- Title
- The construction of phthalocyanine- carbon nanoparticle conjugates for applications in photodynamic therapy and non-linear optics
- Creator
- Matshitse, Refilwe Manyama Stephina
- ThesisAdvisor
- Nyokong, T
- Subject
- Phthalocyanines
- Subject
- Nanodiamonds
- Subject
- Photochemotherapy
- Subject
- Nonlinear optics
- Subject
- Quantum dots
- Date
- 2021-10-29
- Type
- Doctoral theses
- Type
- text
- Identifier
- http://hdl.handle.net/10962/188397
- Identifier
- vital:44750
- Identifier
- 10.21504/10962/188397
- Description
- The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position and sometimes positively charged are reported. The Pcs had either H2, zinc or silicon as central metals and have pyridyloxy, benzothiozole phenoxy, and respective cationic analogues as ring substituents. The Pcs were linked to carbon based nanoparticles such as graphene quantum dots, carbon dots, and detonation nanodiamonds (DNDs) via an ester, amide bond and/or π - π stacking. The physicochemical characteristics of the Pcs were assessed when alone and when in a conjugated system. Both symmetrically and asymmetrically substituted benzothiozole Pcs when quaternised displayed higher triplet and singlet oxygen quantum yields than their unquaternised counterparts. Linkage to carbon nanoparticles (especially to detonation nanodiamonds) had an increasing effect on triplet and singlet oxygen quantum yield. However, a general decrease in singlet oxygen quantum yield on linkage to doped detonation nanodiamonds was associated with the screening effect of DNDs. Heteroatom doped DNDs-Pc nanohybrids have less singlet oxygen than Pcs alone due to molecular structural stability associated with strain that is relatively reduced upon linking Pcs. The In vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. When Pc complexes are alone, there is less phototoxicity with >22% cell viability at concentrations ≤ 50 μg/mL relative to conjugates with <22% cell viability at concentrations ≤ 50 μg/mL. There was no direct relationship between PDT and singlet oxygen quantum yields. Nonlinear optical characteristics of complexes was improved upon conjugation of DNDs. Absorbance, input energy, percentage loading, central metal, substituent of Pc and nature of interaction (covalent, noncovalent) are amongst some of the factors that influence nonlinear absorption properties of materials used in this study. All materials followed reverse saturable absorption through two photon absorption mechanism at the excitation wavelength of 532 nm. Aggregates reduce excited state lifetime and Beff under high concentrations/absorbance. A direct relationship between absorbance and Beff of DNDs nanoconjugated systems at low concentrations result in increased optical limiting characteristics of materials. The findings from this work show the importance of linking (nonlinear optics and photodynamic therapy) and doping (photodynamic therapy) photosensitisers such as phthalocyanines and sometimes boron dipyrromethenes onto carbon based nanoparticles for the enhanced characteristics in variable applications.
- Description
- Thesis (PhD) -- Faculty of Science, Chemistry, 2021
- Format
- computer, online resource, application/pdf, 1 online resource (240 pages), pdf
- Publisher
- Rhodes University, Faculty of Science, Chemistry
- Language
- English
- Rights
- Matshitse, Refilwe Manyama Stephina
- Rights
- Attribution 4.0 International (CC BY 4.0)
- Rights
- Open Access
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| Thumbnail | File | Description | Size | Format | |||
|---|---|---|---|---|---|---|---|
| View Details Download | SOURCE1 | MATSHITSE-PHD-TR21-156.pdf | 10 MB | Adobe Acrobat PDF | View Details Download |