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This study investigates a way to characterize the geology and biology of the seafloor in two Marine Protected Areas on the West Florida Shelf. Characterization of benthic habitats needs to include sufficient detail to represent the complex and heterogeneous bottom types. Characterizations can be interpreted from multiple data sets and displayed as benthic habitat maps. Multibeam sonar bathymetry and backscatter provide full spatial data coverage, but interpretation of such data requires some form of ground truth (to characterize the habitat). Imagery from towed underwater video provides continuous transects of seafloor data, which provide a more efficient method than data from sediment grabs, stationary cameras, or video from slow-moving remotely-operated vehicles while a ship is on station. Two Marine Protected Areas, Steamboat Lumps and Madison-Swanson, were previously mapped by the USGS using a 95 kHz multibeam sonar system. Researchers at the University of South Florida, using a 300 kHz high-resolution multibeam sonar in 2002 and a 400 kHz high-resolution multibeam sonar in 2016, filled in the northeast triangular portion of Madison-Swanson. Bathymetry and backscatter data were compared to towed underwater-video observations. A modified version of the Coastal and Marine Ecological Classification Standard (CMECS), utilizing a scale-based hierarchy, was used for habitat characterization of video images. Identifiers from the geoform and substrate components of CMECS, as well as substrate-influencing biologic components, were characterized using still images at 15-second intervals from towed underwater video collected using the Camera-Based Assessment Survey System (C-BASS). These characterizations were then georeferenced (located in three-dimensional space) for comparison with bathymetry and backscatter data. In Steamboat Lumps, eight substrate variations were identified from video, while in Madison-Swanson 27 substrate variations were identified, including many combinations of hard and soft substrate types. Four new hard-bottom textures are identified from video in Madison-Swanson: exposed high-relief, moderate-relief, and low-relief hard bottom, as well as covered low-relief hard bottom identified by the presence of attached biota. Hard- and mixed-bottom substrate types identified from video are more heterogeneous than can be resolved from 95 kHz Kongsberg EM 1002 multibeam sonar bathymetry and beam-averaged backscatter. However, in soft bottom areas, more changes are evident in beam-averaged backscatter than are visible in video, though this may be attributed to changes in sonar settings. This does not appear to be the case with high-resolution and ultra-high resolution multibeam sonars, such as the 300 kHz Kongsberg EM 3000 and the 400 kHz Reson SeaBat 7125, which can use time-series rather than beam-averaged backscatter. Analyses of the multibeam bathymetry data indicate that 94.5% of Steamboat Lumps is “flat” (slope < 5°) versus “sloping” for the remaining area (5° < slope < 30°). Only 87% of Madison-Swanson is “flat” versus “sloping”. Both marine protected areas have very low rugosity, i.e., the surface of the seafloor is nearly planar.

This study investigated a CNF/dendrimer hydrogel and how different concentrations of the carboxylated CNF and bis-MPA ammonium dendrimer affected the hydrogels’ rheological properties. A third generation bis-MPA ammonium dendrimer was diffused into a dispersion of carboxylated cellulose nanofibrils. The CNF was carboxylated by TEMPO-oxidation and phosphate buffer deprotonating the carboxylic group. The ammonium dendrimers are cationic and, when added to the dispersion, act as a salt together with the CNF-carboxy anion creating a cationic dendrimer salt bridge. These will serve as physical crosslinks, and a CNF/dendrimer network is formed; the structure and the absorbed water make a hydrogel. Amplitude strain sweeps were performed with a rheometer to determine the gels' elastic capabilities in terms of storage modulus, G’ and loss modulus, G” as the function of the shear stress. The result shows that a higher concentration of both CNF dispersion and dendrimer yielded a higher value of the storage modulus and a lower critical strain, meaning that the hydrogel becomes firmer and less elastic. / I denna studie undersöktes en CNF/dendrimer hydrogel och hur olika koncentrationer av den karboxylerade CNF och bis-MPA ammonium dendrimer påverkar hydrogelens reologiska egenskaper. En tredje generations bis-MPA ammonium dendrimer läts diffusera i en dispersion av karboxylerade cellulosa nanofibriller (CNF). CNF karboxylerades via TEMPO-oxidation, varefter en fosfatbuffer adderades för att skapa en anjon. Dendrimerens ammoniumgrupper är katjoner och då den adderas till dispersionen kommer den agera som ett salt tillsammans med CNF-karboxyanjonen vilket skapar en katjonisk dendrimersaltbrygga. Denna agerar som en fysisk tvärbindning och skapar ett nätverk av CNF och dendrimer. Nätverket skapar tillsammans med det absorberade vattnet en hydrogel.  En amplitude strain sweep utfördes för att bestämma gelernas viskoelastiska förmåga, från mätningarna fås elasticitetsmodulen, G’ och den viskösa modulen, G’’ som funktioner av skjuvningen. Resultatet visar att en högre koncentration av CNF-dispersionen och dendrimeren leder till ett högre värde på elasticitetsmodulen samt ett lägre värde för den kritiska skjuvningen. Detta innebär att hydrogelen blir hårdare och mindre elastisk.

COMPARISONS OF FISH SPECIES INSIDE AND OUTSIDE OF MARINE PROTECTED AREAS OFF THE SOUTH CENTRAL COAST OF CALIFORNIA David E. Rasmussen From 2004-2008 and 2008-2009 Cal Poly University researchers conducted two separate tag and recapture studies of nearshore fish populations along California’s central coast. Three locations were sampled that have experienced different degrees of fishing pressure. Big Creek MPA has been closed to all fishing from 1993 onwards and is the farthest from port of all locations. Cambria lies closest to port of the three locations and because of this has the highest fishing pressure. Piedras Blancas lies midway between Cambria and Big Creek. Portions of Cambria and Piedras Blancas were designated as MPAs in 2007. Sampling protocols of these two different studies differed in bait used and size of commercial fish trap. An experiment was conducted to simultaneously compare the different trapping and baiting protocols from the prior studies to find a conversion factor that related catch per unit effort (CPUE), length frequency distributions and captured fish diversity between the two studies, thus providing a means to connect the two data sets for stock assessments and baseline MPA monitoring. Our sampling showed no significant difference in mean fish length or diversity between the two protocols for the five most common nearshore fish species captured, and three of the five species showed no significant difference in CPUE. Cabezon (Scorpaenichthys marmoratus), showed a significantly lower CPUE (50.5%) using the MLPA monitoring protocols compared to the commercial fishing protocol and black and yellow rockfish (Sebastes chrysomelas) had a significantly higher CPUE (310%) using the MLPA monitoring protocol. These findings provide a means of maintaining data continuity across the entire sample region and inclusion of earlier projects in the analyses of nearshore fish populations of the region. With the linkage of these two studies we provide important baseline data for the Cambria MPA from before it was established in 2007. Fish populations were compared on a year-to-year basis within each location, and between the different locations. I found several main factors helped to explain differences in size and abundance across time within individual locations, and across the three locations. These factors were inherent differences in habitat, establishment of MPAs, and changes in fishing pressure and post-larval recruitment. Cabezon were largest within Big Creek, followed by Piedras Blancas and Cambria which held the smallest fish, suggesting that fishing pressure is influencing fish size. However, cabezon were more abundant at Cambria than either other location suggesting that location is influencing abundance. Within Cambria, we are seeing an MPA effect with abundance within the MPA staying stable while the reference site is declining. Gopher rockfish (Sebastes carnatus) and black and yellow rockfish had similar trends with size and abundance between locations. Big Creek and Piedras Blancas held the largest fish, while Cambria was smaller. Both rockfish species were most abundant at Big Creek, followed by Cambria then Piedras Blancas. Size for these species is likely influenced by fishing pressure, and abundance is likely influenced by both fishing pressure and location. Both species increased in abundance 2004-2009 at Cambria, and this could be due to improved levels of post-larval recruitment. There is also a possible MPA effect for gopher rockfish at Cambria with a near significant divergence in size of fish between the MPA and reference site. Kelp greenling (Hexagrammos decagrammus) were similar in size and abundance between all sampling locations. There is a possible MPA effect at Cambria, with a significantly higher abundance than the reference site; however this difference predates the MPA’s establishment but could have been exacerbated by it. Lingcod (Ophiodon elongatus) size did not vary significantly between sites, but they were the most abundant at Cambria, followed by Piedras Blancas, then Big Creek, suggesting that habitat is influencing abundance. There was also a possible MPA effect on abundance of lingcod at Cambria with the MPA having a significantly higher abundance than the reference site. Similarly to the kelp greenling, these differences predated the MPA, but could have been exacerbated by its establishment, and abundance within the MPA has stayed stable, while the reference site was declining. Big Creek and Piedras Blancas have similar Shannon-Weiner diversity values, while Cambria has significantly lower. However, after MPA establishment at Cambria, the MPA has attained significantly higher diversity levels than the reference site. Over the short period of time that the Piedras Blancas and Cambria MPA have been established the populations within them have changed. However, there are no discernable trends in size, abundance and diversity between the MPA and reference sites at both locations. It is likely that with these slower growing, long-lived fish species that it will take more years for differences between the sites to manifest themselves.

The singing voice is a highly personal instrument which occasionally may harvest feelings of MPA (music performance anxiety) and low self-efficacy among singing pupils. This qualitative study investigates pupil-teacher relationships and teachers' handling of MPA and self-efficacy from a pupil’s perspective implemented through semi-structured interviews. The study is permeated by a relational perspective focused on relational competence. Results obtained show that pupils describe the majority of pupil-teacher relationships as good and secure. A dauntless relationship is incused by trust and openness which is obtained through the teachers' ability to listen, show compassion, establish a forgiving atmosphere, attach to and treat the pupil with kindness and respect. The results show the importance of the teachers ability to communicate, read and differentiate relative to the pupil. Concerning MPA the results indicate the importance of teachers' ability to interact with the pupil in a communicative way through compassion, understanding and guidance. Furthermore the results emphasize teachers' ability to adjust the teaching according to individuals and the situation in relational practices. / Sång är ett högst personligt instrument vilket emellanåt kan generera känslor av prestationsångest, även kallat MPA (music performance anxiety), och problematik gällande självtilltro hos sångelever. I denna kvalitativa studie undersöks elev-lärarrelationer samt lärares hantering av prestationsångest och självtilltro ur ett elevperspektiv genom semistrukturerade intervjuer. Undersökningen genomsyras av ett relationellt perspektiv med fokus på lärares relationskompetens. Resultatet visar att elever upplever majoriteten elev- lärarrelationer goda och trygga. En trygg relation präglas av tillit och öppenhet vilket skapas utifrån lärarens förmåga att lyssna, förstå, skapa en tillåtande atmosfär, anknyta till samt bemöta eleven på ett trevligt och respektfullt vis. Samtliga erhållna resultat präglas av lärarens förmåga att kommunicera, läsa av samt förhålla sig till eleven med en adekvat nivå av närhet och distans. Gällande hantering av prestationsångest visar resultatet vikten av lärares förmåga att bemöta eleven både kommunikativt och inkännande, visa förståelse samt vägleda. Vidare understryker resultatet vikten av lärares förmåga att anpassa undervisningen efter individ och undervisningssituation i relationell praktik.

The objective of this research was to develop and validate new macromolecular imaging agents to detect and characterize malignant tumours. Using well-defined, highly branched macromolecules called dendrimers as the structural scaffold, efficient functionalization of the periphery was demonstrated using “click” chemistry in order to prepare multivalent imaging probes. Furthermore, a transmetalation was demonstrated to displace chelated copper with technetium, enabling “click” reactions to be performed in the presence of the dipicolylamine (DPA), a ligand known to chelate many metals. The dendritic scaffold was functionalized with either hydrophobic or hydrophilic targeting vectors. The hydrophobic ligand, an acyloxymethyl ketone targeting the overexpression of cathepsin B exhibited poor in vitro affinity when coupled to either G1 or G2 dendrimers, despite the use of various linkers. A glu-urea-lys dipeptide, representing a hydrophilic prostate specific membrane antigen targeting vector, demonstrated excellent affinity in vitro. The lead compound, a G2 dendrimer bearing four PSMA targeting vectors attached via an alkyl spacer was further investigated in vitro and in vivo. Unfortunately, poor tumor uptake was observed and the compound was hypothesized to hydrolyze readily (<15min), based on the in vitro plasma stability data. To rectify the aforementioned problem, non neo-pentyl esters were replaced with either carbamate or ether linkages. In vitro plasma stability analysis of the analogous compounds demonstrated increased stability. In particular, the ether analogue was found to be most stable, with minimal degradation observed after 4 hours. / Thesis / Doctor of Philosophy (PhD)

The Enhanced Permeability and Retention (EPR) effect has seen considerable exploration by many researchers since it’s discovery by Maeda et al in 1985. Polymers and nanoparticles with a long blood residence half-life can accumulate in some tumour tissues, allowing for the delivery of either diagnostic or therapeutic payloads. We have contributed to this field by the development of methodology to prepare radiolabeled dendrimers which are suitable for EPR effect accumulation with a variety of peripheral functionalities. The first of these was a 99mTc-labeled fifth generation dendron which was peripherally functionalized with low molecular weight poly(ethylene glycol) chains, which was observed to accumulate in xenograft mouse tumours over the course of 6 hours. This work led to the development of improved synthetic means for the preparation of high generation dendrimers with complex peripheral functionality, which hinged on the use of the Strain Promoted Alkyne-Azide Cycloaddition reaction to give high generation dendrimers by a convergent approach. This resulted in the facile preparation of dendrimers with challenging peripheral functionality in reaction times as short as 5 minutes. This SPAAC based convergent synthesis approach was used to prepare 99mTc labeled sulfobetaine and carboxybetaine dendrons of the sixth generation, and these compounds were found to have a size greater than the renal clearance threshold of ~ 5 nm, though it was found that labeling with [99mTc(CO)3]+ was not possible without extensive degradation of the zwitterionic dendrimers. Finally, the dendritic architecture explored for imaging was adapted for use in shielding an enzyme from macromolecules while retaining activity against the native small molecule substrate, and we found that conjugation of high-generation bis-MPA dendrons to α-chymotrypsin was an effective way to eliminate enzyme activity against macromolecules while preserving efficacy against small substrates, indicating this approach may be an effective way to shield proteins from the immune system without interfering with their desired function. This work illustrates the ability to radiolabel polyester dendrimers for tumour imaging through the EPR effect. In addition, it has demonstrated that polymer architecture has a large impact on the properties of polymer-protein conjugates and gives evidence of unique properties that are imparted by the conjugation of high-generation dendrimers onto a protein. / Thesis / Doctor of Science (PhD)

Each year, over 6,000 students complete Master of Public Administration (MPA) degrees in over 200 university accredited programs. Many of these graduates commit to a career in the public service in one of thousands of public sector organizations at all levels of government or in the non-profit sector. Are students qualified to work successfully with multiple <i>"publics"</i> and to work towards achieving the goals of social equity? The core curricula of 123 National Association of School's of Public Affairs and Administration (NASPAA) accredited MPA programs were examined and the analysis focused on the following question: To what extent do NASPAA accredited programs provide cultural competency training to MPA students through their curricula? This dissertation assesses the current state of the field and recommends cultural competency standards to be adopted by public administration programs. / Ph. D.

Dois modificadores de eletrodos, sílica SBA-15 e resina poliestireno, ambos funcionalizados, foram usados na modificação de eletrodos compósitos à base de grafite. A sílica SBA-15 foi sintetizada e, posteriormente, organofuncionalizado pela rota heterogênea utilizando 5-amino-1,3,4-tiadiazol-2-tiol como modificador. O material obtido foi caracterizado por termogravimetria, ressonância magnética nuclear 13C, espectroscopia Raman e espalhamento de raios X a baixo ângulo. Os eletrodos de pasta de carbono modificados com esse material (CPE-SiATT) foram utilizados com êxito no desenvolvimento de um método eletroanalítico para determinação de mercúrio (Hg2+) utilizando voltametria de redissolução anódica de pulso diferencial (DPASV). Após otimização dos parâmetros experimentais a curva analítica apresentou resposta linear no intervalo de 0,5 a 10,0 µmol L-1 com limite de detecção (LOD) de 367 nmol L-1. O método desenvolvido foi empregado na determinação de Hg2+ em revestimento interno de lâmpadas fluorescentes compactas e tubulares. Na comparação com espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite, os resultados concordaram ao nível de confiança de 95% conforme análise estatística usando o teste F e teste t de Student. Também foi desenvolvido um eletrodo de grafite-poliuretana modificado com a resina quelante QuadraPure®MPA (EGPU-QMPA). Esse dispositivo foi empregado no desenvolvimento de um método eletroanalítico para determinação sequencial de Cd2+, Pb2+, Cu2+ e Hg2+ em meio aquoso (mineral, rio e abastecimento urbano) baseado na redissolução anódica desses metais. Após otimização de parâmetros experimentais como composição do eletrodo, velocidade de varredura e potencial de acumulação, as curvas analíticas apresentaram intervalos lineares de 140 a 480 nmol L-1 (Cd2+), 98 a 290 nmol L-1 (Pb2+), 50 a 220 nmol L-1 (Cu2+) e 50 a 290 nmol L-1 (Hg) e os LOD obtidos foram 140,0; 11,96; 19,44 e 21,37 nmol L-1, respectivamente. O método desenvolvido foi aplicado na determinação desses quatro íons nas amostras de água citadas, sendo os resultados encontrados concordantes aos obtidos com a técnica de espectrometria de absorção atômica (FAAS). O etanol combustível foi escolhido para avaliar o desempenho desse mesmo eletrodo em meio não aquoso. Foi desenvolvido um método eletroanalítico para determinação sequencial de Zn2+, Pb2+ e Cu2+ utilizando DPASV. Após otimização dos parâmetros, foram escolhidos LiCl 0,1 mol L-1, como eletrólito suporte, [H+] = 1,0 x 10-3 mol L-1, &nu;= 20 mV s-1 com 5 minutos de acumulação em -1400 mV (&nu;s. SCE). As curvas analíticas apresentaram intervalos lineares de 1,0 a 7,0 µmol L-1 para Zn2+, 0,12 a 0,78 µmol L-1 para Pb2+ e 0,57 a 3,6 µmol L-1 para Cu2+ com limites de detecção de 2,21 x 10-7 mol L-1 (Zn2+), 26,3 x 10-9 mol L-1 (Pb2+), 68,6 x 10-9 mol L-1 (Cu2+). O método desenvolvido foi aplicado em amostras de etanol combustível obtidos de três estabelecimentos diferentes e os resultados concordaram com os obtidos por FAAS ao nível de confiança de 95% quando confrontados estatisticamente pelos testes F e t de Student. Os resultados obtidos neste trabalham mostraram que os CPE-SiATT podem ser empregados na com êxito determinação de Hg2+ em amostras ambientais. Os resultados apresentados neste trabalho mostraram que os dispositivos desenvolvidos podem ser aplicados na determinação de alguns metais tóxicos atendendo os limites impostos pela legislação vigente. Além disso, disso o uso da resina funcionalizada foi um grande avanço no sentido de economia de tempo e estrutura de laboratório já que é obtida comercialmente e pronta para uso. / Two electrode modifiers, SBA-15 silica and polysterene resin, both functionalized had been used in the modification of graphite-based composite electrodes used in the determination of metallic ions in fluorescent lamps powder, waters and ethanol fuel. SBA-15 silica was synthesized and organofunctionalized with 5-amino-1,3,4-thiadiazol-2-tiol and introduced in a carbon paste. The resulting device was used in the determination of mercury in fluorescent lamps internal coating, with a limit of detection (LOD) of 367 nmol L-1, after 3 minutes pre-concentration time at -300 mV (&nu;s. SCE). In the used samples the recovery was of 102% in average. Compared to graphite furnace atomic absorption (GFAAS) the results agreed within 95% confidence interval according to the t and F tests. Other composite electrode made with graphite and polyurethane was modified with the QuadraPure®MPA scavenging resin. In aqueous media such device was used in the determination of Cd2+, Pb2+, Cu2+ e Hg2+ in three water samples: mineral, tap and river. After optimizing experimental parameters such as electrode composition, scan rate (&nu;) and accumulation potential (Eac), as respectively 2.5% (m/m) modifier, 15 mV s-1 and -1000 V, in 0.10 mol L-1 KNO3 pH= 3.0 electrolyte, LOD = 140,0, 11.96, 19.44 and 21.37 nmol L-1, respectively for Cd2+, Pb2+, Cu2+ e Hg2+ ions. The same electrode was evaluated regarding its performance in the determination of Zn2+, Pb2+ e Cu2+ in an hydro-alcoholic medium represented by ethanol fuel, using LiCl as supporting electrolyte with hydrogenionic concentration of 1.0 x 10-3 mol L-1, &nu; = 20mV s-1, Eacc = 5 minutes, at -1400 mV (&nu;s. SCE). Under such conditions LOD = 2.21 x 10-7 mol L-1 (Zn2+), 26.3 x 10-9 mol L-1 (Pb2+), 68.6 x 10-9 mol L-1 (Cu2+) were reached, with recoveries ranging from 96.8 to 100% (Zn2+), 94.3 to 101% ( Pb2+) and 94.4 to 109% (Cu2+). These results suggest that the electrodes are promising devices to be used in those samples, regarded the use of the standard addition procedure can avoid interferences from the species also present in the matrix.

Made available in DSpace on 2017-07-20T12:40:17Z (GMT). No. of bitstreams: 1 Cleverson Santos.pdf: 2904178 bytes, checksum: 85140c2fc4cb486fe6c03e6a011296a3 (MD5) Previous issue date: 2016-05-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This thesis describes the preparation, characterization and application of electrochemical sensors and biosensors, using different modification techniques, based on Au as transducer. The enzymatic biosensor applied on the detection of pesticide carbaryl was built on a gold electrode functionalized with a monolayer of polyamidoamine dendrimer of fourth generation with a cystamine core (PAMAM-G4) on which it was immobilized the acetylcholinesterase enzyme (AChE), with the aid of glutaraldehyde. After evaluate and determine the best conditions for immobilization of the AChE enzyme (glutaraldehyde concentration of 1% (v/v) and the concentration of enzyme units 496 U. mL-1) on the monolayer of PAMAM, the catalytic activity of the enzyme was evaluated by chronoamperometry in presence of enzymatic substrate AChI obtaining = 2.9 . −1 . The biosensor response for carbaryl detection was based on the inhibition of the enzymatic activity caused by the pesticide. It was verified that 5 min in the pesticide solution is sufficient to block the enzyme active sites. After determining the best conditions for the construction of the biosensor, it was applied for carbaryl detection in the concentration range from 1.0 to 9.0 mol. L-1. The detection and quantification limits were found to be 0.0108 mol. L-1 and 0.032 mol. L-1, respectively. In the second chapter, it is reported the development of an immunosensor applied to qualitative detection of antibodies (AB) T. cruzi. The sensor was built on gold electrode modified with the thiol 3-mercaptopropionic acid (MPA) and the antigens (AG) T. cruzi were covalently immobilized on this surface by the reaction with EDC and NHS. The influence of concentration and of immersion time in the AG solution were evaluated using the techniques of cyclic voltammetry and electrochemical impedance spectroscopy in presence of [Fe(CN)6]3-/4- and the results showed that the best conditions were immersion time of 15 minutes and AG concentration of 0.5 g. L-1.The possible sites of non-specific binding were blocked with bovine serum albumin (BSA). The immersion time in the solution (AB) was also evaluated and the results showed that 30 minutes are sufficient for all specific bonds sites were occupied by AB T. cruzi. Selectivity tests in the absence of AB, only in the serum sample, and in the presence of AB Toxoplasma were performed. The results demonstrated that the immunosensor is selective, since it presented charge transfer resistance (Rct) values in the presence of AB T. cruzi 70% higher than the Rct values in presence of possible interferences.Therefore, the immunosensor presents itself as an alternative to qualitative diagnosis of american trypanosomiasis. In the third chapter, it is reported the modification of carbon graphite electrodes (CG) obtained from dry batteries zinc/carbon with Au microparticles obtained by potentiostatic electrodeposition. The variables involved in the electrodeposition process, such as the gold salt concentration, time and deposition potential were evaluated and optimized using cyclic voltammetry technique in the presence of redox couple [Fe(CN)6]3-/4-. The best conditions for the Au deposition were electrodeposition time of 700 s, potential of +0.3 V and concentration of 10.0 mmol. L-1. In these conditions, Au spherical particles were obtained with an average size of 420 nm, which were homogeneously deposited on the surface of GC electrode and promoted the increase of the electroactive area (GC electrode showed an area of 0.12 cm2 and GC/Au electrode presented an area of 0.25 cm2). The GC/Au electrode was applied for the separation and quantification of dopamine and uric acid present in a mixture. The voltammetric results showed that the GC/Au sensor is selective, once the potential peak separation between the DA and UA species was 370 mV. The detection and quantification limits were found to be 1.86 mol. L-1 and 6.09 mol. L-1 for dopamine and uric acid 17.5 mol. L-1 and 58.5 mol. L-1, respectively. In the development of the three electrochemical devices gold electrodes were used. From the results obtained for the three developed electrochemical devices it can be concluded that high electric conductivity, chemical stability, biocompatibility, ability to miniaturization in the form of microstructures and ease of functionalization of Au electrodes make them suitable conductive matrixes for construction of electrochemical sensors and particularly biosensors. / Esta tese descreve a preparação, caracterização e aplicação de sensores e biossensores eletroquímicos, utilizando diferentes técnicas de modificação baseadas no Au como transdutor. O biossensor enzimático aplicado na detecção do pesticida carbaril foi construído sobre um eletrodo de ouro funcionalizado com uma monocamada do dendrímero poliamidoamina de quarta geração com núcleo de cistamina (PAMAMG4),sobre o qual foi imobilizada com o auxílio de glutaraldeído a enzima acetilcolinesterase (AChE).Após avaliar e determinar as melhores condições de imobilização da enzima AChE (concentração de GLUT 1% (v/v) e concentração de unidades enzimáticas 496 U. mL-1) sobre a monocamada de PAMAM,a atividade catalítica da enzima AChE imobilizada foi avaliada por cronoamperometria na presença do substrato enzimático (AChI) obtendo-se o = 2,9 . −1. A resposta do biossensor na detecção de carbaril foi baseada na inibição da atividade enzimática causada pelo pesticida. Foi constatado que 5 min de imersão na solução do pesticida foram suficientes para que os sítios ativos da enzima fossem bloqueados. Após determinar as melhores condições de construção do biossensor, este foi aplicado na detecção de carbaril na faixa de 1,0 a 9,0 mol. L-1. Os limites de detecção e quantificação encontrados foram de 0,0108 mol. L-1 e 0,032 mol. L-1, respectivamente. No segundo capítulo é relatado o desenvolvimento de um imunossensor aplicado na detecção qualitativa de anticorpos (AB) T. cruzi. O sensor foi construído sobre eletrodo de ouro modificado com o tiol ácido 3-mercaptopropiônico (MPA) e sobre esta superfície foram imobilizados covalentemente pela reação com EDC e NHS, os antígenos (AG) T. cruzi. A influência da concentração da solução de AG e do tempo de imersão nesta solução para a construção do imunossensor foram avaliadas utilizando as técnicas de voltametria cíclica e espectroscopia de impedância eletroquímica na presença de [Fe(CN)6]3-/4- e os resultados demonstraram que as melhores condições foram: tempo de 15 min e concentração de 0,5 g. L-1. Os possíveis sítios de ligações não específicas foram bloqueados com albumina de soro bovino (BSA). O tempo de imersão na solução de AB também foi avaliado. Os resultados mostraram que 30 min são suficientes para que todos os sítios de ligações específicos fossem ocupados pelos AB T. cruzi. Testes de seletividade na ausência de AB,apenas em amostra de soro e também na presença de AB de Toxoplasma foram realizados. Os resultados demonstraram que o imunossensor é seletivo, pois este apresentou valores de resistência de transferência de carga (Rct) na detecção de AB T. cruzi 70% maiores do que na detecção dos possíveis interferentes. Portanto, o imunossensor apresenta-se como uma alternativa no diagnóstico qualitativo de tripanossomíase americana. No terceiro capítulo é descrito a modificação de eletrodos de carbono grafite (CG) obtidos de pilhas secas de zinco/carbono com micropartículas de Au obtidas pela eletrodeposição potenciostática. As variáveis envolvidas no processo de eletrodeposição, tais como concentração do sal de ouro, potencial e tempo de deposição foram avaliadas e otimizadas utilizando a técnica de voltametria cíclica na presença do par redox [Fe(CN)6]3-/4-. As melhores condições foram: tempo de 700 s, potencial de +0,3 V e concentração de 10,0 mmol. L-1. Nestas condições, foram obtidas partículas de Au esféricas com tamanho médio de 420 nm, as quais se apresentaram homogeneamente dispersas sobre toda a superfície do eletrodo de CG e promoveram o aumento da área eletroativa, (o eletrodo CG apresentou uma área de 0,12 cm2 e o eletrodo CG/Au uma área 0,25 cm2). O desempenho do eletrodo CG/Au foi avaliado na separação e quantificação de dopamina e ácido úrico presentes em uma mistura. Os resultados voltamétricos demonstraram que o sensor CG/Au é seletivo, pois apresentou separação de potencial pico de 370 mV entre as duas espécies. Os limites de detecção e quantificação encontrados foram de 1,86 mol. L-1 e 6,09 mol. L-1 para dopamina, e 17,5 mol. L-1 e 58,5 mol. L-1 para ácido úrico, respectivamente. A partir dos resultados obtidos para os três dispositivos eletroquímicos desenvolvidos pode-se concluir que a elevada condutividade elétrica, estabilidade química, biocompatibilidade, possibilidade de miniaturização na forma de microestruturas e a facilidade de funcionalização dos eletrodos de Au fazem destes matrizes condutoras apropriadas para construção de sensores e particularmente biossensores eletroquímicos.