Browsing by Author "Waryo, Tesfaye T."
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Item Application on gold nanoparticles-dotted 4-nitrophenylazo graphene in a label-free impedimetric deoxynivalenol immunosensor(MDPI, 2015) Sunday, Christopher Edozie; Masikini, Malua; Wilson, Lindsay; Rassie, Candice; Waryo, Tesfaye T.; Baker, Priscilla; Iwuoha, Emmanuel I.In this paper, we report a new concept to construct a label-free electrochemical inhibition-based immunosensor for the detection of the mycotoxin deoxynivalenol (DON) in cereal samples. The electrochemical impedance spectroscopy of tris(bipyridine) ruthenium (II) chloride was used as a marker enhanced with gold nanoparticles-dotted 4-nitrophenylazo functionalized graphene (AuNp/G/PhNO2) nanocatalyst mediated in Nafion on a glassy carbon electrode. Under the optimized conditions, the formation of immunocomplexes inhibited electron flow and increased the charge transfer resistance of the sensing interface linearly. The change in impedance was proportional to DON concentrations in the range of 6–30 ng/mL with a sensitivity and detection limit of 32.14 ΩL/ng and 0.3 µg/mL, respectively, which compares favorably with the ELISA result. The proposed sensor had a stability of 80.3%, good precision and selectivity in DON standard solution containing different interfering agents, indicating promising application prospect for this strategy in designing impedimetric, electrochemiluminescent, voltammetric or amperometric sensors.Item Aptameric recognition-modulated electroactivity of poly(4-styrenesolfonic acid)-doped polyaniline films for single-shot detection of tetrodotoxin(MDPI, 2015) Fomo, Gertrude; Waryo, Tesfaye T.; Sunday, Christopher Edozie; Baleg, Abd A.; Baker, Priscilla; Iwuoha, Emmanuel I.The work being reported is the first electrochemical sensor for tetrodotoxin (TTX). It was developed on a glassy carbon electrodes (C) that was modified with poly(4-styrenesolfonic acid)-doped polyaniline film (PANI/PSSA). An amine-end functionalized TTX-binding aptamer, 5′-NH2-AAAAATTTCACACGGGTGCCTCGGCTGTCC-3′ (NH2-Apt), was grafted via covalent glutaraldehyde (glu) cross-linking. The resulting aptasensor (C//PANI+/PSSA-glu-NH2-Apt) was interrogated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in sodium acetate buffer (NaOAc, pH 4.8) before and after 30 min incubation in standard TTX solutions. Both CV and EIS results confirmed that the binding of the analyte to the immobilized aptamer modulated the electrochemical properties of the sensor: particularly the charge transfer resistance (Rct) of the PANI+/PSSA film, which served as a signal reporter. Based on the Rct calibration curve of the TTX aptasensor, the values of the dynamic linear range (DLR), sensitivity and limit of detection (LOD) of the sensor were determined to be 0.23–1.07 ng·mL−1 TTX, 134.88 ± 11.42 Ω·ng·mL−1 and 0.199 ng·mL−1 , respectively. Further studies are being planned to improve the DLR as well as to evaluate selectivity and matrix effects in real samples.Item Carcinoembryonic antigen immunosensor developed with organoclay nanogold composite film(ESG, 2014) Kemmegne-Mbouguen, Justin Claude; Ngameni, Emmanuel; Baker, Priscilla; Waryo, Tesfaye T.; Kgarebe, Boitumelo; Iwuoha, Emmanuel I.Organoclay nanogold composite were prepared using gold nanoparticles and the natural Cameroonian clay grafted with amino organosilane. The functionnalization of clay provided abundant amino group to assemble gold nanoparticles. A label-free electrochemical immunosensor for the sensitive determination of carcinoembryonic antigen (CEA) was fabricated by immobilizing anti-CEA onto organoclay nanogold composite film modified electrode by the cross-linking method using glutaraldehyde. In addition, the preparation procedure of the immunosensor was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimal conditions, the resulting immunosensor displayed a high sensitivity for the detection of CEA, and responded to the CEA concentration in two ranges from 0.05 to 5.0 ng/mL (R = 0.991) and from 5.0 to 120.0 ng/mL (R = 0.998) with a detection limit of 0.01 ng/mL.Item Correction: Baker, P. et al. electrochemical aptasensor for endocrine disrupting 17β-estradiol based on a poly(3,4-ethylenedioxylthiopene)-gold nanocomposite platform. Sensors 2010, 10, 9872-9890(MDPI, 2011) Olowu, Rasaq A.; Arotiba, Omotayo A.; Mailu, Stephen N.; Waryo, Tesfaye T.; Baker, Priscilla; Iwuoha, Emmanuel I.Herewith please find corrected structures for Figure 8 in our paper published in Sensors in 2010.Item Determination of anthracene on Ag-Au alloy nanoparticles/overoxidized-polypyrrole composite modified glassy carbon electrodes(MDPI, 2010) Mailu, Stephen N.; Waryo, Tesfaye T.; Ndangili, Peter M.; Ngece, Fanelwa R.; Baleg, Abd A.; Baker, Priscilla; Iwuoha, Emmanuel I.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.Item The development of graphene oxide sheet- and polyanilino-immunosensor systems for lipoarabinomannan (LAM) tuberculosis biomarker(University of the Western Cape, 2017) Wilson, Lindsay Robin; Iwuoha, Emmanuel; Waryo, Tesfaye T.Tuberculosis (TB) is an infectious disease with adverse effect on a global scale. The disease is one of the major causes of death in sub-Saharan Africa. Nearly 70% of TB-infected persons are co-infected by the human immunodeficiency virus (HIV). About 50% of TB/HIV patients are smear negative and up to 28% are sputum scarce, which is a significant problem in South Africa since sputum smear microscopy is the most widely used diagnostic test for TB. The detection of Mycobacterium tuberculosis (MTB) and resistance to the TB drug rifampicin (RIF) are the basis of the GeneXpert MTB/RIF protocol. The GeneXpert MTB/RIF is an automated nucleic acid amplification technique for detecting the DNA that originates from MTB. However, low sensitivity and low concentrations of MTB for DNA amplification are a serious issue associated with the protocol. Therefore, other TB diagnostic methods, such as the ones involving biochemical markers of TB, are becoming very important.Item Electrochemical aptasensor for endocrine disrupting 17β-estradiol based on a poly(3,4-ethylenedioxylthiopene)-gold nanocomposite platform(MDPI, 2010) Olowu, Rasaq A.; Mailu, Stephen N.; Waryo, Tesfaye T.; Baker, Priscilla; Iwuoha, Emmanuel I.; Arotiba, Omotayo A.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.Item Electrochemical characterization of nanostructured SnO2 and TiO2 for potential application as dielectric materials in sulfonated-polyaniline based supercapacitors(University of the Western Cape, 2010) Ngqongwa, Lundi Vincent; Iwuoha, Emmanuel; Waryo, Tesfaye T.; Baker, Priscilla G.L.; Dept. of Chemistry; Faculty of ScienceIn this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).Item Electrochemical determination of phenothrin in fruit juices at graphene oxide-polypyrrole modified glassy carbon electrode(Elsevier, 2018) Tefera, Molla; Tessema, Merid; Admassie, Shimelis; Iwuoha, Emmanuel I.; Waryo, Tesfaye T.; Baker, Priscilla G.L.An electrochemical sensor was developed based on graphen oxide-polypyrrole modified glassy carbon electrode (GO/PPy/GCE) for sensitive determination of phenothrin in fruit samples. GO/PPy/GCE was characterized by scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Ultraviolet-Visible spectroscopy (UV–Vis) and Raman spectroscopy. The sensor was also characterized using electrochemical impedance spectroscopy and cyclic voltammetry. Compared to bare GCE, GO/GCE and PPy/GCE, the reduction peak current of phenothrin increased significantly at GO/PPy/GCE, demonstrating that GO/PPy/GCE exhibited electrocatalytic activity towards the reduction of phenothrin. Under the optimal conditions, the sensor showed a linear relationship over the range of 2.5×10−8-2.0×10−5 M with detection limits of 13.8×10−9 M. In addition, the analytical application of the proposed method was carried out by the determination of phenothrin in fruit juice samples.Item An electrochemical DNA biosensor developed on a nanocomposite platform of gold and poly(propyleneimine) dendrimer(MDPI, 2008) Arotiba, Omotayo A.; Owino, Joseph; Songa, Everlyne; Hendricks, Nicolette; Waryo, Tesfaye T.; Jahed, Nazeem; Baker, Priscilla; Iwuoha, Emmanuel I.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 codeposition 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)6 3-/4-) redox probe, decreased by 81% compared to bare GCE. The conductivity (in PBS) and reduced Rct (in Fe(CN)6 3-/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)6 3-/4- redox probe.Item Electrochemical immunosensor based on polythionine/gold nanoparticles for the determination of Aflatoxin B1(MDPI, 2008) Owino, Joseph H.O.; Arotiba, Omotayo A.; Hendricks, Nicolette; Songa, Everlyne; Jahed, Nazeem; Waryo, Tesfaye T.; Ngece, Rachel F.; Baker, Priscilla; Iwuoha, Emmanuel I.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 immunosensor’s 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.Item Electrodeposition of multi-valent metal oxides at 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid - carbon paste electrode(University of the Western Cape, 2012) Qwesha, Sibusiso; Iwuoha, Emmanuel; Waryo, Tesfaye T.A study on carbon paste electrode (CPE) materials containing 1-methyl-3-octylimidazolium bis (trifluoromethylsulfonyl) imide [MOIM[Tƒ2N] – a hydrophobic room temperature ionic liquid (IL) - is reported. CPEs with (a) the IL as the only binder (ILCPE) and (b) 1:1 (v/v) IL: paraffin mixture as the binder (ILPCPE) were prepared, characterized, and applied to the electrodeposition of films of multivalent transition metal oxides (MV-TMO) from five precursor ions (Fe2+, Mn2+, Cu2+, Co2+, Ce4+) in aq. KCl. Cyclic voltammetry (CV) showed a potential window of +1.5 V to -1.8 V regardless of the electrode type, including the traditional paraffin CP electrode (PCPE). However, the IL increased the background current by 100-folds relative to paraffin. The electrochemical impedance spectroscopy (EIS) of ILPCPE in aq. KCl (0.1M) revealed two phase angle maxima in contrast with the single maxima for PCPE and ILCP. The study also included the CV and EIS investigation of the electrode kinetics of the Fe(CN)6 3-/4 redox system at these electrodes. The electrodeposition of Fe2+, Co2+, and Mn2+ possibly in the form of the MV-TMOs FexOy, CoxOy, and MnxOy, respectively, onto the electrodes was confirmed by the observation of new and stable cathodic and anodic peaks in a fresh precursor ion –free medium. CVs of H2O2 as a redox probe supported the same conclusions. Both ATR-FTIR spectra and SEM image of surface samples confirmed the formation of electrodeposited films. This study demonstrated that the use of this hydrophobic IL alone or in combination with paraffin as a binder gives viable alternative CPE materials with better performance for the electrodeposition of MV-TMOs films than the paraffin CPE. Thus, in combination with the easy preparation methods and physical “morpheability” in to any shape, these CPEs are potentially more useful in electrochemical technologies based on high surface-area MV-TMO films in general, and MnxOy films in particular.Item The use of cyclodextrin template-based metal oxide nanomaterials in the development of electrochemical sensors for phenolic endocrine disruptor compounds(University of the Western Cape, 2010) Masikini, Milua; Waryo, Tesfaye T.; Baker, Priscilla G.; Iwuoha, Emmanuel; Dept. of Chemistry; Faculty of ScienceIron oxide nanoparticles were prepared using co-precipitation method in the presence and absence of beta-cyclodextrin β-CD). Such materials were characterized using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), attenuated total reflection Fourier transform infrared (ATR-FTIR), X-ray diffraction (XRD), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA). The TEM shows that the surface morphology has no difference between nanoparticles prepared in the presence and absence of beta-cyclodextrin β-CD), amorphous particles with high surface area and dimensions of about 100 nm by 500 nm. The amorphous states of nanoparticles are confirmed further by XRD. The ATR-FTIR analysis confirms inclusion complex between β-CD and nanoparticles. The nanoparticles synthesized were used to develop an electrochemical sensor for phenolic endocrine disruptors by modifying the surface area of glassy carbon electrode (GCE). Electrochemical characterization of the iron oxide β-CD nano-composites, studied in 0.1 M potassium chloride (KCl) using chronoamperometry,showed that the surface concentration of the adsorbed composite material was 8.5 x 10-8 mol/cm2. Sensor analysis of bisphenol A (BPA) was carried out using cyclic voltammetry (CV) and square wave voltammetry (SWV) based on amperometric techniques which gave a linear range of 0.50 × 10-6 M to 50 × 10-6 M; limit of detection of 0.156 x 10-6 M and order of magnitude of linearity of 2.03. Hence, the sensor was further used to study 4-tert-octylphenol (TOP); the results showed that the sensitivity and the limit of detection were 11.31 nA L/mol and 0.249 x 10-6 M, respectively and order of magnitude of linearity of 2.00.