Priscilla Baker

Metallo-Graphene Nanocomposite Electrocatalytic Platform for the Determination of Toxic Metal Ions

A Nafion-Graphene (Nafion-G) nanocomposite solution in combination with an in situ plated mercury film electrode was used as a highly sensitive electrochemical platform for the determination of Zn2+, Cd2+, Pb2+ and Cu2+ in 0.1 M acetate buffer (pH 4.6) by square-wave anodic stripping voltammetry (SWASV). Various operational parameters such as deposition potential, deposition time and electrode rotation speed were optimized. The Nafion-G nanocomposite sensing platform exhibited improved sensitivity for metal ion detection, in addition to well defined, reproducible and sharp stripping signals. The linear calibration curves ranged from 1 μg L−1 to 7 μg L−1 for individual analysis. The detection limits (3σ blank/slope) obtained were 0.07 μg L−1 for Pb2+, Zn2+ and Cu2+ and 0.08 μg L−1 for Cd2+ at a deposition time of 120 s. For practical applications recovery studies was done by spiking test samples with known concentrations and comparing the results with inductively coupled plasma mass spectrometry (ICP-MS) analyses. This was followed by real sample analysis.

Electrochemical Aptasensor for Endocrine Disrupting 17β-Estradiol Based on a Poly(3,4-ethylenedioxylthiopene)-Gold Nanocomposite Platform

A simple and highly sensitive electrochemical DNA aptasensor with high affinity for endocrine disrupting 17β-estradiol, was developed. Poly(3,4-ethylenedioxylthiophene) (PEDOT) doped with gold nanoparticles (AuNPs) was electrochemically synthesized and employed for the immobilization of biotinylated aptamer towards the detection of the target. The diffusion coefficient of the nanocomposite was 6.50 × 10−7 cm2 s−1, which showed that the nanocomposite was highly conducting. Electrochemical impedance investigation also revealed the catalytic properties of the nanocomposite with an exchange current value of 2.16 × 10−4 A, compared to 2.14 × 10−5 A obtained for the bare electrode. Streptavidin was covalently attached to the platform using carbodiimide chemistry and the aptamer immobilized via streptavidin—biotin interaction. The electrochemical signal generated from the aptamer–target molecule interaction was monitored electrochemically using cyclic voltammetry and square wave voltammetry in the presence of [Fe(CN)6]−3/−4 as a redox probe. The signal observed shows a current decrease due to interference of the bound 17β-estradiol. The current drop was proportional to the concentration of 17β-estradiol. The PEDOT/AuNP platform exhibited high electroactivity, with increased peak current. The platform was found suitable for the immobilization of the DNAaptamer. The aptasensor was able to distinguish 17β-estradiol from structurally similar endocrine disrupting chemicals denoting its specificity to 17β-estradiol. The detectable concentration range of the 17β-estradiol was 0.1 nM–100 nM, with a detection limit of 0.02 nM.

Electrochemical Immunosensor Based on Polythionine/Gold Nanoparticles for the Determination of Aflatoxin B1

An aflatoxin B1 (AFB1) electrochemical immunosensor was developed by the immobilisation of aflatoxin B1-bovine serum albumin (AFB1-BSA) conjugate on a polythionine (PTH)/gold nanoparticles (AuNP)-modified glassy carbon electrode (GCE). The surface of the AFB1-BSA conjugate was covered with horseradish peroxidase (HRP), in order to prevent non-specific binding of the immunosensors with ions in the test solution. The AFB1 immunosensor exhibited a quasi-reversible electrochemistry as indicated by a cyclic voltammetric (CV) peak separation (ΔEp) value of 62 mV. The experimental procedure for the detection of AFB1 involved the setting up of a competition between free AFB1 and the immobilised AFB1-BSA conjugate for the binding sites of free anti-aflatoxin B1 (anti-AFB1) antibody. The immunosensors differential pulse voltammetry (DPV) responses (peak currents) decreased as the concentration of free AFB1 increased within a dynamic linear range (DLR) of 0.6 - 2.4 ng/mL AFB1 and a limit of detection (LOD) of 0.07 ng/mL AFB1. This immunosensing procedure eliminates the need for enzyme-labeled secondary antibodies normally used in conventional ELISA–based immunosensors.

Electrochemical detection of glyphosate herbicide using horseradish peroxidase immobilized on sulfonated polymer matrix.

This paper describes the use of horseradish peroxidase (HRP) based biosensor for novel detection of glyphosate herbicide. The biosensor was prepared by electrochemically depositing poly(2,5-dimethoxyaniline) (PDMA) doped with poly(4-styrenesulfonic acid) (PSS) onto the surface of a gold electrode followed by electrostatic attachment of the enzyme HRP onto the PDMA-PSS composite film. Fourier transform infrared (FTIR) and UV-Vis spectrometry inferred that HRP was not denatured during its immobilization on PDMA-PSS composite film. The biosensing principle was based on the determination of the cathodic responses of the immobilized HRP to H(2)O(2), before and after incubation in glyphosate standard solutions. Glyphosate inhibited the activity of HRP causing a decrease in its response to H(2)O(2). The determination of glyphosate was achieved in the range of 0.25-14.0 microg L(-1) with a detection limit of 1.70 microg L(-1). The apparent Michaelis-Menten constant (calculated for the HRP/PDMA-PSS biosensor in the presence and absence of glyphosate was found to be 7.73 microM and 7.95 microM respectively.

Cytochrome c biosensor for determination of trace levels of cyanide and arsenic compounds.

An electrochemical method based on a cytochrome c biosensor was developed, for the detection of selected arsenic and cyanide compounds. Boron doped diamond (BDD) electrode was used as a transducer, onto which cytochrome c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH=7) was found to be in the range of (1.1-4.5)×10(-8) A μM(-1) and the detection limits ranged from 4.3 to 9.1 μM. The biosensor is therefore able to measure significantly lower than current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines, for these types of analytes. The protein binding was monitored as a decrease in biosensor peak currents by SWV and as an increase in biosensor charge transfer resistance by electrochemical impedance spectroscopy (EIS). EIS provided evidence that the electrocatalytic advantage of BDD electrode was not lost upon immobilisation of cytochrome c. The interfacial kinetics of the biosensor was modelled as equivalent electrical circuit based on electrochemical impedance spectroscopy data. UV-vis spectroscopy was used to confirm the binding of the protein in solution by monitoring the intensity of the soret bands and the Q bands. FTIR was used to characterise the protein in the immobilised state and to confirm that the protein was not denatured upon binding to the pre-treated bare BDD electrode. SNFTIR of cyt c immobilised at platinum electrode, was used to study the effect of oxidation state on the surface bond vibrations. The spherical morphology of the immobilised protein, which is typical of native cytochrome c, was observed using scanning electron microscopy (SEM) and confirmed the immobilisation of the cytochrome c without denaturisation.

Determination of Anthracene on Ag-Au Alloy Nanoparticles/Overoxidized-Polypyrrole Composite Modified Glassy Carbon Electrodes

A novel electrochemical sensor for the detection of anthracene was prepared by modifying a glassy carbon electrode (GCE) with over-oxidized polypyrrole (PPyox) and Ag-Au (1:3) bimetallic nanoparticles (Ag-AuNPs). The composite electrode (PPyox/Ag-AuNPs/GCE) was prepared by potentiodynamic polymerization of pyrrole on GCE followed by its overoxidation in 0.1 M NaOH. Ag-Au bimetallic nanoparticles were chemically prepared by the reduction of AgNO3 and HAuCl4 using C6H5O7Na3 as the reducing agent as well as the capping agent and then immobilized on the surface of the PPyox/GCE. The nanoparticles were characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the bimetallic alloy nanoparticles. Transmission electron microscopy showed that the synthesized bimetallic nanoparticles were in the range of 20–50 nm. The electrochemical behaviour of anthracene at the PPyox/Ag-AuNPs/GCE with Ag: Au atomic ratio 25:75 (1:3) exhibited a higher electrocatalytic effect compared to that observed when GCE was modified with each constituent of the composite (i.e., PPyox, Ag-AuNPs) and bare GCE. A linear relationship between anodic current and anthracene concentration was attained over the range of 3.0 × 10−6 to 3.56 × 10−4 M with a detection limit of 1.69 × 10−7 M. The proposed method was simple, less time consuming and showed a high sensitivity.

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.

An Electrochemical DNA Biosensor Developed on a Nanocomposite Platform of Gold and Poly(propyleneimine) Dendrimer

An electrochemical DNA nanobiosensor was prepared by immobilization of a 20mer thiolated probe DNA on electro-deposited generation 4 (G4) poly(propyleneimine) dendrimer (PPI) doped with gold nanoparticles (AuNP) as platform, on a glassy carbon electrode (GCE). Field emission scanning electron microscopy results confirmed the co-deposition of PPI (which was linked to the carbon electrode surface by C-N covalent bonds) and AuNP ca 60 nm. Voltammetric interrogations showed that the platform (GCE/PPI-AuNP) was conducting and exhibited reversible electrochemistry (E°′ = 235 mV) in pH 7.2 phosphate buffer saline solution (PBS) due to the PPI component. The redox chemistry of PPI was pH dependent and involves a two electron, one proton process, as interpreted from a 28 mV/pH value obtained from pH studies. The charge transfer resistance (Rct) from the electrochemical impedance spectroscopy (EIS) profiles of GCE/PPI-AuNP monitored with ferro/ferricyanide (Fe(CN)63-/4-) redox probe, decreased by 81% compared to bare GCE. The conductivity (in PBS) and reduced Rct (in Fe(CN)63-/4-) values confirmed PPI-AuNP as a suitable electron transfer mediator platform for voltammetric and impedimetric DNA biosensor. The DNA probe was effectively wired onto the GCE/PPI-AuNP via Au-S linkage and electrostatic interactions. The nanobiosensor responses to target DNA which gave a dynamic linear range of 0.01 - 5 nM in PBS was based on the changes in Rct values using Fe(CN)63-/4- redox probe.

Environmental remediation of heavy metal ions from aqueous solution through hydrogel adsorption: a critical review

Heavy metal ions such as Cd(2+), Pb(2+), Cu(2+), Mg(2+), and Hg(2+) from industrial waste water constitute a major cause of pollution for ground water sources. These ions are toxic to man and aquatic life as well, and should be removed from wastewater before disposal. Various treatment technologies have been reported to remediate the potential toxic elements from aqueous media, such as adsorption, precipitation and coagulation. Most of these technologies are associated with some shortcomings, and challenges in terms of applicability, effectiveness and cost. However, adsorption techniques have the capability of effectively removing heavy metals at very low concentration (1-100 mg/L). Various adsorbents have been reported in the literature for this purpose, including, to a lesser extent, the use of hydrogel adsorbents for heavy metal removal in aqueous phase. Here, we provide an in-depth perspective on the design, application and efficiency of hydrogel systems as adsorbents.

Amperometric nanobiosensor for quantitative determination of glyphosate and glufosinate residues in corn samples.

This study presents a simple, sensitive, rapid, and low-cost amperometric method for direct and quantitative determination of glyphosate and glufosinate herbicides. Electrochemical synthesis and characterization of poly(2,5-dimethoxyaniline)-poly(4-styrenesulfonic acid) (PDMA-PSS) nanoparticles was achieved by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The nanobiosensor was constructed by immobilizing the enzyme horseradish peroxidase (HRP) electrostatically onto the surface of a rotating gold disk electrode modified with PDMA-PSS nanoparticles. The biosensing principle was based on determination of the sensor response to glyphosate and glufosinate by amperometric methods. Hydrogen peroxide (H2O2) was used to measure activity of the enzyme before injection of the herbicides into the electrolyte solution. The enzyme electrode was stable for a long period of time and was used for over 60 measurements. Glyphosate and glufosinate analyses were realized on spiked corn samples within a concentration range of 2.0-78.0 μg L-1, corroborating that the nanobiosensor is sensitive enough to detect herbicides in these matrices. Based on a 20-μL sample injection volume, the detection limits were 0.1 μg L-1 (10-10 M) for both glyphosate and glufosinate without sample clean-up or preconcentration.