Abstract
The work presented in this thesis is broadly concerned with how complexation reactions and molecular motion can be characterized with the standard techniques in optical spectroscopy. The thesis aims to show a relatively broad range of methods for probing physico-chemical properties in fluorophore containing systems using simple instrumentation and well-known and understood theoretical concepts. Overall it is attempted to achieve this goal by presenting five research projects that I have been involved in during my Ph.D. studies which collectively demonstrate some of the many possibilities of gaining information about chemical equilibria, kinetics and molecular motion by monitoring changes in optical properties of the system.
The five presented research projects are largely unrelated to each other both in aim and in what property is probed, however they are all connected in that they are fluorophore containing systems and are characterized using techniques in optical spectroscopy. Of the standard techniques in optical spectroscopy, particular attention has been paid to those based on time-resolved measurements and
polarization, which is reflected in the experiment design in the projects. Not all of the projects are published at the time this thesis was handed in, however in all cases either the published article or a prepared draft is provided as appendices. The research projects and their aim are as follows: Projects 1 and 2 are, in a broad sense, concerned with the characterization of simple chemical reactions by optical spectroscopy. In project 1 simple steady-state absorption and fluorescence
spectroscopy is used to determine the stoichiometries and equilibrium constants in the inclusion complex formation between cyclodextrins and derivatives of the water-insoluble oligo(phenylene vinylene) in aqueous solution. In project 2 the intramolecular excited state association reaction between aniline and anthracene is characterized by both steady-state and time-resolved techniques, where the time resolved fluorescence measurements in particular allowed for the determination of
the reaction rate constants. Projects 3, 4, and 5 are all related to investigations of the fundamental properties of- and applications of- the aza-oxa triangulenium class of dyes. In project 3 the electronic transitions of these dyes are characterized using primarily polarized absorption and emission spectroscopy. In project 4 the nowdetermined properties of the dyes are used to make a fluorescence-based binding-assay capable of detecting the binding of two large biomolecules using fluorescence anisotropy. Finally, project 5 is a work-in-progress detailing the effect of intra-molecular exciton coupling on the optical properties of aza-oxa triangulenium dimers.
The five presented research projects are largely unrelated to each other both in aim and in what property is probed, however they are all connected in that they are fluorophore containing systems and are characterized using techniques in optical spectroscopy. Of the standard techniques in optical spectroscopy, particular attention has been paid to those based on time-resolved measurements and
polarization, which is reflected in the experiment design in the projects. Not all of the projects are published at the time this thesis was handed in, however in all cases either the published article or a prepared draft is provided as appendices. The research projects and their aim are as follows: Projects 1 and 2 are, in a broad sense, concerned with the characterization of simple chemical reactions by optical spectroscopy. In project 1 simple steady-state absorption and fluorescence
spectroscopy is used to determine the stoichiometries and equilibrium constants in the inclusion complex formation between cyclodextrins and derivatives of the water-insoluble oligo(phenylene vinylene) in aqueous solution. In project 2 the intramolecular excited state association reaction between aniline and anthracene is characterized by both steady-state and time-resolved techniques, where the time resolved fluorescence measurements in particular allowed for the determination of
the reaction rate constants. Projects 3, 4, and 5 are all related to investigations of the fundamental properties of- and applications of- the aza-oxa triangulenium class of dyes. In project 3 the electronic transitions of these dyes are characterized using primarily polarized absorption and emission spectroscopy. In project 4 the nowdetermined properties of the dyes are used to make a fluorescence-based binding-assay capable of detecting the binding of two large biomolecules using fluorescence anisotropy. Finally, project 5 is a work-in-progress detailing the effect of intra-molecular exciton coupling on the optical properties of aza-oxa triangulenium dimers.
| Originalsprog | Engelsk |
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| Forlag | Department of Chemistry, Faculty of Science, University of Copenhagen |
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| Status | Udgivet - 2013 |