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This study endeavored to design and develop an innovative closed-loop diagnostic and therapeutic system with the following objectives: (a) the noninvasive detection of glucose concentration in sweat utilizing nanonengineered screen-printed biosensors; (b) the management of measured data through a specialized computer system comprising both hardware and software components, thereby enabling the precise control of therapeutic responses via a patch-based nanomedicine delivery system. This initiative addresses the significant challenges inherent in the management of diabetes mellitus, including the imperative need for glucose-level monitoring to optimize glycemic control. Leveraging chronoamperometric results as a foundational dataset and the in vivo hypoglycemic activity of nanoemulsion formulations, this research underscores the efficacy and accuracy of glucose concentration estimation, decision-making mechanism responses, and transdermal hypoglycemic treatment effects, within the proposed system.

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3D printing technology is a tremendously powerful technology to fabricate electrochemical sensing devices. However, current conductive filaments are not aimed at electrochemical applications and therefore require intense activation protocols to unleash a suitable electrochemical performance. Current activation methods based on (electro)chemical activation (using strong alkaline solutions and organic solvents and/or electrochemical treatments) or combined approaches are time-consuming and require hazardous chemicals and dedicated operator intervention. Here, pioneering spark-discharge-activated 3D-printed electrodes were developed and characterized, and it was demonstrated that their electrochemical performance was greatly improved by the effective removal of the thermoplastic support polylactic acid (PLA) as well as the formation of sponge-like and low-dimensional carbon nanostructures. This reagent-free approach consists of a direct, fast, and automatized spark discharge between the 3D-electrode and the respective graphite pencil electrode tip using a high-voltage power supply. Activated electrodes were challenged toward the simultaneous voltammetric determination of dopamine (DP) and serotonin (5-HT) in cell culture media. Spark discharge has been demonstrated as a promising approach for conductive filament activation as it is a fast, green (0.94 GREEnness Metric Approach), and automatized procedure that can be integrated into the 3D printing pipeline.

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The modification of graphite screen-printed electrodes (SPEs) is reported using an eco-friendly and extremely fast method based on the direct cobalt pin electrode-to-SPE spark discharge at ambient conditions. This approach does not utilize any liquids or chemical templates, does not produce any waste, and allows the in-situ generation of CoxOy nanoparticles onto the electrode surface and the development of efficient electrocatalytic sensing surfaces for the determination of H2O2. Co-spark SPEs were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy and x-ray photoelectron spectroscopy (XPS), revealing the formation of surface confined CoxOy nanoparticles and the diverse oxidation states of cobalt species. Co-spark SPEs were also characterized with cyclic voltammetry and electrochemical impedance spectroscopy. Redox transitions of the surface confined electrocatalysts are demonstrated by electrochemical polarization studies, showing the formation of different oxides (CoxOy), varying the XPS results. Amperometric measurements at 0.3 V vs. Ag/AgCl revealed a linear relationship between the current response and the concentration of H2O2 over the range 1 - 102 µM, achieving a limit of detection (3σ/m) of 0.6 µM. The interference effect of various electroactive species was effectively addressed by employing dual measurements in the absence and presence of the enzyme catalase. The analytical utility of the method was evaluated in antioxidant rich real-world samples, such as energy drinks, demonstrating sufficient recovery.

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Fabric-based microfluidic analytical devices (µADs) have emerged as a promising material for replacing paper µADs thanks to their superior properties in terms of stretchability, mechanical strength, and their wide scope of applicability in wearable devices or embedded in garments. The major obstacle in their widespread use is the lack of a technique enabling their massive fabrication at a negligible-to-nil cost. In response, we report the development of a wax ink with proper thixotropic and hydrophobic properties, fully compatible with automatic screen-printing that allows the one step massive fabrication of microfluidics on a cotton/elastane fabric, with a printing resolution 400 µm (hydrophilic channel) and 1000 µm (hydrophobic barrier), without being necessary any post curing. The cost of the ink (50 g) and of each microfluidic device is ca. 2.3 and 0.007 €, respectively. The active component of the ink was a refined beeswax in a matrix based on ethyl cellulose in 2-butoxy ethyl acetate. Screen-printed fabric µADs were used for the simultaneous colorimetric determination of pH and urea in untreated human sweat by using multivariate regression analysis. This method enabled the direct measurement of urea using urease, regardless of the sweat's pH, and shows strong agreement with a reference method.

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The fabrication of a low-cost eco-friendly sensor platform for the voltammetric determination of trace metals by electrochemical stripping analysis is reported. Plastic conductive electrodes were manufactured via injection moulding from polysterene reinforced with carbon fibres. The platform comprises a carbon counter electrode, a working electrode modified with bismuth nanoparticles generated by spark discharge and a reference electrode coated with AgCl. The sensor fabrication and modification procedures are simple, cost-effective and fast while the materials used are environment-friendly. The utility of the voltammetric platform is demonstrated for stripping analysis of Cd(II) and Pb(II); the limits of detection are 0.7 µg L-1 and 0.6 µg L-1, respectively (with a deposition time of 240 s) which are comparable to conventional Bi-modified sensors and are sufficient to determine the target metals in water and food samples. The scope of the analytical platform for multi-element assays and for the determination of other trace metals is discussed with representative examples. Therefore, this sustainable and economical platform holds great potential for electrochemical sensing of trace metals.

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This tutorial provides the theoretical background, the principles, and applications of Electrochemical Impedance Spectroscopy (EIS) in various research and technological sectors. The text has been organized in 17 sections starting with basic knowledge on sinusoidal signals, complex numbers, phasor notation, and transfer functions, continuing with the definition of impedance in electrical circuits, the principles of EIS, the validation of the experimental data, their simulation to equivalent electrical circuits, and ending with practical considerations and selected examples on the utility of EIS to corrosion, energy related applications, and biosensing. A user interactive excel file showing the Nyquist and Bode plots of some model circuits is provided in the Supporting Information. This tutorial aspires to provide the essential background to graduate students working on EIS, as well as to endow the knowledge of senior researchers on various fields where EIS is involved. We also believe that the content of this tutorial will be a useful educational tool for EIS instructors.

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We present in detail the most known and commonly used methods for the calculation of electrode electroactive area ([Formula: see text]) and heterogeneous electron transfer rate constants ([Formula: see text]). The correct procedure for the calculation of these parameters is often disregarded due to either lack of a minimum theoretical background or oversimplification of each method's limitations and prerequisites. The aim of this work is to provide the theoretical background as well as a detailed guide for the implementation of these measurements by impressing upon the electrochemists the parameters that need to be considered so that the obtained results are safe and useful. Using graphite screen-printed electrodes, [Formula: see text], and [Formula: see text] were calculated with different methods and techniques. Data are compared and discussed.

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In this work, we elaborated the graphite screen-printed electrodes (SPEs) modification with metal nanoparticles formed as a result of spark discharges produced between a metal wire electrode and SPE that are connected to an Arduino board-based DC high voltage power supply. This sparking device allows, on the one hand, the toposelective formation of NPs of controlled dimensions through a direct and liquid-free approach, and on the other hand, controls the number and energy of the discharges delivered to the electrode surface during a single spark event. This way, the potential damage to the SPE surface by the action of heat evolved during the sparking process is considerably minimized compared with the standard setup in which each spark event consists of multiple electrical discharges. Data demonstrated that the sensing properties of the resulting electrodes are significantly improved compared with those achieved when conventional spark generators are employed, as demonstrated for silver-sparked SPEs that exhibit enhanced sensitivity to riboflavin. Sparked AgNp-SPEs were characterized using scanning electron microscopy and voltammetric measurements in alkaline conditions. The analytical performance of sparked AgNP-SPEs was evaluated by various electrochemical techniques. Under optimum conditions, the detection range for DPV was from 1.9 (LOQ) to 100 nM riboflavin (R2 = 0.997), while a limit of detection (LOD, S/N 3) of 0.56 nM was achieved. The analytical utility is demonstrated for the determination of riboflavin in the real matrices of B-complex pharmaceutical preparation and an energy drink.

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Diabetes mellitus' (DM) prevalence worldwide is estimated to be around 10% and is expected to rise over the next decades. Monitoring blood glucose levels aims to determine whether glucose targets are met to minimize the risk for the development of symptoms related to high or low blood sugar and avoid long-term diabetes complications. Continuous glucose monitoring (CGMs) systems emerged almost two decades ago and have revolutionized the way diabetes is managed. Especially in Type 1 DM, the combination of a CGM with an insulin pump (known as a closed-loop system or artificial pancreas) allows an autonomous regulation of patients' insulin with minimal intervention from the user. However, there is still an unmet need for high accuracy, precision and repeatability of CGMs. Graphene was isolated in 2004 and found immediately fertile ground in various biomedical applications and devices due to its unique combination of properties including its high electrical conductivity. In the last decade, various graphene family nanomaterials have been exploited for the development of enzymatic and non-enzymatic biosensors to determine glucose in biological fluids, such as blood, sweat, and so on. Although great progress has been achieved in the field, several issues need to be addressed for graphene sensors to become a predominant material in the new era of CGMs.

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In this work, we investigated the effect of multi-walled carbon nanotubes (MWCNTs) and bio-graphene (bG) on the structure and activity of glucose oxidase (GOx), as well as on the performance of the respective electrochemical glucose biosensors. Various spectroscopic techniques were applied to evaluate conformational changes in GOx molecules induced by the presence of MWCNTs and bG. The results showed that MWCNTs induced changes in the flavin adenine dinucleotide (FAD) prosthetic group of GOx, and the tryptophan residues were exposed to a more hydrophobic environment. Moreover, MWCNTs caused protein unfolding and conversion of α-helix to ß-sheet structure, whereas bG did not affect the secondary and tertiary structure of GOx. The effect of the structural changes was mirrored by a decrease in the activity of GOx (7%) in the presence of MWCNTs, whereas the enzyme preserved its activity in the presence of bG. The beneficial properties of bG over MWCNTs on GOx activity were further supported by electrochemical data at two glucose biosensors based on GOx entrapped in chitosan gel in the presence of bG or MWCNTs. bG-based biosensors exhibited a 1.33-fold increased sensitivity and improved reproducibility for determining glucose over the sweat-relevant concentration range of glucose.

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Medical diagnostic sector is relying on affordable, handheld devices integrating smart biosensing and transducing interfaces that enable clinical analysis with minimal end-user intervention and resource requirements. In response, we propose here, a SIM card-type pH responsive polymer-modified paper-based biosensing device, coupled to a smartphone, for the determination of urinary creatinine. A vertical microfluidic channel was fabricated on a paper strip by wax printing. The hydrophilic area was coated by a poly(methylmethacrylate)/poly(methacrylic acid) random copolymer, PMMA-co-PMAA, and on top of it, creatinine deiminase (CD) was immobilized. Data demonstrated, on the one hand, zero vertical flow of urine through the enzyme-free PMMA-co-PMAA-modified paper strip, i.e., a high selectivity against the components of the matrix, and on the other hand, in the presence of CD, a creatinine -concentration dependent commence of sample's downward flow due to the selective, creatinine-triggered degradation of the copolymer by the enzymatically produced ammonia. This CD/PMMA-co-PMAA paper-based biosensing smart assembly is coupled with three conductive strips, which enable the automatic on/off (sample addition/measurement end) measurement of the copolymer degradation time, through electric resistance measurements. It also features an in-built sample well and wireless communication support through the integration of a Bluetooth® microprocessor incorporated with time and resistance measuring circuits. Using newly synthesized pH responsive PMMA-co-PMAA at different molecular weights and volume fraction ratios offering tunable dissolution properties, the detection range was adjusted over 3-30 mM creatinine to overspread the normal range of creatinine in urine. The device was successfully applied to the determination of urinary creatinine.

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Saliva represents one of the most useful biological samples for non-invasive testing of health status and diseases prognosis and therefore, the development of advanced sensors enabling the determination of biomarkers in unspiked human whole saliva is of immense importance. Herein, we report on the development of a screen-printed graphite sensor modified with carbon nanomaterials generated by spark discharge for the determination of guanine and adenine in unspiked human whole saliva. The designed sensor was developed with a "green", extremely simple, fast (16 s), fully automated "linear mode" sparking process implemented with a 2D positioning device. Carbon nanomaterial-modified surfaces exhibit outstanding electrocatalytic properties enabling the determination of guanine and adenine over the concentration range 5 - 1000 nM and 25 - 1000 nM, while achieving limits of detection (S/N 3) as low as 2 nM and 8 nM, respectively. The sensor was successfully applied to the determination of purine bases in unspiked human whole saliva following a simple assay protocol based on ultrafiltration that effectively alleviates biofouling issues. Recovery was 96-108%.

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A reagent-less DNA sensor has been developed exploiting a combination of gold nanoparticles, modified primers, and isothermal amplification. It is applied to the determination ofKarlodinium armiger, a toxic microalgae, as a model analyte to demonstrate this generic platform. Colloidal gold nanoparticles with an average diameter of 14 ± 0.87 nm were modified with a mixed self-assembled monolayer of thiolated 33-mer DNA probes and (6-mercaptohexyl) ferrocene. Modified primers, exploiting a C3 spacer between the primer-binding site and an engineered single-stranded tail, were used in an isothermal recombinase polymerase amplification reaction to produce an amplicon by two single-stranded tails. These tails were designed to be complementary to a gold electrode tethered capture oligo probe, and an oligo probe immobilized on the gold nanoparticles, respectively. The time required for hybridization of the target tailed DNA with the surface immobilized probe and reporter probe immobilized on AuNPs was optimized and reduced to 10 min, in both cases. Amplification time was further optimized to be 40 min to ensure the maximum signal. Under optimal conditions, the limit of detection was found to be 1.6 fM of target dsDNA. Finally, the developed biosensor was successfully applied to the detection of genomic DNA extracted from a seawater sample that had been spiked with K. armiger cells. The demonstrated generic electrochemical genosensor can be exploited for the detection of any DNA sequence and ongoing work is moving towards an integrated system for use at the point-of-need.

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This review (with 178 references) focuses on inorganic layered materials (ILMs) and the use of their two-dimensional nanosheets in the development of novel electrochemical (bio)sensors, analytical devices, and gas-phase sensing applications. The text is organized in three main sections including the presentation of the most important families of ILMs, a comprehensive outline of various "bottom-up", "top-down," and hydro(solvo)thermal methods that have been used for the production of ILM nanosheets, and finally an evaluative survey on their utility for the determination of analytes with interest in different sectors of contemporary analysis. Critical discussion on the effect of the production method on their electronic properties, the suitability of each nanomaterial in different sensing technologies along with an assessment of the performance of the (bio)sensors and devices that have been proposed within the last 5 years, is enclosed. The perspectives of further improving the utility of 2D inorganic nanosheets in sensing applications, in real-world samples, are also discussed.

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Here we report for the first time the development of a compact, closed bipolar electrochemistry (BPE) device for the determination of antioxidant capacity in real-world samples by recording the onset driving voltage at which an eye-visible reporting event at the cathode pole of bipolar electrode (BE) occurs. The BPE cell consists of two distinct anode and cathode compartments that are electrically connected through a platinum wire BE. The anode pole of the BE is covered by a cellulose acetate thin film to prevent the fouling of the surface, while the cathode pole is embedded into an agarose hydrogel containing phenolphthalein, i.e., an acid-base indicator. The method relies on the oxidation of the reducing compounds in the sample by a fixed amount of H2O2 and the electro oxidation of the remaining H2O2 in the anode pole of the BE. This reaction triggers the reduction of water at the cathodic pole accompanied by the production of hydroxyl ions at different, H2O2 concentration-dependent onset driving voltages. The resulting increase of pH at the cathode pole results in the formation of a pink spot (reporting event), which is visible by the unaided eye. The applicability of the BPE device for the determination of antioxidant capacity in fruit juices and sodas is demonstrated. The analytical results, expressed as Trolox (TEAC) or Vitamin C (CVEAC) equivalent antioxidant capacity, correlate well with those obtained by the CUPRAC method.

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The development of a humidity sensor utilizing vanadium pentoxide xerogel (V2O5·nH2O, VPX) is described. Thin films of VPX were drop-cast onto a low-cost, screen-printed graphite three-electrode electrochemical cell (SPC) and the resulting transducing surface was assessed as a relative humidity (RH%) sensor. The morphology of VPX, its interaction with water vapors as well as the electrochemical properties of VPX/SPC were characterized by scanning electron microscopy, ATR-infrared spectroscopy and electrochemical impedance spectroscopy (EIS), respectively. The sensor possesses high sensitivity (190-500 Ohm/RH%) over a wide range of RH (10-93%), sensor response of 93%, low hysteresis, sufficient storage stability, and a fast response and recovery time, of 52 and 21 s, respectively. EIS data obtained at different RH% values were sufficiently modeled to a single equivalent electric circuit, which describes the conduction mechanism within the VPX film and the electrochemical properties at the electrode/film interfaces. Results demonstrate that the designed sensor is suitable for on-site and real-time monitoring of relative humidity at ambient conditions.

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Flunitrazepam, also known as "Rohypnol" or "Rophy" among other trade and street names, is an extremely potent benzodiazepine that is prescribed to treat severe insomnia. Due to these attributes, flunitrazepam, when is surreptitiously administered to an alcoholic or soft drink, is associated with "drug-facilitated sexual assault". We report here for the first time, a low cost lab-on-a-screen-printed electrochemical cell (SPC) based on iron-sparked graphite working electrode modified with glucose oxidase (GOx) and glucose hydrogel droplets (GluHD) for the detection of flunitrazepam. Iron-spark modification increases the response of the sensor by ca. 3-fold compared with that of the plain electrode, while an in situ deoxygenation process, based on GOx-glucose enzyme reaction, depletes dissolved oxygen. As a result, the method enables interference free voltammetric measurements of the electro reduction of the nitro group of flunitrazepam at ca. -0.71 to -0.78 V vs. Ag printed pseudo reference electrode depending on the sample's matrix, and the detection of the drug at the sub-millimolar level. GOx/GluHD-FeSPC was directly applied to the drop-volume (∼60 µL) detection of flunitrazepam to a wide range of untreated and undiluted spiked samples (Pepsi cola®, Vodka, Whisky, Tequila, Gin, and Rum) of different acidity (pH 2.3-8.4), and alcohol content up to 40% v/v. Data demonstrate the excellent performance of the sensor for point-of-need screening of flunitrazepam and suggest that GOx/GluHD-FeSPC holds promise as an effective analytical tool to prevent phenomena of covert drug administration.

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Electric spark discharge was employed as a green, fast and extremely facile method to modify disposable graphite screen-printed electrodes (SPEs) with copper, nickel and mixed copper/nickel nanoparticles (NPs) in order to be used as nonenzymatic glucose sensors. Direct SPEs-to-metal (copper, nickel or copper/nickel alloys with 25/75, 50/50 and 75/25wt% compositions) sparking at 1.2kV was conducted in the absence of any solutions under ambient conditions. Morphological characterization of the sparked surfaces was performed by scanning electron microscopy, while the chemical composition of the sparked NPs was evaluated with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The performance of the various sparked SPEs towards the electro oxidation of glucose in alkaline media and the critical role of hydroxyl ions were evaluated with cyclic voltammetry and kinetic studies. Results indicated a mixed charge transfer- and hyroxyl ion transport-limited process. Best performing sensors fabricated by Cu/Ni 50/50wt% alloy showed linear response over the concentration range 2-400µM glucose and they were successfully applied to the amperometric determination of glucose in blood. The detection limit (S/N 3) and the relative standard deviation of the method were 0.6µM and <6% (n=5, 2µM glucose), respectively. Newly devised sparked Cu/Ni graphite SPEs enable glucose sensing with distinct advantages over existing glucose chemical sensors in terms of cost, fabrication simplicity, disposability, and adaptation of green methods in sensor's development.

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In this work we describe the fabrication of nanostructured electrocatalytic surfaces based on polyethyleneimine (PEI)-supported rhodium nanoparticles (Rh-NP) over graphite screen-printed electrodes (SPEs) for the determination of hydrogen peroxide in the presence of oxygen. Rh-NP, electrostatically stabilized by citrate anions, were immobilized over graphite SPEs, through coulombic attraction on a thin film of positively charged PEI. The functionalized sensors, polarized at 0.0 V vs. Ag/AgCl/3 M KCl, exhibited a linear response to H2O2 over the concentration range from 5 to 600 µmol L(-1) H2O2 in the presence of oxygen. The 3σ limit of detection was 2 µmol L(-1) H2O2, while the reproducibility of the method at the concentration level of 10 µmol L(-1) H2O2 (n=10) and between different sensors (n=4) was lower than 3 and 5%, respectively. Most importantly, the sensors showed an excellent working and storage stability at ambient conditions and they were successfully applied to the determination of H2O2 produced by autooxidation of polylphenols in tea extracts with ageing. Recovery rates ranged between 97 and 104% suggesting that the as-prepared electrodes can be used for the development of small-scale, low-cost chemical sensors for use in on-site applications.

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