Tetracarboxylic acid cobalt phthalocyanine SAM on gold: Potential applications as amperometric sensor for H2O2 and fabrication of glucose biosensor

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

A model for the integration of provincial and local authority nurses rendering primary health care services in a district

Prior to 1994, the South African Health Department was characterised by a fragmented health care system, which was largely curative and hospital based, with services planned and managed without community involvement and participation. The government, through the establishment of a district health system, integrated the health services with the aim of overcoming the fragmentation, and providing integrated comprehensive health care services that are equitable, accessible, efficient and effective. The integration of health services in Gauteng, meant the devolution of primary health care services from the provincial health department to the local authority health department, because the local authority services are nearer and accountable to the community. The process of integration of health services also meant the closing down of provincial clinics and transferring of provincial authority nurses to the local authority clinics. The transfer process impacted negatively on staff morale and on the resources available for health care delivery to the communities. It is against this background that the researcher decided to investigate the integration process. The researcher then conducted focus group interviews with the local authority nurses, provincial authority nurses and the district management team as these nurses's immediate supervisors. The results revealed that the local and provincial authority nurses were integrated without proper consultation and as a result integration was rejected. The following themes emerged from the results as negative perceptions and obstacles towards integration: lack of consultation, disparities in conditions of service and resistance to change. Positive perceptions also emerged from the results as strategies to improve the integration, and these strategies were used to develop guidelines to operationalise the model. It is envisaged that the proposed model will serve as a theoretical framework for nurse managers from both spheres of government, local and provincial to improve the integration of nurses through proper consultation, and involvement of nurses in the process affecting them. It is further envisaged that the model will serve as guideline to introduce changes within the district health system with more understanding and acceptance by nurses affected. Health care managers will find the model useful to overcome disparities in conditions of service among nurses and, in turn this may boost the moral of nurses and lead to successful integration of provincial and local authority nurses.Health StudiesD.Litt. et Phil (Health Studies

Study of metallophthalocyanines attached onto pre-modified gold surfaces

Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection

Electrochemical sensing and immunosensing using metallophthalocyanines and biomolecular modified surfaces

The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease

Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes

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

Design and evaluation of an electrochemical immunosensor for measles serodiagnosis using measles-specific Immunoglobulin G antibodies

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

Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine

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

Characterization of electrodes modified by one pot or step by step electro-click reaction and axial ligation of iron tetracarboxyphthalocyanine

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

“Turn on” fluorescence enhancement of Zn octacarboxyphthaloyanine-graphene oxide conjugates by hydrogen peroxide

Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyaninereduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences

Iodine-Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction

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