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.
- Full Text:
- Date Issued: 2021
- 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.
- Full Text:
- Date Issued: 2021
The antibacterial and antifungal properties of neutral, octacationic and hexadecacationic Zn phthalocyanines when conjugated to silver nanoparticles
- Mapukata, Sibusisiwe, Sen, Pinar, Osifeko, Olawale L, Nyokong, Tebello
- Authors: Mapukata, Sibusisiwe , Sen, Pinar , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185667 , vital:44408 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102361"
- Description: The syntheses and characterization of novel octacationic and hexadecacationic Pcs is reported. With the aim of enhancing singlet oxygen generation efficiencies and hence antimicrobial activities, these Pcs (including their neutral counterpart) are conjugated to Ag nanoparticles (AgNPs). The obtained results show that the conjugate composed of the neutral Pc has a higher loading of Pcs as well as a greater singlet oxygen quantum yield enhancement (in the presence of AgNPs) in DMSO. The antimicrobial efficiencies of the Pcs and their conjugates were evaluated and compared on S. aureus, E. coli and C. albicans. The cationic Pcs possess better activity than the neutral Pc against all the microorganisms with the hexadecacationic Pc being the best. This work therefore demonstrates that increase in the number of cationic charges on the reported Pcs results in enhanced antimicrobial activities, which is maintained even when conjugated to Ag nanoparticles. The high activity and lack of selectivity of the cationic Pcs when conjugated to Ag NPs against different microorganisms make them good candidates for real life antimicrobial treatments.
- Full Text:
- Date Issued: 2021
- Authors: Mapukata, Sibusisiwe , Sen, Pinar , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185667 , vital:44408 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102361"
- Description: The syntheses and characterization of novel octacationic and hexadecacationic Pcs is reported. With the aim of enhancing singlet oxygen generation efficiencies and hence antimicrobial activities, these Pcs (including their neutral counterpart) are conjugated to Ag nanoparticles (AgNPs). The obtained results show that the conjugate composed of the neutral Pc has a higher loading of Pcs as well as a greater singlet oxygen quantum yield enhancement (in the presence of AgNPs) in DMSO. The antimicrobial efficiencies of the Pcs and their conjugates were evaluated and compared on S. aureus, E. coli and C. albicans. The cationic Pcs possess better activity than the neutral Pc against all the microorganisms with the hexadecacationic Pc being the best. This work therefore demonstrates that increase in the number of cationic charges on the reported Pcs results in enhanced antimicrobial activities, which is maintained even when conjugated to Ag nanoparticles. The high activity and lack of selectivity of the cationic Pcs when conjugated to Ag NPs against different microorganisms make them good candidates for real life antimicrobial treatments.
- Full Text:
- Date Issued: 2021
The antibody assisted detection of HER2 on a cobalt porphyrin binuclear framework and gold functionalized graphene quantum dots modified electrode
- Centane, Sixole, Nyokong, Tebello
- Authors: Centane, Sixole , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185931 , vital:44449 , xlink:href="https://doi.org/10.1016/j.jelechem.2020.114908"
- Description: In this work a novel simple, inexpensive and highly sensitive approach for the antibody assisted detection of the human epidermal growth factor receptor 2 (HER2) is presented. Three sensors using carboxylic group containing gold functionalized graphene quantum dots (SNGQDs@AuNPs), CoP-BNF (cobalt porphyrin binuclear framework) and CoP-BNF/SNGQDs@AuNPs (the conjugate) nanocomposites on a GCE were designed. The sensors were fabricated by covalent immobilization of the antibody to the GCE via an amide bond. The modified GCE was characterized using cyclic voltammetry and impedance spectroscopy. The performance of the sensors was assessed using electrochemical impedance spectroscopy. The selective recognition of the antibody towards HER2 on the electrode led to an increase of the electron transfer resistance (Rct). The different modified electrodes had low detection limit values: 0.0327 ng/mL, 0.0454 ng/mL and 0.1072 ng/mL towards the detection of HER2. The sensors showed good stability and reproducibility. The sensors showed promising potential in clinical applicability, in the detection of HER2 protein in human serum.
- Full Text:
- Date Issued: 2021
- Authors: Centane, Sixole , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185931 , vital:44449 , xlink:href="https://doi.org/10.1016/j.jelechem.2020.114908"
- Description: In this work a novel simple, inexpensive and highly sensitive approach for the antibody assisted detection of the human epidermal growth factor receptor 2 (HER2) is presented. Three sensors using carboxylic group containing gold functionalized graphene quantum dots (SNGQDs@AuNPs), CoP-BNF (cobalt porphyrin binuclear framework) and CoP-BNF/SNGQDs@AuNPs (the conjugate) nanocomposites on a GCE were designed. The sensors were fabricated by covalent immobilization of the antibody to the GCE via an amide bond. The modified GCE was characterized using cyclic voltammetry and impedance spectroscopy. The performance of the sensors was assessed using electrochemical impedance spectroscopy. The selective recognition of the antibody towards HER2 on the electrode led to an increase of the electron transfer resistance (Rct). The different modified electrodes had low detection limit values: 0.0327 ng/mL, 0.0454 ng/mL and 0.1072 ng/mL towards the detection of HER2. The sensors showed good stability and reproducibility. The sensors showed promising potential in clinical applicability, in the detection of HER2 protein in human serum.
- Full Text:
- Date Issued: 2021
The effects of the composition and structure of quantum dots combined with cobalt phthalocyanine and an aptamer on the electrochemical detection of prostate specific antigen
- Nxele, Siphesihle R, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185002 , vital:44315 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109407"
- Description: The ability to functionalize and modify graphene-based quantum dots has also allowed for the tuning of their activity in different applications. A comparative study is carried out in this work where a prostate specific aptamer (PSA) and cobalt phthalocyanine molecule are combined with graphene quantum dots (GQDs), nitrogen doped graphene quantum dots (NGQDs) and graphitic carbon nitride quantum dots (gCNQDs) in order to determine the effects of quantum dots type (and therefore composition) on the electrocatalytic ability of the sensor to detect the analyte of interest. For the detection of prostate-specific antigen, electrochemical impedance spectroscopy (EIS) is employed to determine detection limits as well as sensitivity and selectivity of the aptasensors. Results showed a good performance of all sensors fabricated with the NGQDs based aptasensor showing the best performance with a detection limit of 1.54 pM in EIS as well as negligible interference in mixed samples. This electrode was further verified in spiked human serum samples and good recovery and low detection limits were determined, putting this aptasensor in good stead as a reliable, efficient PSA aptasensor.
- Full Text:
- Date Issued: 2021
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185002 , vital:44315 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109407"
- Description: The ability to functionalize and modify graphene-based quantum dots has also allowed for the tuning of their activity in different applications. A comparative study is carried out in this work where a prostate specific aptamer (PSA) and cobalt phthalocyanine molecule are combined with graphene quantum dots (GQDs), nitrogen doped graphene quantum dots (NGQDs) and graphitic carbon nitride quantum dots (gCNQDs) in order to determine the effects of quantum dots type (and therefore composition) on the electrocatalytic ability of the sensor to detect the analyte of interest. For the detection of prostate-specific antigen, electrochemical impedance spectroscopy (EIS) is employed to determine detection limits as well as sensitivity and selectivity of the aptasensors. Results showed a good performance of all sensors fabricated with the NGQDs based aptasensor showing the best performance with a detection limit of 1.54 pM in EIS as well as negligible interference in mixed samples. This electrode was further verified in spiked human serum samples and good recovery and low detection limits were determined, putting this aptasensor in good stead as a reliable, efficient PSA aptasensor.
- Full Text:
- Date Issued: 2021
The electrochemical detection of prostate specific antigen on glassy carbon electrode modified with combinations of graphene quantum dots, cobalt phthalocyanine and an aptamer
- Nxele, Siphesihle R, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185013 , vital:44316 , xlink:href="https://doi.org/10.1016/j.jinorgbio.2021.111462"
- Description: Herein, a novel aptasensor is developed for the electrochemical detection of prostate specific antigen (PSA) on electrode surfaces modified using various combinations of a Cobalt phthalocyanine (CoPc), an aptamer and graphene quantum dots (GQDs). Electrochemical impedance spectroscopy (EIS) as well as differential pulse voltammetry (DPV) are employed for the detection of PSA. In both analytical techniques, linear calibration curves were observed at a concentration range of 1.2–2.0 pM. The glassy carbon electrode where CoPc and GQDs are placed on the electrode when non-covalently linked followed by addition of the aptamer (GQDs-CoPc(ππ)-aptamer (sequential)) showed the best performance with a limit of detection (LoD) as low as 0.66 pM when using DPV. The detection limits were much lower than the dangerous levels reported for PSA in males tested for prostate cancer. This electrode showed selectivity for PSA in the presence of bovine serum albumin, glucose and L-cysteine. The aptasensor showed good stability, reproducibility and repeatability, deeming it a promising early detection device for prostate cancer.
- Full Text:
- Date Issued: 2021
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185013 , vital:44316 , xlink:href="https://doi.org/10.1016/j.jinorgbio.2021.111462"
- Description: Herein, a novel aptasensor is developed for the electrochemical detection of prostate specific antigen (PSA) on electrode surfaces modified using various combinations of a Cobalt phthalocyanine (CoPc), an aptamer and graphene quantum dots (GQDs). Electrochemical impedance spectroscopy (EIS) as well as differential pulse voltammetry (DPV) are employed for the detection of PSA. In both analytical techniques, linear calibration curves were observed at a concentration range of 1.2–2.0 pM. The glassy carbon electrode where CoPc and GQDs are placed on the electrode when non-covalently linked followed by addition of the aptamer (GQDs-CoPc(ππ)-aptamer (sequential)) showed the best performance with a limit of detection (LoD) as low as 0.66 pM when using DPV. The detection limits were much lower than the dangerous levels reported for PSA in males tested for prostate cancer. This electrode showed selectivity for PSA in the presence of bovine serum albumin, glucose and L-cysteine. The aptasensor showed good stability, reproducibility and repeatability, deeming it a promising early detection device for prostate cancer.
- Full Text:
- Date Issued: 2021
The improved antibacterial efficiency of a zinc phthalocyanine when embedded on silver nanoparticle modified silica nanofibers
- Mapukata, Sivuyisiwe, Britton, Jonathan, Osifeko, Olawale L, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Britton, Jonathan , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185784 , vital:44423 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102100"
- Description: This work reports on the fabrication and modification of electrospun polymer free silica nanofibers (SiO2 NFs) with the aim of creating heterogeneous antibacterial catalysts. The optical and photophysical properties of the obtained NFs i.e. bare SiO2, Ag-SiO2, Pc-SiO2 and Pc@Ag-SiO2 NFs (Pc = phthalocyanine) were compared and reported. The singlet oxygen quantum yields of the Pc-SiO2 and Pc@Ag-SiO2 NFs were also quantified and found to be 0.08 and 0.12, respectively, in water. All the modified SiO2 NFs were found to possess photoactivity against S. aureus with the most effective being the Pc@Ag-SiO2 NFs due to the synergy between the Pc and Ag nanoparticles. The bare SiO2 NFs do not exhibit any antibacterial activity while the Ag-SiO2 and Pc@Ag-SiO2 NFs were found to also exhibit dark toxicity. The generated photocatalysts are attractive because they are active against bacteria and they are easily retrievable post-application. The nanocatalysts reported herein are therefore feasible candidates for real-life antibacterial applications.
- Full Text:
- Date Issued: 2021
- Authors: Mapukata, Sivuyisiwe , Britton, Jonathan , Osifeko, Olawale L , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185784 , vital:44423 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102100"
- Description: This work reports on the fabrication and modification of electrospun polymer free silica nanofibers (SiO2 NFs) with the aim of creating heterogeneous antibacterial catalysts. The optical and photophysical properties of the obtained NFs i.e. bare SiO2, Ag-SiO2, Pc-SiO2 and Pc@Ag-SiO2 NFs (Pc = phthalocyanine) were compared and reported. The singlet oxygen quantum yields of the Pc-SiO2 and Pc@Ag-SiO2 NFs were also quantified and found to be 0.08 and 0.12, respectively, in water. All the modified SiO2 NFs were found to possess photoactivity against S. aureus with the most effective being the Pc@Ag-SiO2 NFs due to the synergy between the Pc and Ag nanoparticles. The bare SiO2 NFs do not exhibit any antibacterial activity while the Ag-SiO2 and Pc@Ag-SiO2 NFs were found to also exhibit dark toxicity. The generated photocatalysts are attractive because they are active against bacteria and they are easily retrievable post-application. The nanocatalysts reported herein are therefore feasible candidates for real-life antibacterial applications.
- Full Text:
- Date Issued: 2021
The photodynamic activities of the gold nanoparticle conjugates of phosphorus (V) and gallium (III) A3 meso-triarylcorroles
- Soy, Rodah C, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
The photophysicochemical properties and photodynamic therapy activity of Schiff base substituted phthalocyanines doped into silica nanoparticles and conjugated to folic acid
- Magadla, Aviwe, Babu, Balaji, Sen, Pinar, Nyokong, Tebello
- Authors: Magadla, Aviwe , Babu, Balaji , Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185407 , vital:44384 , xlink:href="https://doi.org/10.1016/j.poly.2021.115227"
- Description: This work explores the synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetrakis [N,N’–bis (4-(diethylamino)benzylidene) amino)propan-2-yl)oxy) phthalocyaninato] Zn (II) (3) and tetra-phenoxy N,N-dimethyl-4-((methylimino) Zn (II) (4) when the encapsulated into silica nanoparticles (SiNPs) followed by conjugation of folic acid (FA). The synthesised complexes and their doped analogues are examined for their PDT activity using MCF-7 cells. All the complexes showed dark toxicity that is >80%. The folic acid conjugates, MPc@SiNPs-FA showed greater photocytoxicity against MCF-7 cells upon irradiation with laser light.
- Full Text:
- Date Issued: 2021
- Authors: Magadla, Aviwe , Babu, Balaji , Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185407 , vital:44384 , xlink:href="https://doi.org/10.1016/j.poly.2021.115227"
- Description: This work explores the synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetrakis [N,N’–bis (4-(diethylamino)benzylidene) amino)propan-2-yl)oxy) phthalocyaninato] Zn (II) (3) and tetra-phenoxy N,N-dimethyl-4-((methylimino) Zn (II) (4) when the encapsulated into silica nanoparticles (SiNPs) followed by conjugation of folic acid (FA). The synthesised complexes and their doped analogues are examined for their PDT activity using MCF-7 cells. All the complexes showed dark toxicity that is >80%. The folic acid conjugates, MPc@SiNPs-FA showed greater photocytoxicity against MCF-7 cells upon irradiation with laser light.
- Full Text:
- Date Issued: 2021
Thien-2-yl substituted chlorins as photosensitizers for photodynamic therapy and photodynamic antimicrobial chemotherapy
- Babu, Balaji, Sindelo, Azole, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
Turn-on detection of cysteine by a donor-acceptor type quinoline fluorophore: Exploring the sensing strategy and performance in bioimaging
- Muthusamy, Selvaraj, Zhao, Long, Rajalakshmi, Kanagaraj, Zhu, Dongwei, Soy, Rodah, Mack, John, Nyokong, Tebello, Wang, Shengjun, Lee, Kang-Bong, Zhu, Weihua
- Authors: Muthusamy, Selvaraj , Zhao, Long , Rajalakshmi, Kanagaraj , Zhu, Dongwei , Soy, Rodah , Mack, John , Nyokong, Tebello , Wang, Shengjun , Lee, Kang-Bong , Zhu, Weihua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185644 , vital:44406 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109556"
- Description: Tracking the biothiol cysteine (Cys) in living systems is a significant responsibility to balance the redox environment and oxidative stress. A quinoline-7-nitro-1,2,3-benzoxadiazole (Q-NBD) fluorophore has been synthesized and characterized towards examination of Cys. The probe forms a quinoline-substituted phenol (Q-Ph-OH) after thiolysis of the NBD ether bond, leading to an increase of fluorescence at green channel. The turn-on sensing mechanism originates from the change in intramolecular charge transfer (ICT-OFF) along with an aggregation-induced emission (AIE) as suggested by spectroscopy measurements in solutions, time-dependent density-functional theory (TD-DFT) calculations and 1H NMR titration examination. Importantly, Q-NBD exhibited great sensitivity with a low limit of detection value of 89.5 nM and remarkable selectivity in various biothiols towards Cys. The sensor probe was successfully used for detecting both endogenous and exogenous Cys in PC3 living cells and spiked Cys in human urine samples.
- Full Text:
- Date Issued: 2021
- Authors: Muthusamy, Selvaraj , Zhao, Long , Rajalakshmi, Kanagaraj , Zhu, Dongwei , Soy, Rodah , Mack, John , Nyokong, Tebello , Wang, Shengjun , Lee, Kang-Bong , Zhu, Weihua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185644 , vital:44406 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109556"
- Description: Tracking the biothiol cysteine (Cys) in living systems is a significant responsibility to balance the redox environment and oxidative stress. A quinoline-7-nitro-1,2,3-benzoxadiazole (Q-NBD) fluorophore has been synthesized and characterized towards examination of Cys. The probe forms a quinoline-substituted phenol (Q-Ph-OH) after thiolysis of the NBD ether bond, leading to an increase of fluorescence at green channel. The turn-on sensing mechanism originates from the change in intramolecular charge transfer (ICT-OFF) along with an aggregation-induced emission (AIE) as suggested by spectroscopy measurements in solutions, time-dependent density-functional theory (TD-DFT) calculations and 1H NMR titration examination. Importantly, Q-NBD exhibited great sensitivity with a low limit of detection value of 89.5 nM and remarkable selectivity in various biothiols towards Cys. The sensor probe was successfully used for detecting both endogenous and exogenous Cys in PC3 living cells and spiked Cys in human urine samples.
- Full Text:
- Date Issued: 2021
Visible light responsive TiO2-graphene oxide nanosheets-Zn phthalocyanine ternary heterojunction assisted photoelectrocatalytic degradation of Orange G
- Nwahara, Nnamdi, Adeniyi, Omotayo, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Adeniyi, Omotayo , Mashazi, Philani N , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185446 , vital:44387 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113291"
- Description: Herein, we report on the successful fabrication of a visible light-responsive TiO2 - graphene oxide nanosheets – Zn phthalocyanine (TiO2@GONS@ZnPc) ternary structure for the photoelectrochemical degradation of Orange G azo dye. The characterization of TiO2@GONS@ZnPc composite was achieved using various spectroscopic and microscopic techniques. Our results show that the TiO2@GONS@ZnPc surface hybrid heterojunction promotes charge separation and electron migration, significantly improving the degradation efficiency with an applied potential. For the first time, we show the existence of a non-radical activation route for persulfate (PS) using such π electron-rich ZnPc-GONS catalysts. The degradation kinetics were found to follow pseudo first order kinetics. Electron spin resonance analyses suggested that neither hydroxyl radicals nor sulfate radicals were produced therein, and therefore were not responsible for the persulfate-driven oxidation of the OG dye. These findings suggest that both which GONS and ZnPc play a critical role in mediating the eventual charge transfer mediated PS activation. The results illustrate the remarkable capacity of the TiO2@GONS@ZnPc composite to rapidly degrade Orange G by a coupled TiO2@GONS@ZnPc-persulfate system.
- Full Text:
- Date Issued: 2021
- Authors: Nwahara, Nnamdi , Adeniyi, Omotayo , Mashazi, Philani N , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185446 , vital:44387 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113291"
- Description: Herein, we report on the successful fabrication of a visible light-responsive TiO2 - graphene oxide nanosheets – Zn phthalocyanine (TiO2@GONS@ZnPc) ternary structure for the photoelectrochemical degradation of Orange G azo dye. The characterization of TiO2@GONS@ZnPc composite was achieved using various spectroscopic and microscopic techniques. Our results show that the TiO2@GONS@ZnPc surface hybrid heterojunction promotes charge separation and electron migration, significantly improving the degradation efficiency with an applied potential. For the first time, we show the existence of a non-radical activation route for persulfate (PS) using such π electron-rich ZnPc-GONS catalysts. The degradation kinetics were found to follow pseudo first order kinetics. Electron spin resonance analyses suggested that neither hydroxyl radicals nor sulfate radicals were produced therein, and therefore were not responsible for the persulfate-driven oxidation of the OG dye. These findings suggest that both which GONS and ZnPc play a critical role in mediating the eventual charge transfer mediated PS activation. The results illustrate the remarkable capacity of the TiO2@GONS@ZnPc composite to rapidly degrade Orange G by a coupled TiO2@GONS@ZnPc-persulfate system.
- Full Text:
- Date Issued: 2021
The modulation of the photophysical and photodynamic therapy activities of a phthalocyanine by detonation nanodiamonds: Comparison with graphene quantum dots and carbon nanodots
- Matshitse, Refilwe, Managa, Muthumuni, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Managa, Muthumuni , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186690 , vital:44525 , xlink:href="https://doi.org/10.1016/j.diamond.2019.107617"
- Description: A positively charged phthalocyanine (2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ)) was non-covalently linked to carbon based nanoparticles: detonation nanodiamonds (DNDs), carbon dots (CDs) and graphene quantum dots (GQDs) to form nanosembles of DNDs-ZnTPPcQ, GQDs-ZnTPPcQ and CDs-ZnTPPcQ, respectively. Irrespective of its small size and the least number of Pcs (41.67 μg loading per milligram of DNDs), DNDs-ZnTPPcQ gave the highest singlet oxygen quantum yield (0.62) in dimethyl sulfoxide compared to the rest of the conjugates. This resulted in superior PDT activity against MCF7 breast cancer lines, with the lowest cell viability of 28% compared to ZnTPPcQ-CDs and ZnTPPcQ-GQDs at 30.1 ± 0.02% and 31.4 ± 0.23%, respectively.
- Full Text:
- Date Issued: 2020
- Authors: Matshitse, Refilwe , Managa, Muthumuni , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186690 , vital:44525 , xlink:href="https://doi.org/10.1016/j.diamond.2019.107617"
- Description: A positively charged phthalocyanine (2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ)) was non-covalently linked to carbon based nanoparticles: detonation nanodiamonds (DNDs), carbon dots (CDs) and graphene quantum dots (GQDs) to form nanosembles of DNDs-ZnTPPcQ, GQDs-ZnTPPcQ and CDs-ZnTPPcQ, respectively. Irrespective of its small size and the least number of Pcs (41.67 μg loading per milligram of DNDs), DNDs-ZnTPPcQ gave the highest singlet oxygen quantum yield (0.62) in dimethyl sulfoxide compared to the rest of the conjugates. This resulted in superior PDT activity against MCF7 breast cancer lines, with the lowest cell viability of 28% compared to ZnTPPcQ-CDs and ZnTPPcQ-GQDs at 30.1 ± 0.02% and 31.4 ± 0.23%, respectively.
- Full Text:
- Date Issued: 2020
Electrocatalytic activity of a push pull Co (II) phthalocyanine in the presence of graphitic carbon nitride quantum dots
- Nxele, Siphesihle R, Oluwole, David O, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186746 , vital:44530 , xlink:href="https://doi.org/10.1016/j.electacta.2019.134978"
- Description: This work reports for the first time on the use of a conjugate of graphitic carbon nitride quantum dots (gCNQDs) with a push-pull asymmetrical cobalt phthalocyanine (CoPc) for electrochemical sensing. The nanocomposite is immobilized on a glassy carbon electrode (GCE) surface for the use in l-cysteine electrocatalysis. The nanocomposites were characterized using techniques such as X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Raman spectroscopy and electrochemical methods. The nanocomposites were immobilized by the drop-dry method, sequentially or when premixed in solution. Good electrocatalytic oxidation of l-cysteine was observed, especially by the sequentially modified electrode surface, with the CoPc on top of gCNQDs. The sensitivity was determined as 3.5 μA.mM-1 and the limit of detection (LoD) as 101.3 μM for GCE-gCNQDs, 0.65 μA.mM-1 and 0.96 μM for GCE-CoPc, 23.41 μA.mM-1 and 0.41 μM for gCNQDs-CoPc (premixed) and 100.5 μA.mM-1 and 0.02 μM for gCNQDs-CoPc (sequential). The electrode surfaces also showed high stability by continuous cyclization.
- Full Text:
- Date Issued: 2019
- Authors: Nxele, Siphesihle R , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186746 , vital:44530 , xlink:href="https://doi.org/10.1016/j.electacta.2019.134978"
- Description: This work reports for the first time on the use of a conjugate of graphitic carbon nitride quantum dots (gCNQDs) with a push-pull asymmetrical cobalt phthalocyanine (CoPc) for electrochemical sensing. The nanocomposite is immobilized on a glassy carbon electrode (GCE) surface for the use in l-cysteine electrocatalysis. The nanocomposites were characterized using techniques such as X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Raman spectroscopy and electrochemical methods. The nanocomposites were immobilized by the drop-dry method, sequentially or when premixed in solution. Good electrocatalytic oxidation of l-cysteine was observed, especially by the sequentially modified electrode surface, with the CoPc on top of gCNQDs. The sensitivity was determined as 3.5 μA.mM-1 and the limit of detection (LoD) as 101.3 μM for GCE-gCNQDs, 0.65 μA.mM-1 and 0.96 μM for GCE-CoPc, 23.41 μA.mM-1 and 0.41 μM for gCNQDs-CoPc (premixed) and 100.5 μA.mM-1 and 0.02 μM for gCNQDs-CoPc (sequential). The electrode surfaces also showed high stability by continuous cyclization.
- Full Text:
- Date Issued: 2019
Photophysicochemical properties of nanoconjugates of zinc (II) 2 (3)-mono-2-(4-oxy) phenoxy) acetic acid phthalocyanine with cysteamine capped silver and silver–gold nanoparticles
- Oluwole, David O, Prinsloo, Earl, Nyokong, Tebello
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188552 , vital:44764 , xlink:href="https://doi.org/10.1016/j.poly.2016.09.034"
- Description: A novel asymmetrical zinc(II) 2(3)-mono-2-(4-oxy)phenoxy)acetic acid phthalocyanine (complex 1) was synthesized and subsequently linked to cysteamine capped silver (AgNPs) and silver–gold (AgAuNPs) nanoparticles (NPs) via amide bonds. The photophysicochemical properties and in vitro photodynamic therapy activity of complex 1 and its nanoconjugates were investigated. The nanoconjugates showed improved photophysical properties compared to complex 1 alone. The fluorescence, triplet and singlet quantum yields of complex 1 were found to be 20%, 48%, and 43% respectively. Complex 1 showed in vitro dark cytotoxicity, but the dark toxicity was reduced for the combination of complex 1 with AgAuNPs, this combination also gave the best photodynamic therapy activity when compared to complex 1 and its conjugate with AgNPs without AuNPs.
- Full Text:
- Date Issued: 2016
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188552 , vital:44764 , xlink:href="https://doi.org/10.1016/j.poly.2016.09.034"
- Description: A novel asymmetrical zinc(II) 2(3)-mono-2-(4-oxy)phenoxy)acetic acid phthalocyanine (complex 1) was synthesized and subsequently linked to cysteamine capped silver (AgNPs) and silver–gold (AgAuNPs) nanoparticles (NPs) via amide bonds. The photophysicochemical properties and in vitro photodynamic therapy activity of complex 1 and its nanoconjugates were investigated. The nanoconjugates showed improved photophysical properties compared to complex 1 alone. The fluorescence, triplet and singlet quantum yields of complex 1 were found to be 20%, 48%, and 43% respectively. Complex 1 showed in vitro dark cytotoxicity, but the dark toxicity was reduced for the combination of complex 1 with AgAuNPs, this combination also gave the best photodynamic therapy activity when compared to complex 1 and its conjugate with AgNPs without AuNPs.
- Full Text:
- Date Issued: 2016