Metallophthalocyanines as electrocatalysts and superoxide dismutase mimics
- Authors: Matemadombo, Fungisai
- Date: 2010
- Subjects: Mimicry (Chemistry) Electrocatalysis Superoxide dismutase Electrochemistry Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4325 , http://hdl.handle.net/10962/d1004985
- Description: Syntheses, spectral, electrochemical, and spectroelectrochemical studies of iron, cobalt, and manganese phthalocyanines are reported. The novel coordination of cobalt tetracarboxy metallophthalocyanine to an electrode premodified with aryl radicals and its use in the detection of thiocyanate are reported. This work describes the catalytic activity of cobalt phthalocyanine (CoPc) derivatives adsorbed onto glassy carbon electrodes for the electrocatalytical detection of nitrite, Lcysteine, and melatonin. The modified electrodes efficiently detected nitrite. The CoPc derivative modified electrodes proficiently detected L-cysteine whereas an un-modified electrode could not. This work presents the innovative electrochemical detection of melatonin using electrodes adsorbed with CoPc derivatives. These electrodes detected melatonin at more favorable electrochemical parameters relative to an un-modified gold electrode. The limits of melatonin detection of the modified electrodes lay in the 10⁻⁷ to 10⁻⁶ M region. The modified electrodes accurately detected capsule melatonin concentrations as specified by the supplier and could differentiate between a mixture of melatonin, tryptophan, and ascorbic acid. They reliably detected nitrite, L-cysteine, and melatonin in the 10⁻⁴ to 10⁻² M region. Metallophthalocyanine complexes substituted with thio groups were employed as self assembled monolayers (SAMs). Voltammetry, impedance, atomic force microscopy, and scanning electrochemical microscopy proved that the SAMs all act as selective and efficient barriers to ion permeability. All the SAMs in this work can be used as effective electrochemical sensors of nitrite and L-cysteine in the 10⁻⁴ to 10⁻² M region with competitive limits of detection whereas an un-modified electrode cannot detect Lcysteine. The manganese phthalocyanine SAM modified electrodes are arguably better nitrite and L-cysteine electrocatalysts relative to their iron and cobalt counterparts. Manganese phthalocyanines were used as superoxide dismutase (SOD) mimics. All manganese phthalocyanine complexes in this work acted as SOD mimics in an enzymatic system of superoxide production. From cellular studies, complexes 6d, 6e, 8d, 8e act as intracellular SOD mimics and are without significantly high cellular toxicity.
- Full Text:
- Date Issued: 2010
- Authors: Matemadombo, Fungisai
- Date: 2010
- Subjects: Mimicry (Chemistry) Electrocatalysis Superoxide dismutase Electrochemistry Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4325 , http://hdl.handle.net/10962/d1004985
- Description: Syntheses, spectral, electrochemical, and spectroelectrochemical studies of iron, cobalt, and manganese phthalocyanines are reported. The novel coordination of cobalt tetracarboxy metallophthalocyanine to an electrode premodified with aryl radicals and its use in the detection of thiocyanate are reported. This work describes the catalytic activity of cobalt phthalocyanine (CoPc) derivatives adsorbed onto glassy carbon electrodes for the electrocatalytical detection of nitrite, Lcysteine, and melatonin. The modified electrodes efficiently detected nitrite. The CoPc derivative modified electrodes proficiently detected L-cysteine whereas an un-modified electrode could not. This work presents the innovative electrochemical detection of melatonin using electrodes adsorbed with CoPc derivatives. These electrodes detected melatonin at more favorable electrochemical parameters relative to an un-modified gold electrode. The limits of melatonin detection of the modified electrodes lay in the 10⁻⁷ to 10⁻⁶ M region. The modified electrodes accurately detected capsule melatonin concentrations as specified by the supplier and could differentiate between a mixture of melatonin, tryptophan, and ascorbic acid. They reliably detected nitrite, L-cysteine, and melatonin in the 10⁻⁴ to 10⁻² M region. Metallophthalocyanine complexes substituted with thio groups were employed as self assembled monolayers (SAMs). Voltammetry, impedance, atomic force microscopy, and scanning electrochemical microscopy proved that the SAMs all act as selective and efficient barriers to ion permeability. All the SAMs in this work can be used as effective electrochemical sensors of nitrite and L-cysteine in the 10⁻⁴ to 10⁻² M region with competitive limits of detection whereas an un-modified electrode cannot detect Lcysteine. The manganese phthalocyanine SAM modified electrodes are arguably better nitrite and L-cysteine electrocatalysts relative to their iron and cobalt counterparts. Manganese phthalocyanines were used as superoxide dismutase (SOD) mimics. All manganese phthalocyanine complexes in this work acted as SOD mimics in an enzymatic system of superoxide production. From cellular studies, complexes 6d, 6e, 8d, 8e act as intracellular SOD mimics and are without significantly high cellular toxicity.
- Full Text:
- Date Issued: 2010
Remarkable sensitivity for detection of bisphenol A on a gold electrode modified with nickel tetraamino phthalocyanine containing Ni–O–Ni bridges
- Chauke, Vongani, Matemadombo, Fungisai, Nyokong, Tebello
- Authors: Chauke, Vongani , Matemadombo, Fungisai , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261280 , vital:53380 , xlink:href="https://doi.org/10.1016/j.jhazmat.2010.01.061"
- Description: This work reports the electrocatalysis of bisphenol A on Ni(II) tetraamino metallophthalocyanine (NiTAPc) polymer modified gold electrode containing Ni–O–Ni bridges (represented as Ni(OH)TAPc). The Ni(II)TAPc films were electro-transformed in 0.1 mol L−1 NaOH aqueous solution to form ‘O–Ni–O oxo bridges’, forming poly-n-Ni(OH)TAPc (where n is the number of polymerising scans). poly-30-Ni(OH)TAPc, poly-50-Ni(OH)TAPc, poly-70-Ni(OH)TAPc and poly-90-Ni(OH)TAPc films were investigated. The polymeric films were characterised by electrochemical impedance spectroscopy and the charge transfer resistance (RCT) values increased with film thickness. The best catalytic activity for the detection of bisphenol A was on poly-70-Ni(OH)TAPc. Electrode resistance to passivation improved with polymer thickness. The electrocatalytic behaviour of bisphenol A was compared to that of p-nitrophenol in terms of electrode passivation and regeneration. The latter was found to passivate the electrode less than the former. The poly-70-Ni(OH)TAPc modified electrode could reliably detect bisphenol A in a concentration range of 7 × 10−4 to 3 × 10−2 mol L−1 with a limit of detection of 3.68 × 10−9 mol L−1. The sensitivity was 3.26 × 10−4 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2010
- Authors: Chauke, Vongani , Matemadombo, Fungisai , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261280 , vital:53380 , xlink:href="https://doi.org/10.1016/j.jhazmat.2010.01.061"
- Description: This work reports the electrocatalysis of bisphenol A on Ni(II) tetraamino metallophthalocyanine (NiTAPc) polymer modified gold electrode containing Ni–O–Ni bridges (represented as Ni(OH)TAPc). The Ni(II)TAPc films were electro-transformed in 0.1 mol L−1 NaOH aqueous solution to form ‘O–Ni–O oxo bridges’, forming poly-n-Ni(OH)TAPc (where n is the number of polymerising scans). poly-30-Ni(OH)TAPc, poly-50-Ni(OH)TAPc, poly-70-Ni(OH)TAPc and poly-90-Ni(OH)TAPc films were investigated. The polymeric films were characterised by electrochemical impedance spectroscopy and the charge transfer resistance (RCT) values increased with film thickness. The best catalytic activity for the detection of bisphenol A was on poly-70-Ni(OH)TAPc. Electrode resistance to passivation improved with polymer thickness. The electrocatalytic behaviour of bisphenol A was compared to that of p-nitrophenol in terms of electrode passivation and regeneration. The latter was found to passivate the electrode less than the former. The poly-70-Ni(OH)TAPc modified electrode could reliably detect bisphenol A in a concentration range of 7 × 10−4 to 3 × 10−2 mol L−1 with a limit of detection of 3.68 × 10−9 mol L−1. The sensitivity was 3.26 × 10−4 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2010
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