Fluorescence “turn-ON” nanosensor for cyanide ion using supramolecular hybrid of graphene quantum dots and cobalt pyrene-derivatized phthalocyanine
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187594 , vital:44674 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.08.038"
- Description: A functional hybrid of graphene quantum dots (GQDs) and cobalt pyrene-derivatized phthalocyanine (CoPc) used as a sensitive nanoprobe for the recognition of cyanide ion (CN−) is described in this work. The fluorescence of GQDs was quenched upon non-covalent (π-π stacking) hybrid formation with CoPc via a possible energy transfer pathway. However, in the presence of CN−, the interaction between GQDs and CoPc was perturbed, such that the fluorescence of GQDs initially quenched by CoPc was found to be efficiently recovered in the presence of CN−. Amongst the molecules and anions tested to ascertain their effects on the fluorescence behaviour of the hybrid, only CN− ion induced the tunable “off-on” restoration of the fluorescence of GQDs, which demonstrates the selectivity of the hybrid towards CN−. The restored fluorescence signals of the GQDs were linearly modulated by different concentrations of CN− and were used for the quantitative assay of CN− with high sensitivity coupled with rapid detection time. The detection was in the linear range of 1.0–50.0 nM with limits of detection (LOD) of 0.5 nM. The analysis of spiked samples for the recovery of CN− further demonstrated the applicability of the hybrid for the satisfactory detection of the target analyte.
- Full Text:
- Date Issued: 2019
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187594 , vital:44674 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.08.038"
- Description: A functional hybrid of graphene quantum dots (GQDs) and cobalt pyrene-derivatized phthalocyanine (CoPc) used as a sensitive nanoprobe for the recognition of cyanide ion (CN−) is described in this work. The fluorescence of GQDs was quenched upon non-covalent (π-π stacking) hybrid formation with CoPc via a possible energy transfer pathway. However, in the presence of CN−, the interaction between GQDs and CoPc was perturbed, such that the fluorescence of GQDs initially quenched by CoPc was found to be efficiently recovered in the presence of CN−. Amongst the molecules and anions tested to ascertain their effects on the fluorescence behaviour of the hybrid, only CN− ion induced the tunable “off-on” restoration of the fluorescence of GQDs, which demonstrates the selectivity of the hybrid towards CN−. The restored fluorescence signals of the GQDs were linearly modulated by different concentrations of CN− and were used for the quantitative assay of CN− with high sensitivity coupled with rapid detection time. The detection was in the linear range of 1.0–50.0 nM with limits of detection (LOD) of 0.5 nM. The analysis of spiked samples for the recovery of CN− further demonstrated the applicability of the hybrid for the satisfactory detection of the target analyte.
- Full Text:
- Date Issued: 2019
Preparation of NIR absorbing axial substituted tin (iv) porphyrins and their photocytotoxic properties
- Babu, Balaji, Amuhaya, Edith K, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
Synthesis, characterization and photodynamic activity of Sn (iv) triarylcorroles with red-shifted Q bands
- Babu, Balaji, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019
Photophysicochemical and photodynamic therapy properties of metallophthalocyanines linked to gold speckled silica nanoparticles
- Dube, Edith, Oluwole, David O, Niemuwa, Nwaji, Prinsloo, Earl, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
- Full Text:
- Date Issued: 2019
- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
- Full Text:
- Date Issued: 2019
Effect of gold nanoparticles shape and size on the photophysicochemical behaviour of symmetric and asymmetric zinc phthalocyanines
- Dube, Edith, Nyokong, Tebello
- Authors: Dube, Edith , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187569 , vital:44672 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.063"
- Description: Glutathione (GSH) capped Au nanotriangles (AuNTs–GSH) and nanospheres (AuNSs–GSH) are covalently linked to symmetric Zn phthalocyanine (ZnPc) substituted with phenoxy propanoic acid substituents only (complex 1) and two asymmetric ZnPc, each containing one phenoxy propanoic acid and three benzothiazole phenoxy moieties (complex 2), and one phenoxy propanoic acid and no other ligands (complex 3). The photophysicochemical behaviour of Pc complexes and their conjugates were studied. All conjugates displayed improved triplet and singlet oxygen quantum yields with decreases in fluorescence quantum yields compared to their respective Pc complexes. The conjugates of asymmetric complexes 2 and 3, afforded much higher triplet and singlet oxygen quantum yields compared to the symmetric complex 1, and could serve as good candidates for photodynamic therapy
- Full Text:
- Date Issued: 2019
- Authors: Dube, Edith , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187569 , vital:44672 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.063"
- Description: Glutathione (GSH) capped Au nanotriangles (AuNTs–GSH) and nanospheres (AuNSs–GSH) are covalently linked to symmetric Zn phthalocyanine (ZnPc) substituted with phenoxy propanoic acid substituents only (complex 1) and two asymmetric ZnPc, each containing one phenoxy propanoic acid and three benzothiazole phenoxy moieties (complex 2), and one phenoxy propanoic acid and no other ligands (complex 3). The photophysicochemical behaviour of Pc complexes and their conjugates were studied. All conjugates displayed improved triplet and singlet oxygen quantum yields with decreases in fluorescence quantum yields compared to their respective Pc complexes. The conjugates of asymmetric complexes 2 and 3, afforded much higher triplet and singlet oxygen quantum yields compared to the symmetric complex 1, and could serve as good candidates for photodynamic therapy
- Full Text:
- Date Issued: 2019
Effect of gold nanoparticle shape on the photophysicochemical properties of sulphur containing metallophthalocyanines
- Dube, Edith, Nyokong, Tebello
- Authors: Dube, Edith , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187048 , vital:44559 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.12.091"
- Description: In this work tetrakise[(thiopheneethoxy) phthalocyaninato] zinc(II) (1), tetrakise[(thiopheneethoxy) phthalocyaninato] indium (II) chloride (2), tetrakis [(benzo [d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (3), and tetrakis [(benzo [d]thiazol-2-yl phenoxy)phthalocyaninato] indium (II) chloride (4) were linked to both gold nanospheres (AuNSs) and gold nanotriangles (AuNTs) via Au-S and Au-N (the latter for complexes 3 and 4 only) self assembly. The photophysicochemical behaviour of complexes and their conjugates were studied. The conjugates yielded improved triplet and singlet quantum yields, with nanospheres displaying better properties than nanotriangles. The conjugates with a benzothiazole phenoxy substituent also yielded better properties than their thiophene ethoxy counterpart. These conjugates especially those with a benzothiazole phenoxy substituent have potential as photosensitisers for photodynamic therapy applications.
- Full Text:
- Date Issued: 2019
- Authors: Dube, Edith , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187048 , vital:44559 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.12.091"
- Description: In this work tetrakise[(thiopheneethoxy) phthalocyaninato] zinc(II) (1), tetrakise[(thiopheneethoxy) phthalocyaninato] indium (II) chloride (2), tetrakis [(benzo [d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (3), and tetrakis [(benzo [d]thiazol-2-yl phenoxy)phthalocyaninato] indium (II) chloride (4) were linked to both gold nanospheres (AuNSs) and gold nanotriangles (AuNTs) via Au-S and Au-N (the latter for complexes 3 and 4 only) self assembly. The photophysicochemical behaviour of complexes and their conjugates were studied. The conjugates yielded improved triplet and singlet quantum yields, with nanospheres displaying better properties than nanotriangles. The conjugates with a benzothiazole phenoxy substituent also yielded better properties than their thiophene ethoxy counterpart. These conjugates especially those with a benzothiazole phenoxy substituent have potential as photosensitisers for photodynamic therapy applications.
- Full Text:
- Date Issued: 2019
Co (ii) Tetraphenyltetraphenanthroporphyrin@ MWCNTs
- Gu, Tingting, Tao, Jaiyu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Xu, Haijin, Li, Minzhi, Liang, Xu
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
Nonlinear optical properties of metal free and nickel binuclear phthalocyanines
- Kabwe, Kapambwe P, Louzada, Marcel, Britton, Jonathan, Olomola,Temitope O, Nyokong, Tebello, Khene, Samson M
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola,Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola,Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
Chiral Modulation from Molecular to Macroscopic levels by synthetic chiral-amide-bonded porphyrin dimers
- Liang, Xu, Qin, Mingfeng, Zhang, Xiaomei, Mack, John, Soy, Rodah, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
- Full Text:
- Date Issued: 2019
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
- Full Text:
- Date Issued: 2019
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
Physicochemical and antimicrobial photodynamic chemotherapy (against E. coli) by indium phthalocyanines in the presence of silver–iron bimetallic nanoparticles
- Magadla, Aviwe, Oluwole, David O, Managa, Muthumuni, Nyokong, Tebello
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
Nonlinear optical responses of carbazole-substituted phthalocyanines conjugated to graphene quantum dots and in thin films
- Majeed, Shereen A, Nwaji, Njemuwa, Mack, John, Nyokong, Tebello, Makhseed, Saad
- Authors: Majeed, Shereen A , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello , Makhseed, Saad
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186938 , vital:44549 , xlink:href="https://doi.org/10.1016/j.jlumin.2019.04.034"
- Description: Three different phthalocyanine complexes substituted with carbazoles were conjugated to graphene quantum dots (GQDs) through π–π stacking. The morphologies, sizes, and crystallinities of the nanoconjugates were determined using Raman spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The nonlinear optical (NLO) properties of the metallophthalocyanines alone and when conjugated to the GQD nanomaterial in different solvents, as well as after having been embedded in thin films, were studied. The effects of the different substituents and solvents on the NLO properties of the metallophthalocyanines were evaluated. Enhancements in the photophysical properties of the complexes upon conjugation with the nanomaterial were observed. Fluorescence quantum yields, fluorescence lifetimes, triplet quantum yields, and triplet lifetimes were measured for the complexes, and for their conjugates in DMSO.
- Full Text:
- Date Issued: 2019
- Authors: Majeed, Shereen A , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello , Makhseed, Saad
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186938 , vital:44549 , xlink:href="https://doi.org/10.1016/j.jlumin.2019.04.034"
- Description: Three different phthalocyanine complexes substituted with carbazoles were conjugated to graphene quantum dots (GQDs) through π–π stacking. The morphologies, sizes, and crystallinities of the nanoconjugates were determined using Raman spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The nonlinear optical (NLO) properties of the metallophthalocyanines alone and when conjugated to the GQD nanomaterial in different solvents, as well as after having been embedded in thin films, were studied. The effects of the different substituents and solvents on the NLO properties of the metallophthalocyanines were evaluated. Enhancements in the photophysical properties of the complexes upon conjugation with the nanomaterial were observed. Fluorescence quantum yields, fluorescence lifetimes, triplet quantum yields, and triplet lifetimes were measured for the complexes, and for their conjugates in DMSO.
- Full Text:
- Date Issued: 2019
Spectroscopic and nonlinear optical properties of alkyl thio substituted binuclear phthalocyanines
- Makinde, Zainab O, Louzada, Marcel S, Britton, Jonathan, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
Photophysical properties and photodynamic therapy activity of a meso-tetra (4-carboxyphenyl) porphyrin tetramethyl ester–graphene quantum dot conjugate
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
- Full Text:
- Date Issued: 2019
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
- Full Text:
- Date Issued: 2019
Asymmetrical and symmetrical zinc phthalocyanine-cobalt ferrite conjugates embedded in electrospun fibers for dual photocatalytic degradation of azo dyes: Methyl Orange and Orange G
- Mapukata, Sivuyisiwe, Kobayashi, Nagao, Kimura, Mutsumi, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186960 , vital:44551 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.04.048"
- Description: The conjugation of a symmetrical and an asymmetrical zinc phthalocyanine with amine functionalised cobalt ferrite magnetic nanoparticles (CoFe MNPs) for enhanced photophysics and photocatalysis is reported. The MNPs, 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II) (2) and 2, 10, 16, 24 – tetra 5-(phenoxy)-isophthalic acid phthalocyaninato] Zn (II) (3) as well as their respective conjugates are embedded into electrospun polyamide-6 (PA-6) fibers for support and catalyst regeneration. The resulting photocatalyts (CoFe/PA-6, 2/PA-6, 3/PA-6, CoFe-2/PA-6, and CoFe-3/PA-6) were compared based on their photophysical properties and photocatalytic efficiencies in degrading azo dyes; Methyl Orange (MO) and Orange G (OG). CoFe-2/PA-6 and CoFe-3/PA-6 were found to be more effective photocatalysts than their respective electrospun Pcs and MNPs. The degradation of OG was found to follow pseudo first order kinetics and the Langmuir–Hinshelwood model while that of MO does not.
- Full Text:
- Date Issued: 2019
- Authors: Mapukata, Sivuyisiwe , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186960 , vital:44551 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.04.048"
- Description: The conjugation of a symmetrical and an asymmetrical zinc phthalocyanine with amine functionalised cobalt ferrite magnetic nanoparticles (CoFe MNPs) for enhanced photophysics and photocatalysis is reported. The MNPs, 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II) (2) and 2, 10, 16, 24 – tetra 5-(phenoxy)-isophthalic acid phthalocyaninato] Zn (II) (3) as well as their respective conjugates are embedded into electrospun polyamide-6 (PA-6) fibers for support and catalyst regeneration. The resulting photocatalyts (CoFe/PA-6, 2/PA-6, 3/PA-6, CoFe-2/PA-6, and CoFe-3/PA-6) were compared based on their photophysical properties and photocatalytic efficiencies in degrading azo dyes; Methyl Orange (MO) and Orange G (OG). CoFe-2/PA-6 and CoFe-3/PA-6 were found to be more effective photocatalysts than their respective electrospun Pcs and MNPs. The degradation of OG was found to follow pseudo first order kinetics and the Langmuir–Hinshelwood model while that of MO does not.
- Full Text:
- Date Issued: 2019
Dual phototransformation of the pollutants methyl orange and Cr (VI) using phthalocyanine-cobalt ferrite based magnetic nanocomposites
- Mapukata, Sivuyisiwe, Osifeko, Olawale L, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187059 , vital:44561 , xlink:href="https://doi.org/10.1016/j.heliyon.2019.e01509"
- Description: Bifunctional nanocomposites based on zinc phthalocyanines and glutathione capped CoFe2O4 magnetic nanoparticles (GSH-CoFe2O4 MNPs) are applied in a binary system wherein simultaneous photooxidation of methyl orange (MO) and photoreduction of Cr (VI) are conducted. The photoactivity of two zinc Pcs with different functional moieties are compared based on their interactions with GSH-CoFe2O4 MNPs. Conjugation of the Pcs to the GSH-CoFe2O4 MNPs not only enhanced their singlet oxygen production but also their photocatalytic activity in both photooxidation and photoreduction experiments. Using electron paramagnetic resonance (EPR) spectroscopy, the Pc-MNP conjugates reported herein were found to exhibit superparamagnetic behaviour, giving the advantage of easy separation using an external magnetic field post application, an attractive attribute for heterogeneous catalysis. The catalysts reported herein are therefore good candidates as catalysts for real life water purification analyses as they facilitate the treatment of both organic and inorganic water pollutants.
- Full Text:
- Date Issued: 2019
- Authors: Mapukata, Sivuyisiwe , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187059 , vital:44561 , xlink:href="https://doi.org/10.1016/j.heliyon.2019.e01509"
- Description: Bifunctional nanocomposites based on zinc phthalocyanines and glutathione capped CoFe2O4 magnetic nanoparticles (GSH-CoFe2O4 MNPs) are applied in a binary system wherein simultaneous photooxidation of methyl orange (MO) and photoreduction of Cr (VI) are conducted. The photoactivity of two zinc Pcs with different functional moieties are compared based on their interactions with GSH-CoFe2O4 MNPs. Conjugation of the Pcs to the GSH-CoFe2O4 MNPs not only enhanced their singlet oxygen production but also their photocatalytic activity in both photooxidation and photoreduction experiments. Using electron paramagnetic resonance (EPR) spectroscopy, the Pc-MNP conjugates reported herein were found to exhibit superparamagnetic behaviour, giving the advantage of easy separation using an external magnetic field post application, an attractive attribute for heterogeneous catalysis. The catalysts reported herein are therefore good candidates as catalysts for real life water purification analyses as they facilitate the treatment of both organic and inorganic water pollutants.
- Full Text:
- Date Issued: 2019
Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines
- Martynov, Alexander G, Mack, John, May, Aviwe K, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
Evaluation of the photosensitizing properties of zinc and indium tetra cinnamic acid phthalocyanines linked to magnetic nanoparticles on human breast adenocarcinoma cells
- Matlou, Gauta G, Oluwole, David O, Nyokong, Tebello
- Authors: Matlou, Gauta G , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187582 , vital:44673 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.054"
- Description: This work reports on the synthesis, photophysico-chemical properties and photodynamic therapy activity of novel zinc (1) and indium (2) tetra substituted cinnamic acid phthalocyanine (Pc) complexes linked to amino functionalized magnetic nanoparticles (AMNPs) through an amide bond. Asymmetric ZnPc complex (3) showed better triplet and singlet oxygen quantum yields as compared to its symmetrical analogues (1 and 2). The AMNPs (1-AMNPs and 2-AMNPs) linked conjugates depicted increased triplet quantum yields in comparison to their unlinked Pcs, while 3-AMNPs showed a decrease compared to 3. The complexes showed increased in-vitro photo-cytotoxic effect against MCF-7 cells with an increase in drug concentration. At 80 µg/mL, 2 and 3, 2-AMNPs and 3-AMNPs with higher singlet oxygen quantum yields caused more cytotoxic effect on the cancer cells in the presence of light as compared to 1 and 1-AMNPs respectively.
- Full Text:
- Date Issued: 2019
- Authors: Matlou, Gauta G , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187582 , vital:44673 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.054"
- Description: This work reports on the synthesis, photophysico-chemical properties and photodynamic therapy activity of novel zinc (1) and indium (2) tetra substituted cinnamic acid phthalocyanine (Pc) complexes linked to amino functionalized magnetic nanoparticles (AMNPs) through an amide bond. Asymmetric ZnPc complex (3) showed better triplet and singlet oxygen quantum yields as compared to its symmetrical analogues (1 and 2). The AMNPs (1-AMNPs and 2-AMNPs) linked conjugates depicted increased triplet quantum yields in comparison to their unlinked Pcs, while 3-AMNPs showed a decrease compared to 3. The complexes showed increased in-vitro photo-cytotoxic effect against MCF-7 cells with an increase in drug concentration. At 80 µg/mL, 2 and 3, 2-AMNPs and 3-AMNPs with higher singlet oxygen quantum yields caused more cytotoxic effect on the cancer cells in the presence of light as compared to 1 and 1-AMNPs respectively.
- Full Text:
- Date Issued: 2019
Effect of symmetry and metal nanoparticles on the photophysicochemical and photodynamic therapy properties of cinnamic acid zinc phthalocyanine
- Matlou, Gauta G, Managa, Muthumuni, Nyokong, Tebello
- Authors: Matlou, Gauta G , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187026 , vital:44557 , xlink:href="https://doi.org/10.1016/j.saa.2019.02.005"
- Description: In this study, a novel asymmetric cinnamic acid zinc phthalocyanine (ZnPc, 1) containing three tert-butyl substituents is reported. The asymmetric ZnPc (1) is further linked to amino functionalized magnetic nanoparticles (AMNPs) (1-AMNPs) and to cysteine functionalized silver nanoparticles (cys-AgNPs) (1-cys-AgNPs) through an amide bond. 1-AMNPs and 1-cys-AgNPs improved the triplet and singlet oxygen quantum yields of complex 1, this was also observed with the previously reported 2-AMNPs when compared to 2 while 3-AMNPs yielded an unexpected decrease in triplet quantum yield as compared to 3. The silver nanoparticles (1-cys-AgNPs) had a better effect on improving the singlet oxygen quantum yield of complex 1 than the magnetic nanoparticles (1- AMNPs). The Pcs and conjugates recorded low cell cytotoxicity in the dark and high photocytotoxicity against MCF-7 cells in-vitro. MCF-7 cell viabilities of less than 50% were recorded at 80 μg/mL making the Pcs and conjugates under study potential candidates for use as photosensitizers in cancer therapy.
- Full Text:
- Date Issued: 2019
- Authors: Matlou, Gauta G , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187026 , vital:44557 , xlink:href="https://doi.org/10.1016/j.saa.2019.02.005"
- Description: In this study, a novel asymmetric cinnamic acid zinc phthalocyanine (ZnPc, 1) containing three tert-butyl substituents is reported. The asymmetric ZnPc (1) is further linked to amino functionalized magnetic nanoparticles (AMNPs) (1-AMNPs) and to cysteine functionalized silver nanoparticles (cys-AgNPs) (1-cys-AgNPs) through an amide bond. 1-AMNPs and 1-cys-AgNPs improved the triplet and singlet oxygen quantum yields of complex 1, this was also observed with the previously reported 2-AMNPs when compared to 2 while 3-AMNPs yielded an unexpected decrease in triplet quantum yield as compared to 3. The silver nanoparticles (1-cys-AgNPs) had a better effect on improving the singlet oxygen quantum yield of complex 1 than the magnetic nanoparticles (1- AMNPs). The Pcs and conjugates recorded low cell cytotoxicity in the dark and high photocytotoxicity against MCF-7 cells in-vitro. MCF-7 cell viabilities of less than 50% were recorded at 80 μg/mL making the Pcs and conjugates under study potential candidates for use as photosensitizers in cancer therapy.
- Full Text:
- Date Issued: 2019