Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode
- Authors: Mashazi, Philani N , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268806 , vital:54233 , xlink:href="https://doi.org/10.1016/j.electacta.2007.08.044"
- Description: Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (MIII/MII) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where MnIV/MnIII redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10−7 mol L−1 and good linearity for a studied concentration range up to 60 μmol L−1.
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- Date Issued: 2007
Self-assembled monolayers (SAMs) of cobalt tetracarboxylic acidchloride phthalocyanine covalently attached onto a preformed mercaptoethanol SAM
- Authors: Mashazi, Philani N , Ozoemena, Kenneth I , Maree, David M , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283792 , vital:55989 , xlink:href="https://doi.org/10.1016/j.electacta.2005.10.004"
- Description: A feasible method of fabricating phthalocyanine sensor was developed by covalent attachment of cobalt tetracarboxylic acidchloride phthalocyanine (CoTCACIPc) onto a preformed 2-mercaptoethanol (2-ME) self-assembled monolayer (SAM) modified gold electrode (designated as CoTCACIPc-2-ME-SAM). The surface concentration of the CoTCACIPc was found to be 4.58 × 10−10 mol/cm2. The sensor gave a linear response to L-cysteine over the concentration range 0.28–20 μM with a detection limit of 5 × 10−7 M and best response time of 2 s.
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- Date Issued: 2006
Tetracarboxylic acid cobalt phthalocyanine SAM on gold: Potential applications as amperometric sensor for H2O2 and fabrication of glucose biosensor
- Authors: Mashazi, Philani N , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6578 , http://hdl.handle.net/10962/d1004141
- Description: This report describes the applications of cobalt tetracarboxylic acid phthalocyanine (CoTCAPc) self-assembled monolayer (SAM) immobilized onto a preformed 2-mercaptoethanol (Au-ME) SAM on gold surface (Au-ME-CoTCAPc SAM) as a potential amperometric sensor for the detection of hydrogen peroxide (H[subscript 2]O[subscript 2]) at neutral pH conditions. The Au-ME-CoTCAPc SAM sensor showed a very fast amperometric response time of approximately 1 s, good linearity at the studied concentration range of up to 5 μM with a coefficient R² = 0.993 and a detection limit of 0.4 μM oxidatively. Also reductively, the sensor exhibited a very fast amperometric response time (~1 s), linearity up to 5 μM with a coefficient R² = 0.986 and a detection limit of 0.2 μM. The cobalt tetracarboxylic acid phthalocyanine self-assembled monolayer was then evaluated as a mediator for glucose oxidase (GOx)-based biosensor. The GOx (enzyme) was immobilized covalently onto Au-ME-CoTCAPc SAM using coupling agents: N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS), and the results demonstrated a good catalytic behavior. Kinetic parameters associated with the enzymatic and mediator reactions were estimated using electrochemical versions of Lineweaver–Burk and Hanes equation, and the stability of the sensor was tested. The biosensor (Au-ME-CoTCAPc-GOx SAM) electrode showed good sensitivity (7.5 nA/mM) with a good detection limit of 8.4 μM at 3σ, smaller Michaelis–Menten constant (4.8 mM from Hanes plot) and very fast response time of approximately 5 s.
- Full Text:
- Date Issued: 2006