UWCScholar :: Browsing by Author "Iwuoha, Emmanuel I."

Browsing by Author "Iwuoha, Emmanuel I."

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Actuation behaviour of a derivatized pyrrole accordion type polymer
(ESG, 2014) Ward, Meryck; Botha, Shanielle; Iwuoha, Emmanuel I.; Baker, Priscilla
A monomer (Phenazine-2,3-diimino(pyrrole-2-yl)–PDP) derived from the condensation reaction between 2,3-diaminophenazine and a pyrrole derivative has been synthesized as a hinge molecule in the design of a zig-zag polymer. The monomer was polymerized both chemically and electrochemically in order to produce the polymer material, phenazine-2,3-diimino(pyrrole-2-yl (PPDP). During electrochemical polymerization the system was doped using 1,4-napthaquinone sulphonic acid (NQSA) and polyvinylsulfonic acid (PVSA) respectively, to improve conductivity. Characterization of the materials by Fourier transform infrared spectroscopy (FTIR) confirmed the successful linking of the starting materials to produce the hinge molecule and nuclear magnetic resonance spectroscopy (NMR) supported the FTIR data. The electrochemistry of the polymer in the doped and undoped state was evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).
Acylphloroglucinol derivatives from the South African helichrysum niveum and their biological activities
(MDPI, 2015) Popoola, Olugbenga K.; Marnewick, Jeanine L.; Rautenbach, Fanie; Iwuoha, Emmanuel I.; Hussein, Ahmed A.
Abstract: Phytochemical investigation of aerial parts of Helichrysum niveum (H. niveum) using different chromatographic methods including semi-preparative HPLC afforded three new (1–3) and six known (4–10) acylphloroglucinols alongside a known dialcohol triterpene (11). The structures of the isolated compounds were characterized accordingly as 1-benzoyl-3 (3-methylbut-2-enylacetate)-phloroglucinol (helinivene A, 1), 1-benzoyl-3 (2S-hydroxyl-3- methylbut-3-enyl)-phloroglucinol (helinivene B, 2), 8- (2-methylpropanone)-3S, 5, 7-trihydroxyl- 2,2-dimethoxychromane (helinivene C, 3), 1-(2-methylbutanone)-4-O-prenyl-phloroglucinol (4), 1-(2-methylpropanone)-4-O-prennyl-phloroglucinol (5), 1-(butanone)-3-prenyl-phloroglucinol (6), 1- (2-methylbutanone)-3-prenyl-phloroglucinol (7), 1-butanone-3- (3-methylbut-2-enylacetate)- phloroglucinol (8), 1-(2-methylpropanone)-3-prenylphloroglucinol (9), caespitate (10), and 3β-24-dihydroxyterexer-14-ene (11). Excellent total antioxidant capacities were demonstrated by helinivenes A and B (1 and 2) when measured as oxygen radicals absorbance capacity (ORAC), ferric-ion reducing antioxidant power (FRAP), trolox equivalent absorbance capacity (TEAC) and including the inhibition of Fe2+-induced lipid peroxidation (IC50 = 5.12 ± 0.90; 3.55 ± 1.92) µg/mL, while anti-tyrosinase activity at IC50 = 35.63 ± 4.67 and 26.72 ± 5.05 µg/mL were also observed for 1 and 2, respectively. This is the first chemical and in vitro biological study on H. niveum. These findings underpin new perspectives for the
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.
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.
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.
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.
Cytochrome P450-3A4/copper-poly(propylene imine)- polypyrrole star co-polymer Nanobiosensor system for delavirdine – a non-nucleoside reverse transcriptase inhibitor HIV drug
(University of the Western Cape, 2014) Ntshongontshi, Nomaphelo; Iwuoha, Emmanuel I.
HIV and AIDS are among the world's pandemics that pose serious concern to almost every individual in the world. With the current level of availability of anti-retroviral (ARV) drugs and the ease of accessibility of treatment in many countries such as South Africa, the disease can be controlled by suppressing the viral load of an infected individual. These anti HIV drugs such as delavirdine are metabolised by enzymes which are found in the liver microsomes, particularly those of the cytochrome P450 family. Due to the fact that the metabolic rate of a patient determines the effect of the drug, the drug could either have a beneficial or an adverse effect once it is administered. It is therefore imperative that the metabolic profile of a patient is determined at point-of-care is necessary for proper dosing of the ARV drugs. In this project a nanobiosensor system was devised and used for the determination of the metabolism of delavirdine, a non-nucleoside reverse transcriptase inhibitor (NNRTI) ARV drug. The nanobiosensor was prepared by the entrapment of the isoenzyme CYP3A4 into a pre-formed electro active carrier matrice consisting of a dendrimeric copper generation-2 poly (propylene imine)-co-polypyrrole star copolymer (Cu(G2PPI)-co-PPy). The metallo-dendrimer was used as a host for the enzyme and provided thenecessary bio-compatible environment that allowed the direct transfer of electrons between the enzyme's active centres and platinum electrode surface. Copper was the choice of metal used in the study due to its properties. Copper is a malleable, ductile and a good conductor of both heat and electricity. It is a better conductor than most metals. Silver which also belongs to group 1b in the periodic table is a better electrical conductor than copper but copper has better corrosion resistance and is a more abundant and hence it is a cheaper material to use. Cu(G2PPI)-co-PPy was prepared by the incorporation of the copper metal into the G2PPI and the electropolymerization of pyrrole onto the Cu(G2PPI). The incorporation of Cu into G2PPI was determined by FTIR which did not show the presence of the Cu but showed an increase in the intensities of the peaks after the incorporation. The surface morphology of Cu (G2PPI) was confirmed by the use of HRSEM which showed a difference in the surface morphology of the dendrimer moiety with the addition of the copper metal. The HRSEM images after Cu incorporation resulted in the change from rough surface to smooth surface with open cavities which were essential for the entrapment of the biological systems (CYP3A4). Energy dispersive spectrometry (EDS) and HRTEM were used to confirm the presence of spherically shaped copper nanoparticles in the Cu (G2PPI) and were found to have a size distribution of 12-17 nm with an average particle size of 15nm. The star copolymer (Cu(G2PPI)-co-PPy) was characterised using cyclic voltammetrywhere it was confirmed that the material was electroactive and conducting due to electron movement along the polymer chain. A diffusion co-efficient (D₀) value of 8.64 x 10⁻⁵ cm²/s was determined for the material indicating a slow electron transfer kinetics within the diffusion layer. The constructed nanobiosensor was developed using copper poly (propylene imine) – polypyrrole star copolymer, bovine serum albumin and glutaraldehyde coupled to the enzyme CYP3A4. The resultant nanobiosensor parameters include a dynamic linear range (DLR) of 0.01-0.06 nM, a limit of detection (LOD) of 0.025 nM and a sensitivity value of0.379 μA/nM.
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.
Development of Metal Nanoparticle-Doped Polyanilino-Graphene Oxide High Performance Supercapacitor Cells
(University of the Western Cape, 2018) Dywili, Nomxolisi Ruth; Iwuoha, Emmanuel I.
Supercapacitors, also known as ultracapacitors or electrochemical capacitors, are considered one of the most important subjects concerning electricity or energy storage which has proven to be problematic for South Africa. In this work, graphene oxide (GO) was supported with platinum, silver and copper nanoparticles anchored with dodecylbenzenesulphonic acid (DBSA) doped polyaniline (PANI) to form nanocomposites. Their properties were investigated with different characterization techniques. The high resolution transmission electron microscopy (HRTEM) revealed GO's nanosheets to be light, flat, transparent and appeared to be larger than 1.5 ?m in thickness. This was also confirmed by high resolution scanning electron microscopy (HRSEM) with smooth surfaces and wrinkled edges observed with the energy dispersive X-ray analysis (EDX) confirming the presence of the functional groups such as carbon and oxygen. The HRTEM analysis of decorated GO with platinum, silver and copper nanoparticles (NPs) revealed small and uniformly dispersed NPs on the surface of GO with mean particle sizes of 2.3 ± 0.2 nm, 2.6 ± 0.3 nm and 3.5 ± 0.5 nm respectively and the surface of GO showed increasing roughness as observed in HRSEM micrographs. The X-ray fluorescence microscopy (XRF) and EDX confirmed the presence of the nanoparticles on the surface of GO as platinum, silver and copper which appeared in abundance in each spectra. Anchoring the GO with DBSA doped PANI revealed that single GO sheets were embedded into the polymer latex, which caused the DBSA-PANI particles to become adsorbed on their surfaces. This process then appeared as dark regions in the HRTEM images. Morphological studies by HRSEM also supported that single GO sheets were embedded into the polymer latex as composite formation appeared aggregated and as bounded particles with smooth and toothed edges.
Electro chemiluminescence and organic electronics of derivatised poly(aniline sulphonic acid) light-emitting diodes
(University of the Western Cape, 2011) Molapo, Kerileng Mildred; Iwuoha, Emmanuel I.
Electrochemiluminescence (EeL) is applied for industrial applications that have considerable potential, such as clinical diagnostic, analytical chemistry, and light-emitting devices, due to selectivity, sensitivity for detection and quantification of molecules through generation of fluorescence light when electric current is applied on the materials. In EeL the electrochemical reaction allows for precise control over the time and position of the light emitting reaction. The control over time allows one to synchronise the luminescence and the biochemical reaction under study and control over position not only improves sensitivity of the instrument by increasing the signal to noise ratio, but also allows multiple analytical reactions in the same sample to be analyzed using an electrode array. The EeL generation fluorescent materials are based on inorganic semiconductor materials for light-emitting devices. Further progress in this EeL field mainly depends on discovery of new advanced materials, interfacial films and nanoparticle coatings, advances in microfluidics leading to total increase in EeL properties. There has been extensive use of polymers for enhancement of EeL properties. Electrochemiluminescent conjugated polymers constitute a new class of fluorescent polymers that emit light when excited by the flow of an electric current. These new generation fluorescent materials may now challenge the domination by inorganic semiconductor materials for the commercial market of light-emitting devices such as lightemitting diodes and polymer laser devices (PLDs).
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.
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.
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.
Electrochemical Immunosensor based on Cyclodextrin Supramolecular interactions for the detection of human chorionic gonadotropin
(University of the Western Cape, 2012) Wilson, Lindsay; Iwuoha, Emmanuel I.; O’Sullivan, Ciara K.
Glucose oxidase (GOx) and horseradish peroxidase (HRP) are important enzymes for the development of amperometric enzyme linked immunosensors. The selectivity of each enzyme towards its analyte deepens its importance in determining the sensitivity of the resultant immunosensor. In designing immunosensors that have customized transducer surfaces, the incorporation with FAD and iron based enzymes ensures that electron kinetics remains optimal for electrochemical measurement. Various different immobilization strategies are used to produce response signals directly proportional to the concentration of analyte with minimal interferences. The combination of self-assembled monolayers and supramolecular chemistry affords stability and simplicity in immunosensor design. In this work, two electrochemical strategies for the detection of human chorionic gonadotropin(hCG) is presented. This involves the modification of a gold surface with a thiolated β-cyclodextrin epichlorohydrin polymer (βCDPSH) to form a supramolecular inclusion complex with ferrocene (Fc)-functionalised carboxymethyl cellulose polymer (CMC). Cyclic voltammetry indicated that ferrocene is in close proximity to the electrode surface due to the supramolecular complex formed with βCDPSH. Furthermore, strategy (a) for the detection of hCG used α-antihCG labelled (HRP) as reporter conjugate. Strategy (b) maintained the CMC bifunctionalised with Fc and recognition antibody for hCG hormone. However, the system was functionalised with a HRP enzyme and detection is done by using GOx reporter conjugates for in situ production of hydrogen peroxide. The reduction of H2O2 was used for the amperometric detection of hCG by applying a potential of 200 mV. The sensitivity and limit of detection of both strategies were calculated from calibration plots. For strategy (a) the LOD was found to be 3.7283 ng/mL corresponding to 33.56 mIU/mL and a sensitivity of 0.0914 nA ng-1 mL-1. The corresponding values for strategy (b) are 700 pg/mL (6.3 mIU/mL) and 0.94 nA ng-1 mL-1.
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.
Electrochemical poly(ProDOT) dendritic DNA aptamer biosensor for signalling interferon gamma (IFN-ɣ) TB biomarker
(University of the Western Cape, 2017) Sidwaba, Unathi; Iwuoha, Emmanuel I.
Tuberculosis (TB) is an infectious disease that, despite all efforts devoted towards its eradication, remains a threat to many countries including South Africa. Current diagnostic assays do offer better performance than the conventional sputum smear microscopy and tuberculin skin tests. However, these assays have been proven to be affected by various factors including the condition of an individual's immune system and vaccination history. By far, electrochemical biosensors are amongst the currently investigated techniques to address the shortcomings associated with these diagnostics.
Electrochemically reduced graphene oxide pencil-graphite in situ plated bismuth-film electrode for the determination of trace metals by anodic stripping voltammetry
(ESG, 2014) Pokpas, Keagan; Zbeda, Salma; Jahed, Nazeem; Mohamed, Nuralli; Baker, Priscilla; Iwuoha, Emmanuel I.
An electrochemical platform was developed based on a pencil-graphite electrode (PGE) modified with electrochemically reduced graphene oxide (ERGO) sheets and in conjunction with an in situ plated bismuth-film (ERGO-PG-BiE). The ERGO-PG-BiE was used as a sensing platform for determining Zn2+, Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV). ERGO sheets were deposited on to pencil-graphite electrodes by cyclic voltammetric reduction from a graphene oxide (GO) solution. The GO, with flake thicknesses varying between 1.78 to 2.10 nm (2 sheets) was characterized using FT-IR, HR-SEM, HR-TEM, AFM, XRD and Raman spectroscopy. Parameters influencing the electroanalytical response of the ERGO-PG-BiE such as, bismuth-film concentration, deposition potential, deposition time and rotation speed were investigated and optimized. The ERGO-PG-BiE gave well-defined, reproducible peaks with detection limits of 0.19 μg L-1, 0.09 μg L-1 and 0.12 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively, at a deposition time of 120 seconds. For real sample analysis, the enhanced voltammetric sensor proved to be suitable for the detection and quantitation of heavy metals below the US EPA prescribed drinking water standards of 5 mg L-1, 5 μg L-1 and 15 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively.
Electrochemiluminescence of novel polyanilino-rutheniumbipyridyl-imidazo phenanthroline and carboxy-difluoroboradiazaindacene luminophores
(University of the Western Cape, 2015) Molapo, Kerileng Mildred; Iwuoha, Emmanuel I.
Electrochemiluminiscence, (ECL), is an electrochemically-induced process that leads to the generation of measurable luminescent signals at the electrode surface. The luminescent signals occur when electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light. Immobilization of the ECL luminophore on an electrode surface provides enhancement of ECL intensity. This work presents results of the feasibility study focused on the application of novel luminophores for electrochemiluminescence (ECL) sensors. The thesis mainly focuses on studying the ECL of polyanilinorutheniumbipyridyl- imidazo phenanthroline and carboxydifluoroboradiazaindancence luminophores. The influence of the synthetic methods on the electrochemical, structural and photophysical properties of poly(8-anilino-lnaphthalene sulphonic acid) (P ANSA) synthesized by electropolymerization (PANSA) and chemical polymerization (PANSA) were studied. Cyclic voltammetry (CV) data revealed that the electrogenerated PANSA contains species of mixed redox states; with evidence of the presence of penigraniline, emeraldine and leucoemeraldine forms of PANSA. In contrast, the CV of PANSA indicated that it is predominantly in the emeraldine form with a reduction potential at approximately + 0.2 V. The presence of emeraldine moiety in PANSA was confirmed from UV-Vis spectroscopy data. A band gap energy value of 2.5 eV was calculated for the emeraldine in PANSA from the UV data. Comparative study of the charge transfer coefficient, DCT, of the two types of PANSA indicated moderate charge propagation in PANSA (DCT = 1.68 ± 0.1 x 10-8 cm2 s-') which was order of magnitude lower than for PANSA (DCT = 1.68 ± 0.3 x 10-7 cm2 s-'). The differences in the structural properties of the two polymers were reflected in their IR spectra, with evidence of C=C and C=N stretching vibrations observed at 2030, 2158 and 2486 cm-I in PANSA, which are absent in PANSA. The mode of synthesis had a modest impact on the photophysics of the polymers, for example PANSA exhibited a luminescent lifetime of9.00 ± 0.05 ns compared with 11.5 ± 0.07 ns for PANSA. However, time resolved emission anisotropy studies gave a rotational correlation time, p, of 13.8 ± 2.47 ns for PANSA compared to 0.633 ± 0.03 ns for its chemically generated analogue. This suggests a much shorter chain length in the PANSA molecule and higher cross-linking or aggregation in PANSA that can limit incorporation of ruthenium complex on the polymer backbone. As a result, electrochemiluminescent films have been formed by electrodepositing polyaniline, PANI, films in the presence of [Ru(bpY)2PIC]2+; bpy is 2,2'-bipyridyl and PIC is (2,2'-bipyridyl)-2( 4- carboxylphenyl) imidazo [4,5 ][ 1,10] phenanthroline in this work. The homogeneous charge transport diffusion coefficient, DCT, for the Ru2+/3+couple within the PANI film is 2.6 ± 0.9 x 10-10 cm2s-l. The large DCT facilitates a fast regeneration of Ru3+and, coupled to a relatively rigid microenvironment, results in a high ECL intensity in the presence oftripropylamine as co-reactant compared to [Ru(bpY)3f+. Significantly, despite the conducting nature of the polymer backbone, the [Ru(bpy)2PICH2]2+ loaded PANI has the highest efficiency, 1.00%, yet reported for a surface confined ruthenium complex. PANI-Ru complex showed to have many properties that make it an ideal luminophore for sensitive and selective analytical methods; however, it would be useful to have other ECL labels that can span a wide range of wavelengths so that simultaneous determination of several analytes in a single sample can be investigated. In this case, the photophysics, electrochemical and electrochemiluminescent properties of a novel 1,3,5,7 -tetramethyl-8-[ (2-fluorophenyl)-6-methoxy-l ,5-naphthyridine-3-carboxy ]-4,4'difluoroboradiazaindace-ne BODIPY -COOH, dye were demonstrated in this work. The photophysics studies revealed that BODIPY -COOH is highly luminescent: exhibiting sharp absorbance bands, intense emission bands and high emission quantum yield. The quantum yield proved to be solvent dependent and was determined to be 0.88 ± 0.02 and 0.60 ± 0.04 in dimethylsulphoxide (DMSO) and acetonitrile (MeCN), respectively. Electrochemiluminescence (ECL) of BODIPYCOOH in solution was generated in the presence of either benzoyl peroxide (BPO) or hydrogen peroxide. The ECL turn-on potential in the presence of BPO was observed at potentials that are greater than - 1.5 V, and when H202 was used the ECL turn-on potential was significantly fine-tuned to less negative potential of - 0.4 V. Electrochemiluminescent thin films of BODIPY -COOH on Pt electrodes exhibited luminescence properties similar to those of the free dye in solution. However, the solution based approach ECL has its own limitations such as loss of signal due to the diffusion of the ECL reagent out of the detection zone. To overcome loss of signal effects, the introduction of cysteamine and cysteine linkers to the BODIPY dye were employed. It was seen that self-quenching was not sufficient to interfere significantly with the film ECL emission properties and thus the BODIPY thin film can be used in ECL applications. Interestingly, the BODIPY film exhibited the strongest luminescence in water and this is potentially useful in ECL application in biological media.
Enhanced photovoltaic effects of microwave-assisted polyolsynthesized Cu2(Pd/Zn)SnS4 kesterite nanoparticles
(Elsevier, 2023) Nwambaekwe, Kelechi C.; Ramoroka, Morongwa E.; Iwuoha, Emmanuel I.
Kesterite materials show excellent optical and semiconductive properties for use as petype absorber layer in photovoltaic (PV) applications, but they have a high open circuit voltage deficit (Voc,def) due to high antisite defect and secondary phase formation, resulting in poor device performance. This work reports a PV cell composed of Cu2PdSnS4 (CPTS) nanoparticles as an absorber layer yielding highly improved Voc of 900 mV, which is two times that of fabricated pristine Cu2ZnSnS4 (CZTS) PV cell. Improved PV cell parameters such as fillefactor (FF) of 83.4% and power conversion efficiency (PCE) of 1.01% were obtained for CPTS devices which are 3efold that of pristine CZTS devices. Optical studies revealed enhanced redshift absorption for CPTS nanoparticles. Electrochemical studies show improved current production, high electron mobility and low charge resistance for CPTS nanoparticles. This study shows that the improved photovoltaic properties can be attributed to enhancement in the bulk properties when Zn atoms are replaced by Pd atoms in kesterite nanomaterials as absorber layer material for PV applications.
Few-layer binder free graphene modified mercury film electrode for trace metal analysis by square wave anodic stripping voltammetry
(ESG, 2013) Zbeda, Salma; Pokpas, Keagan; Titinchi, Salam J.J.; Jahed, Nazeem; Baker, Priscilla; Iwuoha, Emmanuel I.;
A binding agent free graphene modified glassy carbon electrode in combination with an in situ plated mercury film electrode (Gr-GC-HgFE) was used as a highly sensitive electrochemical platform for the determination of Zn2+, Cd2+ and Pb2+ in 0.1 M acetate buffer (pH 4.6) by square-wave anodic stripping voltammetry (SWASV). Instrumental parameters such as deposition potential, deposition time and electrode rotation speed were optimized. The Gr-GC-HgFE sensing platform exhibited improved sensitivity for metal ion detection, in addition to well defined, reproducible and sharp stripping signals. Two linear calibration curves ranging from 0 –10 μg L−1 and 0 – 60 μg L−1 were identified yielding detection limits of 0.08 μg L−1, 0.05 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for simultaneous analysis and 0.04 μg L−1, 0.11 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for individual analysis when using a deposition time of 120 s. For practical applications recovery studies using tap water samples spiked with target metal ions gave recoveries within 10% of the spiked amount. Much better recoveries were obtained for the individual analysis in comparison with simultaneous analysis.

Browsing by Author "Iwuoha, Emmanuel I."

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