Laser-induced graphene (LIG) electrodes have become popular for electrochemical sensor fabrication due to their simplicity for batch production without the use of reagents. The high surface area and favorable electrocatalytic properties also enable the design of small electrochemical devices while retaining the desired electrochemical performance. In this work, we systematically investigated the effect of LIG working electrode size, from 0.8 mm to 4.0 mm diameter, on their electrochemical properties, since it has been widely assumed that the electrochemistry of LIG electrodes is independent of size above the microelectrode size regime. The background and faradaic current from cyclic voltammetry (CV) of an outer-sphere redox probe [Ru(NH3)6] showed that smaller LIG electrodes had a higher electrode roughness factor and electroactive surface ratio than those of the larger electrodes. Moreover, CV of the surface-sensitive redox probes [Fe(CN)6] and dopamine revealed that smaller electrodes exhibited better electrocatalytic properties, with enhanced electron transfer kinetics. Scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy showed that the physical and chemical surface structure were different at the electrode center versus the edges, so the electrochemical properties of the smaller electrodes were improved by having rougher surface and more density of the graphitic edge planes, and more oxide-containing groups, leading to better electrochemistry. The difference could be explained by the different photothermal reaction time from the laser scribing process that causes different stable carbon morphology to form on the polymer surface. Our results give a new insight on relationships between surface structure and electrochemistry of LIG electrodes and are useful for designing miniaturized electrochemical devices.

Electrochemical impedance spectroscopy (EIS) is a powerful technique for studying the interaction at electrode/solution interfaces. The adoption of EIS for obtaining analytical signals in biosensors based on aptamers is gaining popularity because of its advantageous characteristics for molecular recognition. Neuropeptide Y (NPY), the most abundant neuropeptide in the body, plays a crucial role with its stress-relieving properties. Quantitative measurement of NPY is imperative for understanding its role in these and other biological processes. Although aptamer-modified electrodes for NPY detection using EIS present a promising alternative, the correlation between the data obtained and the adsorption process on the electrodes is not fully understood. Various studies utilize the change in charge transfer resistance when employing an active redox label. In contrast, label-free measurement relies on changes in capacitance. To address these challenges, we focused on the interaction between aptamer-modified planar electrodes and their target, NPY. We proposed utilizing -ω*Z as the analytical signal, which facilitated the analysis of the adsorption process using an analogous Langmuir isotherm equation. This approach differs from implantable microelectrodes, which adhere to the Freundlich adsorption isotherm. Notably, our method obviates the need for a redox label and enables the detection of NPY at concentrations as low as 20 pg/mL. This methodology demonstrated exceptional selectivity, exhibiting a signal difference of over 20-to-1 against potential interfering molecules.

Microenvironmental changes in the chemical surrounding of bacterial cells might have a profound impact on the ecology of biofilms. However, quantifying total amount of picomoles of analyte from a miniscule number of bacteria is an analytical challenge. Here we provide a novel microliter volume hydrogel based electrochemical cell platform suitable of coulometrically measuring hydrogen peroxide (HO) produced by less than 100 cells of , a relevant member of the healthy oral microbiome. A morpholine moiety was incorporated into the polymer structure of the hydrogel to create a controlled microenvironment at biological pH. We calculated the buffering capacity of this hydrogel as 0.257 ± 0.135 over the pH range of 7.2-6.2 by using a novel method designed for buffering hydrogels. The HO sensors coated in microliter volume of buffering hydrogel showed no change in sensitivity within the pH range of 7.0-3.0, allowing for HO measurements of independent of any acid they produce. The novel platform was able to measure down to 22.7 ± 3.5 pmol HO produced by less than 100 bacterial cells, which would otherwise not be attainable in large solution-based assays. These findings indicate that this is a suitable platform for quantifying metabolites from sub-milligram biological samples and may even be suitable for direct analysis of raw biofilms samples with little to no sample pretreatment.

Blocking electrochemistry, a subfield of single-entity electrochemistry, enables in-situ sizing of redox-inactive particles. This method exploits the adsorptive impact of individual insulating particles on a microelectrode, which decreases the electrochemically active surface area of the electrode. Against the background of an electroactive redox reaction in solution, each individual impacting particle results in a discrete current drop, with the magnitude of the drop corresponding to the size of the blocking particle. One significant limitation of this technique is "edge effects", resulting from the inhomogeneous flux of the redox species' diffusion due to increased mass transport to the edge of the disk electrode surface. "Edge effects" cause increased errors in size detection, resulting in poor analytical precision. Here, we use computational simulations to demonstrate that inhomogeneous diffusional edge flux of quasi-reversible redox species is mitigated at lowered overpotentials. This phenomenon is further illustrated experimentally by lowering the applied potential such that the system is operating under a kinetically-controlled regime instead of a diffusion-limited regime, which mitigates edge effects and increases particle sizing precision significantly. In addition, we found this method to be generalizable, as the precision enhancement is not limited to geometrically spherical particles but also occurs for cubic particles. This work presents a simple, novel methodology for edge effect mitigation with general applicability across different particle types.

The fabrication of a cost-efficient cathode is critical for in-situ electrochemical generation of hydrogen peroxide (HO) to remove persistent organic pollutants from groundwater. Herein, we tested a stainless-steel (SS) mesh wrapped banana-peel derived biochar (BB) cathode for in-situ HO electrogeneration to degrade bromophenol blue (BPB) and Congo red (CR) dyes. Furthermore, polarity reversal is evaluated for the activation of BB surface via introduction of various oxygen containing functionalities that serve as active sites for the oxygen reduction reaction (ORR) to generate HO. Various parameters including the BB mass, current, as well as the solution pH have been optimized to evaluate the cathode performance for efficient HO generation. The results reveal formation of up to 9.4 mg/L HO using 2.0 g BB and 100 mA current in neutral pH with no external oxygen supply with a manganese doped tin oxide deposited nickel foam (Mn-SnO@NF) anode to facilitate the oxygen evolution reaction (OER). This iron-free electrofenton (EF) like process enabled by the SSBB cathode facilitates efficient degradation of BPB and CR dyes with 87.44 and 83.63% removal efficiency, respectively after 60 min. A prolonged stability test over 10 cycles demonstrates the effectiveness of polarity reversal toward continued removal efficiency as an added advantage. Moreover, Mn-SnO@NF anode used for the OER was also replaced with stainless steel (SS) mesh anode to investigate the effect of oxygen evolution on HO generation. Although Mn-SnO@NF anode exhibits better oxygen evolution potential with reduced Tafel slope, SS mesh anode is discussed to be more cost-efficient for further studies.

Fast, sensitive, simple, and cheap sensors are highly desirable to be applied in the health system because they improve point-of-care diagnostics, which can reduce the number of cases of infection or even deaths. In this context, here we report the development of a label-free genosensor using a screen-printed electrode modified with 2D-carbonylated graphitic carbon nitride (CN), poly(diallyldimethylammonium) chloride (PDDA), and glutathione-protected gold nanoparticles (GSH-AuNPs) for photoelectrochemical (PEC) detection of SARS-CoV-2. We also made use of Arduino and 3D printing to miniaturize the sensor device. The electrode surface was characterized by AFM and SEM techniques, and the gold nanoparticles by UV-Vis spectrophotometry. For SARS-CoV-2 detection, capture probe DNA was immobilized on the electrode surface. The hybridization of the final genosensor was tested with a synthetic single-strand DNA target and with natural saliva samples using the photoelectrochemistry method. The device presented a linear range from 1 to 10,000 fmol L and a limit of detection of 2.2 and 3.4 fmol L using cpDNA 1A and 3A respectively. The sensibility and accuracy found for the genosensor using cpDNA 1A using biological samples were 93.3 and 80% respectively, indicating the potential of the label-free and portable genosensor to detect SARS-CoV-2 RNA in saliva samples.

The growing ubiquity of recalcitrant organic contaminants in the aqueous environment poses risks to effective and efficient water treatment and reuse. A novel three-dimensional (3D) electrochemical flow-through reactor employing activated carbon (AC) encased in a stainless-steel (SS) mesh as a cathode is proposed for the removal and degradation of a model recalcitrant contaminant -nitrophenol (PNP), a toxic compound that is not easily biodegradable or naturally photolyzed, can accumulate and lead to adverse environmental health outcomes, and is one of the more frequently detected pollutants in the environment. As a stable 3D electrode, granular AC supported by a SS mesh frame as a cathode is hypothesized to 1) electrogenerate HO via a 2-electron oxygen reduction reaction on the AC surface, 2) initiate decomposition of this electrogenerated HO to form hydroxyl radicals on catalytic sites of the AC surface 3) remove PNP molecules from the waste stream via adsorption, and 4) co-locate the PNP contaminant on the carbon surface to allow for oxidation by formed hydroxyl radicals. Additionally, this design is utilized to electrochemically regenerate the AC within the cathode that is significantly saturated with PNP to allow for environmentally friendly and economic reuse of this material. Under flow conditions with optimized parameters, the 3D AC electrode is nearly 20% more effective than traditional adsorption in removing PNP. 30 grams of AC within the 3D electrode can remove 100% of the PNP compound and 92% of TOC under flow. The carbon within the 3D cathode can be electrochemically regenerated in the proposed flow system and design thereby increasing the adsorptive capacity by 60%. Moreover, in combination with continuous electrochemical treatment, the total PNP removal is enhanced by 115% over adsorption. It is anticipated this platform holds great promises to eliminate analogous contaminants as well as mixtures.

The absence of reliable species-specific diagnostic tools for malaria at point-of-care (POC) remains a major setback towards effective disease management. This is partly due to the limited sensitivity and specificity of the current malaria POC diagnostic kits especially in cases of low-density parasitaemia and mixed species infections. In this study, we describe the first label-free DNA-based genosensors based on electrochemical impedance spectroscopy (EIS) for species-specific detection of and . The limits of detection (LOD) for the three species-specific genosensors were down in attomolar concentrations ranging from 18.7 aM to 43.6 aM, which is below the detection limits of previously reported malaria genosensors. More importantly, the diagnostic performance of the three genosensors were compared to quantitative real-time polymerase chain reaction (qPCR) assays using purified genomic DNA and the paired whole blood lysates from clinical samples. Remarkably, all the qPCR-positive purified genomic DNA samples were correctly identified by the genosensors indicating 100% sensitivity for each of the three malaria species. The specificities of the three genosensors ranged from 66.7% to 100.0% with a Therapeutic Turnaround Time (TTAT) within 30 min, which is comparable to the TTAT of current POC diagnostic tools for malaria. This work represents a significant step towards the development of accurate and rapid species-specific nucleic acid-based toolkits for the diagnosis of malaria at the POC.

Electrochemical sensors and biosensors are useful techniques for fast, inexpensive, sensitive, and easy detection of innumerous specimen. In face of COVID-19 pandemic, it became evident the necessity of a rapid and accurate diagnostic test, so the impedimetric immunosensor approach can be a good alternative to replace the conventional tests due to the specific antibody-antigen binding interaction and the fast response in comparison to traditional methods. In this work, a modified electrode with electrosynthesized PEDOT and gold nanoparticles followed by the immobilization of truncated nucleoprotein (N aa160-406aa) was used for a fast and reliable detection of antibodies against COVID-19 in human serum sample. The method consists in analyzing the charge-transfer resistance (R) variation before and after the modified electrode comes into contact with the positive and negative serum sample for COVID-19, using [Fe(CN)] as a probe. The results show a linear and selective response for serum samples diluted in a range of 2.5 × 10 to 20 × 10. Also, the electrode material was fully characterized by Raman spectroscopy, transmission electron microscopy and scanning electron microscopy coupled with EDS, indicating that the gold nanoparticles were well distributed around the polymer matrix and the presence of the biological sample was confirmed by EDS analysis. EIS measurements allowed to differentiate the negative and positive samples by the difference in the R magnitude, proving that the material developed here has potential properties to be applied in impedimetric immunosensors for the detection of SARS-CoV-2 antibodies in about 30 min.

Tracking and monitoring of low concentrations of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) can effectively control asymptomatic transmission of current coronavirus disease 2019 (COVID-19) in the early stages of infection. Here, we highlight an electrochemical immunosensor for sensitive detection of SARS-CoV-2 antigen marker spike protein. The surface-clean Pd-Au nanosheets as a substrate for efficient sensing and signal output have been synthesized. The morphology, chemical states and excellent stable electrochemical properties of this surface-clean heterostructures have been studied. Functionalized superparamagnetic nanoparticles (MNPs) were introduced as sample separators and signal amplifiers. This biosensor was tested in phosphate buffered saline (PBS) and nasopharyngeal samples. The results showed that the sensor has a wide linear dynamic range (0.01 ng mL to 1000 ng mL) with a low detection limit (0.0072 ng mL), which achieved stable and sensitive detection of the spike protein. Therefore, this immunosensing method provides a promising electrochemical measurement tool, which can furnish ideas for early screening and the reasonable optimization of detection methods of SARS-CoV-2.

This study describes the application of a polypyrrole-based sensor for the determination of SARS-CoV-2-S spike glycoprotein. The SARS-CoV-2-S spike glycoprotein is a spike protein of the coronavirus SARS-CoV-2 that recently caused the worldwide spread of COVID-19 disease. This study is dedicated to the development of an electrochemical determination method based on the application of molecularly imprinted polymer technology. The electrochemical sensor was designed by molecular imprinting of polypyrrole (Ppy) with SARS-CoV-2-S spike glycoprotein (MIP-Ppy). The electrochemical sensors with MIP-Ppy and with polypyrrole without imprints (NIP-Ppy) layers were electrochemically deposited on a platinum electrode surface by a sequence of potential pulses. The performance of polymer layers was evaluated by pulsed amperometric detection. According to the obtained results, a sensor based on MIP-Ppy is more sensitive to the SARS-CoV-2-S spike glycoprotein than a sensor based on NIP-Ppy. Also, the results demonstrate that the MIP-Ppy layer is more selectively interacting with SARS-CoV-2-S glycoprotein than with bovine serum albumin. This proves that molecularly imprinted MIP-Ppy-based sensors can be applied for the detection of SARS-CoV-2 virus proteins.

In this study, we demonstrated the unique capability of carbon-based ion-selective electrode (ISE) to perform highly sensitive square wave anodic stripping voltammetry, while maintaining all the properties of an ISE, in terms of sensitivity, detection limit, response time and selectivity. Square wave anodic stripping voltammetry involves deposition and dissolution steps of metal ions, which means adsorption and desorption of metal ions on the conductive ion-selective membrane without losing its ion-sensing property. To demonstrate this capability, we chose a Ca ion-selective microelectrode (μISE) as a potentiometric method and Cu-stripping voltammetry as an amperometric method. The carbon-based ISE surface is capable of quantifying nanomolar to micromolar Cu in both a standard acetate buffer and a complex water sample. The Ca-μISE also showed a Nernstian slope of 29 mV / log [Ca] and a detection limit of 1 μM within the linear range of 1 μM to 10 mM. It thus opens an opportunity to use the low detection limit of anodic stripping voltammetry and the high selectivity of ISE-based potentiometry.

This article outlines examples of where electrochemical investigations of electrocatalysis by proteins immobilised on an electrode reveal fundamental information about electron-proton coupling in catalysis and provide a new way to energise, control and observe multi-enzyme cascades.

Ceramic materials based on naturally occurring clays are a low cost and environmentally friendly alternative to commercial polymer-based membranes in bioelectrochemical systems. In this work, ceramic membranes containing different amounts of iron oxide (1.06, 2.76 and 5.75 vol.%) and sintered at different temperatures (1100, 1200 and 1300 °C) have been elaborated and tested as separators in urine-fed microbial fuel cells (MFCs). The results reveal that the presence of iron oxide in the ceramic membrane composition increases the structural porosity and reduces the pore size for the three temperatures investigated. On the other hand, it was also observed that the iron content mitigates the negative effect of the high sintering temperature on the power performance of the MFCs. In the case of the ceramic membranes sintered at 1300 °C, power output improved ca. 10-fold when the iron oxide content in the membrane increased from 1.06 up to 5.75 vol.% (30.9 and 286.6 µW, respectively). Amongst the different combinations of iron phase content and sintering temperatures, the maximum power output was obtained by MFCs working with separators containing 5.75 vol. % of iron oxide and sintered at 1100 °C (1.045 mW). Finally, the system was stable for 65 days, which supports the long-term functionality of the different materials assessed.

Recently we showed the reduction and oxidation of six natural 2'-deoxynucleosides in the presence of the ambient oxygen using the very broad potential window of a pyrolytic graphite electrode (PGE). Using the same procedure, 2'-deoxynucleoside analogs (dNs) that are parts of an artificially expanded genetic information system (AEGIS) were analyzed. Seven of the eight tested AEGIS dNs provided specific signals (voltammetric redox peaks). These signals, described here for the first time, will be used in future work to analyze DNA built from expanded genetic alphabets, helping to further develop AEGIS technology and its applications. Comparison of the electrochemical behavior of unnatural dNs with the previously documented behaviors of natural dNs also provides insights into the mechanisms of their respective redox processes.

The combination of computer assisted design and 3D printing has recently enabled fast and inexpensive manufacture of customized 'reactionware' for broad range of electrochemical applications. In this work bi-material fused deposition modeling 3D printing is utilized to construct an integrated platform based on a polyamide electrochemical cell and electrodes manufactured from a polylactic acid-carbon nanotube conductive composite. The cell contains separated compartments for the reference and counter electrode and enables reactants to be introduced and inspected under oxygen-free conditions. The developed platform was employed in a study investigating the electrochemical oxidation of aqueous hydrazine coupled to its bulk reaction with carbon dioxide. The analysis of cyclic voltammograms obtained in reaction mixtures with systematically varied composition confirmed that the reaction between hydrazine and carbon dioxide follows 1/1 stoichiometry and the corresponding equilibrium constant amounts to (2.8 ± 0.6) × 10. Experimental characteristics were verified by results of numerical simulations based on the finite-element-method.

Carbon nanotube yarn microelectrodes (CNTYMEs) are an alternative to carbon-fiber microelectrodes (CFMEs) with interesting electrochemical properties because analyte is momentarily trapped in cavities between the CNTs. Here, we compare fast-scan cyclic voltammetry (FSCV) detection of catecholamines, including dopamine, norepinephrine, and epinephrine, at CNTYMEs, CFMEs, as well as cavity carbon nanopipette electrodes (CNPEs). At CFMEs, current decreases dramatically at high FSCV repetition frequencies. At CNTYMEs, current is almost independent of FSCV repetition frequency because the analytes are trapped in the crevices between CNTs, and thus the electrode acts like a thin-layer cell. At CFMEs, small cyclization product peaks are observed due to an intramolecular cyclization reaction to form leucocatecholamine, which is electroactive, and these peaks are largest for the secondary amine epinephrine. At CNTYMEs, more of the leucocatecholamine cyclization product is detected for all catecholamines because of the enhanced trapping effects, particularly at higher repetition rates where the reaction occurs more frequently and more product is accumulated. For epinephrine, the secondary peaks have larger currents than the primary oxidation peaks at 100 Hz, and similar trends are observed with faster scan rates and 500 Hz repetition frequencies. Finally, we examined CNPEs, which also momentarily trap neurotransmitters. Similar to CNTYMEs, at CNPEs, catecholamines have robust cyclization peaks, particularly at high repetition rates. Thus, CNTYMEs and CNPEs have thin layer cell behavior that facilitates high temporal resolution measurements, but catecholamines CVs are complicated by cyclization reactions. However, those additional peaks could be useful in discriminating the analytes, particularly epinephrine and norepinephrine.

This work is presenting for the first time the use of inexpensive and efficient anode material for boosting power production, as well as improving electrofiltration of human urine in tubular microbial fuel cells (MFCs). The MFCs were constructed using unglazed ceramic clay functioning as the membrane and chassis. The study is looking into effective anodic surface modification by applying activated carbon micro-nanostructure onto carbon fibres that allows electrode packing without excessive enlargement of the electrode. The surface treatment of the carbon veil matrix resulted in 3.7 mW (52.9 W m and 1626 mW m) of power generated and almost a 10-fold increase in the anodic current due to the doping as well as long-term stability in one year of continuous operation. The higher power output resulted in the synthesis of clear catholyte, thereby i) avoiding cathode fouling and contributing to the active splitting of both pH and ions and ii) transforming urine into a purified catholyte - 30% salt reduction - by electroosmotic drag, whilst generating - rather than consuming - electricity, and in a way demonstrating electrofiltration. For the purpose of future technology implementation , the importance of simultaneous increase in power generation, long-term stability over 1 year and efficient urine cleaning by using low-cost materials, is very promising and helps the technology enter the wider market.

In this work, a membraneless microbial fuel cell (MFC) with an empty volume of 1.5 mL, fed continuously with hydrolysed urine, was tested in supercapacitive mode (SC-MFC). In order to enhance the power output, a double strategy was used: i) a double cathode was added leading to a decrease in the equivalent series resistance (ESR); ii) the apparent capacitance was boosted up by adding capacitive features on the anode electrode. Galvanostatic (GLV) discharges were performed at different discharge currents. The results showed that both strategies were successful obtaining a maximum power output of 1.59 ± 0.01 mW (1.06 ± 0.01 mW mL) at pulse time of 0.01 s and 0.57 ± 0.01 mW (0.38 ± 0.01 mW mL) at pulse time of 2 s. The highest energy delivered at i equal to 2 mA was 3.3 ± 0.1 mJ. The best performing SC-MFCs were then connected in series and parallel and tested through GLV discharges. As the power output was similar, the connection in parallel allowed to roughly doubling the current produced. Durability tests over ≈5.6 days showed certain stability despite a light overall decrease.

In this work, commercially available Polymethyl-meta-acrylate (PMMA) spectroscopy cells were modified on the external walls with films of TiO, TiO or TiO/TiO mixtures. Film characterization was carried out using SEM and UV-vis spectroscopy. The results of photocatalytic (PC), electro-oxidation (EO), and photoelectrochemical (PEC) experiments on the decolorization of a methyl orange (MO) model dye solution showed that while anatase provides better photocatalytic properties and the partially reduced TiO larger electronic conductivity, the TiO/TiO composite film behaves as a semiconductor substrate that combines the advantages of both materials (for PEC experiments for instance, decolorization values for the model dye solution using TiO, TiO and a TiO/TiO mixed film, corresponded to 35%, 46% and 53%, respectively). In order to test this film as an effective photoanode material in a 3-D type reactor for water treatment processes, a TiO/TiO modified PMMA spectroscopy cell was inserted in an activated carbon (AC) bed so that the semiconductor material could be illuminated using an external UV source positioned inside the PMMA cell. The connected AC particles that were previously saturated with MO dye were used as cathode sites for the oxygen reduction reaction so that the photoelectrochemical reactions that take place in the anode could be complemented with coupled electro-Fenton processes in the cathode. As expected, the combination resulted in an effective decolorization of the dye solution that results from a complex combination of processes. The experimental decolorization data was successfully fitted to a pseudo-first order kinetic model so that a deeper understanding of the contribution of each process in the reactor could be obtained.

Little is known about the adaptation strategies utilized by photosynthetic microorganisms to cope with salinity changes happening in the environment, and the effects on microbial electrochemical technologies. Herein, bioinformatics analysis revealed a metabolism shift in resulting from salt stress, with changes in gene expression allowing accumulation of compatible solutes to balance osmotic pressure, together with the up-regulation of the nitrogen fixation cycle, an electron sink of the photosynthetic electron transfer chain. Using the transcriptome evidence of hindered electron transfer in the photosynthetic electron transport chain induced by adaption to salinity, increased understanding of photo-bioelectrocatalysis under salt stress is achieved. Accumulation of glycine-betaine allows immediate tuning of salinity tolerance but does not provide cell stabilization, with a 40 ± 20% loss of photo-bioelectrocatalysis in a 60 min time scale. Conversely, exposure to or inducing the expression of the gene transfer agent tunes salinity tolerance and increases cell stability. This work provides a proof of concept for the combination of bioinformatics and electrochemical tools to investigate microbial electrochemical systems, opening exciting future research opportunities.