teste de carga constante de alta intensidade (70% da carga máxima atingida em teste incremental prévio) até o limite da tolerância em cicloergômetro. Resultados: Foram observadas cinéticas mais lentas de reoxigenação da [HHb], ([HHb] = 43,7 ± 21,2 vs 27,5 ± 6,7) e do O2 ( O2 = 58,1 ± 25,1 vs 38,8 ± 7,6) nos pacientes com MM em relação aos controles, respectivamente. Estas respostas foram associadas a uma cinética de DC mais rápida em relação ao O2, nos pacientes comparados aos controles (T½DC * 1,44 / O2 = 1,3 ± 0,4 vs 1,7 ± 0,6). Conclusão: Os pacientes com MM na forma OEP apresentam, na recuperação do exercício de alta intensidade, um pagamento elevado do débito de oxigênio contraído no exercício e reoxigenação mais lenta da [HHb]. Estas respostas, associadas à cinética mais rápida do DC em relação ao O2 são indícios de que possa haver um déficit no transporte de oxigênio microvascular, além do comprometimento mitocondrial característico desta doença. / Background: Mitochondrial Myopathy patients (MM) and Progressive External Ophthalmoplegia (PEO) present with respiratory chain dysfunction and inability to increase muscle oxygen extraction and aerobic ATP synthesis, leading to exercise intolerance and slower O2 kinetics. When oxygen extraction is impaired, in an attempt to maintain muscle oxygen uptake, these patients could increase oxygen delivery, thus exhibiting a hyperkinetic cardiovascular and ventilatory response. On the other hand, some evidence of oxygen delivery impairment was found in MM patients, such as a decrease in muscle blood flow in the forearm and a greater capacity for ATP production after oxygen supplementation. Recovery O2 kinetics provides information on tissue oxygen debt repayment and oxygen blood store replenishment after exercise. To our knowledge, recovery O2 kinetics has never been evaluated in MM patients, as well as its integration with the non-invasive cardiovascular and muscle reoxygenation responses. Objective: to contrast oxygen delivery and utilization dynamics on exercise recovery of MM patients and to identify the main pathophysiologic mechanisms of exercise intolerance in these subjects. Methods: Were evaluated in 12 MM patients and 12 healthy controls, the recovery kinetics of: (i) O2 (ii) deoxyhemoglobin variation ([HHb], measured by near-infrared spectroscopy - NIRS) in vastus lateralis, (iii) cardiac output (CO) by transthoracic bioimpedance, after a high-intensity constant work rate test (70% of maximal workload in a previous incremental test) to the limit of tolerance in a cycle ergometer. Results: We detected slower kinetics for [HHb] ([HHb] = 43.7 ± 21.2 vs. 27.5 ± 6.7) and for O2 ( O2 = 58.1 ± 25.1 vs. 38.8 ± 7.6) in MM patients compared to controls, respectively. Additionally, these responses were associated with a faster recovery CO kinetics in relation to O2 kinetics in MM patients compared to controls (T½DC*1,44 / O2 = 1,3 ± 0,4 vs. 1,7 ± 0,6). Conclusion: Patients with MM and PEO present with a higher oxygen debt and slower reoxygenation kinetics in the recovery of a high-intensity exercise test. Those responses were associated with a faster CO recovery in relation to O2 kinetics, indicating a microvascular oxygen transport deficit, besides the characteristic mitochondrial impairment observed in these patients. / TEDE / BV UNIFESP: Teses e dissertações

La mise au point récente d’une nouvelle technique permettant l’enrichissement de l’eau en oxygène par électrolyse relance l’intérêt de recherches sur les bénéfices potentiels de cette modalité d’oxygénation. Dans ce contexte, nos objectifs étaient de caractériser les effets de cette eau enrichie en oxygène sur la respiration mitochondriale, l’oxygénation tissulaire périphérique lors d’un état de stabilité hémodynamique, et sur la performance et la production de stress oxydant lors d’un exercice physique. Les résultats mettent en évidence un effet de l’administration de l’eau enrichie en oxygène par électrolyse au niveau cellulaire et tissulaire.Le mécanisme, expliquant à la fois une meilleure affinité de la mitochondrie pour l’oxygène et les effets sur l’oxygénation périphérique, pourrait être dû à un effet qualitatif sur la diffusion de l’oxygène au niveau tissulaire. / The recent development of a new technique for enriching water in oxygen by electrolysis relaunch the research interest on the potential benefits of this modality of oxygenation. In this context, our objective was to characterize the effects of 02-water on mitochondrial respiration, peripheral tissue oxygenation during a state of hemodynamic stability, and on the performance and the production of oxidative stress in a sub-maximal exercise. The results show an effect of the administration of water enriched in oxygen by electrolysis at the cellular and tissue level. The mechanism explaining both a better affinity of mitochondria for oxygen and the effects on peripheral oxygenation could be due to aqualitative effect on the diffusion of oxygen at the tissue level.

Archaias angulatus, a large symbiont-bearing foraminifer (Order Miliolida) that produces a Mg-calcite shell, is common throughout the Caribbean and warm western Atlantic region. This species lives abundantly in seagrass beds along the Springs Coast of northwest Florida (up to 4 adults per gram of sediment) where spring-fed rivers emerge from a limestone aquifer, and in Florida Bay to the southeast (25 adults/g) where the sediment is primarily biogenic carbonate. In contrast, live specimens are seldom found in the seagrass beds along the central-west coast of Florida, where barrier islands are dominated by quartz sand. My working hypothesis is that substratum and carbonate chemistry, in addition to temperature and salinity, explain differences in abundance of A. angulatus associated with the seagrass meadows along the west Florida coastline and shelf. Water chemistry measurements were taken diurnally over 1-2 day periods at four sites in winter, spring and autumn of 2015. Salinity and temperature were measured in situ, and sealed bottles of seawater were transported to the laboratory for analysis of Dissolved Inorganic Carbon (DIC) and Total Alkalinity (TA). The highest TA was found in the Springs Coast (2766 μmol/kg-seawater, three-season average), along with the lowest salinities, which reveals a strong contribution from the nearby rivers, springs and seeps. A TA end-member regression analysis predicts, and sampling confirms, TA increases with proximity to the river mouth, highlighting the atypical relationship between alkalinity and salinity in this carbonate province. A gradient in the value of TA was seen among the northern three sites, with TA decreasing from the Springs Coast site southward to Fort Desoto; additionally, the pH and calcium carbonate saturation states were higher at the northernmost sites. The highest ratio of TA to DIC among all four sites was found at the southern edge of the Springs Coast, reflecting strong primary production and DIC uptake by the dense meadows of seagrass in the area. A daytime increase in the TA to DIC ratio was seen at all sites; however, the Springs Coast site (~5km from the Weeki Wachee river mouth) exhibited stronger tidal influences on TA and DIC than diurnal influences. Plots of salinity-normalized TA and DIC indicate the Weeki Wachee coastal area is impacted by calcification and dissolution to a greater extent than by photosynthesis and respiration. The gradual relief off the Springs Coast, as well as clarity of the water column, provide ideal physical habitat, and the input from spring-fed sources enhances the water chemistry for calcifying organisms. Presence of A. angulatus in low salinity waters influenced by high alkalinity riverine discharge led to a new hypothesis that calcification in A. angulatus requires high carbonate alkalinity but not necessarily full marine salinity.

First part of this graduation theses "Fundamental and technical analysis of the Telefonica O2 Czech Republic, a.s. equity" concern more about the teoretical approach of the characteristics of the company Telefonica O2, his competitors on the country level as well as on the regional level. This description should prepare the reader to know better the telecomunication sector. The second part is a empirical study. Primarily from the fundamental approach and then from the technical one. These two parts concern about discovering the "buy" os "sell" recommendation for a real investor. Each of the methods are first described and then a brief comment of the results is made.

The purpose of the research was to design, build, test, and recommend a process to economically separate CO from a gas mixture of CO, CO2, and O2. The general method considered in this research to accomplish the separation was liquid absorption in a packed column. Several experiments were performed to identify the best process solution to use in a prototype. The experiments, based on the COSORB process, consisted of CuCl mixed with a complexing agent (metal tri-chloride) and a solvent (metal tetra-chloride, toluene, ethanol, etc.). The best method consisted of an aqueous solution of CuCl and MgCl2, which has previously been used for CO absorption experiments reported in the literature. The absorption takes place at elevated pressure (30 psig) and ambient temperature, and the stripping occurs at approximately 75 ºC. Using the apparatus at approximate design conditions, the highest removal of CO was 88% with a product composition of 48%. The highest product composition achieved was 84%; in this case CO removal was 66%. Product composition was low because a significant amount of CO2 physically absorbed into solution (which also decreased the pH of the solution to about 4, according to calculation). The removal of CO should increase with a taller column and higher liquid flow through the column; however, this might decrease the product composition. Advantages of this process are that the raw materials used are relatively cheap, heating and cooling requirements are lower than similar processes, and operation is relatively simple.

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<p>Aortic bodies (ABs) are putative peripheral arterial chemoreceptors located near the aortic arch. They are hypothesized to contribute to O₂ homeostasis by sensing arterial O₂ content and initiating cardiovascular reflexes during hypoxia; however, information on their cellular physiology is lacking. The primary goal of this thesis was to elucidate chemosensory mechanisms among mammalian (rat) AB cells, located specifically at the bifurcation of the left vagus nerve and recurrent laryngeal nerve (RLN), where they are found in association with a group of local neurons (>30). In vagus nerve-RLN whole-mounts, AB chemoreceptor (type I) cells were immunoreactive against the vesicular acetylcholine (ACh) transporter, and were surrounded by nerve terminals immunopositive for purinergic P2X2 and P2X3 receptor subunits, suggesting that ACh and ATP may act as neurotransmitters as in the related carotid body. In a novel dissociated AB culture model, subsets of type I cells exhibited elevated intracellular Ca²⁺ responses to hypoxia, isohydric hypercapnia, isocapnic acidosis, and acidic hypercapnia, demonstrating their direct chemosensitivity for the first time. Interestingly, surviving local neurons also responded to these chemostimuli, suggesting that they are sensory. Patch clamp electrophysiological and Ca²⁺ imaging studies revealed functional heteromeric P2X2/3 and nicotinic ACh receptors on local neurons, consistent with ACh and/or ATP mediating chemotransmission between receptor cells and local neurons. These neurons were also found to be interconnected by electrical synapses. Finally, the short-term survival of red blood cells (RBCs) in AB cultures, along with the finding that blood-borne factors (e.g. ATP released from RBCs) may have access to AB nerve terminals <em>in situ</em>, implicates RBCs as O₂-sensors in AB function. Altogether, these results suggest an important role for purinergic P2X2/3 receptors on local neurons/nerve terminals and ATP release from type I cells and RBCs, in the unique ability of ABs to sense and process information about blood O₂ content.</p> / Doctor of Philosophy (PhD)

The soft x-rays (wavelengths less than 30 nm) emitted by the sun are responsible for the production of high energy photoelectrons in the D and E regions of the ionosphere, where they deposit most of their energy. The photoelectrons created by this process are the main drivers for dissociation of nitrogen ($N_2$) molecules in the altitude range below 200 km. The dissociation of $N_2$ is one of main mechanisms responsible for the production of nitric oxide (NO) at these altitudes. These processes are important to understand because NO plays a critical role in controlling the temperatures of various regions of Earth's atmosphere. In order to estimate the dissociation rate of $N_2$ we need its dissociation cross-sections. The dissociation cross-sections of $N_2$ due to inelastic collisions with electrons is primarily es- timated from the cross-sections of its excitation states (using predissociation factors) and dissociative ionization channels. Predissociation is the transition without emission of radi- ation from a stable excited state to an unstable excited state of a molecule that leads to dissociation. Unfortunately, the lack of cross-section data, particularly at high electron en- ergies and of higher excited states of N 2 and N 2 + , introduces uncertainty in the dissociation cross-section and subsequently the dissociation rate calculation, which leads to uncertainties in the NO production rate. We have updated a photoelectron model with thoroughly-revised electron impact cross- section data of all major species and experimentally determined predissociation factors. The dissociation rates of $N_2$ using this model are compared to the dissociation rates obtained using another existing (Solomon and Qian [2005]) model. A parameterized version of the updated dissociation rates are used in a one-dimensional global average thermospheric/ ionospheric model, ACE1D (Atmospheric Chemistry and Energetics), to obtain the updated production rates of NO. In the final chapter, we use the ACE1D model to show that the energies deposited by the solar soft x-rays in the lower thermosphere at altitudes between 100 -150 km affect the temperature of the Earth's thermosphere at altitudes well above 300 km. By turning off the input solar flux in the different wavelength bins of the model iteratively, we are able to demonstrate that the maximum change in exospheric temperature is due to changes in the soft solar x-ray bins. We also show, using the thermodynamic heat equation, that the molecular diffusion via non-thermal photoelectrons is the main source of heat transfer to the upper ionosphere/thermosphere. Moreover, these temperature changes and heating effects of the solar soft x-rays are comparable to that of the much stronger He II 30.4nm emission. Finally, we show that the uncertainties in the solar flux irradiance at these soft x-rays wavelengths result in corresponding uncertainties in the modeled exospheric temperature, and these uncertainties increase substantially with increased solar activity. / Doctor of Philosophy / The radiation from the sun covers a wide range of the electromagnetic spectrum. The soft x-rays with wavelengths less than 30 nm are the most energetic and variable part of the spectrum, and would have detrimental effects on humans were they not absorbed by the atmosphere. The absorption of soft x-rays by the Earth's atmosphere at altitudes near 100- 150 km creates ionized and energized particles. These energetic changes can affect and even damage the satellites in low Earth orbit, and can cause radio communication blackouts and radiation storms (large quantities of energetic particles, protons and electrons accelerated by processes at and near the Sun). Therefore, we need to have good models that can quantify these changes in order to correctly predict their effects on our atmosphere, and help to mitigate any harmful effects. The soft x-rays and the extreme ultraviolet (EUV) are responsible for ionization of the major neutral species, $N_2$ , $O_2$ and O, in the Earth's atmosphere, which leads to the production of ions and energetic photoelectrons. These high energy photoelectrons can cause further ion- ization, excitation and dissociation. We study the dissociation of $N_2$ by these photoelectrons to create neutral N atoms. The N atoms created via this process combine with the $O_2$ in the atmosphere to produce nitric oxide (NO), which is one of the most important minor constituents because of its role in regulating atmospheric heating/cooling. The production of NO peaks near 106 km altitude, where most of the energy of the soft x-rays are deposited. However, they also affect the temperature of the upper atmosphere well above this altitude. This is because the energy of the photoelectrons is conducted to the upper atmosphere by collisions of electrons and ions with ambient neutral atoms and molecules, thus increasing their temperature. In this study, we use modeling of soft x-ray irradiance, photoelectron ionization, excitation and dissociation rates and atmospheric neutral temperature to quantify the effects of soft x-rays on the Earth's atmosphere.