Idowu, M.A. (2009) Photophysical and photochemical behaviour of metallophthalocyanines : effect of nanoparticles and molecules of biological importance. PhD thesis, Rhodes university.
Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
|Item Type:||Thesis (PhD)|
|Uncontrolled Keywords:||Electrochemistry; Phthalocyanines; nanoparticles|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||Faculty > Faculty of Science > Chemistry|
|Supervisors:||Nyokong, T. (Prof.)|
|Deposited By:||Rhodes Library Archive Administrator|
|Deposited On:||24 Jun 2010 08:49|
|Last Modified:||06 Jan 2012 16:21|
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