Relevant bibliographies by topics / Chemiluminescence / Dissertations / Theses
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Dissertations / Theses on the topic 'Chemiluminescence'

Author: Grafiati
Published: 4 June 2021
Last updated: 29 July 2024

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1

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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2

Taheri-Kadkhoda, M. "Chemiluminescence of acridines." Thesis, University of Sussex, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375847.

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3

O'Keefe, Eion Seiorse. "Polymer chemiluminescence detection." Thesis, University of Sussex, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.238667.

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4

Then, Edward Thian Hee. "Chemiluminescence from polymers." Thesis, University of Sussex, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.238391.

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5

Grob, Markus. "Chemiluminescence of animal granulocytes /." [S.l.] : [s.n.], 1986. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=8091.

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6

Irons, Gordon Philip. "Electrochemically modified chemiluminescence detection." Thesis, University of Hull, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262415.

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7

Bashirians, George Mamberi. "Metalloporphyrin : catalysed chemiluminescence immunoassay." Thesis, City University London, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358939.

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8

Patel, Jayprakash Lakman. "Luminol chemiluminescence and its applications." Thesis, Imperial College London, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266344.

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9

Alwarthan, Abdulrahman Abdullah. "Chemiluminescence in flow injection analysis." Thesis, University of Hull, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.339162.

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10

Stevenson, James Dexter. "Chemiluminescence selection of catalytic antibodies." Thesis, University of Nottingham, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311765.

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11

Fearon, Peter Killian. "Chemiluminescence studies of polymer oxidation." Thesis, University of Sussex, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.250300.

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12

Thomas, H. D. "Chemiluminescence, a detection method for HPLC." Thesis, University of East Anglia, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383774.

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13

Jonsson, Tobias. "Peroxyoxalate Chemiluminescence for Miniaturized Analytical Flow Systems." Doctoral thesis, Umeå University, Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-16.

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This thesis deals with the peroxyoxalate chemiluminescence (POCL) reaction and its application as a detection technique in flow systems for chemical analysis. Particularly, miniaturized flow systems aimed for separation of molecules. In such systems, a high light intensity and a rapid development of the emission are the desired reaction characteristics, for reasons discussed in this text. The work tries to develop an understanding of the chemical processes involved in POCL, with special emphasis to the species favoring or hindering a rapid light evolution. Hence, is the focus placed on the nature of catalysis and the desired properties of substances acting as catalysts in this reaction. Consequently, the scientific papers on which this work is founded includes both systematic stopped-flow studies of catalyst candidates and of the causes for diminished light emission. In addition, multivariate strategies for reaction optimization in practical analysis situations are treated, and the application of the POCL technique to detection of serum-extracted neuroactive steroids, derivatized with fluorescent moieties, is presented.

From the experiments in this thesis it is clear nucleophilic catalysts are the most efficient enhancing compounds, which means that they must possess a carefully balanced characteristics of nucleophilicity, leaving group ability, and basicity. The investigations also conclude that the feature of basicity efficiently can be delegated to a non-nucleophilic co-catalyst, which allow the use of nucleophilic catalysts that need to be deprotonated to be active. This thesis also shows the importance of minimizing the amount of competing nucleophiles at the site of reaction to maintain the emission. This implies that also solvents and buffer substances should be carefully chosen not to interfere with the emission process.

The most promising combination of catalysts found in this work was 4,5- dichloroimidazole together with 1,2,2,6,6-pentamethylpiperidne. This arrangement was capable of speeding the reaction more than tenfold while increasing the maximum emission intensity by about the same factor.

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14

Klenerman, D. "Infra-red chemiluminescence using a SISAM spectrometer." Thesis, University of Cambridge, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.355881.

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15

Martínez, Muñoz Daniel. "Theoretical studies of the chemiluminescence reactions; luminol." Thesis, Uppsala universitet, Institutionen för kemi - BMC, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-255902.

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The vast majority of chemical reactions occurs only in the ground state, however photochemical reactions like chemiluminescence take place in ground and excited states. In almost all chemiluminescence processes oxygen-oxygen bond breakage is involved. But, there is no general reason to explain why these processes occur via an oxygen-oxygen cleavage. These types of phenomena are usually highly exothermic. Computational chemistry has risen as a powerful tool to characterize and analyze chemical phenomena. Quantum mechanics are utilized to explain chemical observations. Applying these equations, one can compute the chemical properties of any system in any state. In the present study, three chemiluminescence reactions derived from luminol are modeled; nitrogen based, oxygen based and dianion nitrogen based models. The key factor of oxygen-oxygen bond rupture is discussed and rationalized. The electronic potential energy surfaces of the three compounds are computed at complete active space self-consistent field theory. Peroxide compounds compared to the dinitrogenated  compounds show a lower activation energy and they are more exothermic. This study allows us to rationalize why luminol needs to be presented in a basic medium and oxidized in order to produce chemiluminescence.
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16

Sanders, Matthew Graham. "Analytical applications of the peroxyoxalate chemiluminescence reaction." Thesis, University of Plymouth, 1999. http://hdl.handle.net/10026.1/1832.

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The overall objectives of this thesis were to investigate the potential of the peroxyoxalate chemiluminescence (POOL) reaction for the quantitative detection of target analytes in non-aqueous matrices and to compare quantitative performance with fluorescence detection. The target analytes investigated were polycyclic aromatic hydrocarbons (PAHs) and aliphatic amines. These were selected as an important class of compounds in engine exhaust emissions and a detergent additive in diesel fuel respectively. Chapter one outlines the challenges of analysing petroleum products and engine exhaust emissions and discusses the potential of luminescence techniques, particularly chemiluminescence (CL), for the quantification of trace components. The chapter also reviews the technique of flow injection (FT) as a means of sample delivery for CL detection and as a potential technique for field deployment. Liquid chromatography techniques are described as a means of separation of complex matrices, e.g. fuels and engine exhaust particulates, in the laboratory prior to CL detection. The luminescence properties of several PAHs were investigated in Chapter Two. Optimum excitation and emission wavelengths for eleven PAHs in four different solvents were determined using a batch fluorescence technique. A FI approach was used to determine PAH concentrations using fluorescence and POCL detection. Two aryl oxalates; bis(2,4-dinitophenyl)oxalate and bis(2,4,6-trichlorophenyl)oxalate were compared for their suitability for PAH determinations and an investigation of the key variables (e.g. concentration of aryl oxalate and hydrogen peroxide, mobile phase composition and pH) affecting POCL was performed. Recommendations for the optimum conditions for the determination of PAHs by POCL detection were determined, A comparison between a photodiode based detection device and a low power (12V) photomultiplier tube was also described. In Chapter Three the procedure of using POCL detection as a post column liquid chromatography (LC) detector for PAHs has been considered. The performance of the POCL detection system was compared with wavelength programmed fluorescence. Both reversed and normal phase LC was investigated and the suitability of POCL detection with each approach was discussed. Additionally the procedure for the LC separation and analysis of SRM 1649 (Urban Dust/Organics) and SRM 1650 (Diesel Particulate Matter) was described. The relative performance of fluorescence and CL detection are discussed. Chapter four describes the principles of multivariate calibration of spectrophotometric data, and three commonly applied techniques (PCR, PLSI and PLS2). Fluorescence data was obtained for synthetic mixtures of PAHs containing two, three, four and five components. A procedure whereby individual spectra were 'glued' together before undergoing data analysis has been developed and the results obtained discussed. POCL emission spectra for five PAHs were acquired using a two-dimensional charge coupled device (CCD). The sensitivity of the CCD system toward POCL detection of PAHs and a multivariate investigation using benzo[a]pyrene and benzo[k]fluoranthene has been described. The potential of the fluorescence and CL approaches used has been discussed. Chapter five describes the aryl oxalate sulphorhodamine-101 CL reaction and its application to the determination of amines. A FI optimisation of the reaction parameters is presented together with some quantitative data for the detection of a homologous series of amines and dodecylamine (a commonly added detergent compound in diesel fuels). The application of the technique toward the detection of dodecylamine in a diesel fuel matrix and the potential as a field deployable technique was also considered.
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17

Greenwood, Alan. "Electro-generated chemiluminescence with conducting sol-gels." Thesis, University of Hull, 2006. http://hydra.hull.ac.uk/resources/hull:11572.

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18

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 dangereux
Electrogenerated 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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19

Marchegiani, Elisa <1991&gt. "Chemiluminescence DNA-based Nanotechnologies for Bioanalytical Applications." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2021. http://amsdottorato.unibo.it/9832/1/Tesi_finale_corretta.pdf.

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DNA as powerful building molecule, is widely used for the assembly of molecular structures and dynamic molecular devices with different potential applications, ranging from synthetic biology to diagnostics. The feature of sequence programmability, which makes it possible to predict how single stranded DNA molecules fold and interact with one another, allowed the development of spatiotemporally controlled nanostructures and the engineering of supramolecular devices. The first part of this thesis addresses the development of an integrated chemiluminescence (CL)-based lab-on-chip sensor for detection of Adenosine-5-triphosphate (ATP) life biomarker in extra-terrestrial environments.Subsequently, we investigated whether it is possible to study the interaction and the recognition between biomolecules and their targets, mimicking the intracellular environment in terms of crowding, confinement and compartmentalization. To this purpose, we developed a split G-quadruplex DNAzyme platform for the chemiluminescent and quantitative detection of antibodies based on antibody-induced co-localization proximity mechanism in which a split G-quadruplex DNAzyme is led to reassemble into the functional native G-quadruplex conformation as the effect of a guided spatial nanoconfinement.The following part of this thesis aims at developing chemiluminescent nanoparticles for bioimaging and photodynamic therapy applications.In chapter5 a realistic and accurate evaluation of the potentiality of electrochemistry and chemiluminescence (CL) for biosensors development (i.e., is it better to “measure an electron or a photon”?), has been achieved.In chapter 6 the emission anisotropy phenomenon for an emitting dipole bound to the interface between two media with different refractive index has been investigated for chemiluminescence detection.
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20

Gerardi, Richard David, and mikewood@deakin edu au. "Investigations into the analytical applications and fundamental chemistry of the chemiluminescent reactions of Tris(22-bipyridyl)ruthenium(III) with certain Papaver Somniferum alkaloids and other related compounds." Deakin University. School of Biological and Chemical Sciences, 1999. http://tux.lib.deakin.edu.au./adt-VDU/public/adt-VDU20060630.100432.

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The reaction of tris(2,2’-bipyridyl)ruthenium(III) (Ru(bipy) 33+) with various analytes to generate chemiluminescence has been well documented. This investigation sought to undertake a chemiluminometic study of the reactions of Ru(bipy) 33+ with selected Papaver Somniferum alkaloids and specifically synthesised phenethylamines. The investigation, based on a kinetic study, primarily addressed the effect of varying reaction conditions (pH) on Ru(bipy) 33+ chemiluminescence production. To monitor these reactions, a batch chemiluminometer was specifically designed, fabricated and automated to conduct an extensive study on the selected compounds of interest. The instrumentation incorporated a custom built reaction cell and comprised an ‘on-line’ sample preparation system with which calibration standards could be automatically prepared. The instrumentation provided both time-independent (peak area) and time-dependent (kinetic profile) information. A novel approach to the stabilisation of Ru(bipy) 33+ as a chemiluminescencent reagent was also investigated and a recirculating system was employed with the batch chemiluminometer to provide a stable supply of Ru(bipy) 33+. Codeine, thebaine and 6-methoxy-codeine were the Papaver Somniferum alkaloids selected for this study and several N-methylated and N,N-dimethylated phenethylamines and methoxy-substituted phenetheylamines were also synthesised to investigate the affect of pH on the chemiluminescence emission efficiency. The versatility of the batch chemiluminometer facilitated the kinetic study of numerous analytes over a broad pH range. The exemplary performance of the chemiluminometer as an analytical instrument, was demonstrated by the calibration functions, based on peak area data, which exhibited excellent linearity and sensitivity. The estimated detection limits (3σ) for the selected alkaloids were in the range 2 x 10&-9<&/sup;> M to 7 x 10&-9<&/sup;> at pH 5.0 and above, which compared favourably to detection limits for the same compounds determined using FIA. Relative standard deviations (n=5) for peak areas ranged between 1% to 5% with a mean of 3.1% for all calibration standards above 2.5 x 10&-8<&/sup;> M. Correlation between concentration and peak area, irrespective of pH and analyte was excellent, with all but two calibration functions having r-squared values greater than 0.990. The analytical figures of merit exemplified the precision and robustness of the reagent delivery and ‘on-line’ sample preparation, as well as the sensitivity of the system. The employment of the chemiluminometer for the measurement of total chemiluminescence emission (peak area) was in itself a feasible analytical technique, which generated highly reproducible and consistent data. Excellent analytical figures of merit, based on peak area, were similarly achieved for the phenethylamines. The effects of analyte structure on chemiluminescence activity was also investigated for the alkaloids and the phenethylamines. Subtle structural variations between the three alkaloids resulted in either a moderately reduced or enhanced total emission that was two or three fold difference only. A significant difference in reaction kinetics was observed between thebaine and codeine/6-methoxy-codeine, which was dependent upon pH. The time-dependent data, namely the observed rate constants for the initial rise in intensity and for the subsequent decay rate, were obtained by fitting a mathematical function (based on the postulated reaction mechanism) to the raw data. The determination of these rate constants for chemiluminescence reactions highlighted the feasibility for utilising such measurements for quantitative analytical applications. The kinetic data were used to discriminate between analyte responses in order to determine the concentrations of individual analytes in a binary mixture. A preliminary, multi-component investigation performed on a binary mixture of codeine and 6-methoxy-codeine (1:1) successfully determined the concentrations of these individual components using such rate constant measurements. Consequently, variations in kinetics resulted in a significant difference between the relative chemiluminescence response based on peak area measurements and the relative response base on peak height measurements obtained using FIA. With regards to the observed reactivity of secondary amines and tertiary amines, chemiluminescence peak area determinations confirmed the vital role of pH on reaction efficiency, which was governed by structural features and kinetics. The tertiary amines investigated generally produced a greater emission under acidic conditions than the corresponding secondary amines. However, the measured chemiluminescence responses were highly dependent upon pH, with similar peak areas obtained for both amine groups under slightly alkaline conditions.
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21

Jacobson, Karin. "Oxidation of stressed polymers as studied by chemiluminescence." Doctoral thesis, Stockholm : Tekniska högsk, 1999. http://www.lib.kth.se/abs99/jaco0917.pdf.

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22

Andrews, Anthony Robert John. "The chemiluminescence detemination of drugs of forensic interest." Thesis, University of Hull, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306129.

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23

Abbott, R. W. "HPLC of drugs of abuse with chemiluminescence detection." Thesis, University of Hull, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.384671.

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24

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 analytique
Electrogenerated 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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Celina, Mathias. "Chemiluminescence Studies of the Thermal Degradation of Polypropylene." Thesis, Queensland University of Technology, 1990. https://eprints.qut.edu.au/227007/1/T%28AS%29%2035_Celina_1990.pdf.

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Chemiluminescence is a technique which has been used in the past to study oxidation and degradation reactions of polymers, especially polyolefins where it was found that the chemiluminescence emission is proportional to the rate of oxidation. i In this thesis the technique has been applied to further studies of the thermal oxidation of polypropylene and other polyolefins. The chemiluminescence signal obtained during the oxidation of polypropylene powder and film samples has also been compared to other parameters indicating the extent of oxidation, such as embrittlement, carbonyl group formation, changes in crystallinity and weight loss. Techniques applied for this purpose were Differential Scanning Calorimetry, Scanning Electron Microscopy, Infrared Spectroscopy and X-ray diffraction. It was found that chemiluminescence is able to determine slight differences in the oxidation behaviour of the samples studied, due to differences in the structure, morphology or melting point of the material. From characteristic points of the recorded chemiluminescence curves, such as initial rate of oxidation, induction periods or maximum·rates of oxidation it was possible to calculate activation energies and to compare them with published values. A kinetic model which aims to describe the chemiluminescence curve has been applied to the oxidation of polypropylene powder. It was found that the activation energy of the degradation determined by this model was also accessible from other data. Some scepticism on the applicability of this model in relation to published results has been discussed. Furthermore a fundamental chemiluminescence curve for a large temperature range was derived. The main results and features presented in this thesis are the temperature dependence of the initial rate of oxidation of polypropylene powder, the fundamental chemiluminescence curve describing the oxidation of polypropylene powder, the differences in the oxidation of polypropylene powder and film samples and the questionable approach of extrapolation of high temperature oxidations of polyolefins to low temperature conditions.
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26

Reaney, James E. "The use of chemiluminescence for the detection of temperature and fuel-to-air ratio in turbulent premixed flames." Thesis, This resource online, 1992. http://scholar.lib.vt.edu/theses/available/etd-09192009-040312/.

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Johnsson, Erik Lewis. "The use of chemiluminescence for detection of ignition, temperature, and fuel-to-air ratio of flames /." This resource online, 1991. http://scholar.lib.vt.edu/theses/available/etd-05022009-040621/.

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28

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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29

Greenwood, Paul Andrew. "Chemiluminescence as a detection tool for miniaturised analytical systems." Thesis, University of Hull, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.396750.

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30

Marle, Leanne. "Miniaturised analytical systems with chemiluminescence detection for environmental applications." Thesis, University of Hull, 2006. http://hydra.hull.ac.uk/resources/hull:8095.

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This thesis details the use of microfluidic devices and chemiluminescence detection in order to develop a portable method of analysis for measuring chemical species in the environment. Chapter 1 outlines microfluidic technology, including fabrication techniques, fluid manipulation and mixing within the devices. Their advantages for analytical environmental purposes are demonstrated along with a review of their uses in environmental applications. Chemiluminescence detection provides a sensitive method of analysis for measuring chemical species in the environment and chemiluminescence theory and reagents are addressed. Chapter 2 details the development of a portable battery operated chemiluminescence detection system, which can be used in conjunction with microfluidic devices. The fabrication of the micro fluidic devices used in this work is documented. Different micro fluidic channel manifolds were investigated for chemiluminescence reactions and a serpentine design (200 μm width, 65 μm depth) with a channel length of 206 mm was selected as the most suitable design. Methods of fabrication for incorporating immobilised reagents on solid supports within a microfluidic device were also designed. Chapter 3 documents the investigation of the luminol-cobalt(II) chemiluminescence reaction within a microfluidic device using the portable chemiluminescence detection system to produce a miniaturised analytical system for the determination of hydrogen peroxide in rainwater. Enhancement of the chemiluminescence signal by 132 %was achieved by means of using the mirror reaction to apply a reflective surface directly VI to the top of the micro fluidic device. Immobilisation techniques for immobilising luminol using adsorption and covalent attachment onto a solid support were investigated as a means of producing a reagentless system, however poor sensitivity was observed and this was not progressed for the analytical system. Using the luminol-cobalt(II) chemiluminescence reaction within a microfluidic device a method of measuring hydrogen peroxide in the low micromolar concentrations was achieved, producing a limit of detection of 4.7 nmol L⁻¹ with a small sample volume (10 μL min⁻¹). A small reagent consumption size (1.2 mL per hour) and a low waste production size (2.4 mL per hour) were also achieved. This system was then used for the determination of hydrogen peroxide in rainwater samples during rainfall events showing the hydrogen peroxide concentration varied from 0.1 to 3.2 μmol L⁻¹. The method was also applied to the analysis of hydrogen peroxide in snow demonstrating the hydrogen peroxide concentration varied from 0.2 to 0.5 μmol L⁻¹ in samples taken at ground level. Chapter 4 details the development of a heterogeneous (two site) sandwich immunoassay within a microfluidic device to produce a miniaturised analytical system for the determination of E. coli bacteria in seawater. There is a need for rapid sensitive methods of analysis to measure E. coli in seawater as an indicator of faecal contamination. A review of traditional methods and current research on the area is presented. Immunological techniques based on using antibodies to specifically bind to their respective antigens were found to be the most amenable method of analysis for E. coli and an outline of how they work is shown. HRP was selected as the sensitive enzyme label for the antibody in the sandwich immunoassay. The chemiluminescence detection of HRP using the luminol-hydrogen peroxide VB chemiluminescence reaction was investigated within a microfluidic device, the detection was optimised and p-iodophenol was selected as an enhancer for the reaction. The investigation into the immobilisation of E. coli specific antibodies using covalent attachment onto controlled pore glass is presented, an optimal loading of 1.5 μg g⁻¹ was achieved. The development of an ELISA method for the purpose of screening the antibody for their specificity towards different isolates of E. coli and their non-specificity towards other bacteria is detailed. Finally, a microfluidic immunoassay was developed. Regeneration of the immobilised antibodies was achieved using 0.5 mol L⁻¹ sodium hydroxide, allowing the immobilised antibodies to be reused. The microfluidic immunoassay provided a rapid method for the determination of E. coli with an analysis time of 13 min for each sample. The assay also used a low reagent consumption and waste production. This would enable the rapid testing of a number of small samples to provide high temporal and spatial resolution data. Sensitivity provided a problem with the immunoassay and ways to overcome this were addressed.
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Zeng, Jiang. "Chemiluminescence and bioluminescence related to flavins and bacterial luciferase." Thesis, University of Huddersfield, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.387194.

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32

Braynis, H. S. "Chemiluminescence and kinetic studies of gaseous fluorine atom reactions." Thesis, University of Manchester, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377719.

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33

Fredrikssen, Elizabeth Anne. "Chemiluminescence from the thermal oxidation of poly(ethylene terephthalate)." Thesis, University of Sussex, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.298728.

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34

Lancaster, James Steven. "Chemiluminescence detection in flow injection analysis and liquid chromatography." Thesis, University of Hull, 1991. http://hydra.hull.ac.uk/resources/hull:11500.

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This thesis describes the development of chemiluminescence procedures for the detection of some organic compounds of interest to the oil industry. Water soluble tertiary amines were determined using flow-injection analysis with chemiluminescence detection. The chemiluminescence was generated by reacting the aqueous tertiary amine solution with aqueous sodium hypochlorite at pH 11.0, in the presence of rhodamine B, which sensitizes the emission. The simplex optimized flow-injection manifold was used to determine trimethylamine, triethylamine and tripropylamine in water and sea water. A standard-addition calibration procedure was used to determine trimethylamine in an industrial scrubbing medium. The chemiluminescence of tertiary amines was extended to the detection of the non-ionic surfactant, Nonidet AT 85, which contains a tertiary amine group. The flow-injection manifold was simplex optimised for this analyte in sea water. The surfactant was also determined in aqueous extracts of marine sediment. Calibration was by a standard addition procedure. Primary amines were determined by flow-injection analysis after fluorimetric derivatization with o-phthalaldehyde and 2-mercaptoethanol in non-aqueous media. The fluorescent derivative was detected by excitation using the peroxyoxalate chemi-excitation reaction. A pre-column fluorimetric derivatization procedure was developed for the determination of carboxylic acids in non-aqueous media. Straight chain acids over the range C2 to C20 and benzoic acid were derivatized with 9-anthracene methanol, using dicyclohexylcarbodiimide (DCC) as a coupling reagent to yield fluorescent esters. Separation was carried out by reversed-phase high-performance liquid chromatography and the peroxyoxalate chemi-excitation reaction was used to detect the fluorescent species. An automated flow-injection manifold was developed, including computerised data acquisition and automated sample uptake and injection. This enabled the system to operate whilst unattended. The precision of the data was higher than that obtained with the manual system. Finally, a flow-injection manifold was designed which incorporated a monochromator between the flow cell and the detector, thus enabling chemiluminescence spectra to be obtained.
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Zholudov, Yu. "Electrogenerated chemiluminescence in tryptophan / tetraphenylborate system for biosamples assay." Thesis, КрНУ, 2018. http://openarchive.nure.ua/handle/document/7523.

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In this work the results of study of electrochemiluminescence in the system tryptophan / co-reatant tetraphenylborate and analysis of the possibility of its use for measuring the content of the amino acid tryptophan in biological samples are presented.
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36

Assegid, Kirubel. "Development of a gas-phase chemiluminescence detection system for the measurement of arsenic in environmental and biological samples." Fairfax, VA : George Mason University, 2008. http://hdl.handle.net/1920/3000.

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Thesis (M.S.)--George Mason University, 2008.
Vita: p. 93. Thesis director: Abul Hussam. Submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemistry. Title from PDF t.p. (viewed June 30, 2008). Includes bibliographical references (p. 89-92). Also issued in print.
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Griffiths, Helen L. "The role of Fc#gamma#RI in the immune destruction of blood cells." Thesis, University of the West of England, Bristol, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.244308.

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38

Haber, Ludwig Christian. "An investigation into the origin, measurement and application of chemiluminescent light emissions from premixed flames." Thesis, Virginia Tech, 2000. http://hdl.handle.net/10919/31472.

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The chemiluminescent species CH* and OH* are studied in premixed methane combustion to investigate the possible application of their light emissions in gas turbine combustion monitoring systems. The interpretation of integrated and local chemiluminescence measurements are shown to give important qualitative insights into the burning process. The formation path of OH* chemiluminescence is clarified and an accurate chemical kinetic model predicting OH* chemiluminescence emission is developed using GRIMECH 3.0 as a starting point for methane oxidation. CH* chemiluminescence is also modeled but difficulties in obtaining quenching data make the modeling efforts somewhat less successful than that for OH* chemiluminescence. Two combustion models are developed. The first is a semi-empirical model for a Bunsen type flame. The second is a 1-D model for a ceramic honeycomb flat-flame burner using the full chemical kinetics description of the conversion from fuel to products along with a detailed energy equation, accounting for the radiation energy exchange between hot gases and the honeycomb burner ceramic. The results of the modeling calculations show that OH* is superior to CH* chemiluminescence in terms of indicating heat-release rate. The formation of the ratio between CH* and OH* chemiluminescence is shown to be an accurate indicator of equivalence ratio.
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39

Nori, Venkata Narasimham. "Modeling and analysis of chemiluminescence sensing for syngas, methane and jet-A combustion." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2008. http://hdl.handle.net/1853/24681.

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Thesis (Ph.D.)--Aerospace Engineering, Georgia Institute of Technology, 2008.
Committee Chair: Seitzman, Jerry; Committee Member: Jagoda, Jechiel; Committee Member: Lieuwen, Tim; Committee Member: Menon, Suresh; Committee Member: Docquier, Nicolas; Committee Member: Huey, Gregory.
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40

Otamonga, Jean Paul. "Stopped-flow kinetic investigation of manganese-based chemiluminescence oxidation reactions." Thesis, University of Huddersfield, 2013. http://eprints.hud.ac.uk/id/eprint/18054/.

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In order to better understand the mechanism of solution manganese-based chemilumines-cence, the kinetics of a number of chemiluminescent oxidations by manganese species were studied using stopped-flow spectrophotometry. Both the kinetics of the decay of the oxi-dant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn3+(aq) of a range of organic compounds. The most detailed studies were carried out on the oxidation of the relatively simple compounds including glyoxylic acid and glyoxal under pseudo first order conditions and an acidic medium at 25oC. For permanganate under these conditions, the decay is sigmoidal consistent with autocatalysis and for managanese dioxide sol and Mn3+ pseudo first order. Simple mechanisms are suggested and compared with the experimental kinetic data. For per-manganate CL system, the following chemical kinetic model was considered: MnO4- + xsR à MnO2 (k1) MnO2 + xsR à Mn3+ (k2) MnO4- + 3Mn3+ à 4MnO2 (k3) Mn3+ + xsR à (Mn2+)*
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41

Agater, Irena Barbara. "Applications of permanganate chemiluminescence to the analysis of food components." Thesis, University of Huddersfield, 1999. http://eprints.hud.ac.uk/id/eprint/5955/.

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Chemiluminescent oxidations with manganese reagents have been investigated using flow and spectroscopic techniques. An assay has been developed for ascorbic acid using the chemiluminescent oxidation of ascorbic acid with permanganate in acid medium. The assay has a linear range of 5xl 0-7 to 1 X, 0-3 mol dM-3 and has been applied to a range of food supplements and fruit juices. The addition of a manganese (11) catalyst extends the applicability of acid permanganate to the determination of sugars and polyhydric alcohols. The reaction has been optimised for the determination of mono and disaccharides in a flow injection system. Development of a reagent based on manganese (111)i,n a methanol and sulphuric acid solution, has further extended the scope of the reaction enabling the determination of fructose in the range 1 X1 0-7 to 1 X1 0-3 mol d M-3. The reagent has successfully been used in post column detection with HPLC. It has been established that the light emission occurs after manganese (VII) has been reduced and appears to be connected with the production and disappearance of Mn (111). Chemiluminescence spectroscopy has shown that the spectra are the same for a large number of aliphatic and aromatic polyhydroxy compounds. The spectrum remains the same whether the oxidising reagent is Mn (VII), Mn (IV) or Mn (111)i,n dicating that the same emitting species is involved in all these reactions and that it involves Mn(III) and/or Mn(II).
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42

Ahlblad, Gustav. "Imaging chemiluminescence applied to oxidation of rubber materials and polyamide /." Stockholm, 1998. http://www.lib.kth.se/abs98/ahlb0417.pdf.

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43

Wheatley, Robert Alan. "Aldehydic lipid peroxidation products : flow analysis using spectrophotometry and chemiluminescence." Thesis, University of Hull, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.363331.

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44

Shelley, Rachel. "Cobalt biogeochemistry in the Atlantic Ocean using Flow Injection-Chemiluminescence." Thesis, University of Plymouth, 2011. http://hdl.handle.net/10026.1/538.

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As ~ 50% of global photosynthesis occurs in marine environments, the factors regulating this process e.g. trace metal availability, have an impact on the global carbon cycle. The key cyanobacteria genera Prochlorococcus and Synechococcus have an absolute requirement for Co. Dissolved cobalt (dCo) concentrations in the open ocean are extremely low (5–120 pM). A sensitive flow injection technique using chemiluminescence detection (FI-CL) was developed (detection limit 4.5 pM dCo, RSD ≤ 4%). Seawater samples must be UV-irradiated prior to analysis, in order to liberate organically-bound Co. A field study in the Sargasso Sea, demonstrated that aerosol Co was significantly more soluble than aerosol Fe over a range of aerosol dust deposition fluxes (1–1040 μg Fe m-2 d-1) (8-100% for Co versus 0.44-45% for Fe). The dry deposition flux of aerosol Co was of the same order of magnitude as the advective upwelling flux (47-1540 pmol m-2 d-1 and 1.7-1430 pmol m-2 d-1 respectively). Wet deposition, dominated the total aerosol flux (~ 85%). The vertical distribution of dCo influenced Prochlorococcus abundance. A regional study in the eastern North Atlantic gyre demonstrated that the highest rates of N2 fixation occurred with the highest dFe concentrations (9.8 nM N L-1 h-1, 0.6 nM respectively). No increase in primary production following additions of trace metals (Co, Cu, Fe, Zn) was observed. The addition of N resulted in an increase in primary production. However, there was no synergistic effect of trace metal plus N addition, suggesting that alleviation of N-limitation shifted the system to P-limitation. On a meridional transect from ~ 50°N–50°S in the Atlantic Ocean, the highest concentrations of dCo (> 80 pM) coincided with low-O2 (< 150 μM) upwelled water. The lowest dCo (< 20 pM) was observed in the eastern North Atlantic gyre. Lateral advection of continental Co and upwelling were identified as important sources of Co. The highly efficient recycling of Co in the euphotic zone is an important additional source.
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45

Williams, Timothy Paul. "Determination of trace metals by ion-chromatography with chemiluminescence detection." Thesis, University of Plymouth, 1990. http://hdl.handle.net/10026.1/2182.

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46

Waller, Hazel. "Determination of phenolic compounds using hydroxylase enzymes and chemiluminescence detection." Thesis, University of Huddersfield, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.411892.

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47

O'Neil, Alanna R. "Chemiluminescence and High Speed Imaging of Reacting Film Cooling Layers." University of Dayton / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1324042434.

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48

Zangheri, Martina <1987&gt. "Ultrasensitive chemiluminescence bioassays based on microfluidics in miniaturized analytical devices." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amsdottorato.unibo.it/6999/1/Zangheri_Martina_tesi.pdf.

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The activity carried out during my PhD was principally addressed to the development of portable microfluidic analytical devices based on biospecific molecular recognition reactions and CL detection. In particular, the development of biosensors required the study of different materials and procedures for their construction, with particular attention to the development of suitable immobilization procedures, fluidic systems and the selection of the suitable detectors. Different methods were exploited, such as gene probe hybridization assay or immunoassay, based on different platform (functionalized glass slide or nitrocellulose membrane) trying to improve the simplicity of the assay procedure. Different CL detectors were also employed and compared with each other in the search for the best compromise between portability and sensitivity. The work was therefore aimed at miniaturization and simplification of analytical devices and the study involved all aspects of the system, from the analytical methodology to the type of detector, in order to combine high sensitivity with easiness-of-use and rapidity. The latest development involving the use of smartphone as chemiluminescent detector paves the way for a new generation of analytical devices in the clinical diagnostic field thanks to the ideal combination of sensibility a simplicity of the CL with the day-by-day increase in the performance of the new generation smartphone camera. Moreover, the connectivity and data processing offered by smartphones can be exploited to perform analysis directly at home with simple procedures. The system could eventually be used to monitor patient health and directly notify the physician of the analysis results allowing a decrease in costs and an increase in the healthcare availability and accessibility.
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49

Zangheri, Martina <1987&gt. "Ultrasensitive chemiluminescence bioassays based on microfluidics in miniaturized analytical devices." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amsdottorato.unibo.it/6999/.

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The activity carried out during my PhD was principally addressed to the development of portable microfluidic analytical devices based on biospecific molecular recognition reactions and CL detection. In particular, the development of biosensors required the study of different materials and procedures for their construction, with particular attention to the development of suitable immobilization procedures, fluidic systems and the selection of the suitable detectors. Different methods were exploited, such as gene probe hybridization assay or immunoassay, based on different platform (functionalized glass slide or nitrocellulose membrane) trying to improve the simplicity of the assay procedure. Different CL detectors were also employed and compared with each other in the search for the best compromise between portability and sensitivity. The work was therefore aimed at miniaturization and simplification of analytical devices and the study involved all aspects of the system, from the analytical methodology to the type of detector, in order to combine high sensitivity with easiness-of-use and rapidity. The latest development involving the use of smartphone as chemiluminescent detector paves the way for a new generation of analytical devices in the clinical diagnostic field thanks to the ideal combination of sensibility a simplicity of the CL with the day-by-day increase in the performance of the new generation smartphone camera. Moreover, the connectivity and data processing offered by smartphones can be exploited to perform analysis directly at home with simple procedures. The system could eventually be used to monitor patient health and directly notify the physician of the analysis results allowing a decrease in costs and an increase in the healthcare availability and accessibility.
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50

Evans, Raelene Nicole, and mikewood@deakin edu au. "Aqueous/Micellar peroxyoxalate chemiluminescent detection for ion chromatography." Deakin University. School of Biological and Chemical Sciences, 1998. http://tux.lib.deakin.edu.au./adt-VDU/public/adt-VDU20051201.143852.

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This thesis covers the development of the traditionally fluorescent bis(8-quinolinol-5-sulfonic acid) magnesium (II) fluorophore as a chemiluminescent emitter. A brief description of luminescence spectroscopy and its application to analytical chemistry lays the foundation to the discussion of the results obtained herein. This includes the synthesis and identification of two so called ‘water soluble’ aryl oxamides 2,2’-oxalyl-bis(trifluoromethanesulfonyl) imino] ethylene-bis(N- methylpyridinium) trifluoromethane sulfonate (PETQ) and 2,2’-oxalyl-bis(trifluoromethanesulfonyl) imino]ethylene-bis(N-pyridinium) chloride (PETH), previously developed for the US navy as a possible emergency light source, yet the synthetic methodology were incomplete. The inconsistencies of the synthetic methods for PETQ and PETH were overcome with yields satisfactory for their preliminary analytical evaluation. The evaluation of these aryl oxamides, including 4,4’-oxalyI- bis[(trifluoromethanesulfonyl) imino]ethylene-bis(l-methyM-benzylpiperidinium) trifluoromethanesulfonate (BPTQ), 4,4’-oxalyl-bis [(trifluoromethylsulfonyl)imino] ethylene-bis(N-methylmorpholinium)trifluoromethanesulfonate (METQ) and the oxalate bis(2,4,6-trichlorophenyl) oxalate (TCPO) were performed with the peroxyoxalate chemiluminescent reaction using bis(8-quinolinol-5-sulfonic acid) magnesium (II) as the fluorophore. A univariate optimisation of this system resulted in 0,0082 mol 1-1 the detection limit of magnesium in the absence of cationic surfactants and 0.0041 mol 1-1 in their presence for the majority of these compounds. The oxamides were found to be insoluble in water with long ulrasonication periods required to dissolve the compound, with solvents such as acetonitrile preferred. The determination of other chemiluminescent metal-8HQS chelates to replace magnesium -8HQS in the peroxyoxalate were limited to Al (III), Cd (II), Ca (II), In (II) and Zn (II), unfortunately these metals all possessed poorer detection limits than those obtained using magnesium The base reaction conditions used for the flow injection system with chemiluminescent detection were transferred to an ion chromatographic configuration for the separation of magnesium from other cations on an exchange column. After a univariate and simplex optimisation of these conditions, the detection limit of magnesium was found to be 0.0411 mol 1-1 which was less than the limits that could be achieved with fluorescent detection, The further development of this reaction to incorporate the displacement of magnesium from Mg-EDTA by other metals that possessed a higher conditional stability constant than magnesium also proved to be problematic with interferences from not only EDTA but from the eluant (lactic acid) from the cation column. Using this system the detection limits of the displacing metals were found to be in the order of 10 mg 1-1 which was substantially less that what was observed when exactly the same configuration was used with fluorescent detection. The final component of the thesis entails the discussion of the background emission that results from the reaction of oxamides/oxalates with hydrogen peroxide. A detailed investigation into the reaction of TCPO and hydrogen peroxide in the presence of various additives, such as imidazole , heavy atoms and triethylamine illustrated the existence of a further intermediate in fee mechanism for this reaction. The species responsible for this emission was attributed to the degradation product 2,4,6-trichlorophenyi of TCPO, which was supported by the non-existent background present with the oxamides that do not contain this degradation product.
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