Modulation of the optical properties of chiral porphyrin dimers by introducing bridged chiral amide-bonds
- Qin, Mingfeng, Zhang, Zhen, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
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- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
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Naked Eye and Colorimetric Detection of Cyanide with a 1, 3‐Diethyl‐2‐thiobarbituric Acid Substituted Ferrocene Chemosensor
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
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- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
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Nanohybrid electrocatalyst based on cobalt phthalocyanine-carbon nanotube-reduced graphene oxide for ultrasensitive detection of glucose in human saliva
- Adeniyi, Omotayo, Nwahara, Nnamdi, Mwanza, Daniel, Nyokong, Tebello, Mashazi, Philani N
- Authors: Adeniyi, Omotayo , Nwahara, Nnamdi , Mwanza, Daniel , Nyokong, Tebello , Mashazi, Philani N
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231356 , vital:49880 , xlink:href="https://doi.org/10.1016/j.snb.2021.130723"
- Description: The current diabetes management systems require collecting blood samples via an invasive and painful finger pricking leading to the formation of callus, scarring and loss of sensibility to patients due to continuous monitoring. Therefore, a non-invasive and painless method of determining glucose levels would be desirable to diabetes patients who need constant monitoring. Saliva glucose measurement is a non-invasive alternative for diabetes management. A highly sensitive, stable, and selective non-enzymatic electrochemical sensor that can accurately quantify saliva glucose is required. A single-walled carbon nanotube/reduced graphene oxide/cobalt phthalocyanines nanohybrid modified glassy carbon electrode (GCE-SWCNT/rGO/CoPc) has been fabricated for the non-enzymatic determination of glucose in human saliva. The SWCNT/rGO/CoPc was characterized using various spectroscopic, microscopic, and electrochemical techniques. The synergistic effect between SWCNT, rGO, and CoPc facilitated excellent electron transfer process that improved the sensor sensitivity. The GCE-SWCNT/rGO/CoPc sensor exhibited two linear responses in the 0.30 μM to 0.50 mM and 0.50–5.0 mM glucose concentration ranges, and the detection limit was 0.12 μM. The sensor had an excellent saliva glucose detection sensitivity of 992.4 μA·mM−1·cm−2 and high specificity for glucose in the presence of other coexisting analytes. In addition, it showed good storage stability, reusability, and a fast response time of about 1.2 s. The GCE-SWCNT/rGO/CoPc nanohybrid electrode showed excellent potential for developing accurate, non-invasive, and painless glucose sensing.
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- Authors: Adeniyi, Omotayo , Nwahara, Nnamdi , Mwanza, Daniel , Nyokong, Tebello , Mashazi, Philani N
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231356 , vital:49880 , xlink:href="https://doi.org/10.1016/j.snb.2021.130723"
- Description: The current diabetes management systems require collecting blood samples via an invasive and painful finger pricking leading to the formation of callus, scarring and loss of sensibility to patients due to continuous monitoring. Therefore, a non-invasive and painless method of determining glucose levels would be desirable to diabetes patients who need constant monitoring. Saliva glucose measurement is a non-invasive alternative for diabetes management. A highly sensitive, stable, and selective non-enzymatic electrochemical sensor that can accurately quantify saliva glucose is required. A single-walled carbon nanotube/reduced graphene oxide/cobalt phthalocyanines nanohybrid modified glassy carbon electrode (GCE-SWCNT/rGO/CoPc) has been fabricated for the non-enzymatic determination of glucose in human saliva. The SWCNT/rGO/CoPc was characterized using various spectroscopic, microscopic, and electrochemical techniques. The synergistic effect between SWCNT, rGO, and CoPc facilitated excellent electron transfer process that improved the sensor sensitivity. The GCE-SWCNT/rGO/CoPc sensor exhibited two linear responses in the 0.30 μM to 0.50 mM and 0.50–5.0 mM glucose concentration ranges, and the detection limit was 0.12 μM. The sensor had an excellent saliva glucose detection sensitivity of 992.4 μA·mM−1·cm−2 and high specificity for glucose in the presence of other coexisting analytes. In addition, it showed good storage stability, reusability, and a fast response time of about 1.2 s. The GCE-SWCNT/rGO/CoPc nanohybrid electrode showed excellent potential for developing accurate, non-invasive, and painless glucose sensing.
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Photo-sonodynamic combination activity of cationic morpholino-phthalocyanines conjugated to nitrogen and nitrogen-sulfur doped graphene quantum dots against MCF-7 breast cancer cell line in vitro
- Nene, Lindokhule Cindy, Nyokong, Tebello
- Authors: Nene, Lindokhule Cindy , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231334 , vital:49878 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102573"
- Description: In this work, we explore the reactive oxygen species (ROS) generation abilities of cationic morpholino-substituted-phthalocyanine (Pc) conjugated to nitrogen (NGQDs) and nitrogen-sulfur (NSGQDs) doped-graphene quantum dots upon irradiation with light for photodynamic therapy (PDT), ultrasound for sonodynamic therapy (SDT) and the combination of both in photo-sonodynamic therapy (PSDT). The in vitro cytotoxicity studies were conducted using the Michigan Cancer Foundation-7 breast cancer cell lines (MCF-7 cells). For PDT treatments, only the 1O2 was detected for all the sensitizers, whereas both the 1O2 and •OH radicals were evident after SDT and PSDT treatments. An increase in the 1O2 generation was observed for the conjugates compared to the GQDs and the Pc alone. However, the •OH radicals were reduced in the conjugates compared to the GQDs and the Pc alone. The NGQDs generally showed better ROS generation efficacy compared to the NSGQDs, alone and in the conjugates. The combination therapy also shows improved efficacy compared to the monotherapies for the Pcs and Pc-GQDs conjugates.
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- Authors: Nene, Lindokhule Cindy , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231334 , vital:49878 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102573"
- Description: In this work, we explore the reactive oxygen species (ROS) generation abilities of cationic morpholino-substituted-phthalocyanine (Pc) conjugated to nitrogen (NGQDs) and nitrogen-sulfur (NSGQDs) doped-graphene quantum dots upon irradiation with light for photodynamic therapy (PDT), ultrasound for sonodynamic therapy (SDT) and the combination of both in photo-sonodynamic therapy (PSDT). The in vitro cytotoxicity studies were conducted using the Michigan Cancer Foundation-7 breast cancer cell lines (MCF-7 cells). For PDT treatments, only the 1O2 was detected for all the sensitizers, whereas both the 1O2 and •OH radicals were evident after SDT and PSDT treatments. An increase in the 1O2 generation was observed for the conjugates compared to the GQDs and the Pc alone. However, the •OH radicals were reduced in the conjugates compared to the GQDs and the Pc alone. The NGQDs generally showed better ROS generation efficacy compared to the NSGQDs, alone and in the conjugates. The combination therapy also shows improved efficacy compared to the monotherapies for the Pcs and Pc-GQDs conjugates.
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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.
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- 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.
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Photocatalytic desulfurization of dibenzothiophene using asymmetrical zinc (II) phthalocyanines conjugated to silver-magnetic nanoparticles
- Mgidlana, Sithi, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185953 , vital:44451 , xlink:href="https://doi.org/10.1016/j.ica.2020.119970"
- Description: Asymmetrical Zn(II) phthalocyanines: mono (4-carboxy phenoxy) tris (phenylazo phenoxy) (1), mono (4-amino phenoxy) tris (phenylazo phenoxy) (2), mono (4-propanoic acid phenoxy) tris (phenylazo phenoxy) (3) zinc(II) phthalocyanines are synthesized and covalently linked to mercaptohexanol (mph) or mercaptopropionic acid (mpa) functionalized dimerized silver-magnetic nanoparticles (Ag-M). Complexes 1 and 3 are covalently linked to nanomaterials via ester bond whereas complex 2 is covalently linked to nanoparticles (NPs) via amide bond. The conjugates of complexes 1–3 with NPs gave higher singlet oxygen quantum than the Pcs alone. Electrospun fibers were fabricated from polystyrene (PS) solutions containing complexes 1 to 3 and their conjugates. The functionalized PS fibers were used for the phototransformation of dibenzothiophene. The increase in photocatalytic properties of phthalocyanines was observed in the presence of Ag-M with 3 alone and its conjugate with mph capped silver-magnetic nanoparticles showing the larger catalytic activity towards the transformation of dibenzothiophene.
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- Authors: Mgidlana, Sithi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185953 , vital:44451 , xlink:href="https://doi.org/10.1016/j.ica.2020.119970"
- Description: Asymmetrical Zn(II) phthalocyanines: mono (4-carboxy phenoxy) tris (phenylazo phenoxy) (1), mono (4-amino phenoxy) tris (phenylazo phenoxy) (2), mono (4-propanoic acid phenoxy) tris (phenylazo phenoxy) (3) zinc(II) phthalocyanines are synthesized and covalently linked to mercaptohexanol (mph) or mercaptopropionic acid (mpa) functionalized dimerized silver-magnetic nanoparticles (Ag-M). Complexes 1 and 3 are covalently linked to nanomaterials via ester bond whereas complex 2 is covalently linked to nanoparticles (NPs) via amide bond. The conjugates of complexes 1–3 with NPs gave higher singlet oxygen quantum than the Pcs alone. Electrospun fibers were fabricated from polystyrene (PS) solutions containing complexes 1 to 3 and their conjugates. The functionalized PS fibers were used for the phototransformation of dibenzothiophene. The increase in photocatalytic properties of phthalocyanines was observed in the presence of Ag-M with 3 alone and its conjugate with mph capped silver-magnetic nanoparticles showing the larger catalytic activity towards the transformation of dibenzothiophene.
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Photocatalytic desulfurization of dibenzothiophene using methoxy substituted asymmetrical zinc (II) phthalocyanines conjugated to metal tungstate nanomaterials
- Mgidlana, Sithi, Nwahara, Nnamdi, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185760 , vital:44421 , xlink:href="https://doi.org/10.1016/j.poly.2021.115053"
- Description: We report on the syntheses of three asymmetrical zinc(II) phthalocyanine endowed with benzoic acid, phenylpropanoic acid, and phenylacetic acid units: (1), (2), and (3), respectively. Metal tungstate nanoparticles, capped with glutathione were prepared and characterized using analytical techniques. Complexes were covalently linked to nickel tungstate (NiWO4) and bismuth tungstate (Bi2WO6) through an amide bond. The complexes and the conjugates with nanomaterial were evaluated for singlet oxygen generating ability. Complexes 1–2 and their conjugates generate higher singlet oxygen compared to 3 and its corresponding conjugates. The conjugates show degradation of dibenzothiophene (DBT) in fuel with shorter half-lives and greater initial rate values compared to phthalocyanines alone.
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- Authors: Mgidlana, Sithi , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185760 , vital:44421 , xlink:href="https://doi.org/10.1016/j.poly.2021.115053"
- Description: We report on the syntheses of three asymmetrical zinc(II) phthalocyanine endowed with benzoic acid, phenylpropanoic acid, and phenylacetic acid units: (1), (2), and (3), respectively. Metal tungstate nanoparticles, capped with glutathione were prepared and characterized using analytical techniques. Complexes were covalently linked to nickel tungstate (NiWO4) and bismuth tungstate (Bi2WO6) through an amide bond. The complexes and the conjugates with nanomaterial were evaluated for singlet oxygen generating ability. Complexes 1–2 and their conjugates generate higher singlet oxygen compared to 3 and its corresponding conjugates. The conjugates show degradation of dibenzothiophene (DBT) in fuel with shorter half-lives and greater initial rate values compared to phthalocyanines alone.
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Photocytotoxicity of heavy-atom-free thiobarbituric acid functionalized pyrene derivatives against MCF-7 cancer cells
- Babu, Balaji, Ali, Thaslima A, Ochappan, Thivagar, Mack, John, Nyokong, Tebello, Sethuraman, Mathur G
- Authors: Babu, Balaji , Ali, Thaslima A , Ochappan, Thivagar , Mack, John , Nyokong, Tebello , Sethuraman, Mathur G
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190556 , vital:45005 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102102"
- Description: Two thiobarbituric acid-functionalized pyrene derivatives (P1, P2) have been synthesized to explore the photophysical properties and photodynamic activity of dyes of this type. Both compounds exhibit an intense intramolecular charge transfer (ICT) band at ca. 470 nm, which is absent in the spectra of the precursor. P1 and P2 exhibit singlet oxygen generation on irradiation with light with moderate singlet oxygen yields of 0.36 and 0.32, respectively, in DMSO. P1 showed better photodynamic activity against MCF-7 cells with an IC50 value of 18.3 μM under illumination at 455 nm for 60 min with a Thorlabs M455L3 LED (330 mW.cm−2).
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- Authors: Babu, Balaji , Ali, Thaslima A , Ochappan, Thivagar , Mack, John , Nyokong, Tebello , Sethuraman, Mathur G
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190556 , vital:45005 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102102"
- Description: Two thiobarbituric acid-functionalized pyrene derivatives (P1, P2) have been synthesized to explore the photophysical properties and photodynamic activity of dyes of this type. Both compounds exhibit an intense intramolecular charge transfer (ICT) band at ca. 470 nm, which is absent in the spectra of the precursor. P1 and P2 exhibit singlet oxygen generation on irradiation with light with moderate singlet oxygen yields of 0.36 and 0.32, respectively, in DMSO. P1 showed better photodynamic activity against MCF-7 cells with an IC50 value of 18.3 μM under illumination at 455 nm for 60 min with a Thorlabs M455L3 LED (330 mW.cm−2).
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Photodynamic activity of 2, 6-dibrominated dimethylaminophenylbuta-1, 3-dienylBODIPY dyes
- Khubeka, Gugu, Babu, Balaji, Prinsloo, Earl, Kobayashi, Nagao, Mack, John, Nyokong, Tebello
- Authors: Khubeka, Gugu , Babu, Balaji , Prinsloo, Earl , Kobayashi, Nagao , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190804 , vital:45030 , xlink:href="https://doi.org/10.1142/S1088424620500509"
- Description: Mono- and disubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes were successfully prepared, and their in vitro photodynamic activities against MCF-7 breast cancer cells were evaluated with a Thorlabs M660L4 660 nm LED (336 J · cm−2)−2). The IC5050 value of the monophenylbuta-1,3-dienylBODIPY was ca. 2.1 μμM, while that of the diphenylbuta-1,3-dienylBODIPY was > 50 μμM. Both dyes exhibited minimal dark toxicity. The results demonstrate that monosubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes merit further in-depth study for use as photosensitizer dyes in photodynamic therapy.
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- Authors: Khubeka, Gugu , Babu, Balaji , Prinsloo, Earl , Kobayashi, Nagao , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190804 , vital:45030 , xlink:href="https://doi.org/10.1142/S1088424620500509"
- Description: Mono- and disubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes were successfully prepared, and their in vitro photodynamic activities against MCF-7 breast cancer cells were evaluated with a Thorlabs M660L4 660 nm LED (336 J · cm−2)−2). The IC5050 value of the monophenylbuta-1,3-dienylBODIPY was ca. 2.1 μμM, while that of the diphenylbuta-1,3-dienylBODIPY was > 50 μμM. Both dyes exhibited minimal dark toxicity. The results demonstrate that monosubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes merit further in-depth study for use as photosensitizer dyes in photodynamic therapy.
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Photodynamic activity of Sn (IV) tetrathien-2-ylchlorin against MCF-7 breast cancer cells
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185920 , vital:44448 , xlink:href="https://doi.org/10.1039/d0dt03958f"
- Description: A new readily-synthesized Sn(IV) tetraarylchlorin with thien-2-yl substituents (SnC) has been prepared and fully characterized by various spectroscopic techniques and its photophysical and photochemical properties, such as the singlet oxygen quantum yield (ΦΔ), fluorescence quantum yield (ΦF), triplet lifetime (τT) and photostability, have been evaluated. SnC has an unusually high ΦΔ value of 0.89 in DMF. Studies on the photodynamic activity against MCF-7 breast cancer cells exhibited a very low IC50 value of 0.9 μM and high phototoxicity (dark versus light) indices of >27.8 after irradiation with a 660 nm Thorlabs LED (280 mW cm−2). The results demonstrate that Sn(IV) tetraarylchlorins of this type are suitable candidates for further in-depth PDT studies.
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- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185920 , vital:44448 , xlink:href="https://doi.org/10.1039/d0dt03958f"
- Description: A new readily-synthesized Sn(IV) tetraarylchlorin with thien-2-yl substituents (SnC) has been prepared and fully characterized by various spectroscopic techniques and its photophysical and photochemical properties, such as the singlet oxygen quantum yield (ΦΔ), fluorescence quantum yield (ΦF), triplet lifetime (τT) and photostability, have been evaluated. SnC has an unusually high ΦΔ value of 0.89 in DMF. Studies on the photodynamic activity against MCF-7 breast cancer cells exhibited a very low IC50 value of 0.9 μM and high phototoxicity (dark versus light) indices of >27.8 after irradiation with a 660 nm Thorlabs LED (280 mW cm−2). The results demonstrate that Sn(IV) tetraarylchlorins of this type are suitable candidates for further in-depth PDT studies.
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Photodynamic antimicrobial action of asymmetrical porphyrins functionalized silver-detonation nanodiamonds nanoplatforms for the suppression of Staphylococcus aureus planktonic cells and biofilms
- Openda, Yolande I, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Openda, Yolande I , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190544 , vital:45004 , xlink:href="https://doi.org/10.3389/fchem.2021.628316"
- Description: New asymmetrical porphyrin derivatives containing a p-hydroxyphenyl moiety and p-acetylphenyl moieties along with their functionalized silver-detonation nanodiamonds nanohybrids were characterized and their photophysicochemical properties were established. The study provides evidence that the metalated porphyrin derivatives were red-shifted in absorption wavelength and possessed high singlet oxygen quantum yield comparative to the unmetalated core, thus making them suitable agents for photodynamic antimicrobial chemotherapy. As a result of conjugation to detonation nanodiamonds and silver nanoparticles, these compounds proved to be more effective as they exhibited stronger antibacterial and anti-biofilm activities on the multi-drug resistant S. aureus strain due to synergetic effect, compared to Ps alone. This suggests that the newly prepared nanohybrids could be used as a potential antimicrobial agent in the treatment of biofilms caused by S. aureus strain.
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- Authors: Openda, Yolande I , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190544 , vital:45004 , xlink:href="https://doi.org/10.3389/fchem.2021.628316"
- Description: New asymmetrical porphyrin derivatives containing a p-hydroxyphenyl moiety and p-acetylphenyl moieties along with their functionalized silver-detonation nanodiamonds nanohybrids were characterized and their photophysicochemical properties were established. The study provides evidence that the metalated porphyrin derivatives were red-shifted in absorption wavelength and possessed high singlet oxygen quantum yield comparative to the unmetalated core, thus making them suitable agents for photodynamic antimicrobial chemotherapy. As a result of conjugation to detonation nanodiamonds and silver nanoparticles, these compounds proved to be more effective as they exhibited stronger antibacterial and anti-biofilm activities on the multi-drug resistant S. aureus strain due to synergetic effect, compared to Ps alone. This suggests that the newly prepared nanohybrids could be used as a potential antimicrobial agent in the treatment of biofilms caused by S. aureus strain.
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Photodynamic inactivation of Staphylococcus Aureus with Schiff base substituted Zinc phthalocyanines through conjugation to silver nanoparticles
- Sen, Pinar, Nyokong, Tebello
- Authors: Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185688 , vital:44415 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130012"
- Description: We present the preparation of Schiff base substituted neutral phthalocyanines derived from aldehyde-substituted phthalocyanine which are conjugated to silver nanoparticles through covalent-like strong interactions. The photophysicochemical properties of the nanoconjugates and the Pcs alone were studied comparatively. The photodynamic antimicrobial chemotherapy (PACT) activities. of prepared photosensitizers was investigated against Gram-positive bacterium (Staphylococcus aureus). Unlike Pcs alone, conjugated phthalocyanines to silver nanoparticles showed excellent photodynamic antimicrobial activity with the 100% reduction percentage upon illumination.
- Full Text:
- Authors: Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185688 , vital:44415 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130012"
- Description: We present the preparation of Schiff base substituted neutral phthalocyanines derived from aldehyde-substituted phthalocyanine which are conjugated to silver nanoparticles through covalent-like strong interactions. The photophysicochemical properties of the nanoconjugates and the Pcs alone were studied comparatively. The photodynamic antimicrobial chemotherapy (PACT) activities. of prepared photosensitizers was investigated against Gram-positive bacterium (Staphylococcus aureus). Unlike Pcs alone, conjugated phthalocyanines to silver nanoparticles showed excellent photodynamic antimicrobial activity with the 100% reduction percentage upon illumination.
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Photodynamic therapy activities of phthalocyanine-based macromolecular photosensitizers on MCF-7 breast cancer cells
- Ahmetali, Erem, Sen, Pinar, Süer, N Ceren, Nyokong, Tebello, Erin, Tarik, Sener, M Kasim
- Authors: Ahmetali, Erem , Sen, Pinar , Süer, N Ceren , Nyokong, Tebello , Erin, Tarik , Sener, M Kasim
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185655 , vital:44407 , xlink:href="https://doi.org/10.1080/10601325.2021.1934012"
- Description: Poly(oxanorbornene)s with zinc(II) phthalocyanine side chains have been synthesized by ring-opening metathesis polymerization. The incorporation of zinc(II) phthalocyanine into cationic polymer has given poly(oxanorbornene)s noteworthy photophysicochemical properties and the capacity to generate singlet oxygen under light irradiation. To investigate photosensitizer’s properties of the newly synthesized polymers P6 and P7: fluorescence (ΦF), singlet oxygen (ΦΔ) and triplet (ΦT) quantum yields of polymers have been measured in dimethyl sulfoxide and aqueous medium. Singlet oxygen quantum yields of P6 and P7 have been found to be 0.22 and 0.20 in dimethyl sulfoxide, respectively. Then, photodynamic therapy activities of polymers (P1-P7) against human breast adenocarcinoma cell line (MCF-7 cells) have been investigated. The copolymer P5 bearing pendant zinc(II) phthalocyanine and triethyl phosphonium functionalities has showed enhanced PDT activity with less than 10% viable cells at 60 μg/mL.
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- Authors: Ahmetali, Erem , Sen, Pinar , Süer, N Ceren , Nyokong, Tebello , Erin, Tarik , Sener, M Kasim
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185655 , vital:44407 , xlink:href="https://doi.org/10.1080/10601325.2021.1934012"
- Description: Poly(oxanorbornene)s with zinc(II) phthalocyanine side chains have been synthesized by ring-opening metathesis polymerization. The incorporation of zinc(II) phthalocyanine into cationic polymer has given poly(oxanorbornene)s noteworthy photophysicochemical properties and the capacity to generate singlet oxygen under light irradiation. To investigate photosensitizer’s properties of the newly synthesized polymers P6 and P7: fluorescence (ΦF), singlet oxygen (ΦΔ) and triplet (ΦT) quantum yields of polymers have been measured in dimethyl sulfoxide and aqueous medium. Singlet oxygen quantum yields of P6 and P7 have been found to be 0.22 and 0.20 in dimethyl sulfoxide, respectively. Then, photodynamic therapy activities of polymers (P1-P7) against human breast adenocarcinoma cell line (MCF-7 cells) have been investigated. The copolymer P5 bearing pendant zinc(II) phthalocyanine and triethyl phosphonium functionalities has showed enhanced PDT activity with less than 10% viable cells at 60 μg/mL.
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Photophysicochemical behaviour of phenoxy propanoic acid functionalised zinc phthalocyanines when grafted onto iron oxide and silica nanoparticles: Effects in photodynamic antimicrobial chemotherapy
- Dube, Edith, Soy, Rodath, Shumba, Mumyaradzi, Nyokong, Tebello
- Authors: Dube, Edith , Soy, Rodath , Shumba, Mumyaradzi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185465 , vital:44389 , xlink:href="https://doi.org/10.1016/j.jlumin.2021.117939"
- Description: This work reports on the covalent linkage of (3-aminopropyl)triethoxysilane (APTES) functionalised iron oxide (IONPs–APTES) and silica (SiNPs–APTES) nanoparticles with zinc(II) tetra–([3–(4–phenoxy) propanoic acid) phthalocyanine] (1) and zinc(II) mono–([3–(4–phenoxy) propanoic acid) phthalocyanine (2) via an amide bond to form the conjugates, 1–IONPs-APTES, 1–SiNPs–APTES, 2-IONPs-APTES and 2-SiNPs-APTES). The photophysicochemical behaviour of the conjugates was investigated. These were characterized by a decrease in the fluorescence quantum yields and lifetimes, and an increase in the triplet quantum yield and singlet oxygen quantum yield when compared to complex 1 and 2 alone. The conjugates to IONPs-APTES displayed higher ΦT than those of SiNPs-APTES probably due to the heavy atom effect of iron compared to silica and the high loading capacity of the relatively smaller iron oxide NPs, however, there was no significant difference in the ΦΔ values of 2-IONPs-APTES (ΦΔ=0.59) and 2-SiNPs-APTES (ΦΔ=0.58), suggesting that the energy transfer process between the excited triplet state of 2-IONPs-APTES and ground state molecular oxygen was not effective. Photodynamic antimicrobial chemotherapy (PACT) studies showed that linkage of Pcs to NPs improves their photoinactivation capability against Staphylococcus aureus and Escherichia coli. IONPs-APTES and its conjugates generally displayed the highest log reductions than SiNPs-APTES and its conjugates except for studies after 75 min of irradiation for S. Aureus where the log reductions are the same. 2-IONP-APTES was recovered using a magnet after each photodegradation cycle and its stability after 3 cycles confirmed re-usability.
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- Authors: Dube, Edith , Soy, Rodath , Shumba, Mumyaradzi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185465 , vital:44389 , xlink:href="https://doi.org/10.1016/j.jlumin.2021.117939"
- Description: This work reports on the covalent linkage of (3-aminopropyl)triethoxysilane (APTES) functionalised iron oxide (IONPs–APTES) and silica (SiNPs–APTES) nanoparticles with zinc(II) tetra–([3–(4–phenoxy) propanoic acid) phthalocyanine] (1) and zinc(II) mono–([3–(4–phenoxy) propanoic acid) phthalocyanine (2) via an amide bond to form the conjugates, 1–IONPs-APTES, 1–SiNPs–APTES, 2-IONPs-APTES and 2-SiNPs-APTES). The photophysicochemical behaviour of the conjugates was investigated. These were characterized by a decrease in the fluorescence quantum yields and lifetimes, and an increase in the triplet quantum yield and singlet oxygen quantum yield when compared to complex 1 and 2 alone. The conjugates to IONPs-APTES displayed higher ΦT than those of SiNPs-APTES probably due to the heavy atom effect of iron compared to silica and the high loading capacity of the relatively smaller iron oxide NPs, however, there was no significant difference in the ΦΔ values of 2-IONPs-APTES (ΦΔ=0.59) and 2-SiNPs-APTES (ΦΔ=0.58), suggesting that the energy transfer process between the excited triplet state of 2-IONPs-APTES and ground state molecular oxygen was not effective. Photodynamic antimicrobial chemotherapy (PACT) studies showed that linkage of Pcs to NPs improves their photoinactivation capability against Staphylococcus aureus and Escherichia coli. IONPs-APTES and its conjugates generally displayed the highest log reductions than SiNPs-APTES and its conjugates except for studies after 75 min of irradiation for S. Aureus where the log reductions are the same. 2-IONP-APTES was recovered using a magnet after each photodegradation cycle and its stability after 3 cycles confirmed re-usability.
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Positively charged styryl pyridine substituted Zn (II) Phthalocyanines for Photodynamic Therapy and Photoantimicrobial Chemotherapy
- Magadla, Aviwe, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
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- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
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Promising photodynamic antimicrobial activity of polyimine substituted zinc phthalocyanine and its polycationic derivative when conjugated to nitrogen, sulfur, co-doped graphene quantum dots against Staphylococcus aureus
- Sen, Pinar, Nyokong, Tebello
- Authors: Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185304 , vital:44363 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102300"
- Description: Antimicrobial resistance is a most important problem facing the treatment of infectious diseases. Antimicrobial photodynamic therapy is an alternative treatment strategy, considered to be cost-effective and feasible. For this purpose, octa-imine substituted ZnPc (3) have been prepared and conjugated to nitrogen, sulfur co-doped graphene quantum dots (N,S-GQDs) through π-π stacking. The photophysical and photochemical properties of Pc alone and and Pc-conjugated to the GQD nanomaterial such as absorption, fluorescence, fluorescence life time, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions before in vitro cell studies. The PACT activity of prepared structures was investigated against Gram-positive (Staphylococcus aureus). Our results suggest that the in the case of conjugation of zinc Pc to N,S-GQDs, photodynamic inactivation increased with the 100 % reduction percentage.
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- Authors: Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185304 , vital:44363 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102300"
- Description: Antimicrobial resistance is a most important problem facing the treatment of infectious diseases. Antimicrobial photodynamic therapy is an alternative treatment strategy, considered to be cost-effective and feasible. For this purpose, octa-imine substituted ZnPc (3) have been prepared and conjugated to nitrogen, sulfur co-doped graphene quantum dots (N,S-GQDs) through π-π stacking. The photophysical and photochemical properties of Pc alone and and Pc-conjugated to the GQD nanomaterial such as absorption, fluorescence, fluorescence life time, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions before in vitro cell studies. The PACT activity of prepared structures was investigated against Gram-positive (Staphylococcus aureus). Our results suggest that the in the case of conjugation of zinc Pc to N,S-GQDs, photodynamic inactivation increased with the 100 % reduction percentage.
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Push-pull type Co (III) corroles
- Niu, Yingjie, Zhu, Weihua, Mack, John, Dubazana, Nadine, Nyokong, Tebello, Fu, Bo, Xu, Haijun, Liang, Xu
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
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- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
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Solar Driven Photocatalytic Activity of Porphyrin Sensitized TiO2
- Otieno, Sebastien, Lanterna, Anabel E, Mack, John, Derese, Solomon, Amuhaya, Edith K, Nyokong, Tebello, Scaiano, Juan C
- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
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- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
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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.
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- 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.
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Synthesis, theoretical calculations and laser flash photolysis studies of selected amphiphilic porphyrin derivatives used as biofilm photodegradative materials
- Openda, Yolande I, Ngoy, Bokolombe P, Muva, Jules T, Nyokong, Tebello
- Authors: Openda, Yolande I , Ngoy, Bokolombe P , Muva, Jules T , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190589 , vital:45008 , xlink:href="https://doi.org/10.1039/D1NJ02651H"
- Description: Photodynamic antimicrobial activities of gallium and indium porphyrins as well as their quaternized derivatives have been investigated against S. aureus and E. coli biofilms, as well as on their planktonic (free floating) cells using a light emitting diode lamp at 415 nm. The studied photosensitizers show considerable ability to generate singlet oxygen and the quaternized molecules 2a and 3a are potential photodynamic antimicrobial chemotherapy (PACT) agents with log10 colony forming units >9 for E. coli and S. aureus planktonic cells. The quaternized derivatives are found to have higher ability to significantly suppress the biofilms of both S. aureus and E. coli in vitro. Therefore, this demonstrates that they are potentially suitable photosensitive agents for PACT use. The TD-B3LYP/LanL2DZ calculations were performed to evaluate the singlet excitation energies of quaternized and non-quaternized porphyrins in vacuo. Our study shows excellent agreement between time-dependent density-functional theory (TD-DFT) excited energies and experimental S1 > S0 excitation energies. The small deviation observed between the calculated and experimental spectra arises from the solvent effect. The excitation energies observed in these UV-visible spectra mostly originated from electron promotion between the highest occupied molecular orbital (HOMO) for the less intense band and the HOMO−1 for the most intense band of the ground states to the lower unoccupied molecular orbital (LUMO) of the excited states.
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- Authors: Openda, Yolande I , Ngoy, Bokolombe P , Muva, Jules T , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190589 , vital:45008 , xlink:href="https://doi.org/10.1039/D1NJ02651H"
- Description: Photodynamic antimicrobial activities of gallium and indium porphyrins as well as their quaternized derivatives have been investigated against S. aureus and E. coli biofilms, as well as on their planktonic (free floating) cells using a light emitting diode lamp at 415 nm. The studied photosensitizers show considerable ability to generate singlet oxygen and the quaternized molecules 2a and 3a are potential photodynamic antimicrobial chemotherapy (PACT) agents with log10 colony forming units >9 for E. coli and S. aureus planktonic cells. The quaternized derivatives are found to have higher ability to significantly suppress the biofilms of both S. aureus and E. coli in vitro. Therefore, this demonstrates that they are potentially suitable photosensitive agents for PACT use. The TD-B3LYP/LanL2DZ calculations were performed to evaluate the singlet excitation energies of quaternized and non-quaternized porphyrins in vacuo. Our study shows excellent agreement between time-dependent density-functional theory (TD-DFT) excited energies and experimental S1 > S0 excitation energies. The small deviation observed between the calculated and experimental spectra arises from the solvent effect. The excitation energies observed in these UV-visible spectra mostly originated from electron promotion between the highest occupied molecular orbital (HOMO) for the less intense band and the HOMO−1 for the most intense band of the ground states to the lower unoccupied molecular orbital (LUMO) of the excited states.
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