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Dissertations / Theses on the topic 'Cyclic voltammetry'
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Helfrick, John C. "Cyclic square wave voltammetry." Diss., Georgia Institute of Technology, 1989. http://hdl.handle.net/1853/30681.
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Mizzon, Giulia. "Bioelectrochemistry by fluorescent cyclic voltammetry." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:6a1134dd-c24d-4e60-ac83-936a6918131f.
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Understanding the factors influencing the ET characteristics of redox proteins confined at an electrochemical interface is of fundamental importance from both pure (fundamental science) and applied (biosensory) perspectives. This thesis reports on progress made in the emerging field of coupled electrochemical characterization and optical imaging in moving the analysis of redox-active films to molecular scales. More specifically the combination of cyclic voltammetry and wide-field Total Internal Reflection (TIRF) microscopy, here named ‘Fluorescent Cyclic Voltammetry’ (FCV), was applied to monitoring the response of surface-confined redox active proteins at submonolayer concentrations. The combined submicrometre spatial resolution and photon capture efficiency of an inverted TIRF configuration enabled the redox reactions of localized populations of proteins to be directly imaged at scales down to a few hundreds of molecules. This represents a 6-9 orders of magnitude enhancement in sensitivity with respect to classical current signals observed in bioelectrochemical analysis. Importantly, measurements of redox potentials at this scale could be achieved from both natural and artificially designed bioelectrochemical fluorescent switches and shed fundamental light on the thermodynamic and kinetic dispersion within a population of surface confined metalloproteins. The first three chapters of this thesis provide an overview of the relevant literature and a theoretical background to both the rapidly expanding fields of electroactive monolayers bioelectrochemistry and TIRF imaging. The initial design and construction of a robust electrochemically and optically addressable fluorescent switch, crucial to the applicability of FCV is reported in chapter 5. The generation of optically transparent, and chemically modifiable electrode surfaces suitable for FCV are also described. Chapter 6 describes the response of the surface confined azurin-based switch. Analysis of the spatially-resolved redox reaction of zeptomole samples in various conditions enables the mapping of thermodynamic dispersion across the sampled areas. In chapter 7 the newly developed FCV detection method was extended to investigate more complex bioelectrochemical systems containing multiple electron transferring redox centres and responding optically at different wavelengths. This approach provides a platform for spectral resolution of different electrochemical processes on the same sample. Finally in chapter 8 an electrochemical procedure is proposed for investigating the kinetic response of redox proteins using a fundamentally new methodology based on interfacial capacitance. In using variations in the surface chemistry to tune the rate of electron transfer, the approach was shown to be a robust and facile means of characterising redox active films in considerably more detail than possible through standard electrochemical methodologies. Ultimately, it can be applied to probe dispersion within protein populations and represents a powerful means of analysing molecular films more generally.
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Kollipara, Suresh Babu. "Organic Electrochemical Transistors for Fast Scan Cyclic Voltammetry." Thesis, Linköpings universitet, Fysik och elektroteknik, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-98676.
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The work presented in the thesis is about the evaluation of Organic Electrochemical Transistors (OECTs) for fast scan cyclic voltammetry (FSCV). FSCV is a method which has been used for real time dopamine sensing both in vivo and in vitro. The method is sensitive to noise and could therefore benefit from signal preamplification at the point of sensing, which could be achieved by incorporation of OECTs. In this study the OECTs are based on the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). The gate consists of gold microelectrodes of different sizes to be used one at a time. When dopamine is reacted at the gate electrode, the redox state of the PEDOT:PSS OECT channel is modulated and the resulting change in drain current can be measured. The gate current, which contains the sensing information, is after filtering obtained by differentiating the channel potential with respect to time. The derived gate current is plotted in cyclic voltammogram for different dopamine concentrations and the amplitude of the oxidation/reduction peaks can be used to determine the dopamine concentration. In this thesis for the first time it is demonstrated that OECTs can be used for FSCV detection of dopamine. The results are discussed and an outlook on future work is given.
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Tichter, Tim [Verfasser]. "Theory of Cyclic Voltammetry at Macroporous Electrodes / Tim Tichter." Berlin : Freie Universität Berlin, 2020. http://d-nb.info/1220288314/34.
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Brubaker, Joel Patrick. "A Diffusion Model for Cyclic Voltammetry with Nanostructured Electrode Surfaces." University of Dayton / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1418273596.
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Bolinger, Roman Wilhelm. "The deployment of digital simulation tools to verify cyclic voltammetry experiments /." Zürich, 2000. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=13637.
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Isaac, Christian James. "Redox active metal complexes : synthesis and DNA binding studies." Thesis, University of Newcastle Upon Tyne, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.287813.
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Gruden, Roman, Andreas Buchholz, and Olfa Kanoun. "Electrochemical analysis of water and suds by impedance spectroscopy and cyclic voltammetry." Universitätsbibliothek Chemnitz, 2014. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-149036.
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Optimum detergent dosage during a washing process depends on water quality, degree of pollution and quantity of laundry. Particularly, water quality is an important factor. Other parameters like carbonate- or non-carbonate hardness and calcium / magnesium (Ca / Mg) ratio in addition to total hardness of water have an impact on the amount of detergent. This work discusses the possibilities realizing a detergent sensor that measures important parameters for the washing process and assess the ideal necessary amount of detergent during the washing process. The approach is to combine impedance spectroscopy with cyclic voltammetry in order to determine both water quality and concentration of detergent in the suds which build up the basis for an optimum detergent dosage. The results of cyclic voltammetry show that it is possible to identify the Ca / Mg ratio and the carbonate hardness separately, which is necessary for the optimization of the washing process. Impedance measurements identify total hardness and detergent concentrations.
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Rodriguez-Ibarra, Veronica 1963. "Cyclic voltammetry of mercapto compounds and their reaction products with arsenic species." Thesis, The University of Arizona, 1993. http://hdl.handle.net/10150/278356.
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The electrochemical behavior of L-cysteine, 3-mercaptopropionic acid, dimercaptopropanesulfonic acid and dimercaptosuccinic acid, was examined at a mercury film electrode, gold electrode and platinum electrode. The effect of scan rate, pH and concentration were determined by cyclic voltammetry. The comparison of the cyclic voltammograms, established a great similarity among the monomercapto compounds at different molecular weight and structure and among the dimercapto compounds that were studied. Differences between the behavior of dimercapto and monomercapto compounds were also established. The cyclic voltammetry of arsenic is affected by the presence of cysteine, and the formation of an arsenic-cysteine complex is established by the shift of the oxidation potential of elemental arsenic at a gold electrode.
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Zuurbier, Richard James. "Novel aspects of platinum porphyrin chemistry." Thesis, Brunel University, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.307537.
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Aherne, Christine M. "Electrochemical and structural properties of some 1,2,3,5 and 1,3,2,4 dithiadiazolylium salts and related compounds." Thesis, Durham University, 1995. http://etheses.dur.ac.uk/5121/.
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This work centres around the electrochemical and structural studies of 1,2,3,5 and 1,3,2,4 dithiadiazolylium salts and associated radical derivatives. Chapter one provides a brief history of sulphur nitrogen chemistry, in particular developments of 1,2,3,5 and 1,3,2,4 dithiadiazolyUum/ heterocyclic species. Also a quick outline of the pathways my research took are discussed. The following chapter is solely dedicated to the electrochemical investigations of (i) mono substituted aryl 1,2,3,4 and 1,3,2,4, (ii) di substituted aryl 1,2,3,4 and 1,3,2,4 and (iii) pyridyl 1,2,3,5 dithiadiazolylium salts and associated derivatives. This electrochemical process of interest involved the reduction of the 6π dithiadiazolylium cation going to the 7π radical. This was studied using a technique called Cyclic Voltammetry. Results from this survey revealed that all the derivatives studied were quasi-reversible to the same degree under these experimental conditions. The E(_pc/2) potentials of meta and Para derivatives were observed to increase with acceptor property of the substituent group attached. Using the relationship E(_pc/2) = σp, when the potentials of these derivatives were plotted against corresponding Hammett a values two excellent linear free energy relationships for both sets of derivatives were seen to exist. For the other systems this is not found to be so. Rationalisation of these responses are described by examination of electronic, solvent and steric factors of analogous benzoic acid and dithiadiazolylium/zolyl derivatives and how they compare with each other. Chapter three concentrates on the structural properties of dithiadiazolyls and discusses the potential of these types of derivatives to form conducting, charge transfer or magnetically interesting materials. The X-ray structures of the following compounds were obtained and are described in detail: pMeS-C(_6)H(_4)-CNSSN•, pF-C(_6)H(_4)-CNSSN•, pCF(_3)-C(_6)H(_4)-CNSSN•, pNO(_2)-C(_6)H(_4)-CNSSN•, mBr- C(_6)H(_4)-CNSSN•, mClpMe-C(_6)H(_4)-CNSSN•,| mC(_5)H(_4)N-CNSSN• and pC(_5)F(_4)N-CNSSN•. Comparisons of how these and similar dithiadiazolyl compounds pack with a view to rationalising packing trends, in order to molecular tailor materials for applications, is tackled as well. The forth chapter concerns the experimental details of this research and features information on technical procedures, synthetic routes and characterisation on the compounds examined. Finally chapter five attempts to bridge the results of the previous chapters all together.
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Ndjeri-Ndjouhou, Marthe. "Synthèse et caractérisation de la birnessite électrodéposée : application à la dégradation du glyphosate." Thesis, Evry-Val d'Essonne, 2012. http://www.theses.fr/2012EVRY0001/document.
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Ce travail de thèse a eu pour thème central la birnessite, un oxyde de manganèse ubiquiste dans le milieu naturel et jouant un rôle fondamental dans la géochimie des sols. La première partie de cette thèse a été consacrée à l’électrodépôt et à la caractérisation de la birnessite par des méthodes électrochimiques couplées à la diffraction des rayons X. La caractérisation DRX in-situ au cours de l’électrodépôt a permis de mettre en évidence, lorsqu’on est en présence du cation électrolytique Na+, la formation d’un précurseur, la busérite, alors qu’en présence du cation électrolytique K+, la synthèse aboutit directement à la birnessite sans formation d’intermédiaire. La réduction électrochimique de la birnessite a également été étudiée en fonction du milieu ([Mn(II)], pH, potentiel). Cette dernière se réduit en hausmannite(Mn3O4), feitknechtite (-MnOOH), ou en composé amorphe de Mn(II), selon les conditions expérimentales. Dans la deuxième partie de cette thèse, les films minces ont été utilisés pour étudier la réactivité de la birnessite vis-à-vis du glyphosate, ainsi que celle de son principal métabolite l’AMPA (acide amino-méthyl-phosphonique). Le glyphosate est dégradé avec formation simultanée d’AMPA, de formaldéhyde, d’ions phosphate, nitrate et ammonium sans modification macroscopique de la birnessite. Les quatre derniers sous-produits sont également obtenus lors de la dégradation de l’AMPA par la birnessite. Les bons rendements de dégradation obtenus au cours des interactions glyphosate/birnessite et AMPA/birnessite laissent envisager une possible application de ces échantillons pour le traitement des eaux uséesThis thesis has been focused on birnessite, a ubiquitous manganese oxide in the environment, which plays a fundamental role in soil geochemistry. The first part of this thesis has been devoted to the electrodeposition and the characterizations of birnessite by electrochemical methods coupled with X-ray diffraction. The in-situ XRD characterization during electrodeposition has shown, in presence of the electrolytic cation Na+, the formation of a precursor, buserite, whereas no precursor is formed in presence of electrolytic cation K+, the synthesis leading directly to birnessite. The electrochemical reduction of birnessite has also been studied in function of the medium ([Mn (II)], pH, potential). Birnessite is reduced into hausmannite (Mn3O4), feitknechtite (-MnOOH), or an amorphous compound of Mn (II), as function of experimental conditions. In the second part of this thesis, the thin films have been used to study the reactivity of birnessite for degrading glyphosate and its metabolite AMPA (amino-methyl phosphonic). Glyphosate is degraded with simultaneous formation of AMPA, formaldehyde, phosphate ion, nitrate ion and ammonium ion, without macroscopic modification of birnessite. The last four by-products are also obtained during the degradation of AMPA by birnessite. The good yields obtained during glyphosate / birnessite and AMPA / birnessite interactions permit to envisage a possible application of these thin films for the treatment of wastewater
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Öijerholm, Johan. "Ionic Transport in Metal Oxides Studied in situ by Impedance Spectroscopy and Cyclic Voltammetry." Doctoral thesis, KTH, Kemi, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-4312.
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Ionic transport in metal oxides is crucial for the functioning of a broad range of different components, such as heat resistant alloys designed for high temperature applications and oxide electrolytes in solid oxide fuel cells. This thesis presents results from in situ electrochemical studies of properties related to ionic transport in metal oxides that are important for their applications as protective oxides and ionic conductors. Heat resistant alloys of alumina-former type are known to form an adherent, slowly growing and protective aluminium oxide (Al2O3) scale that protects metals from chemical degradation at high temperature. In situ impedance spectroscopy was used to study highly pure and dense samples of a-alumina in the temperature range 400 – 1000 °C. It was shown that surface conduction on the sample could severely distort the measurement below 700 °C. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements. By varying the grain size of the sintered alpha-alumina samples, the influence of grain size on the overall conductivity of the a-alumina was studied. It was shown that the activation energy for conductivity increased as the grain size decreased. Molecular dynamics calculations were performed in order to elucidate whether Al- or O ions are dominant in the ionic conductivity of the alpha-alumina. Comparing the calculation and experimental results, the dominating charge carrier was suggested to be oxygen ions. Moreover, the ionic transport in thermally grown alumina-like oxide scales formed on a FeCrAl alloy was studied in situ by impedance spectroscopy between 600 and 1000 °C. It was shown that the properties of these scales differ largely from those of pure and dense alpha-alumina. Furthermore, the conductivity is mainly electronic, due to the multiphase/multilayer microstructure and substantial incorporation of species from the base metal. However, the diffusivity obtained from the ionic conductivity was in line with diffusion data in literature obtained by other methods such as thermogravimetry. Besides, the initial stage of oxidation of a number of Fe-, Ni- and Co-based alloys at temperatures between 500 and 800 °C was studied in situ by high temperature cyclic voltammetry, in which the oxygen activity was changed over a wide range. From the resulting voltammograms the redox reactions occurring on the alloy surface could be identified. It was concluded that the base metal oxidized readily on these alloys before a protective chromia- or alumina-like scale is formed. The base metal oxide is most likely incorporated into the more protective oxide. Further, the oxygen ionic conductivity of highly pure and fully dense yttria-stabilized zirconia produced by spark plasma sintering was studied by impedance spectroscopy. The aim was to evaluate intrinsic blocking effects on the ionic conduction associated with the space charge layer in the grain boundary region. It was observed that the ionic conductivity of the spark plasma sintered oxides is equal or slightly higher than what has been achieved by conventional sintering methods. In addition, it was shown that the specific grain boundary conductivity increases with decreasing grain size, which can be explained by a decreasing Schottky barrier height (i.e., decreasing blocking effect). The quantitative results from this work verify the space charge model describing the influence of grain size on the ionic conductivity of yttria-stabilized zirconia through dopant segregation and oxygen vacancy depletion along the grain boundaries.QC 20100825
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Chew, Mei. "Investigation of uranium redox chemistry and complexation across the pH range by cyclic voltammetry." Thesis, Loughborough University, 2013. https://dspace.lboro.ac.uk/2134/13475.
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The current option for the management of Intermediate-Level Waste (ILW) and High-Level Waste (HLW) in the UK is to store it in stainless steel containers and then placed in a deep underground Geological Disposal Facility (GDF). This may subsequently be backfilled with a cementitious material generating very high pH conditions. The eventual corrosion of the stainless steel canisters containing the waste used for disposal will lead to reducing conditions thereby promoting a low Eh environment. Electrochemical experiments are needed to determine which uranium species is/are present at a particular pH and to model the redox behaviour of aqueous uranium in a potential GDF. The main aim of this project is to use cyclic voltammetry to deduce peak potentials for the various uranium redox couples in aqueous solution across the pH range and in particular the hyperalkaline range, as the surroundings of a GDF will be in high pH conditions. Data in the literature have been obtained only under acidic conditions where they were subsequently extrapolated to obtain data for alkaline conditions in some reports. Is this valid however? Experiments are therefore needed to obtain fundamental data under alkaline conditions to fill in gaps in the literature. In addition to radionuclides, complexing organic ligands present in a cementitious repository could have an important effect on the immobilisation of radionuclides in concrete. This is due to the ability of the ligands to form complexes with cations, thereby enhancing their solubility and mobility in the cement pore water. Four different ligands were investigated in this project that are relevant to nuclear waste disposal which comprised of carbonate, ethylenediaminetetraacetic acid (EDTA), gluconic acid and α-isosaccharinic acid (α-ISA). The peak potentials of each uranium redox reaction in aqueous solution were measured and the potentials were compared in ligand and non-ligand systems. The voltammograms were compared to obtain their similarities and differences in terms of the shape of the cyclic voltammograms, peak potentials, reversibility, current responses and etc. Analysis of the similarities and differences was needed to be able to increase the understanding of the complexation effects of these ligands with uranium under different pH conditions in aqueous solution.
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Öijerholm, Johan. "Ionic transport in metal oxides studied in situ by impedance spectroscopy and cyclic voltammetry /." Stockholm : Division of Corrosion Science, Department of Chemistry, School of Chemical Science and Engineering, Royal Institute of Technology, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-4312.
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Chu, Suk-ling. "The first synthesis and structure of diazatetrathiafulvalenes and some spectroscopic and cyclic voltammetric measurements /." [Hong Kong : University of Hong Kong], 1993. http://sunzi.lib.hku.hk/hkuto/record.jsp?B13544548.
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朱淑玲 and Suk-ling Chu. "The first synthesis and structure of diazatetrathiafulvalenes and somespectroscopic and cyclic voltammetric measurements." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1993. http://hub.hku.hk/bib/B31211392.
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Long, Hunter Wayne. "Improving Fast-Scan Cyclic Voltammetry and Raman Spectroscopy Measurements of Dopamine and Serotonin Concentrations via the Elastic Net." Thesis, Virginia Tech, 2016. http://hdl.handle.net/10919/71679.
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Dopamine and serotonin are two neurotransmitters known to both play a very important role in the human brain. For example, the death of dopamine producing neurons in a region of the brain known as the substantia nigra are known to cause the motor symptoms of Parkinson's disease. Also, many antidepressants are believed to work by increasing the extracellular level of serotonin in the brain. For the first time, it is now possible to measure the release of these two chemicals at sub-second time resolution in a human brain using a technique known as fast-scan cyclic voltammetry, for example from patients undergoing deep brain stimulation (DBS) electrode implantation surgery.
In this work, we aimed to assess the feasibility of obtaining veridical dual measurements of serotonin and dopamine from substrates with mixtures of both chemicals. In the wet lab, data was collected on known concentrations of dopamine and serotonin and then used to make models capable of estimating the concentration of both chemicals from the voltammograms recorded in the patients. A method of linear regression known as the elastic net was used to make models from the wet lab data. The wetlab data was used to compare the performance of univariate and multivariate type models over various concentration ranges from 0-8000nM of dopamine and serotonin. Cross validation revealed that the multivariate model outperformed the univariate model both in terms of the linear correlation between predictions and actual values, and pH induced noise. The pH induced noise for the univariate model was 3.4 times greater for dopamine and 4.1 times greater for serotonin than the multivariate model.
Raman spectroscopy was also investigated as a possible alternative to fast-scan cyclic voltammetry. Raman spectroscopy could have several benefits over fast-scan cyclic voltammetry, including the ability to chronically implant the measurement probe into a patient's brain and make observations over a long period of time. Raman spectroscopy data was collected on known concentrations of dopamine to investigate its potential in making in vivo measurements, however this data collection failed. Therefore, simulations were made which revealed the potential of the elastic net algorithm to determine the Raman spectra of several neurotransmitters simultaneously, even when they are in mixtures and the spectra are obstructed by the noisy background. The multivariate type model outperformed the univariate type model on Raman spectroscopy data and was able to predict dopamine with an error of 805nM RMS and serotonin with an error of 475nM RMS after being trained on concentrations smaller than 5uM of both dopamine and serotonin. In addition, the original Raman spectra of both neurotransmitters was extracted from the noise and reproduced very accurately by this method.Master of Science
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Hopwood, Sarah Elizabeth. "Control of serotonin release in the dorsal and median raphe nuclei." Thesis, Queen Mary, University of London, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.369264.
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Osipovich, Nikolai P., Sergei K. Poznyak, Vladimir Lesnyak, and Nikolai Gaponik. "Cyclic voltammetry as a sensitive method for in situ probing of chemical transformations in quantum dots." Royal Society of Chemistry, 2016. https://tud.qucosa.de/id/qucosa%3A36419.
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The application of electrochemical methods for the characterization of colloidal quantum dots (QDs) attracts considerable attention as these methods may allow for monitoring of some crucial parameters, such as energetic levels of conduction and valence bands as well as surface traps and ligands under real conditions of colloidal solution. In the present work we extend the applications of cyclic voltammetry (CV) to in situ monitoring of degradation processes of water-soluble CdTe QDs. This degradation occurs under lowering of pH to the values around 5, i.e. under conditions relevant to bioimaging applications of these QDs, and is accompanied by pronounced changes of their photoluminescence. Observed correlations between characteristic features of CV diagrams and the fluorescence spectra allowed us to propose mechanisms responsible for evolution of the photoluminescence properties as well as degradation pathway of CdTe QDs at low pH.
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McGovern, William Robert. "Characterization of carbon-molecule-metal junctions by cyclic voltammetry, raman spectroscopy and X-Ray photoelectron spectroscopy." The Ohio State University, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=osu1114560996.
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Tammela, Petter. "Preparation and characterization of a metal hydride electrode." Thesis, Uppsala universitet, Oorganisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-180160.
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Metal hydrides are used as anode material in nickel metal hydride batteries and are of particular interest because of the potential to be a part of energy systems completely involving renewable sources (e.g. solar power, wind power etc.). Preparation and electrochemical characterization of metal hydride electrodes have not previously been performed at the Department of Chemistry – Ångström Laboratory. Two basic techniques that are desired to be used in the characterization are cyclic voltammetry and chronopotentiometry. This thesis work is aimed at preparation and electrochemical characterization of a metal hydride electrode and, as a complement, study the electrode with X-ray diffraction. LaNi3.55Co0.75Mn0.4Al0.3, a standard material for metal hydride electrodes previously studied by Khaldi et al. was chosen, to ensure that electrochemical absorption of hydrogen was possible, and to be able to compare electrochemical results [1-3]. LaNi3.55Co0.75Mn0.4Al0.3 was synthesized with arc melting, with additional annealing at 900˚C for five days, ground in a cemented carbide ball mill and sieved to less than 56 µm. Electrodes were prepared containing 90 wt.-% of LaNi3.55Co0.75Mn0.4Al0.3 powder, 5 wt.-% of polytetrafluoroethylene and 5 wt.-% of carbon black. The hydrogen absorption and desorption capabilities of the electrode were studied electrochemically with cyclic voltammetry and chronopotentiometry, and the structural changes associated with absorption of hydrogen was studied with X-ray diffraction. The capacity increased, probably from activation of the material, during initial cycling up to the maximum capacity of 294 mAh/g, obtained after 9 cycles, followed by a small decrease, probably caused by corrosion and passivation of the material, in capacity of the remaining 11 cycles. Activation of the material causes the charge and the discharge potential to shift to a more positive and a more negative value, respectively. The final values for the charge potential and the discharge potential were -841mV and -945 mV vs. Hg/HgO, respectively, after 16 cycles. Khalid et al. [1-3]reported a maximum capacity of 300 mAh/g, a charge potential of about -960 mV and a discharge potential of about -840 mV after 16 cycles the results obtained in this study are considered to be in good agreement with those reported. X-ray diffraction of the electrodes revealed, as expected, a cell volume change of the charged electrode compared to the discharged electrode. The change in cell volume corresponds to an estimated capacity of 303 mAh/g, which is very close to the, above mentioned, electrochemically obtained maximum capacity of 294 mAh/g.
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Yeary, Amber J. "Cetyltrimethylammonium Halide-Coated Electrodes for the Detection of Dopamine in the Presence of Interferents." Wright State University / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=wright1323471405.
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Ntshongontshi, Nomaphelo. "Cytochrome P450-3A4/copper-poly(propylene imine)- polypyrrole star co-polymer Nanobiosensor system for delavirdine – a non-nucleoside reverse transcriptase inhibitor HIV drug." University of the Western Cape, 2014. http://hdl.handle.net/11394/4446.
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>Magister Scientiae - MScHIV and AIDS are among the world's pandemics that pose serious concern to almost every individual in the world. With the current level of availability of anti-retroviral (ARV) drugs and the ease of accessibility of treatment in many countries such as South Africa, the disease can be controlled by suppressing the viral load of an infected individual. These anti HIV drugs such as delavirdine are metabolised by enzymes which are found in the liver microsomes, particularly those of the cytochrome P450 family. Due to the fact that the metabolic rate of a patient determines the effect of the drug, the drug could either have a beneficial or an adverse effect once it is administered. It is therefore imperative that the metabolic profile of a patient is determined at point-of-care is necessary for proper dosing of the ARV drugs. In this project a nanobiosensor system was devised and used for the determination of the metabolism of delavirdine, a non-nucleoside reverse transcriptase inhibitor (NNRTI) ARV drug. The nanobiosensor was prepared by the entrapment of the isoenzyme CYP3A4 into a pre-formed electro active carrier matrice consisting of a dendrimeric copper generation-2 poly (propylene imine)-co-polypyrrole star copolymer (Cu(G2PPI)-co-PPy). The metallo-dendrimer was used as a host for the enzyme and provided thenecessary bio-compatible environment that allowed the direct transfer of electrons between the enzyme's active centres and platinum electrode surface. Copper was the choice of metal used in the study due to its properties. Copper is a malleable, ductile and a good conductor of both heat and electricity. It is a better conductor than most metals. Silver which also belongs to group 1b in the periodic table is a better electrical conductor than copper but copper has better corrosion resistance and is a more abundant and hence it is a cheaper material to use. Cu(G2PPI)-co-PPy was prepared by the incorporation of the copper metal into the G2PPI and the electropolymerization of pyrrole onto the Cu(G2PPI). The incorporation of Cu into G2PPI was determined by FTIR which did not show the presence of the Cu but showed an increase in the intensities of the peaks after the incorporation. The surface morphology of Cu (G2PPI) was confirmed by the use of HRSEM which showed a difference in the surface morphology of the dendrimer moiety with the addition of the copper metal. The HRSEM images after Cu incorporation resulted in the change from rough surface to smooth surface with open cavities which were essential for the entrapment of the biological systems (CYP3A4). Energy dispersive spectrometry (EDS) and HRTEM were used to confirm the presence of spherically shaped copper nanoparticles in the Cu (G2PPI) and were found to have a size distribution of 12-17 nm with an average particle size of 15nm. The star copolymer (Cu(G2PPI)-co-PPy) was characterised using cyclic voltammetrywhere it was confirmed that the material was electroactive and conducting due to electron movement along the polymer chain. A diffusion co-efficient (D₀) value of 8.64 x 10⁻⁵ cm²/s was determined for the material indicating a slow electron transfer kinetics within the diffusion layer. The constructed nanobiosensor was developed using copper poly (propylene imine) – polypyrrole star copolymer, bovine serum albumin and glutaraldehyde coupled to the enzyme CYP3A4. The resultant nanobiosensor parameters include a dynamic linear range (DLR) of 0.01-0.06 nM, a limit of detection (LOD) of 0.025 nM and a sensitivity value of0.379 μA/nM.
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Waqar, Ammar Bin. "Exploration of Electrodeposition of Aluminum-Nickel Alloys and Multilayers in Organic Chloroaluminate Ionic Liquids." Scholar Commons, 2014. https://scholarcommons.usf.edu/etd/5397.
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Aluminum-nickel (Al-Ni) alloys and Al/Ni bilayers were successfully electrodeposited from AlCl3-EMIM-NiCl2 electrolyte at room temperature. Dissolution of NiCl2 was shown to be favorable in Lewis basic (with molar ratio of AlCl3 < 0.5) AlCl3-EMIM solution. The use of electrochemically active Cu working electrode as opposed to inert W induced additional Cu oxidation and dissolution in the cyclic voltammetry scan. The reduction potentials of Al and Ni were found to be ~ – 0.3 and 0.15 V vs. Al/Al3+ respectively. Increasing [NiCl2] in the electrolyte leads to an increase of Ni concentration in the deposited structures. Dense and well-adherent Al-Ni alloys with Ni concentration up to 17.7 at.% were deposited by potential control. XRD analysis revealed that the deposited Al-Ni exhibit a supersaturated fcc crystalline structure. The visual appearance of the deposits ranged from bright silver, dull silver, grey, to black, where the darker shade typically indicated higher Ni content. SEM analysis revealed that the surface morphology of the deposits ranged from nodular to flake-like structures. Al-Ni alloy typically showed nodular morphology with cauliflower structure. Flake structures, which were independent of substrate roughness, were found to develop under pulsed potential deposition with 1:1 duty ratio.
The concentration of Ni in electrodeposited Al-Ni alloys increases nonlinearly with the increase in molarity of NiCl2. Al and Ni contents increase with increasing the time of positive and negative cycle of the pulse respectively. Decreasing the frequency by half resulted in almost double the amount of Ni in the deposited alloy. A smoother substrate increased Ni concentration from 6 to 17.7 at.%. Al/Ni bilayer was successfully deposited in 1.5:1 AlCl3-EMIM containing 0.026 M NiCl2. Deposition of Al on Ni was achieved using constant potential and pulse potential control. The deposition of Ni on Al is complicated since the deposition potential of Ni lies in the vicinity of Al stripping potential thus inducing competition between Ni deposition and Al stripping.
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Patel, Kishan. "Determination of the hydrogen peroxide concentration in rotenone induced dopaminergic cells using cyclic voltammetry and amplex red." Honors in the Major Thesis, University of Central Florida, 2012. http://digital.library.ucf.edu/cdm/ref/collection/ETH/id/600.
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Parkinson's disease (PD) is a neurodegenerative condition that affects millions of people worldwide. The exact etiology of PD is unknown. However, it is well established that environmental factors contribute to the onset of PD. In particular, chemicals such as the insecticide Rotenone have been shown to increase the death of dopaminergic (DA) neurons by increasing levels of reactive oxygen species (ROS). ROS such as hydrogen peroxide (H2O2) have been shown to be elevated above basal levels in PD patients. Currently, to measure H2O2 concentrations, a commercially available (Amplex® Red) fluorescent assay is used. However, the assay has limitations: it is not completely specific to hydrogen peroxide and can only measure extracellular ROS concentrations. This research focuses on testing an electrochemical sensor that uses cyclic voltammetry to quantitatively determine concentrations of H2O2 released from a cell culture. The sensor was first tested in normal cell culture conditions. Next, chemical interference was reduced and the sensor was optimized for accuracy by altering protein concentrations in the media. Finally, Rotenone was added to a cell culture to induce H2O2 production. Near real-time measurements of H2O2 were taken using the sensor and comparisons made to the fluorescent assay method. Overall, we are trying to determine if the electrochemical sensor can selectively and quantitatively measure H2O2 released from cells. Being able to track the production, migration and concentration of H2O2 in a cell can help researchers better understand its mechanism of action in cell death and oxidative damage, thus getting closer to finding a cure for PD.B.S.
Bachelors
Burnett School of Biomedical Sciences
Molecular and Microbiology
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Potgieter, Dawid. "Using fast-scan cyclic voltammetry to investigate monoamine release in BAC transgenic rodent models of Parkinson's disease." Thesis, University of Oxford, 2014. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.665164.
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Parkinson's disease (PD) is the most common neurodegenerative movement disorder. Nigrostriatal dopamine (DA) neurons are particularly susceptible to degeneration in PD, and the concomitant loss of DA signalling in the striatum is believed to underlie the motor symptoms of PD. Transgenic rodent models expressing PD-related genes have previously revealed changes to DA synapse function as one of the earliest stages of PD progression, often preceding protein aggregation and cell death. However, such models often rely on foreign gene promoter elements that do not accurately replicate the genetic expression pattern and protein levels found in PD. This thesis explores the electrically evoked release of two monoamines, DA and 5- HT (serotonin), in mice that express wild-type human (-synuclein at a range of levels, through a bacterial artificial chromosome vector (BAC), on a mouse synuclein-null background. Potential mechanisms underlying monoamine neurotransmission deficits were also investigated. Furthermore, this thesis explored the evoked release of DA in BAC transgenic rats that express the G2019S and R1441C mutant forms of the human Leucine-rich repeat kinase 2 (LRRK2) gene. All of the models covered express PD-related genes under regulation of endogenous promoter elements, which increases the physiological relevance of gene expression pattern and levels of gene expression in comparison to transgenes with foreign promoters. Fast-scan cyclic voltammetry, using carbon fibre microelectrodes, was used to sample electrically evoked DA and 5-HT in acute brain slices. High performance liquid chromatography was used to determine DA content. Mice that express relatively high levels of human (-synuclein (SNCA-C mice), at approximately double the level ofWT mice, have a -30% deficit in evoked DA release from the dorsal striatum, but not the ventral striatum, when compared to control mice (Snca -j-). Investigations performed here showed that the DA release deficit depends on the level of human (-synuclein expression. It was also identified that SNCA-C mice do not have detectable changes to the responsiveness ofDA D2 autoreceptors that regulate DA release. However, DA release in SNCA-C mice was more responsive than Snca -j- controls to the vesicle mobilising properties of cocaine, which suggests altered vesicle mobilisation as a possible mode of action for (-synuclein overexpression. No changes to 5-HT release, explored in substantia , nigra, were observed in SNCA-C mice suggesting that the deficit in neurotransmission does not apply to all monoamines. Rats that express the G2019S or R1441C mutant forms ofLRRK2 revealed an agedependent deficit of evoked DA release in the dorsal striatum, but not the ventral striatum. This deficit in DA release was not accompanied by changes to striatal DA content or the rate of DA uptake, which suggests a change in DA releasability. Taken together, these data suggest that PD related forms of SNCA and LRRK2 cause changes to DA function by affecting DA releasability from axons. Findings presented here are in agreement with other literature to suggest changes in DA synapse function as one of the earliest stages of PD pathophysiology, and may contribute to a deeper understanding of the molecular mechanisms involved in PD.
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Kathiwala, Mehjabin Abdul Majid. "Measurement of stress and disease markers in biological fluids by fast scan cyclic voltammetry and HPLC-UV." [Gainesville, Fla.] : University of Florida, 2009. http://purl.fcla.edu/fcla/etd/UFE0024706.
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Rustin, Gavin James Mr. "The Analysis of the Decomposition of Hydrogen Peroxide Using a Schiff Base Copper Complex By Cyclic Voltammetry." Digital Commons @ East Tennessee State University, 2014. https://dc.etsu.edu/honors/224.
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Copper(II) complexes of Schiff bases can be used in the catalysis of hydrogen peroxide to create water and oxygen. The mechanism and the kinetics of this disproportionation reaction by a dimeric copper(II) complex [CuSALAD]2 are studied in this experiment, where SALAD refers to a Schiff Base ligand formed from salicyaldehyde and 1S,2S-D(+)-1-phenyl-2-amino-1,3-propanediol. By using cyclic voltammetry, the oxidation-reduction processes of a reaction may be monitored. The [CuSALAD]2 is initially reacted with a base such as imidazole to form the catalytic species, and the ratio of the copper(II) complex to the imidazole was found to be 1:4, consistent with previous electron absorption (UV-Vis) spectroscopy experiments. The reduction and oxidation half waves of the copper(II) catalyst are followed via cyclic voltammetry to determine if the copper(II) center undergoes reduction to copper(I) during the hydrogen peroxide catalysis. It appears that while the major oxidation and reduction half wave potentials, E1/2=6.51x10-2V, are unchanged during the decomposition, an additional oxidation wave (E1/2=1.43x10-1V) is observed in the absence of oxygen, suggesting some portion of the copper is reduced. With this information, a mechanism was proposed having copper as a catalyst and creating an intermediate that would form the water and the elemental oxygen.
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Palmero, David A. "Comparison of cyclic voltammetry and HPLC for the determination of phenol in over-the counter sore throat sprays /." View abstract, 1999. http://library.ctstateu.edu/ccsu%5Ftheses/1540.html.
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Thesis (M.S.)--Central Connecticut State University, 1999.Thesis advisor: James V. Arena, Ph. D. " ... in partial fulfillment of the requirements for the degree of Master of Science in Chemistry." Includes bibliographical references (leaf 48).
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Qian, Zepeng. "CYCLIC VOLTAMMETRIC DETERMINATION OF 17-α-ETHINYL ESTRADIOL ON DISPOSABLE SCREEN-PRINTED CARBON ELECTRODES." Miami University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=miami1565371346943373.
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Fattori, Alberto. "Electrochemical and spectroelectrochemical studies of dyes used in dye-sensitized solar cells." Thesis, University of Bath, 2010. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.538162.
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Electrochemical and spectroelectrochemical techniques were employed to investigate the redox characteristics of dyes for dye sensitized solar cells (DSCs) adsorbed at the surface of fluorine-doped tin oxide (FTO) and FTO TiO2 electrodes. In this work are studied Ru-based dyes such as cis-bis(isothiocyanato)-bis(2,2’-bipyridyl- 4,4’dicarboxylato)-ruthenium(II) (N719) and (cis-RuLL'(SCN)2 with L=4,4'- dicarboxylic acid-2,2'-bipyridine and L'=4,4'-dinonyl-2,2'-bipyridine) known as Z907, and indoline organic dyes coded as D102, D131, D149, and D205. The adsorption, diffusion and stability of adsorbed dyes were studied using cyclic voltammetry in acetonitrile and 0.1 M NBu4PF6. The adsorption technique at FTO electrodes was optimized in order to be reproducible so that electrochemical studies as a function of dye coverage were carried out. Langmuirian binding constants were approximately estimated for all dyes adsorbed at FTO electrodes. Rate constants for the chemical degradation of the oxidized dye were also obtained. Is shown that degradation of the dyes mainly occurs at the surface of FTO and only insignificant degradation is evident once the dyes are adsorbed on TiO2. The degradation of dye adsorbed on FTO is shown to affect charge transport from the nonporous TiO2 via electron hopping. Spectroelectrochemical studies of indoline dyes adsorbed on FTO/TiO2 electrodes revealed a red shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near IR that suggest delocalization of holes in the dye layer. This is consistent with observation that the diffusion coefficient for hole conduction in the adsorbed dye layer is several orders of magnitude higher for the organic dyes compared to the Ru-based dyes. DSCs fabricated using indoline dyes showed good performance. Incident photon-tocurrent conversion efficiency (IPCE) spectra and I-V characteristics are presented.
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Siebritz, Robert Matthew. "The preparation of an immunosensor for the detection of microcystins and nodularins by immobilisation of a labelled antibody onto a polymer modified electrode." University of the Western Cape, 2011. http://hdl.handle.net/11394/5220.
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Masters of ScienceSouth African dams and reservoirs are increasingly showing the propensity to support sustained populations of Cyanobacteria (blue green algae). These photosynthetic bacteria occur throughout the world and can rapidly form blooms in eutrophic water systems. The occurrence of these photosynthetic bacteria, in our dwindling drinking water source dams, poses a serious, economic, as well as a health, threat to and arid country like South Africa due to is potential to produce of toxic metabolites like Microcystins and Nodularins (MCN). MCN's are cyclic peptides toxins, harmful to humans and animals, and its toxicological mechanism is based on a strong inhibition of protein phosphatises in the liver. This may lead to severe liver damage and increased tumour development. Rural communities consuming untreated water in South Africa are most at risk due the high toxicity of MCN’s at low doses.We endeavour to develop an immunosensor for the detection of Microcystins and nodularins using anti-sheep IgG antibody labelled with horseradish peroxidase (HRP) immobilised on a modified glassy-carbon polymer surface. The immunosensor will be applied to water samples for MCN’s as a group of compounds recognised by the ADDA moiety common to all MCN congeners. The immunosensor will provide immediate confirmation and quantification of MCN’s in situ. A competitive Enzyme Linked Immuno-Sorbant Assay (ELISA) and High Performance liquid Chromatography (HPLC) will be used to validate results of our immunosensor. Elisa's are widely used as a screening test method for MCN's. The antibody-antigen specificity forms the bases for the recognition of target compound (MCN's) by antibodies which bind to a compound which is labelled with a colour indicator, and quantified by spectrophotometry.
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Washington, Marlena Patrice. "Investigations of Opto-Electronically Interesting Materials Featuring Phosphorus-Carbon Double Bonds." Case Western Reserve University School of Graduate Studies / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=case1278691072.
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Farao, Al Cerillio. "Synthetic strategies for denatured cytochrome-c analogues towards analytical reporting of NOx species." University of the Western Cape, 2019. http://hdl.handle.net/11394/7012.
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Philosophiae Doctor - PhDNitric oxide (NO) plays a key role as biological messenger in the biological system, however detection and quantification thereof has always posed significant problems. NOx is a principal constituent of air pollutants. There are seven oxides of nitrogen of which N2O, NO and NO2 are most important. NO is a free radical and reacts extremely fast with oxygen, peroxides and superoxides. It’s these reactions which are responsible for NO’s fleeting existence. The specific detection and quantification of NO still remains challenging. Most techniques rely on the measurements of secondary nitrite and nitrate species. Electrochemical techniques using ultra micro-electrode systems presented the possibility of direct detection of NO, offering a range of favourable characteristics; good selectivity towards NO, good sensitivity, fast response, long-term stability and ease of handling. Electrochemical detection of NO relies on the modification of electrode surfaces and exploiting the redox properties of NO. NO can either be oxidized or reduced electrochemically depending on the nature of the solution. Under cathodic current NO is reduced to nitrosyl, a highly unstable derivative of NO. These nitrosyls are subject to a serious of chemical reactions to eventually form nitrous oxide. Due to the interferences presented by the electrochemical reduction of NO, the electro oxidation of NO is therefore the methodology of choice for NO detection. The electrochemical oxidation of NO occurs at positive potentials around 800 mV vs. Ag/AgCl. However this potential range is not only favourable to NO oxidation but can lead to the oxidation of several other biological species. These interfering species are biologically present at concentrations higher than NO therefore selectivity is of the highest order when designing these electrode systems. Some nitric oxide sensors are limited in their sensitivity, stability and reproducibility. Direct electron transfer between redox proteins and conductive membrane layers has been scrutinized for years in an attempt to reproduce the mechanistic charge transfer processes for sensor application. However, literature reports have presented many arguments on the complexities associated with depositing these enzymes on electrode surfaces for the purpose of reproducing direct electron transfer at metalloprotein centres. The study sets out to design a material which could mimic the electrochemistry of denatured cytochrome-c. To achieve this it was imperative to design a polymer which could reproduce the electrochemistry of the ligands coordinated to the metal centre of the metalloprotein. A novel Schiff base was synthesized by cross-linking naphthalene to pyrrole to produce the monomer, N,N-bis((1H-pyrrol-2-yl)methylene)naphthalene-2,3-diamine). The monomer was electrodeposited on a screen print carbon electrode (SPCE) vs. Ag/AgCl and served as a supporting layer for denatured cytochrome-c. Cytochrome-c is classified as a metalloprotein. These metalloproteins possess metal centres which when denatured unfolds and allows access to the metal centre. Cytochrome-c was subjected to thermal denaturation which opened up the iron centre. The denatured metalloprotein was cross-linked to the ligand to reconstruct the heme centre environment. This was believed to facilitate the electrochemical activity of the system and allow for electrochemical analysis of these metalloproteins for sensor application. The redox behaviour of the sensors were modelled in phosphate buffer solution (PBS) with cyclic voltammetry. Electrochemical analysis reported the sensors to possess reversible electrochemistry with diffusion control characteristics. The sensor recorded a redox system in the negative potentials range. Following the establishment of the electrochemical profile of the sensor an attempt was made to produce a synthetic analogue of denatured cytochrome-c. Iron (II) was chelated to the monomer N,N-bis((1H-pyrrol-2-yl)methylene)naphthalene-2,3-diamine) to form an iron ligand complex. The complex was subjected to a series of characterization techniques which confirmed coordination to the metal centre. The iron ligand complex was electrodeposited on a SPCE over the potential window of -1 V and 1 V to model the electrochemical behaviour of the sensor. The material was found to be electroactive. Subsequent electrochemical analysis revealed the system to have electrochemical properties, analogous to that of the denatured cytochrome-c system. The sensor was applied in NO and NO2 studies and displayed an affinity towards NO. Based on extrapolated values it was postulated that the lower limit range for NO detection was in the range of 30 to 40 nM. The potentials recorded were lower than the reported oxidation potentials for nitric oxide. The sensor displayed stability and selectivity towards nitric oxide within a complex matrix. The complex matrix employed in this study was synthetic urine that was synthesised in the lab. The sensor displayed the capacity for linear range of NO detection with very low error margins.
2021-09-01
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Zosiwe, Mlandeli Siphelele Ernest. "Cytochrome P450 2E1/Nickel-Poly(propylene imine) dendrimeric nanobiosensor for pyrazinamide - A first line TB Drug." University of the Western Cape, 2015. http://hdl.handle.net/11394/4703.
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>Magister Scientiae - MScThe tuberculosis (TB) disease to this day remains one of the world’s prominent killerdiseases. Pyrazinamide (PZA) is one of the most commonly prescribed anti- tuberculosis (anti-TB) drugs due to its ability to significantly shorten the TB treatment period from the former nine months to the current six months duration. However, excess PZA in the body causes hepatotoxicity and damages the liver. This hepatotoxicity, together with the resistance of the bacteria to treatment drugs, poor medication and inappropriate dosing, greatly contribute to the high incidents of TB deaths and diseases that are due to side effects (such as liver damage). This brings about the calls for alternative methods for ensuring reliable dosing of the drug, which will be specific from person to person due to inter-individual differences in drug metabolism. A novel biosensor system for monitoring the metabolism of PZA was prepared with a Ni-PPI-PPy star copolymer and cytochrome P450 2E1 (CYP2E1) deposited onto a platinum electrode. The nanobiosensor system exhibited enhanced electro-activity that is attributed to the catalytic effect of the incorporated star copolymer. The biosensor had a sensitivity of 0.142 µA.nM-1, and a dynamic linear range (DLR) of 0.01 nM-0.12 nM (1.231 – 7.386 ng/L PZA). The limit of detection of the biosensor was found to be 0.00114 nM (0.14 ng/L) PZA. From the HPLC peakconcentration (Cmax) of PZA determined 2 h after drug intake is 2.79 – 3.22 ng.L-1,which is very detectable with the nanobiosensor as it falls within the dynamic linear range.
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Leve, Zandile Dennis. "Determination of paracetamol at the electrochemically reduced graphene oxide-metal nanocomposite modified pencil graphite (ERGO-MC-PGE) electrode using adsorptive stripping differential pulse voltammetry." University of Western Cape, 2020. http://hdl.handle.net/11394/7350.
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>Magister Scientiae - MScThis project focuses on the development of simple, highly sensitive, accurate, and low cost electrochemical sensors based on the modification of pencil graphite electrodes by the electrochemical reduction of graphene oxide-metal salts as nanocomposites (ERGO-MC-PGE; MC = Sb or Au nanocomposite). The electrochemical sensors ERGO-Sb-PGE and ERGO-Au-PGE were used in the determination of paracetamol (PC) in pharmaceutical formulations using adsorptive stripping differential pulse voltammetry. The GO was prepared from graphite via a modified Hummers’ method and characterized by FTIR and Raman spectroscopy to confirm the presence of oxygen functional groups in the conjugated carbon-based structure whilst, changes in crystalline structure was observed after XRD analysis of graphite and GO.
2023-10-07
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Huang, Long. "Copper Electrodeposition on Iridium, Ruthenium and Its Conductive Oxide Substrate." Thesis, University of North Texas, 2003. https://digital.library.unt.edu/ark:/67531/metadc4416/.
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The aim of this thesis was to investigate the physical and electrochemical properties of sub monolayer and monolayer of copper deposition on the polycrystalline iridium, ruthenium and its conductive oxide. The electrochemical methods cyclic voltammetry (CV) and chronocoulometry were used to study the under potential deposition. The electrochemical methods to oxidize the ruthenium metal are presented, and the electrochemical properties of the oxide ruthenium are studied.
The full range of CV is presented in this thesis, and the distances between the stripping bulk peak and stripping UPD peak in various concentration of CuSO4 on iridium, ruthenium and its conductive oxide are shown, which yields thermodynamic data on relative difference of bonding strength between Cu-Ru/Ir atoms and Cu-Cu atoms. The monolayer of UPD on ruthenium is about 0.5mL, and on oxidized ruthenium is around 0.9mL to 1.0mL. The conductive oxide ruthenium presents the similar properties of ruthenium metal. The pH effect of stripping bulk peak and stripping UPD peak of copper deposition on ruthenium and oxide ruthenium was investigated. The stripping UPD peak and stripping bulk peak disappeared after the pH ≥ 3 on oxidized ruthenium electrode, and a new peak appeared, which means the condition of pH is very important. The results show that the Cl- , SO42- , Br- will affect the position of stripping bulk peak and stripping UPD peak: the stripping bulk peak will shift and decrease if the concentration of halide ions is increasing, and the monolayer of UPD will increase at the same time.
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Hlongwa, Ntuthuko Wonderboy. "Nanoparticles-infused lithium manganese phosphate coated with magnesium-gold composite thin film - a possible novel material for lithium ion battery olivine cathode." University of the Western Cape, 2014. http://hdl.handle.net/11394/4467.
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>Magister Scientiae - MScArchitecturally enhanced electrode materials for lithium ion batteries (LIB) with permeable morphologies have received broad research interests over the past years for their promising properties. However, literature based on modified porous nanoparticles of lithium manganese phosphate (LiMnPO₄) is meagre. The goal of this project is to explore lithium manganese phosphate (LiMnPO₄) nanoparticles and enhance its energy and power density through surface treatment with transition metal nanoparticles. Nanostructured materials offer advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The material can store lithium ions but have large structure change and volume expansion during charge/discharge processes, which can cause mechanical failure. LiMnPO₄ is a promising, low cost and high energy density (700 Wh/kg) cathode material with high theoretical capacity and high operating voltage of 4.1 V vs. Ag/AgCl which falls within the electrochemical stability window of conventional electrolyte solutions. LiMnPO₄ has safety features due to the presence of a strong P–O covalent bond. The LiMnPO₄ nanoparticles were synthesized via a sol-gel method followed by coating with gold nanoparticles to enhance conductivity. A magnesium oxide (MgO) nanowire was then coated onto the LiMnPO₄/Au, in order to form a support for gold nanoparticles which will then form a thin film on top of LiMnPO₄ nanoparticles crystals. The formed products will be LiMnPO₄/Mg-Au composite. MgO has good electrical and thermal conductivity with improved corrosion resistance. Thus the electronic and optical properties of MgO nanowires were sufficient for the increase in the lithium ion diffusion. The pristine LiMnPO₄ and LiMnPO₄/Mg-Au composite were examined using a combination of spectroscopic and microscopic techniques along with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiMnPO₄/Mg-Au composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiMnPO₄ due to the presence of the conductive additives in the LiMnPO₄/Mg-Au composite. This is demonstrated in the values of the diffusion coefficient (D) and the values of charge and discharge capacities determined through cyclic voltammetry. For the composite cathode, D= 2.0 x 10⁻⁹ cm²/s while for pristine LiMnPO₄ D = 4.81 x 10⁻¹⁰ cm2/s. The charge capacity and the discharge capacity for LiMnPO₄/Mg-Au composite were 259.9 mAh/g and 157.6 mAh/g, respectively, at 10 mV/s. The corresponding values for pristine LiMnPO₄ were 115 mAh/g and 44.75 mAh/g, respectively. A similar trend was observed in the results obtained from EIS measurements. These results indicate that LiMnPO₄/Mg-Au composite has better conductivity and will facilitate faster electron transfer and therefore better electrochemical performance than pristine LiMnPO₄. The composite cathode material (LiMnPO₄/Mg-Au) with improved electronic conductivity holds great promise for enhancing electrochemical performances, discharge capacity, cycle performance and the suppression of the reductive decomposition of the electrolyte solution on the LiMnPO₄ surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiMnPO₄ nanopowder cathode material.
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Paschkewitz, Timothy Michael. "Ammonia Production at Ambient Temperature and Pressure: An Electrochemical and Biological Approach." Diss., University of Iowa, 2012. https://ir.uiowa.edu/etd/4893.
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The majority of power generated worldwide is from combustion of fossil fuels. The sustainability and environmental impacts of this non renewable process are severe. Alternative fuels and power generation systems are needed, however, to cope with increasing energy demands. Ammonia shows promise for use in power generation, however it is costly to produce and very few methods of using it as a fuel are developed. To address the need for alternative methods of ammonia synthesis, this research designed and tested a bioelectrochemical device that generates NH3 through electrode induced enzyme catalysis. The ammonia generating device consists of an electrode modified with a polymer that contains whole cell Anabaena variabilis, a photosynthetic cyanobacterium. A. variabilis contains nitrogenase and nitrate/nitrite reductase, catalysts for the production of ammonia. In this system, the electrode supplies driving force and generates a reductive microenvironment near cells to facilitate enzymatic production of NH3 at ambient temperatures and pressures.
Farm animal wastes contain significant amounts of NO2- and NO3-, which can leech into groundwater sources and contaminate them. The system described here recycles NO2- and NO3- to NH4sup+ by the nitrate/nitrite reductase enzyme. Unlike nitrogen fixation by the nitrogenase enzyme whose substrate is atmospheric N2, the substrates for nitrate/nitrite reductase are NO2- and NO3-. The ammonia produced by this system shows great potential as a crop fertilizer.
While the substrates and enzymatic basis for ammonia production by nitrogenase and nitrate/nitrite reductase are very different, there is utility in the comparison of commercially produced ammonia by the Haber Bosch synthesis and by the bioelectrocatalytic device described here. In one day, the Haber Bosch process produces 1800 tons of NH3 at an energetic cost of $500/ton. Per ton of ammonia, the Haber Bosch process consumes 28 GJ of energy. The bioelectrocatalytic device produces 1 ton of NH3 for $10/ton, consuming only 0.04 GJ energy, which can be obtained by sunlight via installation of a photovoltaic device. Thus, the system presented here demonstrates ammonia production with significant impact to the economy.
NH3 production by the bioelectrocatalytic is dependent upon A. var. cell density and electrode polarization. The faradaic current response from cyclic voltammetry is linearly related to cell density and ammonia production. Without electrode polarization, immobilized A. var. do not produce ammonia above the basal level of 2.8 ± 0.4 ΜM. Ten minutes after cycled potential is applied across the electrode, average ammonia output increases to 22 ± 8 ΜM depending on the mediator and substrate chemicals present. Ammonia is produced by this system at 25 °℃ and 1 atm. The electrochemical basis for enhanced NH3 by immobilized cyanobacteria is complex with multiple levels of feedback.
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SWANSON, DALE DORSETT. "ELECTROCHEMICAL AND SPECTROSCOPIC STUDIES OF THIOETHER COORDINATION COMPLEXES (CYCLIC VOLTAMMETRY, OCTAHEDRAL LOW-SPIN METALS, BLUE COPPER PROTEINS, ELECTRON PARAMAGNETIC RESONANCE)." Diss., The University of Arizona, 1985. http://hdl.handle.net/10150/188102.
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The bis 1,4,7-trithiacyclononane (1,4,7-TTCN) complexes of iron, cobalt, nickel and copper are reported in this work. Their properties have been examined using computer-controlled electrochemical and spectroscopic techniques. These TTCN complexes form readily, are unusually symmetrical and support electron transfer reactions at the metal center. The cobalt(II) complex is octahedral, low spin and symmetrical. Four oxidation states of cobalt-TTCN complex are observed; two one-electron transfer processes are reversible. Copper (II) bis 1,4,7-TTCN is unusually symmetrical evidenced by both solid phase and ambient temperature aqueous phase electron paramagnetic resonance spectra. An unusually high redox potential for the copper complex indicates extraordinary stability of the Cu(I) oxidation state but evidently not at the expense of Cu(II) stability. The complex also has a high formation constant compared to other copper-thioether complexes. This unusual strength of thioether donor is attributed to ligand geometry. The 1,4,7-TTCN molecule is the only known cyclic polythioether to have all sulfur atoms endodentate. This structure contributes to thermodynamic stability of complexes as the ground state configuration of the free ligand is maintained in the complex.
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Guan, Shaoliang. "Determination of the role of nanoparticle active sites in catalytic hydrogenation reactions by cyclic voltammetry and novel in-situ surface spectroscopy." Thesis, Cardiff University, 2014. http://orca.cf.ac.uk/73388/.
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Cyclic Voltammetry, Surface Enhanced Raman Spectroscopy and SHell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) have been used to investigate two types of heterogeneously catalysed hydrogenation reactions – hydrogenation of selected alkynes and the Orito reaction. Using a spectro-electrochemical flowcell, which is designed and built in-house, the selectivity and reactivity of the reactions on platinum surfaces have been truly discovered. By studying hydrogenation of a range of alkyne molecules, including 2-butyne-1,4-diol, 2-pentyne, 4-octyne, propargyl alcohol and 2-methyl-3-butyn-2-ol, on different platinum surfaces, it was found that alkyne adsorption on Pt defect sites produces a long-lived di-sigma/pi- alkene complex which may undergo further hydrogenation to produce alkane. This complex may form on different surfaces with various orientations. However, depending on the specific molecules, the intermediate may not survive on some surfaces due to the steady state conditions arising from the catalytic reaction whereby adsorption of alkyne and hydrogenative desorption of reaction intermediates determines the overall surface coverage of intermediate as a function of potential. Alkene selectivity can be increased by blocking defect sites, using polyvinylpyrrolidone or bismuth, leaving only platinum{111} terraces available for catalysis. By studying ethyl pyruvate (EP) adsorption on different surfaces of platinum and palladium, it was found that EP half-hydrogenated state (HHS) is a critical intermediate of the hydrogenated product which only forms on the step sites of the platinum surface at the hydrogen evolution reaction potential. However, another new intermediate adsorbate, which is believed to be a η1 species and is believed to be a precursor of the HHS only forms on the terraces of the surface. By studying the surface intermediates formed during hydrogenation of EP at palladium modified platinum single crystal electrodes, it was found that there was no unequivocal evidence for bands pertaining to EP adsorption on palladium could be identified under hydrogenating conditions due to the reconstruction of the palladium adlayer to reveal Pt subsurface sites.
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Pal, Chandana. "Thin films of non-peripherally substituted liquid crystalline phthalocyanines A." Thesis, Brunel University, 2014. http://bura.brunel.ac.uk/handle/2438/8997.
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Three non-peripherally substituted liquid crystalline bisphthalocyanine (Pc) compounds have been studied to examine the role of central metal ions lutetium (Lu), and gadolinium (Gd) and substituent chain lengths, i.e. octyl (C8H17) and hexyl (C6H13), in determining the physical properties. For the octyl substituted Pc molecules, the head-to-tail or Jaggregates within the as-deposited spun films produced a redshift of the optical absorption Q bands in relation to their 0.01 mgml-1 solutions. Annealing at 80˚C produced a well-ordered discotic liquid crystalline (LC) mesophase causing additional redshifts irrespective of the metal ion in case of C8LuPc2 and C8GdPc2. Formation of face-to-face or H-aggregated monomers led to blueshifts of the Q bands with respect to solution spectra for C6GdPc2, both as-deposited and annealed films. Stretching and bending vibrations of pyrrole, isoindole, and metal-nitrogen bonds in Pc rings showed Raman bands at higher energy for smaller metal ion. However, no change was observed for the difference in chain lengths. As-deposited C8LuPc2 and C6GdPc2 produced comparable Ohmic conductivity, of the value 67.55 Scm-1 and 42.31 Scm-1, respectively. C8GdPc2 exhibited two orders of magnitude less conductivity than the other two due to the size effect of the central ion and side chain length. On annealing, an increase of Ohmic conductivity was noticed in the isostructural octyl substituted phthalocyanines on contrary to a reduced conductivity in hexyl substituted one. An optical band shift of the C8LuPc2 and C8GdPc2 thin films occurred on oxidation by bromine vapour. Oxidations of Pc-coated ITO were also achieved by applying potential at 0.88 V and 0.96 V electrochemically for the C8LuPc2 and C8GdPc2 compounds, respectively. To explore the applications of these compounds in biosensing, in situ interaction studies between bromine oxidised compounds and biological cofactors nicotinamide adenine dinucleotide (NADH) and L-ascorbic acid (vitamin C) were carried out using optical absorption spectroscopy. Thin films of a non-peripherally octyl substituted LC lead phthalocyanine was exposed to 99.9 % pure hydrogen sulfide gas to produce hybrid nanocomposites consisting of lead sulphide quantum dots embedded in the analogous metal free phthalocyanine matrix. Trapping of charge carriers caused hysteresis in the current-voltage characteristics of the film on interdigitated gold electrodes. The charge hopping distance was found to be 9.05 nm, more than the percolation limit and responsible for forming two well-defined conducting states with potential application as a memristor.
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Amirat, S., R. Rehamnia, R. Bensalem, M. Bordes, and J. Creus. "Nucleation and Growth of the Zn-Fe Alloy from a Chloride Electrolyte." Thesis, Sumy State University, 2013. http://essuir.sumdu.edu.ua/handle/123456789/35313.
Full textAbstract:
In this study, the kinetics of Zn-Fe codeposition was investigated in chloride acidic solution using
cyclic voltammetry. Anomalous codeposition is detected and this mechanism depends on the Zn(II) / Fe(II)
concentration ratio in the electrolytic bath. The study of early stages of electrodeposition showed that Zn-
Fe follows a theoretical response to instantaneous nucleation evolves into a progressive nucleation
according to the model of Scharifker and Hills. The morphology and structure of the coatings is discussed
using characterization techniques. Dense, uniform, and singlephased Zn-Fe coatings could be obtained
with a Zn-Fe ratio of 1/3.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35313
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Abu, Eme A. "Spectroelectrochemical sensing of tris (2,2 bipyridyl) ruthenium (II) dichloride hexahydrate in low ionic strength samples and the spectroelectrochemical characterization of aeruginosin A." University of Cincinnati / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1337351210.
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Kalil, Haitham Fawzy Mohamed. "NANOMATERIALS-BASED SENSORS FOR PEROXYNITRITE DETECTION AND QUANTIFICATION." Cleveland State University / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=csu151336709631904.
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Kosillo, Polina. "Investigating circuits underlying acetylcholine-evoked striatal dopamine release in health and disease." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:1675813e-0b07-4ede-9094-cdc442679394.
Full textAbstract:
Dopamine (DA) is a key striatal neuromodulator central to normal functioning of the basal ganglia. Identifying and characterizing circuits governing striatal DA transmission is necessary for understanding DA involvement in adaptive behaviour and pathology. Properties of evoked striatal DA release can be examined using fast-scan cyclic voltammetry at carbon fibre microelectrodes, a technique enabling live monitoring of transmitter release events with sub-millisecond resolution. Experimental work presented in this thesis employed this approach to study regulation of striatal DA by acetylcholine (ACh) in health and disease in acute brain slices. Synchronous activity in a small population of striatal cholinergic interneurons (ChIs) was previously shown to directly drive striatal DA release. Here using optogenetic approach I explore physiological relevance of ChI-evoked drive of striatal DA by examining whether corticostriatal and thalamostriatal afferents to ChIs can trigger ACh-evoked DA events. Following floxed vector injections in motor cortex or caudal intralaminar thalamus of CaMK2a-Cre mice I examine the properties of evoked DA upon light activation of channelrhodopsin-2-transduced inputs to striatal ChIs. These experiments revealed that both cortical and thalamic afferents are capable of driving ACh-evoked DA release, but operate using a different complement of post-synaptic ionotropic glutamate receptors and display distinct release recovery profiles. I further explore if rebound excitation in a population of striatal ChIs could drive DA events by examining whether ACh-evoked DA release follows optical inhibition of striatal ChIs selectively expressing hyperpolarizing halorhodopsin 3.0 or archaerhodopsin 3.0 in ChAT-Cre mice. This work showed that hyperpolarizing ion pumps were not successful in triggering ChI-evoked DA release. I also investigate whether cholinergic brainstem innervation of striatum could contribute to or drive ACh-evoked striatal DA events in ChAT-Cre rat, concurrently showing that ChI-evoked DA release is not a species artefact, and is present in mouse and rat alike. Current results also suggest that cholinergic brainstem afferents do not drive or contribute to striatal ACh-evoked DA events. Close interaction between DA and ACh systems further indicates that ACh could impact dopaminergic dysfunction. To explore this I examined the state of ACh transmission in a mouse model of Parkinson’s disease overexpressing human wild type alpha–synuclein protein. These animals present with impaired striatal DA release from young age, but DA deficits could be mediated by changes in ACh tone. Here I show that impaired striatal DA release is the results of primary DA axon dysfunction, although in ventral striatum DA release deficits could be partially compensated by increased ACh tone at nicotinic receptors. I further show that the functional state of muscarinic ACh receptors in not altered following decreased DA transmission, although the data from aged animals suggest that alpha–synuclein-dependent changes in vesicle handling could contribute to impaired DA releasability. Finally, I show that vesicle handling may indeed be altered in this mouse model as impaired DA release is evident with short stimulation protocols, while with prolonged depolarization of DA axon terminals alpha–synuclein-overexpressor mice are better able to sustain evoked DA release. Overall, the main body of work presented in this thesis examined the processes regulating striatal DA transmission via ACh system. In particular, I show that ChI-evoked drive of striatal DA release can be recruited physiologically and further establish that changes in ACh transmission are not the primary drivers of impaired DA releasability in a mouse model of Parkinson’s disease overexpressing human alpha–synuclein protein.
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Maoela, Manki Sarah. "Spectroelectrochemical determination of the antioxidant properties of carpobrotus mellei and carpobrotus quadrifidus natural products." Thesis, University of the Western Cape, 2009. http://hdl.handle.net/11394/3299.
Full textAbstract:
Philosophiae Doctor - PhDSouth African Carpobrotus species have been found to contain hydrolysable tannins,various flavonoids e.g. rutin and hyperoside, phytosterols and aromatic acids which have a diverse range of pharmacological properties including antimicrobial and, antioxidant activities. The main aim of the thesis was to determine the natural products in C. mellei and C. quadrifidus using chromatographic techniques and electrochemical analysis. The antioxidant activity of both Carpobrotus species was determined by using a superoxide dismutase (SOD) biosensor. ESI-LC-MS was used to separate and determine flavonoids in C. mellei and C. quadrifidus. 8 flavonoid compounds: catechin, epicatechin, epicatechin-epicatechin, coumarylquinic acid, isorhamnetin, quercetin-hexose (hyperoside), rutin and myricetin-deoxyhexose were identified. Cyclic and square wave voltammetry were used to detect flavonoids from C. mellei and C. quadrifidus. Catechin was detected in the ethyl acetate extract of C. mellei and C. quadrifidus. The oxidation potential of the plant extracts were observed at +150.6 mV to +1072.6 mV. The oxidation mechanism proceeds in sequential steps, related to the catechol moiety, -OH groups in C ring and the resorcinol group. The oxidation process of the catechol moiety involves a two electron - two proton reversible reaction and forms o-quinone. This occurs first at low potential and is a reversible reaction. The hydroxyl group in the C ring and resorcinol group oxidise there after and undergo an irreversible reaction. UV-vis and FTIR spectroscopy were used to confirm the presence of catechin in the ethyl acetate extract of both plants.UV-visible spectroelectrochemistry confirmed the oxidation process of catechin at constant potential. Since C. mellei and C. quadrifidus were confirmed to contain flavonoids by ESI-LC-MS and electrochemical analysis, the antioxidant activity was further investigated using a SOD biosensor. The superoxide dismutase (SOD) enzyme was immobilised with 1% Nafion on a platinum electrode. Detection limit and sensitivity of the SOD biosensor were found to be 0.03918 μmol L-1 and 1.44 μA(μmol L-1)-1, respectively. The results showed that C. mellei and C. quadrifidus have antioxidant activity, with relative antioxidant capacity (RAC) of 24% and 42%, respectively. May 2009
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Blavo, Selasi Ofoe. "Model Pt- and Pd-based Electrocatalysts for Low Temperature Fuel Cells Applications." Scholar Commons, 2013. http://scholarcommons.usf.edu/etd/4639.
Full textAbstract:
In the search for alternative energy technologies, low temperature fuel cells continue to feature as technologies with the most promise for mass commercialization. Among the low temperature fuel cells, alkaline and proton exchange membrane fuel cells are the most popular. Alkaline fuel cells have typically been used for water generation as well as auxiliary power for space shuttles. Their bulkiness however makes them undesirable for other applications, especially in automobiles, where there is a great demand for alternative technologies to internal combustion engines. Proton exchange membrane fuel cells on the other hand possess numerous qualities including their compact size, high efficiency and versatility. Their mass implementation has however been delayed, because of cost among other reasons. Most of this cost is owed to the Pt/C catalyst that accounts for about half of the price of the PEM Fuel Cell. This catalyst is used to drive the sluggish oxygen reduction reaction that occurs at the cathode of the PEM Fuel Cell.
To overcome this obstacle, which is to make PEM Fuel Cell technology more affordable, reducing the amount Pt has traditionally been the approach. Another approach has been to find new ideal catalyst-support combinations that increase the intrinsic activity of the supported material. One more strategy has been to find lower cost alternative materials to Pt through synthetic and kinetic manipulations to rival or exceed the current oxygen reduction reaction activity benchmark.
To this end, Palladium has garnered significant interest as a monometallic entity. Its manipulation through synthetic chemistry to achieve different morphologies - which favor select lattice planes - in turn promotes the oxygen reduction reaction to different degrees. In bimetallic or, in more recent times multimetallic frameworks, geometric and ligand effects can be used to form ideal compositions and morphologies that are synergistic for improved oxygen reduction reaction kinetics.
In this dissertation, we have explored three different approaches to make contributions to the catalysis and electrocatalysis body of literature. In the first instance, we look at the influence of ligand effects through the active incorporation of a PVP capping agent on the stability of ~3nm Pt NPs. Washed (no capping agent) and unwashed (with capping agent) batches of NPs were evaluated via cyclic voltammogram analyses to evaluate differences there might be between them. It was found that the current density measurements for unwashed particle batches were higher. This increase in current density was attributed to the monodentate and bidentate ligand bonding from the PVP, which increased as a function of cycle number and plateaued when the PVP was completely decomposed. The complete decomposition of PVP during the CV experiment was estimated to occur around 200 cycles.
The remaining portion of the dissertation explores the electrocatalytic properties of Palladium based NPs. The first instance, a monometallic study of Palladium cubes and dendrites was aimed at building on a recent publication on the enhanced ORR activity that was achieved with a PdPt bimetallic dendrite morphology. In our work, we sought to isolate the dendritic morphology properties of the monometallic Pd composition in order to understand what advantages could be achieved via this morphology. Pd cubes were used as a comparison, since they could be generated through the combination of a similar set of reagents simply by switching the order of addition. It was found that while there was no significant variation in the ORR activity as a function of morphology / shape, there was an interesting interaction between hydrogen and the palladium NPs in the hydrogen oxidation region that varied as a function of shape. This led to further sorption and ethylene hydrogenation studies, which suggested that, the interaction between hydrogen and Pd depended on the environment. Within the electrochemical environment, the ECSA measured, suggested that hydrogen was being reversibly absorbed into the sub-surface octahedral sites of Pd. The higher ECSA for Pd cubes corroborated with higher sorption for Pd cubes as well. However ethylene hydrogenation showed that the fringes of the Pd dendrites provided additional sites for reaction, which in turn translated to higher conversion. Furthermore, through a Koutecky-Levich analysis, it was found out that the Pd dendrites while exhibiting slightly lower activity, favored the 4-electron oxygen reduction process more than the Pd cubes.
In the last part of this dissertation we explored the electrocatalytic properties of Pd-based bimetallic NPs under different morphologies including nanocages and sub-10nm alloys. With the inclusion of Ag, it was found out, through Koutecky-Levich analysis that the 4-electron process was better observed under alkaline conditions using a 0.1M NaOH(aq) electrolyte solution instead of a 0.1M HClO4 (aq) for acidic media testing. It was found that, for PdAg nanocage morphologies, where the Pd galvanically replaced the Ag to form cages, the four-electron process was suited to thinner Pd shells. Indeed the average electron numbers measured for Ag nanocubes coated with a 6nm shell was in agreement, within reason of literature values for bulk Ag. However, since the binding energy that both metals have for OH is so close, the potential for contributions to the ORR kinetics in alkaline media by Pd is a potential consideration.
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Woodvine, Helena Louise. "Development and characterisation of microelectrode and nanoelectrode systems." Thesis, University of Edinburgh, 2012. http://hdl.handle.net/1842/9570.
Full textAbstract:
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.