Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-05-02Bitstream added on 2014-06-13T18:29:00Z : No. of bitstreams: 1 almeida_gg_me_ilha.pdf: 925010 bytes, checksum: ba70af9cfa40dd107474b49097634afa (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Apresenta-se neste trabalho o estudo das propriedades estruturais e termodinâmicas dos líquidos acetona (ACT), N-metilformamida (NMF) e de suas misturas, utilizando-se simulação computacional com método Monte Carlo. O estudo foi realizado com o intuito de se entender melhor os mecanismos moleculares envolvidos na estabilização enzimática em meios não aquosos, uma vez que há um aumento significativo no uso de biocatálise nas indústrias química e farmacêutica nos últimos anos. Os resultados estruturais obtidos para os líquidos puros foram comparados com os obtidos por difratometria de nêutrons com substituição isotópica e posterior refinamento por meio do método EPSR (refinamento estrutural por potencial empírico). As simulações foram feitas no ensemble isotérmico- isobárico com temperatura de 298 K e pressão de 1 atm. A energia de interação intermolecular foi calculada utilizando-se o potencial de pares clássico 6-12 Lennard-Jones somado ao potencial de Coulomb. Os valores teóricos obtidos para o calor de vaporização e densidade estão em bom acordo com os experimentais para os líquidos puros. Verificou-se uma boa concordância entre a estrutura teórica e experimental dos líquidos (especialmente para a NMF). Na análise dos líquidos puros foi constatada diferença estrutural e termodinâmica entre eles, sobretudo em decorrência da presença de ligações de hidrogênio na NMF e ausência destas na ACT. Para a mistura, observou-se uma maior energia de interação entre moléculas de NMF do que de ACT, devido à presença de ligações de hidrogênio na primeira. Verificou-se também a formação de ligações de hidrogênio entre moléculas dos dois líquidos, com um aumento da força de interação por ligações de hidrogênio encontradas entre moléculas de NMF à medida que se adiciona acetona... / This work presents the study of structural and thermodynamic properties of acetone (ACT) - N-methylformamide (NMF) mixtures using Monte Carlo simulation. The study has been performed in order to better understand the molecular mechanisms involved in the enzyme’s stabilization in no aqueous media, since there is a significant increase in the use of biocatalysis in pharmaceutical and chemical industries in recent years. The structural results obtained for the pure liquids were compared with those obtained by neutron diffraction with isotopic substitution and subsequent refinement by the EPSR (empirical potential refinement) method. The simulations were performed in the isothermal-isobaric ensemble with a temperature of 298 K and 1 atm. The intermolecular energy was calculated using the classical 6-12 Lennard-Jones plus Coulomb pair potential. The theoretical values obtained for the heat of vaporization and density are in good agreement with the experimental data for pure liquids. There was a good agreement between experimental and theoretical structure of liquids (especially for NMF). In the pure liquids’ analysis was found structural and thermodynamic differences among them, mainly due to the presence of hydrogen bonds in the NMF and the lack of it in the ACT. In the mixture, the interaction energy between the NMF molecules is larger than between the ACT molecules, also a consequence of the presence of hydrogen bonds in the first ones. It was also found the formation of hydrogen bonds between the two liquids, with an increase in the strength of hydrogen bond interaction between the NMF molecules as ACT was added due to some sort of solvophobic effect. The concentration’s influence on the dipolar correlation between the molecules of the liquid has been explored with discussion of the structure in the solvation shells in the mixture... (Complete abstract click electronic access below)

Orientador: João Manuel Marques Cordeiro / Banca: Rosangela da Silva de Laurentiz / Banca: José Roberto dos Santos Politi / Resumo: Apresenta-se neste trabalho o estudo das propriedades estruturais e termodinâmicas dos líquidos acetona (ACT), N-metilformamida (NMF) e de suas misturas, utilizando-se simulação computacional com método Monte Carlo. O estudo foi realizado com o intuito de se entender melhor os mecanismos moleculares envolvidos na estabilização enzimática em meios não aquosos, uma vez que há um aumento significativo no uso de biocatálise nas indústrias química e farmacêutica nos últimos anos. Os resultados estruturais obtidos para os líquidos puros foram comparados com os obtidos por difratometria de nêutrons com substituição isotópica e posterior refinamento por meio do método EPSR (refinamento estrutural por potencial empírico). As simulações foram feitas no ensemble isotérmico- isobárico com temperatura de 298 K e pressão de 1 atm. A energia de interação intermolecular foi calculada utilizando-se o potencial de pares clássico 6-12 Lennard-Jones somado ao potencial de Coulomb. Os valores teóricos obtidos para o calor de vaporização e densidade estão em bom acordo com os experimentais para os líquidos puros. Verificou-se uma boa concordância entre a estrutura teórica e experimental dos líquidos (especialmente para a NMF). Na análise dos líquidos puros foi constatada diferença estrutural e termodinâmica entre eles, sobretudo em decorrência da presença de ligações de hidrogênio na NMF e ausência destas na ACT. Para a mistura, observou-se uma maior energia de interação entre moléculas de NMF do que de ACT, devido à presença de ligações de hidrogênio na primeira. Verificou-se também a formação de ligações de hidrogênio entre moléculas dos dois líquidos, com um aumento da força de interação por ligações de hidrogênio encontradas entre moléculas de NMF à medida que se adiciona acetona... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work presents the study of structural and thermodynamic properties of acetone (ACT) - N-methylformamide (NMF) mixtures using Monte Carlo simulation. The study has been performed in order to better understand the molecular mechanisms involved in the enzyme's stabilization in no aqueous media, since there is a significant increase in the use of biocatalysis in pharmaceutical and chemical industries in recent years. The structural results obtained for the pure liquids were compared with those obtained by neutron diffraction with isotopic substitution and subsequent refinement by the EPSR (empirical potential refinement) method. The simulations were performed in the isothermal-isobaric ensemble with a temperature of 298 K and 1 atm. The intermolecular energy was calculated using the classical 6-12 Lennard-Jones plus Coulomb pair potential. The theoretical values obtained for the heat of vaporization and density are in good agreement with the experimental data for pure liquids. There was a good agreement between experimental and theoretical structure of liquids (especially for NMF). In the pure liquids' analysis was found structural and thermodynamic differences among them, mainly due to the presence of hydrogen bonds in the NMF and the lack of it in the ACT. In the mixture, the interaction energy between the NMF molecules is larger than between the ACT molecules, also a consequence of the presence of hydrogen bonds in the first ones. It was also found the formation of hydrogen bonds between the two liquids, with an increase in the strength of hydrogen bond interaction between the NMF molecules as ACT was added due to some sort of solvophobic effect. The concentration's influence on the dipolar correlation between the molecules of the liquid has been explored with discussion of the structure in the solvation shells in the mixture... (Complete abstract click electronic access below) / Mestre

Orientador: Marcela Rocha de Oliveira Carrilho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-09T14:06:10Z (GMT). No. of bitstreams: 1 Bail_Michele_M.pdf: 616698 bytes, checksum: d6737bc67e911ea44d56c9e9884e2c55 (MD5) Previous issue date: 2007 / Resumo: O objetivo deste estudo foi avaliar a eficácia de diferentes métodos empregados na eliminação dos solventes incorporados a sistemas de união com características hidrofílicas diferentes. As hipóteses avaliadas consideraram que a eliminação/retenção dos solventes seria dependente: 1) da característica hidrofílica da resina; 2) da técnica e intervalo de tempo empregados na eliminação desses solventes; 3) do tipo de solvente empregado. Três resinas experimentais, R2, R3 e R5, foram formuladas de modo a exibirem características hidrofílicas distintas, dadas pela seleção e proporcionamento de monômeros, comumente empregados na odontologia. A resina R2 era a menos hidrofílica e R5 a mais hidrofílica. Acetona ou etanol foram adicionados a cada resina numa proporção de 50% (em peso). A eliminação dos solventes foi verificada por método gravimétrico, aplicado antes e após a realização dos seguintes tratamentos: 1) jato de ar à temperatura ambiente (JAAmb) por 15s; 2) JAAmb por 30s; 3) JAAmb por 60s; 4) jato de ar aquecido (JAAq) por 15s; 5) JAAq por 30s ou 6) JAAq por 60s. Os dados foram analisados por análise de variância e teste de Bonferroni (a =0,05). Nenhum tratamento eliminou completamente o solvente incorporado às resinas. Maior eliminação do solvente foi verificada para a resina menos hidrofílica R2, sendo que, para maioria das condições avaliadas: R2 > R3 e R2 > R5 (p<0,05). Quanto maior tempo de aplicação dos métodos de evaporação, maior a eliminação do solvente, sendo que aos 60s o percentual de massa perdida foi significativamente maior do que aos 15s (p<0,05). Aplicação do JAAq resultou, em geral, na maior eliminação de solvente quando comparado ao JAAmb (p<0,05). Não houve diferença na capacidade de evaporação dos solventes, acetona e etanol (p>0,05). A eliminação de solventes em adesivos mais hidrofílicos pode ser favorecida adotando se períodos de evaporação mais longos do que os indicados pelos fabricantes e aplicando-se jato de ar aquecido / Abstract: The aim of the present study was to evaluate the ability of different methods to eliminate the solvents incorporated into experimental adhesives with different degree of hydrophilicity. The anticipated hypotheses considered that the elimination/retention of the organic solvents would be dependent on: 1) the hydrophilic features of the experimental resins; 2) the method and time employed to eliminate these solvents; 3) the sort of solvent incorporated into the resin. A series of resin comonomers were blended to create three experimental adhesive resins, R2, R3 and R5, with an increasing degree of hydrophilicity. Resin R2 is the most hydrophobic and R5 is the most hydrophilic. The solvents, acetone and ethanol, were added to each experimental resin in a proportion of 50 wt%, generating six different mixtures. The elimination of these solvents was verified by means a gravimetric method applied before and after the following treatments: 1) application of an air-drying at room temperature for 15 s (ART); 2) ART for 30s; 3) ART for 60s; 4) application of heat-air drying (AH - 40 ± 1°C) for 15s; 5) AH for 30s or 6) AH for 60s. Data were analyzed by ANOVA and Bonferroni¿s test (a =0,05). None of the treatments was able to eliminate completely the solvent incorporated into the experimental resins. The highest elimination of solvent was observed for the resin R2, being that for most of conditions: R2 > R3 and R2 > R5 (p<0.05). The percentage of solvent evaporation increased proportionally with the increase of the time of the air-drying application, being significantly higher in the 60s when compared to 15s (p<0.05). In general, the application of the AH resulted in higher elimination of the solvent when compared to that obtained by the application of the ART (p<0.05). The solvent elimination, in general, did not depend on the sort of the solvent incorporated into the resin (p>0.05). The elimination of solvents from hydrophilic resins can be favored by extending the time for solvent evaporation and applying heat-air drying / Mestrado / Materiais Dentarios / Mestre em Materiais Dentários

Acetone in exhaled breath is gaining attention as a non-invasive means of quantifying blood glucose levels in Diabetics. This calls for development of novel biosensors for the detection of trace concentrations of acetone present in human breath. Traditional gas detection systems, such as GC/MS and chemiresistive sensors, are currently used for this purpose. However, these systems have limitations with regards to size, cost, and operating temperature. This work presents the K2W7O22/Ti3C2 nanocomposite sensor as breath acetone sensor that overcomes the limitations in traditional detection systems. Sensing experiments were conducted using 5 different sensor materials in varying ratios. KWO/Ti3C2 - ratio 2:1 (annealed) and KWO/Ti3C2 - ratio 2:1 (Unannealed) showed excellent sensitivity to 2.85ppm and 5.4ppm acetone concentration. These materials were then implemented in a prototype device. Material and device test results confirm the potentials of the novel KWO/Ti3C2 nanocomposite as a good sensor for breath acetone detection.

This master thesis deals with the surface treatment of parts made of plastic produced using FDM technology and design of technological device for surface treatment. The thesis describes FDM principles, according to performed experiments in a technological device there are suggested technological conditions for the surface treatment of parts made of ABS plastic. In the end of the thesis, there are calculated costs of the technological device and its operating costs, also mechanical properties, surface roughness and other specifications from before and after the treatment are compared.

Acetone-butanol-ethanol (ABE) fermentation from wastewater microalgae by Clostridium saccharoperbutylacetonicum N1-4 is a novel bioprocess that utilizes waste substrate to generate valuable solvents. Butanol, the most abundant product resulting from ABE fermentation, is an environmentally safe and high performing fuel that can be utilized as a drop-in-fuel; however, high operational costs and low ABE yield present challenge in scale-up of the process. The utilization of algae as a substrate requires pretreatment prior to fermentation to increase the bioavailability of the algal fermentable sugars and to improve the conditions of the pre-fermentation medium. The purpose of this thesis was to optimize wastewater microalgae pretreatment through (1) the optimization of microalgae saccharification, and (2) the use of cheese whey as co-substrate and supplement. Optimal conditions for sugar liberation from wastewater algae through acid hydrolysis were determined for subsequent fermentation to acetone, butanol, and ethanol (ABE). Acid concentration, retention time, and temperature were evaluated to define optimal hydrolysis conditions by assessing sugar and ABE concentrations, and the associated costs. Additionally, the effect of cheese whey as a supplement and substrate was determined for acetone, butanol, and ethanol (ABE) fermentation from wastewater microalgae. Three media constituents, potassium phosphate, magnesium sulfate, and ferrous sulfate, were evaluated to assess their need as supplements in the medium to be inoculated, when 50 g/L of cheese whey was present. The optimization of wastewater microalgae pretreatment results in increasing ABE production and decreasing process costs.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Nutrition and Food Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Bibliography: leaves 370-377. / by James Chi-Yung Leung. / Ph.D.

Analysis of seaweed as a vector for microplastics is an integral part of understanding the formation and deposition of micro-sized plastic waste in seawater. The project itself originated due to the influx of seaweed (and mismanaged plastic waste) residing on the shores of St. Kitts and Nevis and the constant deposition of plastic pollution intertwined within the seaweed. The natural occurrence of the two together lead to the consideration of fragmented plastics remaining on the seaweed. The objective of this research is to stain, identify, and quantify the concentration of microplastics sourced from both store-bought and environmental seaweed samples. A Nile red solution dissolved in either acetone or methanol was used to stain the microplastics, as per a proven method. The fluorescence of the stained microplastics was measured (excitation: 523-543 nm and emission: 580-640 nm) to identify potential dissolution. The seaweed was washed of microplastics and the solid particles collected were evaluated using infrared (IR) spectroscopy. The fluorescence and infrared spectrum results were compared to spectra within the Spectral data base system (SDBS) for the most common plastics: polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polypropylene (PP), polycarbonate (PC). The use of a fluorescence microscope allowed for direct quantification of microplastics over a specific area of the sample and therefore allowed for further identification of microplastic presence.

Triacetone Triperoxide (TATP) is a primary high explosive that can be synthesized using commercially available starting materials and has grown in use among terrorists over the past several years. Additives present in the precursors were investigated to see if they carry through the TATP synthesis and can be detected in the final product potentially aiding in the identification of the source. Additives identified in the acetones were also identified in pre-blast and in some post-blast samples. However, these additives are present in trace quantities relative to the TATP, which coupled with the volatility and short lifetimes of some of the additives in TATP samples limit their detection in pre-blast and post-blast material. TATP prepared with different acids in the laboratory could generally be discriminated by observing the change in composition of the headspace of the samples upon heating and by IMS analysis of the crystals. The analysis of TATP synthesized on a larger scale was compared to the laboratory results of pre-blast material and post-blast debris. As in the laboratory samples, organic additives were also detected in the large-scale pre-blast samples and the identification of the additives in post-blast debris was consistent with the results obtained in the laboratory detonations.

This work seeks to compare various Acetone-Butanol-Ethanol (ABE) fermentation extraction chemicals on an economic and environmental basis. The chemicals considered are: decane, a decane/oleyl alcohol blend, decanol, a decanol/oleyl alcohol blend, 2-ethyl-hexanol, hexanol, mesitylene, and oleyl alcohol. To facilitate comparison a pure-distillation base case was also considered. The aforementioned extractants are a mix of both toxic and non-toxic extractants. Non-toxic extractants can be used directly in fermentation reactors, improving overall fermentation yield by removal of toxic butanol. The extractants were modelled in Aspen Plus V8.8 and separation trains were designed to take advantage of extractant properties. The separation section of the plant was then integrated with upstream and downstream units to determine the Minimum Butanol Selling Prices (MBSP) for second generation extractive ABE fermentation. Upstream processes include biomass (switchgrass) solids processing, biomass pre-treatment/saccharification and fermentation while downstream processes include utility generation and wastewater treatment. The cost of CO2 equivalent emissions avoided (CCA) was used as a metric to compare environmental impact of each process as compared to gasoline. The economic best and environmental best extractant is shown to be 2-ethyl-hexanol with a MBSP of $1.58/L and a CCA of $471.57/tonne CO2 equivalent emissions avoided. Wastewater treatment, which is often ignored in other works, was found to makeup over 30% of total installed capital cost for all extractants. / Thesis / Master of Applied Science (MASc)