Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Syntheses and photochemical properties of octasubstituted phthalocyaninato zinc complexes
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304841 , vital:58495 , xlink:href="https://doi.org/10.1002/jpp.388"
- Description: In this work a selection of octasubstituted phthalocyaninato zinc complexes were synthesized and their photochemistry studied. The substituents included cholesterol (3a), estrone (3b), naphthol (3c) and phenoxy groups substituted with CH3 (3d), C(CH3)3 (at two positions, 3e), C(CH3)3 (3f), NO2 (3g), NH2 (3h), COH (3i), COOH (3j), and H (3k). In general, complexes containing electron-donating groups attached to the phenoxy ring (e.g. 3e and 3f) were found to be photochemically unstable with photobleaching quantum yields of the order of 10−3. In the presence of electron-withdrawing groups (3g, 3i, and 3j) the photobleaching quantum yields were of the order of 10−6 to 10−5. Singlet oxygen quantum yields (ΦΔ) ranged from 0.01 to 0.73. The lowest ΦΔ was observed for the highly aggregated complex 3c. All the complexes showed aggregation at high concentrations. Electrochemical reduction using a thin-layer spectroelectrochemistry cell showed that the complexes become more monomeric following reduction.
- Full Text:
- Date Issued: 2001
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304841 , vital:58495 , xlink:href="https://doi.org/10.1002/jpp.388"
- Description: In this work a selection of octasubstituted phthalocyaninato zinc complexes were synthesized and their photochemistry studied. The substituents included cholesterol (3a), estrone (3b), naphthol (3c) and phenoxy groups substituted with CH3 (3d), C(CH3)3 (at two positions, 3e), C(CH3)3 (3f), NO2 (3g), NH2 (3h), COH (3i), COOH (3j), and H (3k). In general, complexes containing electron-donating groups attached to the phenoxy ring (e.g. 3e and 3f) were found to be photochemically unstable with photobleaching quantum yields of the order of 10−3. In the presence of electron-withdrawing groups (3g, 3i, and 3j) the photobleaching quantum yields were of the order of 10−6 to 10−5. Singlet oxygen quantum yields (ΦΔ) ranged from 0.01 to 0.73. The lowest ΦΔ was observed for the highly aggregated complex 3c. All the complexes showed aggregation at high concentrations. Electrochemical reduction using a thin-layer spectroelectrochemistry cell showed that the complexes become more monomeric following reduction.
- Full Text:
- Date Issued: 2001
Synthesis, photophysical and photochemical studies of germanium and tin phthalocyanine complexes
- Maree, Suzanne, Phillips, David, Nyokong, Tebello
- Authors: Maree, Suzanne , Phillips, David , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289667 , vital:56661 , xlink:href="https://doi.org/10.1142/S108842460200004X"
- Description: This work reports on the synthesis of tin and germanium phthalocyanine complexes containing phenoxy and substituted phenoxy groups as phthalocyanine ring substituents. The compounds studied are: dichlorogermanium phthalocyanine complexes containing eight phenoxy (4a), o-methyl phenoxy (4b) or estrone (4c) groups on the ring. The corresponding dichlorotin complexes (5a, 5b and 5c) and diiodotin complex (6a) were also investigated, as well as diestrone phthalocyaninato tin (7). Germanium octaphenoxy phthalocyanine complexes undergo phototransformation rather than direct photobleaching, whereas tin octaphenoxy phthalocyanine complexes undergo a photobleaching process, which is mediated by photoreduction of the phthalocyanine ring. Tin octaphenoxy phthalocyanine complexes gave higher ΦΔ values than the corresponding germanium complexes. Also tin phthalocyanine complexes containing an unsubstituted ring gave higher ΦΔ values than the corresponding octaphenoxy substituted complexes. The triplet quantum yields increased with the increase in electron-donating power of the ring substituents.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Suzanne , Phillips, David , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289667 , vital:56661 , xlink:href="https://doi.org/10.1142/S108842460200004X"
- Description: This work reports on the synthesis of tin and germanium phthalocyanine complexes containing phenoxy and substituted phenoxy groups as phthalocyanine ring substituents. The compounds studied are: dichlorogermanium phthalocyanine complexes containing eight phenoxy (4a), o-methyl phenoxy (4b) or estrone (4c) groups on the ring. The corresponding dichlorotin complexes (5a, 5b and 5c) and diiodotin complex (6a) were also investigated, as well as diestrone phthalocyaninato tin (7). Germanium octaphenoxy phthalocyanine complexes undergo phototransformation rather than direct photobleaching, whereas tin octaphenoxy phthalocyanine complexes undergo a photobleaching process, which is mediated by photoreduction of the phthalocyanine ring. Tin octaphenoxy phthalocyanine complexes gave higher ΦΔ values than the corresponding germanium complexes. Also tin phthalocyanine complexes containing an unsubstituted ring gave higher ΦΔ values than the corresponding octaphenoxy substituted complexes. The triplet quantum yields increased with the increase in electron-donating power of the ring substituents.
- Full Text:
- Date Issued: 2002
Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes
- Tau, Prudence, Ogunsipe, Abimbola O, Maree, Suzanne, Maree, M David, Nyokong, Tebello
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
Photochemical studies of binuclear phenoxysubstituted phthalocyanines containing catecholate bridges
- Seotsanyana-Mokhosi, Itumeleng, Maree, Suzanne, Maree, M David, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304808 , vital:58492 , xlink:href="https://doi.org/10.1142/S1088424603000239"
- Description: Binuclear ZnPc complexes covalently bridged by catechol units have been synthesized and their absorption and photochemical properties examined. The complexes studied are 1,2-bis-2',9',16',23'-triphenoxyphthalocyaninatozinc benzene (6a), 1,2-bis-2'-9',16',23'-tri-4-carboxyphe-noxyphthalocyaninatozinc benzene (6b), 1,2-bis-2',9',16',23'-tri-4-nitrophenoxyphthalocyaninato- zinc benzene (6c) and 1,2-bis-2'-9',16',23'-tri-4-tert-butylphenoxyphthalocyaninatozinc benzene (6d). Larger intramolecular coupling was observed for 6b and 6c, containing the carboxyphenoxy and nitrophenoxy substituents, respectively, than for 6a and 6d. A single Q band peak was observed for the fluorescence spectra of 6b and 6c, whereas, 6a and 6d showed a split Q band. The absence of the high energy fluorescence peaks corresponding to absorbance peaks in the 640 nm region, suggests that the intramolecular coupling is broken by excitation for complexes 6b and 6c.
- Full Text:
- Date Issued: 2003
Photochemical studies of binuclear phenoxysubstituted phthalocyanines containing catecholate bridges
- Authors: Seotsanyana-Mokhosi, Itumeleng , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304808 , vital:58492 , xlink:href="https://doi.org/10.1142/S1088424603000239"
- Description: Binuclear ZnPc complexes covalently bridged by catechol units have been synthesized and their absorption and photochemical properties examined. The complexes studied are 1,2-bis-2',9',16',23'-triphenoxyphthalocyaninatozinc benzene (6a), 1,2-bis-2'-9',16',23'-tri-4-carboxyphe-noxyphthalocyaninatozinc benzene (6b), 1,2-bis-2',9',16',23'-tri-4-nitrophenoxyphthalocyaninato- zinc benzene (6c) and 1,2-bis-2'-9',16',23'-tri-4-tert-butylphenoxyphthalocyaninatozinc benzene (6d). Larger intramolecular coupling was observed for 6b and 6c, containing the carboxyphenoxy and nitrophenoxy substituents, respectively, than for 6a and 6d. A single Q band peak was observed for the fluorescence spectra of 6b and 6c, whereas, 6a and 6d showed a split Q band. The absence of the high energy fluorescence peaks corresponding to absorbance peaks in the 640 nm region, suggests that the intramolecular coupling is broken by excitation for complexes 6b and 6c.
- Full Text:
- Date Issued: 2003
- «
- ‹
- 1
- ›
- »