Search Results (28)

This study investigates the development and sensing profile of synthetic melanin nanoparticle-coated electrodes for the electrochemical detection of heavy metals, including lead (Pb), cadmium (Cd), cobalt (Co), zinc (Zn), nickel (Ni), and iron (Fe). Synthetic melanin films were prepared in situ by the deacetylation of diacetoxy indole (DAI) to dihydroxy indole (DHI), followed by the deposition of DHI monomers onto indium tin oxide (ITO) and glassy carbon electrodes (GCE) using cyclic voltammetry (CV), forming a thin layer of synthetic melanin film. The deposition process was characterized by electrochemical quartz crystal microbalance (EQCM) in combination with linear sweep voltammetry (LSV) and amperometry to determine the mass and thickness of the deposited film. Surface morphology and elemental composition were examined using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). In contrast, Fourier-transform infrared (FTIR) and UV–Vis spectroscopy confirmed the melanin’s chemical structure and its polyphenolic functional groups. Differential pulse voltammetry (DPV) and amperometry were employed to evaluate the melanin films’ electrochemical activity and sensitivity for detecting heavy metal ions. Reproducibility and repeatability were rigorously assessed, showing consistent electrochemical performance across multiple electrodes and trials. A comparative analysis of ITO, GCE, and graphite electrodes was conducted to identify the most suitable substrate for melanin film preparation, focusing on stability, electrochemical response, and metal ion sensing efficiency. Finally, the applicability of melanin-coated electrodes was tested on in-house heavy metal water samples, exploring their potential for practical environmental monitoring of toxic heavy metals. The findings highlight synthetic melanin-coated electrodes as a promising platform for sensitive and reliable detection of iron with a sensitivity of 106 nA/ppm and a limit of quantification as low as 1 ppm. Full article

In this work, the influence of surface functionalization due to synthesis conditions of graphene oxide quantum dots GOQDs was evaluated for dopamine (DA) detection. GOQDs were synthesized using HNO₃ (6 M or 8 M) through a liquid-phase oxidation method. The characterization (HRTEM, FTIR, Raman, and XRD) and evaluation by amperometry (AMP) and differential pulse voltammetry (DPV) showed that GOQDs-8 synthesized with higher oxygen content were more sensitive and selective in DA detection than GOQDs-6. The synergistic effects of electrostatic attraction from glassy carbon electrode negatively charged surface, functionalization for inner-sphere mechanism, and edge effect from lower particle size resulted in amplified electrochemical signal achieving detection at nanomolar level using AMP and DPV. When evaluated using AMP, GCE/GOQDs-8 showed a sensitivity of 0.0422 μA μM^–1, a limit of detection (LOD) of 17.6 nM, a linear range from 0.1 to 100 μM, and minimal interference for uric acid, levodopa, and acetaminophen. In contrast, using DPV, the GCE/GOQDs-8 exhibited a sensitivity of 0.0616 μA μM^–1, a LOD of 506 nM, and a linear range from 0.1–30 μM with remarkable selectivity from all interferent species. The assay of GOQDs-8/GCE sensor in normal human serum proved to be feasible for the practical determination of DA. The recovery obtained was in the range of 94.1 to 112.8% with a relative standard deviation (RSD), n = 3 of less than 3.62%. The oxygen-rich material showed a promising performance that can be further improved with additional nanocarbon or conducting polymers supports. Full article

Sensitivity in the sub-nanomolar concentration region is required to determine important protein biomarkers, e.g., ferritin. As a prerequisite for high sensitivity, in this paper, the affinity of the functional monomer to the macromolecular target ferritin in solution was compared with the value for the respective molecularly imprinted polymer (MIP)-based electrodes, and the influence of various surface modifications of the electrode was investigated. The analytical performance of ferritin sensing was investigated using three different carbon electrodes (screen-printed carbon electrodes, single-walled-carbon-nanotube-modified screen-printed carbon electrodes, and glassy carbon electrodes) covered with a scopoletin-based MIP layer. Regardless of the electrode type, the template molecule ferritin was mixed with the functional monomer scopoletin, and electropolymerization was conducted using multistep amperometry. All stages of MIP preparation were followed by evaluating the diffusional permeability of the redox marker ferricyanide/ferrocyanide through the polymer layer by differential pulse voltammetry. The best results were obtained with glassy carbon electrodes. The MIP sensor responded up to 0.5 µM linearly with a K_d of 0.30 µM. Similar results were also obtained in solution upon the interaction of scopoletin and ferritin using fluorescence spectroscopy, resulting in the quenching of the scopoletin signal, with a calculated K_d of 0.81 µM. Moreover, the binding of 1 µM ferritin led to 49.6% suppression, whereas human serum albumin caused 8.6% suppression. Full article

Bisphenol A (BPA) has been classified as an endocrine-disrupting substance that may cause adverse effects on human health and the environment. The development of simple and sensitive electrochemical biosensors is crucial for the rapid and effective quantitative determination of BPA. This work presents a study on electrochemical sensors utilizing gold nanoparticle-modified multi-walled carbon nanotubes (CNT/AuNPs). Glassy carbon electrodes (GCEs) and screen-printed electrodes (SPEs) were conveniently modified and used for BPA detection. AuNPs were electrodeposited onto the CNT-modified electrodes using the galvanostatic method. The electrodes were properly modified and characterized by using Raman spectroscopy, cyclic voltammetry (CV), and electrochemical impedance analysis (EIS). The electrochemical response of the sensors was studied using differential pulse voltammetry (DPV) and constant potential amperometry (CPA) for modified GCE and SPE electrodes, respectively, and the main analytical parameters were studied and optimized. Problems encountered with the use of GCEs, such as sensor degradation and high limit of detection (LOD), were overcome by using modified SPEs and a flow injection device for the measurements. Under this approach, an LOD as low as 5 nM (S/N = 3) was achieved and presented a linear range up to 20 μM. Finally, our investigation addressed interference, reproducibility, and reusability aspects, successfully identifying BPA in both spiked and authentic samples, including commercial and tap waters. These findings underscore the practical applicability of our method for accurate BPA detection in real-world scenarios. Notably, the integration of SPEs and a flow injection device facilitated simplified automation, offering an exceptionally efficient and reliable solution for precise BPA detection in water analysis laboratories. Full article

In human blood serum, the concentration of magnesium ions typically ranges from 0.7 mM to 1.05 mM. However, exceeding the upper limit of 1.05 mM can lead to the condition known as hypermagnesemia. In this regard, a highly sensitive and selective electrochemical sensor for Mg(II) ion detection was successfully fabricated by immobilizing cerium oxide (CeO₂) microcuboids, synthesized via microwave radiation method, onto the surface of glassy carbon electrode (GCE). Cyclic voltammetry studies revealed the exceptional electrocatalytic effect of CeO₂ microcuboid-modified GC electrode, particularly in relation to the irreversible reduction signal of Mg(II). The microcuboid-like structure of CeO₂ microparticles facilitated enhanced adsorption of Mg(II) ion ($\Gamma =2.17\times {10}^{-7}$mol cm⁻²) and electron transfer ($k_s=8.94$ s⁻¹) between the adsorbed Mg(II) ions and GCE. A comprehensive analysis comparing the performance characteristics of amperometry, differential pulse voltammetry, cyclic voltammetry, and square wave voltammetry was conducted. The square wave voltammetry-based Mg(II) sensor exhibited remarkable sensitivity of 2.856 μA mM⁻¹, encompassing a broad linear detection range of 0–3 mM. The detection and quantification limits were impressively low, with values of 19.84 and 66.06 μM, respectively. Remarkably, the developed electrode showed a rapid response time of less than 140 s. Multiple linear regression and partial least squares regression models were employed to establish a mathematical relationship between magnesium ion levels and electrochemical parameters. Notably, the proposed sensor exhibited excellent anti-interferent ability, repeatability, stability, and reproducibility, enabling the fabricated electrode to be used effectively for Mg(II) ion sensing in real-world samples. Full article

The present study reports the development and application of a flow injection analysis (FIA) system for the simultaneous determination of uric acid (UA) and caffeine (CAF) using cathodically pretreated boron-doped diamond electrode (CPT-BDD) and multiple-pulse amperometry (MPA). The electrochemical profiles of UA and CAF were analyzed via cyclic voltammetry in the potential range of 0.20–1.7 V using 0.10 mol L⁻¹ H₂SO₄ solution as supporting electrolyte. Under optimized conditions, two oxidation peaks at potentials of 0.80 V (UA) and 1.4 V (CAF) were observed; the application of these potentials using multiple-pulse amperometry yielded concentration linear ranges of 5.0 × 10⁻⁸–2.2 × 10⁻⁵ mol L⁻¹ (UA) and 5.0 × 10⁻⁸–1.9 × 10⁻⁵ mol L⁻¹ (CAF) and limits of detection of 1.1 × 10⁻⁸ and 1.3 × 10⁻⁸ mol L⁻¹ for UA and CAF, respectively. The proposed method exhibited good repeatability and stability, and no interference was detected in the electrochemical signals of UA and CAF in the presence of glucose, NaCl, KH₂PO₄, CaCl₂, urea, Pb, Ni, and Cd. The application of the FIA-MPA method for the analysis of environmental samples resulted in recovery rates ranging between 98 and 104%. The results obtained showed that the BDD sensor exhibited a good analytical performance when applied for CAF and UA determination, especially when compared to other sensors reported in the literature. Full article

The development of efficient H₂O₂ sensors is crucial because of their multiple functions inside and outside the biological system and the adverse effects that a higher concentration can cause. This work reports a highly sensitive and selective non-enzymatic electrochemical H₂O₂ sensor achieved through the hybridization of Co₃S₄ and graphitic carbon nitride nanosheets (GCNNS). The Co₃S₄ is synthesized via a hydrothermal method, and the bulk g-C₃N₄ (b-GCN) is prepared by the thermal polycondensation of melamine. The as-prepared b-GCN is exfoliated into nanosheets using solvent exfoliation, and the composite with Co₃S₄ is formed during nanosheet formation. Compared to the performances of pure components, the hybrid structure demonstrates excellent electroreduction towards H₂O₂. We investigate the H₂O₂-sensing performance of the composite by cyclic voltammetry, differential pulse voltammetry, and amperometry. As an amperometric sensor, the Co₃S₄/GCNNS exhibits high sensitivity over a broad linear range from 10 nM to 1.5 mM H₂O₂ with a high detection limit of 70 nM and fast response of 3 s. The excellent electrocatalytic properties of the composite strengthen its potential application as a sensor to monitor H₂O₂ in real samples. The remarkable enhancement of the electrocatalytic activity of the composite for H₂O₂ reduction is attributed to the synergistic effect between Co₃S₄ and GCNNS. Full article

Nitrite is a ubiquitous pollutant in modern society. Developing new strategies for its determination is very important, and electroanalytical methods present outstanding performance on this task. However, the use of bare electrodes is not recommended because of their predisposition to poisoning and passivation. We herein report a procedure to overcome these limitations on carbon fiber microelectrodes through pulsed amperometry. A three-pulse amperometry approach was used to reduce the current decay from 47% (after 20 min under constant potential) to virtually 0%. Repeatability and reproducibility were found to have an RSD lower than 0.5% and 7%, respectively. Tap water and synthetic inorganic saliva samples were fortified with nitrite, and the results obtained with the proposed sensor were in good agreement with the amount added. Full article

In this article, we report the development of an electrochemical biosensor for the determination of the SARS-CoV-2 spike protein (rS). A gold disc electrode was electrochemically modified to form the nanocrystalline gold structure on the surface. Then, it was further altered by a self-assembling monolayer based on a mixture of two alkane thiols: 11-mercaptoundecanoic acid (11-MUA) and 6-mercapto-1-hexanol (6-MCOH) (SAM_mix). After activating carboxyl groups using a N-(3-dimethylaminopropyl)-N’-ethyl-carbodiimide hydrochloride and N-hydroxysuccinimide mixture, the rS protein was covalently immobilized on the top of the SAM_mix. This electrode was used to design an electrochemical sensor suitable for determining antibodies against the SARS-CoV-2 rS protein (anti-rS). We assessed the association between the immobilized rS protein and the anti-rS antibody present in the blood serum of a SARS-CoV-2 infected person using three electrochemical methods: cyclic voltammetry, differential pulse voltammetry, and potential pulsed amperometry. The results demonstrated that differential pulse voltammetry and potential pulsed amperometry measurements displayed similar sensitivity. In contrast, the measurements performed by cyclic voltammetry suggest that this method is the most sensitive out of the three methods applied in this research. Full article

We report the synthesis and investigation of Au–Ru composite with highly developed specific surface area exhibiting excellent electrocatalytic performance suitable for detection of such hydrophobic metabolites as epinephrine in the physiological environment. This electrode material was fabricated using two-stage laser-assisted metal deposition technique. The morphological and structural studies of Au–Ru were performed using methods of scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction spectroscopy (XRD). The voltammetric methods, including cyclic voltammetry (CV), differential pulse voltammetry (DPV) and direct amperometry, were used to analyze the composite’s electrochemical properties. The Au–Ru sensor exhibited two linear ranges of the non-enzymatic epinephrine detection: 0.01–10 μM and 10–1000 μM. The calculated sensitivities within these two ranges were 32.8 and 3.3 μA μM${}^{-1}$ cm${}^{-2}$, whereas the corresponding limits of detection were 9 and 20 nM, respectively. The Au–Ru sensor also revealed good stability and reproducibility, as well as high selectivity towards epinephrine detection in the presence of a number of the interfering species. Full article

A metallomesogen based on an Zn(II) coordination complex was employed as precursor to obtain a complex matrix nanoplatform for the fabrication of a high-performance electrochemical hybrid sensor. Three representative paste electrodes, which differ by the weight ratio between Zn(II) metallomesogen and carbon nanotubes (CNT), i.e., PE_01, PE_02 and PE_03, were obtained by mixing the materials in different amounts. The composition with the largest amount of CNT with respect to Zn complex, i.e., PE_03, gives the best electrochemical signal for uric acid detection by cyclic voltammetry in an alkaline medium. The amphiphilic structure of the Zn(II) coordination complex likely induces a regular separation between the metal centers favoring the redox system through their reduction, followed by stripping, and is characterized by enhanced electrocatalytic activity towards uric acid oxidation. The comparative detection of uric acid between the PE_03 paste electrode and the commercial zinc electrode demonstrated the superiority of the former, and its great potential for the development of advanced electrochemical detection of uric acid. Advanced electrochemical techniques, such as differential-pulsed voltammetry (DPV) and square-wave voltammetry (SWV), allowed for the highly sensitive detection of uric acid in aqueous alkaline solutions. In addition, a good and fast amperometric signal for uric acid detection was achieved by multiple-pulsed amperometry, which was validated by urine analysis. Full article

Engineering electrode surfaces through the electrodeposition of gold may provide a range of advantages in the context of biosensor development, such as greatly enhanced surface area, improved conductivity and versatile functionalization. In this work we report on the development of an electrochemical biosensor for the laccase-catalyzed assay of two catecholamines—dopamine and L-epinephrine. Variety of electrochemical techniques—cyclic voltammetry, differential pulse voltammetry, electrochemical impedance spectroscopy and constant potential amperometry have been used in its characterization. It has been demonstrated that the laccase electrode is capable of sensing dopamine using two distinct techniques—differential pulse voltammetry and constant potential amperometry, the latter being suitable for the assay of L-epinephrine as well. The biosensor response to both catecholamines, examined by constant potential chronoamperometry over the potential range from 0.2 to −0.1 V (vs. Ag|AgCl, sat KCl) showed the highest electrode sensitivity at 0 and −0.1 V. The dependencies of the current density on either catecholamine’s concentration was found to follow the Michaelis—Menten kinetics with apparent constants K_M^app = 0.116 ± 0.015 mM for dopamine and K_M^app = 0.245 ± 0.031 mM for L-epinephrine and linear dynamic ranges spanning up to 0.10 mM and 0.20 mM, respectively. Calculated limits of detection for both analytes were found to be within the sub-micromolar concentration range. The biosensor applicability to the assay of dopamine concentration in a pharmaceutical product was demonstrated (with recovery rates between 99% and 106%, n = 3). Full article

Sodium diclofenac (DCF) presence reported in water use cycle at various concentrations including trace levels necessitates continuous development of advanced analytical method for its determination. In this work, ease electrochemical methods for DCF determination based on voltammetric and amperometric techniques were proposed using a simple combination of graphene with multi-walled carbon nanotubes as paste electrode. Integration of the graphene with multi-walled carbon nanotubes enlarged the electroactive surface area of the electrode and implicitly enhanced the electrochemical response for DCF determination. On the basis of the sorption autocatalytic effect manifested at low concentration of DCF, we found that the preconcentration step applied prior to differential-pulsed voltammetry (DPV) and multiple-pulsed amperometry (MPA) allowed for the enhancement of the electroanalytical performance of the DCF electrochemical detections, which were validated by testing in tap water. The lowest limit of detection (LOD) of 1.40 ng·L⁻¹ was found using preconcentration prior to DPV under optimized operating conditions, which is better than that reached by other carbon-based electrodes reported in the literature. Full article

Two paste electrodes based on graphene quantum dots and carbon nanotubes (GRQD/CNT) and one modified with a homoleptic liquid crystalline Cu(I) based coordination complex (Cu/GRQD/CNT) were obtained and morphostructurally and electrochemically characterized in comparison with simple CNT electrode (CNT) for doxorubicine (DOX) detection in aqueous solutions. GRQD/CNT showed the best electroanalytical performance by differential pulse voltammetry technique (DPV). Moreover, applying a preconcentration step prior to detection stage, the lowest limit of detection (1 ng/L) and the highest sensitivity (216,105 µA/mg·L⁻¹) in comparison with reported literature data were obtained. Cu/GRQD/CNT showed good results using multiple pulse amperometry technique (MPA) and a favorable shifting of the potential detection to mitigate potential interferences. Both GRQD-based paste electrodes have a great potential for practical utility in DOX determination in water at trace concentration levels, using GRQD/CNT with DPV and in pharmaceuticals formulations using Cu/GRQD/CNT with MPA. Full article

The development of fast and easy-to-use methods for gemcitabine detection is of great interest for pharmaceutical formulation control in both research laboratories and hospitals. In this study, we report a simple, fast and direct electrochemical method for gemcitabine detection using a boron-doped diamond electrode. The electrochemical oxidation of gemcitabine on a boron-doped diamond electrode was found to be irreversible in differential pulse voltammetry, and scan rate influence studies demonstrated that the process is diffusion-controlled. The influence of the pH and supporting electrolytes were also tested, and the optimized differential pulse voltammetry method was linear in the range of 2.5–50 μg/mL, with a detection limit of 0.85 μg/mL in phosphate-buffered saline (pH 7.4; 0.1 M). An amperometric method was also optimized for gemcitabine detection. The linear range of the method was 0.5–65 μg/mL in phosphate-buffered saline of pH 7.4 as well as pH 5.5, the limit of detection being 0.15 μg/mL. The optimized differential pulse voltammetry and amperometric detection strategies were successfully applied to pharmaceutical formulations, and the results were compared to those obtained by high-performance liquid chromatography and UV-Vis spectrophotometry with good correlations. Full article