Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Mwanza, Daniel, Mvango, Sindisiwe, Khene, Samson M, Nyokong, Tebello, Mashazi, Philani N
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
Fluorescence behaviour of supramolecular hybrids containing graphene quantum dots and pyrene-derivatized phthalocyanines and porphyrins
- Achadu, Ojodomo John, Managa, Muthumuni, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
- Full Text:
- Date Issued: 2017
Graphene quantum dots anchored onto mercaptopyridine-substituted zinc phthalocyanine-Au@ Ag nanoparticle hybrid: Application as fluorescence “off-on-off” sensor for Hg2+ and biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
- Full Text:
- Date Issued: 2017
Graphene quantum dots coordinated to mercaptopyridine-substituted phthalocyanines: Characterization and application as fluorescence “turn ON” nanoprobes
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
- Date Issued: 2017
Graphene quantum dots decorated with maleimide and zinc tetramaleimido-phthalocyanine: Application in the design of “OFF-ON” fluorescence sensors for biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
- Date Issued: 2017
Halogen substituted A2B type Co (III) triarylcorroles
- Niu, Yingjie, Li, Minzhi, Zhang, Qianchong, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
Highly efficient CCl bond cleavage and unprecedented CC bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
- Liang, Xu, Huang, Tingting, Li, Minzhi, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Nwaji, Njemuwa, Oluwole, David O, Mack, John, Louzada, Marcel, Khene, Samson M, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles
- Dube, Edith, Nwaji, Njemuwa, Oluwole, David O, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Laser induced photodegradation of Orange G using phthalocyanine–cobalt ferrite magnetic nanoparticle conjugates electrospun in polystyrene nanofibers
- Mapukata, Sivuyisiwe, Chindeka, Francis, Sekhosana, Kutloano E, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Chindeka, Francis , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188617 , vital:44769 , xlink:href="https://doi.org/10.1016/j.mcat.2017.06.028"
- Description: Conjugates of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) and zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) with amine and carboxyl functionalised cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs), respectively were electrospun into polystyrene (PS) fibers. The resulting composites; ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on their photophysical properties and photocatalytic efficiencies in degrading Orange G (OG) using laser as the photoexcitation source. The photocatalytic efficiencies of ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on them having different lengths in the linkage chains between the Pcs and CoFe2O4 MNPs and different sizes. Covalent linkage of the Pcs to the CoFe2O4 MNPs enhanced the singlet oxygen and reactive oxygen species (ROS) production of the Pcs and CoFe2O4, respectively hence ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were found to be more effective photocatalysts than their respective Pcs and CoFe2O4 MNPs. Moreover, the kinetic analyses of the photodecomposition of OG showed that the degradation was in agreement with both pseudo-first order kinetics and followed the Langmuir–Hinshelwood model.
- Full Text:
- Date Issued: 2017
- Authors: Mapukata, Sivuyisiwe , Chindeka, Francis , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188617 , vital:44769 , xlink:href="https://doi.org/10.1016/j.mcat.2017.06.028"
- Description: Conjugates of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) and zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) with amine and carboxyl functionalised cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs), respectively were electrospun into polystyrene (PS) fibers. The resulting composites; ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on their photophysical properties and photocatalytic efficiencies in degrading Orange G (OG) using laser as the photoexcitation source. The photocatalytic efficiencies of ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on them having different lengths in the linkage chains between the Pcs and CoFe2O4 MNPs and different sizes. Covalent linkage of the Pcs to the CoFe2O4 MNPs enhanced the singlet oxygen and reactive oxygen species (ROS) production of the Pcs and CoFe2O4, respectively hence ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were found to be more effective photocatalysts than their respective Pcs and CoFe2O4 MNPs. Moreover, the kinetic analyses of the photodecomposition of OG showed that the degradation was in agreement with both pseudo-first order kinetics and followed the Langmuir–Hinshelwood model.
- Full Text:
- Date Issued: 2017
Nanocomposites of sulphur-nitrogen co-doped graphene oxide nanosheets and cobalt mono carboxyphenoxy phthalocyanines for facile electrocatalysis
- Shumba, Munyaradzi, Centane, Sixolile, Chindeka, Francis, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Centane, Sixolile , Chindeka, Francis , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239665 , vital:50753 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.03.006"
- Description: Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode.
- Full Text:
- Date Issued: 2017
- Authors: Shumba, Munyaradzi , Centane, Sixolile , Chindeka, Francis , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239665 , vital:50753 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.03.006"
- Description: Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode.
- Full Text:
- Date Issued: 2017
Nanosecond optical nonlinearities in low symmetry phthalocyanine nanoconjugates studied using the Z-scan technique
- Nwaji, Njemuwa, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188172 , vital:44729 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.08.053"
- Description: In this study, the photophysical, and nonlinear optical limiting properties of low symmetry tris[(4-benzo[d] thiazol-2-ylphenoxy)-2-phenoxyl acetic acid phthalocyaninato] zinc (II) (3) conjugated to metallic nanoparticles have been investigated using open aperture Z-scan techniques at 532 nm. The nonlinear optical response demonstrated that the studied complex and the nanoconjugates exhibits higher excited state absorption cross-section resulting from S1 and T1 compared to ground state absorption. Enhanced optical limiting performance was observed when the complex was conjugated to nanoparticles with 3SA-AuNPs showing the best optical limiting threshold of 0.39 J/cm2.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188172 , vital:44729 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.08.053"
- Description: In this study, the photophysical, and nonlinear optical limiting properties of low symmetry tris[(4-benzo[d] thiazol-2-ylphenoxy)-2-phenoxyl acetic acid phthalocyaninato] zinc (II) (3) conjugated to metallic nanoparticles have been investigated using open aperture Z-scan techniques at 532 nm. The nonlinear optical response demonstrated that the studied complex and the nanoconjugates exhibits higher excited state absorption cross-section resulting from S1 and T1 compared to ground state absorption. Enhanced optical limiting performance was observed when the complex was conjugated to nanoparticles with 3SA-AuNPs showing the best optical limiting threshold of 0.39 J/cm2.
- Full Text:
- Date Issued: 2017
Nonlinear optical dynamics of benzothiazole derivatized phthalocyanines in solution, thin films and when conjugated to nanoparticles
- Nwaji, Njemuwa, Jones, Benjamin, Mack, John, Oluwole, David O, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Jones, Benjamin , Mack, John , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190426 , vital:44993 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.05.042"
- Description: Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Jones, Benjamin , Mack, John , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190426 , vital:44993 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.05.042"
- Description: Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.
- Full Text:
- Date Issued: 2017
Photophysical behavior and photodynamic therapy activity of conjugates of zinc monocarboxyphenoxy phthalocyanine with human serum albumin and chitosan
- Oluwole, David O, Prinsloo, Earl, Nyokong, Tebello
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188497 , vital:44759 , xlink:href="https://doi.org/10.1016/j.saa.2016.09.032"
- Description: Zincmonocarboxyphenoxy phthalocyanine (ZnMCPPc) was linked to human serum albumin (HSA) and chitosan via amide bond formation. The photophysical behavior and photodynamic therapy (PDT) activity (against human breast adenocarcinoma cell line (MCF-7 cells) of ZnMCPPc alone and its conjugates were investigated. The conjugates showed improved fluorescence, triplet and singlet oxygen quantum yields when compared to ZnMCPPc alone. The in vitro dark cytotoxicity and PDT studies were carried out at a dose of 3.6 μg/mL to 57.1 μg/mL. The in vitro dark cytotoxicity studies of ZnMCPPc showed cell viability more than 50% at 28.6 μg/mL and 57.1 μg/mL, while the conjugates showed > 50% in all their tested concentrations (3.6 to 57.1) μg/mL. Thus, conjugation of ZnMCPPc to HSA and chitosan improves its dark cytotoxicity, an important criteria for molecules meant for photodynamic therapy. Complex 1 showed the most efficacious PDT activity with cell viability more than 50% at concentration range of (14.3 to 57.1) μg/mL in comparison to the conjugates which only showed more than 50% cell viability at 28.6 μg/mL and 57.1 μg/mL for 1-HSA and 57.1 μg/mL for 1-Chitosan.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188497 , vital:44759 , xlink:href="https://doi.org/10.1016/j.saa.2016.09.032"
- Description: Zincmonocarboxyphenoxy phthalocyanine (ZnMCPPc) was linked to human serum albumin (HSA) and chitosan via amide bond formation. The photophysical behavior and photodynamic therapy (PDT) activity (against human breast adenocarcinoma cell line (MCF-7 cells) of ZnMCPPc alone and its conjugates were investigated. The conjugates showed improved fluorescence, triplet and singlet oxygen quantum yields when compared to ZnMCPPc alone. The in vitro dark cytotoxicity and PDT studies were carried out at a dose of 3.6 μg/mL to 57.1 μg/mL. The in vitro dark cytotoxicity studies of ZnMCPPc showed cell viability more than 50% at 28.6 μg/mL and 57.1 μg/mL, while the conjugates showed > 50% in all their tested concentrations (3.6 to 57.1) μg/mL. Thus, conjugation of ZnMCPPc to HSA and chitosan improves its dark cytotoxicity, an important criteria for molecules meant for photodynamic therapy. Complex 1 showed the most efficacious PDT activity with cell viability more than 50% at concentration range of (14.3 to 57.1) μg/mL in comparison to the conjugates which only showed more than 50% cell viability at 28.6 μg/mL and 57.1 μg/mL for 1-HSA and 57.1 μg/mL for 1-Chitosan.
- Full Text:
- Date Issued: 2017
Photophysical properties of a series of alloyed and non-alloyed water-soluble l-cysteine-capped core quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188486 , vital:44758 , xlink:href="https://doi.org/10.1016/j.jallcom.2016.10.276"
- Description: Photophysical properties of quantum dots (QDs) such as their photoluminescence (PL) quantum yield (QY), exciton lifetime and PL stability are important parameters used to unravel their chemical and physical characteristics. In this work, we have comparatively investigated the photophysical properties of a series of L-cysteine-capped non-alloyed (CdTe and CdSe) and alloyed (CdZnTe, CdSeS, CdSeTe and CdSeTeS) core QDs. Each of the QDs varied in their size and PL emission wavelength. We observe no physical relationship between the PL QY of the QDs and their PL stability. Based on the PL stability assessment, CdTe QDs with a high PL QY value of 88% exhibited poor PL stability while moderate PL stability was observed for CdZnTe (QY = 78%); CdSe (QY = 3%); and CdSeTe QDs (QY = ∼3%). Alloyed CdSeS (QY = ∼69%) and CdSeTeS (QY = 23%) QDs exhibited good PL stability and can serve as potential fluorophores for a wide range of chemical and biological applications. Generally, it is proposed that the structural nature of the QDs played a significant role in their overall photophysical properties. The information provided in this work will assist in the selection of core QDs suitable for different applications.
- Full Text:
- Date Issued: 2017
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188486 , vital:44758 , xlink:href="https://doi.org/10.1016/j.jallcom.2016.10.276"
- Description: Photophysical properties of quantum dots (QDs) such as their photoluminescence (PL) quantum yield (QY), exciton lifetime and PL stability are important parameters used to unravel their chemical and physical characteristics. In this work, we have comparatively investigated the photophysical properties of a series of L-cysteine-capped non-alloyed (CdTe and CdSe) and alloyed (CdZnTe, CdSeS, CdSeTe and CdSeTeS) core QDs. Each of the QDs varied in their size and PL emission wavelength. We observe no physical relationship between the PL QY of the QDs and their PL stability. Based on the PL stability assessment, CdTe QDs with a high PL QY value of 88% exhibited poor PL stability while moderate PL stability was observed for CdZnTe (QY = 78%); CdSe (QY = 3%); and CdSeTe QDs (QY = ∼3%). Alloyed CdSeS (QY = ∼69%) and CdSeTeS (QY = 23%) QDs exhibited good PL stability and can serve as potential fluorophores for a wide range of chemical and biological applications. Generally, it is proposed that the structural nature of the QDs played a significant role in their overall photophysical properties. The information provided in this work will assist in the selection of core QDs suitable for different applications.
- Full Text:
- Date Issued: 2017
Photophysical properties of GaCl 5, 10, 15, 20-tetra (1-pyrenyl) porphyrinato incorporated into Pluronic F127 micelle
- Managa, Muthumuni, Britton, Jonathan, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Managa, Muthumuni , Britton, Jonathan , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233101 , vital:50056 , xlink:href="https://doi.org/10.1016/j.jlumin.2016.12.043"
- Description: GaCl 5,10,15,20-Tetra(1-pyrenyl)porphyrin (GaClTPyP) was successfully synthesised and encapsulated into Pluronic F127. The unmetallated 5,10,15,20-tetra(1-pyrenyl)porphyrin (H2TPyP) precursor was also encapsulated into Pluronic F127. The fluorescence quantum yield for GaClTPyP at 0.045 was lower than that of H2TPyP at 0.13 due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state, lowering the fluorescence. Fluorescence quantum yield values increased when GaClTPyP or H2TPyP were encapsulated in Pluronic F127. GaClTPyP/Pluronic F127 showed higher values of the binding constant (Kb) as well as Stern-Volmer constant (Ksv) when compared to H2ClTPyP/Pluronic F127. It was determined from fluorescence quenching studies for GaClTPyP was located more in the inner core (hydrophobic) of Pluronic F127 and H2TPyP more on the outer region. Single oxygen quantum yields (Ф△) were determined to be 0.32 and 0.53 for GaClTPyP and GaClTPyP/Pluronic F127 respectively, an increase for the latter compared to the former.
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Britton, Jonathan , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233101 , vital:50056 , xlink:href="https://doi.org/10.1016/j.jlumin.2016.12.043"
- Description: GaCl 5,10,15,20-Tetra(1-pyrenyl)porphyrin (GaClTPyP) was successfully synthesised and encapsulated into Pluronic F127. The unmetallated 5,10,15,20-tetra(1-pyrenyl)porphyrin (H2TPyP) precursor was also encapsulated into Pluronic F127. The fluorescence quantum yield for GaClTPyP at 0.045 was lower than that of H2TPyP at 0.13 due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state, lowering the fluorescence. Fluorescence quantum yield values increased when GaClTPyP or H2TPyP were encapsulated in Pluronic F127. GaClTPyP/Pluronic F127 showed higher values of the binding constant (Kb) as well as Stern-Volmer constant (Ksv) when compared to H2ClTPyP/Pluronic F127. It was determined from fluorescence quenching studies for GaClTPyP was located more in the inner core (hydrophobic) of Pluronic F127 and H2TPyP more on the outer region. Single oxygen quantum yields (Ф△) were determined to be 0.32 and 0.53 for GaClTPyP and GaClTPyP/Pluronic F127 respectively, an increase for the latter compared to the former.
- Full Text:
- Date Issued: 2017
Photophysical studies of meso-tetrakis (4-nitrophenyl) and meso-tetrakis (4-sulfophenyl) gallium porphyrins loaded into Pluronic F127 polymeric micelles
- Managa, Muthumuni, Ngoy, Bokolombe P, Mafukidze, Donovan M, Britton, Jonathan, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
Photophysicochemical behaviour of anionic indium phthalocyanine when grafted onto AgxAuy and porous silica nanoparticles
- Dube, Edith, Oluwole, David O, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188899 , vital:44796 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.05.071"
- Description: This work reports on the synthesis of glutathione functionalised Ag3Au1 (Ag rich alloy, denoted as AgAu) and Ag1Au3 (Au rich alloy – denoted as AuAg) nano alloys as well as aminopropyl triethoxylsilane capped Ag1Au3 doped silica nanoparticles (NPs). The NPs were covalently linked to indium(III) chloride 2,9(10),16(17),23(24)–tetra–(3–carboxyphenoxy)phthalocyanine (1) via amide bond to form 1–AgAuNPs–GSH and 1–AuAgNPs–GSH. The AgAuNPs were also doped into aminopropyl triethoxylsilane (APTES) silica NPs (SiNPs-APTES) followed by linkage to complex 1 to form 1–AgAu-SiNPs–APTES. The photophysicochemical behaviour of complex 1 and its nanoconjugates were investigated. Decrease in the fluorescence quantum yields and lifetimes was observed in the conjugates in comparison to 1 alone. The singlet oxygen quantum yield for 1–AgAuNPs–GSH and 1–AuAgNPs–GSH decreased probably due to the screening effect caused by the NPs, while that of 1–AgAu-SiNPs–APTES increased in dimethylsulfoxide probably due to the permeability of the porous silica matrix to molecular oxygen.
- Full Text:
- Date Issued: 2017
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188899 , vital:44796 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.05.071"
- Description: This work reports on the synthesis of glutathione functionalised Ag3Au1 (Ag rich alloy, denoted as AgAu) and Ag1Au3 (Au rich alloy – denoted as AuAg) nano alloys as well as aminopropyl triethoxylsilane capped Ag1Au3 doped silica nanoparticles (NPs). The NPs were covalently linked to indium(III) chloride 2,9(10),16(17),23(24)–tetra–(3–carboxyphenoxy)phthalocyanine (1) via amide bond to form 1–AgAuNPs–GSH and 1–AuAgNPs–GSH. The AgAuNPs were also doped into aminopropyl triethoxylsilane (APTES) silica NPs (SiNPs-APTES) followed by linkage to complex 1 to form 1–AgAu-SiNPs–APTES. The photophysicochemical behaviour of complex 1 and its nanoconjugates were investigated. Decrease in the fluorescence quantum yields and lifetimes was observed in the conjugates in comparison to 1 alone. The singlet oxygen quantum yield for 1–AgAuNPs–GSH and 1–AuAgNPs–GSH decreased probably due to the screening effect caused by the NPs, while that of 1–AgAu-SiNPs–APTES increased in dimethylsulfoxide probably due to the permeability of the porous silica matrix to molecular oxygen.
- Full Text:
- Date Issued: 2017
Photophysicochemical behaviour of metallophthalocyanines when doped onto silica nanoparticles
- Oluwole, David O, Nyokong, Tebello
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188518 , vital:44761 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.08.053"
- Description: Aluminum(III) chloride 2,9(10),16(17),23(24)–tetra–(4–tert–butylphenoxy)phthalocyanine (1), zinc(II) 2,9(10),16(17),23(24)–tetra–(4–tert–butylphenoxy)phthalocyanine (2), zinc(II) 1,8(11),15(18),22(25)–tetra–(4–tert–butylphenoxy) phthalocyanine (3) and zinc(II) 2,9(10),16(17),23(24)–tetra–(4–carboxylphenoxy) phthalocyanine (4) were doped onto silica nanoparticles (SiNPs). There were no significant changes in fluorescence quantum yields and lifetimes of the metallophthalocyanines ( MPcs) when doped onto SiNPs. The triplet quantum yields of the MPcs alone range from 0.22 to 0.85 and in the presence of SiNPs the values range from 0.17 to 0.89. We observed a general decrease of triplet quantum yields of phthalocyanines in the conjugates except for 2 where there was an increase. The values were highly affected by aggregation. Complexes 1 and 3 were highly aggregated when doped onto SiNPs, while 2 and 4 did not show much aggregation.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188518 , vital:44761 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.08.053"
- Description: Aluminum(III) chloride 2,9(10),16(17),23(24)–tetra–(4–tert–butylphenoxy)phthalocyanine (1), zinc(II) 2,9(10),16(17),23(24)–tetra–(4–tert–butylphenoxy)phthalocyanine (2), zinc(II) 1,8(11),15(18),22(25)–tetra–(4–tert–butylphenoxy) phthalocyanine (3) and zinc(II) 2,9(10),16(17),23(24)–tetra–(4–carboxylphenoxy) phthalocyanine (4) were doped onto silica nanoparticles (SiNPs). There were no significant changes in fluorescence quantum yields and lifetimes of the metallophthalocyanines ( MPcs) when doped onto SiNPs. The triplet quantum yields of the MPcs alone range from 0.22 to 0.85 and in the presence of SiNPs the values range from 0.17 to 0.89. We observed a general decrease of triplet quantum yields of phthalocyanines in the conjugates except for 2 where there was an increase. The values were highly affected by aggregation. Complexes 1 and 3 were highly aggregated when doped onto SiNPs, while 2 and 4 did not show much aggregation.
- Full Text:
- Date Issued: 2017
The effect of point of substitution and silver based nanoparticles on the photophysical and optical nonlinearity of indium carboxyphenoxy phthalocyanine
- Oluwole, David O, Ngxeke, Sixolisile M, Britton, Jonathan, Nyokong, Tebello
- Authors: Oluwole, David O , Ngxeke, Sixolisile M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188596 , vital:44768 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.07.032"
- Description: Indium(III) chloride 1,8(11),15(18),22(25)-tetra-(3-carboxyphenoxy) phthalocyanine (1) and indium(III) chloride 2,9(10),16(17),23(24)-tetra–(3-carboxyphenoxy) phthalocyanine (2) were covalently linked to glutathione capped silver nanoparticles (AgNPs–GSH) and silver selenide/zinc sulfide (Ag2Se/ZnS–GSH) quantum dots via amide bond formation. The photophysical and nonlinear optical behaviour of the metallophthalocyanines and their conjugates with nanoparticles were investigated using the open aperture Z–scan technique. Complex 2 showed enhanced photophysical properties compared to 1. The conjugates revealed improved triplet state quantum yields (except for 1-AgNPs-GSH which afforded lower triplet state quantum yields in comparison to 1) and nonlinear optical activities in comparison to the Pc complexes. The synthesized complexes, nanoparticles and their conjugates could be potential nonlinear optical materials due to their good nonlinear optical activities.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Ngxeke, Sixolisile M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188596 , vital:44768 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.07.032"
- Description: Indium(III) chloride 1,8(11),15(18),22(25)-tetra-(3-carboxyphenoxy) phthalocyanine (1) and indium(III) chloride 2,9(10),16(17),23(24)-tetra–(3-carboxyphenoxy) phthalocyanine (2) were covalently linked to glutathione capped silver nanoparticles (AgNPs–GSH) and silver selenide/zinc sulfide (Ag2Se/ZnS–GSH) quantum dots via amide bond formation. The photophysical and nonlinear optical behaviour of the metallophthalocyanines and their conjugates with nanoparticles were investigated using the open aperture Z–scan technique. Complex 2 showed enhanced photophysical properties compared to 1. The conjugates revealed improved triplet state quantum yields (except for 1-AgNPs-GSH which afforded lower triplet state quantum yields in comparison to 1) and nonlinear optical activities in comparison to the Pc complexes. The synthesized complexes, nanoparticles and their conjugates could be potential nonlinear optical materials due to their good nonlinear optical activities.
- Full Text:
- Date Issued: 2017