Improved Photophysical and Photochemical Properties of Thiopheneethoxy Substituted Metallophthalocyanines on Immobilization onto Gold‐speckled Silica Nanoparticles
- Dube, Edith, Oluwole, David O, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187699 , vital:44688 , xlink:href="https://doi.org/10.1111/php.12879"
- Description: This work reports on the synthesis of tetrakis-[(thiophineethoxy) phthalocyaninato] indium(II) chloride (3). The photophysical behavior of complex 3 was compared to that of the Zn derivative (tetrakis-[(thiophineethoxy) phthalocyaninato] zinc(II) (complex 2)). The compounds were interacted with gold-speckled silica (GSS) nanoparticles via Au–S self assembly to afford the conjugates (2–GSS and 3–GSS). The photophysicochemical behavior of the compounds and their conjugates were assessed. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet and singlet oxygen quantum yields in comparison with complexes 2 and 3 alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187699 , vital:44688 , xlink:href="https://doi.org/10.1111/php.12879"
- Description: This work reports on the synthesis of tetrakis-[(thiophineethoxy) phthalocyaninato] indium(II) chloride (3). The photophysical behavior of complex 3 was compared to that of the Zn derivative (tetrakis-[(thiophineethoxy) phthalocyaninato] zinc(II) (complex 2)). The compounds were interacted with gold-speckled silica (GSS) nanoparticles via Au–S self assembly to afford the conjugates (2–GSS and 3–GSS). The photophysicochemical behavior of the compounds and their conjugates were assessed. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet and singlet oxygen quantum yields in comparison with complexes 2 and 3 alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
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
Glycosylated zinc phthalocyanine-gold nanoparticle conjugates for photodynamic therapy
- Dube, Edith, Oluwole, David O, Nwaji, Njemuwa, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234524 , vital:50205 , xlink:href="https://doi.org/10.1016/j.saa.2018.05.081"
- Description: In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 μg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with more than 50% viable cells at concentration ≥ 40 μg/mL in comparison to 3-AuNS with more than 50% viable cells at concentration ≥ 80 μg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.
- Full Text:
- Date Issued: 2018
- Authors: Dube, Edith , Oluwole, David O , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234524 , vital:50205 , xlink:href="https://doi.org/10.1016/j.saa.2018.05.081"
- Description: In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 μg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with more than 50% viable cells at concentration ≥ 40 μg/mL in comparison to 3-AuNS with more than 50% viable cells at concentration ≥ 80 μg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.
- Full Text:
- Date Issued: 2018
Synthesis and photophysical properties of nanocomposites of aluminum tetrasulfonated phthalocyanine covalently linked to glutathione capped CdTe/CdS/ZnS quantum dots
- Oluwole, David O, Britton, Jonathan, Mashazi, Philani N, Nyokong, Tebello
- Authors: Oluwole, David O , Britton, Jonathan , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241379 , vital:50934 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.04.015"
- Description: Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was covalently linked with different sizes of glutathione capped CdTe/CdS/ZnS quantum dots (QDs). The photophysical and Förster resonance energy transfer (FRET) properties of the nanoconjugates were investigated. The CdTe/CdS/ZnS(6.3) nanocomposite showed the highest enhancement in its photophysical properties while (CdTe/CdS/ZnS(3.2) nanocomposite showed the least. Highest FRET efficiency was observed in the linked CdTe/CdS/ZnS(6.3) nanocomposites at 93%. Hence, the combination of CdTe/CdS/ZnS with ClAlTSPc exhibited excellent photophysical properties.
- Full Text:
- Date Issued: 2015
- Authors: Oluwole, David O , Britton, Jonathan , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241379 , vital:50934 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.04.015"
- Description: Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was covalently linked with different sizes of glutathione capped CdTe/CdS/ZnS quantum dots (QDs). The photophysical and Förster resonance energy transfer (FRET) properties of the nanoconjugates were investigated. The CdTe/CdS/ZnS(6.3) nanocomposite showed the highest enhancement in its photophysical properties while (CdTe/CdS/ZnS(3.2) nanocomposite showed the least. Highest FRET efficiency was observed in the linked CdTe/CdS/ZnS(6.3) nanocomposites at 93%. Hence, the combination of CdTe/CdS/ZnS with ClAlTSPc exhibited excellent photophysical properties.
- Full Text:
- Date Issued: 2015
Physicochemical behavior of nanohybrids of mono and tetra substituted carboxyphenoxy phthalocyanine covalently linked to GSH–CdTe/CdS/ZnS quantum dots
- Oluwole, David O, Nyokong, Tebello
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189480 , vital:44850 , xlink:href="https://doi.org/10.1016/j.poly.2014.10.024"
- Description: Zinc monocarboxyphenoxy and tetracarboxyphenoxy phthalocyanines were covalently linked with three different sizes of glutathione capped core/shell/shell {CdTe/CdS/ZnS(4.2), CdTe/CdS/ZnS(5.1) and CdTe/CdS/ZnS(6.7)}; a core shell {CdTe/CdS(3.1)} and core {CdTe(2.4)} quantum dots. The physicochemical behavior and Förster resonance energy transfer (FRET) processes of the nanohybrids were investigated. The highest FRET efficiency was observed with CdTe/CdS/ZnS(6.7) nanohybrids with 98% and the least efficiency was observed with CdTe(2.4) nanohybrids with 85%. The CdTe/CdS/ZnS(6.7) also showed the best physicochemical behavior. These good physicochemical properties make the synthesized nanohybrids viable photosensitizers.
- Full Text:
- Date Issued: 2015
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189480 , vital:44850 , xlink:href="https://doi.org/10.1016/j.poly.2014.10.024"
- Description: Zinc monocarboxyphenoxy and tetracarboxyphenoxy phthalocyanines were covalently linked with three different sizes of glutathione capped core/shell/shell {CdTe/CdS/ZnS(4.2), CdTe/CdS/ZnS(5.1) and CdTe/CdS/ZnS(6.7)}; a core shell {CdTe/CdS(3.1)} and core {CdTe(2.4)} quantum dots. The physicochemical behavior and Förster resonance energy transfer (FRET) processes of the nanohybrids were investigated. The highest FRET efficiency was observed with CdTe/CdS/ZnS(6.7) nanohybrids with 98% and the least efficiency was observed with CdTe(2.4) nanohybrids with 85%. The CdTe/CdS/ZnS(6.7) also showed the best physicochemical behavior. These good physicochemical properties make the synthesized nanohybrids viable photosensitizers.
- Full Text:
- Date Issued: 2015
The photo-physicochemical properties and in vitro photodynamic therapy activity of differently substituted-zinc (II)-phthalocyanines and graphene quantum dots conjugates on MCF7 breast cancer cell line
- Nene, Lindokuhle C, Managa, Muthumuni E, Oluwole, David O, Mafukidze, Donovan M, Sindelo, Azole, Nyokong, Tebello
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
Novel nano-dyad of homoleptic sandwich-type phthalocyanines with nitrogen doped graphene quantum dots for nonlinear optics
- Oluwole, David O, Nwaji, Njemuwa, Nene, Lindokuhle C, Mokone, Lesedi, Dube, Edith, Nyokong, Tebello
- Authors: Oluwole, David O , Nwaji, Njemuwa , Nene, Lindokuhle C , Mokone, Lesedi , Dube, Edith , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233386 , vital:50086 , xlink:href="https://doi.org/10.1039/C8NJ01707G"
- Description: The syntheses of neodymium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (2), bis europium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (3), bis dysprosium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (4) and their conjugated analogues with nitrogen doped quantum dots (NGQDs) are reported herein. The optical nonlinearity of the sandwich-type phthalocyanine complexes and their conjugates with NGQDs were studied in dimethyl sulfoxide using the open aperture Z-scan technique at an excitation wavelength of 532 nm with a 10 ns pulse. The nonlinear absorption coefficient (βeff) value of the samples ranges from 15 cm GW−1 to 89.6 cm GW−1. Complex 4 and its conjugates afforded a strong optical limiting behaviour compared to the other samples. These fabricated complexes and their conjugates with NGQDs could serve as a plausible nonlinear optical (NLO) material due to their fascinating NLO properties.
- Full Text:
- Date Issued: 2018
- Authors: Oluwole, David O , Nwaji, Njemuwa , Nene, Lindokuhle C , Mokone, Lesedi , Dube, Edith , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233386 , vital:50086 , xlink:href="https://doi.org/10.1039/C8NJ01707G"
- Description: The syntheses of neodymium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (2), bis europium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (3), bis dysprosium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (4) and their conjugated analogues with nitrogen doped quantum dots (NGQDs) are reported herein. The optical nonlinearity of the sandwich-type phthalocyanine complexes and their conjugates with NGQDs were studied in dimethyl sulfoxide using the open aperture Z-scan technique at an excitation wavelength of 532 nm with a 10 ns pulse. The nonlinear absorption coefficient (βeff) value of the samples ranges from 15 cm GW−1 to 89.6 cm GW−1. Complex 4 and its conjugates afforded a strong optical limiting behaviour compared to the other samples. These fabricated complexes and their conjugates with NGQDs could serve as a plausible nonlinear optical (NLO) material due to their fascinating NLO properties.
- Full Text:
- Date Issued: 2018
Fabrication of efficient nonlinear optical absorber using Zn phthalocyanine-semiconductor quantum dots conjugates
- Mgidlana, Sithi, Oluwole, David O, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187496 , vital:44663 , xlink:href="https://doi.org/10.1016/j.poly.2018.11.024"
- Description: In this paper, we report on the synthesis of Zn(II) phthalocyanine derivatives and their conjugates with core/shell and core/shell/shell semiconductor quantum dots (SQDs). Zn(II) mono amino-carboxyethylphenoxy phthalocyanine (1), Zn(II) mono 3-carboxyphenoxy-tris(pyridin-2-yloxy) phthalocyanine (2) and Zn(II) mono aminophenoxy-tris(benzothiazole) phthalocyanine (3) were synthesized. The photophysical and optical limiting properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs were investigated in dimethyl sulfoxide. The optical limiting behaviour of the Pc complexes and their conjugates were measured by the open aperture Z-scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. The conjugates outperformed the Pc complexes alone with the conjugates of 2-SQDs affording highest nonlinear absorption coefficient (βeff) value of ∼80 cm/GW and lowest limiting threshold (Ilim) value of ∼0.27 J·cm−2 as compared to other samples while complex 1 gave low βeff and high Ilim values of 42.2 cm/GW and 1.39 J·cm−2, respectively.
- Full Text:
- Date Issued: 2019
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187496 , vital:44663 , xlink:href="https://doi.org/10.1016/j.poly.2018.11.024"
- Description: In this paper, we report on the synthesis of Zn(II) phthalocyanine derivatives and their conjugates with core/shell and core/shell/shell semiconductor quantum dots (SQDs). Zn(II) mono amino-carboxyethylphenoxy phthalocyanine (1), Zn(II) mono 3-carboxyphenoxy-tris(pyridin-2-yloxy) phthalocyanine (2) and Zn(II) mono aminophenoxy-tris(benzothiazole) phthalocyanine (3) were synthesized. The photophysical and optical limiting properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs were investigated in dimethyl sulfoxide. The optical limiting behaviour of the Pc complexes and their conjugates were measured by the open aperture Z-scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. The conjugates outperformed the Pc complexes alone with the conjugates of 2-SQDs affording highest nonlinear absorption coefficient (βeff) value of ∼80 cm/GW and lowest limiting threshold (Ilim) value of ∼0.27 J·cm−2 as compared to other samples while complex 1 gave low βeff and high Ilim values of 42.2 cm/GW and 1.39 J·cm−2, respectively.
- Full Text:
- Date Issued: 2019
First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots
- Oluwole, David O, Yagodin, Alexey V, Mkhize, Nhlakanipho C, Sekhosana, Kutloana E, Martynov, Alexander G, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
Effects of the carboxylic acid substituents on the photophysical and nonlinear optical properties of asymmetrical Zn (II) phthalocyanines–quantum dots conjugates
- Mgidlana, Sithi, Oluwole, David O, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187662 , vital:44684 , xlink:href="https://doi.org/10.1080/24701556.2018.1503684"
- Description: This work reports on three asymmetrical Zn(II) phthalocyanines, namely: zinc(II) 3–(4-phenoxy)propanoic acid) phthalocyanine(1), zinc(II) 3–(4-phenoxy carboxylic acid) phthalocyanine (2) and zinc(II) 3–(4–oxy)phenoxy)acetic acid phthalocyanine (3) when covalently linked to glutathione(GSH) capped CdTe/ZnSe and CdTe/ZnSe/ZnO quantum dots (QDs). Of the Pc complexes alone, 1 afforded the highest triplet quantum yield (ΦT) value of 0.67 with corresponding largest nonlinear absorption coefficient (βeff) value of 14.0 cm/GW compared to 2 and 3. The conjugates afforded improved triplet quantum yield and nonlinear optical behavior in comparison to the Pc complexes alone.
- Full Text:
- Date Issued: 2018
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187662 , vital:44684 , xlink:href="https://doi.org/10.1080/24701556.2018.1503684"
- Description: This work reports on three asymmetrical Zn(II) phthalocyanines, namely: zinc(II) 3–(4-phenoxy)propanoic acid) phthalocyanine(1), zinc(II) 3–(4-phenoxy carboxylic acid) phthalocyanine (2) and zinc(II) 3–(4–oxy)phenoxy)acetic acid phthalocyanine (3) when covalently linked to glutathione(GSH) capped CdTe/ZnSe and CdTe/ZnSe/ZnO quantum dots (QDs). Of the Pc complexes alone, 1 afforded the highest triplet quantum yield (ΦT) value of 0.67 with corresponding largest nonlinear absorption coefficient (βeff) value of 14.0 cm/GW compared to 2 and 3. The conjugates afforded improved triplet quantum yield and nonlinear optical behavior in comparison to the Pc complexes alone.
- Full Text:
- Date Issued: 2018
Investigation of novel substituted zinc and aluminium phthalocyanines for photodynamic therapy of epithelial breast cancer
- Mohammed, Imadalulla, Oluwole, David O, Nemakal, Majunatha, Sannegowda, Lokesh K, Nyokong, Tebello
- Authors: Mohammed, Imadalulla , Oluwole, David O , Nemakal, Majunatha , Sannegowda, Lokesh K , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186824 , vital:44537 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107592"
- Description: A series of phthalonitrile ligands were synthesized by nucleophilic substitution reaction using the hydroxyl or sulfanyl group precursors and the nitro moiety of the nitrophthalonitrile to yield corresponding oxy or sulfanyl bridged ligands. These ligands were subsequently subjected to cyclocondensation reaction with diamagnetic metal ions like zinc and aluminium to afford symmetrically substituted zinc and aluminium phthalocyanine (Pc) complexes and polymers. The ligands and Pc complexes were characterized by 1 H nuclear magnetic resonance, fourier transform infrared, ultraviolet visible and mass spectrometric techniques. Additionally, thermal gravimetric, and elemental analyzer were used for characterization of the Pc complexes. The photophysical and photochemical behaviour of the Pc complexes were investigated in dimethyl sulfoxide. Additionally, the complexes were tested against epithelial breast cancer cells for photodynamic therapy (PDT) effect. The substituted ZnPc complexes afforded higher singlet oxygen quantum yields as compared to the AlPc analogue. All the complexes showed innocuous invitro dark cytotoxicity and moderate PDT effect.
- Full Text:
- Date Issued: 2019
- Authors: Mohammed, Imadalulla , Oluwole, David O , Nemakal, Majunatha , Sannegowda, Lokesh K , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186824 , vital:44537 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107592"
- Description: A series of phthalonitrile ligands were synthesized by nucleophilic substitution reaction using the hydroxyl or sulfanyl group precursors and the nitro moiety of the nitrophthalonitrile to yield corresponding oxy or sulfanyl bridged ligands. These ligands were subsequently subjected to cyclocondensation reaction with diamagnetic metal ions like zinc and aluminium to afford symmetrically substituted zinc and aluminium phthalocyanine (Pc) complexes and polymers. The ligands and Pc complexes were characterized by 1 H nuclear magnetic resonance, fourier transform infrared, ultraviolet visible and mass spectrometric techniques. Additionally, thermal gravimetric, and elemental analyzer were used for characterization of the Pc complexes. The photophysical and photochemical behaviour of the Pc complexes were investigated in dimethyl sulfoxide. Additionally, the complexes were tested against epithelial breast cancer cells for photodynamic therapy (PDT) effect. The substituted ZnPc complexes afforded higher singlet oxygen quantum yields as compared to the AlPc analogue. All the complexes showed innocuous invitro dark cytotoxicity and moderate PDT effect.
- Full Text:
- Date Issued: 2019
Optimizing phthalocyanine based dye-sensitized solar cells: The role of reduced graphene oxide
- Chindeka, Francis, Mashazi, Philani N, Britton, Jonathan, Fomo, Gertrude, Oluwole, David O, Sindelo, Azole, Nyokong, Tebello
- Authors: Chindeka, Francis , Mashazi, Philani N , Britton, Jonathan , Fomo, Gertrude , Oluwole, David O , Sindelo, Azole , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187770 , vital:44695 , xlink:href="https://doi.org/10.1016/j.synthmet.2018.10.021"
- Description: Dye-sensitized solar cells (DSSC) were fabricated by incorporating graphene materials as catalysts at the counter electrode. Platinum was also used as a catalyst for comparison purposes. Different phthalocyanines: hydroxyl indium tetracarboxyphenoxy phthalocyanine (1), chloro indium octacarboxy phthalocyanine (2) and dibenzoic acid silicon phthalocyanine (3) were used as dyes. Complex 3 gave the highest power conversion efficiency (η) of 3.19% when using nitrogen doped reduced graphene oxide nanosheets (NrGONS) as a catalyst at the counter electrode, and TiO2 containing rGONS at the anode. The value is close to 3.8% obtained when using Pt catalyst instead of NrGONS at the cathode, thus confirming that NrGONS is a promising candidate to replace the more expensive Pt. The study also shows that placing rGONS on both the anode and cathode improves efficiency.
- Full Text:
- Date Issued: 2018
- Authors: Chindeka, Francis , Mashazi, Philani N , Britton, Jonathan , Fomo, Gertrude , Oluwole, David O , Sindelo, Azole , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187770 , vital:44695 , xlink:href="https://doi.org/10.1016/j.synthmet.2018.10.021"
- Description: Dye-sensitized solar cells (DSSC) were fabricated by incorporating graphene materials as catalysts at the counter electrode. Platinum was also used as a catalyst for comparison purposes. Different phthalocyanines: hydroxyl indium tetracarboxyphenoxy phthalocyanine (1), chloro indium octacarboxy phthalocyanine (2) and dibenzoic acid silicon phthalocyanine (3) were used as dyes. Complex 3 gave the highest power conversion efficiency (η) of 3.19% when using nitrogen doped reduced graphene oxide nanosheets (NrGONS) as a catalyst at the counter electrode, and TiO2 containing rGONS at the anode. The value is close to 3.8% obtained when using Pt catalyst instead of NrGONS at the cathode, thus confirming that NrGONS is a promising candidate to replace the more expensive Pt. The study also shows that placing rGONS on both the anode and cathode improves efficiency.
- Full Text:
- Date Issued: 2018
Evaluation of the photosensitizing properties of zinc and indium tetra cinnamic acid phthalocyanines linked to magnetic nanoparticles on human breast adenocarcinoma cells
- Matlou, Gauta G, Oluwole, David O, Nyokong, Tebello
- Authors: Matlou, Gauta G , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187582 , vital:44673 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.054"
- Description: This work reports on the synthesis, photophysico-chemical properties and photodynamic therapy activity of novel zinc (1) and indium (2) tetra substituted cinnamic acid phthalocyanine (Pc) complexes linked to amino functionalized magnetic nanoparticles (AMNPs) through an amide bond. Asymmetric ZnPc complex (3) showed better triplet and singlet oxygen quantum yields as compared to its symmetrical analogues (1 and 2). The AMNPs (1-AMNPs and 2-AMNPs) linked conjugates depicted increased triplet quantum yields in comparison to their unlinked Pcs, while 3-AMNPs showed a decrease compared to 3. The complexes showed increased in-vitro photo-cytotoxic effect against MCF-7 cells with an increase in drug concentration. At 80 µg/mL, 2 and 3, 2-AMNPs and 3-AMNPs with higher singlet oxygen quantum yields caused more cytotoxic effect on the cancer cells in the presence of light as compared to 1 and 1-AMNPs respectively.
- Full Text:
- Date Issued: 2019
- Authors: Matlou, Gauta G , Oluwole, David O , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187582 , vital:44673 , xlink:href="https://doi.org/10.1016/j.jlumin.2018.09.054"
- Description: This work reports on the synthesis, photophysico-chemical properties and photodynamic therapy activity of novel zinc (1) and indium (2) tetra substituted cinnamic acid phthalocyanine (Pc) complexes linked to amino functionalized magnetic nanoparticles (AMNPs) through an amide bond. Asymmetric ZnPc complex (3) showed better triplet and singlet oxygen quantum yields as compared to its symmetrical analogues (1 and 2). The AMNPs (1-AMNPs and 2-AMNPs) linked conjugates depicted increased triplet quantum yields in comparison to their unlinked Pcs, while 3-AMNPs showed a decrease compared to 3. The complexes showed increased in-vitro photo-cytotoxic effect against MCF-7 cells with an increase in drug concentration. At 80 µg/mL, 2 and 3, 2-AMNPs and 3-AMNPs with higher singlet oxygen quantum yields caused more cytotoxic effect on the cancer cells in the presence of light as compared to 1 and 1-AMNPs respectively.
- Full Text:
- Date Issued: 2019
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
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
Physicochemical and antimicrobial photodynamic chemotherapy (against E. coli) by indium phthalocyanines in the presence of silver–iron bimetallic nanoparticles
- Magadla, Aviwe, Oluwole, David O, Managa, Muthumuni, Nyokong, Tebello
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
Optical limiters with improved performance based on nanoconjugates of thiol substituted phthalocyanine with CdSe quantum dots and Ag nanoparticles
- Oluwole, David O, Yagodin, Alexey V, Britton, Jonathan, Martynov, Alexander G, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Oluwole, David O , Yagodin, Alexey V , Britton, Jonathan , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238286 , vital:50605 , xlink:href="https://doi.org/10.1039/C7DT03867D"
- Description: Two alternative synthetic approaches affording a low-symmetry A3B-type phthalocyanine 1 bearing two [2′-(2′′-mercaptoethoxy)ethoxy] anchoring substituents were developed. Due to the presence of thiol groups, this phthalocyanine could be conjugated with TOPO-capped (TOPO - trioctylphosphine)-capped CdSe quantum dots (CdSe-QDs) or oleylamine capped silver nanoparticles (Ag-NPs). The nonlinear optical behaviour of starting phthalocyanine, quantum dots, nanoparticles and their conjugates was studied by using an open aperture Z-scan technique, revealing that the grafting of 1 onto the nanomaterials resulted in a significant enhancement of the optical limiting of 1-Ag and 1-CdSe in comparison with the individual components. The conjugate 1-CdSe, being the first example of Pc-based thiol conjugated with quantum dots, revealed superior limiting characteristics with a limiting threshold below 0.18 J cm−2.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Yagodin, Alexey V , Britton, Jonathan , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238286 , vital:50605 , xlink:href="https://doi.org/10.1039/C7DT03867D"
- Description: Two alternative synthetic approaches affording a low-symmetry A3B-type phthalocyanine 1 bearing two [2′-(2′′-mercaptoethoxy)ethoxy] anchoring substituents were developed. Due to the presence of thiol groups, this phthalocyanine could be conjugated with TOPO-capped (TOPO - trioctylphosphine)-capped CdSe quantum dots (CdSe-QDs) or oleylamine capped silver nanoparticles (Ag-NPs). The nonlinear optical behaviour of starting phthalocyanine, quantum dots, nanoparticles and their conjugates was studied by using an open aperture Z-scan technique, revealing that the grafting of 1 onto the nanomaterials resulted in a significant enhancement of the optical limiting of 1-Ag and 1-CdSe in comparison with the individual components. The conjugate 1-CdSe, being the first example of Pc-based thiol conjugated with quantum dots, revealed superior limiting characteristics with a limiting threshold below 0.18 J cm−2.
- Full Text:
- Date Issued: 2017
Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis
- Ramírez-García, Gonzalo, Oluwole, David O, Nxele, Siphesihle Robin, d’Orlyé, Fanny, Nyokong, Tebello, Bedioui, Fethi, Varenne, Anne
- Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
- Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
- Full Text:
- Date Issued: 2017
- Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
- Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Optical nonlinearity of pentadecylphenoxyl substituted sandwich–type metallophthalocyanines in the presence of Ag–CdSeTe/ZnTeSe nanocrystals: Effects of conjugation and central metals
- Oluwole, David O, Nyokong, Tebello
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187899 , vital:44708 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.01.009"
- Description: Novel pentadecylphenoxyl substituted homoleptic sandwich–type metallophthalocyanines: bis (complexes 2 and 4 containing Eu and Dy, respectively) and tris (complexes 3 and 5 containing Eu and Dy, respectively) 2,9,16,23–tetrakis–(3–pentadecylphenoxyl) phthalocyanines and cadmium based (Ag–CdSeTe/ZnTeSe) nanocrystals (NCs) were synthesized. The nonlinear optical (NLO) behavior of the metallophthalocyanines and their composites with NCs were investigated using the open aperture Z–scan technique at excitation wavelength of 532 nm with 10 ns pulse. All of the samples exhibited interesting NLO attributes: among all the sandwich–type complexes, complex 5 afforded the most efficient NLO features accounting for large nonlinear absorption coefficient (βeff) value of 3500 cm/GW and limiting threshold (Ilim) value of 0.43 J cm−2. Overall, the composites of the triple decker sandwich–type complexes with Ag–CdSeTe/ZnTeSe yielded the best NLO characteristics with 3 and 5 accounting for the largest βeff value of 5500 cm/GW and Ilim value of 0.09 J cm−2. The synthesized complexes and their composites with NCs could be viable and efficient NLO absorber due to their interesting NLO activities.
- Full Text:
- Date Issued: 2018
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187899 , vital:44708 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.01.009"
- Description: Novel pentadecylphenoxyl substituted homoleptic sandwich–type metallophthalocyanines: bis (complexes 2 and 4 containing Eu and Dy, respectively) and tris (complexes 3 and 5 containing Eu and Dy, respectively) 2,9,16,23–tetrakis–(3–pentadecylphenoxyl) phthalocyanines and cadmium based (Ag–CdSeTe/ZnTeSe) nanocrystals (NCs) were synthesized. The nonlinear optical (NLO) behavior of the metallophthalocyanines and their composites with NCs were investigated using the open aperture Z–scan technique at excitation wavelength of 532 nm with 10 ns pulse. All of the samples exhibited interesting NLO attributes: among all the sandwich–type complexes, complex 5 afforded the most efficient NLO features accounting for large nonlinear absorption coefficient (βeff) value of 3500 cm/GW and limiting threshold (Ilim) value of 0.43 J cm−2. Overall, the composites of the triple decker sandwich–type complexes with Ag–CdSeTe/ZnTeSe yielded the best NLO characteristics with 3 and 5 accounting for the largest βeff value of 5500 cm/GW and Ilim value of 0.09 J cm−2. The synthesized complexes and their composites with NCs could be viable and efficient NLO absorber due to their interesting NLO activities.
- Full Text:
- Date Issued: 2018
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