The growth of the World’s population always comes with a higher demand of energy. Covering this demand requires finding new energy sources and especially ones that manage the risks of further global warming. Biomass energy is considered as one of the clean energy resources, and widely available. Lignin is a lignocellulosic biomass polymer that constitutes the second most abundant polymer in biomass. The interest of lignin in science laboratories is due to its availability and sustainability that could produce a new supply of fuels and valuable chemicals. Among the different methods of lignin conversion into fine chemicals, heterogeneous catalysis seems to be a perfect method because it reduces the activation energies for reaction and it separates the product from the catalyst. In this work, the conversion of lignin by a heterogeneous catalyst was explored under ultrahigh vacuum conditions using three surface science techniques: Infrared Reflection Absorption Spectroscopy, X-ray Photoelectron Spectroscopy, and Temperature Programmed Desorption. Because of the difficulties of using lignin under UHV conditions due to its physical properties, lignin model molecules with the same chemical structure are the only way to gain better understanding of lignin reactivity. In the present work, Veratrol, 1,3-dimethoxybenzene, and 1,4-dimethoxybenzene were used on Pt(111) surface as lignin models. The reactivity of veratrol on Pt(111) showed the formation of 1,2-benzoquinone by the dehydrogenation of the two methyl groups, which gave three desorption products: catechol (observed here for the first time), hydrogen, and carbon monoxide. The isomers 1,3 and 1,4 desorbed hydrogen and carbon monoxide of their monolayer desorption predictably. 1,3-dimethoxybenzene showed the formation of benzene at certain temperatures. 1,4-dimethoxybenzene adsorbed on Pt(111) via the carbon species of its aromatic ring. The three isomers show slightly different adsorption geometries which lead to rather different decomposition pathways. This study of such complex behavior is a great example of the sensitivity of selectivity in heterogeneous catalysis, even for very similar isomers. The detailed thesis is a continuous work of the route forwarding lignin valorization by increasing the complexity of the models of lignin.

Proefschrift Universiteit van Amsterdam. / Met lit. opg. en een samenvatting in het Nederlands.

No description available.

Na mesma proporção que fontes de água potável são reduzidas, a competição por elas tem aumentado, conseqüência imediata da expansão de áreas urbanas e de novas demandas agro-industriais. Os conflitos gerados por esta competição tendem a comprometer o desenvolvimento sustentável e o progresso de uma forma geral, uma vez que resultam em perda de eficácia para vultuosos investimentos públicos e privados e em prejuízos para os usuários menos estruturados. Considerando os fatos acima, o objeto deste trabalho é o estabelecimento de cenários de alocação das disponibilidades hídricas entre usuários de água da bacia do Sapucaí-Mirim/Grande, visando determinar a convivência harmoniosa das várias finalidades de uso provenientes do mesmo recurso hídrico. Tal meta poderá ser alcançada através da análise dos indicadores de desempenho - confiabilidade, vulnerabilidade e resiliência - do sistema os quais serão obtidos com o auxílio do modelo de simulação IRAS (Interactive River Aquifer Simulation). / In the same proportion that fresh water sources are been reduced, competition for its has grown, immediate consequence of urban areas expansion and new agroindustrial demands. Conflicts generated by this competition tend to affect the sustainable development and the progress as well, once this competitiveness situation means efficacy loss to large amounts of public and privy investments, and also injuries to less structured users. Considering above facts, the goal of this paperwork is to establish water availability allocation scenarios between Sapucai-Mirim/Grande basin\'s users, aiming to settle a balanced distribution of the several use finalities came from the same water resource. Such goal can be reached through system performance indicators analysis - reliability, vulnerability and resilience - which will be estimated through IRAS simulation model aid.

Orientador: Rinaldo Poncio Mendes / Resumo: A candidemia constitui um grande problema em hospitais terciários, por sua elevada incidência – 3,9 casos por 1.000 admissões e letalidade – 50 a 72%. Assim, o objetivo deste estudo foi avaliar a taxa de infecções da corrente sanguínea por Candida spp., em um período de sete anos, determinar o perfil de sensibilidade dos isolados a antifúngicos, caracterizar as espécies do complexo Candida glabrata e avaliar aspectos epidemiológicos, clínicos e terapêuticos dos pacientes-fonte. Methodology. O perfil de sensibilidade antifúngica foi realizado no equipamento Vitek2. A análise molecular de C. glabrata foi realizada por PCR utilizando-se primer senso CGL1 e antisenso CGL2 e de C. nivariensis e C. bracarensis por PCR multiplex com o primer senso NIV-f e BRA-f e antisenso universal UNI-5.8S. Aspectos epidemiológicos, clínicos e terapêuticos foram coletados de prontuário eletrônico e registrados em ficha padronizada para este estudo. Results. Foram avaliados 84 isolados de hemocultura e os dados clínicos de 59 pacientes. A taxa de incidência de candidemia (por 1.000 admissões) foi maior em mulheres que em homens (0,76 vs 0,54; p<0,0001), não se alterou ao longo dos anos e variou em função da unidade de internação, predominando na Clínica Cirúgica, Clínica Médica, Oncologia e Unidade de terapia Intensiva. C. albicans foi a espécie predominante e, dentre as não-C. albicans, a C. glabrata foi a mais frequente. Todos os isolados do complexo C. glabrata foram identificadas como C. glabra... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Background. Candidemia is the major problem in hospitals because of its high incidence - 3.9 cases per 1,000 admissions and lethality - 50 to 72%. Therefore, the objective of this study was to evalue the rate of the bloodstream infecction by Candida spp, to determine the sensitivity profile of the antifungal isolated, characterize the Candida glabrata complex species and to evaluate the epidemiological aspects, clinical and therapeutic patients sources. Methodology. The antifungal sensitivity profile was performed into Vitek2 device. Molecular analysis of C. glabrata was performed by PCR using primers ford CGL1 and reverse CGL2 and C. nivariensis and C. bracarensis by multiplex PCR with primers ford NIV-f and BRA-f universal reverse UNI-5.8S. Epidemiological, clinical and therapeutic aspects were collected from an electronic medical record and registered in a standard form for this study. Results. Were evaluated 84 patients with hemoculture and clinical data from 59 patients. The incidence rate of candidemia (per 1,000 admissions) was higher in women than men (0.76 vs 0.54, p <0.0001), not very different through out the years and varied according to the hospitalization unit, predominating in the Clínica Surgical, Clinical Medicine, Oncology and Intensive Care Unit. C. albicans was a predominant genus and, among non-C. albicans, C. glabrata was more frequent. All compounds of the C. glabrata complex were as C. glabrata stricto sensu. Predisposing factors - gastric surgery, use... (Complete abstract click electronic access below) / Mestre

Na mesma proporção que fontes de água potável são reduzidas, a competição por elas tem aumentado, conseqüência imediata da expansão de áreas urbanas e de novas demandas agro-industriais. Os conflitos gerados por esta competição tendem a comprometer o desenvolvimento sustentável e o progresso de uma forma geral, uma vez que resultam em perda de eficácia para vultuosos investimentos públicos e privados e em prejuízos para os usuários menos estruturados. Considerando os fatos acima, o objeto deste trabalho é o estabelecimento de cenários de alocação das disponibilidades hídricas entre usuários de água da bacia do Sapucaí-Mirim/Grande, visando determinar a convivência harmoniosa das várias finalidades de uso provenientes do mesmo recurso hídrico. Tal meta poderá ser alcançada através da análise dos indicadores de desempenho - confiabilidade, vulnerabilidade e resiliência - do sistema os quais serão obtidos com o auxílio do modelo de simulação IRAS (Interactive River Aquifer Simulation). / In the same proportion that fresh water sources are been reduced, competition for its has grown, immediate consequence of urban areas expansion and new agroindustrial demands. Conflicts generated by this competition tend to affect the sustainable development and the progress as well, once this competitiveness situation means efficacy loss to large amounts of public and privy investments, and also injuries to less structured users. Considering above facts, the goal of this paperwork is to establish water availability allocation scenarios between Sapucai-Mirim/Grande basin\'s users, aiming to settle a balanced distribution of the several use finalities came from the same water resource. Such goal can be reached through system performance indicators analysis - reliability, vulnerability and resilience - which will be estimated through IRAS simulation model aid.

Die Wechselwirkung von Wasser und CO2 mit Oxidoberflächen ist vor allem ein bedeutsames Thema für Umweltnaturwissenschaftler. Der Gebrauch von Wasser als Wasserstoff-Ressource für die Reduktion/Hydrierung von CO2 würde zu einer Reduktion der CO2-Emmissionen in der Atmosphäre führen. Trotz einiger Fortschritte in diesem Bereich sind weitere grundlegende Studien notwendig, um die Wechselwirkung von Wasser und CO2 mit Metalloxidoberflächen zu verstehen und darauf aufbauend eine rationale Gestaltung Katalyse-Prozesse zu ermöglichen. Die vorliegende Arbeit präsentiert grundlegende Studien der Adsorption von Wasser und CO2 auf wohldefinierten Fe3O4(111) Filmen, welche auf einem Pt(111) Einkristall aufgewachsen wurden. Die Oberfläche wurde zuerst durch Adsorption von CO als Sondenmolekül gestützt. Es zeigt sich, dass die Magnetitoberfläche aus einer 1/4-Monoschicht tetraedrisch angeordneter Fe3+-Ionen auf einer dicht gepackten Sauerstoffschicht besteht. Auf dieser gut charakterisierten Oberfläche wurde die Wechselwirkung mit Wasser und CO2 sodann detailliert untersucht. Kombinierte IRAS- und TPD-Daten deckten auf, dass Wasser leicht an der Oberfläche dissoziiert und unter Einbeziehung von Sauerstoffatomen aus dem Wasser selbst bzw. von der Oxidoberfläche zwei Hydroxylspezies bildet. Diese Spezies fungieren als Anker für die molekulare Wasseradsorption, die schließlich zu einer geordneten Struktur führt. DFT-Rechnungen rationalisieren diese Ergebnisse im Rahmen einer kooperativen Bildung des Wasserstoffbrückenbindungsnetzwerkes. Die Magnetitoberfläche scheint hingegen eher träge gegenüber der CO2-Chemisorption zu sein. Bei niedrigen Temperaturen kann die Bildung schwacher chemisorbierter Spezies als durch Oberflächendefekte bedingt interpretiert werden. In jedem Fall spielt bei höheren Temperaturen das Vorhandensein von Wasser auf der regulären Oberfläche eine entscheidende Rolle in der CO2-Aktivierung und fördert die Bildung von Bikarbonat-Spezies. / The interaction of water and CO2 with oxide surfaces is nowadays a hot topic especially for environmental scientists. The use of water as hydrogen for CO2 reduction/hydrogenation would be the most ideal process, which would contribute to reduce CO2 emission into the atmosphere and minimize the dependence of society on fossil fuels. Despite certain advances in this field, further fundamental studies need to be addressed to understand the interaction of water and CO2 with metal-oxide surfaces for a rational design of heterogeneous catalytic processes. This work presents a fundamental study of the adsorption of water and CO2 on well-defined Fe3O4(111) films grown on Pt(111) single crystal. To understand the adsorption properties of the iron oxide film, the surface has been characterized using CO as probe molecule. The characterization showed that the magnetite surface is terminated by a 1/4 monolayer of tetrahedrally coordinated Fe3+ ions on top of a close-packed oxygen layer. On this well characterized surface, the interaction with water and CO2 has been investigated in detail. Combined IRAS and TPD data revealed that water readily dissociates on the surface, forming two hydroxyl species, OwH and OsH, involving oxygen atoms from the water (w) itself and from the oxide surface (s), respectively. At increasing coverage, these species act as anchors for molecular water adsorption ultimately giving rise to a long-range ordered architecture. DFT calculations rationalized these data in the framework of cooperative formation of the hydrogen bonding network. Moreover, Fe3O4(111) seems to be rather inert towards CO2 chemisorption at low temperatures, and the formation of weak chemisorbed species may be interpreted as driven by surface imperfections. At higher temperatures, the presence of water on the regular surface (induced and/or just as residual gas adsorption) plays a critical role in the CO2 activation, promoting the formation of bicarbonate-like species.

Since the identi cation of proto-planetary nebulae (PPNe) as transition objects between the asymptotic giant branch stars and planetary nebulae more than two decades ago, astronomers have attempted to characterise these exciting objects. Today many questions still elude a conclusive answer, partly due to the sheer diversity observed within this small subset of stellar objects, and partly due to the low numbers detected. Fortunately, many of these objects display a rich spectrum of emission/absorption lines that can be used as diagnostics for these nebulae. This dissertation presents a study of six PPNe using the relatively new (at NIR wavelengths) integral eld spectroscopy technique. This method has allowed the investigation of distinct regions of these nebulae, and in certain cases the application of magneto-hydrodynamic shock models to the data. The goal of this research has been to investigate the evolution of PPNe by detailed examination of a small sample of objects consisting of a full range of evolutionary types. Near-IR ro-vibrational lines were employed as the primary tool to tackle this problem. In all six sources the 1!0S(1) line is used to map the spatial extent of the H2. In three of these objects the maps represent the rst images of their H2 emission nebulae. In the case of the earliest-type object (IRAS 14331-6435) in this sample, the line map gives the rst image of its nebula at any wavelength. In the only M-type object (OH 231.8+4.2) in the sample, high-velocity H2 is detected in discrete clumps along the edges of the bipolar out ow, while a possible ring of slower moving H2 is found around the equatorial region. This is the rst detection of H2 in such a late-type object but due its peculiarities, it is possibly not representative of what is expected of M-type objects. In IRAS 19500-1709, an intermediate-type object, the line map shows the H2 emission to originate in clumpy structures along the edges of a bipolar shell/out ow. The remaining three objects have all been the subject of previous studies but in each case new H2 lines are detected in this work along with other emission lines (Mg ii, Na i &amp; CO). In the case of IRAS 16594-4656, MHD shock models have been used to determine the gas density and shock velocity. Two new python modules/classes have been written. The rst one to deal with the data cubes, extract ux measurements, rebin regions of interest, and produce line maps. The second class allows the easy calculation of many important parameters, for example, excitation temperatures, column density ratio values, extinction estimates from several line-pairs, column density values, and total mass of the H2. The class also allows the production of input les for the shock tting procedure, and simulated shocks for testing this tting process. A new framework to t NIR shock models to data has been developed, employing Monte Carlo techniques and the extensive computing cluster at the University of Hertfordshire (UH). This method builds on the approach used by many other authors, with the added advantages that this framework provides a method of correctly sampling the shock model parameter space, and providing error estimates on the model t. Using this approach, data from IRAS 16594-4656 have been successfully modelled using the shock models. A full description of this class of stellar objects from such a small sample is not possible due to their diverse nature. Although H2 was detected across the full spectral vi range of post-AGB objects, the phase at which H2 emission begins is still not clear. The only M-type object in this work is a peculiar object and may not be representative of a typical post-AGB star. The H2 PPNe appear to be located at lower Galactic latitudes (b 20 ) than the total PPNe population, possibly pointing to an above average mass and hence younger age of these objects.

<p>The interaction of carboxylic acids with copper is a phenomenon found both outdoors and, more commonly, indoors. The influence on copper of some carboxylic acids (formic, acetic, propionic, and butyric) have so far been studied at concentrations levels at least three or four orders of magnitude higher than actual indoor conditions (< 20 ppb, volume parts per billion), and with only limited emphasis on any mechanistic approach. In this licentiate study a unique analytical setup has been successfully applied for <i>in situ </i>characterization and quantification of corrosion products formed during initial atmospheric corrosion of copper in the presence of acetic, formic or propionic acid. The setup is based on monitoring mass changes by the quartz crystal microbalance (QCM) and simultaneously identifying the chemical species by infrared reflection-absorption spectroscopy (IRAS). Post-analysis of corrosion products was performed by coulometric reduction (mass of copper (I) oxide formed), grazing incidence x-ray diffraction (phase identification) and atomic force microscopy (surface topography).</p><p>The absolute amounts of mass of individual constituents in the corrosion products, mainly copper (I) oxide or cuprite, copper (II) carboxylate and water or hydroxyl groups, have been deduced<i> in situ</i> during exposure in 120 ppb of carboxylic acid concentration, 95% relative humidity and 20ºC. An overall result is the consistency of analytical information obtained. For copper (I) oxide the quantified data estimated from IRAS, QCM or coulomeric reduction agrees with a relative accuracy of 12 % or better.</p><p>The interaction of copper with the carboxylic acids seems to follow two spatially separated main pathways. A proton-induced dissolution of cuprous ions followed by the formation of copper (I) oxide, and a carboxylate-induced dissolution followed by the formation of copper (II) carboxylate. The first pathway is initially very fast but levels off with a more uniform growth over the surface. This pathway dominates in acetic acid. The second pathway exhibits a more constant growth rate and localized growth, and dominates in formic acid. Propionic acid exhibits low rates for both pathways. The difference between the carboxylic acids with respect to both total corrosion rate and carboxylate-induced dissolution can be attributed to differences in acid dissociation constant and deposition velocity.</p>

Submitted by Nadir Basilio (nadirsb@uninove.br) on 2015-07-17T14:17:18Z No. of bitstreams: 1 Walquiria Barcelos de Figueiredo.pdf: 11234029 bytes, checksum: dbf21e923a2bfae3e29f6be02048db53 (MD5) / Made available in DSpace on 2015-07-17T14:17:18Z (GMT). No. of bitstreams: 1 Walquiria Barcelos de Figueiredo.pdf: 11234029 bytes, checksum: dbf21e923a2bfae3e29f6be02048db53 (MD5) Previous issue date: 2014-11-19 / The present study aimed to point out the reasons of failure of supply of inputs to an Intensive Care Unit (ICU) of a tertiary public hospital, identifying the risks associated with lack of essential materials in patient care and the occurrence of Healthcare Associated Infection (HAI). For this purpose, a study delineated as action research was conducted, as well as surveys and document analysis of recorded cases of HAI in the studied unit between 2012 and 2013, apart from the content analysis of the spreadsheet input supply. A literature search was conducted on standards, legislation and scientific articles related to the subject. Aiming to understand the perception of the professional group, a survey instrument was applied to the staff of the unit in a form of a semi-structured questionnaire. Through opportunities for improvement related to the management and control of essential materials, care of patients, a scoring model to material considered essential to the ICU, based on the classification system into categories ABC and XYZ was proposed. According to the criticality of the missing material to be used in sector, it was possible to generate a report to the Sub Committee on Hospital Infection Control and the administrative sector, to help in emergency procurement and distribution of basic materials for the assistance and thus minimize the occurrence of adverse events and consequently increased professional satisfaction and patient safety. / O presente estudo objetivou levantar quais as razões das falhas de abastecimento dos insumos de uma Unidade de Terapia Intensiva (UTI) de um hospital público terciário, identificando os riscos associados à falta de materiais essenciais na assistência ao paciente e na ocorrência de infecções relacionadas à saúde (IRAS). Para isso, foi realizado um estudo delineado como pesquisa-ação, além de levantamentos e análise documental dos casos registrados de IRAS na unidade entre 2012 e 2013, bem como análise de conteúdo das planilhas de fornecimento de insumos. Uma pesquisa bibliográfica também foi realizada, sobre normas, legislações e artigos científicos relacionados ao assunto. Com o objetivo de compreender a percepção do grupo profissional, um instrumento de pesquisa foi aplicado na forma de questionário semiestruturado à equipe da unidade estudada. Através das oportunidades de melhoria relacionadas à gestão e controle de materiais essenciais para o cuidado de pacientes, foi proposto um modelo de pontuação a esses materiais considerados fundamentais para a UTI, baseado no sistema de classificação em categorias ABC e XYZ. De acordo com a criticidade do material em falta a ser utilizado no setor, foi possível gerar um relatório à Subcomissão de Controle de Infecção Hospitalar e ao setor administrativo, para auxiliar na aquisição emergencial e distribuição dos materiais básicos para a assistência, e desta forma minimizar a ocorrência de eventos adversos e aumentar, consequentemente, a satisfação dos profissionais e segurança dos pacientes.