Facile deposition of gold nanoparticle thin films on semi-permeable cellulose substrate
- Sosibo, Ndabenhle, Mdluli, Phumlani, Mashazi, Philani N, Tshikhudo, Robert, Skepu, Amanda, Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Sosibo, Ndabenhle , Mdluli, Phumlani , Mashazi, Philani N , Tshikhudo, Robert , Skepu, Amanda , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242638 , vital:51063 , xlink:href="https://doi.org/10.1016/j.matlet.2012.08.043"
- Description: This study reports the facile method for the deposition of gold nanoparticle thin film onto a monoporous semi-permeable cellulose membrane through the diffusion of borohydride ions leading to the reduction of AuCl4− ions. The synthesis of gold nanoparticle thin film was deposited on one side of the membrane that was exposed to AuCl4− ions while the other side containing a reducing agent remained clear. The gold nanoparticle thin film exhibited a broad surface plasmon resonance (SPR) peak at 529 nm. Various characterization techniques were employed and all demonstrated the presence of gold thin film. The reported method represents a simplistic method for the deposition of gold nanoparticle thin films and various other metal nanoparticles may be deposited following this method.
- Full Text:
- Date Issued: 2012
- Authors: Sosibo, Ndabenhle , Mdluli, Phumlani , Mashazi, Philani N , Tshikhudo, Robert , Skepu, Amanda , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242638 , vital:51063 , xlink:href="https://doi.org/10.1016/j.matlet.2012.08.043"
- Description: This study reports the facile method for the deposition of gold nanoparticle thin film onto a monoporous semi-permeable cellulose membrane through the diffusion of borohydride ions leading to the reduction of AuCl4− ions. The synthesis of gold nanoparticle thin film was deposited on one side of the membrane that was exposed to AuCl4− ions while the other side containing a reducing agent remained clear. The gold nanoparticle thin film exhibited a broad surface plasmon resonance (SPR) peak at 529 nm. Various characterization techniques were employed and all demonstrated the presence of gold thin film. The reported method represents a simplistic method for the deposition of gold nanoparticle thin films and various other metal nanoparticles may be deposited following this method.
- Full Text:
- Date Issued: 2012
Synthesis, density functional theory, molecular dynamics and electrochemical studies of 3-thiopheneacetic acid-capped gold nanoparticles
- Sosibo, Ndabenhle M, Mdluli, Phumlane S, Mashazi, Philani N, Dyan, Busiswa, Revaprasadu, Neerish, Nyokong, Tebello, Tshikhudo, Robert T, Skepu, Amanda, Van Der Lingen, Elma
- Authors: Sosibo, Ndabenhle M , Mdluli, Phumlane S , Mashazi, Philani N , Dyan, Busiswa , Revaprasadu, Neerish , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , Van Der Lingen, Elma
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246446 , vital:51477 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.09.057"
- Description: Gold nanoparticles capped with a bifunctional ligand, 3-thiopheneacetic acid (3-TAA) were synthesised by borohydride reduction at room temperature. The transmission electron microscopy (TEM) analysis showed that the particle aggregates and had semi-linear partial linkages that could be attributed to multi-modal binding of the ligand with various gold nanoparticles through the terminal thiolether (–S–) group and oxygen of the carboxylic (–COOH) group. This bimodal interaction led to limited stability of the resultant nanoparticles when tested using highly electrolytic media. To investigate further, density functional theory (DFT) quantum chemical and molecular dynamic calculations were conducted. The energetically favorable binding modes of the ligand to gold nanoparticle surfaces using the Gaussian program were studied. The DFT results showed kinetic stability of Au–3-TAA–Au interactions leading to inter-particle coupling or aggregation. Electrochemical analysis of the resultant nature of the capping agent revealed that 3-thiopheneacetic acid did not form a polymer during the preparation of Au–3-TAA. The cyclic voltammograms of Au–3-TAA nanoparticles coated glassy carbon electrode showed a typical gold character with the oxidation and reduction peaks at 1.4 V and 0.9 V, respectively.
- Full Text:
- Date Issued: 2012
- Authors: Sosibo, Ndabenhle M , Mdluli, Phumlane S , Mashazi, Philani N , Dyan, Busiswa , Revaprasadu, Neerish , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , Van Der Lingen, Elma
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246446 , vital:51477 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.09.057"
- Description: Gold nanoparticles capped with a bifunctional ligand, 3-thiopheneacetic acid (3-TAA) were synthesised by borohydride reduction at room temperature. The transmission electron microscopy (TEM) analysis showed that the particle aggregates and had semi-linear partial linkages that could be attributed to multi-modal binding of the ligand with various gold nanoparticles through the terminal thiolether (–S–) group and oxygen of the carboxylic (–COOH) group. This bimodal interaction led to limited stability of the resultant nanoparticles when tested using highly electrolytic media. To investigate further, density functional theory (DFT) quantum chemical and molecular dynamic calculations were conducted. The energetically favorable binding modes of the ligand to gold nanoparticle surfaces using the Gaussian program were studied. The DFT results showed kinetic stability of Au–3-TAA–Au interactions leading to inter-particle coupling or aggregation. Electrochemical analysis of the resultant nature of the capping agent revealed that 3-thiopheneacetic acid did not form a polymer during the preparation of Au–3-TAA. The cyclic voltammograms of Au–3-TAA nanoparticles coated glassy carbon electrode showed a typical gold character with the oxidation and reduction peaks at 1.4 V and 0.9 V, respectively.
- Full Text:
- Date Issued: 2012
Selective adsorption of PVP on the surface of silver nanoparticles
- Mdluli, Phumlani S, Sosibo, Ndabenhle M, Mashazi, Philani N, Nyokong, Tebello, Tshikhudo, Robert T, Skepu, Amanda, van der Lingen, Elma
- Authors: Mdluli, Phumlani S , Sosibo, Ndabenhle M , Mashazi, Philani N , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , van der Lingen, Elma
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247143 , vital:51550 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.07.049"
- Description: The use of surfactants to affect the shape evolution of silver nanoparticles is explored. This allows one to fine-tune the morphological evolution and the optical properties of the metal nanoparticles. Polyvinyl pyrrolidone (PVP) has been used as a surfactant to control the growth of silver nanoparticles at room temperature. In this paper, molecular dynamics simulations were performed to understand regio-selective adsorption of PVP that leads to the preferential growth of silver nanoparticles in dimethylformamide (DMF). The interaction energies between PVP and Ag(1 1 0), Ag(1 0 0) and Ag(1 1 1) crystal planes were calculated and in addition the length density profile of the surfactant on silver surfaces was also examined. Importantly, it has been demonstrated that the length distribution profiles analysis obtained from the molecular dynamics study fully explained the adsorption of PVP on the surface of silver nanoparticles through the carbonyl group of the PVP ring. The application of molecular dynamics simulation technique is important in understanding the evolution of silver nanoparticles and is vital in choosing the right surfactants.
- Full Text:
- Date Issued: 2011
- Authors: Mdluli, Phumlani S , Sosibo, Ndabenhle M , Mashazi, Philani N , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , van der Lingen, Elma
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247143 , vital:51550 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.07.049"
- Description: The use of surfactants to affect the shape evolution of silver nanoparticles is explored. This allows one to fine-tune the morphological evolution and the optical properties of the metal nanoparticles. Polyvinyl pyrrolidone (PVP) has been used as a surfactant to control the growth of silver nanoparticles at room temperature. In this paper, molecular dynamics simulations were performed to understand regio-selective adsorption of PVP that leads to the preferential growth of silver nanoparticles in dimethylformamide (DMF). The interaction energies between PVP and Ag(1 1 0), Ag(1 0 0) and Ag(1 1 1) crystal planes were calculated and in addition the length density profile of the surfactant on silver surfaces was also examined. Importantly, it has been demonstrated that the length distribution profiles analysis obtained from the molecular dynamics study fully explained the adsorption of PVP on the surface of silver nanoparticles through the carbonyl group of the PVP ring. The application of molecular dynamics simulation technique is important in understanding the evolution of silver nanoparticles and is vital in choosing the right surfactants.
- Full Text:
- Date Issued: 2011
The effects of carbon nanotubes on the electrocatalysis of hydrogen peroxide by metallo-phthalocyanines
- Mashazi, Philani N, Mugadza, Tawanda, Sosibo, Ndabenhle, Mdluli, Phumlani, Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Mashazi, Philani N , Mugadza, Tawanda , Sosibo, Ndabenhle , Mdluli, Phumlani , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247174 , vital:51553 , xlink:href="https://doi.org/10.1016/j.talanta.2011.07.069"
- Description: The pre-grafted screen-printed gold electrode modified with phenyl-amino monolayer was investigated for covalent immobilization of phenyl-amine functionalized single-walled carbon nanotubes (PA-SWCNT) and metal tetra-amino phthalocyanine (MTAPc) using Schiff-base reactions with benzene-1,4-dicarbaldehyde (BDCA) as cross-linker. The PA-SWCNT and MTAPc modified electrodes were applied as hybrids for electrochemical sensing of H2O2. The step-by-step fabrication of the electrode was followed using electrochemistry, impedance spectroscopy, scanning electron microscopy and Raman spectroscopy and all these techniques confirmed the fabrication and the immobilization of PA-SWCNT, MnTAPc and CoTAPc onto gold surfaces. The apparent electron transfer constant (kapp) showed that the carbon nanotubes and metallo-phthalocyanines hybrids possess good electron transfer properties compared to the bare, pre-grafted and the MTAPc modified gold electrode surfaces without PA-SWCNT. The electrochemical sensing of hydrogen peroxide was successful with PA-SWCNT–MTAPc hybrid systems showing higher electrocatalytic currents compared to the other electrodes. The analytical parameters obtained using chronoamperometry gave good linearity at H2O2 concentrations ranging from 1.0 to 30.0 μmol L−1. The values for the limit of detection (LoD) were found to be of the orders of 10−7 M using the 3δ for all the electrodes. The PA-SWCNT–MTAPc modified SPAuEs were much more sensitive compared to PA–MTAPc modified SPAuEs.
- Full Text:
- Date Issued: 2011
- Authors: Mashazi, Philani N , Mugadza, Tawanda , Sosibo, Ndabenhle , Mdluli, Phumlani , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247174 , vital:51553 , xlink:href="https://doi.org/10.1016/j.talanta.2011.07.069"
- Description: The pre-grafted screen-printed gold electrode modified with phenyl-amino monolayer was investigated for covalent immobilization of phenyl-amine functionalized single-walled carbon nanotubes (PA-SWCNT) and metal tetra-amino phthalocyanine (MTAPc) using Schiff-base reactions with benzene-1,4-dicarbaldehyde (BDCA) as cross-linker. The PA-SWCNT and MTAPc modified electrodes were applied as hybrids for electrochemical sensing of H2O2. The step-by-step fabrication of the electrode was followed using electrochemistry, impedance spectroscopy, scanning electron microscopy and Raman spectroscopy and all these techniques confirmed the fabrication and the immobilization of PA-SWCNT, MnTAPc and CoTAPc onto gold surfaces. The apparent electron transfer constant (kapp) showed that the carbon nanotubes and metallo-phthalocyanines hybrids possess good electron transfer properties compared to the bare, pre-grafted and the MTAPc modified gold electrode surfaces without PA-SWCNT. The electrochemical sensing of hydrogen peroxide was successful with PA-SWCNT–MTAPc hybrid systems showing higher electrocatalytic currents compared to the other electrodes. The analytical parameters obtained using chronoamperometry gave good linearity at H2O2 concentrations ranging from 1.0 to 30.0 μmol L−1. The values for the limit of detection (LoD) were found to be of the orders of 10−7 M using the 3δ for all the electrodes. The PA-SWCNT–MTAPc modified SPAuEs were much more sensitive compared to PA–MTAPc modified SPAuEs.
- Full Text:
- Date Issued: 2011
Critical assessment of the quartz crystal microbalance with dissipation as an analytical tool for biosensor development and fundamental studies
- Fogel, Ronen, Mashazi, Philani N, Nyokong, Tebello, Limson, Janice L
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice L
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice L
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode
- Mashazi, Philani N, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- 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.
- Full Text:
- Date Issued: 2007
- 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.
- Full Text:
- Date Issued: 2007
Self-assembled monolayers (SAMs) of cobalt tetracarboxylic acidchloride phthalocyanine covalently attached onto a preformed mercaptoethanol SAM
- Mashazi, Philani N, Ozoemena, Kenneth I, Maree, David M, Nyokong, Tebello
- 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.
- Full Text:
- Date Issued: 2006
- 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.
- Full Text:
- Date Issued: 2006