Fabrication of asymmetrical morpholine phthalocyanines conjugated chitosan-polyacrylonitrile nanofibers for improved photodynamic antimicrobial chemotherapy activity
- Sindelo, Azole, Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229873 , vital:49719 , xlink:href="https://doi.org/10.1016/j.pdpdt.2022.102760"
- Description: The work is based on the synthesis and photodynamic antimicrobial chemotherapy (PACT) activities of neutral (1 and 2) and cationic (1Q and 2Q) morpholine substituted phthalocyanines. For applicability, these complexes were covalently linked to modified polyacrylonitrile (PAN) to form 1-PAN, 2-PAN, 1Q-PAN, and 2Q-PAN, respectively. Chitosan was conjugated to PAN (to form PAN-CS) which was then linked to the Pcs to form PAN-CS-1, PAN-CS-2, PAN-CS-1Q, and PAN-CS-2Q, respectively. Singlet oxygen quantum yields improved following the inclusion of chitosan. The PACT activities of the complexes alone and when anchored to both PAN and PAN-CS was evaluated against bacteria: S. aureus, E. coli and fungi C. albicans. Cationic phthalocyanine showed high efficacy values of >7 log reduction value for all microorganisms. These results translated into excellent bacterial colony reduction of >90% against both S. aureus and C. albicans after 1 h of photoirradiation on PAN-CS support.
- Full Text:
- Date Issued: 2022
- Authors: Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229873 , vital:49719 , xlink:href="https://doi.org/10.1016/j.pdpdt.2022.102760"
- Description: The work is based on the synthesis and photodynamic antimicrobial chemotherapy (PACT) activities of neutral (1 and 2) and cationic (1Q and 2Q) morpholine substituted phthalocyanines. For applicability, these complexes were covalently linked to modified polyacrylonitrile (PAN) to form 1-PAN, 2-PAN, 1Q-PAN, and 2Q-PAN, respectively. Chitosan was conjugated to PAN (to form PAN-CS) which was then linked to the Pcs to form PAN-CS-1, PAN-CS-2, PAN-CS-1Q, and PAN-CS-2Q, respectively. Singlet oxygen quantum yields improved following the inclusion of chitosan. The PACT activities of the complexes alone and when anchored to both PAN and PAN-CS was evaluated against bacteria: S. aureus, E. coli and fungi C. albicans. Cationic phthalocyanine showed high efficacy values of >7 log reduction value for all microorganisms. These results translated into excellent bacterial colony reduction of >90% against both S. aureus and C. albicans after 1 h of photoirradiation on PAN-CS support.
- Full Text:
- Date Issued: 2022
Photocatalytic and solar radiation harvesting potential of a free-base porphyrin-zinc (II) phthalocyanine heterodyad functionalized polystyrene polymer membrane for the degradation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
- Date Issued: 2021
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
- Date Issued: 2021
Fabrication of electrospun fibers from a porphyrin linked to polyacrylonitrile polymer for photocatalytic transformation of phenols
- Jones, Benjamin M, Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Jones, Benjamin M , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186196 , vital:44472 , xlink:href="https://doi.org/10.1016/j.molstruc.2020.128191"
- Description: A novel mono-porphyrin (2) was employed for the photodegradation of 4-chlorophenol and 4-n-nonylphenol at pH 10.60. A partially modified polyacrylonitrile (PAN) polymer was utilized only as a support system for the photosensitiser to allow the formation of a covalent linkage. Complex 2 showed singlet oxygen values of 0.70 in dimethyl formamide and when conjugated (2-PAN) showed 0.39 in water. When employed against 4-chlorophenol a degradation efficiency (η) of 29.1% was achieved at 0.20 mol L−1 over a period of 10 min. When employed against 4-n-nonylphenol we obtained a η of 26.7% at 0.17 mol L−1 over a period of 10 min.
- Full Text:
- Date Issued: 2020
- Authors: Jones, Benjamin M , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186196 , vital:44472 , xlink:href="https://doi.org/10.1016/j.molstruc.2020.128191"
- Description: A novel mono-porphyrin (2) was employed for the photodegradation of 4-chlorophenol and 4-n-nonylphenol at pH 10.60. A partially modified polyacrylonitrile (PAN) polymer was utilized only as a support system for the photosensitiser to allow the formation of a covalent linkage. Complex 2 showed singlet oxygen values of 0.70 in dimethyl formamide and when conjugated (2-PAN) showed 0.39 in water. When employed against 4-chlorophenol a degradation efficiency (η) of 29.1% was achieved at 0.20 mol L−1 over a period of 10 min. When employed against 4-n-nonylphenol we obtained a η of 26.7% at 0.17 mol L−1 over a period of 10 min.
- Full Text:
- Date Issued: 2020
Photodynamic antimicrobial chemotherapy of a dimethylamino-functionalized asymmetric zinc (II) phthalocyanine and its quaternized derivative against Staphylococcus aureus when supported on asymmetric polystyrene polymer membranes
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186168 , vital:44470 , xlink:href="https://doi.org/10.1016/j.reactfunctpolym.2020.104634"
- Description: Membrane applications are hindered by fouling. Photoactive membranes (containing photosensitizers) show photodynamic antimicrobial chemotherapy (PACT) activity which reduces biological fouling. In this work we use phthalocyanines (Pcs) as photosensitizers. The Pcs used are: 2-(4-carboxyphenoxy)-9(10), 16(17), 23(24)-tris(dimethylamino) phthalocyaninato zinc(II) (1) and the quaternized 2-(4-carboxyphenoxy)-9(10), 16(17), 23(24)-tris(trimethylamino) phthalocyanine zinc(II) methyl sulfate (2). Complex 2 showed an enhanced singlet oxygen quantum yield (ΦΔ) of 0.76 compared to 0.53 for 1. Complex 2 showed enhanced PACT activity against Staphylococcus aureus giving a log reduction value of 9.4, while its precursor (complex 1) gave 0.08. The complexes were then conjugated to amine-functionalized polystyrene and embedded into polystyrene to form membranes resulting in ΦΔ values of 0.24 and 0.27 for complexes 1 and 2 respectively in water. The latter membrane showed better PACT activity.
- Full Text:
- Date Issued: 2020
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186168 , vital:44470 , xlink:href="https://doi.org/10.1016/j.reactfunctpolym.2020.104634"
- Description: Membrane applications are hindered by fouling. Photoactive membranes (containing photosensitizers) show photodynamic antimicrobial chemotherapy (PACT) activity which reduces biological fouling. In this work we use phthalocyanines (Pcs) as photosensitizers. The Pcs used are: 2-(4-carboxyphenoxy)-9(10), 16(17), 23(24)-tris(dimethylamino) phthalocyaninato zinc(II) (1) and the quaternized 2-(4-carboxyphenoxy)-9(10), 16(17), 23(24)-tris(trimethylamino) phthalocyanine zinc(II) methyl sulfate (2). Complex 2 showed an enhanced singlet oxygen quantum yield (ΦΔ) of 0.76 compared to 0.53 for 1. Complex 2 showed enhanced PACT activity against Staphylococcus aureus giving a log reduction value of 9.4, while its precursor (complex 1) gave 0.08. The complexes were then conjugated to amine-functionalized polystyrene and embedded into polystyrene to form membranes resulting in ΦΔ values of 0.24 and 0.27 for complexes 1 and 2 respectively in water. The latter membrane showed better PACT activity.
- Full Text:
- Date Issued: 2020
A comparative study of the singlet oxygen generation capability of a zinc phthalocyanine linked to graphene quantum dots through π-π stacking and covalent conjugation when embedded in asymmetric polymer membranes
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187461 , vital:44655 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.11.096"
- Description: Following the establishment of graphene quantum dots as potential phthalocyanine supports in photoactive membrane preparation for phthalocyanines lacking linkage functional groups, the practical efficiency of p-p stacking versus covalent linkage was investigated. Synthesized materials were characterized using FT-IR, Raman, powder X-ray diffraction, and UVeVis spectroscopies and also by transmission electron and scanning electron microscopies. Phthalocyanine loadings onto graphene quantum dots of 0.40 mg/mg and 0.14 mg/mg (Pc mass/conjugate mass) for the p-p stacked and covalent linked conjugates respectively were observed. Covalent linkage to graphene quantum dots proved to be functionally superior to p-p linkage, where singlet oxygen quantum yield value of the phthalocyanine in the membrane for the covalent linked conjugate was approximately twice that of the p-p stacked membrane.
- Full Text:
- Date Issued: 2019
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187461 , vital:44655 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.11.096"
- Description: Following the establishment of graphene quantum dots as potential phthalocyanine supports in photoactive membrane preparation for phthalocyanines lacking linkage functional groups, the practical efficiency of p-p stacking versus covalent linkage was investigated. Synthesized materials were characterized using FT-IR, Raman, powder X-ray diffraction, and UVeVis spectroscopies and also by transmission electron and scanning electron microscopies. Phthalocyanine loadings onto graphene quantum dots of 0.40 mg/mg and 0.14 mg/mg (Pc mass/conjugate mass) for the p-p stacked and covalent linked conjugates respectively were observed. Covalent linkage to graphene quantum dots proved to be functionally superior to p-p linkage, where singlet oxygen quantum yield value of the phthalocyanine in the membrane for the covalent linked conjugate was approximately twice that of the p-p stacked membrane.
- Full Text:
- Date Issued: 2019
Spectroscopic characterization and photodynamic antimicrobial chemotherapy of phthalocyanine-silver triangular nanoprism conjugates when supported on asymmetric polymer membranes
- Mafukidze, Donovan M, Sindelo, Azole, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186927 , vital:44548 , xlink:href="https://doi.org/10.1016/j.saa.2019.04.054"
- Description: Silver triangular nanoprisms were synthesized and conjugated to zinc (ZnPc) and indium (InPc) phthalocyanines prior to embedding in asymmetric membranes. Conjugation of nanoparticles increased triplet state and singlet oxygen quantum yields of the phthalocyanines as well as enhancing photodynamic antimicrobial chemotherapy (PACT) activity against bacteria (S. aureus). The ZnPc derivative showed higher PACT activity when compared to the InPc, possibly due to degradation of the latter in aqueous media.
- Full Text:
- Date Issued: 2019
- Authors: Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186927 , vital:44548 , xlink:href="https://doi.org/10.1016/j.saa.2019.04.054"
- Description: Silver triangular nanoprisms were synthesized and conjugated to zinc (ZnPc) and indium (InPc) phthalocyanines prior to embedding in asymmetric membranes. Conjugation of nanoparticles increased triplet state and singlet oxygen quantum yields of the phthalocyanines as well as enhancing photodynamic antimicrobial chemotherapy (PACT) activity against bacteria (S. aureus). The ZnPc derivative showed higher PACT activity when compared to the InPc, possibly due to degradation of the latter in aqueous media.
- Full Text:
- Date Issued: 2019
Synthesis and photophysicochemical properties of novel axially di-substituted silicon (IV) phthalocyanines and their photodynamic antimicrobial chemotherapy (PACT) activity against Staphylococcus aureus
- Sen, Pinar, Sindelo, Azole, Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Sen, Pinar , Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186757 , vital:44531 , xlink:href="https://doi.org/10.1016/j.synthmet.2019.116203"
- Description: In this study, novel silicon (IV) phthalocyanine axially di-substituted with benzimidazole moieties (3) and its quaternized derivative (4) have been synthesized and fully characterized. The photophysical and photochemical properties of both phthalocyanines such as absorption, fluorescence and, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions. These new silicon phthalocyanines exhibited low fluorescence but produced high singlet oxygen yields in both DMSO (compound 3 and 4) and aqueous media (compound 4). The quaternization of Si(IV)Pc (3) improved the triplet state quantum yield (ΦT) 0.61 to 0.83, consequently singlet oxygen generation (ΦΔ) increased to 0.69 from 0.42. Photodynamic antimicrobial chemotherapy activities (PACT) of Si(IV)Pc photosensitizers were determined towards Staphylococcus aureus. The higher efficiency was obtained with cationic derivative (4) giving reduction percentage value of 99.75%.
- Full Text:
- Date Issued: 2019
- Authors: Sen, Pinar , Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186757 , vital:44531 , xlink:href="https://doi.org/10.1016/j.synthmet.2019.116203"
- Description: In this study, novel silicon (IV) phthalocyanine axially di-substituted with benzimidazole moieties (3) and its quaternized derivative (4) have been synthesized and fully characterized. The photophysical and photochemical properties of both phthalocyanines such as absorption, fluorescence and, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions. These new silicon phthalocyanines exhibited low fluorescence but produced high singlet oxygen yields in both DMSO (compound 3 and 4) and aqueous media (compound 4). The quaternization of Si(IV)Pc (3) improved the triplet state quantum yield (ΦT) 0.61 to 0.83, consequently singlet oxygen generation (ΦΔ) increased to 0.69 from 0.42. Photodynamic antimicrobial chemotherapy activities (PACT) of Si(IV)Pc photosensitizers were determined towards Staphylococcus aureus. The higher efficiency was obtained with cationic derivative (4) giving reduction percentage value of 99.75%.
- Full Text:
- Date Issued: 2019
The photo-physicochemical properties and in vitro photodynamic therapy activity of differently substituted-zinc (II)-phthalocyanines and graphene quantum dots conjugates on MCF7 breast cancer cell line
- Nene, Lindokuhle C, Managa, Muthumuni E, Oluwole, David O, Mafukidze, Donovan M, Sindelo, Azole, Nyokong, Tebello
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
Incorporation of metal free and Ga 5, 10, 15, 20-tetrakis (4-bromophenyl) porphyrin into Pluronic F127-folic acid micelles
- Managa, Muthumuni, Ngoy, Bucolome P, Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bucolome P , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233256 , vital:50073 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.09.045"
- Description: ClGa 5,10,15,20-Tetrakis (4-bromophenyl) porphyrinato (ClGaTBrPP) and its metal free derivative were successfully synthesized and incorporated into Pluronic F127 polymeric micelles that has been conjugated to folic acid (FA) to form ClGaTBrPP-F127-FA (or H2TBrPP-F127-FA). For comparison, ClGaTBrPP-F127 and H2TBrPP-F127 (without FA) were also formed. The singlet oxygen quantum yield for ClGaTBrPP-F127-FA was higher (ΦΔ = 0.44) than that of H2TBrPP-F127-FA (ΦΔ = 0.37), due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state. The same applies to ClGaTBrPP-F127 (ΦΔ = 0.47) and H2TBrPP-F127 (ΦΔ = 0.41). Thus, ΦΔ values decreased in the presence of FA, but still high enough for practical application of the nanodrug system. The binding constants Kb were determined to be 1.08 × 104 M−1, 2.51 × 105 M−1, 1.52 × 103 and 2.68 × 103 for H2TBrPP+F127-FA, ClGaTBrPP+F127-FA, ClGaTBrPP-F127 and H2TBrPP-F127, respectively. The Kp values were determined in biphasic octanol and water system.
- Full Text:
- Date Issued: 2018
- Authors: Managa, Muthumuni , Ngoy, Bucolome P , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233256 , vital:50073 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.09.045"
- Description: ClGa 5,10,15,20-Tetrakis (4-bromophenyl) porphyrinato (ClGaTBrPP) and its metal free derivative were successfully synthesized and incorporated into Pluronic F127 polymeric micelles that has been conjugated to folic acid (FA) to form ClGaTBrPP-F127-FA (or H2TBrPP-F127-FA). For comparison, ClGaTBrPP-F127 and H2TBrPP-F127 (without FA) were also formed. The singlet oxygen quantum yield for ClGaTBrPP-F127-FA was higher (ΦΔ = 0.44) than that of H2TBrPP-F127-FA (ΦΔ = 0.37), due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state. The same applies to ClGaTBrPP-F127 (ΦΔ = 0.47) and H2TBrPP-F127 (ΦΔ = 0.41). Thus, ΦΔ values decreased in the presence of FA, but still high enough for practical application of the nanodrug system. The binding constants Kb were determined to be 1.08 × 104 M−1, 2.51 × 105 M−1, 1.52 × 103 and 2.68 × 103 for H2TBrPP+F127-FA, ClGaTBrPP+F127-FA, ClGaTBrPP-F127 and H2TBrPP-F127, respectively. The Kp values were determined in biphasic octanol and water system.
- Full Text:
- Date Issued: 2018
Graphene quantum dot-phthalocyanine polystyrene conjugate embedded in asymmetric polymer membranes for photocatalytic oxidation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
- Full Text:
- Date Issued: 2017
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
- Full Text:
- Date Issued: 2017
Photophysical studies of meso-tetrakis (4-nitrophenyl) and meso-tetrakis (4-sulfophenyl) gallium porphyrins loaded into Pluronic F127 polymeric micelles
- Managa, Muthumuni, Ngoy, Bokolombe P, Mafukidze, Donovan M, Britton, Jonathan, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
Synthesis and singlet oxygen production by a phthalocyanine when embedded in asymmetric polymer membranes
- Mafukidze, Donovan M, Mashazi, Philani N, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
Synthesis, characterisation and evaluation of functionalized Lignocelluloses-clay nanocomposites for organic pollutant removal from water
- Authors: Mafukidze, Donovan M
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11356 , http://hdl.handle.net/10353/d1021296
- Description: PMPSgLig-NaMMT nanocomposites were prepared from methacryloxypropyltrimethoxysilane (MPS), lignocellulose and montmorillonite clay. The potential enhancement of organic pollutant adsorption capabilities of PMPSgLig-NaMMT nanocomposite from water through functionalization was investigated. PMPSgLig-NaMMT was functionalized by esterification and etherification using different methods so as to increase the surface hydrophobicity of the material and hence improve its compatibility with the target pollutants. Specific chemical routes specially tailored for PMPSgLig-NaMMT were established for functionalization mostly based on the common esterification (Fischer esterification) and etherification (Williamson‟s etherification) reactions. In the functionalization methods, factors such as pH environment, nanocomposite composition, nature of functionalization moiety, and use of or absence of solvents and their variations were studied. FT-IR, XRD, SEM and TGA were used to characterize the synthesized and functionalized nanoadsorbents. The techniques showed successful functionalization via esterification and etherification methods albeit to different extents, with clear retention of the material‟s original structure though there were signs of degradation with some methods. Characterization was supported by adsorption studies to validate implications and draw conclusions. The use of 1,10-phenathroline as a model organic pollutant in water in the adsorption studies showed that adsorbents conformed to monolayer adsorption following pseudo-second order kinetics for adsorption of organic pollutants accurately represented. Most importantly the studies revealed the significant impact of the nanocomposite composition on the overall absorbent performance. Adsorption studies also showed that functionalization via esterification methods gave rise to better adsorbents.
- Full Text:
- Date Issued: 2015
- Authors: Mafukidze, Donovan M
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11356 , http://hdl.handle.net/10353/d1021296
- Description: PMPSgLig-NaMMT nanocomposites were prepared from methacryloxypropyltrimethoxysilane (MPS), lignocellulose and montmorillonite clay. The potential enhancement of organic pollutant adsorption capabilities of PMPSgLig-NaMMT nanocomposite from water through functionalization was investigated. PMPSgLig-NaMMT was functionalized by esterification and etherification using different methods so as to increase the surface hydrophobicity of the material and hence improve its compatibility with the target pollutants. Specific chemical routes specially tailored for PMPSgLig-NaMMT were established for functionalization mostly based on the common esterification (Fischer esterification) and etherification (Williamson‟s etherification) reactions. In the functionalization methods, factors such as pH environment, nanocomposite composition, nature of functionalization moiety, and use of or absence of solvents and their variations were studied. FT-IR, XRD, SEM and TGA were used to characterize the synthesized and functionalized nanoadsorbents. The techniques showed successful functionalization via esterification and etherification methods albeit to different extents, with clear retention of the material‟s original structure though there were signs of degradation with some methods. Characterization was supported by adsorption studies to validate implications and draw conclusions. The use of 1,10-phenathroline as a model organic pollutant in water in the adsorption studies showed that adsorbents conformed to monolayer adsorption following pseudo-second order kinetics for adsorption of organic pollutants accurately represented. Most importantly the studies revealed the significant impact of the nanocomposite composition on the overall absorbent performance. Adsorption studies also showed that functionalization via esterification methods gave rise to better adsorbents.
- Full Text:
- Date Issued: 2015
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