The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules
- Fanchiotti, Brenda Gomes, Machado, Marcella Piffer Zamprogno, de Paula, Letícia Camilato, Durmuş, Mahmut, Nyokong, Tebello, da Silva, Gonçalves, da Silva, André Romero
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
Physicochemical and photodynamic antimicrobial chemotherapy studies of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines
- Osifeko, Olawale L, Durmuş, Mahmut, Nyokong, Tebello
- Authors: Osifeko, Olawale L , Durmuş, Mahmut , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7255 , http://hdl.handle.net/10962/d1020264 , http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Description: The synthesis and photophysicochemical properties of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines (InPcs) are presented in this study. General trends are described for quantum yields of fluorescence, triplet, singlet oxygen and photodegradation as well as lifetimes of fluorescence and triplet state of these compounds. The complexes exhibited high singlet oxygen quantum yields (ФΔ) ranging from 0.44 to 0.66 in DMF, and from 0.44 to 0.69 in DMSO and ФΔ = 0.31 for the quartenized tetra substituted InPc which is soluble in water. The triplet quantum yields (ФT) ranged from 0.77 to 0.95 in DMF and from 0.77 to 0.94) in DMSO. The tetra substituted photosensitizers do not differ in their inactivation of bacteria with over 8 log reduction of viable bacteria when compared with the mono substituted photosensitizer which could only manage a 1 log reduction. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Full Text: false
- Date Issued: 2015
- Authors: Osifeko, Olawale L , Durmuş, Mahmut , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7255 , http://hdl.handle.net/10962/d1020264 , http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Description: The synthesis and photophysicochemical properties of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines (InPcs) are presented in this study. General trends are described for quantum yields of fluorescence, triplet, singlet oxygen and photodegradation as well as lifetimes of fluorescence and triplet state of these compounds. The complexes exhibited high singlet oxygen quantum yields (ФΔ) ranging from 0.44 to 0.66 in DMF, and from 0.44 to 0.69 in DMSO and ФΔ = 0.31 for the quartenized tetra substituted InPc which is soluble in water. The triplet quantum yields (ФT) ranged from 0.77 to 0.95 in DMF and from 0.77 to 0.94) in DMSO. The tetra substituted photosensitizers do not differ in their inactivation of bacteria with over 8 log reduction of viable bacteria when compared with the mono substituted photosensitizer which could only manage a 1 log reduction. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Full Text: false
- Date Issued: 2015
Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines
- Durmuş, Mahmut, Yaman, Hanif, Göl, Cem, Ahsen, Vefa, Nyokong, Tebello
- Authors: Durmuş, Mahmut , Yaman, Hanif , Göl, Cem , Ahsen, Vefa , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247133 , vital:51549 , xlink:href="https://doi.org/10.1016/j.dyepig.2011.02.007"
- Description: The synthesis and characterization of the new zinc phthalocyanine derivatives, tetra- (non-peripheral, 5) and octa-(peripheral, 6) substituted with 2-mercaptopyridine and their respective quaternized derivatives (8 and 9) are reported. Photochemical and photophysical properties of the new complexes are compared with those of the previously reported peripherally tetra-substituted complexes 7 and 10. The quaternized compounds exhibit excellent solubility in water, making them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. Spectroscopic, aggregation, photophysical and photochemical properties of these complexes are also investigated and compared. Photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yield) properties of these phthalocyanine photosensitizers are very important for the assessment of these complexes as PDT agents. In this study, the effects of the position of the substituents and quaternization of the substituents on the photophysical and photochemical parameters of the zinc phthalocyanines are also reported. This study also showed that the water-soluble quaternized zinc phthalocyanines strongly bind to blood plasma proteins such as bovine serum albumin (BSA).
- Full Text:
- Date Issued: 2011
- Authors: Durmuş, Mahmut , Yaman, Hanif , Göl, Cem , Ahsen, Vefa , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247133 , vital:51549 , xlink:href="https://doi.org/10.1016/j.dyepig.2011.02.007"
- Description: The synthesis and characterization of the new zinc phthalocyanine derivatives, tetra- (non-peripheral, 5) and octa-(peripheral, 6) substituted with 2-mercaptopyridine and their respective quaternized derivatives (8 and 9) are reported. Photochemical and photophysical properties of the new complexes are compared with those of the previously reported peripherally tetra-substituted complexes 7 and 10. The quaternized compounds exhibit excellent solubility in water, making them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. Spectroscopic, aggregation, photophysical and photochemical properties of these complexes are also investigated and compared. Photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yield) properties of these phthalocyanine photosensitizers are very important for the assessment of these complexes as PDT agents. In this study, the effects of the position of the substituents and quaternization of the substituents on the photophysical and photochemical parameters of the zinc phthalocyanines are also reported. This study also showed that the water-soluble quaternized zinc phthalocyanines strongly bind to blood plasma proteins such as bovine serum albumin (BSA).
- Full Text:
- Date Issued: 2011
Photophysicochemical and Fluorescence quenching studies of benzyloxyphenoxy substituted zinc phthalocyanines
- Durmuş, Mahmut, Nyokong, Tebello
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species
- Sehlotho, Nthapo, Durmuş, Mahmut, Ahsen, N, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Durmuş, Mahmut , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Durmuş, Mahmut , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- D’Souza, Sarah, George, Reama, Göksel, Meltem, Atilla, Devrim, Durmuş, Mahmut, Nyokong, Tebello
- Authors: D’Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7279 , http://hdl.handle.net/10962/d1020315
- 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. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.08.017
- Full Text: false
- Authors: D’Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7279 , http://hdl.handle.net/10962/d1020315
- 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. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.08.017
- Full Text: false
Photophysical and photochemical properties of a novel thiol terminated low symmetry zinc phthalocyanine complex and its gold nanoparticles conjugate
- Mthethwa, Thandekile P., Tuncel, Sinem, Durmuş, Mahmut, Nyokong, Tebello
- Authors: Mthethwa, Thandekile P. , Tuncel, Sinem , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7329 , http://hdl.handle.net/10962/d1020590
- Description: A novel thiol functionalized zinc phthalocyanine complex (ZnPcSH) is reported in this work. This complex was conjugated to gold nanoparticles. The photophysical and photochemical properties of the complex and the conjugate were investigated. Upon conjugation a blue shift was observed from the UV-Vis spectra. The conjugate showed a decrease in the fluorescence quantum yield and lifetime. An increase in the triplet quantum yield and lifetime was observed for ZnPcSH following conjugation to gold nanoparticles. Both ZnPcSH and its conjugate with gold nanoparticles showed high singlet oxygen quantum yields with the conjugate being higher than the Pc alone. , Original publication is available at http://dx.doi.org/10.1039/C3DT32698E
- Full Text:
- Authors: Mthethwa, Thandekile P. , Tuncel, Sinem , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7329 , http://hdl.handle.net/10962/d1020590
- Description: A novel thiol functionalized zinc phthalocyanine complex (ZnPcSH) is reported in this work. This complex was conjugated to gold nanoparticles. The photophysical and photochemical properties of the complex and the conjugate were investigated. Upon conjugation a blue shift was observed from the UV-Vis spectra. The conjugate showed a decrease in the fluorescence quantum yield and lifetime. An increase in the triplet quantum yield and lifetime was observed for ZnPcSH following conjugation to gold nanoparticles. Both ZnPcSH and its conjugate with gold nanoparticles showed high singlet oxygen quantum yields with the conjugate being higher than the Pc alone. , Original publication is available at http://dx.doi.org/10.1039/C3DT32698E
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