Photophysical properties and photodynamic therapy activities of detonated nanodiamonds-BODIPY-phthalocyanines nanoassemblies
- Matshitse, Refilwe, Ngoy, Bokolombe P, Managa, Muthumuni, Mack, John, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
- Full Text:
- Date Issued: 2019
- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
- Full Text:
- Date Issued: 2019
Theoretical and photodynamic therapy characteristics of heteroatom doped detonation nanodiamonds linked to asymmetrical phthalocyanine for eradication of breast cancer cells
- Matshitse, Refilwe, Tshiwawa, Tendamudzimu, Managa, Muthumuni, Nwaji, Njemuwa, Lobb, Kevin A, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Tshiwawa, Tendamudzimu , Managa, Muthumuni , Nwaji, Njemuwa , Lobb, Kevin A , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186089 , vital:44462 , xlink:href="https://doi.org/10.1016/j.jlumin.2020.117465"
- Description: An amide mono substituted benzothiozole phthalocyanine: zinc(II) 3-(4-((3,17,23-tris(4-(benzo [d]thiazol-2-yl)phenoxy)-9-yl)oxy) phenyl)amide phthalocyanine (NH2BzPc) was covalently linked to undoped and heteroatom doped detonation nanodiamonds (DNDs): B@DNDs, P@DNDs, S@DNDs, N@DNDs, and SandN@DNDs There is a drastic decrease in highest occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) energy gaps for nanoconjugates compared to DNDs alone. B@DNDs-NH2BzPc, SandN@DNDs-NH2BzPc, and P@DNDs-NH2BzPc showed superior photodynamic therapy (PDT) effects. DNDs-NH2BzPc also had a small HOMO-LUMO gap, but did not show improved PDT activity compared to the Pc alone, suggesting doping of DNDs is important. This study shows improved PDT effect on Michigan Cancer Foundation-7 breast cancer lines at 7.63%, 7.62% and 6.5% cell viability for P@DNDs-NH2BzPc, SandN@DNDs-NH2BzPc and B@DNDs-NH2BzPc, respectively.
- Full Text:
- Date Issued: 2020
- Authors: Matshitse, Refilwe , Tshiwawa, Tendamudzimu , Managa, Muthumuni , Nwaji, Njemuwa , Lobb, Kevin A , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186089 , vital:44462 , xlink:href="https://doi.org/10.1016/j.jlumin.2020.117465"
- Description: An amide mono substituted benzothiozole phthalocyanine: zinc(II) 3-(4-((3,17,23-tris(4-(benzo [d]thiazol-2-yl)phenoxy)-9-yl)oxy) phenyl)amide phthalocyanine (NH2BzPc) was covalently linked to undoped and heteroatom doped detonation nanodiamonds (DNDs): B@DNDs, P@DNDs, S@DNDs, N@DNDs, and SandN@DNDs There is a drastic decrease in highest occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) energy gaps for nanoconjugates compared to DNDs alone. B@DNDs-NH2BzPc, SandN@DNDs-NH2BzPc, and P@DNDs-NH2BzPc showed superior photodynamic therapy (PDT) effects. DNDs-NH2BzPc also had a small HOMO-LUMO gap, but did not show improved PDT activity compared to the Pc alone, suggesting doping of DNDs is important. This study shows improved PDT effect on Michigan Cancer Foundation-7 breast cancer lines at 7.63%, 7.62% and 6.5% cell viability for P@DNDs-NH2BzPc, SandN@DNDs-NH2BzPc and B@DNDs-NH2BzPc, respectively.
- Full Text:
- Date Issued: 2020
The photophysicochemical properties and photodynamic therapy activity of phenyldiazenyl phenoxy substituted phthalocyanines when incorporated into Pluronic® F127 micelles
- Motloung, Banele M, Sekhosana, Kutloano E, Managa, Muthumuni, Prinsloo, Earl, Nyokong, Tebello
- Authors: Motloung, Banele M , Sekhosana, Kutloano E , Managa, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186769 , vital:44532 , xlink:href="https://doi.org/10.1016/j.poly.2019.114157"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of 4(4-phenyldiazenyl) phenoxy substituted indium (III) (InPc) and zinc (ZnPc) phthalocyanines when alone or incorporated into Pluronic_ F127 micelles are presented in this study. The InPc exhibited higher singlet oxygen (UD) at 0.47 compared to the ZnPc at 0.20 in dimethylsulfoxide. The UD values in the presence of Pluronic_ F127 and in water, were 0.32 for InPc and 0.09 for ZnPc. The triplet quantum yields (UT) were 0.92 for InPc and 0.32 for ZnPc in DMSO. The PDT activity followed the same trend as the singlet oxygen quantum yields. At the highest concentration, InPc in Pluronic_ F127 gave 22% cell viability compared to 34% for complex ZnPc. The partition coefficient Kp values were determined using the water and octanol system. InPc had a larger Kp suggesting that it is more likely to be taken up by the cancer cells, hence it exhibited better PDT activity.
- Full Text:
- Date Issued: 2019
- Authors: Motloung, Banele M , Sekhosana, Kutloano E , Managa, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186769 , vital:44532 , xlink:href="https://doi.org/10.1016/j.poly.2019.114157"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of 4(4-phenyldiazenyl) phenoxy substituted indium (III) (InPc) and zinc (ZnPc) phthalocyanines when alone or incorporated into Pluronic_ F127 micelles are presented in this study. The InPc exhibited higher singlet oxygen (UD) at 0.47 compared to the ZnPc at 0.20 in dimethylsulfoxide. The UD values in the presence of Pluronic_ F127 and in water, were 0.32 for InPc and 0.09 for ZnPc. The triplet quantum yields (UT) were 0.92 for InPc and 0.32 for ZnPc in DMSO. The PDT activity followed the same trend as the singlet oxygen quantum yields. At the highest concentration, InPc in Pluronic_ F127 gave 22% cell viability compared to 34% for complex ZnPc. The partition coefficient Kp values were determined using the water and octanol system. InPc had a larger Kp suggesting that it is more likely to be taken up by the cancer cells, hence it exhibited better PDT activity.
- Full Text:
- Date Issued: 2019
Photo-physicochemical properties and in vitro photodynamic therapy activity of morpholine-substituted Zinc (II)-Phthalocyanines π-π stacked on biotinylated graphene quantum dots
- Nene, Lindokuhle, Managa, Muthumuni, Nyokong, Tebello
- Authors: Nene, Lindokuhle , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186993 , vital:44554 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.03.002"
- Description: Two morpholine-substituted Zn(II) phthalocyanines, complex 4 and the cationic 5, were synthesized and conjugated to graphene quantum dots (GQDs) and biotinylated GQDs (GQDs-biotin) by non-covalent π-π interactions. The GQDs-biotin are prepared as potential nanoparticle-based Pc delivery vector combined with a receptor-mediated transport system using biotin. The photo-physicochemical properties of the Pc complexes and their corresponding conjugates were studied. Upon conjugation, the fluorescence quantum yields decrease for 4 and 5, however, the triplet quantum yields were increased for the conjugates. All samples demonstrated singlet oxygen generation. For conjugated complexes, the singlet quantum yields decreased due to the screening effect in some cases. An increase in the photodynamic therapy activities upon quaternization was observed for the conjugates, with the cell viability decreasing from 66.2% to 51.2% after treatment for 4-GQDs and 5-GQDs, respectively. A relatively better performance was also observed for the cationic complex in combination with the biotin functionalized GQDs, 5-GQDs-biotin, where the cell viability was 34.9% after treatment. Moreover, the cellular uptake of 5-GQDs-biotin over 24 h was relatively higher compared to Pc complex alone and other PcsGQDs conjugates.
- Full Text:
- Date Issued: 2019
- Authors: Nene, Lindokuhle , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186993 , vital:44554 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.03.002"
- Description: Two morpholine-substituted Zn(II) phthalocyanines, complex 4 and the cationic 5, were synthesized and conjugated to graphene quantum dots (GQDs) and biotinylated GQDs (GQDs-biotin) by non-covalent π-π interactions. The GQDs-biotin are prepared as potential nanoparticle-based Pc delivery vector combined with a receptor-mediated transport system using biotin. The photo-physicochemical properties of the Pc complexes and their corresponding conjugates were studied. Upon conjugation, the fluorescence quantum yields decrease for 4 and 5, however, the triplet quantum yields were increased for the conjugates. All samples demonstrated singlet oxygen generation. For conjugated complexes, the singlet quantum yields decreased due to the screening effect in some cases. An increase in the photodynamic therapy activities upon quaternization was observed for the conjugates, with the cell viability decreasing from 66.2% to 51.2% after treatment for 4-GQDs and 5-GQDs, respectively. A relatively better performance was also observed for the cationic complex in combination with the biotin functionalized GQDs, 5-GQDs-biotin, where the cell viability was 34.9% after treatment. Moreover, the cellular uptake of 5-GQDs-biotin over 24 h was relatively higher compared to Pc complex alone and other PcsGQDs conjugates.
- Full Text:
- Date Issued: 2019
Synthesis of a near infrared-actuated phthalocyanine-lipid vesicle system for augmented photodynamic therapy
- Nwahara, Namdi, Managa, Muthumuni, Stoffels, Mihlali, Britton, Jonathan, Prinsloo, Earl, Nyokong, Tebello
- Authors: Nwahara, Namdi , Managa, Muthumuni , Stoffels, Mihlali , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185395 , vital:44383 , xlink:href="https://doi.org/10.1016/j.synthmet.2021.116811"
- Description: The efficacy of photodynamic therapy (PDT) is often limited by the poor bio-distributive properties of conventional photosensitizers and the local hypoxic microenvironment that characterises most solid tumours. Herein, a novel in situ oxygenic lipid formulation for photodynamic therapy (PDT) is reported. Such a hybrid was synthesized by adsorbing bimetallic nanozyme, MnO2@PtNPs (NPs = nanoparticles) onto graphene quantum dots (GQDs) – zinc (II) phthalocyanine conjugates, followed by liposomal encapsulation, affording it enhanced water solubility. The MnO2@PtNPs, which are is shown to possess excellent catalase-like properties surpassing that of MnO2 or PtNPs alone, serves to catalyze H2O2 to O2, while the zinc (II) phthalocyanine (1) serves to transform the formed oxygen to generate cytotoxic singlet oxygen immediately. We show that by combining each function of the respective building blocks, the as-synthesized 1-GQDs-MnO2@PtNPs-liposomes not only maintains the properties of oxygen supplementation through H2O2 catalysis but also displays cooperative properties for enhanced singlet oxygen production. Consequently, a remarkably improved PDT efficacy was observed for 1-GQDs-MnO2@PtNPs-liposomes in both normoxia and hypoxia. These results demonstrate the potential applicability of such nanozyme constituted 1-GQDs-MnO2@PtNPs-liposomes for achieving tumour treatment in hypoxic conditions by PDT.
- Full Text:
- Date Issued: 2021
- Authors: Nwahara, Namdi , Managa, Muthumuni , Stoffels, Mihlali , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185395 , vital:44383 , xlink:href="https://doi.org/10.1016/j.synthmet.2021.116811"
- Description: The efficacy of photodynamic therapy (PDT) is often limited by the poor bio-distributive properties of conventional photosensitizers and the local hypoxic microenvironment that characterises most solid tumours. Herein, a novel in situ oxygenic lipid formulation for photodynamic therapy (PDT) is reported. Such a hybrid was synthesized by adsorbing bimetallic nanozyme, MnO2@PtNPs (NPs = nanoparticles) onto graphene quantum dots (GQDs) – zinc (II) phthalocyanine conjugates, followed by liposomal encapsulation, affording it enhanced water solubility. The MnO2@PtNPs, which are is shown to possess excellent catalase-like properties surpassing that of MnO2 or PtNPs alone, serves to catalyze H2O2 to O2, while the zinc (II) phthalocyanine (1) serves to transform the formed oxygen to generate cytotoxic singlet oxygen immediately. We show that by combining each function of the respective building blocks, the as-synthesized 1-GQDs-MnO2@PtNPs-liposomes not only maintains the properties of oxygen supplementation through H2O2 catalysis but also displays cooperative properties for enhanced singlet oxygen production. Consequently, a remarkably improved PDT efficacy was observed for 1-GQDs-MnO2@PtNPs-liposomes in both normoxia and hypoxia. These results demonstrate the potential applicability of such nanozyme constituted 1-GQDs-MnO2@PtNPs-liposomes for achieving tumour treatment in hypoxic conditions by PDT.
- Full Text:
- Date Issued: 2021
Acetophenone substituted phthalocyanines and their graphene quantum dots conjugates as photosensitizers for photodynamic antimicrobial chemotherapy against Staphylococcus aureus
- Openda, Yolande I, Sen, Pinar, Managa, Muthumuni, Nyokong, Tebello
- Authors: Openda, Yolande I , Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186507 , vital:44506 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.101607"
- Description: This work reports on the synthesis and characterization of novel acetophenone substituted phthalocyanines along with the self-assembled nanoconjugates formed via π-π stacking interaction between the synthesized unmetalated (2), zinc (3) and indium (4) phthalocyanines and graphene quantum dots (GQDs) to form 2@GQDs, 3@GQDs and 4@GQDs. The complexes and conjugates exhibited high singlet oxygen ranging from 0.20 to 0.79 in DMSO for Pcs and nanoconjugates where in all cases, the indium complexes showed the highest singlet oxygen quantum yields. The photodynamic antimicrobial chemotherapy activity of both phthalocyanines and nanoconjugates were tested against Staphylococcus aureus. 4@GQDs was found to be highly effective causing a 9.68 log reduction of the bacteria at 10 μM (based on Pc) when compared to 3.77 log reduction of 3@GQDs.
- Full Text:
- Date Issued: 2020
- Authors: Openda, Yolande I , Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186507 , vital:44506 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.101607"
- Description: This work reports on the synthesis and characterization of novel acetophenone substituted phthalocyanines along with the self-assembled nanoconjugates formed via π-π stacking interaction between the synthesized unmetalated (2), zinc (3) and indium (4) phthalocyanines and graphene quantum dots (GQDs) to form 2@GQDs, 3@GQDs and 4@GQDs. The complexes and conjugates exhibited high singlet oxygen ranging from 0.20 to 0.79 in DMSO for Pcs and nanoconjugates where in all cases, the indium complexes showed the highest singlet oxygen quantum yields. The photodynamic antimicrobial chemotherapy activity of both phthalocyanines and nanoconjugates were tested against Staphylococcus aureus. 4@GQDs was found to be highly effective causing a 9.68 log reduction of the bacteria at 10 μM (based on Pc) when compared to 3.77 log reduction of 3@GQDs.
- Full Text:
- Date Issued: 2020
New type of metal-free and Zinc (II), In (III), Ga (III) phthalocyanines carrying biologically active substituents: Synthesis and photophysicochemical properties and photodynamic therapy activity
- Sen, Pinar, Managa, Muthumuni, Nyokong, Tebello
- Authors: Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186971 , vital:44552 , xlink:href="https://doi.org/10.1016/j.ica.2019.03.010"
- Description: This study reports on novel phthalocyanines having benzimidazole units which are known to have biological properties. 4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) substituted metal-free, Zn(II), In(III) and Ga(III) phthalocyanines were synthesized, these newly synthesized molecules that were substituted by oxygen bridges were fully characterized. For the purpose of determining their potency for photodynamic therapy, the photophysicochemical properties were investigated in DMSO. The H2Pc (4) showed higher fluorescence quantum yield and fluorescence lifetime as compared to metallated phthalocyanines derivatives. However, the highest singlet oxygen (ΦΔ) and triplet state quantum yields (ΦT) values were obtained with the In(III)Pc (5).
- Full Text:
- Date Issued: 2019
- Authors: Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186971 , vital:44552 , xlink:href="https://doi.org/10.1016/j.ica.2019.03.010"
- Description: This study reports on novel phthalocyanines having benzimidazole units which are known to have biological properties. 4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) substituted metal-free, Zn(II), In(III) and Ga(III) phthalocyanines were synthesized, these newly synthesized molecules that were substituted by oxygen bridges were fully characterized. For the purpose of determining their potency for photodynamic therapy, the photophysicochemical properties were investigated in DMSO. The H2Pc (4) showed higher fluorescence quantum yield and fluorescence lifetime as compared to metallated phthalocyanines derivatives. However, the highest singlet oxygen (ΦΔ) and triplet state quantum yields (ΦT) values were obtained with the In(III)Pc (5).
- Full Text:
- Date Issued: 2019