Made available in DSpace on 2014-06-11T19:22:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-12-20Bitstream added on 2014-06-13T20:28:32Z : No. of bitstreams: 1 goncalves_gs_me_arafcf.pdf: 376750 bytes, checksum: d261fb301fa1b4c966236fbf2eb5c9d0 (MD5) / Universidade Estadual Paulista (UNESP) / O presente trabalho consiste no desenvolvimento de um método analítico para determinação de biotina, utilizando-se a potenciometria indireta. O objetivo é apresentar a validação de método analítico como um processo que estime a eficiência do método proposto na rotina do laboratório para garantia da qualidade total. É um método que envolve equipamento simples e pouco dispendioso como o potenciômetro, que possibilita medir com precisão o valor da concentração de biotina. O doseamento quantitativo de biotina baseia-se no estudo das reações oscilantes do analito perante as análises da titulação indireta utilizando potenciômetro automático. A concentração de biotina foi determinada com massa adicionada conhecida numa matriz que simula uma cápsula, contendo aerosil (1%), estearato de magnésio (1%), celulose microcristalina (20%), amido (40%) e lactose q.s.p. Os resultados mostraram um valor médio de biotina (massa adicionada de aproximadamente 25 mg) determinada de 99,4% com desvio-padrão de 0,0345. As condições experimentais como temperatura, vidraria e concentração dos reagentes foram otimizadas. Os parâmetros investigados no processo de validação para demonstrar o desempenho do método foram: especificidade, linearidade, intervalo, precisão tanto repetitividade, quanto intermediária, exatidão e robustez. O tratamento estatístico dos dados da validação do método analítico envolveu a determinação da média, do desvio padrão e do coeficiente de variação. Para obtenção da curva de calibração se fez necessária a determinação da equação da reta, regressão linear e coeficiente de correlação linear. Este método apresenta grande aplicabilidade em soluções turvas, fluorescentes, opacas ou coradas, ou quando não existem, ou não podem aplicar-se indicadores visuais apropriados. Há possibilidade de determinação... / The present work shows the development of an analytical method for the determination of biotin by using indirect potentiometry. The main goal is to present the validation of analytical methods as a process to estimate the efficiency of the proposed methodology in the laboratory routine for the guaranty of total quality. This method involves simple and low cost devices as the potentiometer, which allows the precise measurement of biotin concentration. The quantitative dosing of biotin is based on the study of the oscillating chemical reactions with the analyte by performing the analysis of the indirect titration with an automatic potentiometer. Biotin concentration was determined by adding a known mass to a matrix that simulates a capsule containing aerosol (1%), estearato de magnésio (1%), celulose microcristalina (20%), amido (40%) e lactose q.s.p. The results showed an average value for the determination of biotin (added mass was ca. 25 mg) of 99.4% with a standard deviation of 0.0345. The experimental conditions as temperature, glassware, and concentration of the chemicals were optimized. The investigated parameters of the validation procedure to demonstrate the performance of the method were: specificity, linearity, interval, precision (repeatability and intermediate), exactness and robustness. The statistical treatment of the data for the validation of the analytical method involved the determination of the average value, standard deviation, and the variation coefficient. In order to obtain the calibration curve, the line´s equation, the linear regression and the coefficient of linear correlation were determined. This method shows great applicability for turbid, fluorescent, opaque or color solutions, or if an appropriate visual indicator is not available or cannot be applied. The method also shows the possibility for the determination of a sequence of equivalence... (Complete abstract click electronic access below)

Les capteurs de gaz électrochimiques sont l’un des moyens les plus directs pour convertir la composition chimique d’un gaz en signal électrique mesurable. A ce titre, ils ont été largement étudiés et font aujourd’hui partie des solutions de détection les plus courantes. Toutefois, ils sont souvent basés sur un électrolyte YSZ, ce qui implique des températures de travail élevées (600°C).Afin de pouvoir réaliser une cellule de capteur fonctionnant à plus basse température (300°C), les conditions de dépôt des électrolytes Bi4V2O11 et BITAVOX (Bi2TaxV1-xO5,5) par pulvérisation cathodique magnétron en conditions réactives (PVD) ont été étudiées. L’impact de l’épaisseur des films ainsi que celui du taux de substitution du vanadium par le tantale sur les propriétés structurale et de conduction ont été déterminés.Par la suite, deux types de cellules ont été réalisés en déposant des électrodes à la surface de l’électrolyte par PVD. Le premier utilise des électrodes de platine dense et de nanofils de LASCO (La1-x-yAgxSryCoO3). Néanmoins, le comportement de ce capteur aux plus basses températures est assez complexe. Aussi, des électrodes de platine et d’or ont ensuite été étudiées, amenant à une réponse plus simple et apparaissant dès 200°C. / Electrochemical sensors are one of the most direct ways to convert the chemical composition of a gas into measurable electric signals. As such, they have been widely investigated and are now one of the most common detection solutions. However, they are often based on YSZ electrolyte, which implies high working temperatures (600°C).In order to build a sensor cell which could operate at lower temperature (300°C), deposition parameters of Bi4V2O11 and BITAVOX (Bi2TaxV1-xO5.5) electrolytes by the mean of reactive magnetron sputtering (PVD) were investigated. The impact of film thickness and that of tantalum substitution rate on the V site on structural and conduction properties were determined.Then, two different kinds of cells were realised by depositing electrodes onto the electrolyte surface. The first one used dense platinum and LASCO (La1-x-yAgxSryCoO3) nanowires electrodes. Nevertheless, this sensor exhibited a rather complex behaviour at lowest temperatures. Then, gold and platinum electrodes were investigated, which led to a more simple response of the sensor. Furthermore, this response started at 200°C.

A series of five linked β-cyclodextrin (βCD) dimers N,N-bis(6 [superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-succinamide, 66βCD₂su, N-((2[superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A-deoxy-6 [superscript]A -β-cyclodextrinyl)-urea, 36βCD₂su, N,N-bis((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -deoxy-3 [superscript]A-β-cyclodextrinyl)-succinamide, 33βCD₂su, N,N-bis(6[superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-urea, 66βCD₂ur, and N-((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A -deoxy-6 [superscript]A -β-cyclodextrinyl)urea, 36βCD₂ur, has been prepared. The complexation of 6-(4’-(toluidinyl)naphthalene-2-sulphonate, TNS⁻, by βCD and the five linked βCD dimers was characterized by UV, fluorescence and 2D ¹H ROESY NMR spectroscopy. In aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K, TNS⁻ forms host-guest complexes with βCD of stoichiometry βCD.TNS⁻ (K₁ = 3020 and 3320 dm³ mol⁻¹) and βCD₂.TNS⁻ (K₂ = 57 and 11 dm³ mol⁻¹) where the first and second values were determined in UV and fluorescence studies, respectively. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur, the analogous K₁ = 16100, 10900, 10700, 55100 and 18300 dm³ mol⁻¹ and K₁ = 12500, 8700, 9600, 38000 and 9800 dm³ mol⁻¹(fluorimetric studies), respectively. ¹H 2D ROESY NMR studies provided evidence for variation of the mode of complexation of the TNS⁻ guest as the βCD host is changed. The factors affecting complexation are discussed. UV and ¹H NMR studies showed that 6-(4’-(t-butyl)-phenyl)naphthalene-2-sulphonate, BNS⁻, and its dimer, (BNS⁻)₂, form host-guest complexes with βCD of the stoichiometry βCD.BNS⁻ (K₁ = 5.54 × 10⁴ dm³ mol⁻¹ ) and βCD.BNS₂ ²⁻(K₂ = 3.07 × 10² dm³ mol⁻¹ ) where the complexation constant K₁ = [βCD.BNS⁻]/([βCD][BNS⁻] and K₂ = [βCD.(BNS⁻)₂]/([βCD.BNS⁻][BNS⁻]) in aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur the analogous K₁ = 125, 74, 10.2, 364 and 16.1 (× 10⁴ dm³ mol⁻¹ ) and K₂ = 25.7, 2.30, 2.57, 17.6 and 17.2 (× 10² dm³ mol⁻¹ ), respectively. For the dimerisation of BNS⁻ K[subscript]d = 2.63 × 10² dm³ mol⁻¹ . Fluorimetric studies showed that the complexation stability for βCD.BNS⁻, forms βCD. BNS⁻, 66βCD₂su.BNS⁻, 36βCD₂su.BNS⁻, 33βCD₂su. BNS⁻, 66βCD₂ur.BNS⁻ and 36βCD₂ur. BNS⁻ characterized by K₁ = 4.67, 330, 101, 11.0, 435 and 29.6 (× 10⁴ dm³ mol⁻¹ ), respectively. The factors affecting the variations in these data are discussed. The enantioselectivity of substituted βCDs 6 [superscript]A -[bis (carboxylatomethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDidaH₂) and (2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -[bis(carboxylatomethyl)amino]-3[superscript]A -deoxy-β-cyclodextrin (3βCDidaH₂) and 6 [superscript]A -[tris(carboxylatomethyl)(2- aminoethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDedtaH₃) and their Eu³ ⁺ complexes in forming host-guest complexes with six enantiomeric guests in D₂O was studied by 1D and 2D ¹H NMR (600 MHz) spectroscopy. The guests are D/L-tryptophanate (Trp⁻), 4-hydroxyl-D/L-phenylglycinate (4HOPhg⁻), D/L-histidinate (His⁻), D/L-pheniramine (Phm), D/L-phenylglycinate (Phg⁻) and (D/L)-β-phenylserinate (βPhs⁻). Enantioselective host-guest complexation was observed between the [Eu(6βCDida)]⁺ , [Eu(3βCDida)]⁺ and [Eu(6βCDedta)] complexes and Trp⁻, [Eu(6βCDida)]⁺ and [Eu(3βCDida)]⁺ and 4HOPhg⁻, and βCD, 6βCDida²⁻, 3βCDida²⁻, 6βCDedta³⁻ and the Eu³⁺complexes of the three substituted βCDs and Phm. The His⁻, Phg⁻ and βPhs⁻ enantiomers showed no evidence for selective host-guest complexation. The preparation of 3βCDidaH₂ and 6βCDedtaH₃ and the determination of their pK[subscript]a s are also reported. In collaboration with the research group of Prof. Matthew A. Tarr, (University of New Orleans, USA), the 6βCDida²⁻ and the 6βCDedta³⁻ has been utilized to improve Fenton oxidation of aromatic pollutants. To further support to this work, the binary complexation of Fe² ⁺ by 6βCDida²⁻ has been studied by potentiometric titrations. A series of six modified poly(acrylic acid)s 3% substituted with either βCD or the adamantyl moiety with different length of substituent chain was synthesised. To advance the understanding and control of aqueous supramolecular assembly, the host-guest interactions between the βCD substituted poly(acrylic acid)s and adamantane-1-carboxylic; adamantyl substituted poly(acrylic acid)s with βCD and linked βCD dimers; and between both βCD and adamantyl substituted poly(acrylic acid)s have been studied. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1311237 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

ABA type tri-block amphiphilic polyelectrolyte consisting of poly(methyl methacrylate-block-methacrylic acid-block-methyl methacrylate) (P(MMA-b-MAA-b-MMA)) was synthesized by atom transfer radical polymerization technique (ATRP) and the self-assembly behavior of the polymers in aqueous solution was studied over the course of neutralization. Combination of potentiometric and conductometric titrations along with dynamic light scattering (DLS) techniques were used to investigate the size and shape of aggregates at various degrees of neutralization. The effect of hydrophobic-hydrophilic (MMA-MAA) ratio and polymer chain length on the aggregation behavior during neutralization was studied. P(MMA-b-MAA-b-MMA) with longer MMA segment self-assembles via the close association mechanism through stronger self-entanglement of MMA chains, whereas P(MMA-b-MAA-b-MMA) with shorter MMA chain self-assembles via the open association mechanism, as confirmed by transmission electron microscopy (TEM). Conductometric titration was used to determine the counterion condensation during the course of neutralization. When the charge density of micelle approaches a critical value as neutralization progresses, counterion condensation of Na+ ions on the polymer chains occurs. The effect of counterion condensation on the aggregation behavior during neutralization was elucidated. / Singapore-MIT Alliance (SMA)

In this study, an improved potentiometric intracellular glucose biosensor was fabricated with immobilization of glucose oxidase on a ZnO nanoporous material. The ZnO nanoporous material with a wall thickness around 200 nm was grown on the tip of a borosilicate glass capillary and used as a selective intracellular glucose sensor for the measurement of glucose concentrations in human adipocytes and frog oocytes. The results showed a fast response within 4 s and a linear glucosedependent electrochemical response over a wide range of glucose concentration (500 nM-10 mM). The measurements of intracellular glucose concentrations with our biosensor were consistent with the values of intracellular glucose concentrations reported in the literature. The sensor also demonstrated its capability by detecting an increase in the intracellular glucose concentration induced by insulin. We found that the ZnO nanoporous material provides sensitivity as high as 1.8 times higher than that obtained using ZnO nanorods under the same conditions. Moreover, the fabrication method in our experiment is simple and the excellent performance of the developed nanosensor in sensitivity, stability, selectivity, reproducibility and anti-interference was achieved. All these advantageous features of this intracellular glucose biosensor based on functionalised ZnO nanoporous material compared to ZnO nanorods demonstrate a promising way of enhancing glucose biosensor performance to measure reliable intracellular glucose concentrations within single living cells. / <p>Original Publication:Alimujiang Fulati, Syed M. Usman Ali, Muhammad H. Asif, Naveed Ul Hassan Alvi, Magnus Willander, Cecilia Brännmark, Peter Strålfors, Sara I. Börjesson and Fredrik Elinder, An intracellular glucose biosensor based on nanoflake ZnO, 2010, Sensors and actuators. B, Chemical, (150), 2, 673-680.http://dx.doi.org/10.1016/j.snb.2010.08.021Copyright: Elsevier Science B.V., Amsterdam.http://www.elsevier.com/</p>

A series of five linked β-cyclodextrin (βCD) dimers N,N-bis(6 [superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-succinamide, 66βCD₂su, N-((2[superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A-deoxy-6 [superscript]A -β-cyclodextrinyl)-urea, 36βCD₂su, N,N-bis((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -deoxy-3 [superscript]A-β-cyclodextrinyl)-succinamide, 33βCD₂su, N,N-bis(6[superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-urea, 66βCD₂ur, and N-((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A -deoxy-6 [superscript]A -β-cyclodextrinyl)urea, 36βCD₂ur, has been prepared. The complexation of 6-(4’-(toluidinyl)naphthalene-2-sulphonate, TNS⁻, by βCD and the five linked βCD dimers was characterized by UV, fluorescence and 2D ¹H ROESY NMR spectroscopy. In aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K, TNS⁻ forms host-guest complexes with βCD of stoichiometry βCD.TNS⁻ (K₁ = 3020 and 3320 dm³ mol⁻¹) and βCD₂.TNS⁻ (K₂ = 57 and 11 dm³ mol⁻¹) where the first and second values were determined in UV and fluorescence studies, respectively. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur, the analogous K₁ = 16100, 10900, 10700, 55100 and 18300 dm³ mol⁻¹ and K₁ = 12500, 8700, 9600, 38000 and 9800 dm³ mol⁻¹(fluorimetric studies), respectively. ¹H 2D ROESY NMR studies provided evidence for variation of the mode of complexation of the TNS⁻ guest as the βCD host is changed. The factors affecting complexation are discussed. UV and ¹H NMR studies showed that 6-(4’-(t-butyl)-phenyl)naphthalene-2-sulphonate, BNS⁻, and its dimer, (BNS⁻)₂, form host-guest complexes with βCD of the stoichiometry βCD.BNS⁻ (K₁ = 5.54 × 10⁴ dm³ mol⁻¹ ) and βCD.BNS₂ ²⁻(K₂ = 3.07 × 10² dm³ mol⁻¹ ) where the complexation constant K₁ = [βCD.BNS⁻]/([βCD][BNS⁻] and K₂ = [βCD.(BNS⁻)₂]/([βCD.BNS⁻][BNS⁻]) in aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur the analogous K₁ = 125, 74, 10.2, 364 and 16.1 (× 10⁴ dm³ mol⁻¹ ) and K₂ = 25.7, 2.30, 2.57, 17.6 and 17.2 (× 10² dm³ mol⁻¹ ), respectively. For the dimerisation of BNS⁻ K[subscript]d = 2.63 × 10² dm³ mol⁻¹ . Fluorimetric studies showed that the complexation stability for βCD.BNS⁻, forms βCD. BNS⁻, 66βCD₂su.BNS⁻, 36βCD₂su.BNS⁻, 33βCD₂su. BNS⁻, 66βCD₂ur.BNS⁻ and 36βCD₂ur. BNS⁻ characterized by K₁ = 4.67, 330, 101, 11.0, 435 and 29.6 (× 10⁴ dm³ mol⁻¹ ), respectively. The factors affecting the variations in these data are discussed. The enantioselectivity of substituted βCDs 6 [superscript]A -[bis (carboxylatomethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDidaH₂) and (2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -[bis(carboxylatomethyl)amino]-3[superscript]A -deoxy-β-cyclodextrin (3βCDidaH₂) and 6 [superscript]A -[tris(carboxylatomethyl)(2- aminoethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDedtaH₃) and their Eu³ ⁺ complexes in forming host-guest complexes with six enantiomeric guests in D₂O was studied by 1D and 2D ¹H NMR (600 MHz) spectroscopy. The guests are D/L-tryptophanate (Trp⁻), 4-hydroxyl-D/L-phenylglycinate (4HOPhg⁻), D/L-histidinate (His⁻), D/L-pheniramine (Phm), D/L-phenylglycinate (Phg⁻) and (D/L)-β-phenylserinate (βPhs⁻). Enantioselective host-guest complexation was observed between the [Eu(6βCDida)]⁺ , [Eu(3βCDida)]⁺ and [Eu(6βCDedta)] complexes and Trp⁻, [Eu(6βCDida)]⁺ and [Eu(3βCDida)]⁺ and 4HOPhg⁻, and βCD, 6βCDida²⁻, 3βCDida²⁻, 6βCDedta³⁻ and the Eu³⁺complexes of the three substituted βCDs and Phm. The His⁻, Phg⁻ and βPhs⁻ enantiomers showed no evidence for selective host-guest complexation. The preparation of 3βCDidaH₂ and 6βCDedtaH₃ and the determination of their pK[subscript]a s are also reported. In collaboration with the research group of Prof. Matthew A. Tarr, (University of New Orleans, USA), the 6βCDida²⁻ and the 6βCDedta³⁻ has been utilized to improve Fenton oxidation of aromatic pollutants. To further support to this work, the binary complexation of Fe² ⁺ by 6βCDida²⁻ has been studied by potentiometric titrations. A series of six modified poly(acrylic acid)s 3% substituted with either βCD or the adamantyl moiety with different length of substituent chain was synthesised. To advance the understanding and control of aqueous supramolecular assembly, the host-guest interactions between the βCD substituted poly(acrylic acid)s and adamantane-1-carboxylic; adamantyl substituted poly(acrylic acid)s with βCD and linked βCD dimers; and between both βCD and adamantyl substituted poly(acrylic acid)s have been studied. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1311237 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

A series of five linked β-cyclodextrin (βCD) dimers N,N-bis(6 [superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-succinamide, 66βCD₂su, N-((2[superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A-deoxy-6 [superscript]A -β-cyclodextrinyl)-urea, 36βCD₂su, N,N-bis((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -deoxy-3 [superscript]A-β-cyclodextrinyl)-succinamide, 33βCD₂su, N,N-bis(6[superscript]A-deoxy-6[superscript]A-β-cyclodextrinyl)-urea, 66βCD₂ur, and N-((2 [superscript]A S,3 [superscript]A S)-3 [superscript]A-deoxy-3 [superscript]A-β-cyclodextrinyl)-N’-(6 [superscript]A -deoxy-6 [superscript]A -β-cyclodextrinyl)urea, 36βCD₂ur, has been prepared. The complexation of 6-(4’-(toluidinyl)naphthalene-2-sulphonate, TNS⁻, by βCD and the five linked βCD dimers was characterized by UV, fluorescence and 2D ¹H ROESY NMR spectroscopy. In aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K, TNS⁻ forms host-guest complexes with βCD of stoichiometry βCD.TNS⁻ (K₁ = 3020 and 3320 dm³ mol⁻¹) and βCD₂.TNS⁻ (K₂ = 57 and 11 dm³ mol⁻¹) where the first and second values were determined in UV and fluorescence studies, respectively. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur, the analogous K₁ = 16100, 10900, 10700, 55100 and 18300 dm³ mol⁻¹ and K₁ = 12500, 8700, 9600, 38000 and 9800 dm³ mol⁻¹(fluorimetric studies), respectively. ¹H 2D ROESY NMR studies provided evidence for variation of the mode of complexation of the TNS⁻ guest as the βCD host is changed. The factors affecting complexation are discussed. UV and ¹H NMR studies showed that 6-(4’-(t-butyl)-phenyl)naphthalene-2-sulphonate, BNS⁻, and its dimer, (BNS⁻)₂, form host-guest complexes with βCD of the stoichiometry βCD.BNS⁻ (K₁ = 5.54 × 10⁴ dm³ mol⁻¹ ) and βCD.BNS₂ ²⁻(K₂ = 3.07 × 10² dm³ mol⁻¹ ) where the complexation constant K₁ = [βCD.BNS⁻]/([βCD][BNS⁻] and K₂ = [βCD.(BNS⁻)₂]/([βCD.BNS⁻][BNS⁻]) in aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm⁻³ and 298.2 K. For 66βCD₂su, 36βCD₂su, 33βCD₂su, 66βCD₂ur and 36βCD₂ur the analogous K₁ = 125, 74, 10.2, 364 and 16.1 (× 10⁴ dm³ mol⁻¹ ) and K₂ = 25.7, 2.30, 2.57, 17.6 and 17.2 (× 10² dm³ mol⁻¹ ), respectively. For the dimerisation of BNS⁻ K[subscript]d = 2.63 × 10² dm³ mol⁻¹ . Fluorimetric studies showed that the complexation stability for βCD.BNS⁻, forms βCD. BNS⁻, 66βCD₂su.BNS⁻, 36βCD₂su.BNS⁻, 33βCD₂su. BNS⁻, 66βCD₂ur.BNS⁻ and 36βCD₂ur. BNS⁻ characterized by K₁ = 4.67, 330, 101, 11.0, 435 and 29.6 (× 10⁴ dm³ mol⁻¹ ), respectively. The factors affecting the variations in these data are discussed. The enantioselectivity of substituted βCDs 6 [superscript]A -[bis (carboxylatomethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDidaH₂) and (2 [superscript]A S,3 [superscript]A S)-3 [superscript]A -[bis(carboxylatomethyl)amino]-3[superscript]A -deoxy-β-cyclodextrin (3βCDidaH₂) and 6 [superscript]A -[tris(carboxylatomethyl)(2- aminoethyl)amino]-6 [superscript]A -deoxy-β-cyclodextrin (6βCDedtaH₃) and their Eu³ ⁺ complexes in forming host-guest complexes with six enantiomeric guests in D₂O was studied by 1D and 2D ¹H NMR (600 MHz) spectroscopy. The guests are D/L-tryptophanate (Trp⁻), 4-hydroxyl-D/L-phenylglycinate (4HOPhg⁻), D/L-histidinate (His⁻), D/L-pheniramine (Phm), D/L-phenylglycinate (Phg⁻) and (D/L)-β-phenylserinate (βPhs⁻). Enantioselective host-guest complexation was observed between the [Eu(6βCDida)]⁺ , [Eu(3βCDida)]⁺ and [Eu(6βCDedta)] complexes and Trp⁻, [Eu(6βCDida)]⁺ and [Eu(3βCDida)]⁺ and 4HOPhg⁻, and βCD, 6βCDida²⁻, 3βCDida²⁻, 6βCDedta³⁻ and the Eu³⁺complexes of the three substituted βCDs and Phm. The His⁻, Phg⁻ and βPhs⁻ enantiomers showed no evidence for selective host-guest complexation. The preparation of 3βCDidaH₂ and 6βCDedtaH₃ and the determination of their pK[subscript]a s are also reported. In collaboration with the research group of Prof. Matthew A. Tarr, (University of New Orleans, USA), the 6βCDida²⁻ and the 6βCDedta³⁻ has been utilized to improve Fenton oxidation of aromatic pollutants. To further support to this work, the binary complexation of Fe² ⁺ by 6βCDida²⁻ has been studied by potentiometric titrations. A series of six modified poly(acrylic acid)s 3% substituted with either βCD or the adamantyl moiety with different length of substituent chain was synthesised. To advance the understanding and control of aqueous supramolecular assembly, the host-guest interactions between the βCD substituted poly(acrylic acid)s and adamantane-1-carboxylic; adamantyl substituted poly(acrylic acid)s with βCD and linked βCD dimers; and between both βCD and adamantyl substituted poly(acrylic acid)s have been studied. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1311237 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Made available in DSpace on 2014-06-11T19:26:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-05-04Bitstream added on 2014-06-13T19:33:34Z : No. of bitstreams: 1 lima_aa_me_rcla.pdf: 3417647 bytes, checksum: fb16521eccec72d4c2efba2f0b35b489 (MD5) / Devido principalmente ao aumento populacional que tem ocorrido nos últimos anos, a demanda de água para o abastecimento público na região noroeste do Estado de São Paulo tem sido cada vez maior. No município de São José do Rio Preto (SP), o abastecimento de água tem sido realizado por meio da captação do rio Preto e afluentes e por poços existentes tanto no Sistema Aqüífero Bauru como no Botucatu/Pirambóia (Aqüífero Guarani). A água subterrânea responde por 70% do abastecimento local, sendo o Aqüífero Bauru o mais requisitado em virtude das boas condições que este apresenta como reservatório de água e também pela facilidade construtiva e operacional do poço tubular. A super explotação do aqüífero em questão se mostra cada vez mais acentuada, exigindo mais controle para sua exploração. O objetivo desta pesquisa foi avaliar alguns dos principais parâmetros hidráulicos, caracterizar o comportamento do fluxo subterrâneo e suas propriedades, propor condições necessárias para a construção de poços tubulares para captação de água subterrânea no Aqüífero Bauru, enfatizando a proteção sanitária, e, dessa forma, sugerir medidas adequadas para o gerenciamento dos recursos hídricos, como também para o auxílio ao Plano Diretor do município. Na análise conjunta dos parâmetros, importantes observações foram feitas a respeito da vulnerabilidade à contaminação do Aqüífero, servindo esta pesquisa não somente como uma referência para a análise de alguns parâmetros hidrogeológicos na área de estudo, mas também como apoio às medidas preventivas a serem praticadas por empreendimentos que podem, de forma direta ou indireta, estar interferindo na qualidade da água subterrânea do município de São José do Rio Preto (SP) / The population growth that has taken place in recent years has been the main reason for the increasing demand for water for public supply in the northwestern region of the state of São Paulo, Brazil. In the municipality of São José do Rio Preto, the water supply has drawn from the catchment of the Preto river and its tributaries, as well as from wells in the Bauru Aquifer and in the Botucatu/Pirambóia Aquifer (Guarani Aquifer). Ground water accounts for 70 percent of the local supply, with the Bauru Aquifer being the most resorted to due to its great capability as a water reservoir and the favorable conditions for building and operating a tube well. This aquifer has been increasingly over-exploited, and this situation requires tighter controls of its exploration. This study aimed at evaluating some key hydraulic parameters, describing the behavior of the underground flow and its properties, setting forth the required conditions for the construction of a tube well to catch underground water from the Bauru Aquifer with an emphasis on sanitary protection, and, therefore, suggesting appropriate measures for water resource management, as well as for supporting the municipality s Plano Diretor (Master Plan). The overall analysis of the parameters includes important observations on the aquifer s vulnerability to contamination. In this sense, this paper not only constitutes a reference work for the analysis of certain hydrogeological parameters in this field of study, but also supports preventive measures to be implemented by any agents that might be affecting, directly or indirectly, the quality of the underground water in the municipality of São José do Rio Preto.

Orientador: Antonio Celso de Oliveira Braga / Banca: Daniel Marcos Bonotto / Banca: José Domingos Faraco Gallas / Resumo: Devido principalmente ao aumento populacional que tem ocorrido nos últimos anos, a demanda de água para o abastecimento público na região noroeste do Estado de São Paulo tem sido cada vez maior. No município de São José do Rio Preto (SP), o abastecimento de água tem sido realizado por meio da captação do rio Preto e afluentes e por poços existentes tanto no Sistema Aqüífero Bauru como no Botucatu/Pirambóia (Aqüífero Guarani). A água subterrânea responde por 70% do abastecimento local, sendo o Aqüífero Bauru o mais requisitado em virtude das boas condições que este apresenta como reservatório de água e também pela facilidade construtiva e operacional do poço tubular. A super explotação do aqüífero em questão se mostra cada vez mais acentuada, exigindo mais controle para sua exploração. O objetivo desta pesquisa foi avaliar alguns dos principais parâmetros hidráulicos, caracterizar o comportamento do fluxo subterrâneo e suas propriedades, propor condições necessárias para a construção de poços tubulares para captação de água subterrânea no Aqüífero Bauru, enfatizando a proteção sanitária, e, dessa forma, sugerir medidas adequadas para o gerenciamento dos recursos hídricos, como também para o auxílio ao Plano Diretor do município. Na análise conjunta dos parâmetros, importantes observações foram feitas a respeito da vulnerabilidade à contaminação do Aqüífero, servindo esta pesquisa não somente como uma referência para a análise de alguns parâmetros hidrogeológicos na área de estudo, mas também como apoio às medidas preventivas a serem praticadas por empreendimentos que podem, de forma direta ou indireta, estar interferindo na qualidade da água subterrânea do município de São José do Rio Preto (SP) / Abstract: The population growth that has taken place in recent years has been the main reason for the increasing demand for water for public supply in the northwestern region of the state of São Paulo, Brazil. In the municipality of São José do Rio Preto, the water supply has drawn from the catchment of the Preto river and its tributaries, as well as from wells in the Bauru Aquifer and in the Botucatu/Pirambóia Aquifer (Guarani Aquifer). Ground water accounts for 70 percent of the local supply, with the Bauru Aquifer being the most resorted to due to its great capability as a water reservoir and the favorable conditions for building and operating a tube well. This aquifer has been increasingly over-exploited, and this situation requires tighter controls of its exploration. This study aimed at evaluating some key hydraulic parameters, describing the behavior of the underground flow and its properties, setting forth the required conditions for the construction of a tube well to catch underground water from the Bauru Aquifer with an emphasis on sanitary protection, and, therefore, suggesting appropriate measures for water resource management, as well as for supporting the municipality’s Plano Diretor (Master Plan). The overall analysis of the parameters includes important observations on the aquifer’s vulnerability to contamination. In this sense, this paper not only constitutes a reference work for the analysis of certain hydrogeological parameters in this field of study, but also supports preventive measures to be implemented by any agents that might be affecting, directly or indirectly, the quality of the underground water in the municipality of São José do Rio Preto. / Mestre

Ao longo dos anos a medicina vem se desenvolvendo rapidamente e junto com ela desenvolvem-se os métodos e processos de diagnósticos. Estes métodos ficam mais rápidos, precisos e cada vez menos invasivos graças ao desenvolvimento de dispositivos diagnósticos a cada dia menores e que produzam respostas confiáveis. Os biossensores são, sem dúvida, os grandes responsáveis pela miniaturização, barateamento e rapidez de diversos métodos diagnósticos e procedimentos clínicos utilizados diariamente. Dentre os diferentes tipos de biossensores existentes, destacamos os biossensores embasados em transistores de efeito de campo (FETs), mais precisamente os biossensores a base de transistor de efeito de campo de porta estendida (EGFET). Analisamos nesse trabalho os procedimentos de medida utilizando filmes finos de óxido de estanho dopados com flúor (FTO) como membrana sensível a íons H+ acoplados à porta de um EGFET, que podem servir de base para a construção de um biossensor no futuro. Já existem artigos na literatura atual que fazem uso de FTO como membrana sensível a íons H+ e OH-. Entretanto, nenhum dos artigos disponíveis faz um bom controle de alguns parâmetros, em alguns casos relativamente simples, ou se fazem não deixam claro de que maneira estão controlando esses parâmetros. Tais parâmetros são de fundamental importância na resposta final dos sensores uma vez que eles interferem significativamente no sinal dos mesmos. Mostramos no presente trabalho que parâmetros como a luz, a sequência em que os pHs são medidos pela amostra, o procedimento de limpeza das amostras e até as características morfológicas das amostras são importantes no processo de adsorção e retirada de íons da superfície da membrana. Mostramos também que cada amostra necessita uma rotina diferente quanto à sequência de medidas e até mesmo procedimentos de limpeza para que seu rendimento seja máximo, e como diferentes amostras evoluem ao longo do tempo. Como solução aos problemas citados, descrevemos o uso correto de duas amostras que apresentaram reprodutibilidade em seus dados e invariância entre os resultados coletados por diferentes sequências de medidas. Por fim, deixamos uma proposta sobre a dinâmica que ocorre durante os processos de adsorção e retirada de íons H+ e OH- na superfície dos filmes. Com base em nossa proposta fizemos cálculos teóricos estimados da quantidade de cargas que são adsorvidas na superfície do filme para as diferentes situações encontradas durante os experimentos. / Over the years the medicine has been developing rapidly and along with it develop methods and diagnostic procedures. These methods become faster, more accurate and less invasive thanks to the development of diagnostic devices each day minors and producing reliable answers. The biosensors are undoubtedly the major responsible for miniaturization, cheaper and rapidity of various diagnostic methods and clinical procedures used every day. Among the different types of existing biosensors, we highlight the biosensors grounded in field effect transistors (FETs), more precisely the biosensor based in extended gate field effect transistor (EGFET). We analyzed on this work measurement procedures using tin oxide thin films doped with fluorine (or fluorine tin oxide FTO) as sensitive the membrane to H+ ions bounded to the gate of an EGFET, which can serve as a basis for building a biosensor in the future. Articles has already been written reporting the use of the FTO as sensitive membrane to ion H+ and OH-. However, none article available makes a good control of some parameters, in some cases relatively simple, or if they do not make it clear the way they are controlling these parameters. These parameters are of crucial importance in the final response of the sensors since they interfere significantly in signal of the sensors. So, we shown in this work, which parameters as light, the sequence in which the pHs are measured by the sample, the cleaning procedure of samples and even the morphological characteristics of the samples are important in the process of adsorption and ion withdrawal of membrane surface. We shown also that each sample requires a different routine on the following measures and even cleaning procedures for your maximum income is, and how different samples evolve over time. As a solution to the problems cited, we describe the correct use of two samples that showed reproducibility in your data and invariance between the results collected by different sequences of measures. Finally, we leave a proposal on the dynamics that occurs during adsorption processes and withdrawal ion H+ and OH- on the surface of the films. Based on our proposal did theoretical calculations estimated quantity of loads that are adsorb on the surface of the film for the different situations encountered during experiments.