Bio-Inspired Materials for Electrochemical Sensors

Electrochemical biosensors are a rapidly growing research area that has greatly improved its specificity, accuracy, and precision in the detection of biomolecules in contemporary literature and industry alike. Typically, these systems exist in a three-electrode conformation with a working electrode functioning as the anode, a counter electrode functioning as the cathode, and a reference electrode allowing for the control of potential in the system. The method by which these sensors work is through the sharing of electrons via redox reactions with the target molecule and the working electrode or modifications on its surface. By exploiting the function of biomaterials that participate in natural substrate-binding redox phenomena, new opportunities for detecting critical molecules in complex situations can be created. In this dissertation, three distinct electrochemical biosensors were created by mimicking natural phenomena and implementing materials that directly or indirectly participate in the corresponding reactions. First, a dopamine sensor was created via a composite of lignin-derived graphene oxide and the marine algae-derived polysaccharide kappa carrageenan. Different ratios of GO, a known electrooxidizing catalyst of dopamine, with kappa carrageenan were used to create a binder-free film for dropcasting on the working electrode. It was designed on the principle of its interactions with the nervous system when injected in rats to induce analgesia, interfering with standard dopamine behavior. The system demonstrated a linear range of 1 - 250 μmol L-1 and a limit of detection of 0.14 μmol L-1 (s/n=3). In the second chapter, a sensor for the human and animal health hazard nitrite was constructed using the transition metal sulfide NiS. Transition metal sulfides are the catalytic center for nitrite oxidation to nitrate in nitrogen fixing bacteria found in the environment. This section utilized a novel electrodeposition method for creating a binderfree layer of NiS on the surface of the glassy carbon electrode. This system demonstrated a linear range of 0.04 – 1 μM, 1 – 5.3 μM and a detection limit of 0.01 μM. For the final chapter, a novel sensor was created for the cryoprotective sugar trehalose, an indicator of bacterial contamination in meat and produce without any electrochemical assay precedent. This system utilized the interactions found between alkali earth metal ions and trehalose in which the two molecules form complexes. Magnesium phthalocyanine, which is a commercially available dye, as well as synthesized magnesium tetraphenylporphyrin and calcium tetraphenylporphyrin were implemented as drop-casted coatings on the working electrode to electrodeposit trehalose on the surface and detect its oxidation via squarewave anodic stripping voltammetry in the complex media Luria-Bertani broth. The system was also used to gauge fluctuations in E. coli in broth by autoclaving the cultures and directly testing the media containing lysed bacteria. The system demonstrated a linear range of 0.25 mM – 100 mM, with magnesium mesotetraphenylporphyrin exhibiting the highest repeatability

Electrochemical Nanocomposite Single-Use Sensor for Dopamine Detection

In this work, we report the development of a simple and sensitive sensor based on graphite screen-printed electrodes (GSPEs) modified by a nanocomposite film for dopamine (DA) detection. The sensor was realized by electrodepositing polyaniline (PANI) and gold nanoparticles (AuNPs) onto the graphite working electrode. The sensor surface was fully characterized by means of the cyclic voltammetry (CV) technique using [Fe(CN)6]4−/3− and [Ru(NH3)6]2+/3+ as redox probes. The electrochemical behavior of the nanocomposite sensor towards DA oxidation was assessed by differential pulse voltammetry (DPV) in phosphate buffer saline at physiological pH. The sensor response was found to be linearly related to DA concentration in the range 1–100 μM DA, with a limit of detection of 0.86 μM. The performance of the sensor in terms of reproducibility and selectivity was also studied. Finally, the sensor was successfully applied for a preliminary DA determination in human serum samples