Usisipho Feleni

Polyanilino-Carbon Nanotubes Derivatised Cytochrome P450 2E1 Nanobiosensor for the Determination of Pyrazinamide Anti-Tuberculosis Drugs

Pyrazinamine (PZA) is one of the most commonly prescribed anti-tuberculosis (anti-TB) drug due to its ability to significantly shorten the TB treatment period. However, excess PZA in the body causes hepatotoxicity and liver damage. This, therefore, calls for new methods for ensuring reliable dosing of the drug, which will differ from person to person due to interindividual differences in drug metabolism. A novel biosensor system for monitoring the metabolism of PZA was prepared with nanocomposite of multi-walled carbon nanotubes (MWCNTs), polyaniline (PANI) and cytochrome P450 3A4 (CYP3A4) electrochemically deposited on a glassy carbon electrode (GCE). The nanocomposite biosensor system exhibited enhanced electroactivity that is attributable to the catalytic effect of the incorporated MWCNTs. The biosensor had a sensitivity of 7.80 μA/μg mL-1 PZA and a dynamic linear range of 4.92 160 ng/mL PZA.

Optoelectronics of Stochiometrically Controlled Palladium Telluride Quantum Dots

Water dispersed PdTe semiconducting nanocrystals were synthesized and stabilised with 3-mercaptopropionic acid (3-MPA). HRTEM studies revealed the formation of spherical nanoparticles of average size ~4 nm with good crystallinity. UV-visible spectral analysis and band gap measurements confirmed that the nanocrystals are indeed semiconductors. This semiconducting characteristic was supported by electrochemical impedance spectroscopy (EIS) data which gave Bode plots with absolute frequency and a maximum frequency phase angle values of 38.3° and 75°, respectively. Electroanalysis of the film on glassy carbon electrode (GCE) verified the retention of the ability of Pd to adsorb hydrogen on its surface as well as absorb hydrogen within its lattice.

Electrochemical Ultra-Low Detection of Isoniazid Using a Salicylaldamine Functionalised G1-DAB-(NH2)4 Dendritic Sensor vs. UV-VIS Spectrophotometric Detection

A poly(propyleneimine) based dendrimer was synthesised and successfully functionalised with a copper centre within its branches. The dendrimer and corresponding metallodendrimer were successfully characterised using FTIR, HR-TEM and HR-SEM in order to determine the effect of the inclusion of copper into the dendritic structure. The incorporation of copper caused crystallinity as revealed in the HR-TEM and a sheet-like morphology as shown in the HR-SEM images. The resulting metallodendrimer was then applied as an electrocatalytic platform for the sensing of a first line TB drug called isoniazid. This method was compared to a routine laboratory detection using UV-Vis and was found to be much more sensitive to trace amounts of isoniazid in solution. The electrochemical detection was found to have a limit of detection (LOD) of 0.233 nM compared to 11.47 nM using the Ultraviolet-visible spectroscopy method.

A Novel Polyaniline Nanocomposite with Doping Effects of Poly(Methyl Methacrylate) and TiO2 Nanoparticles

Polyaniline (PANI) is a globally investigated conductive polymer with a variety of applications in various fields due to its ease of synthesis and modification. One method of enhancing the physico-chemical properties and processability of PANI is the incorporation of polymers and nanoparticles to form composite and hybrid materials with new features. This study reports the electrochemical synthesis of a polyaniline nanocomposite that incorporates titanium dioxide nanoparticles (TiO2) and poly (methyl methacrylate) (PMMA). The significant effects of PMMA and TiO2 nanoparticles on structural, morphological, optical and electrochemical properties of native polyaniline were investigated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, cyclic voltammetry (CV) and square wave voltammetry (SWV). The formation and deformation of relevant peaks observed from the FTIR spectra confirm the intrusion of PMMA and TiO2 into PANI while the voltammetric results show that the incorporation of both dopants significantly enhanced the electroactivity of PANI in a neutral pH medium.

Cytochrome P450-3A4/Copper-Poly(Propylene Imine)-Polypyrrole Star Co-Polymer Nanobiosensor System for Delavirdine - A Non-Nucleoside Reverse Transcriptase Inhibitor HIV Drug

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 to ensure proper dosing of the ARV drugs. In this study a nanobiosensor system was devised and used for the determination of the metabolism of delavirdine (DLV), 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 the necessary bio-compatible environment that allowed the direct transfer of electrons between the enzyme’s active centres and platinum electrode surface. (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 Fourier transform infrared (FTIR) spectroscopy 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-2Py) was confirmed by the use of high resolution scanning electron microscopy (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). The energy band gap of (Cu(G2PPI)-co-PPy) were determined to be 3.85 eV, signifying that the copolymer is characteristic of a biocompatible semiconductive platform for applications in biosensors. The star copolymer (Cu(G2PPI)-co-PPy) was characterized using cyclic voltammetry where it was confirmed that the material was electroactive and conducting due to electron movement along the polymer chain. A diffusion co-efficient (Do) 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 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 of 0.379 μA/nM.

Tin Selenide Quantum Dots Electrochemical Biotransducer for the Determination of Indinavir - A Protease Inhibitor Anti-Retroviral Drug

Biocompatibility of tin selenide quantum dots was achieved by the incorporation of 3-mercaptopropionic acid (3-MPA) as a capping agent, which also improved the stability and the solubility of the material. The UV-Vis spectrophotometric analysis of the quantum dots revealed a broad absorption band at ~ 330 nm (with a corresponding band gap, Eg, value of 3.75 eV), which is within the range of values expected for quantum dots materials. The 3-mercaptopropionic acid-capped tin selenide (3-MPA-SnSe) quantum dots were used to develop an electrochemical biosensor for indinavir, which is a protease inhibitor antiretroviral (ARV) drug. The biosensor was prepared by the self-assembly of L-cysteine on a gold electrode that was functionalised with 3-MPA-SnSe quantum dots, followed by cross-linking with cytochrome P450-3A4 (CYP3A4) using 1-ethyl-3(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). The electrocatalytic properties of the biosensor included a characteristic cyclic voltammetric reduction peak at-380 mV, which was used to detect the response of the biosensor to indinavir. The sensor performance parameters included response time and limit of detection (LOD) values of 11 s and 3.22 pg/mL, respectively. The test concentration range studied (0.014 – 0.066 ng/mL) gave a linear calibration plot for indinavir, and it was lower than the physiological plasma concentration index (i.e. maximum plasma concentrations, Cmax,) of indinavir (5 - 15 ng/mL) normally observed 8 h after intake. This indicates that the biosensor can be very useful in the case of ultra-rapid metabolisers where very low Cmax values are expected