Nanostructured polyamic acid electrocatalysts for reliable analytical reporting of sulphonamides as contaminants of emerging concern

Philosophiae Doctor - PhDPolyamic acid (PAA) nanostructured materials were successfully produced by electrochemical deposition and electrospinning using polyvinlypyrrolidone (PVP) as supporting polymer. Polyamic acid thin film and nanofibers were deposited directly at the surface of a screen-printed carbon electrode (SPCE) as electro-catalysts for reliable analytical reporting of sulphonamide as contaminants of emerging concern by electrochemical techniques. Fourier transform infrared (FTIR) spectroscopy was used to confirm the structural integrity of the PAA electrospun nanofibers compared to the chemical synthesized PAA. Brunauer-Emmett-Teller (BET) was used to determine the surface area of the nanofibers. The surface morphology and surface thickness of the polyamic acid (PAA) nanofibers on the screen-printed electrodes was studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Cyclic voltammetry (CV) was used to study redox behavior of the nanostructured PAA modified screen-printed carbon electrodes. Electrochemical parameters surface concentration, diffusion coefficient, formal potential and peak separation were determined. Three sulphonamides were selected based on the United States of protection agency (US EPA) and World Health Organization (WHO) list of emerging contaminants and detected sulphonamides in environmental waters in South Africa and other African regions. The selected sulfonamides were evaluated at the unmodified and modified screen-printed carbon electrodes. The sulphonamides were evaluated in three different supporting electrolytes at pH 7 to enhance electrochemical signal reporting. Sulfadiazine (SDZ), sulfamethoxazole (SMX) and sulfamethazine (SMZ) displayed peaks at 0.80 V vs Ag/AgCl in 0.1 M tris-HCl using square wave voltammetry at the unmodified transducer. At the PAA thin film transducer, SDZ, SMX and SMZ displayed well-defined analytical oxidative peaks at 0.77 V 0.82 V and 0.83 V vs Ag/AgCl respectively. The LOD (n=3) for SDZ was found to be 12.14 ųM with a correlation coefficient of 0.9950. The LOD (n=3) for SMX and SMZ was found to 14.59 ųM (R2 =0.9928) and 10.41 ųM (R2 =0.9963). These sulphonamides were also electro-analytical evaluated at the screen-printed carbon PAA nanofiber modified transducer. SDZ, SMX and SMZ produced well-defined analytical signals at 0.79 V, 0.81 V and 0.78 V vs Ag/AgCl respectively. The determined LOD (n=3) for the individual sulphonamides was 8.26 ųM, 16.59 ųM and 8.81 ųM SDZ, SMX and SMZ respectively. The linearity correlation coefficient (R2) was determined to be 0.9977, 0.9956 and 0.9974 respectively. The efficacy of the proposed nanostructured PAA thin film modified screen-printed carbon sensor was evaluated by performing recovery studies for the selected sulphonamides using square wave voltammetry. Tap water was used to simulate environmental matrix. The recoveries of SDZ with respect to each concentration were 98.84% (RSD 4.98%) to 40.58% (RSD 6.74%). For SMX the recoveries were 154.17% (RSD 11.00%) to 111.03% (RSD 16.80%). The recoveries for SMZ with respect to each concentration were 184% (RSD 8.19%) to 90.26 (RSD 18.26%) indicating the reliability of the analytical results

Polyamic acid-graphene oxide nanocomposite for electrochemical screening of antibiotic residues in water

>Magister Scientiae - MScPollution of water sources, aquifers and wetland systems caused by industry, agriculture, and municipally treated wastewater is a worldwide problem that contributes to the scarcity of clean and potable water. Rivers, channels, lakes, oceans, and ground water are often contaminated by a variety of organic substances that can affect aquatic life and threaten human health. Organic compounds such as antibiotics that are not effectively removed by modern day water treatment technology are a growing threat to water quality and health. The emergence of antibiotics in the environment particularly aquatics have become a matter of concern as they may result in induction and spread of bacterial resistance which may be harmful to humans or animals. After administration, antibiotics for human use or their metabolites are excreted into the effluent and reach the sewage treatment plant (STP). Not all Antibiotics in sewage treatment plants are eliminated. Consequently they can pass through the sewage system and may end up in environmental and even potable water systems. Antibiotic residues have been reportedly found in places such as hospital wastewaters, wastewater treatment plants and surface waters all over the world with concentrations ranging from approximately 60-120000 ng/, 2-580 ng/L and 5-1300 ng/L respectively. The current methods that are used to detect antibiotics can be quite expensive and time consuming due to sample preparation (necessary for detection of very low concentrations of antibiotics in water) and technology used in the instruments. Electrochemical sensors and biosensors are simple systems, with high selectivity and sensitivity for individual measurements and cost effectiveness. The development of composites based on conductive phases dispersed in polymeric matrices has led to important advances in analytical electrochemistry. Polyamic acid and graphene oxide are both materials with well-defined electrochemistry and are easily processable in the design of various sensor formats. In this study we present a novel polyamic acid - graphene oxide (PAA/GO) electrode which was prepared for electrochemical screening of antibiotic residues in aqueous systems. Polyamic acid (PAA) and graphene oxide (GO) were successfully synthesized independently and characterized using SEM which was used to study the morphology of the PAA, FTIR spectroscopy to confirm chemical structures and functional groups as well as CV and SWV which were used to identify the unique electrochemical behavior of PAA and GO respectively. Polyamic acid-graphene oxide nanocomposite was prepared and characterized by CV, SWV, FTIR and SEM. The novel electrode (PAA/GO/SPCE) was prepared by electrochemically depositing PAA/GO (0.03 mg/mL) onto SPCE electrodes using 5 cycles between −1000 mV and 1000 mV at 50 mVs. The analytical performance of the electrochemical sensor towards detection of neomyxin and norlfoxacin was compared to standard Uv-vis spectroscopy method. The Uv-vis spectroscopy showed LOD of 1.61x10-5 M and 1.41x10-5 M for norfloxacin and neomycin respectively. The PAA/GO electrochemical sensor had a LOD of 3.37x10-7 M for norfloxacin and 1.066x10-6 M for neomycin. Sensitivity of the UV/vis method was comparable to electrochemical sensor sensitivity for neomycin and norfloxacin

Spectroscopy, morphology, and electrochemistry of electrospun polyamic acid nanofibers

Polyamic acid (PAA) nanofibers produced by using the electrospinning method were fully characterized in terms of morphology and spectroscopy. A PAA nanofiber–modified screen-printed carbon electrode was applied to the detection of selected sulfonamides by following an electroanalytical protocol. The polyamic acid (PAA) nanofibers were characterized using Fourier transform infrared (FTIR) spectroscopy to study the integrity of polyamic acid functional groups as nanofibers by comparing them to chemically synthesized polyamic acid. A scanning electron microscope (SEM) was used to confirm the morphology of the produced nanofibers and 3D arrangement at the electrode interface. The Brunauer–Emmett–Teller (BET) method was used to determine the surface area of the nanofibers. Atomic force microscopy (AFM) was used to study the porosity and surface roughness of the nanofibers