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Knight, Andrew William. "Analytical electrogenerated chemiluminescence." Thesis, University of Hull, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.318378.
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Yurdakul, Saruhan. "Electrophoresis of electrogenerated bubbles." Thesis, Imperial College London, 1991. http://hdl.handle.net/10044/1/58542.
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The fundamental understanding of the interfacial charge on gas bubbles and the consequences of such charge are essential in understanding the behaviour of physicochemical systems involving liquid/gas and solid/liquid/gas interfaces. Such interfaces are involved in many industrial processes such as electrolytic gas evolution, particle flotation and bubble coalescence. The knowledge of such interfaces will aid mass transfer calculations. This thesis describes the application of a laser Doppler anemometer (LDA) system to the measurement of bubble electrophoretic mobilities, giving a measure of adsorbed charge. Single bubbles were electrogenerated in surfactant-free electrolytes, characterised by bubble rise rates, and their behaviour investigated in an electric field applied parallel to the direction of rise, so that, depending on the field direction, an increase or a decrease in the rise velocities was obtained. This field orientation served to decouple the hydrodynamic and field-induced charge polarisation. The velocity measurements using LDA showed a large degree of scatter despite numerous modifications to the optics and the signal processing. This culminated in the belief that a double LDA system was necessary to optimise the reliability and accuracy of the technique. Measurements using a Kodak high speed camera and recording system showed that the bubbles were negatively charged over the pH range studied (3-11), as indicated by their migration towards the anode under the influence of an applied electric field, with mobilities showing a radius and field dependence, implying that the adsorbed charge at the gas/electrolyte interface was mobile and polarisable. Large mobilities (10-60 x 10"® m2 s"^ V"^) were observed in comparison with results from previous bubble electrophoresis experiments with lateral fields. This was explained in terms of the enhanced charge polarisation occurring in the parallel electric field to the rise vector. A qualitative explanation for the decoupling of the hydrodynamic and field-induced charge polarisation has also been provided. In a separate series of experiments, under sufficient field conditions to overcome buoyancy forces, rising bubbles were stopped and held stationary. It was shown by extrapolation that bubbles possessed an iso electric point between pH 2 and 3, being positively charged below pH 2 and negatively charged above pH 3, supporting the hypothesis that the preferential adsorption of OH /H+ ions gives rise to the net charge. A laser reflection technique was investigated to measure the thickness of a liquid film formed between a bubble and the planar gas/electrolyte interface when they are in close proximity of each other. Preliminary investigations on macroscopic soap films showed the technique to be suitable for studying film thinning rates, though further refinement is necessary to study microscopic transient films. Electrophoresis measurements using a high speed camera have shown that bubbles preferentially adsorbed OH-/H+ ions from the solution in the absence of surfactants. This charge resided on a highly mobile interface and could be polarised by the actions of the hydrodynamics and the electric field. The laser Doppler anemometer system requires further development to achieve more accurate bubble velocity profiles in order to detect the small changes that occur.
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Barrett, Z. S. "The electrogenerated chemiluminescent imaging of metals." Thesis, Swansea University, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.636045.
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This thesis details the characterisation and development of the luminol Electrogenerated Chemiluminescence (ECL) reaction to enable it to spatially resolve dissimilar metal compositions at a single conductive metal surface. The large difference in ECL emission from iron and tin has been exploited to detect penetrative defects in the surface of commercial tinplate and is presented in chapter 4. Reaction conditions are selected based on the data shown in the chapter 3 such that the exposed iron substrate emits ECL at a greater intensity than the surrounding intact tin coating. In this way the defects are rapidly exposed and can be photographed using an image intensified CCD camera. Chapter 5 continues on the theme of defect detection but describes the use of ECL in exposing failures in five types of commercial galvanised coatings. In a similar manner to tinplate the reaction is optimised such that the exposed substrate emits a much greater light intensity when compared to the zinc coating. Given the success of the technique at studying macro features, efforts were made to develop the process further to allow observation of micro features and in particular the copper rich phases present in AA2024-T3. Chapter 6 details the investigations made to optimise ECL for micro use. In chapter 7, the newly optimised technique is used to follow the dealloying and redistribution of copper at the surface of AA2024-T3 - an important aerospace alloy. Again the dissimilar emission phenomenon is exploited, this time from copper and aluminium. It is shown that the origin of surface copper when the alloy is dealloyed in NaCl is predominantly from the copper rich S-phase particles rather than the matrix.
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Li, Haidong. "Electrogenerated chemiluminescence : from materials to sensing applications." Thesis, Bordeaux, 2017. http://www.theses.fr/2017BORD0560/document.
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Le phénomène d’électro chimiluminescence (ECL), également appelé chimiluminescence électrogénérée, consiste en la génération de l’état excité d’un émetteur suite à des réactions de transfert d’électrons se produisant initialement à la surface de l’électrode. L’état excité ainsi produit retourne à l’état fondamental en émettant de la lumière. Les réactions ECL se classent principalement en 2 grandes voies mécanistiques: les réactions d’annihilation et les réactions impliquant un co-réactif sacrificiel. Cette dernière voie a conduit à de très nombreuses applications en chimie analytique. Dans ce manuscrit, j’ai présenté mes travaux de thèse qui ont suivis 3 directions complémentaires depuis l’échelle moléculaire jusqu’à l’échelle macroscopique: la recherche de nouveaux luminophores ECL, l’étude de films d’hydrogels stimulables et le développement de nouvelles applications analytiques de l’ECL.Dans une première partie, j’ai étudié les propriétés ECL de 3 types de luminophores organiques. Ces composés ont montré des caractéristiques électrochimiques et ECL remarquables. L’efficacité ECL de ces luminophores organiques peut être modulée enjouant sur leurs structures respectives. Des luminophores de type spirofluorène ont produit une émission ECL très intense et les nanoparticules organiques correspondantes ont pu être utilisées comme nano-émetteurs ECL. L’étude des propriétés électrochimiques, photochimiques et ECL de luminophores cationiques de type triangulène et hélicène a été réalisée et présentée avec un formalisme montrant un «mur» ECL ou une cartographie ECL complète.Dans une seconde partie, la préparation de films d’hydrogels thermo-stimulables à base de poly(N-isopropylacrylamide) ou pNIPAM incorporant des centres redoxRu(bpy)3 a été réalisée sur des électrodes de carbone vitreux (GCE) et aussi sur des fibres de carbone par polymérisation radicalaire induite électrochimiquement. Les études ECL sur les GCEs modifiées ont montré que le facteur principal gouvernant les propriétés ECL est la distance entre les sites Ru(bpy)3. Le dépôt de tels films de pNIPAM-Ru(bpy)3 par électrochimie bipolaire ouvre de nouvelles possibilités pour le développement de micro-objets stimulables hybrides. Dans une dernière partie, comme la chimie analytique constitue un des plus importants attraits de l’ECL, deux applications analytiques sont présentées en utilisant,d’une part, des co-réactifs de type amine modifié par l’acide phénylboronique, et,d’autre part, des faisceaux de fibres optiques recouverts d’or. La réaction de complexation de saccharides par le groupe phénylboronique modifie les propriétés électrochimiques du co-réactif amine en rendant son oxydation à l’électrode inefficace,ce qui provoque la diminution du signal ECL. En changeant la longueur de l’espaceur de ces co-réactifs qui portent deux groupements phénylboroniques, nous avons pu mesurer sélectivement la concentration de D-glucose et de D-fructose. Mon travail a enfin porté sur le développement d’un objet analytique basé sur un faisceau de fibresoptiques doré qui est adressé sans contact par électrochimie bipolaire. L’ECL ainsi générée du système Ru(bpy)32+/TPrA a permis de réaliser un outil activable à distance permettant une mesure déportée via le faisceau. Ce nouvel objet analytique original devrait permettre d’étendre les mesures ECL à des environnements confinés ou dangereuxElectrogenerated chemiluminescence (ECL) involves the energetic electron transfer reactions at the electrode with the generation of excited state of emitter, which then relax to the ground state and emit light. These ECL reactions can be divided into two main pathways: the annihilation and sacrificial co-reactant reactions. The latter has found a lot of applications in analytical chemistry. In this thesis, ECL studies towardt hree complementary directions are presented, ranging from the molecular scale tomacroscopic scale : the research of new ECL luminophores, the study of stimuli-responsive hydrogel films, and the development of new ECL assays.Firstly, I have studied three types of organic dyes for ECL investigations. These organic dyes exhibit interesting electrochemical and ECL properties. ECL efficiencies of the organic dyes can be tuned by the modification of the structures. Spirofluorene dyes show strong ECL emission, and thus its fluorescence organic nanoparticles(FONs) prepared in water were used as ECL nano-emitters. We also established an energetic ECL “wall” representation and then move forward creating ECL “map”upon electrochemical, photoluminescence and ECL studies on cationic triangulenes and cationic helicenes dyes, respectively.Secondly, the preparation of thermo-responsive poly(N-isopropylacrylamide)(pNIPAM) hydrogel films covalently incorporating Ru(bpy)3 redox centers were achieved on glassy carbon electrode (GCE) or carbon fiber by electrochemically induced free radical polymerization. ECL studies on the modified GCEs have provided the main factor (the average distance of Ru(bpy)3 sites) that governs the ECL process, leading to deciphering the enhanced ECL in the films. The deposition of the films on carbon fiber by bipolar electrochemistry (BPE) has opened new route to for the development of smart hybrid micro objects. Finally, analytical application is one of the most important features of ECL. We presented two different ECL assays using either the phenylboronic acid modified amine based co-reactants or gold coated optical fiber bundle. The binding of saccharides with boronic acid modified tertiary amines makes the oxidation of amines group inefficient, which decreases ECL signal response. By changing linker length of a bis-boronic acid amine co-reactant, we are able to determine D-glucose and D-fructose selectively. We also studied the ECL generation of Ru(bpy)32+/TPrA systemon the gold coated optical fiber bundle in a wireless manner by BPE, then transmission and remote detection at the opposite end of the same object. This methodmay extend the applicability of ECL assays in the confined or hazardous environments
电化学发光（ECL）的发生是由于在电极表面通过电子转移反应生成了发光体的激发态跃迁到基态，并伴随着发光。这些电子转移反应可划分为两种主要的途径：正负自由基湮灭反应和共反应物反应。而后者被广泛应用于分析化学领域。在本论文中，我们在电化学发光领域中进行了广泛的研究，具体有三个研究方向：新型电化学发光光团的研究、响应水凝胶膜的制备以及电化学发光分析的研究。首先，我们选择了三种不同类型的有机荧光分子用于电化学发光的研究。这些有机荧光分子展现出许多电化学和电化学发光特性。其中，螺芴荧光分子展现出了非常强的电化学发光。而且用它制备的荧光有机纳米颗粒（FONs）在水相中也可以产生电化学发光。基于对阳离子型三角烯和阳离子型螺烯的电化学、光谱学以及电化学发光的研究，我们分别建立了鉴别电化学发光“墙”和“图谱”。其次，利用自由基电聚合的方法，我们实现了在玻碳电极和碳纤维表面上制备热刺激-响应的聚异丙基丙烯酰胺（p-NIPAM）共价嫁接三联吡啶钌Ru(bpy)3 荧光分子的水凝胶膜。通过对玻碳电极上水凝胶膜的电化学发光的研究，我们发现了控制水凝胶膜中电化学发光的主要因素，从而揭秘了水凝胶膜中电化学发光增强的成因。而且，利用双电极化学（BPE）的方法，我们将此类水凝胶膜的制备应用于碳纤维上，以发展灵敏杂化微米级器件。最后，鉴于化学分析是电化学发光最重要的特征，我们构建两种不同的电化学发光分析体系：一种是基于硼酸化学修饰的三丙胺共反应物；另一种是利用镀金光导纤维。硼酸对糖类的结合弱化了三丙胺的电化学氧化效率，因此影响电化学发光的强度。通过改变双硼酸修饰共混物之间碳链的长度，我们实现了对葡萄糖和果糖的选择性检测。我们还研究了在镀金光导纤维上三联吡啶钌/三丙胺体系的 电化学发光。此研究是在双电极体系进行的，镀金光导纤维无需外部接线，镀金部位产生的发光透过光纤传输的光纤的远端，再进行检测，因此达到了电化学发光的远程检测。这一方法可应用于狭窄危险环境中的电化学发光分析。
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Sentic, Milica. "Electrogenerated chemiluminescence : from mechanistic insights to bioanalytical applications." Thesis, Bordeaux, 2015. http://www.theses.fr/2015BORD0307/document.
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La chimiluminescence électrogénérée (ECL) est une technique analytique puissante exploitée pour la détection autant au niveau industriel que dans le domaine de la recherche scientifique ou du diagnostic clinique. La sensibilité élevée et la bonne sélectivité de cette technique font de l'ECL une méthode analytique de choix pour un large éventail d'applications, dont la plus importante est son utilisation commerciale dans un grand nombre de tests immunologiques à base de billes fonctionnalisées. Dans cette thèse, nous avons cherché à étudier le phénomène ECL et son application pour le développement de nouvelles techniques analytiques.Dans la première partie de ce travail, nous utilisons les techniques d'imagerie pour étudier les mécanismes ECL se produisant sur les billes utilisées pour les tests immunologiques. La cartographie de la réactivité au niveau d'une seule microparticule fonctionnalisée avec un complexe de ruthénium fournit une nouvelle stratégie visant à tester l'efficacité du co-réactif et montre des effets optiques associés de focalisation.Dans la deuxième partie, la conception d'un test immunologique pour la détection de l'anti-transglutaminase pour le diagnostic de la maladie coeliaque est présentée en utilisant des ensembles de nanoélectrodes comme plates-formes bioélectroanalytiques. Nous avons également étudié les caractéristiques de l'ECL générée par des réseaux de nanoélectrodes dopées au bore-diamant en tant que matériaux prometteurs pour des applications biologiques ainsi que l'efficacité ECL de deux co-réactifs sur ces réseaux.L'électrochimie bipolaire est un processus sans contact que nous avons exploité pour contrôler le mouvement d'objets conducteurs exposés à un champ électrique en l'absence de contact ohmique direct. Dans la troisième partie de ma thèse, nous présentons l'ECL couplée à l'électrochimie bipolaire pour le suivi d’objets autonomes luminescents. Nous avons élargi ce concept à la détection enzymatique dynamique de glucose en utilisant l'émission de lumière ECL comme signal analytiqueElectrogenerated chemiluminescence (ECL) is a powerful analytical technique exploited for clinical, industrial and research applications. The high sensitivity and good selectivity, makes ECL a tool-of-choice analytical method for a broad range of assays, most importantly for a large number of commercialized bead-based immunoassays. In the present thesis, we aimed to study the ECL phenomenon and its application in development of new analytical methods.In the first part of this work, we used an imaging technique to investigate the ECL mechanisms operating in bead-based assays. Spatial reactivity mapping at the level of a single functionalised bead provides a new strategy to test the co-reactant efficiency and shows associated optical focusing effects.In the second part, the design of a novel anti-transglutaminase ECL immunoassay for celiac disease diagnostic is shown using nanoelectrode ensembles as bioelectroanalytical platforms. We also studied the characteristics of ECL generated by arrays of boron-doped-diamond nanoelectrodes (BDD NEAs) as a promising materials for bioapplications. The ECL efficiency of two co-reactants at BDD NEAs was investigated.Finally, bipolar electrochemistry is a ‘‘wireless’’ process that was exploited for the controlled motion of conductive objects exposed to an electric field in the absence of direct ohmic contact. In the third part of the thesis, we report ECL coupled to bipolar electrochemistry for tracking the autonomous trajectories of swimmers by light emission. We further expanded this concept for dynamic enzymatic sensing of glucose concentration gradient using ECL light emission as an analytical readout
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Diaz, Miguel Angel. "Electrowinning coupled to gold leaching by electrogenerated chlorine." Thesis, Imperial College London, 1987. http://hdl.handle.net/10044/1/38284.
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Janakiraman, Umamaheswari. "Analysis of electrogenerated chemiluminescence of PPV type conducting polymers." Doctoral thesis, [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=968755305.
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Brandon, Nigel Peter. "The growth kinetics and interfacial properties of electrogenerated bubbles." Thesis, Imperial College London, 1985. http://hdl.handle.net/10044/1/37645.
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Mateo-Alonso, Aurelio. "Radical-anions of macrocyclic 1,6 dialkoxyphenazines as chiral electrogenerated bases." Thesis, Queen Mary, University of London, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.407425.
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O'Malley, Rachel Louise. "Time resolved x-ray absorption spectroscopy studies of electrogenerated species." Thesis, University of Cambridge, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.616121.
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Bazzi, Sakna. "Electrogenerated divalent samarium for CO₂ activation : applications in carboxylic acid synthesis." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS397.
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La réduction du CO₂ est considérée comme une des approches les plus intéressantes pour convertir ce gaz en produits chimique d’intérêt tels que les acides carboxyliques. Le marché de ces composés devrait augmenter considérablement au cours des prochaines années, d'où la nécessité de trouver des méthodes de production durables et respectueuses de l'environnement. Les complexes de samarium divalents sont reconnus pour leur fort pouvoir réducteur monoélectronique, ce qui en fait des réactifs de choix pour la réduction de certains groupes fonctionnels difficiles à réduire tels que le CO₂. Cependant, dans la littérature, bien que ce réactif ait été utilisé en association avec le CO₂, prouvant ainsi que la réduction du CO₂ est possible, mais jamais à notre connaissance pour des applications synthétiques. Nous rapportons ici l'activation du CO₂ initiée par le samarium bivalent électrogénéré. Grâce à notre méthode, récemment mise au point, pour la production électrochimique in situ d’espèces divalentes de samarium, la synthèse de dérivés de l’acide benzoïque a été réalisée avec succès. De plus, les conditions d'activation électrocatalytique du CO₂ ont été établies dans ce travail et appliquées non seulement à la préparation des acides phénylacétiques à partir de dérivés du chlorure de benzyle, mais également à l'hydrocarboxylation régiosélective des analogues du styrène et du phénylacétylène. Ce protocole à base de Sm (II) électrogénéré offre la prochaine génération de systèmes durables pour la transformation du CO₂ en molécules de haute valeur sous des conditions douces et sans l'ajout de co-réducteursCO₂ activation is considered one of the most attractive tools to convert this cheap, abundant and non-toxic gas into valuable chemical feedstocks such as carboxylic acids. The market value of these compounds is expecting a significant increase in the next few years, thus the urgent need for sustainable and eco-friendly production pathways. Divalent samarium complexes are known for their strong monoelectronic reductive power that made them the perfect choice for the reduction of some challenging functional groups. Indeed, in the literature, this reagent has been used in combination with CO₂ but only to achieve the reductive disproportionation of CO₂ while no example reported C-C bond formation via CO₂ activation using the Sm(II) complexes. Herein, we report the CO₂ activation initiated by electrogenerated divalent samarium. Taking advantage of our recently developed method for the in situ generation of Sm(II) species, the synthesis of benzoic acid derivatives was successfully achieved. Furthermore, electrocatalytic CO₂ activation conditions were established in this work and applied not only for the preparation of phenylacetic acids from benzyl chloride derivatives but also for the regioselective hydrocarboxylation of styrene and phenylacetylene analogs. This electrochemical Sm(II)-based protocol offers the next generation of sustainable system to transform CO₂ into highly valued molecules under mild conditions and without the addition of co-reductants
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Horcajada, Roberto. "Radical-anions of chiral and achiral 1,6-diaminophenazine derivatives as electrogenerated bases." Thesis, Queen Mary, University of London, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.401860.
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Zhao, Ming. "In situ reflection absorption spectroscopic techniques for the study of electrogenerated species." Case Western Reserve University School of Graduate Studies / OhioLINK, 1993. http://rave.ohiolink.edu/etdc/view?acc_num=case1057154581.
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Palma, Cando Alex Uriel [Verfasser]. "Electrogenerated Films of Carbazole- and Thiophene-Based Microporous Polymer Networks / Alex Uriel Palma Cando." Wuppertal : Universitätsbibliothek Wuppertal, 2017. http://d-nb.info/1128844540/34.
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Chen, Zuofeng, and 陳作鋒. "Studies on a novel type of electrogenerated chemiluminescence and electroanalysis of biomolecules at fluorosurfactant-modifiedelectrodes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B41634196.
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Chen, Zuofeng. "Studies on a novel type of electrogenerated chemiluminescence and electroanalysis of biomolecules at fluorosurfactant-modified electrodes." Click to view the E-thesis via HKUTO, 2009. http://sunzi.lib.hku.hk/hkuto/record/B41634196.
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Stewart, Alasdair J. "An investigation into the electrogenerated chemiluminescence of near-infrared quantum dots for application in biomedical sensing." Thesis, University of Strathclyde, 2014. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=24248.
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The objective of this work is two-fold; investigation of the electrochemical and electrochemiluminescent (ECL) properties of near-infrared (NIR) quantum dots (QDs) in buffer and whole blood; and their subsequent incorporation into ECL biosensing systems with potential application in whole blood analysis. QDs exhibited size-dependent optical and electrochemical properties with the largest QDs demonstrating ECL emission in the NIR region (811 nm). This should improve light penetration through whole blood, a prediction that has not yet been investigated for the ECL process. NIR QDs were shown to be flexible ECL emitters and optimisation of system parameters was implemented to obtain maximum ECL performance. This was achieved using a QD-chitosan film on a glassy carbon electrode with potassium persulfate co-reactant in phosphate buffered saline at pH 7.4. Intense reductive and oxidative ECL signals were generated directly in whole blood, which was at least ten times more intense than t hat achieved using visible region emitting QDs. The response exhibited sensitivity to blood samples spiked with clinically relevant analytes, homocysteine and dopamine, establishing the viability of NIR ECL as a detection method from whole blood. To expand the integration of NIR QDs into biosensing systems, a selective biosensor for cholesterol was developed that exhibited good stability, specificity and a clinically relevant linear range (1-5 mM). Detection in human serum was possible, however, radical quenching in whole blood limited its use as a biosensor in this environment in its current form, demonstrating the complications that can arise with analysis from such a complex matrix. For that reason, an alternative biosensor design that used conditions optimised in earlier work was used to improve system sensitivity. Fabrication of an immunosensor for IgG resulted in an ECL signal that was detected in whole blood. Following significant development, it is envisaged such a system can form the basis of a new generation of NIR ECL biosensors capable of detection directly from whole blood.
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Adam, Catherine. "Réseaux nanostructurés de fibres optiques pour la réalisation de capteurs électrochimiques et luminescents." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2013. http://tel.archives-ouvertes.fr/tel-00933333.
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La structuration et la fonctionnalisation de réseaux de fibres optiques ont été utilisées afin de réaliser différents capteurs électrochimiques et luminescents. Ce type de support permet de concevoir des capteurs capables de détecter à distance dans un milieu confiné, difficilement accessible ou dangereux. Deux capteurs pour la détection du mercure cationique (Hg2+) sont décrits dans cette thèse. Le premier utilise un dérivé de la rhodamine, qui est lié de façon covalente à la surface en verre du réseau, par silanisation. Le signal fluorescent de cette sonde est augmenté en présence de mercure ce qui permet de le quantifier. Le second capteur combine l'électrochimie sur ces réseaux de fibres optiques, grâce à une fine couche conductrice déposée à sa surface. Le réseau est ensuite modifié avec un complexe de Ruthénium(II), qui peut être électropolymérisé par l'intermédiaire de la fonction cyclopentadithiophène (CPDT). La détection du mercure est alors réalisée par électrochimiluminescence (ECL), qui est collectée à distance, grâce aux propriétés électro-modulables du film polymère. Les réseaux de fibres optiques nanostructurés ont également été utilisés pour la réalisation d'une sonde SECM, présentant un réseau dense de nanoélectrodes collectives. La réalisation d'un tel outil utilise le positionnement basé sur les forces de cisaillement et peut être utilisé pour la structuration de surfaces conductrices ou isolantes par SECM.
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Milutinovic, Miléna. "Immobilisation d'hydrogel redox pour la détection par électrochimiluminescence." Thesis, Bordeaux 1, 2011. http://www.theses.fr/2011BOR14411/document.
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Ce travail de thèse a pour objectif l’étude de l’électrochimiluminescence (ECL) et son application pour le développement de nouvelles techniques analytiques. De par son importante sensibilité, l’ECL est une technique performante pour des applications telles que les diagnostics cliniques ou la chimie environnementale (présence d’agents contaminants dans l’eau ou la nourriture). L’immobilisation du luminophore ECL est réalisée généralement sur une phase solide. Cette étape constitue une phase essentielle pour obtenir une méthode d’immobilisation rapide, simple, flexible et efficace de ces luminophores ECL, tout en permettant une utilisation pour des systèmes variés. La première partie de ce travail présente l’optimisation de la déposition électrochimique de films de métallopolymère de ruthénium et son application pour la détection enzymatique. Un film d'épaisseur micrométrique de cet hydrogel redox a été préparé par voltamétrie cyclique. Cet hydrogel immobilisé a permis la détection d’un substrat modèle (le glucose) en utilisant l'enzyme glucose déshydrogénase. La seconde partie se concentre sur le développement d’une nouvelle méthode de photodéposition d’un polymère. Celle-ci permet l’immobilisation de centres actifs sur des régions sélectives. En utilisant les techniques de photolithographie, les figures du masque sont projetées sur la surface des électrodes. Cela permet la réalisation de spots micrométriques dont la taille, forme et épaisseur sont modulables. Les propriétés électrochimiques des films nanométriques obtenus sont comparables à ceux obtenues par électrodéposition. De même, les spectres ECL réalisés avec polymères immobilisés par ces deux stratégies sont identiques. Ces résultats montrent que les états excités induits lors de l’ECL sont identiques avec les deux techniques d’immobilisation. Le développement d'un tel procédé constitue une alternative prometteus pour la réalisation de réseaux de spots ECL différenciés et permettant la détection multipléxée par imagerie ECL. Dans la troisième partie de ce travail, nous avons associé la spectroélectrochimie et l'imagerie ECL pour contribuer à l’étude des mécanismes ECL au niveau d'une bille micrométrique fonctionnalisée par des complexes de ruthénium. En combinant microscopie de fluorescence et imagerie ECL, la distribution des sites électroactifs et des sites ECL a pu être mise en évidence. A partir de cette étude, nous pouvons clarifier les mécanismes conduisant à l'émission ECL au niveau de ces billes fonctionnaliséesThe main goal of this thesis was to study electrogenerated chemiluminescence (ECL) and its application in development of new analytical techniques. Due to its high sensitivity, ECL presents a powerful method for applications in clinical diagnostic and environmental chemistry (presence of contaminants in water or food). The immobilisation of an ECL luminophore is usually performed on a solid phase. This step is an essential point to obtain a technique for fast, simple, flexible and effective immobilisation of ECL luminophores with possibility of applications in various configurations. The first part of this work presents the optimisation of the electrochemical deposition of a ruthenium metallopolymer and its application in enzymatic detection. A redox hydrogel film with micrometric thickness was prepared using cyclic voltammetry. This immobilised hydrogel allows the detection of model substrate (glucose) using enzyme glucose dehydrogenase. The second part of this thesis is focused on the development of a new photodeposition method for the ECL polymer immobilisation. This method allows region-selective immobilisation of active centres. Using photolithographic methods, the figures from the mask are projected on the electrode surface. This allows the formation of micrometric spots which size, shape and thickness is modulated. Electrochemical properties of obtained nanometric films are comparable with those of electrodeposited films. Also, ECL spectra recorded with both immobilisation strategies are identical. It shows that the ECL excited state is the same. The obtained photopatterns were imaged using ECL. The development of such process presents an alternative for realisation of different ECL spot arrays and allows multiplexed detection by ECL imaging. In the third part of this work we have associated spectroelectrochemistry and ECL imaging to study the ECL mechanisms at the level of a single microbead, functionalised with ruthenium complex. Combining fluorescence microscopy and ECL imaging, the distribution of electroactive and ECL sites have been highlighted. From this study we can clarify the mechanism that leads to ECL emission at the level of functionalised beads
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Vasconcelos, Vanessa Moura. "Degradação eletroquímica/química dos corantes têxteis Reativo Azul 19 e Reativo Preto 5 utilizando eletrodos de diamante dopado com boro e H2O2 eletrogerado em eletrodo de carbono vítreo reticulado." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-25112015-092817/.
Full textAbstract:
A problemática envolvendo os efluentes têxteis decorre principalmente da elevada coloração que apresentam, devido à presença de corantes que além de serem quimicamente estáveis, podem ser tóxicos e/ou carcinogênicos. Logo, quando são descartados in natura no meio ambiente causam problemas estéticos e, sobretudo, ambientais mesmo em baixas concentrações, além da possibilidade de serem nocivos à saúde humana e dos animais. Neste contexto, o objetivo deste trabalho foi estudar a degradação eletroquímica de dois corantes têxteis, Reativo Azul 19 (RA-19) e o Reativo Preto 5 (RP-5) via Oxidação Anódica (OA), utilizando ânodos de Diamante Dopado com Boro (DDB) suportados em titânio ou em nióbio, via processo Eletro-Fenton (EF) e pela combinação dos processos com H2O2 eletrogerado e OA (CP), usando um eletrodo de Carbono Vítreo Reticulado (CVR) como cátodo. As degradações foram realizadas em célula eletroquímica de um compartimento e em reator de fluxo do tipo filtro-prensa com dois compartimentos. A eficiência das degradações foi monitorada pelas técnicas de espectrofotometria no UV-VIS, Cromatografia Líquida de Alta Eficiência (CLAE) e análise do teor de Carbono Orgânico Total (COT). As variáveis estudadas foram densidade de corrente (10-100 mA cm-2 em célula e 4-41 mA cm-2 em reator), dopagem do eletrodo de DDB/Ti (5.000 e 15.000 ppm B/C), concentração inicial dos íons Fe2+ (0-0,10 mmol L-1) e dos corantes (10-250 mg L-1). As degradações dos corantes apresentaram uma cinética de pseudo ordem zero; exceto quando o corante RP-5 foi degradado pelo processo EF, sendo o melhor ajuste ao modelo de pseudo primeira ordem. Além disso, em iguais condições eletroquímicas o corante RP-5 foi degradado em menor tempo em relação ao RA-19; sendo que em todos os processos estudados os corantes foram totalmente removidos. Considerando a OA em célula com os eletrodos de DDB/Ti, a degradação foi positivamente influenciada pelo aumento da densidade de corrente e dopagem do eletrodo, especialmente em relação a cinética. Além disso, os corantes RA-19 e RP-5 foram completamente removidos em 35 e 50 min de eletrólise quando 100 mA cm-2 foi aplicada ao eletrodo de DDB/Ti dopado com 15.000 ppm relação B/C. Em 2 h, 37% em mineralização foi observado para ambos os corantes e a toxicidade do RA-19 diminuiu contra as bactérias Vibrio fischeri. Ainda nessa condição total mineralização foi alcançada após 8 h de degradação. A remoção de COT foi favorecida utilizando o reator contendo os eletrodos de DDB/Nb e CVR ao invés da célula eletroquímica, chegando a percentuais de 84 e 82% em 30 e 90 min para os corantes RA-19 e RP-5 que foram removidos em 7,5 e 5 min, respectivamente, quando a densidade de 41 mA cm-2 foi aplicada ao DDB/Nb durante a degradação via exclusivamente OA. Entre os processos realizados no reator, o EF foi o energeticamente mais favorável, promovendo remoção em COT de 60 e 74% para os corantes RA-19 e RP-5 com consumo energético de 204 e 208 kWh kg-1, além disso, a completa remoção dos corantes ocorreu em 15 e 7,5 min, respectivamente, quando o eletrólito continha íons Fe2+ na concentração de 0,10 mmol L-1 e aplicando-se -0,4 V vs Ag/AgCl ao eletrodo de CVR. Na degradação os corantes via CP o RA-19 e RP-5 foram completamente removidos em 30 e 15 min com mineralização de 72 e 82% em 90 min associada a consumos energéticos de 562 e 745 kWh kg-1, respectivamente, quando 41 mA cm-2 foi aplicada ao DDB/Nb. Por fim, concluiu-se que os resultados das degradações dos corantes foram promissores, já que rápida remoção dos corantes foi observada, além da parcial mineralização. Logo os processos propostos podem ser aplicados na remoção dos corantes em água; sendo necessários realizar mais estudos, principalmente em relação ao material eletródico e configuração do sistema eletroquímico visando a aplicação industrial.The main problem involving the textile wastewater is theirs high coloration since they present dyes, which are chemically stable and can be toxic and/or carcinogenic. Therefore, when the textile wastewater are discarded in nature in the environment, even in low concentrations, they may cause not only aesthetic and environmental problems, but also can be harmful to human and animal health. In this context, the aim of the study was to evaluate the electrochemical degradation of two textile dyes, Reactive Blue 19 (RB-19) and Black 5 (RB-5) via Anodic Oxidation (AO) using as anodes Boron Doped Diamond electrodes (BDD) supported on titanium or niobium, via Electro-Fenton (EF) process and by combination of processes with electrogenerated H2O2 and AO (CP) using a Reticulated Vitreous Carbon electrode (RVC) as cathode. The degradations assays were carried out in an electrochemical cell with one compartment and in a filter-press flow reactor with two compartments. The efficiency of degradation was monitored by UV-VIS spectrophotometry, High Performance Liquid Chromatography (HPLC) and analysis of Total Organic Carbon (TOC). The variables studied were current density (10-100 mA cm-2 for cell and 4-41 mA cm-2 for reactor), doping of the BDD/Ti electrodes (5,000 e 15,000 ppm B/C), initial concentration of the Fe2+ ions (0-0,10 mmol L-1) and dyes (10-250 mg L-1). The kinetic results showed that the removal of dyes followed the model of pseudo zero order; except when the RB-5 dye was degraded by EF process, which the best fitted was to pseudo first order model. Furthermore, for equal conditions the RB-5 was degraded in less time in comparison to the RB-19. In addition, the dyes were fully removed in all the processes studied. Regarding the AO in cell with BDD/Ti, the degradation was positively influenced by the increasing in current density and doping of the electrode, primarily the kinetics parameters. In addition, total removal of RB-19 and RB-5 was achieved in 35 and 50 min of electrolysis when 100 mA cm-2 was applied to the electrode doped with 15,000 ppm ratio B/C. In 2 h, 37% in mineralization was attained for both dyes and the toxicity effect of the RB-19 decreased against the bacteria Vibrio fischeri. In this condition, total TOC removed was also reached after 8 h. The TOC removal was enhanced using the reactor fitted with BDD/Nb and RVC instead of the electrochemical cell, achieving TOC removal of 84 and 82% in 30 and 90 min for RB-19 and RB-5 which were removed in 7.5 and 5 min, respectively, when 41 mA cm-2 was applied to the BDD/Nb in the degradation exclusively via AO. Among the processes carried out in the reactor, the EF was the energetically most favourable since TOC removal of 60 and 74% for RB-19 and RB-5 with energy consumption of 204 and 208 kWh kg-1 were noted. In addition, the RB-19 and RB-5 were completely removed in 15 and 7.5 min, respectively, when the electrolyte containing 0.10 mmol L-1 of Fe2+ ions and -0.4 V vs Ag/AgCl was applied to CVR electrode. The combination of processes with electrogenerated H2O2 and AO for degradation of the dyes removed the RB-19 and RB-5 in 30 and 15 min with mineralization of 71.6 and 81.8% in 90 min associated to energy consumptions of 562 and 745 kWh kg-1 respectively, when 41 mA cm-2 was applied to BDD/Nb. Therefore, the degradation results of the dyes were promised since quickly removal of the dyes and partial mineralization were observed hence the proposed processes could be used to remove the dyes from water. However, more studies are needed to enable an industrial application, especially regarding the electrode material and configuration of the electrochemical system.
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Miao, Chia-Wu, and 繆佳紋. "Determination of cyromazine with electrogenerated chemiluminescence." Thesis, 2004. http://ndltd.ncl.edu.tw/handle/35984380699865310365.
Full textAbstract:
碩士淡江大學
化學學系
92
This paper describes the use of tris(2,2''-bipyridine)ruthenium(II)(Ru(bpy)32+) electrogenerated chemiluminescence(ECL) at present of Ru(bpy)32+ and analyte as coreactant coupled flow injection analysis for determination of cyromazine. In the Ru(bpy)32+ ECL system, emission is resulted from the relaxation of Ru(bpy)32+*. This excited state species is obtaind from the reaction of Ru(bpy)33+ with reducing agent(i.e. Cyromazine). Ru(bpy)33+ could be generated by the oxidation of Ru(bpy)32+ at potential 1.4 V(vs. Ag/AgCl).A typical calibr- ation plot of cyromazine at 1.4 V (vs. Ag/AgCl), in 0.15 M, pH 9 phosphate buffer contained 0.5 mM Ru(bpy)32+, flow rate =1 ml/min, 20 μl sample loop, linear concentration range is up to 1 mM(correlation coefficient = 0.991). The detection limit for cyromazine is 0.19μM(S/N=3),and the relative standard deviation of twenty repetitivedetection is 2 %(n=20).
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Bae, Yoonjung. "Electrochemistry and electrogenerated chemiluminescence of semiconductor nanoparticles." Thesis, 2005. http://hdl.handle.net/2152/2387.
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Sartin, Matthew McCullough 1982. "The electrogenerated chemiluminescence of unique organic chromophores." Thesis, 2007. http://hdl.handle.net/2152/3667.
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Electrogenerated chemiluminescence (ECL) studies were performed on several interesting compounds. A series of silole-based (silacyclopentadiene) chromophores was examined to understand the effects of their structure on the electrochemistry and spectroscopy of these compounds. A case was observed in which high steric hindrance improved ECL by inhibiting internal conversion and protecting radicals from secondary reactions. Another case was observed in which steric effects induced a rotation in the silole substituents, increasing secondary reactions and lowering quantum efficiency ([Phi subscript PL]). Spiro-FPA, which consists of two DPA centers, exhibits excimer formation despite high steric hindrance, due to its ability to form di-ions, which have a greater electrostatic attraction to one another than mono-ions. The compound (dppy)BTPA is a highly solvatochromic, boron-containing chromophore that was examined in a variety of solvents. Of note is the emission in pure acetonitrile, which is prominent in the ECL spectrum, but barely visible in the photoluminescence. Finally, B⁸ amide, a compound based on the laser dye, BODIPY, was examined. It exhibited unusual ECL characteristics. These include a strong, long-wavelength emission and transients that are clearly visible for 20 min or more, but display dramatically varying light intensities with each pulse. Evidence for the contribution of a film formed with the oxidation product is presented. Additionally, ECL simulations are performed using a general physics software package to better understand some of the observed phenomena.
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Chiu, Hsing-Hua, and 丘幸華. "Study on Electrogenerated Chemiluminescence of Arylethynylacridine Systems." Thesis, 2004. http://ndltd.ncl.edu.tw/handle/06196130582560764050.
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Chiang, Mei-Tsu, and 江美足. "Development of Capillary Electrophoresis with Electrogenerated Chemiluminescence Detection." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/61426600023102264526.
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Chen, Chih-Yuan, and 陳志源. "Electrogenerated Chemiluminescence of Stilbene Intramolecular Charge Transfer System." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/40021850788142892478.
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Omer, Khalid Mohammad. "The electrogenerated chemiluminescence of highly fluorescent organic chromophores and nanoparticles." Thesis, 2009. http://hdl.handle.net/2152/ETD-UT-2009-12-481.
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Electrogenerated chemiluminescence (ECL) of new, highly fluorescent molecules was studied. Six novel, highly fluorescent, green emitters were synthesized by incorporating an acceptor group like 2,1,3-Benzothiadiazole between different donor groups. The structural effects on the electrochemical, spectroscopic, and ECL behavior are shown in detail. Stable electrochemistry and high PL quantum yield were observed. Most of the ECL was visible by the naked eye. Well-known, fluorescent, polyaromatic hydrocarbons (PAH), like 9,10-diphenylanthracene derivatives, pyrene, and anthracene were incorporated between two bulky fluorene derivative groups. The fluorene substitutions block the active positions of the PAH cores, permitting the formation of stable radical ions upon electrochemical oxidation or reduction. Such a tailoring led to increase electrochemical reversibility and tuning of the ECL wavelength. Fluorene-based DPA (FDF) is characterized by a highly efficient and stable blue-cyan color. Another interesting type of molecules was star-shaped structures. The effects of structure on the electrochemistry and spectroscopy of a series of star-shaped, rigid molecules was examined. T1-T4 is composed of oligofluorene arms with truxene as a central core basically there were weak donor and weak acceptors. The ECL quantum efficiency was near 80% for the long-arm T4. One of the interesting goals in ECL is to find ECL emitters in aqueous media. Organic nanoparticles (ONPs) were chosen to achieve this goal. An organic nanoparticle (ONPs) is still challenging area in nanoscience. The key factor of such a challenge comes from the difficulty to control the size and shape of the prepared nanoparticles. ONPs of common hydrocarbon ECL emitters like rubrene and 9,10-diphenylanthracene (DPA) were prepared in aqueous solution using a reprecipitation method. ECL of rubrene NPs was observed when tripropylamine (TPrA) was used as a coreactant, and weaker ECL of DPA NPs was observed when the oxalate ion was used as a coreactant. The ECL of ONPs in aqueous media may open a new field in ECL, allowing the exploration of more phenomena in organic nanoscience. Organic nanoparticle ECL (especially if one able to make small size to be diffused easily) has potential application as a tag for the analysis of biologically interesting molecules.text
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Nepomnyashchii, Alexander Borisovich. "Electrochemical and electrogenerated chemiluminescence studies of the BODIPY dyes." Thesis, 2011. http://hdl.handle.net/2152/ETD-UT-2011-08-3754.
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Electrochemical and electrogenerated chemiluminescence properties of the BODIPY (boron dipyrromethene) dyes are presented. Some specific features of the BODIPY dyes are obtained and described in the current dissertation. Separation of around 1.0-1.2 V is noticed between two oxidation and reduction waves for one center which is very different from 0.5 V seen for the polycyclic hydrocarbons. Cathodic and anodic stability is shown to depend upon absence or presence of certain degree of substitution. Different ways of electrochemical dimerization are explored and compared with the chemical dimerization. Photophysical and electrochemical properties of monomer, chemically synthesized dimer, trimer and polymer are described and the characteristic features determined.text
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Wang, Jun-Sheng, and 王俊勝. "Development of Electrogenerated Chemiluminescent and Electrochemical System for Pesticides Determination." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/24261159405295273879.
Full textAbstract:
博士淡江大學
化學學系博士班
93
The goal of this dissertation is to develop various schemes for pesticides determination based on biosensor, electrochemical, and electrogenerated chemiluminescent (ECL) system. The schemes offer solutions to measure non-electroactive species and to minimize electrode fouling. We propose an enzyme based biosensor for propanil determination. The aryl acylamidase (EC 3.5.1.13) was modified onto disposable strip for biosensor development. The enzymatic reaction for propanil can produce 3,4-dichloroaniline which is detectable at oxidative potential. The results show both higher selectivity and longer linearity than inhibition based pesticide biosensors. A preoxidation treatment was used for 2,4,6-trichlorophenol detection. In this study, ammonium cerium (IV) nitrate was used as an oxidant to convert 2,4,6-trichlorophenol to 2,6-dichloro-1,4-benzoquinone. This product is easily reducted at -50 mV (vs. Ag/AgCl). The scheme shows high sensitivity and limited interferences for 2,4,6-trichlorophenol determination. A continuously automatic pulse scheme is used to clean the electrode fouling in oxidative detection scheme. This system is integrated with continuous pulse cleaning program, computerized potentiostat, and automatic flow injection analysis (AFIA). It was used to avoid the electrode surface poison from ethylene thiourea oxidation. The result shows good reproducibility for ethylene thiourea determination. At the last, the ECL scheme is based on the reaction of Ru(bpy)32+ and its related coreactant to detect nonelectroactive aliphatic amines. The Ru(bpy)32+ is a good luminescence that has both high qutumatic efficiency and stability. The rapid, stable and highly sensitive system was established to Nicotine and Dinoseb detection. On the basis of above results, this dissertation has demonstrated several methods to solve the disadvantages of previous detection by using enzyme, chemical pretreatment, automatic pulse cleaning, and ECL system. Their merits include easy operation, prompt response, high selectivity, high sensitivity, and good reproducibility for pesticides determination. In the future, the schemes can be applied to clinical, pharmaceutic, and environmental analysis. Otherwise, they will be developed to portable device for local and home-care applications.
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Chen, Ting-Yu, and 陳丁右. "Electrogenerated Chemiluminescence for the Intramolecular Charge Transfer of Ethyne Systems." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/94631649774157743133.
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Suk, Jung Don. "Electrochemistry and electrogenerated chemiluminescence of unique organic chromophores and organic nanoparticles." Thesis, 2011. http://hdl.handle.net/2152/ETD-UT-2011-05-2916.
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Electrogenerated chemiluminescence (ECL) studies were performed on several interesting compounds. A series of BODIPY derivatives was examined to understand the structural effects on the electrochemical, spectroscopic, and ECL behavior. Stable electrochemistry and high fluorescence in the green to the red regions were observed. PB, MCPB, DCPB and PM580 produced intense ECL, strong enough to be seen with the naked eye in a lighted room. Unlike MCPB and DCPB, PB produced the multiple ECL peaks. Totally blocked BODIPY compound showed the improvement of fluorescence and ECL quantum yield due to the stability of radicals. Strong signal of EPR data during the oxidative electrolysis was obtained by simultaneous electrochemical-electron paramagnetic resonance technique with home-made cell. Several new antrhacene derivatives such as a variety of 2- and 4-fold anthracene-functionalized tetraarylbimesityls and a series of 9-naphthylanthracene based dimer and trimer were studied. They showed one wave on the oxidation and reduction because of a sequence, two or more electron transfers during the annihilation of the radical ions. Depended on the structure, some of them exhibited excimer formation on ECL spectra. Azide-BTA compound which consists of two triphenylamine and 2,1,3-benzothiadiazole groups at the ends bridged by a fluorene moiety was synthesized and examined. The compound is a newly synthesized D-A-[pi]-A-D molecule which had reversibility upon electrochemical oxidation and reduction, and also showed intense red fluorescence and stable red ECL emission. Using a simple reprecipitation method, well-dispersed and spherical organic nanoparticles of Azide-BTA and 9-naphthylanthracene based dimer were prepared in an aqueous solution. Controlling the preparation condition, the size of nanoparticles can be minimized to 15 nm. Especially we prepared the organic nanoparticles of 9-naphthylanthracene based dimer dispersed in organic solvent, MeCN, one of the preferred solvents for electrochemical studies and ECL.text
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Pang, Song-Man, and 彭崇文. "The development and application of carbon nanoparticle in Electrogenerated Chemiluminescence (ECL)." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/5t7wqg.
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碩士國立中興大學
化學系所
103
The development and application in Electrogenerated chemiluminescence (ECL) of fluorescent carbon nanoparticles (CNPs) is focused on this study. Which is prepared by electrochemical exfoliation of carbon fiber in a suitable solution condition with narrow size distribution, and good long-term stability. ECL signal of CNPs was observed in cyclic voltammetry(CV) as potential scanning between 0.4 to 2.3 V vs Ag/AgCl reference electrode and the ECL mechanisms of CNPs and CNPs-Ru(bpy)32+ were proposed. The cyclic voltammetry-generated chemiluminescent (CV-ECL) reactions of a series of aminoglycoside antibiotics were investigated in a flow system using carbon nanoparticle(CNPs)and Indium tin oxide(ITO) electrodes. The carbon nanoparticle were found to participate as an electrocatalyst in an oxidative-reductive ECL mechanism with tris(2,2’-bipyridyl)ruthenium(II) (Ru(bpy)32+) and aminoglycoside antibiotics(e.g., gentamycin, streptomycin, dihydrostreptomycin, Lincomycin with secondary or Tertiary amine in molecule structure). After adding CNPs, the detection limit is 0.0347, 0.0350, 0.1187, 0.0169 μM (S/N = 3) for gentamycin, streptomycin, dihydrostreptomycin and lincomycin respectively, were obtained under the optimized conditions. Before adding CNPs the detection limit is 0.0732, 0.3186, 0.2308, 0.0668 μM (S/N = 3) for gentamycin, dihydrostreptomycin, streptomycin and lincomycin respectively. It represents CNPs can be a electrocatalyst in ECL mechanism with (Ru(bpy)32+) and aminoglycoside antibiotics. The developed method was successfully applied to the determination of gentamycin and Lincomycin in real samples with recoveries in the range of 98.25?103.50% (n = 3).
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Janakiraman, Umamaheswari [Verfasser]. "Analysis of electrogenerated chemiluminescence of PPV type conducting polymers / von Umamaheswari Janakiraman." 2003. http://d-nb.info/968755305/34.
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Wu, Ping-Hong, and 吳炳宏. "Determination of miglitol with Electrogenerated chemiluminescence detector and it’s application on HPLC." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/7haw8r.
Full textAbstract:
碩士淡江大學
化學學系碩士班
103
There are two parts in this study. The first one, determination of miglitol with Electrogenerated chemiluminescence ( ECL ) with flow injection analysis ( FIA ) was fabricated. In electrode surface Ru(bpy)32+ go through electron-transfer reaction with miglitol (co-reactant) to form excited state Ru(bpy)32+＊, and excited state Ru(bpy)32+＊ back to the ground state that emit light by vibrational energy relaxation( VR ). In this analysis system, the linear range of miglitol is between 0.1 μM and 10 μM (R2=0.999), sensitivity is 570.5 /μM, detection limit (S/N=3) is 58.11 nM, and relative standard deviation of twenty repetitive detection is 0.52%. The second one, we combine ECL with HPLC to seprate interference in urine samples. HPLC is used to separate miglitol and matrix in urine samples and determination of miglitol by PMT. The linear range in HPLC-ECL system is between 1 μM and 30 μM, detection limit (S/N=3) is 0.78 μM.
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Hsu, Hsien-Yi, and 徐先億. "Electrogenerated Chemiluminescence for the Intramolecular Charge Transfer of Polycyclic Aromatic Compound Systems." Thesis, 2004. http://ndltd.ncl.edu.tw/handle/19575070030854000436.
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Choi, Jai-pil. "Electrogenerated chemiluminescence with amine and benzoyl peroxide coreactants: reactivity and reaction mechanism studies." Thesis, 2003. http://hdl.handle.net/2152/503.
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Choi, Jai-pil Bard Allen J. "Electrogenerated chemiluminescence with amine and benzoyl peroxide coreactants reactivity and reaction mechanism studies /." 2003. http://wwwlib.umi.com/cr/utexas/fullcit?p3117890.
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Wang, Yui-Hsiang, and 王昱翔. "Study on Electrogenerated ChemiLuminescence of Butadiynyl-quinolines and Acenaphthenequinones Conjugated Donor-Aceceptor Molecules." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/arhkrj.
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碩士國立臺北科技大學
化學工程所
93
Tow series of π-conjugated bipolar compounds Butadiynyl-quinolines and Acenaphthenequinones having inherent redox centers have been synthesized and their UV-Vis absorption, fluorescence emission and electrochemical behavior are studied. Electrogenerated ChemiLuminescence of these molecule bear weak, strong is also studied. The observed electronic properties are explained by means of Density Functional Theory ( DFT-B3LYP/6-31G ) calculations. The structure-property relationships of all the molecules are discussed.
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ZHANG, ZHI-CHENG, and 張志成. "Electrogenerated chemiluminescence and photoluminescence processes involving tricarbonylchloro (1,10-phenanthroline) rhenium(Ⅰ) and related complexes." Thesis, 1992. http://ndltd.ncl.edu.tw/handle/81067225298258997315.
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Felton, Greg Andrew Nicholas Bauld Nathan L. "Electroorganic synthesis inter- and intra-molecular anion radical cycloadditions, and electrogenerated base promoted coupling reactions /." 2005. http://repositories.lib.utexas.edu/bitstream/handle/2152/1545/feltong16722.pdf.
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Felton, Greg Andrew Nicholas. "Electroorganic synthesis: inter- and intra-molecular anion radical cycloadditions, and electrogenerated base promoted coupling reactions." Thesis, 2005. http://hdl.handle.net/2152/1545.
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Calhoun, Robert Lee. "Electrochemisty and electrogenerated chemiluminescence of Ru(phen)₂dppz(BF₄)₂ both free and intercalated into DNA." Thesis, 2007. http://hdl.handle.net/2152/3006.
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Wei, We-Cheng, and 魏瑋琤. "Development and Application of Preanodized Screen Printed Carbon Electrode for Electrogenerated Chemiluminescence of Ru(bpy)32+." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/32733185437506093618.
Full textAbstract:
碩士國立中興大學
化學系所
100
We investigated the electrogenerated chemiluminescence (ECL) behavior of Ru(bpy)32+ system at screen printed carbon electrodes (SPCEs) preanodized under different electrolytes. Background ECL signals were observed at a bare SPCE because of the presence of hydroxyl groups on the electrode surface. The SPCEs preanodized under NaOH solution (designated as SPCE*/NaOH) produced the most hydroxyl groups and caused 5.25 times higher ECL signal than that of a bare SPCE. It shows the advantage of the SPCE*/NaOH to detect CN─ based on the inhibited signal under the Fe(bpy)32+─ECL system. Note that the proposed system is much cheaper than the commonly used Ru(bpy)32+─ECL system. On the other hand, the background ECL signal from the oxygen functionalities can be diminished by applying the SPCE*/H3BO3 for ECL analysis applications. The negligible hydroxyl groups at the SPCE*/H3BO3 provides good sensitivity for the detection of epinephrine in Ru(bpy)32+─ECL system.
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Fabrizio, Eve Frances. "Electrogenerated chemiluminescence of 9,10-substituted Benzo(k)fluoranthenes and of surface bound Ru(bpy)₃²⁺ on platinum silicide." 2001. http://hdl.handle.net/2152/11935.
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Lai, Rebecca Yun Kay 1977. "Electrogenerated chemiluminescence of phenylquinoline-phenothiazine donor-acceptor molecules, dipyrromethene-BF₂ laser dyes and bent-pyrene-containing cyclophanes." 2003. http://hdl.handle.net/2152/12190.
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Lai, Rebecca Yun Kay Bard Allen J. "Electrogenerated chemiluminescence of phenylquinoline-phenothiazine donor-acceptor molecules, dipyrromethene-BF₂ laser dyes and bent-pyrene-containing cyclophanes." 2003. http://wwwlib.umi.com/cr/utexas/fullcit?p3119629.
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Chow, Kwok-Fan. "Development of wireless DNA microarray sensors." Thesis, 2010. http://hdl.handle.net/2152/ETD-UT-2010-08-1554.
Full textAbstract:
The development of wireless DNA microelectrochemical microarray sensors is described. The operational principles of these sensors are based on bipolar electrochemistry. Bipolar electrodes are used to fabricate the wireless microarrays in this work. The systems are configured so that DNA sensing is carried out at the cathodic end of a bipolar electrode (BPE) and the result of the sensing experiment is reported at the anodic end of the BPE.
There are two types of reporting platforms developed in this study. The first type relies on the emission of electrogenerated chemiluminescence (ECL). The system is configured so that ECL is emitted at the anodic end of the BPE when the target DNA is hybridized to the capture probe DNA immobilized on the cathodic end of the BPE. However, when there is no hybridization reaction occurs, there is no ECL emission on the electrode surface.
The second type of reporting platform developed is based on silver electrodissolution at the anodic end of a BPE. When a reduction reaction occurs at the cathodic end of a BPE, it triggers oxidation and dissolution of silver deposited at the anodic end of the BPE. The loss of silver can easily be detected by the naked eye. This detection principle is used for DNA detection: when the target DNA is hybridized to capture probe DNA on the BPE, the BPE becomes shorter. However, if target DNA does not hybridize to the electrode surface, the length of the BPE remains the same.
The BPE microarrays described in this work eliminate the need for complicated microfabrication procedures and instrumentation. For example, as many as 1000 BPEs can be simultaneously controlled using just two driving electrodes and a simple power supply. To fully utilize BPE microarrays for specific sensing tasks, a method based on robotic spotting was developed to modify the cathodic end of each BPE in the array. Because each BPE in a microarray is individually addressable, this development allows each BPE to perform a particular sensing operation.text
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Shen, Mei. "The electrogenerated chemiluminescence of novel organic donor-acceptor emitters as well as study heterogeneous electron transfer kinetics using scanning electrochemical microscopy." Thesis, 2011. http://hdl.handle.net/2152/ETD-UT-2011-08-3838.
Full textAbstract:
New modalities and novel emitters were investigated for the production of electrogenerated chemiluminescence (ECL). In annihilation ECL, a light-emitting excited state is formed upon reaction of two electrochemically generated species, typically a radical anion and a radical cation. Donor-acceptor (DA) molecules provide a means of generating these two reactive species within the same molecule but where the oxidized and reduced centers are separated; furthermore, they allow one to explore the ECL properties of multiply charged radical ions. Three new efficient ECL-emitting donor-acceptor molecules were investigated.
The effects of conjugation in the electrochemistry of diphenylaminospirobifluorenylfumaronitrile (FPhSPFN), which has the structure of D-X-A-A-X-D, where X is a linker, as well as the effects of the stability of its (multiply charged) radical ions on its red ECL emission (λmax= 708 nm) were studied; the molecule
shows solvatochromism and different emission yields on both photoluminescence and ECL in benzene:acetonitrle mixtures. The possibility of generating ECL through multiply charged radical ions was further tested with the very efficient 1b emitter (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole). Two reversible oxidations and one reduction were observed. The more sluggish reduction is proposed to be a consequence of a long distance electron transfer to the buried acceptor center; further confirmation of this effect was pursued by application of the scanning electrochemical microscope (SECM) to model systems. 1b emits intense ECL with λmax= 635 nm and with an efficiency 330% of the ECL standard 9, 10-diphenylanthracene and similar intensity to the red emitting standard tris(2,2′-bipyridine)ruthenium(II) perchlorate (Rubpy). The generation of asymmetric chronoamperometric ECL pulses upon generation of radical anion-radical dication annihilation events was explained by the use of digital simulation, and proven to be a consequence of asymmetry in the amount of generated charges rather than instability of the electrogenerated species. ECL was also produced from a film of a red fluorophore 1a (4,7-bis(4-(n-hexyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole) with a coreactant in PBS buffer solution.
The electrochemical synthesis of carbon quantum Dots (C QDs) in inert atmosphere was explored using highly oriented pyrolytic graphite as the starting material, for its later use in the production of ECL in the radical annihilation mode. FT-IR (ATR), mass spectrometry (desorption chemical ionization), Raman and TEM analysis were used to characterize the C QDs.text
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Walker, Erin Kate. "Transparent carbon electrodes for spectroelectrochemical studies." Thesis, 2012. http://hdl.handle.net/2152/ETD-UT-2012-08-5954.
Full textAbstract:
This dissertation describes the assessment and use of carbon optically transparent electrodes (C-OTEs) based on pyrolyzed photoresist films (PPFs) as a platform for spectroelectrochemical investigations. C-OTEs are examined for use in UV-Vis spectroelectrochemistry and electrogenerated chemiluminescence and compared to non-transparent glassy carbon (GC) and the conventional transparent electrode indium tin oxide (ITO). Chapter 1 provides a general overview of transparent electrodes, carbon electrodes, and spectroelectrochemistry. Chapter 2 details a UV-Vis spectroelectrochemical investigation of electrogenerated graphitic oxides (EGO) on the surface of the C-OTE in the presence of KCl. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectroscopy are used to determine EGO composition. Several supporting electrolytes are investigated to determine the mechanism of EGO formation. Chapter 3 details experiments to electrochemically access the exciton emission from self-assembled double-walled tubular J-aggregates via electrogenerated chemiluminescence (ECL). Optimization of ECL intensity with respect to the coreactant concentration and the supporting electrolyte pH is performed on opaque glassy carbon electrodes. ECL and fluorescence spectra are compared, and C-OTEs are utilized to determine the source of disagreement between the spectra. Chapter 4 describes the preparation and characterization (i.e. transparency, thickness, sheet resistance, rms roughness, and electroactive surface area) of C-OTEs and explores C-OTEs for general use in ECL under a variety of conditions. Simultaneous cyclic voltammograms and ECL transients are obtained for three thicknesses of PPFs and compared to non-transparent GC and the conventional transparent electrode ITO in both front face and transmission electrode cell geometries. Despite positive potential shifts in oxidation and ECL peaks, attributed to the internal resistance of the PPFs that result from their nanoscale thickness, the PPFs display similar ECL activity to GC, including the low oxidation potential observed for amine coreactants on hydrophobic electrodes. Overall, C-OTEs are promising electrodes for spectroelectrochemical applications because they yield higher ECL than ITO in both oxidative-reductive and reductive-oxidative ECL modes, are more stable in alkaline solutions, display a wide potential window of stability, and have tunable transparency for more efficient detection of light in the transmission cell geometry. Future directions for this research are discussed in Chapter 5, which outlines several approaches to designing and improving spectroelectrochemical sensors.text
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SENTHILKUMAR, KRISHNAN, and 柯山度. "Electrochemical sensing applications based on an azo/hydrazo functional group containing polymelamine modified screen printed carbon electrode and electrogenerated chlorine assisted immobilization of 2,8-dihydroxyadenine." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/31796445913248829238.
Full textAbstract:
博士國立中興大學
化學系所
103
Azo and hydroazo fuctional group containing polymelamine modified screen printed carbon electrode (polymelamine-SPCE) has been applied for electrocatalytic application. The polymelamine film thickness has been measured using atomic force microscopy as 2.4 μm. This functional group involving in quasi-reversible reaction in 0.1 M, pH 7 PBS and heterogenous electron transfer rate of the polymelamine was calculated using Laviron equation as 2.05 s-1. First study focused on the determination of free chlorine using the polymelamine-SPCE. It is based on EC’ mechanism, electrocatalytic detection of free chlorine with the azo functionality of polymelamine first reduced electrochemically followed by oxidization with free chlorine in a cyclic manner. Then, we devoted for the ammonia determination with an indirect method by utilizing the above free chlorine polymelamine system. In the presence of free chlorine, ammonia is known to get oxidized to nitrogen and nitrogen chloride. The decrease in free chlorine concentration signal indirectly represents the ammonia concentration. The determination of cysteine and homocysteine in the presence of other amino acids using polymelamine-SPCE was further carried out. This can be revealed as oxidized hydrazo functionality (azo) chemically reduced with thiol containing amino acid then electrochemical system continuously regenerates the azo. The regeneration energy was used as a transduction signal of the homocysteine/cysteine. Finally, the electrogenerated chlorine was utilized for adenine oxidized product immobilization. This immobilized product was found to catalyze NADH at 52 mV Vs Ag/AgCl which is 240 mV less than that of unmodified electrode.