Double-and quintuple-decker phthalocyaninato chelates as optical limiters in solution and thin film
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186733 , vital:44529 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107836"
- Description: The rare-earth quintuple-decker phthalocyaninato chelates (3a and 3b) were synthesized from their parent rare-earth double-decker phthalocyaninato precursors (2b and 2a). After extensive structural elucidation, these complexes were subjected to various spectroscopic techniques to investigate their electronic behavior. It was found that complexes 3a and 3b existed as the oxidized forms. When investigating the optical limiting properties, all these complexes were found to exhibit reverse saturable absorption, with complex 2a showing a more enhanced open-aperture Z-Scan signature than complex 2b. Interestingly, complexes 3a and 3b (in solution) exhibited better open-aperture Z-Scan signatures than their parent rare-earth double-decker phthalocyaninato precursors (2b and 2a). However, thin films fabricated from these complexes did not show an improvement in the optical limiting properties when compared to 2a, 3a, 3b except for that which was prepared from 2b. This study shows the importance of extensive π-electron system in phthalocyaninato complexes for optical limiting applications.
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- Date Issued: 2020
Nonlinear optical response and electrocatalytic activity of cobalt phthalocyanine clicked zinc oxide nanoparticles
- Authors: Mpeta, Lekhetho S , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186179 , vital:44471 , xlink:href="https://doi.org/10.1016/j.ica.2020.119661"
- Description: In this article, we report on the linking of cobalt tetrakis (4-pentyn-oxy) phthalocyanine (CoTPPc) to ZnO nanoparticles via click chemistry. Subsequently, electrocatalytic activity and nonlinear optical properties were investigated (the latter using an open Z-scan technique at 532 nm). The linking of CoTPPc with ZnO resulted in the lowest limiting intensity value of 0.27 J.Cm−2, the βeff (cmW−1) values were found to be 1.51 × 10-8 and 7.10 × 104 for ZnO and CoTPPc-ZnO respectively. The catalytic rate constants (M−1s−1) (and limits of detection) were 4.1 × 104 (12.87 µM), 5.7 × 104 (8.62 µM) and 7.36 × 104 (4.35 µM) for ZnO, CoTPPc and CoTPPc-ZnO. Hence linking ZnO nanoparticles to CoTPPc result in the enhancement of both nonlinear optical behaviour and catalytic activity.
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- Date Issued: 2020
Photodynamic antimicrobial chemotherapy of asymmetric porphyrin-silver conjugates towards photoinactivation of Staphylococcus aureus
- Authors: Shabangu, Samuel M , Babu, Balaji , Soy, Rodah C , Managa, Muthumuni , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186536 , vital:44509 , xlink:href="https://doi.org/10.1080/00958972.2020.1739273"
- Description: Asymmetric mono-carboxy-porphyrins, (5-(4-carboxyphenyl)10,15, 20-tris(pentafluorophenyl)porphyrinato zinc(II) (1), 5-(4- carboxyphenyl)10,15,20-triphenylporphyrinato zinc(II) (2) and 5-(4- carboxyphenyl)10,15,20-tris(2-thienyl)porphyrinato zinc(II) (3), were linked to Ag nanoparticles (AgNPs) through amide bonds and selfassembly (the latter only for 3). The porphyrins and conjugates were used for photodynamic antimicrobial chemotherapy (PACT) against Staphylococcus aureus. PACT uses singlet oxygen for antimicrobial activity. Complex 3 and its conjugates had higher singlet oxygen quantum yields and higher log reduction when compared with the rest of the porphyrins and corresponding conjugates. These high log reductions for 3 and its conjugate were attributed to the presence of sulfur groups whereby there was more interaction with the bacterial membrane.
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- Date Issued: 2020
‘There is nothing to hold onto here’:
- Authors: Shabangu, Samuel M , Babu, Balaji , Soy, Rodah C , Managa, Muthumuni , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/156410 , vital:39987 , DOI: 10.1080/00958972.2020.1739273
- Description: Asymmetric mono-carboxy-porphyrins, (5-(4-carboxyphenyl)−10,15,20-tris(pentafluorophenyl)porphyrinato zinc(II) (1), 5-(4-carboxyphenyl)−10,15,20-triphenylporphyrinato zinc(II) (2) and 5-(4-carboxyphenyl)−10,15,20-tris(2-thienyl)porphyrinato zinc(II) (3), were linked to Ag nanoparticles (AgNPs) through amide bonds and self-assembly (the latter only for 3). The porphyrins and conjugates were used for photodynamic antimicrobial chemotherapy (PACT) against Staphylococcus aureus. PACT uses singlet oxygen for antimicrobial activity. Complex 3 and its conjugates had higher singlet oxygen quantum yields and higher log reduction when compared with the rest of the porphyrins and corresponding conjugates. These high log reductions for 3 and its conjugate were attributed to the presence of sulfur groups whereby there was more interaction with the bacterial membrane.
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- Date Issued: 2020
Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push-pull Effects of Substituents
- Authors: Nkhahle, Reitumetse , Sekhosana, Kutloano E , Centane, Sixolile , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186904 , vital:44546 , xlink:href="https://doi.org/10.1002/elan.201800837"
- Description: A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the p-p stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 mM being recorded.
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- Date Issued: 2019
The photophysicochemical properties and photodynamic therapy activity of phenyldiazenyl phenoxy substituted phthalocyanines when incorporated into Pluronic® F127 micelles
- Authors: Motloung, Banele M , Sekhosana, Kutloano E , Managa, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186769 , vital:44532 , xlink:href="https://doi.org/10.1016/j.poly.2019.114157"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of 4(4-phenyldiazenyl) phenoxy substituted indium (III) (InPc) and zinc (ZnPc) phthalocyanines when alone or incorporated into Pluronic_ F127 micelles are presented in this study. The InPc exhibited higher singlet oxygen (UD) at 0.47 compared to the ZnPc at 0.20 in dimethylsulfoxide. The UD values in the presence of Pluronic_ F127 and in water, were 0.32 for InPc and 0.09 for ZnPc. The triplet quantum yields (UT) were 0.92 for InPc and 0.32 for ZnPc in DMSO. The PDT activity followed the same trend as the singlet oxygen quantum yields. At the highest concentration, InPc in Pluronic_ F127 gave 22% cell viability compared to 34% for complex ZnPc. The partition coefficient Kp values were determined using the water and octanol system. InPc had a larger Kp suggesting that it is more likely to be taken up by the cancer cells, hence it exhibited better PDT activity.
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- Date Issued: 2019
The effect of the cobalt and manganese central metal ions on the nonlinear optical properties of tetra (4-propargyloxyphenoxy) phthalocyanines
- Authors: Mwanza, Daniel , Louzada, Marcel , Britton, Jonathan , Sekhosana, Kutloano E , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233357 , vital:50083 , xlink:href="https://doi.org/10.1039/C8NJ00748A"
- Description: The metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (Mn(OAc)TPrOPhOPc) tetra propargyloxyphenoxy phthalocyanines were evaluated for their potential as optical limiting materials. The effect of the substituents and the central metal ions on the nonlinear optical properties was evaluated. The metal-free phthalocyanine exhibited better nonlinear optical properties when compared to the cobalt and manganese complexes owing to the metal ions quenching the excited state due to their half-filled d-orbitals. The nonlinear absorption coefficient (βeff, ×10−5 m MW−1) followed the trend of H2TPrOPhOPc > CoTPrOPhOPc > Mn(OAc)TPrOPhOPc. The values βeff (×10−5 m MW−1) using 532 nm Nd:YAG (560 nm monochromatic Ekspla) laser sources were 23.5 > 14.3 > 9.20 (14.4). The second-order nonlinear coefficient obtained using density functional theory calculations, the theoretical hyper-Rayleigh scattering (βHRS, ×10−28 esu), showed the decreasing trend for H2TPrOPhOPc (2.28) > CoTPrOPhOPc (2.10) > Mn(OAc)TPrOPhOPc (1.86). The 4-(propargyloxy)phenoxy substituents enhanced the optical limiting properties of the synthesized phthalocyanines.
- Full Text:
- Date Issued: 2018
The Primary Demonstration of Exciton Coupling Effects on Optical Limiting Properties of Blue Double-Decker Lanthanide Phthalocyanine Salts
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
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- Date Issued: 2018
Effects of charge on the photophysicochemical properties of zinc phthalocyanine derivatives doped onto silica nanoparticles
- Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
- Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
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- Date Issued: 2017
Laser induced photodegradation of Orange G using phthalocyanine–cobalt ferrite magnetic nanoparticle conjugates electrospun in polystyrene nanofibers
- 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.
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- Date Issued: 2017
Optical limiting response of multi-walled carbon nanotube-phthalocyanine nanocomposite in solution and when in poly (acrylic acid)
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188628 , vital:44770 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.03.067"
- Description: Bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24)-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) is linked to amino-functionalized multi-walled carbon nanotubes (MWCNT) to form 3-MWCNT. Z-scan technique was employed to experimentally determine the nonlinear absorption coefficient from the open-aperture data. The limiting threshold values as low as 0.045 J cm−2 were found in solution. The conjugate (3-MWCNT) gave better optical limiting behavior than complex 3 alone.
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- Date Issued: 2016
Fluorescence behavior of glutathione capped CdTe@ ZnS quantum dots chemically coordinated to zinc octacarboxy phthalocyanines
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
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- Date Issued: 2013
Synthesis, photophysical and nonlinear optical behavior of neodymium based trisphthalocyanine
- Authors: Sekhosana, Kutloano E , Amuhaya, Edith K , Khene, M Samson , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7243 , http://hdl.handle.net/10962/d1020247
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex. , Original publication is available at http://dx.doi.org/10.1016/j.ica.2014.11.029
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