Azadipyrromethenes for applications in photodynamic antimicrobial chemotherapy, photodynamic therapy and optical limiting
- Authors: Dubazana, Nadine
- Date: 2020
- Subjects: Dyes and dyeing -- Chemistry , Photochemotherapy , Cancer -- Photochemotherapy , Anti-infective agents , Staphylococcus aureus , Nonlinear optics , Azadipyrromethenes , BODIPY
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166150 , vital:41333
- Description: Azadipyrromethenes, azaBODIPYs and zinc azadipyrromethene complexes were prepared and characterised to examine the effect on their photophysical properties of incorporating phenyl groups at the 1,3,5,7-positions with electron-donating and withdrawing groups at the para-positions. To enhance their ability to generate singlet oxygen, appropriate structural modifications were made through the addition of a Zn(II) ion or halogenation at the 2,6 positions. In vitro photodynamic therapy (PDT) studies targeting MCF-7 human breast cancer cells were carried out. To evaluate and understand the effectiveness of the dyes as photosensitisers, cellular uptake, phototoxicity and the half-maximal inhibitory concentration (IC50) values were analysed. Photodynamic antimicrobial chemotherapy (PACT) studies were also carried out to study the effectiveness of the dyes against Staphylococcus aureus (S. aureus). Dyes with donor-π-acceptor (D-π-A) properties were synthesised and tested against the second harmonic of the Nd:YAG laser in optical limiting (OL) studies. The second-order hyperpolarisability, third-order susceptibility and nonlinear absorption coefficient values were determined. The results suggest that 1,3,5,7-azaBODIPY dyes may be less suitable for use in this context than analogous D-π-A 3,5-distyrylBODIPY dyes. Molecular modelling was carried out to identify the structure-property relationships of the synthesised dyes by analysing trends in the energies of the frontier molecular orbitals (MOs) and spectroscopic properties.
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BODIPY dyes for application in the photo-oxidation of pollutants, photodynamic antimicrobial chemotherapy, and nonlinear optics
- Authors: Kelechi, Lebechi Augustus
- Date: 2020
- Subjects: Dyes and dyeing -- Chemistry , Fluorescent probes , Fluorescence spectroscopy
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/140298 , vital:37859
- Description: The synthesis and structural characterization of a series of BODIPY dyes to analyze both the effects of halogenations at the 2,6-positions and the introduction of styryl groups at the 3,5-positions. The photophysical properties of these dyes were investigated to determine their suitability as singlet oxygen-generating photosensitiser dyes for application in photocatalytic degradation of azo dyes and in photodynamic antimicrobial chemotherapy (PACT). Upon halogenation, the dyes showed high to moderate singlet oxygen quantum yields. The potential utility of electrospun polystyrene (PS) nanofibres embedded with halogenated BODIPY dyes for the photocatalytic degradation of Orange G and Methyl Orange from textile industry effluents were investigated. A comparison of the singlet oxygen quantum yield of the BODIPY dyes in solution and when embedded in the PS nanofibres support demonstrates that its photosensitiser properties are maintained in the nanofibre mats. The photocatalytic degradation properties of the PS nanofibres for Orange G and Methyl Orange were determined by using a 530 nm and 660 nm light-emitting diodes. The rate of photodegradation increases with both the Orange G and Methyl Orange concentrations and follows pseudo-first-order kinetics. The PACT activities of brominated BODIPYs on Escherichia coli and Staphylococcus aureus were investigated. Log reduction values of over 9 were obtained during the photoinactivation of Staphylococcus aureus. To be able to red-shift the main spectral band of the BODIPY dyes into the therapeutic window, styryl groups were introduced at the 3,5-positions through a modified Knoevenagel condensation reaction. Because the red-shifted spectral band lies above 532 nm, the second harmonic of the Nd:YAG laser, there is very minute absorption at this wavelength. One of the novel brominated BODIPY dyes was investigated for its potential utility as optical limiting materials in nonlinear optics (NLO), and the dyes demonstrated typical nonlinear absorption behaviour characterised by reverse saturable absorption (RSA) in Z-scan measurements. Excellent optical limiting parameters were obtained for third-order susceptibility and hyperpolarisability.
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The preparation of BODIPY and porphyrin dyes and their cyclodextrin inclusion complexes and Pluronic® F-127 encapsulation micelles for use in PDT and PACT
- Authors: Molupe, Nthabeleng
- Date: 2019
- Subjects: Dyes and dyeing -- Chemistry , Drug delivery systems , Fluorescence spectroscopy , Cancer -- Photochemotherapy , Photosensitizing compounds -- Therapeutic use , Cyclodextrins -- Biotechnology , Nanoparticles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117574 , vital:34528
- Description: Several novel BODIPY dyes ((4,4′-difluoro-1,7-tetramethyl-3,5-(3-dithiophene)-2,6-diiodo-8-(4-dimethylamino)-4-bora-3a,4a-diaza-s-indacene (1c), 4,4′-difluoro-1,7-tetramethyl-3,5-(3 dithiophene)-2,6-diiodo-8-(4-methylthio)-4-bora-3a,4a-diaza-s-indacene (3c) and 4,4′-difluoro-1,7-tetramethyl-3,5-(4-dibenzyloxybenzene)-2,6-diiodo-8-(4-methylbenzoate)-4 bora-3a,4a-diaza-s-indacene (4c)) and porphyrins (tetraacenaphthylporphyrin (7a) and Sn(IV) tetraacenaphthylporphyrin (7b)) were synthesized and characterized. Previously reported BODIPY dyes (4,4′-difluoro-1,7-tetramethyl-3,5-(2-dihydroxy)-2,6-diiodo-8-(4-bromo)-4-bora-3a,4a-diaza-s-indacene (5) and 4,4′-difluoro-1,7-tetramethyl-3,5-(2-dithiophene)-2,6-diiodo-8-(phenyl)-4-bora-3a,4a-diaza-s-indacene (6)) were also used. Pluronic® F-127 and cyclodextrins were used as solubilizing drug delivery agents for the synthesized BODIPY dyes. The encapsulation of BODIPY dyes with Pluronic® F-127 micelles improved the water solubility of the BODIPY 5. Further modification of Pluronic® F-127 by coating with folate-functionalized chitosan for targeted delivery of BODIPY 1c and 6 was explored. The BODIPY dyes and their encapsulation complexes exhibited significant inhibition of human MCF-7 breast cancer cell growth. When cyclodextrins were used as nanocarriers, the inclusion complexes of BODIPY 4c with mβCD were found to enhance the water-solubility of the dye. Greater photoinactivation of Staphylococcus aureus was observed for the inclusion complexes when compared to the effect of solutions of non-complexed BODIPY 4c. The cyclodextrin inclusion complexes of porphyrin 7b with mβCD were also found to enhance the water-solubility of 7b. When the photodynamic effect was evaluated, solutions of the porphyrin alone and their inclusion complexes were found to have significant photodynamic effects against human MCF-7 breast cancer cells.
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Donor-acceptor effects on the optical limiting properties of BODIPY dyes
- Authors: Hlatshwayo, Zweli Thabiso
- Date: 2018
- Subjects: Dyes and dyeing -- Chemistry , Photosensitizing compounds -- Therapeutic use , Cancer -- Photochemotherapy , Upconversion nanoparticles (UCNPs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63368 , vital:28397
- Description: The main objectives of the research described in this thesis were firstly to synthesize and characterize a series of structurally related BODIPY dyes that are potentially suitable for use in applications, secondly to conjugate a carboxylic acid substituted BODIPY dye to amine-functionalized upconversion nanoparticles (UCNPs) through an amide bond to enable singlet oxygen production upon irradiation at 978 nm in the biological window for tissue penetration for biomedical applications, and thirdly to compare the nonlinear optical (NLO) properties of various BODIPY dyes to determine whether push-pull effects enhance their utility for optical limiting (OL) applications. Halogenated BODIPY cores with high singlet oxygen quantum yields were prepared, which absorb in the green portion of the visible region and making it difficult to treat deeper skin tumors in the context of photodynamic therapy (PDT) applications. UCNPs generally absorb in the near-infrared (NIR) region (978 nm), and this is advantageous because, this is where absorption by water, cells and tissues is minimized. NaYF4: Yb/Er/Gd UCNPs were synthesized, amine functionalized and successfully conjugated to a halogenated carboxylic acid functionalized BODIPY. This allowed for favorable Förster resonance energy transfer (FRET) since one of the emission wavelengths of the NaYF4: Yb/Er/Gd UCNPs overlaps with the main absorption band of the BODIPY at 540 nm. The conjugate was irradiated at 978 nm, but instability of the BODIPY dye was observed, which made singlet oxygen quantum yield determination impossible. An enhanced singlet oxygen quantum yield value was observed upon irradiation of the conjugate at 540 nm, suggesting that further studies of this system are warranted. The OL properties of BODIPY cores and dyes, which are π-extended at the 3,5-positions with styryl groups, were studied in a series of different organic solvents at 532 nm by using the z-scan technique on a nanosecond timescale. Many of the dyes were used to compare the effects of introducing electron donor and acceptor groups on the OL properties of the dyes. The dipole moments of these dyes were found to correlate with the OL response. The OL results indicate that BODIPY dyes with push-pull properties, which are π-extended at the 3,5-positions with styryl groups, can be considered as viable candidates for use in OL applications. The studies sought to establish the effect of ESA in the triplet manifold as compared to the singlet manifold in as far as the OL response is concerned. The most promising dyes were embedded in polystyrene thin films, and this was found to significantly enhance their OL properties.
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