Photolytic changes in the morphology of porphyrin-phthalocyanine nanostructures (P-PcNs) in the presence of platinum and gold salts
- Authors: George, Reama C , D'Souza, Sarah , Durmus, Mahmut , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190416 , vital:44992 , xlink:href="https://doi.org/10.1080/24701556.2017.1284085"
- Description: Porphyrin-phthalocyanine nanostructures (P-PcNs) have been fabricated by electrostatic self-assembly of two oppositely charged molecules. The negatively charged molecule, meso-tetra-(4-phenylsulphonate)porphyrin (HT) and the positively charged species; {1,(4)-tetrakis-[(N-methyl(3-pyridyloxy) phthlocyaninato] chloro gallium(III)} sulphate, {2,(3)-tetrakis-[(N-methyl{(2-mercaptopyridine) phthalocyaninato} hydroxy manganese(III)} sulphate, {1,(4)-tetrakis-[(N-methyl-(3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate, {2,3-octakis-{[(N-methyl-2-mercaptopyridine) phthalocyaninato] acetato manganese(III)} sulphate, {2,(3)-tetrakis-[(N-methyl(3-pyridyloxy) phthlocyaninato] choro gallium(III)} sulphate, {2,3-octakis-[(N-methy-3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate, and {2,(3)-tetrakis-[(N-methyl (3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate. Transmission electron microscopic (TEM) images showed that the formed nanostructures ranged from nanosheets to nanorods and nanotubes. The UV-Vis spectra confirmed that the molecules formed J-aggregates. The P-PcNs were exposed to incandescence light in the presence of platinum and gold salts. It was observed that the presence of platinum salts resulted in the destruction of the P-PcNs with possible formation of a Pt-Pc complex. While with the gold salt, the structures of P-PcNs were not only retained but were also enhanced to longer nanorods and nanofibers with the formation of gold nanoparticles.
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- Date Issued: 2017
The effect of shaped nanoparticles on the photophysicochemical behaviour of metallophthalocyanines
- Authors: D'Souza, Sarah
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/529 , vital:19967
- Description: The synthesis, spectroscopic characterization and photophysicochemical analysis of novel and known metallophthalocyanines are reported in this thesis. The novel lowsymmetry compounds were extensively studied. Selected phthalocyanines were conjugated to a variety of nanoparticles consisting of silver (AgNPs), gold (AuNPs) and zinc oxide (ZnO NPs) in order to improve their photophysical and photochemical behaviour. As with the phthalocyanines, the nanoparticles and phthalocyaninenanoparticle conjugates were thoroughly investigated. Research on the effect of the solvent used, as well as the influence of nanoparticle composition and shape on the properties of the phthalocyanines, were performed. The findings showed that there was a general increase in triplet quantum yields of the phthalocyanines in the presence of the nanoparticles. It was also noted that the use of different solvents directly affected the photophysicochemical properties. In the case of the nanoparticle conjugates, photophysical and photochemical changes were observed. Of significance were the gold nanostars, which decreased the degree of phthalocyanine aggregation in water, resulting in increased fluorescence lifetimes. The studies also revealed that the effect of the nanoparticle shape on the phthalocyanine properties was highly dependent on the nanoparticle material. The photodynamic antimicrobial activity of selected phthalocyanine-zinc oxide nanoparticle conjugates was investigated against Staphylococcus aureus (S. aureus) in solution. The phthalocyanines alone exhibited remarkable growth inhibition, however the presence of the nanoparticles in the conjugates increased the photoinactivation of S. aureus.
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- Date Issued: 2016
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
- Full Text:
- Date Issued: 2015
The effects of gold coated and uncoated zinc oxide nanohexagons on the photophysicochemical properties of the low symmetry zinc phthalocyanine
- Authors: D'Souza, Sarah , Ogbodu, Rachael , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189077 , vital:44814 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.06.088"
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results.
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- Date Issued: 2015
Synthesis and characterization of quantum dots designed for biomedical use
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloana E , D'Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A , Nyokong, Tebello , Höpfner, Michael
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241516 , vital:50946 , xlink:href="https://doi.org/10.1016/j.ijpharm.2014.03.037"
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with L-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy.
- Full Text:
- Date Issued: 2014
Effects of gold nanoparticle shape on the aggregation and fluorescence behaviour of water soluble zinc phthalocyanines
- Authors: D'Souza, Sarah , Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232500 , vital:49997 , xlink:href="https://doi.org/10.1039/C3NJ00146F"
- Description: The absorption and fluorescence response as well as the fluorescence quantum yields and lifetimes of sulfonated phthalocyanines and alkyl carboxylic acid substituted zinc phthalocyanines in the presence of differently shaped water soluble gold nanoparticles were studied. The respective phthalocyanines are known to be highly aggregated in water, which is reported to markedly reduce the excited state lifetimes. This paper shows that in the presence of star shaped gold nanoparticles, the degree of phthalocyanine aggregation in water is greatly reduced, but the aggregation status of the phthalocyanines does not change for spherical Au nanoparticles. Since gold nanoparticles have already proven to be useful in numerous nanomedicinal and nanomedical applications, the disaggregation of phthalocyanines is an added advantage.
- Full Text:
- Date Issued: 2013
Fluorescence behavior of glutathione capped CdTe@ ZnS quantum dots chemically coordinated to zinc octacarboxy phthalocyanines
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
- Full Text:
- Date Issued: 2013
Photophysical behavior of zinc monoaminophthalocyanines linked to mercaptopropionic acid-capped CdTe quantum dots
- Authors: D'Souza, Sarah , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247634 , vital:51602 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.03.005"
- Description: Photosensitizing properties of zinc monoaminophthalocyanine (2) {in the absence or presence of mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs)} were compared with those of mono-aminophenoxy zinc phthalocyanine (3), zinc tetrasulfonated phthalocyanine and zinc phthalocyanine. Complexes 2 and 3 were also linked to the MPA capped CdTe quantum dots through the formation of an amide bond. High triplet state quantum yields were obtained for the linked QD–phthalocyanine derivatives (complexes 2 and 3) compared to when complexes 2 and 3 were mixed with MPA QDs without a chemical bond.
- Full Text:
- Date Issued: 2011
Synthesis and photophysical studies of CdTe quantum dot-monosubstituted zinc phthalocyanine conjugates
- Authors: D'Souza, Sarah , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247825 , vital:51621 , xlink:href="https://doi.org/10.1016/j.ica.2010.12.027"
- Description: The linkage of unsymmetrically monosubstituted 4-aminophenoxy zinc phthalocyanine (ZnAPPc, 5) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N(3-dimethylaminopropyl) carbodiimide and N-hydroxy succinimide, which facilitate formation of an amide bond to form the QD–ZnAPPc-linked conjugate. The formation of the amide bond was confirmed using Raman and IR spectroscopies. Atomic force microscopy (AFM) and UV–Vis spectroscopy were used further to characterise the conjugate. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QD–ZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates. The linked L-cys and TGA QDs conjugates (QD–ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked.
- Full Text:
- Date Issued: 2011
The photophysical properties of low symmetry phthalocyanines in conjunction with quantum dots
- Authors: D'Souza, Sarah
- Date: 2011
- Subjects: Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4331 , http://hdl.handle.net/10962/d1004992 , Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Description: he synthesis, extensive spectroscopic characterization and photophysical studies of low symmetry zinc phthalocyanine have been conducted. Comparisons have been made taking into consideration the influence of the solvent properties as well as substituent type and position. Photosensitizing properties of the zinc phthalocyanine derivatives in the presence of thiol capped CdTe quantum dots (QDs) were compared. The QDs were used as energy transfer donors and to facilitate with energy transfer through Förster resonance energy transfer (FRET) from the QDs to the MPcs. The linkage of unsymmetrically substituted 4-monoaminophenoxy zinc phthalocyanine (ZnAPPc) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N3 dimethylaminopropyl)carbodiimide (EDC) and N-hydroxy succinimide (NHS), which facilitate formation of an amide bond to form the QD-ZnAPPc-linked complex. The formation of the amide bond was confirmed using UV-Vis, Raman and IR spectroscopies, as well as AFM (atomic force microscopy). Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QDZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates for MPA only. The linked L-cys and TGA complexes (QD-ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked. High triplet state quantum yields were obtained for the linked QD-phthalocyanine derivatives (ZnAPPc)and monoaminozinc phthalocyanine (ZnAPc) compared to when ZnAPPc and ZnAPc were mixed with MPA QDs without a chemical bond.
- Full Text:
- Date Issued: 2011
The effects of gold coated and uncoated zinc oxide nanohexagons on the photophysicochemical properties of the low symmetry zinc phthalocyanine
- Authors: D'Souza, Sarah , Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7280 , http://hdl.handle.net/10962/d1020317
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.088
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