Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions
- Zugle, Ruphino, Litwinski, Christian, Nyokong, Tebello
- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
- Full Text:
- Date Issued: 2011
- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
- Full Text:
- Date Issued: 2011
Conjugates of low-symmetry Ge, Sn and Ti carboxy phthalocyanines with glutathione caped gold nanoparticles
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247003 , vital:51536 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.08.009"
- Description: This work reports on conjugation of low symmetry Ge (GeMCPc), Ti (TiMCPc) and Sn (SnMCPc) carboxy phthalocyanines with glutathione capped gold nanoparticles (GSH-AuNPs). The photophysical behaviour of the novel phthalocyanines–GSH-AuNPs conjugate was investigated and compared to the monocarboxy Pcs and to the mixture of Pc with GSH-AuNPs without a chemical bond. Blue shifting of Q band of the phthalocyanines was observed on linking to GSH-AuNPs. An improvement in triplet lifetimes was obtained for all the MPcs–GSH-AuNPs-linked conjugates compared to the MPcs alone. The highest triplet quantum yield of 0.75 and the longest triplet lifetime of 130 μs were obtained for the GeMCPc–GSH-AuNPs-linked conjugate. Fluorescence quantum yields and lifetimes were low for the conjugates due to quenching by the nanoparticles.
- Full Text:
- Date Issued: 2011
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247003 , vital:51536 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.08.009"
- Description: This work reports on conjugation of low symmetry Ge (GeMCPc), Ti (TiMCPc) and Sn (SnMCPc) carboxy phthalocyanines with glutathione capped gold nanoparticles (GSH-AuNPs). The photophysical behaviour of the novel phthalocyanines–GSH-AuNPs conjugate was investigated and compared to the monocarboxy Pcs and to the mixture of Pc with GSH-AuNPs without a chemical bond. Blue shifting of Q band of the phthalocyanines was observed on linking to GSH-AuNPs. An improvement in triplet lifetimes was obtained for all the MPcs–GSH-AuNPs-linked conjugates compared to the MPcs alone. The highest triplet quantum yield of 0.75 and the longest triplet lifetime of 130 μs were obtained for the GeMCPc–GSH-AuNPs-linked conjugate. Fluorescence quantum yields and lifetimes were low for the conjugates due to quenching by the nanoparticles.
- Full Text:
- Date Issued: 2011
Optimizing the electrocatalytic activity of surface confined Co macrocyclics for the electrooxidation of thiocyanate at pH 4
- Tshangana, Charmaine, Pavez, Jorge, Gulppi, Miguel A, De Mattos, Ivanildo Luiz, Arratia-Perez, Ramiro, Linares-Flores, Cristian, Paez, Maritza, Nyokong, Tebello, Zagal, Jos H
- Authors: Tshangana, Charmaine , Pavez, Jorge , Gulppi, Miguel A , De Mattos, Ivanildo Luiz , Arratia-Perez, Ramiro , Linares-Flores, Cristian , Paez, Maritza , Nyokong, Tebello , Zagal, Jos H
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247726 , vital:51612 , xlink:href="https://doi.org/10.1002/elan.201000599"
- Description: We have studied the trends in catalytic activity of several Co macrocyclics confined on the surface graphite electrodes for the oxidation of thiocyanate. A plot of log i (at constant E) versus the formal potential of the catalyst gives a volcano correlation, indicating that the Co(II/I) redox potential needs to be tuned, in order to achieve maximum reactivity. Graphite electrodes modified with Co phthalocyanine at pH 4 exhibit linear amperometric response for thiocyanate concentration in the range 10−7 and 10−3 M. Theoretical calculations show that electrocatalytic activity (as log i at constant E) plotted versus the energy of the LUMO of the Co complex also gives a volcano correlation.
- Full Text:
- Date Issued: 2011
- Authors: Tshangana, Charmaine , Pavez, Jorge , Gulppi, Miguel A , De Mattos, Ivanildo Luiz , Arratia-Perez, Ramiro , Linares-Flores, Cristian , Paez, Maritza , Nyokong, Tebello , Zagal, Jos H
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247726 , vital:51612 , xlink:href="https://doi.org/10.1002/elan.201000599"
- Description: We have studied the trends in catalytic activity of several Co macrocyclics confined on the surface graphite electrodes for the oxidation of thiocyanate. A plot of log i (at constant E) versus the formal potential of the catalyst gives a volcano correlation, indicating that the Co(II/I) redox potential needs to be tuned, in order to achieve maximum reactivity. Graphite electrodes modified with Co phthalocyanine at pH 4 exhibit linear amperometric response for thiocyanate concentration in the range 10−7 and 10−3 M. Theoretical calculations show that electrocatalytic activity (as log i at constant E) plotted versus the energy of the LUMO of the Co complex also gives a volcano correlation.
- Full Text:
- Date Issued: 2011
Electrochemical behavior of phthalocyanines containing high oxidation state central metals
- Chauke, Vongani, Arslanoglu, Yasin, Nyokong, Tebello
- Authors: Chauke, Vongani , Arslanoglu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247111 , vital:51547 , xlink:href="https://doi.org/10.1016/j.poly.2011.05.028"
- Description: The syntheses of 2,(3)-(peripheral) and 1,(4)-(non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium(IV) oxide (5a and 6a, respectively), vanadium(IV) oxide (7a and 8a, respectively) and tantalum(V) hydroxide (9a, peripheral only) and their electrochemical characterization are presented in this report. Their electrochemistry is compared to that of thiophenyl and thiobenzyl substituted derivatives. The non-peripherally substituted complexes are more difficult to reduce than peripherally substituted derivatives. In addition, the mercaptopyridine substituted derivatives are more difficult to reduce compared to benzylmercapto and phenylmercapto derivatives, and aryl easier reduce than alkyl substitution. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes.
- Full Text:
- Date Issued: 2011
- Authors: Chauke, Vongani , Arslanoglu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247111 , vital:51547 , xlink:href="https://doi.org/10.1016/j.poly.2011.05.028"
- Description: The syntheses of 2,(3)-(peripheral) and 1,(4)-(non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium(IV) oxide (5a and 6a, respectively), vanadium(IV) oxide (7a and 8a, respectively) and tantalum(V) hydroxide (9a, peripheral only) and their electrochemical characterization are presented in this report. Their electrochemistry is compared to that of thiophenyl and thiobenzyl substituted derivatives. The non-peripherally substituted complexes are more difficult to reduce than peripherally substituted derivatives. In addition, the mercaptopyridine substituted derivatives are more difficult to reduce compared to benzylmercapto and phenylmercapto derivatives, and aryl easier reduce than alkyl substitution. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes.
- Full Text:
- Date Issued: 2011
Redox activity of CdTe quantum dots linked to nickel tetraaminophthalocyanine
- Khene, Samson, Nyokong, Tebello
- Authors: Khene, Samson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246457 , vital:51478 , xlink:href="https://doi.org/10.1016/j.microc.2011.06.024"
- Description: Cadmium tellurite quantum dots (CdTe-QDs) are linked to nickel tetraamino phthalocyanine (CdTe-QDs-NiTAPc) through an amide bond. Differential pulse voltammetry shows that that NiTAPc stabilizes the QDs against oxidative disintegration into metallic products on oxidation. Electrocatalytic oxidation of 2, 4-dichlorophenol (DCP) and pentachlorophenol (PCP) on CdTe-QDs and CdTe-QDs-NiTAPc adsorbed or electrodeposited onto a gold electrode were studied. Adsorbed CdTe-QDs-NiTAPc shows the lowest potential for DCP and PCP oxidation and it is also more stable to fouling by PCP and its oxidation products compared to adsorbed CdTe-QDs without NiTAPc. Electrodeposited CdTe-QDs or CdTe-QDs-NiTAPc show the best activity in terms of enhanced currents towards the oxidation of the chlorophenols.
- Full Text:
- Date Issued: 2011
- Authors: Khene, Samson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246457 , vital:51478 , xlink:href="https://doi.org/10.1016/j.microc.2011.06.024"
- Description: Cadmium tellurite quantum dots (CdTe-QDs) are linked to nickel tetraamino phthalocyanine (CdTe-QDs-NiTAPc) through an amide bond. Differential pulse voltammetry shows that that NiTAPc stabilizes the QDs against oxidative disintegration into metallic products on oxidation. Electrocatalytic oxidation of 2, 4-dichlorophenol (DCP) and pentachlorophenol (PCP) on CdTe-QDs and CdTe-QDs-NiTAPc adsorbed or electrodeposited onto a gold electrode were studied. Adsorbed CdTe-QDs-NiTAPc shows the lowest potential for DCP and PCP oxidation and it is also more stable to fouling by PCP and its oxidation products compared to adsorbed CdTe-QDs without NiTAPc. Electrodeposited CdTe-QDs or CdTe-QDs-NiTAPc show the best activity in terms of enhanced currents towards the oxidation of the chlorophenols.
- Full Text:
- Date Issued: 2011
Photocatalytic behaviour of tantalum (V) phthalocyanines in the presence of gold nanoparticles towards the oxidation of cyclohexene
- Chauke, Vongani P, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chauke, Vongani P , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247904 , vital:51628 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.023"
- Description: This paper presents the photocatalytic oxidation of cyclohexene using (OH)3TaPc derivatives in the absence or presence of gold nanoparticles (AuNPs). The photochemical parameters that include photodegradation (ΦP) and singlet oxygen (ΦΔ) quantum yields are also reported in this work. The ΦΔ values were 0.47 and 0.36 for complexes 1a and 1b, respectively. The ΦΔ values improved drastically in the presence of AuNPs to 0.75 and 0.88, respectively. The ΦP values ranged from 1.02 to 2.45 × 10−6, showing stability of TaPc derivatives in the absence and presence of AuNPs. The photocatalytic products identified using gas chromatograph (GC) are cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. The percentage conversion values were higher in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The product yield percentage values for both TaPc complexes (1a and 1b) and TaPc in the presence of AuNPs ranged from 6.3 to 21.2%.
- Full Text:
- Date Issued: 2011
- Authors: Chauke, Vongani P , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247904 , vital:51628 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.023"
- Description: This paper presents the photocatalytic oxidation of cyclohexene using (OH)3TaPc derivatives in the absence or presence of gold nanoparticles (AuNPs). The photochemical parameters that include photodegradation (ΦP) and singlet oxygen (ΦΔ) quantum yields are also reported in this work. The ΦΔ values were 0.47 and 0.36 for complexes 1a and 1b, respectively. The ΦΔ values improved drastically in the presence of AuNPs to 0.75 and 0.88, respectively. The ΦP values ranged from 1.02 to 2.45 × 10−6, showing stability of TaPc derivatives in the absence and presence of AuNPs. The photocatalytic products identified using gas chromatograph (GC) are cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. The percentage conversion values were higher in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The product yield percentage values for both TaPc complexes (1a and 1b) and TaPc in the presence of AuNPs ranged from 6.3 to 21.2%.
- Full Text:
- Date Issued: 2011
Synthesis and photophysical properties of a novel zinc photosensitizer and its gold nanoparticle conjugate
- Moeno, Sharon, Antunes, Edith M, Nyokong, Tebello
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
- Full Text:
- Date Issued: 2011
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
- Full Text:
- Date Issued: 2011
Photophysical and photochemical behavior of electrospun fibers of a polyurethane polymer chemically linked to lutetium carboxyphenoxy phthalocyanine
- Zugle, Ruphino, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello
- Authors: Zugle, Ruphino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
- Full Text:
- Date Issued: 2011
- Authors: Zugle, Ruphino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
- Full Text:
- Date Issued: 2011
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