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Prostate cancer (PCa) appears among the most frequently diagnosed types of malignancies in males. Because of the high demand and increasing detection rate of early PCa, alongside the specificity limitations of the gold standard clinical tools available for the diagnosis and prognosis of prostate cancer, there is an urgent need for more reliable PCa markers and highly sensitive diagnostic tools to avoid under-treatment and over-diagnosis. PCA3, or prostate cancer antigen 3, is a potential prostate cancer biomarker that is more specific and useful for preventing unnecessary repeat biopsies, particularly in men with persistently high prostate-specific antigen indices after a negative biopsy. Additionally, an electrochemically based biosensor would prove to be a powerful diagnostic tool for PCA3 detection in urine because of its simplicity, sensitivity, and cost-effectiveness, in contrast to the more traditional PCa diagnostics that depend on blood testing. This paper aimed to design a novel and simple electrochemical impedimetric biosensor based on a label-free RNA-aptamer (CG3-PCA3) as the molecular recognition element for detecting PCA3. The proposed aptasensor for the detection of PCA3 has been developed using a screen-printed carbon electrode (SPCE) modified by gold nanoparticles (AuNPs), further improving sensitivity and allowing the immobilisation of thiolate aptamers on its surface. The findings presented here demonstrated a high sensitivity to PCA3, with a detection limit of 20 fM in artificial urine and 1 fM in buffer. These results indicate that the PCA3 aptasensor could be a promising tool for routine PCa diagnosis due to its high sensitivity and cost-effectiveness.

The paper describes the development and application of a screen-printed electrode cell with a graphite-ink working electrode modified by a molecularly imprinted electropolymerized polypyrrole for the voltammetric determination of the herbicide 4‑chloro-2-methylphenoxyacetic acid (MCPA). The method exploits the direct measurement of the analyte by applying the differential pulse voltammetry (DPV) technique, taking advantage of the irreversible oxidation peak at about +1.0 V vs. Ag/AgCl pseudo reference electrode. The presence of the molecularly imprinted polypyrrole enhances the sensor's selectivity and sensitivity. A chemometric approach has been crucial for quantitative analysis because of the peak's broad and not well-defined shape. Firstly, a proper pretreatment of the voltammetric signals is identified, proving the most effective is the first-derivative function transformation of the signal. The Partial Least Square regression (PLS) is the tool applied for MCPA quantification. A preliminary PLS model has been developed and validated in dihydrogen phosphate solution at pH 5.5, aiming to optimize the data treatment approach. Then, the same approach is used to develop a PLS model analyzing tap water samples fortified with MCPA and other pesticides as possible interferents to simulate contaminated natural waters. The model correctly predicted the analyte concentration in the range of 2.5–75 μM, assuring the reliability and robustness of the sensor for the possible quantification of MCPA in wastewater samples.

The mass production of screen-printed electrochemical devices with integrated electrodes has facilitated the widespread adoption of electroanalytical methods. The SPEs (screen-printed electrodes) overcome some obstacles associated with the use of conventional electrochemical cells, making them accessible to untrained operators. Despite their advantages, SPEs require activation/modification of the working electrode (WE) to enhance sensitivity. Nanomaterials, with metal nanoparticles (NPs) dispersed in polymers and/or carbon NPs has gaining popularity for this purpose. In this study, we describe a modification of carbon SPEs (SPCEs) using Pt NPs and reduced graphene oxide (ERGO). The Pt-ERGO@SPCE is prepared by galvanostatic reduction of drop-casted precursors directly onto the WE surface, eliminating complex synthetic steps and high temperatures. After optimizing Pt amount and reduction extent, the modified SPCEs were tested for detecting hydroquinone (HQ) and bisphenol A (BPA). DPV results show significantly increased sensitivity for the quantification of both compounds. The modified SPCEs demonstrates promising performance: precision (5 % HQ, 8 % BPA), detection limits (1.4 μM HQ, 4.6 μM BPA), sensitivity (1688 μA mM−1 HQ, 441 μA mM−1 BPA), and recoveries (98–113 % HQ, 98–104 % BPA). This simple electrode modification holds great potential, allowing the preparation of the sensor by personnel who may lack access to well-equipped laboratories, particularly in developing countries.

Hydrogen is the kind of pure, renewable energy that is required for the world to begin relying less and less on the fossil fuels that it currently consumes. The production of hydrogen by electrocatalytic water splitting is deemed to be preferable to the consumption of fossil fuels for the generation of clean and reliable energy. A catalyst's ability to catalyze is significantly influenced by the number of exposed active sites in the catalyst. Thus, the purpose of the current work is to offer a simple and inexpensive strategy to synthesize a double non-noble metal catalyst of VSe2/MoSe2 via one-step hydrothermal synthesis for catalytic Hydrogen evolution reaction (HER). The strong and unique orientation interaction between the nanosheet-like structure of VSe2 and the nanoflower-like structure of MoSe2 in the nanocomposite significantly improved the electron transfer kinetics. Subsequently, the electrochemical hydrogen production performance of the hybrid VSe2/MoSe2 is enhanced as compared to its constituent materials. Electrochemical characterizations prove that the VSe2/MoSe2 nanocomposite enhances the electrochemical activity performance with the lowest onset potential (330 mV) and a low value of Tafel plot (66 mV/decade) in comparison with sole MoSe2 and VSe2. In addition, the nanocomposite shows a low charge transfer resistance of 65 Ω, which further advocates the HER polarization curve and Tafel plot.

This work reports the first bioplatform to assist in the early and reliable diagnosis of autoimmune diseases by quadruple determination of autoantibodies (Abs) produced against extractable nuclear antigens (ENAs): La/SSB-Abs, Ro/SSA-Abs, U1snRNP70-Abs and smRNP-Abs. The bioplatform involves indirect immunoassays on the surface of magnetic microcarriers (independent batches for each of the target autoantibodies) and amperometric transduction using the H2O2/hydroquinone (HQ) system on a disposable multiple electrode platform. The magnetic microcarriers were modified with the corresponding antigens using His-tag and carbodiimide/succinimide chemistries and employed for the selective capture of the corresponding autoantibodies. Thereafter, they were enzymatically labelled with a secondary antibody conjugated with horseradish peroxidase (HRP) and magnetically captured on each of the working surfaces of the quadruple platform. The evaluation of the analytical and operational characteristics of the bioplatform for the amperometric determination of standards, performed under optimized experimental conditions, confirmed the bioplatform competitiveness in terms of sensitivity and point-of-care application compared to commercially available ELISA methodologies for the single determination of target Abs. The developed bioplatform was applied to the analysis of serum samples from healthy individuals and from patients with two prevalent autoimmune diseases (systemic lupus erythematosus, SLE, and Sjögren's syndrome, SS). The obtained results proved the potential of the bioplatform for the differential diagnosis of these two autoimmune diseases through the accurate, simple, and rapid multidetermination of the four target Abs.

To overcome the limitations of insufficient sensitivity and poor specificity of portable screen-printed carbon electrode-electrochemical sensors (SPCE-EC) in practical applications, we prepared carrier composites of carboxylic single-walled carbon nanotubes vertically grafted by covalent organic frameworks (v-COF@SWCNTs-COOH) and coated with a molecularly imprinted polymer (MIP) of sulfadimidine (SM 2 ). 55 °C hot steam elution is more eco-friendly than traditional organic solvent elution. The results showed that when the mass ratio of DBA to DBA-SWCNTs was 1:1, the v-COF@SWCNTs-COOH obtained by the two-step synthesis method could increase the electrical signal up to 2.33-fold of the bare electrode. The bifunctional monomer MIP prepared on the above structure enhanced the signal response by 2.91-fold, with a high imprint factor of 20. The assembled MIP/v-COF@SWCNTs-COOH/SPCE were analyzed by differential pulse voltammetry (DPV) with a high sensitivity of 0.21 nM for LOD and 0.70 nM for LOQ. In milk and fish samples, the recovery rate was 95.0 %-104.8 %. The validation of authentic pork samples with the statutory LC-MS/MS method showed no significant difference (P > 0.05). The sensor's performance indicators remained robust after five repeated uses. Therefore, the MIP/v-COF@SWCNTs-COOH/SPCE combines the cheapness and portability of SPCE, while the sensitivity and specificity of small molecule detection were significantly improved., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Xiaoqun Wei reports financial support was provided by National Natural Science Foundation Project (No.32372424). Xiaoqun Wei reports financial support was provided by Lingnan Modern Agricultural Science and Technology Guangdong Provincial Laboratory Heyuan Branch Independent Research Project, China (No.DT20220005). Xiaoqun Wei reports financial support was provided by Jieyang City, China (No.skjcx043). Xiaoqun Wei reports financial support was provided by Jiangmen City, China(No.2023760100210008457). Xiaoqun Wei reports financial support was provided by Guangdong Provincial Department of Agriculture, China (No.2023KJ130). Xiaoqun Wei has patent #2024104192748 issued to Xiaoqun Wei, Shuomeng Bai, Peiqiao Liu, Zhenlin Xu, Hong Wang, Yudong Shen, Hongtao Lei, Yuanming Sun, Shujian Chen. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Monitoring the concentration of antibiotics in body fluids is essential to optimizing the therapy and minimizing the risk of bacteria resistance, which can be made with electrochemical sensors tailored with appropriate materials. In this paper, we report on sensors made with screen-printed electrodes (SPE) coated with fullerene (C60), reduced graphene oxide (rGO) and Nafion (NF) (C60-rGO-NF/SPE) to determine the antibiotic metronidazole (MTZ). Under optimized conditions, the C60-rGO-NF/SPE sensor exhibited a linear response in square wave voltammetry for MTZ concentrations from 2.5 × 10−7 to 34 × 10−6 mol/L, with a detection limit of 2.1 × 10−7 mol/L. This sensor was also capable of detecting MTZ in serum and urine, with recovery between 94% and 100%, which are similar to those of the standard chromatographic method (HPLC-UV). Because the C60-rGO-NF/SPE sensor is amenable to mass production and allows for MTZ determination with simple principles of detection, it fulfills the requirements of therapeutic drug monitoring programs.

Herein, we report the environmental impact quantification of a newly developed fully printed electrochemical device to assist a colorimetric detection of phosphate in saliva. The evaluation of the analytical procedure was performed according to the principles of Green Analytical Chemistry and White Analytical Chemistry. The standard method for phosphate detection relies on a reaction between phosphate and molybdate in presence of antimony potassium tartrate and ascorbic acid, using strong acid conditions and high volumes of reagents (100–500 mL). To deliver an eco-friendly method, we have combined a screen-printed electrode with a liquid electrolyte battery and inkjet-printed conductive paths to develop a fully printed device on a flexible polymer substrate avoiding the use of ascorbic acid and using a small amount of reagents. The printed sensor was first developed and optimized for phosphate detection in saliva, allowing for a detection limit equal to 26 µM and satisfactory repeatability (relative standard deviation value of 7.5%). Finally, the AGREE and the RGB assessment tools were applied for a quantitative evaluation of the proposed sensor and reference method, in agreement with the Green Analytical and White Analytical principles. The results demonstrated the lower environmental impact of the proposed sensor, as well as the suitability of this novel approach for phosphate detection in saliva.

A novel simple, environmentally friendly and portable method to determine vitamin E in edible oils based on reversed-phase dispersive liquid-liquid microextraction combined with electrochemical detection using screen-printed carbon electrodes (SPCEs) has been developed. Vitamin E was extracted from oil samples into a 4 M HCl aqueous solution and determined by differential pulse voltammetry using SPCEs. The extraction conditions optimized by experimental design (i.e., Plackett–Burman and central composite designs) were: aqueous 4 M HCl extractant volume, 43 µL; extraction time, 2 min; centrifugation time, 10 min; and centrifugation speed, 3000 rpm. The proposed method requires a standard addition calibration approach, and the working range showed good linearity from 0 to 20 mg L−1, with a correlation coefficient ranging from 0.990 to 0.995 (N=5). The methodological limit of detection was between 1 and 3 mg L−1. The repeatability of the proposed method was evaluated at 15 mg L−1, and the relative standard deviation ranged between 10 and 15% (n=5). For the quantification of vitamin E in ten commercial samples of olive, sesame, soybean, sunflower and a mixture of sunflower and corn oils, the volume of the extractant phase (i.e., 4 M HCl aqueous solution) was increased up to 100 µL and satisfactory recoveries were obtained in the range of 85–115%, confirming the applicability of the method.

Background: The availability of new surface enhanced Raman scattering (SERS) substrates is essential to develop quantitative analytical methods. Electrochemistry is an easy, fast and reproducible methodology to prepare SERS substrates on screen-printed electrodes (SPEs)., Results: This work proposes new SPEs based on a three-electrode system all made of silver. Using the same ink for the whole electrode system facilitates the fabrication process, reduces production costs, and leads to excellent analytical performance. The results showed that Raman enhancement depends strongly on the type of silver ink. To demonstrate the capabilities of the new electrodes developed, 4-aminosalicylic acid was determined in complex matrices and in the presence of strong interfering compounds such as salicylic acid and acetylsalicylic acid. The proposed analytical method is based on the electrochemical surface oxidation enhanced Raman scattering (EC-SOERS) strategy. AgCl nanocrystals are generated on the working electrode surface, which amplify the Raman signal of 4-aminosalicylic acid. Good figures of merit were obtained both in the absence and in the presence of the interfering compounds, achieving a correct estimation of a 4-aminosalicylic test sample in complex matrices., Significance: The new SPEs have been demonstrated to be very sensitive and reproducible which, together to the high specificity of the Raman signal, makes this methodology very attractive for chemical analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

A novel cost-effective disposable porous graphene electrode (P-GE) modified with bismuth nanoneedles (nano-BiNDs) is proposed as a "mercury-free" sensor for detecting heavy metals through smartphone-assisted electrochemical sensing. The P-GE was fabricated using screen-printing. Nano-BiNDs were generated on the P-GE by potentiostatic electrodeposition. Using an optimal potential of -1.20 V (vs. pseudo-Ag/AgCl) and a deposition time of 200 s, the nano-BiNDs had an average length and width of 189 ± 5 nm and 20 ± 2 nm, respectively. The analytical performances of the fabricated sensing platform were demonstrated by detecting Cd 2+ and Pb 2+ using square-wave anodic stripping voltammetry (SWASV) under optimized conditions. In the optimal conditions, the fabricated sensor exhibited sharp, well-defined stripping peaks for Cd 2+ and Pb 2+ with excellent peak-to-peak separation. The linear detection ranges were from 0.01 to 50 μg mL -1 for Cd 2+ and 0.006-50 μg mL -1 for Pb 2+ . The detection limits for Cd 2+ and Pb 2+ were 3.51 and 2.10 ng mL -1 , respectively. The developed portable sensor demonstrated high sensitivity, good repeatability, reproducibility, and anti-interference properties. The proposed portable sensor quantified Cd 2+ and Pb 2+ in commercial seaweed products with good accuracy, consistent with the results obtained using the standard ICP-OES method., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In situ detection and quantification of reaction intermediates and products is of paramount importance in applied and fundamental research. In the present work, differential electrochemical mass spectrometry (DEMS) is coupled with flow injection analysis (FIA) to study the hydrogen evolution reaction (HER) on a carbon screen-printed electrode (SPE) modified with a carbon-supported platinum (Pt/C) catalyst. Using this approach, the gaseous and volatile species produced during an electrochemical reaction of interest can be detected and quantified. The reported results support the viability of the novel setup, which can be employed not only for the HER, but also for a vast diversity of electrochemical reactions occurring at various modified SPEs.

The DCL gene in Fusarium oxysporum f. sp. cubense Race 4 (Foc4) is a pivotal pathogenic factor causing banana fusarium wilt. Precise DCL detection is crucial for Foc4 containment. Here, we present a novel ssDNA-hDNA coupling electrochemical biosensor for highly specific DCL detection. The sensing interface was formed via electrodeposition of a composite containing reduced graphene oxide (rGO) and gold nanoparticles (AuNPs) onto a carbon screen-printed electrode (SPE), followed by thiol-modified ssDNA functionalization. Additionally, the incorporation of hDNA, with methylene blue (MB) at both ends, binds to ssDNA through base complementarity, forming an ssDNA-hDNA coupling probe with bismethylene blue. This sensing strategy relies on DCL recognition by the hDNA probe, leading to DNA hairpin unfolding and detachment of hDNA bearing two MBs from ssDNA, generating a robust "on-off" signal. Empirical results demonstrate the sensor's amplified electrical signals, reduced background currents, and an extended detection range (6.02 × 10 6 -3.01 × 10 10  copies/μL) with a limit of detection (3.01 × 10 6  copies/μL) for DCL identification. We applied this sensor to analyze soil, banana leaves, and fruit samples, confirming its high specificity and stability. Moreover, post-sample detection, the sensor exhibits reusability, offering a cost-effective and rapid approach for banana wilt detection., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A new type of buckypaper of MWCNT with entrapped Nimodipine (NMD) drug was constructed. NMD features a nitroaromatic group that is electroreducible, and a dihydropyridine ring that can be electrooxidized. From the perspective of the nitroaromatic group's reductive capability, we have devised amperometric and voltammetric analytical strategies, including both differential pulse and linear voltammetric techniques. These methods are implemented using glassy carbon electrodes (GCE) modified with buckypaper (BP) disks composed of multiwalled carbon nanotubes (MWCNT), which are capable of adsorbing NMD. Furthermore, by capitalizing on the oxidative capacity of the dihydropyridine ring, we have designed strategies that involve amperometry using screen-printed electrodes (SPE) modified with BP-MWCNT mini discs within a Batch Injection Analysis Cell (BIAS) designed for SPE. The developed sensor was applied successfully to determine the drug in commercial tablets. The analytical parameters of this sensor were adequate, with a recovery value of 98.24 % and detection and quantification limits of 7.01 mgL -1 and 23.35 mgL -1 , respectively using the DPV method., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:J.A.Squella reports financial support, administrative support, article publishing charges, equipment, drugs, or supplies, and travel were provided by FONDECYT. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The current COVID-19 pandemic has made patent the need for rapid and cost-effective diagnostic tests, crucial for future infectious outbreaks. Loop-mediated isothermal amplification (LAMP) is a promising and decentralized alternative to qPCR. In this work we have developed a sensitive, fast, and simple innovative methodology for quantification of SARS-CoV-2 RNA copies, combining reverse-transcription LAMP with electrochemical detection. This is based on the oxidation of phenol red (PR), a visual and electroactive LAMP indicator, which oxidation peak potential (E p ) changes with the progress of the LAMP reaction. Using that E p shift as analytical signal, a calibration curve was obtained for fragment N1 copies of SARS-CoV2 (which provided better results than N or S fragments), with a potential shift of 16.2 mV per order of magnitude, and a practical limit of detection of 21 copies·μL -1 . Moreover, the precision of E p is excellent (RSD < 2%): 557 ± 5 mV for negative and 602 ± 7 mV for positive (2148 N fragment RNA copies·µL -1 · -1 ) LAMP controls. This methodology has been applied to the analysis of nasopharyngeal swab samples, resulting in total concordance with clinical RT-qPCR results. Advances towards fully decentralization have been achieved by designing and fabricating a small portable heater for isothermal procedures, obtaining comparable results to those from a commercial benchtop thermal cycler., Competing Interests: Declaration of competing interest M.T.F.-A. declares she is one of the founders of Micrux Technologies, a company engaged in the development of miniaturized electrodes and electrochemical/microfluidic equipment and remains a consultant and shareholder. She declares it has not influenced the work reported in this paper. The rest of authors declare no competing financial interest., (Copyright © 2023. Published by Elsevier B.V.)

Fused deposition modeling (FDM) 3D printing is a promising additive manufacturing technique to produce low-cost disposable electrochemical devices. However, the print of devices like well-known screen-printed electrodes (all electrodes on the same device) is difficult using the available technology (few materials available for production of working electrodes). In this paper we present a procedure to produce disposable and robust electrochemical devices by FDM 3D printing that allows reproducible analysis of small volumes (50-2000 μL). The device consists of just two printed parts that allow easy coupling of different conductive materials for using as disposable or non-disposable working electrodes with reproducible geometric area. Printed counter and pseudo-reference electrodes can also be easily fitted into the microcell. Moreover, conventional counter (platinum wire) and mini reference electrodes can also be used. As a proof of concept, paracetamol, cocaine and uric acid were used as model analytes using different materials as working electrodes. Linear calibration curves (r > 0.99) with similar slopes (0.29 ± 0.01 μA μmol L -1 ; RSD = 3.4%) were obtained by square wave voltammetry (SWV) using a complete printed system and different volumes of standard solutions of paracetamol (50, 100, and 200 μL). For uric acid, a linear range of 10-125 μmol L -1 (r > 0.99), was obtained using differential pulse voltammetry as the electrochemical technique and a disposable laser-induced graphene base as the working electrode. With the coupling of boron-doped diamond working electrode, screening tests were successfully performed in seized cocaine samples with selective detection of cocaine in the presence of its most common adulterants. The production cost per unit of a complete electrochemical system is around US 5.00. In large-scale production, only the working electrode needs to be replaced while the microcell and counter/pseudo reference electrodes do not need to be discarded., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, we proposed a biosensor for trypsin proteolytic activity assay using immobilization of model peptides on screen-printed electrodes (SPE) modified with gold nanoparticles (AuNPs) prepared by electrosynthetic method. Sensing of proteolytic activity was based on electrochemical oxidation of tyrosine residues of peptides. We designed peptides containing N-terminal cysteine residue for immobilization on an SPE, modified with gold nanoparticles, trypsin-specific cleavage site and tyrosine residue as a redox label. The peptides were immobilized on SPE by formation of chemical bonds between mercapto groups of the N-terminal cysteine residues and AuNPs. After the incubation with trypsin, time-dependent cleavage of the immobilized peptides was observed by decline in tyrosine electrochemical oxidation signal. The kinetic parameters of trypsin, such as the catalytic constant (k cat ), the Michaelis constant (K M ) and the catalytic efficiency (k cat /K M ), toward the CGGGRYR peptide were determined as 0.33 ± 0.01 min -1 , 198 ± 24 nM and 0.0016 min -1  nM -1 , respectively. Using the developed biosensor, we demonstrated the possibility of analysis of trypsin specificity toward the peptides with amino acid residues disrupting proteolysis. Further, we designed the peptides with proline or glutamic acid residues after the cleavage site (CGGRPYR and CGGREYR), and trypsin had reduced activity toward both of them according to the existing knowledge of the enzyme specificity. The developed biosensor system allows one to perform a comparative analysis of the protease steady-state kinetic parameters and specificity toward model peptides with different amino acid sequences., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, we report an impedimetric system for the detection of antibodies against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) Spike protein. The sensing platform is based on recombinant Spike protein (SCoV2-rS) immobilized on the phytic acid doped polyaniline films (PANI-PA). The affinity interaction between immobilized SCoV2-rS protein and antibodies in the physiological range of concentrations was registered by electrochemical impedance spectroscopy. Analytical parameters of the sensing platform were tuned by the variation of electropolymerization times during the synthesis of PANI-PA films. The lowest limit of detection and quantification were obtained for electropolymerization time of 20 min and equalled 8.00 ± 0.20 nM and 23.93 ± 0.60 nM with an equilibrium dissociation constant of 3 nM. The presented sensing system is label-free and suitable for the direct detection of antibodies against SARS-CoV-2 in real patient serum samples after coronavirus disease 2019 and/or vaccination., Competing Interests: Declaration of competing interest All authors have participated in (a) conception and design, or analysis and interpretation of the data; (b) drafting the article or revising it critically for important intellectual content; and (c) approval of the final version. This manuscript has not been submitted to, nor is under review at, another journal or other publishing venue. The authors have no affiliation with any organization with a direct or indirect financial interest in the subject matter discussed in the manuscript., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In the present study, the objective was to evaluate in situ interaction between Benzo[a]anthracene 7,2-dione 7-oxime (BZA) and calf thymus dsDNA (ct-dsDNA) using electroanalytical genosensor. Analytical techniques based on Ultraviolet/Visible (UV-Vis) spectroscopy and electroanalytical were used to investigate the interaction processes in solution and immobilized on carbon screen-printed electrodes modified with electrochemical mediator Meldola blue. In addition, was possible to evaluate the degree of damage caused to the genetic material by the analyte through of toxicity estimate (S%). The interaction evaluated by genosensor showed processes of intercalation, degradation, and breaks of the double strand of ct-dsDNA, suggesting that the interaction simulates highly toxic (values varying from 0.6 to 0.8 μA in 48 h of interaction), such as 8-oxoguanine (+0.48 V), which is a by-product of guanine oxidation. Furthermore, monitoring A (+1.10 V) after 1 h showed an S% value between 50 and 90%, indicative of high toxicity, and monitoring G (+0.85 V), which showed S>90%, indicated no toxicity after 10 min. Overall, the electroanalytical genosensor developed in a miniaturized system displayed good reproducibility and stability over time being a quick alternative for assesses the degree of toxicity between toxic xenobiotics and biologically electroactive molecules, such as DNA., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

This study presents a novel strategy to fabricate an electrochemical sensor based on a screen-printed electrode (SPE) modified by a bimetallic Mn 2+ /Fe 3+ metal-organic framework (MnFe-MOF) for the direct determination of organophosphate pesticide chlorpyrifos. Square wave voltammetry technique was employed for the electroanalysis, and the limit of detection remained as low as 0.85 nM or 0.29 ppb in a wide linearity range of 1.0 × 10 -9 to 1.0 × 10 -7  M. The sensor also demonstrated exceptional repeatability and anti-interference performance. Moreover, MnFe-MOF was synthesized using terephthalic acid as the building block using a one-pot solvothermal approach. Multiple characterization studies confirmed the formation of the MOF. The bimetallic MnFe-MOF exhibited high adsorption and electrocatalytic properties towards chlorpyrifos due to the hetero-metal synergism arising between the Mn 2+ and Fe 3+ ions, owing to which it was employed as the electrode material for non-enzymatic electro-determination of chlorpyrifos. The proposed sensor displayed a satisfactory recovery of the spiked pesticide in real-sample matrices., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Himmat Singh Kushwaha reports a relationship with Malaviya National Institute of Technology that includes: employment., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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%., (Copyright © 2021 Elsevier B.V. All rights reserved.)

For the first time, a simple and sensitive electrochemical sensor based on a screen printed electrode (SPE) modified with titanium dioxide (TiO 2 ) and polytriazine imide submicrostructured composite (TiO 2 -PTI) has been developed for the simultaneous detection of fipronil (FIP) and its toxic metabolite fipronil sulfone (FIP-S). The submicrostructured composite material based on TiO 2 and PTI was obtained by simple hydrothermal treatment of the Ti peroxocomplexes in the presence of pristine. This carbon nitride allotrope has better crystallinity and conductivity than its graphitic analog. It was found that the TiO 2 -PTI submicrostructured composite enhanced the electrochemical sensing of the SPE electrode towards FIP and its metabolite FIP-S in 0.1 M Britton-Robinson buffer (pH 10) at the oxidation potentials of 0.82 V and 0.94 V, respectively. In addition, it showed good stability and reproducibility for the determination of both analytes. Under optimal conditions, the peak currents by square wave voltammetry were found to vary linearly with FIP and FIP-S concentrations in the range from 0.01 to 10 μM and from 10 to 50 μM, with a detection limit of 8.42 nM, 3.6 μg/kg for FIP and 9.72 nM, 4.04 μg/kg for FIP-S. This sensor was successfully used to detect FIP and FIP-S in eggs and water samples with good recoveries of 90%-106.6%., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The exceptional properties of 2D layered black phosphorus (BP) make it a promising candidate for electrochemical sensing applications and, even though BP is considered unstable and tends to degrade by the presence of oxygen and moisture, its oxidation can be beneficial in some situations. In this work, we present an unequivocal demonstration that the exposition of BP-based working electrodes to normal ambient conditions can indeed be advantageous, leading to an enhancement of voltammetric sensing applications. This point was proved using a BP modified screen-printed carbon electrode (BP-SPCE) for the voltammetric determination of dopamine (DA) as a model target analyte. Oxidized BP-SPCE (up to 35% of P x O y at the surface) presented an enhanced analytical performance with a 5-fold and 2-fold increase in sensitivity, as compared to bare-SPCE and non-oxidized BP-SPCE stored in anhydrous atmosphere, respectively. Good detection limit, repeatability, reproducibility, stability, selectivity, and accuracy were also achieved. Overall, the results presented herein display the prominent possibilities of preparing and working with BP based-sensors in normal ambient settings and showcase their implementation under physiological conditions., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Electron transfer in metalloproteins is a driving force for many biological processes and widely distributed in nature. Rubredoxin B (RubB) from Mycobacterium tuberculosis is a first example among [1Fe-0S] proteins that support catalytic activity of terminal sterol-monooxygenases enabling its application in metabolic engineering. To explore the tolerance of RubB to the specific amino acid changes we evaluated the effect of surface mutations on its electrochemical properties. Based on the RubB fold we also designed the mutant with a putative additional site for protein-protein interactions to further evaluate electron transfer and electrochemical properties. The investigation of redox properties of mutant variants of RubB was done using screen-printed graphite electrodes (SPEs) modified with stable dispersion of multi-walled carbon nanotubes (MWCNTs). The redox potentials (midpoint potentials, E 0Ꞌ ) of mutants did not significantly differ from the wild type protein and vary in the range of -264 to -231 mV vs. Ag/AgCl electrode. However, all mutations affect electron transfer rate between the protein and electrode. Notably, the modulation of the protein-protein interactions was observed for the insertion mutant suggesting the possibility of tailoring of rubredoxin for the selected redox-partner. Overall, RubB is tolerant to the significant modifications in its structure enabling rational engineering of novel redox proteins., (Copyright © 2021. Published by Elsevier B.V.)

This work proposes a voltammetric aptasensor to detect deoxynivalenol (DON) mycotoxin. The development steps of the aptasensor were partnered for the first time to a computational study to gain insights onto the molecular mechanisms involved into the interaction between a thiol-tethered DNA aptamer (80mer-SH) and DON. The exploited docking study allowed to find the binding region of the oligonucleotide sequence and to determine DON preferred orientation. A biotinylated oligonucleotide sequence (20mer-BIO) complementary to the aptamer was chosen to carry out a competitive format. Graphite screen-printed electrodes (GSPEs) were electrochemically modified with polyaniline and gold nanoparticles (AuNPs@PANI) by means of cyclic voltammetry (CV) and worked as a scaffold for the immobilization of the DNA aptamer. Solutions containing increasing concentrations of DON and a fixed amount of 20mer-BIO were dropped onto the aptasensor surface: the resulting hybrids were labeled with an alkaline phosphatase (ALP) conjugate to hydrolyze 1-naphthyl phosphate (1-NPP) substrate into 1-naphthol product, detected by differential pulse voltammetry (DPV). According to its competitive format, the aptasensor response was signal-off in the range 5.0-30.0 ng·mL -1 DON. A detection limit of 3.2 ng·mL -1 was achieved within a 1-hour detection time. Preliminary experiments on maize flour samples spiked with DON yielded good recovery values., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Enhancement of Raman intensity due to the electrochemical surface-enhanced Raman scattering (EC-SERS) effect is an interesting alternative to overcome the lack of sensitivity traditionally associated with Raman spectroscopy. Furthermore, activation of metallic screen-printed electrodes (SPEs) by electrochemical route leads to the reproducible generation of nanostructures with excellent SERS properties. EC-SERS procedure proposed in this work for the detection of several pesticides (thiram, imidacloprid and chlorpyrifos) with different nature, uses gold SPEs as SERS substrates, but also includes a preconcentration step as the initial and essential stage. Taking into account the small volume of solution employed, only 60 µL, the preconcentration cannot be performed for more than 15 min in order to ensure the proper contact of the solution with WE, RE and CE. Furthermore, selected temperature, 34 °C, is not very high to allow the exhaustive control of the drop volume. Optimization of preconcentration parameters (time and temperature) displays a crucial step, particularly in the detection of low concentrations of pesticides, because it will provide higher Raman intensity in EC-SERS experiments. After the initial step, gold SPEs were electrochemically activated by cyclic voltammetry, allowing the detection of very low concentration (µg·L -1 ) of pesticides due to the generation of fresh nanostructures with SERS effect., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A new electroanalytical methodology was developed for the sensitive and selective determination of formaldehyde in wood-based products (WBPs), featuring an extraction process using a Headspace Liquid Acceptor System (HLAS), and detection by square-wave voltammetry (SWV) on unmodified screen-printed carbon electrodes (SPCEs). HLAS, here presented for the first time, captures and derivatizes formaldehyde released from the sample by using the acetylacetone reagent as acceptor solution. The product of formaldehyde with acetylacetone, in the presence of ammonium salt, is 3,5-diacetyl-1,4-dihydrolutidine (DDL) which we have found to be electrochemically active at unmodified SPCEs, generating a selective oxidation peak at +0.4 V. Detection and quantification limits of 0.57 and 1.89 mg kg -1 were obtained, together with intra- and inter-day precisions below 10% (as relative standard deviation, RSD). The methodology was used to determine formaldehyde content in seven WBPs, with similar results being obtained by the developed HLAS-SPCE method and the European standard method EN 717-3, with a profound reduction of total analysis time. The developed HLAS-SPCE combines the use of a new sample preparation procedure for volatiles with, as far as we know, the first determination of formaldehyde (as the derivative product, DDL) on unmodified SPCEs, offering a promising alternative for the determination of formaldehyde in WBPs and other samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Early detection of cancer increases the possibility for an adequate and successful treatment of the disease. Therefore, in this work, a disposable electrochemical immunosensor for the front-line detection of the ExtraCellular Domain of the Human Epidermal growth factor Receptor 2 (HER2-ECD), a breast cancer biomarker, in a simple and efficient manner is presented. Bare screen-printed carbon electrodes were selected as the transducer onto which a sandwich immunoassay was developed. The affinity process was detected through the use of an electroactive label, core/shell CdSe@ZnS Quantum Dots, by differential pulse anodic stripping voltammetry in a total time assay of 2 h, with an actual hands-on time of less than 30 min. The proposed immunosensor responded linearly to HER2-ECD concentration within a wide range (10-150 ng/mL), showing acceptable precision and a limit of detection (2.1 ng/mL, corresponding to a detected amount (sample volume = 40 μL) of 1.18 fmol) which is about 7 times lower than the established cut-off value (15 ng/mL). The usefulness of the developed methodology was tested through the analysis of spiked human serum samples. The reliability of the presented biosensor for the selective screening of HER2-ECD was confirmed by analysing another breast cancer biomarker (CA15-3) and several human serum proteins., (Copyright © 2019 Elsevier B.V. All rights reserved.)