Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-01-26Bitstream added on 2014-06-13T19:12:22Z : No. of bitstreams: 1 sa_ac_me_ilha.pdf: 1061286 bytes, checksum: b370fdf160f4689709efe584af803c2a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo deste trabalho esta resumido através de três etapas. 1 - A primeira etapa consistiu em funcionalizar e caracterizar a sílica gel com grupos 3- aminopropiltrietoxisilano. Nesta etapa o material obtido (Si) foi caracterizado por técnicas de Ressonância Magnética Nuclear no estado sólido (24Si e 13C) e espectroscopia vibracional (FTIR). 2- Numa segunda etapa promoveu-se a adsorção de íons de cobre (II) e de cobalto (II) na superfície da sílica (Si). Os materiais obtidos (SiCu e SiCo) foram caracterizados por espectroscopia vibracional e voltametria cíclica. 3- Na terceira etapa reagiu-se os materiais preparados (SiCu e SiCo) com nitroprussiato de sódio para formar os complexos binucleares (SiCuNP e SiCoNP). Estes materiais também foram caracterizados por espectroscopia vibracional e voltametria cíclica. Estes materiais foram utilizados na construção do eletrodo de pasta de grafite e testados na oxidação eletrocatalítica de substâncias biologicamente importantes tais como a hidrazina e N-acetilcisteína sendo empregado para isto a técnica de voltametria cíclica. Observou-se que o eletrodo de SiCuNP apresentam dois pares redox nos potenciais (Em)1 = 0,34 V e (Em)2 = 0,76 V vs Ag/AgCl, O primeiro foi atribuído ao processo de oxidação do par Cu(I)/Cu(II) e o segundo ao processo de oxidação Fe(II)(CN)5NO / Fe(III)(CN)5NO do complexo binuclear. O sistema SiCoNP foram observados dois pares redox distintos com os seguintes potenciais médios (Em); (Em)1 = 0,29 V e (Em)2 = 0,56 V vs Ag/AgCl, o primeiro foi atribuído ao processo redox do par Co(II)/Co(III) e o segundo ao processo redox Fe(II)(CN)5NO / Fe(III)(CN)5NO do complexo binuclear formado. O sistema SiCuNP foi sensível a concentração de hidrazina apresentando um limite de detecção e sensibilidade amperométrica de 3,07×10-4 mol L-1 e 5,84×10-6 A / mol L-1... / The objective of this work is summarized in three stages. 1 - The first stage functionalizes and characterizes the silica gel with 3-aminopropyltriethoxysilane groups. At this stage the material obtained (Si) was characterized by solid state Nuclear Magnetic Resonance techniques (24Si and 13C) and vibrational spectroscopy (FTIR). 2 - The second stage promotes the adsorption of copper (II) and cobalt (II) ions on the surface of the silica (Si). The materials obtained (SiCu and SiCo) were characterized by vibrational spectroscopy and cyclic voltammetry. 3 - The third stage prepares the reaction of the materials (SiCu and SiCo) with sodium nitroprusside to form the binuclear complex (SiCuNP and SiCoNP). These materials were characterized by vibrational spectroscopy and cyclic voltammetry. These materials were used to construct the electrode carbon paste and were tested for electrocatalytic oxidation of biologically important substances such as hydrazine and N-acetylcysteine using the cyclic voltammetry technique. It was observed that the electrode SiCuNP has two redox pairs in the potential (Em)1 = 0.34 V and (Em)2 = 0.76 V vs. Ag/AgCl, the first was attributed to the oxidation process of the pair Cu(I)/Cu(II) and the second to the oxidation process Fe(II)(CN)5NO / Fe(III)(CN)5NO of the binuclear complex. For the SiCoNP system, two distinct redox couples were observed with the following mean potentials (Em); (Em)1 = 0.29 V and (Em)2 = 0.56 V vs Ag/AgCl, the first one was assigned to the redox process of the Co(II)/Co(III) pair and the second one to the redox process Fe(II)(CN)5NO / Fe(III)(CN)5NO of the binuclear complex formed. The SiCuNP system was sensitive to the hydrazine concentration, exhibiting a detection limit and amperometric sensitivity of 3.07×10-4 mol L-1 and 5.84×10-6 A / mol L-1 respectively and was also... (Summary complete electronic access click below)

The main objective of this Diploma Thesis is studying the possibility of detection of nitro derivatives of aromatic hydrocarbons by using chemically modified working electrodes in electrochemical analysis. Compounds analyzed in this work were 1-nitronaphthalene and 6- nitrochrysene - these compounds were chosen on previous experience with surface modified working electrodes (the chemical/physical properties of these substances). All the analyses were performed by using differential pulse voltammetry (DPV) on hanging mercury drop electrode (HMDE) in classic three-electrode system. The original premise of chemical modification of electrode surface is the change of its selectivity towards different compounds - meaning the change of the electrochemical response. The modification agent used in this thesis is 1-octanethiol. Its thiol group offers great potential of strong interaction with the metal surface of the mercury electrode. Voltammetric responses of both compounds were recorded in acidic, neutral and basic solutions (pH=2, pH=7, pH=12) including the responses when the electrode surface was modified. Next objective was the optimization of the modification procedure itself (transferring of the mercury drop from one media to another without damaging or tearing it off from the capillary orifice)....

Magistrinio darbo tikslas yra sukurti kompiuterinį amperometrinio biojutiklio su chemiškai modifikuotu elektrodu modelį ir ištirti jo savybes. Modelis papildo egzistuojančius modelius mediatoriaus sluoksniu. Mediatoriaus koncentracija sluoksnyje nėra konstanta, tirpsta biojutiklio veikimo eigoje. Darbe apžvelgiama medžiaga apie amperometrinius biojutiklius, biojutiklio modeliavimo aspektus, mediatoriaus tirpimo priežastis ir veikimo principus. Vėliau suformuluojamas pasirinkto biojutiklio matematinis modelis. Matematiniame modelyje pateikiamos diferencialinės lygtys su dalinėmis išvestinėmis, aprašančios biojutiklyje vykstančias reakcijas ir difuzijas. Pagal matematinį modelį yra sudaromas skaitinis modelis. Pagal žinomus analizinius sprendimus modelis yra ratifikuojamas. Remiantis skaitiniu modeliu buvo sukurta programinė įranga įgyvendinanti diferencialinių lygčių su dalinėmis išvestinėmis sprendimo metodą (išreikštinę baigtinių skirtumų schemą) ir simuliuojanti biojutiklio veikimą. Programinė įranga yra karkasas, leidžiantis nagrinėti sumodeliuoto biojutiklio savybes bei charakteristikas. Buvo ištirtos substrato ir mediatoriaus koncentracijų, mediatoriaus, fermento, difuzijos sluoksnių, bei mediatoriaus sluoksnio difuzijos koeficiento įtakos biojutiklio generuojamos srovės tankiui. Be to gauti dviejų modelių palyginimo rezultatai parodė sumodeliuoto biojutiklio modelio skirtumus ir panaudojimo prasmingumą. / The aim of master thesis is to model amperometric biosensor with chemically modified electrode, introducing into existing model one more additional mediator layer. Mediator concentration inside the layer is changing during the biosensor action. Master thesis content consists of: enzyme kinetics introduction, biosensor modeling peculiarities exploration, chemically modified electrode information, biosensor action aspects description. Following chapter concentrates on mathematical modeling of particular biosensor type. Mathematical model represents differential equations with partial derivatives describing the reactions and diffusion inside biosensor. Next, numerical model is formulated. The explicit method technique was used. Based on numerical model software was made and validated. Using software the biosensor action was simulated in order to investigate biosensor properties and characteristics. In this work several properties were analyzed: impact of substrate and mediator concentrations, size of mediator, enzyme and diffusion layers, mediator layer diffusion coefficient on biosensor response. This model was compared with previous introduced model and it was shown that there is some difference between them and there is a reason to use new model.