Review on Surface-Modified Electrodes for the Enhanced Electrochemical Detection of Selective Serotonin Reuptake Inhibitors (SSRIs).

Selective serotonin re-uptake inhibitors (SSRIs) are one of the most commonly prescribed classes of antidepressants used for the treatment of moderate to severe depressive disorder, personality disorders and various phobias. This class of antidepressants was created with improved margins of safety. However, genetic polymorphism may be responsible for the high variability in patients' responses to treatment, ranging from failure to delayed therapeutic responses to severe adverse effects of treatment. It is crucial that the appropriate amount of SSRI drugs is administered to ensure the optimum therapeutic efficacy and intervention to minimise severe and toxic effects in patients, which may be the result of accidental and deliberate cases of poisoning. Determining SSRI concentration in human fluids and the environment with high sensitivity, specificity and reproducibility, and at a low cost and real-time monitoring, is imperative. Electrochemical sensors with advanced functional materials have drawn the attention of researchers as a result of these advantages over conventional techniques. This review article aims to present functional materials such as polymers, carbon nanomaterials, metal nanomaterials as well as composites for surface modification of electrodes for sensitive detection and quantification of SSRIs, including fluoxetine, citalopram, paroxetine, fluvoxamine and sertraline. Sensor fabrication, sensor/analyte interactions, design rationale and properties of functional material and the electrocatalytic effect of the modified electrode on SSRI detection are discussed.

Influence of electrode surface charge on current production by Geobacter sulfurreducens microbial anodes.

Positively charged electrode surfaces are thought to enhance electrostatic interaction with mostly negatively charged bacteria cell surface, thereby improving microbial fuel cell performance. In this work, electrostatic self-assembly of charged polymers was used to systematically modify the surface of indium tin coated electrodes. Evaluation was based on start-up time, maximum current, biofilm thickness and coulombic efficiency of microbial Geobacter sulfurreducens anodes. Coated electrodes were polarized to +0.1 V vs. SHE as biological duplicates. The thickest biofilms and in turn highest current density and shortest start-up time was achieved for negatively charged electrode surfaces like non-coated ITO or polystyrol sulfonate coated electrodes, while positively charged chitosan, negatively charged alginate and positively charged polyethylene imine, in the particular order, produced thinner biofilms, with less current and longer start-up time. This finding contradicted the initial hypothesis. Most experiments on electrode surface modifications are accompanied by an increase in available electrode surface which makes it difficult to extract solely the effect caused by the surface modification. Our study showed the importance of considering also factors other than the surface charge, e.g. potential interactions of the surface modification with the conditioning film and the medium, namely the attraction of cations by a negatively charged surface.

Recombinant Histidine-Tagged Nano-protein-based Highly Sensitive Electro-Sensing Device for Salivary Cortisol.

We have developed a powerful biosensing strategy for immobilizing histidine-tagged (His-Tag)-oriented recombinant nano-protein immobilization on a chemically modified glassy carbon electrode (GCE) surfaces via (S)-N-(5-amino-1-carboxypentyl)iminodiacetic acid (ANTA) acting as a chelating Ni2+ centered interaction. Here, we introduce a label-free electro-sensor to quantify cortisol levels in saliva samples for point-of-care testing (POCT). The high specificity of the chemically modified GCE was established by genetically bio-engineered metal-binding sites on the selected recombinant apoferritin (R-AFTN) nano-protein to impart functionality to its surface and by coating the carbon surface with the self-assembled monolayers of 4-aminobenzoic acid (4-ABA) attached to ANTA groups complexed with Ni2+ transition metal ions. Despite the variety of conventional assays available to monitor cortisol levels, they require bulky exterior outfits, which hinders use in the healthcare systems. Therefore, we performed a rapid, easy-to-implement, and low-cost quantitative electro-sensor to enable the real-time detection of cortisol levels in saliva samples. As a result, the cortisol electro-sensor fabricated with high specificity utilizing a GCE could measure cortisol levels with a detection limit of 0.95 ng/ml and sensitivity of 7.91 µA/(ng/mL), which is a practical approach in human saliva. Thus, protein nanoprobe-based cortisol biosensing showed high sensitivity and selectivity for the direct electro-sensing of cortisol for POCT.

Electrodeposited platinum-iridium coating improves in vivo recording performance of chronically implanted microelectrode arrays.

Reliable single unit neuron recordings from chronically implanted microelectrode arrays (MEAs) are essential tools in the field of neural engineering. However, following implantation, MEAs undergo a foreign body response that functionally isolates them from the brain and reduces the useful longevity of the array. We tested a novel electrodeposited platinum-iridium coating (EPIC) on penetrating recording MEAs to determine if it improved recording performance. We chronically implanted the arrays in rats and used electrophysiological and histological measurements to compare quantitatively the single unit recording performance of coated vs. uncoated electrodes over a 12-week period. The coated electrodes had substantially lower impedance at 1 kHz and reduced noise, increased signal-to-noise ratio, and increased number of discernible units per electrode as compared to uncoated electrodes. Post-mortem immunohistochemistry showed no significant differences in the immune response between coated and uncoated electrodes. Overall, the EPIC arrays provided superior recording performance than uncoated arrays, likely due to lower electrode impedance and reduced noise.

Enhanced current production by Desulfovibrio desulfuricans biofilm in a mediator-less microbial fuel cell.

In this study, a mediator-less microbial fuel cell (MFC) inoculated with a sulfate-reducing bacterium (SBR), Desulfovibrio desulfuricans, was equipped with bare and surface-treated graphite felt electrodes. Electrochemical treatment of the anode surface facilitated biofilm formation on the electrode, resulting in rapid and enhanced current production. The maximum current density of the treated anode was 233±24.2mA/m(2), which was 41% higher than that of the untreated anode. The electron transfer rate also increased from 2.45±0.04 to 3.0±0.02µmol of electrons/mg of protein·min. Biofilm formation on the treated anode was mainly due to the strong hydrogen or peptide bonds between the amide groups of bacterial materials (including cytochrome c) and carboxyl groups formed on the electrodes. These results provide useful information on direct electron transfer by SRB in a mediator-less MFC through cytochrome c and the effects of the electrochemical treatment of electrodes on MFC performance.

Affinity binding via zinc(II) for controlled orientation and electrochemistry of histidine-tagged nitrate reductase in self-assembled monolayers.

Monolayers of Cu(II)-complexes on electrode surfaces are frequently applied for the immobilization and controlled orientation of His-tagged redox proteins. However, affinity binding is limited to applications that require potentials less negative than the reduction potential of the metal complexes. In order to overcome this limitation, we used Zn(2+) cations on nitrilotriacetic acid (NTA) modified carbon electrodes for the coordination of His-tagged nitrate reductase (NaR). The NTA modified electrodes were prepared upon diazotation and electrochemical reduction of an aniline functionalized NTA ligand. After coordination of Zn(2+) to the bound NTA ligand, self-assembly of NaR is achieved via coordination of the imidazole groups from the His-tag to the NTA-Zn(II) complex. The electrochemical investigations of the NaR monolayer on NTA-Zn(II) films demonstrate the catalytic activity for reduction of nitrate to nitrite in the presence of methyl viologen. The catalytic current density correlates with the one expected for a fully active enzyme monolayer. Moreover, the reduction of Zn(2+) is not observed at the potential necessary for the reduction of methyl viologen. Therefore, affinity binding based on Zn(2+) may be used for the immobilization and electrochemical applications of His-tagged NaR.