Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- D'Souza, Sarah, Mashazi, Philani N, Britton, Jonathan, Nyokong, Tebello
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes
- Mashazi, Philani N, Nyokong, Tebello
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
Electrode modification using alkynyl substituted Fe (II) phthalocyanine via electrografting and click chemistry for electrocatalysis
- Nxele, Siphesihle R, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
Iodine-Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction
- Nyoni, Stephen, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189434 , vital:44846 , xlink:href="https://doi.org/10.1002/elan.201400499"
- Description: 4-(4,6-Diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV-vis, X-ray photoelectron, electron paramagnetic resonance and infra-red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine-doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine-doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite.
- Full Text:
- Date Issued: 2015
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189434 , vital:44846 , xlink:href="https://doi.org/10.1002/elan.201400499"
- Description: 4-(4,6-Diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV-vis, X-ray photoelectron, electron paramagnetic resonance and infra-red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine-doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine-doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite.
- Full Text:
- Date Issued: 2015
Photophysical properties of zinc phthalocyanine–uridine single walled carbon nanotube–conjugates
- Ogbodu, Rachael O, Amuhaya, Edith K, Mashazi, Philani N, Nyokong, Tebello
- Authors: Ogbodu, Rachael O , Amuhaya, Edith K , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193586 , vital:45350 , xlink:href="https://doi.org/10.1016/j.saa.2015.04.040"
- Description: The photophysical properties of the conjugate of uridine and zinc mono carboxy phenoxy phthalocyanine (ZnMCPPc–uridine, 4) are reported in this work. The conjugate was also adsorbed onto single walled carbon nanotubes (ZnMCPPc–uridine–SWCNT, 5). The X-ray photoelectron spectroscopy of 4 showed three N 1s peaks while that of 5 showed four N 1s peak, a new peak at 399.4 eV of 5 was assigned to pyrrolidonic nitrogen, due to the interaction of the pyrrolic nitrogen of 4 with the oxygen moiety of SWCNT–COOH in 5. The triplet lifetime, triplet and singlet oxygen quantum yields of the zinc mono carboxy phenoxy phthalocyanine increased by over 40% in the presence of uridine. SWCNTs resulted in only a small quenching of the triplet state parameters of 4.
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Rachael O , Amuhaya, Edith K , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193586 , vital:45350 , xlink:href="https://doi.org/10.1016/j.saa.2015.04.040"
- Description: The photophysical properties of the conjugate of uridine and zinc mono carboxy phenoxy phthalocyanine (ZnMCPPc–uridine, 4) are reported in this work. The conjugate was also adsorbed onto single walled carbon nanotubes (ZnMCPPc–uridine–SWCNT, 5). The X-ray photoelectron spectroscopy of 4 showed three N 1s peaks while that of 5 showed four N 1s peak, a new peak at 399.4 eV of 5 was assigned to pyrrolidonic nitrogen, due to the interaction of the pyrrolic nitrogen of 4 with the oxygen moiety of SWCNT–COOH in 5. The triplet lifetime, triplet and singlet oxygen quantum yields of the zinc mono carboxy phenoxy phthalocyanine increased by over 40% in the presence of uridine. SWCNTs resulted in only a small quenching of the triplet state parameters of 4.
- Full Text:
- Date Issued: 2015
Synthesis and photophysical properties of nanocomposites of aluminum tetrasulfonated phthalocyanine covalently linked to glutathione capped CdTe/CdS/ZnS quantum dots
- Oluwole, David O, Britton, Jonathan, Mashazi, Philani N, Nyokong, Tebello
- Authors: Oluwole, David O , Britton, Jonathan , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241379 , vital:50934 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.04.015"
- Description: Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was covalently linked with different sizes of glutathione capped CdTe/CdS/ZnS quantum dots (QDs). The photophysical and Förster resonance energy transfer (FRET) properties of the nanoconjugates were investigated. The CdTe/CdS/ZnS(6.3) nanocomposite showed the highest enhancement in its photophysical properties while (CdTe/CdS/ZnS(3.2) nanocomposite showed the least. Highest FRET efficiency was observed in the linked CdTe/CdS/ZnS(6.3) nanocomposites at 93%. Hence, the combination of CdTe/CdS/ZnS with ClAlTSPc exhibited excellent photophysical properties.
- Full Text:
- Date Issued: 2015
- Authors: Oluwole, David O , Britton, Jonathan , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241379 , vital:50934 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.04.015"
- Description: Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was covalently linked with different sizes of glutathione capped CdTe/CdS/ZnS quantum dots (QDs). The photophysical and Förster resonance energy transfer (FRET) properties of the nanoconjugates were investigated. The CdTe/CdS/ZnS(6.3) nanocomposite showed the highest enhancement in its photophysical properties while (CdTe/CdS/ZnS(3.2) nanocomposite showed the least. Highest FRET efficiency was observed in the linked CdTe/CdS/ZnS(6.3) nanocomposites at 93%. Hence, the combination of CdTe/CdS/ZnS with ClAlTSPc exhibited excellent photophysical properties.
- Full Text:
- Date Issued: 2015
Characterization of electrodes modified by one pot or step by step electro-click reaction and axial ligation of iron tetracarboxyphthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
Design and evaluation of an electrochemical immunosensor for measles serodiagnosis using measles-specific Immunoglobulin G antibodies
- Mashazi, Philani N, Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Mashazi, Philani N , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241705 , vital:50962 , xlink:href="https://doi.org/10.1016/j.talanta.2013.06.036"
- Description: The design of electrochemical immunosensors for the detection of measles-specific antibodies is reported. The measles-antigen modified surface was used as an antibody capture surface. The detection of measles-specific IgG antibodies was accomplished using the voltammetric method and horse-radish peroxidase (HRP) labeled secondary antibody (anti-IgG) as a detecting antibody. The potential applications of the designed immunosensor were evaluated in buffer and serum solutions. The immunosensor exhibited good linearity at concentrations less than 100 ng mL−1 with R2=0.997 and the limit of detection of 6.60 ng mL−1 at 3σ. The potential application of the immunosensor was evaluated in the deliberately infected human and newborn calf serum samples with measles-IgG antibody mimicking real-life samples. The designed electrochemical immunosensor could differentiate between infected and un-infected serum samples as higher catalytic currents were obtained for infected serum samples.
- Full Text:
- Date Issued: 2013
- Authors: Mashazi, Philani N , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241705 , vital:50962 , xlink:href="https://doi.org/10.1016/j.talanta.2013.06.036"
- Description: The design of electrochemical immunosensors for the detection of measles-specific antibodies is reported. The measles-antigen modified surface was used as an antibody capture surface. The detection of measles-specific IgG antibodies was accomplished using the voltammetric method and horse-radish peroxidase (HRP) labeled secondary antibody (anti-IgG) as a detecting antibody. The potential applications of the designed immunosensor were evaluated in buffer and serum solutions. The immunosensor exhibited good linearity at concentrations less than 100 ng mL−1 with R2=0.997 and the limit of detection of 6.60 ng mL−1 at 3σ. The potential application of the immunosensor was evaluated in the deliberately infected human and newborn calf serum samples with measles-IgG antibody mimicking real-life samples. The designed electrochemical immunosensor could differentiate between infected and un-infected serum samples as higher catalytic currents were obtained for infected serum samples.
- Full Text:
- Date Issued: 2013
Electrochemical impedimetric immunosensor for the detection of measles-specific IgG antibodies after measles infections
- Mashazi, Philani N, Tetyana, Phumlani, Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Mashazi, Philani N , Tetyana, Phumlani , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241677 , vital:50960 , xlink:href="https://doi.org/10.1016/j.bios.2013.04.028"
- Description: The detection of measles-specific primary antibodies (IgG) using electrochemical impedimetric immunosensors is reported. The optimum conditions for electrode saturation were reached after 40 min for 1 μg ml−1 antibody concentrations. Surface roughness using AFM increased with each immobilization or antigen-antibody reaction step clearly confirming the surface modification and recognition between antigen and antibody. The human serum (HS) and new-born calf serum (NCS) spiked with antigen-specific antibody were studied to mimic the real sample analysis. The HS and NCS sera containing antibodies due to measles exhibited correlation between the increasing antibody serum concentrations and the charge-transfer resistance (electrochemically measured). This work clearly showed the potential use of impedance as the preferred electrochemical method for detecting measles-antibodies in label-free manner.
- Full Text:
- Date Issued: 2013
- Authors: Mashazi, Philani N , Tetyana, Phumlani , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241677 , vital:50960 , xlink:href="https://doi.org/10.1016/j.bios.2013.04.028"
- Description: The detection of measles-specific primary antibodies (IgG) using electrochemical impedimetric immunosensors is reported. The optimum conditions for electrode saturation were reached after 40 min for 1 μg ml−1 antibody concentrations. Surface roughness using AFM increased with each immobilization or antigen-antibody reaction step clearly confirming the surface modification and recognition between antigen and antibody. The human serum (HS) and new-born calf serum (NCS) spiked with antigen-specific antibody were studied to mimic the real sample analysis. The HS and NCS sera containing antibodies due to measles exhibited correlation between the increasing antibody serum concentrations and the charge-transfer resistance (electrochemically measured). This work clearly showed the potential use of impedance as the preferred electrochemical method for detecting measles-antibodies in label-free manner.
- Full Text:
- Date Issued: 2013
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
Applications of polymerized metal tetra-amino phthalocyanines towards hydrogen peroxide detection
- Mashazi, Philani N, Togo, Chumunorwa, Limson, Janice L, Nyokong, Tebello
- Authors: Mashazi, Philani N , Togo, Chumunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261840 , vital:53451 , xlink:href="https://doi.org/10.1142/S1088424610001994"
- Description: This work reports the use of metallo tetra-amino phthalocyanines (MTAPc, M = Co and Mn) polymer thin films on gold and glassy carbon electrode surfaces for the detection and monitoring of hydrogen peroxide (H2O2). The polymer-modified electrodes were characterized using electrochemical and microscopic-based methods. Atomic force microscopy (AFM) was used to study the bare and polymer-modified ITO surfaces. The electrocatalytic reduction of H2O2 with glassy carbon polymer-modified electrodes gave higher current densities compared to their gold counterparts. The electroanalytical properties of H2O2 were obtained using a real-time calibration curve of the amperometric determination in pH 7.4 aqueous solution. The limits of detection (LoD) of the polymer-modified electrodes towards electroreduction of H2O2 were of the order of 10–7 M, with high sensitivity ranging from 6.0–15.4 mA.mM-1.cm-2.
- Full Text:
- Date Issued: 2010
- Authors: Mashazi, Philani N , Togo, Chumunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261840 , vital:53451 , xlink:href="https://doi.org/10.1142/S1088424610001994"
- Description: This work reports the use of metallo tetra-amino phthalocyanines (MTAPc, M = Co and Mn) polymer thin films on gold and glassy carbon electrode surfaces for the detection and monitoring of hydrogen peroxide (H2O2). The polymer-modified electrodes were characterized using electrochemical and microscopic-based methods. Atomic force microscopy (AFM) was used to study the bare and polymer-modified ITO surfaces. The electrocatalytic reduction of H2O2 with glassy carbon polymer-modified electrodes gave higher current densities compared to their gold counterparts. The electroanalytical properties of H2O2 were obtained using a real-time calibration curve of the amperometric determination in pH 7.4 aqueous solution. The limits of detection (LoD) of the polymer-modified electrodes towards electroreduction of H2O2 were of the order of 10–7 M, with high sensitivity ranging from 6.0–15.4 mA.mM-1.cm-2.
- Full Text:
- Date Issued: 2010
Probing electrochemical and electrocatalytic properties of cobalt (II) and manganese (III) octakis (hexylthio) phthalocyanine as self-assembled monolayers
- Mashazi, Philani N, Antunes, Edith M, Nyokong, Tebello
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
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
Tetracarboxylic acid cobalt phthalocyanine SAM on gold: Potential applications as amperometric sensor for H2O2 and fabrication of glucose biosensor
- Mashazi, Philani N, Ozoemena, Kenneth I, Nyokong, Tebello
- 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
- 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.
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- Date Issued: 2006