There is huge academic interest and clinical need associated with the development of biomarker immunoassays where general aims are the generation of highly specific, convenient and sensitive sensing formats. In this project, a powerful electrochemical technique, electrochemical impedance spectroscopy (EIS), is applied in the establishment of powerful biomarker detecting protocols. Firstly, ultrasensitive, label-free and reusable insulin sensors, based on an antibody-PEGylated thiol self-assembly monolayer (PEG thiol SAM) interface, were produced and characterised via Faradaic EIS, presenting a detection limit (LOD) of 1.2 pM, a linear range across four orders of magnitude, and high sensitivity in even 50 % serum. By applying similar surface chemistry, a label-free biosensor, specific for the detection of α-synuclein antibodies, was fabricated. The α-synuclein interfaces used enabled the reliable detecting of this biomarker in patient sample serum. The concentration levels in the control and a patient group were determined to be significantly different, and, significantly, this difference was consistently across two different cohorts. Strikingly, this could potentially underpin an entirely new means of early Parkinson’s disease (PD) diagnosis. Non-Faradaic EIS methods were additionally applied to label-free insulin assays at both PEG thiol SAM and zwitterionic polymer film interfaces. The latter presented not only an exceptionally non-fouling interface, but also one seemingly both highly biocompatible and facilitating enhanced receptor: target binding. Finally, impedance assays, though potent, generally, operate by sampling only one of a limited number of available experimental variables, typically, Rct for Faradaic EIS, or C or Z for non-Faradaic EIS. Work carried out herein also explores the generation and utility of a portfolio of mathematically derived immittance functions all obtained from the same raw data sets. A particular focus was the examination of whether these were capable of increasing assay sensitivity and efficiency above normal impedance treatments.

Micro- and nano-electrodes have distinct advantages over large electrodes, including their decreased iR drop and enhanced mass transport due to radial diffusion characteristics which leads to the ready establishment of a steady state (or near steady-state) signal without convection. This enhanced mass transport also leads to increased current densities and signal to noise ratios. However, there is a need for fabrication techniques which reproducibly give micro- and nano-electrodes of controlled size and shape. The optimisation of systematic arrays on the nano-scale, open up possibilities for developing highly sensitive electrode devices, for use in physical chemistry and the determination of fast electrode kinetics and rates of reaction, as well as to provide highly sensitive electroanalytical devices, able to detect very low concentrations of substrates. This thesis first presents work involving the fabrication and characterisation on silicon substrates of square platinum microelectrodes. There is already an established theory for the behaviour of microdisc electrodes however, it is easier to make microsquares reproducibly using pixellated photomasks. The voltammetric and ac impedance characteristics of these electrodes in background electrolyte and in the presence of ferri/ferrocyanide redox couple are presented and the response is theoretically analysed. A combination of computer simulation, theory and experimentation show that these electrodes have increased current densities (14% greater) compared with a microdisc of equivalent radius and an alternative theoretical expression is presented to calculate the limiting current of microsquares at all dimensions. This thesis then discusses the development and optimisation of novel nano-band cavity array electrodes (CaviArE), using standard photo-microlithographic techniques. The resulting architecture encloses a Platinum nanoband of 50 nm width within each array element that is positioned half way up the vertical edges of shallow square cavities (depressions), with a total depth of 1050 nm. The width of the square cavity and the separation of the array elements can be controlled and systematically altered, with great accuracy. The CaviArE devices are shown to give quantitative pseudo-steady-state responses characteristic of multiple nanobands, whilst passing overall currents consistent with a macroelectrode. The array has a much enhanced signal-tonoise ratio compared with an equivalent microsquare array, as it has 0.167% of the area and is therefore markedly less affected by non-Faradaic currents, while it passes comparable Faradaic currents. At high sweep rates the response is also virtually unaffected by solution stirring. The impedammetric characteristics presented show different diffusional regimes at high, medium and low frequencies, associated with diffusion within individual square cavities, outside of the cavity and finally across the whole array as the diffusional fields of the neighbouring array elements overlap. Justification and fitting of equivalent circuits to these frequency regions provide details about the charge transfer, capacitance and diffusional processes occurring. The results show that these systems are highly sensitive to surface transfer effects and a rate constant for ferricyanide of 1.99 cm s-1 was observed, suggesting fast kinetic processes can be detected. Together, these characteristics make nanoband electrode arrays, with this architecture, of real interest for sensitive electroanalytical applications, and development of devices for industrial application is currently being undertaken.

Today there are numerous methods to slow down a corrosion process of metallic materials. However, due to environmental effects and health risk issues, several traditional corrosion inhibitors have to be phased out. Hence, it is of great importance to develop new corrosion inhibitors that are “green”, safe, smart and multifunctional. In this essay, the focus is on mussel adhesive protein (MAP) and its possibility to reduce the rate of the corrosion process. The protein exhibit great adhesive strength and protective properties, allowing it to adhere to a multitude of different surfaces and is therefore of great interest of corrosion science. The protein Mefp-1, derived from the blue mussel´s foot, had been pre-adsorbed on the carbon steel surface and provided good corrosion inhibition in a basic chloride solution for a short exposure time. The protection was further improved with the assist of iron and ceria ions by formation of protein/ions complexes within the surface films and thus enhanced the corrosion protection for longer exposure time. Ceria nanoparticles were used in order to create a multi-layer composite film with an even higher corrosion protection. The results suggest a denser film compared to previous samples and a more uniform surface.

The human skin is the largest and most complex body organ but accessible and attractive for biomarker sampling and transdermal drug delivery. The two procedures are significantly impacted by several biophysical properties of the skin, especially the pH and stratum corneum (SC)hydration. The varying levels of pH on the skin surface usually impact the permeability barrier function of the SC, contributing to the onset of dermatological disorders such as incontinence-associated dermatitis (IAD). Consequently, this scholarly work provides a comprehensive in vitro investigation of the effect of pH on the skin including the effect of artificial urine. The pig skin membranes were used to conduct electrical impedance spectroscopy (EIS)experiments using a four-electrode Franz cell set-up. Artificial urine and buffered solution with varying pH gradients were utilized to induce reversible changes in effective membrane capacitance (Ceff) and membrane resistance (Rmem). The in vitro investigation revealed that exposure to urine changed the electrical impedance properties of the skin. Specifically, we found that the application of artificial urine to the skin reduced skin resistance. At the same time, we also find systematic changes in skin capacitance. Skin capacitance increased with increased pH. Hence the two skin impedance parameters showed a clear effect of artificial urine on the skin. These changes, i.e., the decrease of Rmem and increase of Ceff of skin membranes when they are exposed to artificial urine, can be interpreted as skin barrier deterioration The information provided herein is relevant in describing the detrimental effect of urine on the skin, which probably makes skin barrier more permeable.

Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-04-30Bitstream added on 2014-06-13T19:09:17Z : No. of bitstreams: 1 perez_l_me_bauru.pdf: 2493638 bytes, checksum: 26329bfa30a60d575a769d58ce9d9493 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A oxidação do metanol apresenta problemas acentuadamente complexos que ainda não foram satisfatoriamente solucionados. Possui um mecanismo duplo caminho, ou seja, diretamente a CO2 ou pelo caminho alternativo via intermediários. Também como intermediário/produto da reação ocorre a formação de CO que é usualmente identificado como o agente bloqueador da superfície eletródica devido à sua adsorção irreversível. Baseado em um estudo recente da reação de oxidação do metanol sobre Pt por espectroscopia de impedância eletroquímica (EIE), este trabalho teve por objetivo aplicar a técnica de EIE no estudo da eletrocatálise da reação de oxidação do metanol sobre fases intermetálicas ordenadas de PtMn, PtSb e PtSn em meio ácido, visto que os metais Mn, Sb e Sn por apresentarem característica oxifílica, podem formar mais facilmente espécies OH que promovem a oxidação de intermediários fortemente adsorvidos nos sítios ativos da superfície eletródica. Os intermetálicos também apresentam maior distância entre os sítios da platina o que pode favorecer uma configuração de adsorção vertical da molécula de CO que é mais fácil de oxidar quando comparado a uma configuração em ponte. Uma análise prévia da atividade catalítica desses materiais para a reação de oxidação do metanol foi realizada empregando-se as técnicas de voltametria cíclica cronoamperometria. Os resultados obtidos mostraram que o processo de oxidação do metanal utilizando os intermetálicos apresentou um deslocamento para valores menos positivos do potencial de início de oxidação, necessitando de uma menor demanda energética para que o processo de oxidação ocorra sobre a superfície destes intermetálicos. A oxidação do metanol apresentou densidade de corrente de corrente de pico superior para esses materiais quando comparado... / Methanol oxidation reaction congregates very complex constraints that were not conveniently solved so far. This reaction usually follows a dual pathway, i.e. direct oxidation to CO2 or through an alternative path via stable intermediates. CO is the most commom identified intermediate of the reaction and surface blocking agent due to its irreversible adsorption characteristic. The here in research is based on recent study performed with the methanol oxidation reaction on Platinum by employing the Electrochemical Impedance Spectroscopy (EIS) technique. The aim of the research was to investigate the methanol oxidation reaction on PtMn, PtSb and PtSn ordered intermetallic surfaces, in acid medium, by means of the EIS technique. These materials were selected to the study since they have oxophilic metals (Mn, Sb and Sn) that could provide OH species on the electrode surface at electrode potentials less positive than polycrystalline Platinum under the same experimental conditions. Moreover, these surfaces also exhibits a larger Pt-Pt distance in comparison to polycrystalline Platinum that inhibits the stable bridge configuration adsorption of CO. The electrochemical data obtained have demonstrated that ehe methanol oxidation reaction on the studied surfaces presented a less positive onset potential as compared to Pt. The materials also have exhibited a higher maxima current densities and lower susceptibility for CO blocking than Pt. EIS spectra obtained fot the reaction taking place on Pt, PtSb and PtSn have presented an inductive component that is characteristic of stable intermediate adsorption process. Steady state measurements have pointed to a change in the mechanism of the reaction probably due to the action of surface oxygenated species. Furthemore, the EIS technique has been proved o be a powerful tool to investigate... (Complete abstract click electronic access below)

Orientador: Antonio Carlos Dias Ângelo / Banca: Joelma Perez / Banca: Mauro Coelho dos Santos / Resumo: A oxidação do metanol apresenta problemas acentuadamente complexos que ainda não foram satisfatoriamente solucionados. Possui um mecanismo duplo caminho, ou seja, diretamente a CO2 ou pelo caminho alternativo via intermediários. Também como intermediário/produto da reação ocorre a formação de CO que é usualmente identificado como o agente bloqueador da superfície eletródica devido à sua adsorção irreversível. Baseado em um estudo recente da reação de oxidação do metanol sobre Pt por espectroscopia de impedância eletroquímica (EIE), este trabalho teve por objetivo aplicar a técnica de EIE no estudo da eletrocatálise da reação de oxidação do metanol sobre fases intermetálicas ordenadas de PtMn, PtSb e PtSn em meio ácido, visto que os metais Mn, Sb e Sn por apresentarem característica oxifílica, podem formar mais facilmente espécies OH que promovem a oxidação de intermediários fortemente adsorvidos nos sítios ativos da superfície eletródica. Os intermetálicos também apresentam maior distância entre os sítios da platina o que pode favorecer uma configuração de adsorção vertical da molécula de CO que é mais fácil de oxidar quando comparado a uma configuração em ponte. Uma análise prévia da atividade catalítica desses materiais para a reação de oxidação do metanol foi realizada empregando-se as técnicas de voltametria cíclica cronoamperometria. Os resultados obtidos mostraram que o processo de oxidação do metanal utilizando os intermetálicos apresentou um deslocamento para valores menos positivos do potencial de início de oxidação, necessitando de uma menor demanda energética para que o processo de oxidação ocorra sobre a superfície destes intermetálicos. A oxidação do metanol apresentou densidade de corrente de corrente de pico superior para esses materiais quando comparado... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Methanol oxidation reaction congregates very complex constraints that were not conveniently solved so far. This reaction usually follows a dual pathway, i.e. direct oxidation to CO2 or through an alternative path via stable intermediates. CO is the most commom identified intermediate of the reaction and surface blocking agent due to its irreversible adsorption characteristic. The here in research is based on recent study performed with the methanol oxidation reaction on Platinum by employing the Electrochemical Impedance Spectroscopy (EIS) technique. The aim of the research was to investigate the methanol oxidation reaction on PtMn, PtSb and PtSn ordered intermetallic surfaces, in acid medium, by means of the EIS technique. These materials were selected to the study since they have oxophilic metals (Mn, Sb and Sn) that could provide OH species on the electrode surface at electrode potentials less positive than polycrystalline Platinum under the same experimental conditions. Moreover, these surfaces also exhibits a larger Pt-Pt distance in comparison to polycrystalline Platinum that inhibits the stable bridge configuration adsorption of CO. The electrochemical data obtained have demonstrated that ehe methanol oxidation reaction on the studied surfaces presented a less positive onset potential as compared to Pt. The materials also have exhibited a higher maxima current densities and lower susceptibility for CO blocking than Pt. EIS spectra obtained fot the reaction taking place on Pt, PtSb and PtSn have presented an inductive component that is characteristic of stable intermediate adsorption process. Steady state measurements have pointed to a change in the mechanism of the reaction probably due to the action of surface oxygenated species. Furthemore, the EIS technique has been proved o be a powerful tool to investigate... (Complete abstract click electronic access below) / Mestre

La tribocorrosion peut être définie comme l’ étude de l’influence des facteurs environnementaux (chimiques et/ou électrochimiques) et mécanique (frottement) sur le comportement tribologique de surfaces en mouvement relatifs. En raison de leurs caractéristiques particulières: performances mécaniques, associées à une faible densité, bonne tenue à la corrosion, biocompatibilité, le titane et ses alliages sont souvent utilisés dans le domaine médical comme implants dentaires et orthopédiques. Cependant, leur faible résistance vis-À-Vis du frottement en milieu agressif et plus spécifiquement biologique reste un frein à leur usage courant dans le domaine prothétique. Pour améliorer la résistance à la corrosion et à l'usure du titane et de ses alliages, différentes méthodes de modification de la surface ont été proposées durant ces dernières décennies. Dans ce cadre, le but de ce travail est de comparer les comportements en corrosion et tribocorrosion du titane commercialement pur (cp Ti), avec ce même matériau ayant subi au préalable les traitements suivants :- soit une étape d'oxydation thermique à 650 °C à l’air durant 48 h (formation d’un film d'oxyde de titane (TiO2) en surface),- soit un dépôt électrochimique de calcium phosphate (CaP) en surface,- soit un dépôt électrochimique de calcium phosphate (CaP) suivi d’une tape d’oxydation thermique à 650 °C à l’air durant 6 h (formation d’un dépôt de type CaP/TiO2 en surface). Les phases cristallines des films modifiés ont été identifiées par diffraction des rayons X (XRD). La microscopie électronique à balayage (MEB) en combinaison avec la spectroscopie à dispersion d'énergie (EDS) a été utilisée pour caractériser la morphologie et la composition de ces films.Le comportement en corrosion pure des échantillons cp Ti avec ou sans modifications de surface à été étudié in situ à partir des mesures électrochimiques de suivi du potentiel en circuit ouvert (OCP), de la spectroscopie d'impédance électrochimique (EIS) et du tracé de courbes de polarisation potentio-Dynamiques.Le comportement en tribocorrosion à été étudié quant à lui à l'aide d'un tribomètre de type pion-Disque apte à travailler en milieu aqueux et permettant outre l’enregistrement des paramètres tribologiques classiques, la mise en œuvre in situ des techniques électrochimiques utilisées lors de l’étude en corrosion pure. Caractérisation et analyses de la surface(composition, morphologie, rugosité …) sont effectuées avant et après chaque étude de comportement (corrosion et tribocorrosion). Un protocole pour la culture des cellules sur la surface de titane a été validé, en se basant sur les résultats expérimentaux préliminaires. / Tribocorrosion is defined as the study of the interplay between chemical, electrochemical and mechanical processes that leads to a degradation of passivating materials in a corrosive environment. Due to the low density, excellent mechanical properties, high corrosion resistance and good biocompatibility, titanium and its alloys are widely used as dental and orthopedic implants. However, the poor wear resistant and bio-Inert properties limit their further development as more efficient and economic biomedical implants. To improve the corrosion-Wear resistance and even bioactivity of metallic implants, different surface modification methods are imposed in the past decades.The aim of this work is to provide a deep insight in the area of corrosion and tribocorrosion behavior of commercially pure titanium (cp Ti) under the guidance of a tribocorrosion protocol for passivating materials. And then three different surface modification treatments, as:- one-Step thermal oxidation at 650 °C for 48 h in air atmosphere to form a titania (TiO2) film on the surface of cp Ti.- one-Step electrochemical deposition of calcium phosphate (CaP) bioactive film on the surface of cp Ti.- electrochemical deposition of CaP bioactive film followed by thermal oxidation at 650 °C for 6 h in air atmosphere to form a CaP/TiO2 bioceramic film on cp Ti surface.The crystalline phases of the modified films were identified by X-Ray diffraction (XRD). Scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS) was used to characterize the morphology and composition of these films on cp Ti surface. In situ electrochemical measurements, like open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization are used to characterize the corrosion behavior of cp Ti samples without or with surface modification. The tribocorrosion behavior was investigated in an aqueous environment by combining a pin-On-Disc tribometer with the in situ electrochemical equipment. The classical tribological parameters could be also recorded under mechanical loaded condition. Surface characterization and analysis (like chemical composition, morphology, roughness...) are carried out before and after each corrosion and tribocorrosion test. A protocol for the culture of cells on the surface of titanium was validated, basing on the preliminary experimental results.

This thesis deals with novel electrolytes for magnesium batteries. Prepared electrolytes were composed of affordable solvents and chemicals, which can be handled at normal laboratory conditions. Specifically, solutions of tetrahydrofurane and dimethylsulfoxide with magnesium chloride, aluminium chloride, nitrilotriacetic acid and disodium ethylenediaminetetraacetic acid, were prepared. To determine electrolyte ability of magnesium stripping and deposition, the cyclic voltammetry was used. The kinetics of electrochemical reactions in terms of polarization resistance was studied by electrochemical impedance spectroscopy. Based on scanning electron microscopy and EDS analysis, the effect of atmospheric oxygen and humidity on magnesium electrode corrosion during cycling was discussed.

Conducting vertical nanopillar arrays can serve as three-dimensional nanostructured electrodes with improved performance for electrical recording and electrochemical sensing in bio-electronics applications. However, vertical nanopillar-array electrodes made of inorganic conducting materials by conventional nanofabrication approach still faces challenges in high manufacturing costs, poor scalability, and limited choice of carrier substrates. Here, we report a new type of conducting nanopillar arrays composed of multi-walled carbon nanotubes (MWCNTs) doped polymeric nanocomposites, which are manufactured over the wafer-scale on both rigid and flexible substrates by direct nanoimprinting of perfluoropolyether nanowell-array templates into uncured MWCNT/polymer mixtures. By controlling the MWCNT ratios and the annealing temperatures during the fabrication process, MWCNT/polymer nanopillar arrays can possess outstanding electrical properties with high DC conductivity (~4 S/m) and low AC electrochemical impedance (~104 Ω at 1000 Hz). Moreover, by electrochemical impedance spectroscopy (EIS) measurements and equivalent circuit modeling-analysis, we can decompose the overall impedance of MWCNT/polymer nanopillar arrays in the electrolyte into multiple bulk and interfacial circuit components, and thus can illustrate their different dependence on the MWCNT ratios and the annealing temperatures. In particular, we find that a proper annealing process can significantly reduce the anomalous ion diffusion impedance and improve the impedance properties of MWCNT/polymer nanopillars in the electrolyte. / Master of Science / Conducting vertical nanopillar arrays can serve as three-dimensional nanostructured electrodes with improved performance for electrical recording and electrochemical sensing in nano-bioelectronics applications. However, vertical nanopillar-array electrodes made of inorganic conducting materials by conventional nanofabrication approach still faces challenges in high manufacturing costs, poor scalability, and limited choice of carrier substrates. Compared to conventional nanofabrication approaches, nanoimprint lithography exhibits unique advantages for low-cost scalable manufacturing of nanostructures on both rigid and flexible substrates. Very few studies, however, have been conducted to achieve the scalable nanoimprinting fabrication of conducting nanopillar arrays made of MWCNT/polymer nanocomposites. Here, I'm reporting a new type of conducting nanopillar arrays composed of multi-walled carbon nanotubes (MWCNTs) doped polymeric nanocomposites, which can be manufactured over the wafer-scale on both rigid and flexible substrates by direct nanoimprinting of the perfluoropolyether nanowell-array template into uncured MWCNT/polymer mixtures. We find that the nanoimprinted conducting nanopillar arrays can possess appealing electrical properties with a high DC conductivity (~4 S/m) and a low AC electrochemical impedance (~104 Ω at 1000 Hz) in the physiologically relevant electrolyte solutions (1X PBS). Furthermore, I've conducted a systematic equivalent circuit modeling analysis of measured EIS results to understand the effects of the MWCNT ratios and the annealing temperatures on the impedance of different bulk and interfacial circuit components for MWCNT/polymer nanopillar arrays in the electrolyte.

Polypyrrol (PPy) ist ein typischer Vertreter der intrinsisch leitfähigen Polymere und wird auf zahlreichen Gebieten, wie Analytik, Korrosionsschutz oder Elektrotechnik angewendet. Dabei nutzt man die elektronische Schaltbarkeit, die Stabilität und die gute Oxidierbarkeit sowie die Wasserlöslichkeit der Monomere aus. Im Rahmen dieser Arbeit wurde der Einfluss verschiedener Parameter, wie Temperatur, Monomerkonzentration und Leitsalz, auf die elektrochemische Polymerisation von Pyrrol untersucht. Des Weiteren sollte die Wirkung eines statischen Magnetfeldes auf die Synthese und das Ionenaustauschverhalten überprüft werden. Als Messverfahren kamen die elektrochemische Quarzmikrowaage (EQCM) und die elektrochemische Impedanzspektroskopie (EIS) zum Einsatz. Bei der Auswertung der EQCM-Daten wurde ein von Efimov entwickeltes mathematisches Modell zur Bestimmung des komplexen Schermoduls angewendet. Dadurch war eine in situ Verfolgung der viskoelastischen Eigenschaften während der Abscheidung und des Ionenaustausches möglich. Um den hydrodynamischen Einfluss auf die Synthese von PPy zu untersuchen, wurden Messungen an einer rotierenden Scheibenelektrode durchgeführt. Die daraus gewonnenen Erkenntnisse vermittelten eine Vorstellung, wie sich eine durch den magnetohydrodynamischen Effekt hervorgerufene Rührung auf die Grenzströme der potentiostatischen Abscheidung verschiedener PPy|Leitsalz Systeme auswirkt. Ferner ist die Abscheidung von PPy aus Phosphorsäure betrachtet worden, da diese Schichten eine Relevanz für den Korrosionsschutz besitzen.