Orientador: Walace Alves de Oliveira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T13:24:33Z (GMT). No. of bitstreams: 1 Lima_JoaquimMatiasBittencourt_M.pdf: 2410483 bytes, checksum: eb7f40c8e6feac1eec3059a9a6ccfb12 (MD5) Previous issue date: 1979 / Resumo: Foi desenvolvido o estudo de um padrão ebuliométrico para solventes não aquosos. Benzila foi escolhido como soluto e benzeno como padrão. Foram medidas as elevações na temperatura de ebulição do benzeno, causadas pela adição de benzila, e os coeficientes osmótico e de atividade puderam ser avaliados. A aparelhagem e o método operacional são descritos. São discutidos os diversos tipos de sensores de temperatura que podem ser utilizados e apresentadas as razões pelas quais foram escolhidos termístores para tal fim. Os termistores foram calibrados, e com base em calibração anterior, foram avaliadas as alterações nas suas características. São propostas equações para que, por método analítico, sejam medidas as elevações de temperatura, o coeficiente de atividade e o coeficiente osmótico. Foi discutido o desvio da idealidade apresentado pelo padrão. É proposto um método comparativo para determinação de constante de equilíbrio, permitindo com que, utilizando o padrão ebuliométrico, fosse determinada a constante de dimerização do ácido benzóico em benzeno, cujo resultado, comparado com dados oriundos da literatura, apresentou boa concordância / Abstract: The behavior of benzil as an ebulliometric standard for non-aqueous solvents was studied. Boiling-temperature elevations due to addition of benzil in benzene were measured and osmotic and activity coefficients were calculated. The apparatus and procedure are discussed. Several types of temperature sensors are mentioned and thermistors were chosen to be used. The thermistors were calibrated and the changes in their parameters were evaluated based on results of previous calibration. Equations are given which permit the calculation of boiling-temperature elevation of benzene solutions as well as osmotic and activity coefficients. The departure from ideal behavior is discussed. A comparative method for the ebulliometric determination of equilibrium constants is proposed. The dimerization constant of benzoic acid in benzene was determined by this method and the results are in good agreement with literature values / Mestrado / Quimica Organica / Mestre em Química

Abstract: Styrene and methyl methacrylate have been polymerized successfully through atom transfer radical polymerization (ATRP) in aqueous dispersed media (emulsion ATRP). The thesis is divided into four experimental parts. In the first part, a water-soluble initiator was prepared for emulsion ATRP and utilized under various conditions in the presence of two ligands N, N, N’, N’’, N’’-Pentamethyldiethylenetriamine and 2,2’-bipyridine to attain activation/deactivation only in the oil phase with Tween 20 as a non-ionic surfactant. The initiator was synthesized by the reaction of diethanolamine with α-Bromoisobutyryl bromide in anhydrous tetrahydrofuran. 1H NMR spectroscopy (500 MHz, deuterium oxide, or chloroform-d) was performed to confirm the successful synthesis of the initiator and polystyrenes. In the second and third parts, two commercial initiators were used, poly(ethylene glycol) methyl ether 2-bromoisobutyrate (Mn= 2000 g/mol), and 2-hydroxyethyl 2-bromoisobutyrate (Mn= 211.05 g/mol). BPY, tris(2-pyridylmethyl) amine and 4, 4’-dinonyl -2, 2’-dipyridyl were used as the ligands with various molar ratios. Polyoxyethylene (80) sorbitan monooleate, and polyoxyethylene (20) oleyl ether were used as non-ionic surfactants. In the fourth part, a macroinitiator was synthesized by the reaction of polyoxyethylene (20) stearyl ether with α-Bromoisobutyryl bromide. The formation of the macroinitiator as well as the successful synthesis of poly(ethylene glycol)-b-polystyrene, and poly(ethylene glycol)-b-poly(methyl methacrylate) block copolymers were confirmed by Fourier transform infrared and 1H NMR spectroscopies. The molecular weight of the resulting polymers, as well as the stability of the emulsion systems, were evaluated by gel permeation chromatography and dynamic light scattering, respectively.

The photochemical reactions occurring in aqueous solutions of octacyanomolybdate(V) ion, Mo(CN)_8^3-, during irradiation with light of 365 and 436 nm wavelengths were studied. The quantum yields and reaction products were determined for neutral, unbuffered solutions as well as solutions buffered at pH 4.0, 7.0, and 9.0. The results of these studies showed that the Mo(CN)_8^3- ion is rapidly reduced by light to a Mo(IV) complex. In neutral or acidic media, the initial photoreduction product was found to be the red heptacyanoaquomolybdate(IV) ion, Mo(CN)_7(H_2O)^3-. Photolysis in basic solution gave the yellow heptacyanohydroxomolybdate(IV) ion, Mo(CN)_7(OH)^4-, as an unstable intermediate. Hydrolysis of this complex to the blue tetracyanohydroxooxomolybdate(IV) ion, Mo0(OH)(CN)_4^3-, occurred rapidly in base. In each case, cyanogen, (CN)_2, and cyanate ion, OCN^-, were formed. Additionally, in neutral solutions, the formation of hydrogen ion during the irradiation of the sample gave a rapid drop in the pH of the solution. Measurements of the product quantum yields for Mo(IV) complexes, *_Mo(IV), gave values that were always greater than one and which increased rapidly with increasing pH of the irradiated solutions, The values were the same for both irradiating wavelengths, showing no wavelength effect for the reaction, The quantum yields determined for *_Mo(IV) were 1.51, 1.59, 3.10, and 4.29 for pH 4 , neutral pH, pH 7, and pH 9 solutions respectively. From the experimental results, a reaction mechanism is suggested for each of the aqueous media used, The initial photolytic reactions are the same in all solutions with subsequent thermal reactions being responsible for the variation of *_Mo(IV) with the pH of the solution.

<p> Using a potentiometric method on 10^-4M and 10^-5M Al(NO3)3 solutions at constant ionic strength (0.1 M KNO3) and temperature (25°C), titration curves were defined and examined with respect to three variables (total aluminum concentration, pH range, and time) in order to assess the reversibility of the aqueous system.</p> <p> Increasing pH titration interval decreased reversibility while increasing time interval led to a slight increase in reversibility. Decreasing the total aluminum concentration also slightly improved reversibility. Overall, the reversibility of the system was observed to be poor.</p> <p> Computer models were compared to experimental titration data in order to derive the speciation schemes which best fit the data. Polynuclear hydrolysis schemes fit the data best for the concentration levels as follows: Al^3+, Al(OH)4^-, and Al6(OH)15^3+ for 10^-5M Alt. Al^3+, Al(OH)4^-, and Al8(OH)20^4+ and/or Al13(OH)32^7+ for 10^-4M Alt. / Thesis / Master of Science (MSc)

<p> The sulfur cycle is perhaps one of earth's most important cycles. Biologically sulfur is the main constituent needed to form building blocks such as amino acids. Ecologically, it can devastate forests, lakes and ecosystems in one of it's many forms. Industrially (and perhaps naturally) it is the source of our acid rain problem. </p> <p> An estimation of sulfide fluxes emitted into the atmosphere is extremely variant due to the lack of efficient means of measuring these fluxes. Several simplistic measuring devices have been employed to estimate the oceanic, continental and atmospheric fluxes. Problems have arisen due to the non-uniform distribution of sulfur sources such as industries, volcanoes and marshlands. </p> <p> In the specific case estimates of fluxes have of organic volatile been deduced and not sulfides, actually measured to any great extent. The fundamental reason for this being the lack of an efficient means of recording data in the field to support the flux estimates. </p> <p> This study has attempted to secure the efficiency of adsorption tubes used to sample in situ freshwater sulfide fluxes. Optimal preparation involved using Molecular Sieve SA (60/80 mesh) contained and activated in pyrex glass tubing (6mm. o.d.). Proper activation occurred at 300C for 8 hours under a constant helium flow. </p> <p> Adsorption of sulfides was by helium induced release of gases at room/atmospheric temperatures. After 15 minutes, the adsorption tube was recapped and stored at (-8C) for no more than 7 days. At this time, the tubes were analyzed. </p> <p> Analysis was by GC/HECD in the laboratory. A custom made heat desorber (at 270C), in conjunction with liquid nitrogen and hot water sufficiently trapped the released sulfides from the adsorption tube. Calibrated data obtained in the laboratory provided for proper analytical interpretations of the flux of sulfides emitted from the sample. </p> / Thesis / Bachelor of Science (BSc)

<p> This thesis is an experimental study of the effects of injecting dilute polymer solutions into a turbulent boundary layer developed on a flat plate submerged in water.</p> <p> A flat plate having a plexiglass surface together with a separate leading edge piece were specially designed for observing the boundary layer phenomena. Aqueous polymer solutions were introduced into the boundary layer through a slit situated in the leading edge piece. Hot-film anemometer technique was employed in the measurements of velocity profiles, turbulence intensities and lateral correlation coefficients at several locations on the plate. The investigation was carried out for two Reynolds Numbers, based on the length of the plate, of 2.4 x 10^5 and 6.4 x 10^5. The variation in the drag force with respect to the polymer concentrations and the injection rates was assessed based on the velocity profile data. It was found that the momentum diffusivity was smaller than for pure water, and that the presence of the polymer molecules seemed to promote a more uniform distribution of the sizes of the turbulence eddies.</p> / Thesis / Master of Engineering (MEngr)

<p> The major part of the present work dealt with adapting the droplet technique to the study of nucleation from solution of some analytically important metal chelates. Precipitation from homogenous solution was introduced as the means of gradually increasing the supersaturation in the droplets. This new method of producing supersaturation enabled the extention of the droplet technique to nucleation studies of sparingly soluble substances. </p> <p> In addition, a second novel way of achieving supersaturation in the droplets was devised. In contrast to the first method, which increased the amount of solute at constant droplet volume, the second method maintained the amount of solute constant, while gradually reducing the volume of the droplet. This permitted studies on nucleation from solution of soluble substances to be carried out isothermally. </p> <p> The two techniques mentioned above were applied successfully to the study of nucleation from solution of four analytically important metal chelates and to several inorganic salts, respectively. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

Connective tissue remodeling is an important area of study in biomedical engineering with respect to cancer and wound healing. Tissue remodeling components may be involved in the pathogenesis of open-angle glaucoma. Risk factors for open angle glaucoma include increased intraocular pressure (IOP), male gender, and advanced age. In a 1963 study, the hormone relaxin decreased IOP in the human eye through a mechanism that may involve the up-regulation of tissue remodeling matrix metalloproteinases (MMPs). The effects of age and gender on MMP and protein activity in porcine aqueous humor were determined in this study to identify correlations existing between MMP activity and glaucoma risk factors. Gelatin zymography identified MMPs at 66 kD and approximately 105 kD. The concentration of the 66 kD band compared to human MMP-2 standard was 0.22 ± 0.06 ng/ml for the adult female (AF) samples and 0.28 ± 0.04 ng/ml for the juvenile samples. This difference in concentration was statistically significant (p < 0.05). The concentration of the protease migrating to 66 kD was statistically independent of gender. Casein zymograms identified two non-MMP proteinases at 51 kD and 80 kD. The average total protein concentration for all aqueous humor samples was 2.54 ± 0.89 mg/ml. The mean IgG, transferrin, and albumin concentrations for all aqueous humor samples was 11.4 ± 4.2 mg/ml, 17.11 ± 6.8 mg/ml, and 78.0 ± 26.3 mg/ml respectively. Results from these experiments establish baseline levels of MMP and protein activity, allowing for identification of potential changes caused by relaxin in tissue culture studies. / Master of Science

The hydrodynamic behaviour of fine suspended aqueous sediments, and stability of the bedforms they create once settled, are governed by the physical properties (e.g., size, shape, porosity and density) of the flocculated particles in suspension (flocs). Consequently, accurate prediction of the transport and fate of sediments and of the nutrients and pollutants they carry depends on our ability to characterise aqueous flocs. Current research primarily focuses on characterising flocs based on their external gross-scale (>1 μm) properties (e.g., gross morphology, size and settling velocity) using in situ techniques such as photography and videography. Whilst these techniques provide valuable information regarding the outward behaviour of flocculated sediment (i.e. transport and settling), difficulties associated with extracting 3D geometries from 2D projections raises concerns regarding their accuracy and key parameters such as density can only be estimated. In addition, they neglect to inform on the internal micro- and nano-scale structure of flocs, responsible for much of their behaviour and development. Transmission electron microscope (TEM) and environmental electron microscope may be used to obtain nano-scale information in, essentially, 2D but there is a large scale gap between this information and the macro-scale of optical techniques. To address this issue this study uses 3D tomographic imaging over a range of spatial scales. Whilst commonly used in materials science and the life sciences, correlative tomography has yet to be applied in the environmental sciences. Threading together 3D Xray micro-computed tomography (X-ray μCT) and focused ion beam nano-tomography (FIBnt) with 2D TEM makes material characterisation from the centimetre to nanometre-scale possible. Here, this correlative imaging strategy is combined with a non-destructive stabilisation procedure and applied to the investigation of flocculated estuarine sediment, enabling the multi length-scale properties of flocs to be accurately described for the first time. This work has demonstrated that delicate aqueous flocs can be successfully stabilised via a resin embedding process and contrasted for both electron microscopy and X-ray tomography imaging. The 3D information obtained can be correlated across all length-scales from nm to mm revealing new information about the structure and morphology of flocs. A new system of characterising floc structure can be defined based on the association of particles and their stability in the structure rather than simply their size. This new model refutes the postulate that floc structures are fractal in nature.