Search Results (18)

This paper proposes an environmentally friendly sensor for determining trace amounts of diclofenac (DCF)—an activated glassy carbon electrode (aGCE). Such a sensor was achieved by simple surface activation of a glassy carbon electrode to perform five cyclic voltammetric scans from −1.5 to 2.5 V at a scan rate (υ) of 100 mV/s in 0.1 M NaOH. This type of activation results in the formation of surface functional groups, which provide several advantages such as the creation of new active sites, the improvement of electron transfer dynamics, and sensor electrocatalytic activity. The electrode prepared in this way was used to develop a new differential pulse adsorptive stripping voltammetric procedure (DPAdSV) for rapid, simple, and sensitive DCF analysis. Thanks to this procedure, the following calibration curve range was obtained: 1–100 nM with low detection and quantification limits of 0.25 and 0.83 nM, respectively. To show the practical application of the method, DCF was successfully determined in commercially available pharmaceutical preparations with the standard addition method. Full article

This paper shows the fabrication of a new environmentally friendly sensor, an activated glassy carbon electrode with an in situ deposited bismuth film (aGCE/BiF), to determine Cd(II) and Pb(II) at the nanotrace level. The electrochemical activation of the GCE surface was achieved in a solution of 0.1 M phosphate-buffered saline (PBS) of pH = 7 by performing five cyclic voltammetric scans in the range of −1.5–2.5 V at ν of 100 mV/s. The newly developed electrode provides several advantages, such as an increased electron active surface (compared to the glassy carbon electrode) and improved electron transfer kinetics. As a result, the new voltammetric procedure (square-wave anodic stripping voltammetry, SWASV) was established and optimized. With the SWASV method, the following calibration curves and low detection limits (LODs) were obtained for Cd(II) and Pb(II), respectively: 5–100 nM, 0.62 nM, 2–200 nM, and 0.18 nM. The newly prepared method was used to determine the amounts of Pb(II) and Cd(II) in the certified reference material, and the results agreed with the certified values. Moreover, the procedure was successfully applied to determine the Cd(II) and Pb(II) in river samples. The official and standard addition methods validated the measurement results. Full article

Cyclic voltammetry (CV) can be applied as a reliable method for the determination of chloride ions in a range from several to a couple hundred (about 200) ppm. Since the standard potential of chloride ion/gaseous chlorine is 1.36 V vs. normal hydrogen electrode (NHE), the efficient oxidation of Cl⁻ ion occurs at very positive electrode potentials, usually higher than +1.7 V vs. NHE. It is possible to observe this phenomenon only at noble-metal or inert carbon electrodes. Many other solutes, usually organic compounds, are often oxidized at this potential. This is the reason why the determination of Cl⁻ content directly from an increase in the oxidation current is not reliable and could lead to overestimated values. However, gaseous chlorine, generated at a positive potential dissolve in the analyzed solution, could be reduced in the reverse scan of a cyclic voltammetric curve. Optimization of the experimental procedure using statistical tools enables the development of an improved method for the direct quantification of chloride ions in acid copper electroplating baths. Under the proposed experimental conditions, the calibration curve (Cl₂ voltammetric reduction current vs. chloride ions concentration) is represented by the linear model for the concentration of chlorides ranging from 10 to 200 mg/dm³. The developed method for analyzing chloride ions in an acid sulfate electroplating copper bath has many unique properties. It is fast; the time of a single analysis is less than 20 min. In automatic mode, it can be repeated up to 50 times a day. The method does not require processing of the sample of the analyzed bath before measurement. As a result, no additional chemical reagents are used, and the test sample can be returned to the plating bath. Full article

Atenolol is a medication belonging to the class of drugs known as beta-blockers, used to treat high blood pressure (hypertension) and irregular heartbeats (arrhythmia). Their presence in the environment has serious impacts on humans, animals, and the water ecosystem. In this context, the aim of this study was to develop a simple voltammetric method for the determination of atenolol (ATN) using carbon paste electrodes modified with the nanomaterials TiO₂ and rGO/TiO₂. The analytical performance of the modified sensor was evaluated using square wave voltammetry and cyclic voltammetry in 0.1 mol L⁻¹ acid sulfuric solution (H₂SO₄), pH 2. The nanocomposite electrode CPE/rGO/TiO₂ exhibited excellent electrocatalytic activity towards ATN oxidations at 0.1 mol L⁻¹ H₂SO₄ compared with unmodified carbon paste electrodes CPEs and those modified with titanium oxide, CPE/TiO₂. Different experimental and conditional parameters were optimized, such as supporting electrolytes, pH, amplitude, frequency, etc. Under optimal conditions, linear calibration curves were obtained, ranging from 1.7 to 23.2 µmol L⁻¹ for ATN with detection limits of 0.05 μmol L⁻¹. The modified nanocomposite CPE/rGO/TiO₂ sensor showed good sensitivity and good repeatability (RSD ≤ 0.61%) for ATN determination. The proposed sensor is mechanically robust and presented reproducible results and a long useful life. In order to verify the usefulness of the developed methods, the nanocomposite sensor CPE/rGO/TiO₂ was applied for the detection of atenolol in real samples (pharmaceutical tablets without any pre-treatment). The excipients present in the tablets did not interfere in the assay. Recoveries ranging from 97.7% to 106% were obtained. The results showed that the CPE/rGO/TiO₂ voltammetric sensor could be successfully applied in the routine quality control of ATN in complex matrices. Full article

Solid-state supercapacitors with gel electrolytes have emerged as a promising field for various energy storage applications, including electronic devices, electric vehicles, and mobile phones. In this study, nanocomposite gel membranes were fabricated using the solution casting method with perfluorosulfonic acid (PFSA) ionomer dispersion, both with and without the incorporation of 10 wt.% montmorillonite (MMT). MMT, a natural clay known for its high surface area and layered structure, is expected to enhance the properties of supercapacitor systems. Manganese oxide, selected for its pseudocapacitive behavior in a neutral electrolyte, was synthesized via direct co-precipitation. The materials underwent structural and morphological characterization. For electrochemical evaluation, a two-electrode Swagelok cell was employed, featuring a carbon xerogel negative electrode, a manganese dioxide positive electrode, and a PFSA polymer membrane serving as both the electrolyte and separator. The membrane was immersed in a 1 M Na₂SO₄ solution before testing. A comprehensive electrochemical analysis of the hybrid cells was conducted and compared with a symmetric carbon/carbon supercapacitor. Cyclic voltammetric curves were recorded, and galvanostatic charge–discharge tests were conducted at various temperatures (20, 40, 60 °C). The hybrid cell with the PFSA/MMT 10 wt.% exhibited the highest specific capacitance and maintained its hybrid profile after prolonged cycling at elevated temperatures, highlighting the potential of the newly developed membrane. Full article

In this work, a new voltammetric procedure for acyclovir (ACY) trace-level determination has been described. For this purpose, an electrochemically activated screen-printed carbon electrode (aSPCE) coupled with well-conductive electrolyte (CH₃COONH₄, CH₃COOH and NH₄Cl) was used for the first time. A commercially available SPCE sensor was electrochemically activated by conducting cyclic voltammetry (CV) scans in 0.1 mol L⁻¹ NaOH solution and rinsed with deionized water before a series of measurements were taken. This treatment reduced the charge transfer resistance, increased the electrode active surface area and improved the kinetics of the electron transfer. The activation step and high conductivity of supporting electrolyte significantly improved the sensitivity of the procedure. The newly developed differential-pulse adsorptive stripping voltammetry (DPAdSV) procedure is characterized by having the lowest limit of detection among all voltammetric procedures currently described in the literature (0.12 nmol L⁻¹), a wide linear range of the calibration curve (0.5–50.0 and 50.0–1000.0 nmol L⁻¹) as well as extremely high sensitivity (90.24 nA nmol L⁻¹) and was successfully applied in the determination of acyclovir in commercially available pharmaceuticals. Full article

The electrochemical properties of methylisothiazolinone (MIT), the most widely used preservative, were investigated by cyclic (CV) and differential pulse voltammetry (DPV) to develop a new method for its determination. To our knowledge, this is the first demonstration of a voltammetric procedure for the determination of MIT on a boron-doped diamond electrode (BDDE) in a citrate–phosphate buffer (C-PB) environment. The anodic oxidation process of methylisothiazolinone, which is the basis of this method, proved to be diffusion-controlled and proceeded with an irreversible two-electron exchange. The radical cations, as unstable primary products, were converted in subsequent chemical reactions to sulfoxides and sulfones, and finally to more stable final products. Performed determinations were based on the DPV technique. A linear calibration curve was obtained in the concentration range from 0.7 to 18.7 mg L⁻¹, with a correlation coefficient of 0.9999. The proposed procedure was accurate and precise, allowing the detection of MIT at a concentration level of 0.24 mg L⁻¹. It successfully demonstrated its suitability for the determination of methylisothiazolinone in household products without the need for any separation steps. The proposed method can serve as an alternative to the prevailing chromatographic determinations of MIT in real samples. Full article

Self-assembled monolayers (SAMs) of terpyridine-based transition metal (ruthenium and osmium) complexes, anchored to gold substrate via tripodal anchoring groups, have been investigated as possible redox switching elements for molecular electronics. An electrochemical study was complemented by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) methods. STM was used for determination of the SAM conductance values, and computation of the attenuation factor β from tunneling current–distance curves. We have shown that SAMs of Os-tripod molecules contain larger adlayer structures compared with SAMs of Ru-tripod molecules, which are characterized by a large number of almost evenly distributed small islands. Furthermore, upon cyclic voltammetric experimentation, Os-tripod films rearrange to form a smaller number of even larger islands, reminiscent of the Ostwald ripening process. Os-tripod SAMs displayed a higher surface concentration of molecules and lower conductance compared with Ru-tripod SAMs. The attenuation factor of Os-tripod films changed dramatically, upon electrochemical cycling, to a higher value. These observations are in accordance with previously reported electron transfer kinetics studies. Full article

The purpose of our research was to develop a new enzymatic biosensor, GPH-MnPc-Tyr/SPE, using as a support screen-printed carbon electrode (SPE) modified with graphene, manganese phthalocyanine, and tyrosinase, with the aim of developing sensitive detection of chlorogenic acid (CGA). To immobilise tyrosinase on the sensor surface, crosslinking with the glutaraldehyde technique was used, thus increasing the enzyme bioactivity on this electrode. The modified electrode has a great catalytic effect on the electrochemical redox of chlorogenic acid, compared to the simple, unmodified SPE. The peak current response of the biosensor for CGA was linear in the range of 0.1–10.48 μM, obtaining a calibration curve using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Subsequently, the detection limit (LOD) and the quantification limit (LOQ) were determined, obtaining low values, i.e., LOD = 1.40 × 10⁻⁶ M; LOQ = 4.69 × 10⁻⁶ M by cyclic voltammetry and LOD = 2.32 × 10⁻⁷ M; LOQ = 7.74 × 10⁻⁷ M, by square-wave voltammetry (SWV). These results demonstrate that the method is suitable for the detection of CGA in nutraceutical formulations. Therefore, GPH-MnPc-Tyr/SPE was used for the quantitative determination of CGA in three products, by means of cyclic voltammetry. The Folin–Ciocalteu spectrophotometric assay was used for the validation of the results, obtaining a good correlation between the voltammetric method and the spectrophotometric one, at a confidence level of 95%. Moreover, by means of the DPPH method, the antioxidant activity of the compound was determined, thus demonstrating the antioxidant effect of CGA in all nutraceuticals studied. Full article

Herein, two title compounds, N-benzoyl-N′-(4′-cyanophenyl)thiourea (1) and N-(4-nitrobenzoyl)-N′-(4′-cyanophenyl)thiourea (2) were synthesized in a high yield, via different applications of aroyl isocyanate and 4-aminobenzonitrile. The structure of the prepared compounds was characterized by elemental analysis and FT-IR, ¹H, and ¹³C-NMR spectroscopic methods. The crystal structure of the title compound 1 was determined by an X-ray single-crystal technique and an intramolecular C=O…H-N hydrogen bond and intermolecular C=S…H-N and C=S…H-C hydrogen interactions, which were observed for the crystal structure. The molecular electrostatic potential (MEP) and the Mulliken atomic charges of title compounds 1 and 2 were theoretically calculated and interpreted. Cyclic voltammetric (CV) experiments for the compounds were performed with the glassy carbon electrode. The reduction in potential values of the different functional groups such as nitro and cyano in title compounds were investigated using CV curves. Full article

The present paper developed a new enzymatic biosensor whose support is a screen-printed electrode based on carbon nanofibers modified with cobalt phthalocyanine and laccase (CNF-CoPc-Lac/SPE) to determine the p-coumaric acid (PCA) content by cyclic voltammetry and square wave voltammetry. Sensor modification was achieved by the casting and cross-linking technique, using glutaraldehyde as a reticulation agent. The biosensor’s response showed the PCA redox processes in a very stable and sensitive manner. The calibration curve was developed for the concentration range of p-coumaric acid of 0.1–202.5 μM, using cyclic voltammetry and chronoamperometry. The biosensor yielded optimal results for the linearity range 0.4–6.4 μM and stood out by low LOD and LOQ values, i.e., 4.83 × 10⁻⁷ M and 1.61 × 10⁻⁶ M, respectively. PCA was successfully determined in three phytoproducts of complex composition. The results obtained by the voltammetric method were compared to the ones obtained by the FTIR method. The amount of p-coumaric acid determined by means of CNF-CoPc-Lac/SPE was close to the one obtained by the standard spectrometric method. Full article

Surface chemistry information is crucial in understanding catalytic and sensing mechanisms. However, resolving the outermost monolayer composition of metallic nanoporous materials is challenging due to the high tortuosity of their morphology. In this study, we first elaborate on the capabilities and limitations of atom probe tomography (APT) in resolving interfaces. Subsequently, an electrochemical approach is designed to characterize the surface composition of nanoporous gold (NPG), developed from dealloying an inexpensive precursor (95 at. % Ag, 5 at. % Au), by the means of aqueous electrochemical measurements of the selective electrosorption of sulfide ions, which react strongly with Ag, but to a significantly lesser extent with Au. Accordingly, cyclic voltammetry was performed at various scan rates on NPG in alkaline aqueous solutions (0.2 M NaOH; pH 13) in the presence and absence of 1 mM Na₂S. Calibrations via similar voltammetric measurements on pure polycrystalline Ag and Au surfaces allowed for a quantitative estimation for the Ag surface coverage of NPG. The sensitivity threshold for the detection of the adsorbate–Ag interaction was assessed to be approximately 2% Ag surface coverage. As curves measured on NPG only showed featureless capacitive currents, no faradaic charge density associated with sulfide electrosorption could be detected. This study opens a new avenue to gain further insight into the monolayer surface coverage of metallic nanoporous materials and assists in enhancement of the interpretation of APT reconstructions. Full article

A voltammetric and scanning electrochemical microscopy (SECM) investigation was performed on an inherently chiral oligomer-coated gold electrode to establish its general properties (i.e., conductivity and topography), as well as its ability to discriminate chiral electroactive probe molecules. The electroactive monomer (S)-2,2′-bis(2,2′-bithiophene-5-yl)-3,3′-bibenzothiophene ((S)-BT₂T₄) was employed as reagent to electrodeposit, by cyclic voltammetry, the inherently chiral oligomer film of (S)-BT₂T₄ (oligo-(S)-BT₂T₄) onto the Au electrode surface (resulting in oligo-(S)-BT₂T₄-Au). SECM measurements, performed in either feedback or competition mode, using the redox mediators [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ in aqueous solutions, and ferrocene (Fc), (S)-FcEA, (R)-FcEA and rac-FcEA (FcEA is N,N-dimethyl-1-ferrocenylethylamine) in CH₃CN solutions, indicated that the oligomer film, as produced, was uncharged. The use of [Fe(CN)₆]³⁻ allowed establishing that the oligomer film behaved as a porous insulating membrane, presenting a rather rough surface. This was inferred from both the approach curves and linear and bidimensional SECM scans, which displayed negative feedback effects. The oligomer film acquired semiconducting or fully conducting properties when the Au electrode was biased at potential more positive than 0.6 V vs. Ag|AgCl|KCl. Under the latter conditions, the approach curves displayed positive feedback effects. SECM measurements, performed in competition mode, allowed verifying the discriminating ability of the oligo-(S)-BT₂T₄ film towards the (S)-FcEA and (R)-FcEA redox mediators, which confirmed the results obtained by cyclic voltammetry. SECM linear scans indicated that the enantiomeric discriminating ability of the oligo-(S)-BT₂T₄ was even across its entire surface. Full article

This paper focuses on the examination of glucose oxidation processes at an electrode material composed of gold nanoparticles embedded in a titanium template. Three different conditions were investigated: the chloride content in the electrolyte, its ionic conductivity and the presence of a Nafion coating. The impact of the provided environment on the oxidation reaction was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Two models, namely: chemisorption and incipient hydrous oxide/adatom mediator (IHOAM), were applied to explain the complex voltammetric responses of the electrodes exposed to solutions of varied glucose concentrations. Three different phenomena were observed for the studied cases. The first is related to the transition between the dominant mechanism of glucose oxidation from the IHOAM model to the chemisorption model. This happens only in an electrolyte containing chlorides after exceeding a certain amount of glucose. The second effect exhibits a bottleneck nature resulting from the presence of Nafion on the electrode’s surface. In this case, mass transport through the semi-permeable polymer is hampered, due to the blocking of channels and physical internal cross-linking. This leads to a preconcentration of glucose inside the pores resulting in an increase in both the material sensitivity and the linear range of the calibration curve. Lastly, the third effect is manifested in a low concentration of the supporting electrolyte. It is based on the fact that mass transport of hydroxyl ions is governed not only by diffusion, but also by migration. These three effects have a tremendous impact on the glucose oxidation mechanism and reveal its very complex nature. Full article

Caffeic acid may be accurately detected in food supplements by using cyclic voltammetry and carbon screen-printed sensors modified with various nanomaterials. Sensor characterization by cyclic voltammetry in reference solutions has shown that carbon nanotubes or carbon nanofibers significantly improve the sensor response in terms of sensitivity and reversibility. Screen-printed sensors were then used in order to study the electrochemical behavior of caffeic acid in aqueous solution at pH 3.6. A redox process was observed in all cases, which corresponds to a reversible redox process involving the transfer of two electrons and two protons. The role of nanomaterials in the increment of sensor performance characteristics was evidenced. Calibration curves were developed for each sensor, and the detection (LOD) and quantification (LOQ) limits were calculated. Low LOD and LOQ values were obtained, in the 10⁻⁷ to 10⁻⁹ M range, which demonstrates that the method is feasible for quantification of caffeic acid in real samples. Caffeic acid was quantitatively determined in three food supplements using the most sensitive sensor, namely the carbon nanofiber sensor. The Folin–Ciocalteu spectrophotometric assay was used to validate the results obtained with the sensor. The results obtained by using the voltammetric method were consistent with those obtained by using the spectrophotometric method, with no statistically significant differences between the results obtained at 95% confidence level. Full article