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A special issue of Chemosensors (ISSN 2227-9040). This special issue belongs to the section "Electrochemical Devices and Sensors".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 47354

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Prof. Dr. Constantin Apetrei

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Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, “Dunărea de Jos” University of Galaţi, 47 Domnească Street, 800008 Galaţi, Romania
Interests: electrochemical sensor; biosensor; nanomaterial; electroanalysis; multivariate data analysis
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Dear Colleagues,

The electrochemical sensors and biosensors are useful tools able to detect low concentrations of different compounds in small sample volumes, with high selectivity and sensitivity, and it could be easily miniaturized for the development of the portable analytical devices. These systems are useful for on-site, on line, in line, or real time analysis. The analytical performance characteristics of (bio)sensors are improved by using voltammperometric techniques for the detection of the targeted compounds. Furthermore, different electroactive compounds, nanomaterials, and/or enzymes are used for the increment of the selectivity. The aim of this Special Issue on “Voltammperometric Sensors” is to present the state-of-the-art on voltamperommetric (bio)sensors, which allow the detection of one or more different chemical species from the complex solutions, and the recent advances in the field. For this purpose, the reviews covering the theoretical and practical aspects on the field of voltamperommetric (bio)sensors are welcome. The papers devoted to the development, the characterization and the applications of voltamperommetric (bio)sensors, individually and as multisensory systems, in the analysis of real samples are expected.

Prof. Dr. Constantin Apetrei
Guest Editor

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Keywords

sensor
biosensor
voltammperometry
enzyme
nanomaterial
multisensory system
food
environment

Published Papers (14 papers)

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Research

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13 pages, 2663 KiB

Open AccessArticle

Differential Pulse Voltammetric Detection of Acetaminophen Using Nickel Phthalocyanine/CeO₂-Modified ITO Electrodes

by Emiliano C. Gomes, Camila L. Ribeiro, Vianney O. Santos, Jr. and Leonardo G. Paterno

Chemosensors 2023, 11(3), 154; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors11030154 - 23 Feb 2023

Cited by 2 | Viewed by 1511

Abstract

The present contribution reports a novel electrode based on an ITO substrate surface-modified with a nanofilm of nickel tetrasulfonated phthalocyanine (NiTsPc) with cerium oxide nanoparticles (CeO₂) for the effective differential pulse voltammetric detection of acetaminophen, which is a contaminant of emerging concern (CEC). The optimized ITO/NiTsPc/CeO₂ electrode responds linearly (r² > 0.99) to acetaminophen in the range of 0.4 to 11.2 µM, with a limit of detection (S/N = 3) of 54.7 nM. This response is reproducible for fourteen consecutive runs (RSD = 10.97%) and insensitive to the presence of interfering CECs (amoxicillin, atenolol, caffeine, diclofenac, ethinyl estradiol, and ibuprofen) at the same concentration. The electrode can be used to detect acetaminophen in tap water, synthetic urine, and pharmaceutical tablets, in which it performs similarly to UV-Vis spectroscopy at a 95% confidence level. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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21 pages, 6013 KiB

Open AccessEditor’s ChoiceArticle

Development of a Novel Electrochemical Biosensor Based on Organized Mesoporous Carbon and Laccase for the Detection of Serotonin in Food Supplements

by Dorin Dăscălescu and Constantin Apetrei

Chemosensors 2022, 10(9), 365; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors10090365 - 11 Sep 2022

Cited by 9 | Viewed by 2021

Abstract

Serotonin is a biogenic amine that has multiple roles in the human body and is mainly known as the happiness hormone. A new laccase (Lac)-based biosensor has been developed for the qualitative and quantitative determination of serotonin in three dietary supplements from three different manufacturers. The enzyme was immobilized on an organized mesoporous carbon-modified carbon screen-printed electrode (OMC-SPE) by the drop-and-dry method, the active surface being pretreated with glutaraldehyde. With the new biosensor, serotonin was selectively detected from different solutions. Square-wave voltammetry was the technique used for the quantitative determination of serotonin, obtaining a detection limit value of 316 nM and a quantification limit value of 948 nM in the linearity range of 0.1–1.2 µM. The pH for the determinations was 5.2; at this value, the biocatalytic activity of the laccase was optimal. At the same time, the electrochemical performance of the OMC-SPE/Lac biosensor was compared with that of the unmodified sensor, a performance that highlighted the superiority of the biosensor and the very important role of the enzyme in electrodetection. The results obtained from the quantitative determination of serotonin by square-wave voltammetry were compared with those from the FTIR method, revealing a very good correlation between the results obtained by the two quantitative determination methods. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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12 pages, 2513 KiB

Open AccessEditor’s ChoiceArticle

Polyethylenimine-Based Electrochemical Sensor for the Determination of Caffeic Acid in Aromatic Herbs

by Felipe Zamarchi, Tânia Regina Silva, João Paulo Winiarski, Edson Roberto Santana and Iolanda Cruz Vieira

Chemosensors 2022, 10(9), 357; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors10090357 - 02 Sep 2022

Cited by 17 | Viewed by 2140

Abstract

An electrochemical sensor based on carbon paste modified with polyethyleneimine was developed and employed for the determination of caffeic acid in aromatic herbs. The sensor was prepared by mixing polyethylenimine (1.5% v/v), graphite powder, and mineral oil. The polyethylenimine-based electrode showed an enhancement of charge transfer at the electrode–solution interface and a higher current intensity for the electrochemical reaction of caffeic acid, in comparison to the unmodified electrode. The calibration plot of caffeic acid constructed in 0.1 mol L⁻¹ acetate buffer (pH 5.0) by square wave voltammetry was linear in the range of 1.25 to 19.9 μmol L⁻¹ with a limit of detection of 0.13 μmol L⁻¹, respectively. Finally, the proposed sensor was employed to monitor the caffeic acid with accuracy in dried Thymus vulgaris and Salvia officinalis samples, with recovery results from 93 to 105%. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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13 pages, 3093 KiB

Open AccessArticle

Ni–Co–Te Nanocomposites with Multi-Dimensional Hierarchical Structure for Electrochemical Acetaminophen Sensing

by Jin-Jia Ye, Zhi-Yuan Wang, Han-Wei Chang and Yu-Chen Tsai

Chemosensors 2022, 10(8), 336; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors10080336 - 17 Aug 2022

Viewed by 1329

Abstract

In this study, Ni–Co–Te nanocomposites with multi-dimensional hierarchical structure were successfully prepared using a hydrothermal method. Ni–Co–Te nanocomposites used as electrode materials afford enhanced electroactive properties for electrochemical acetaminophen sensing. Field emission scanning electron microscopy (FESEM), field emission transmission electron microscopy (FETEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) were used to characterize the morphological and structural properties to boost their further promotion in acetaminophen sensing. The electrochemical performance of Ni–Co–Te nanocomposites was characterized by electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)). The lower electronegativity of the telluride atom and unique structural features of Ni–Co–Te nanocomposites endow the materials with promising performance in acetaminophen sensing (including linear range from 2.5 to 1000 μM, sensitivity of 0.5 μAμM⁻¹cm⁻², limit of detection of 0.92 μM, and excellent selectivity). The results indicated that Ni–Co–Te nanocomposites can serve as promising electrode materials for practical application in electrochemical acetaminophen sensing. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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11 pages, 2426 KiB

Open AccessArticle

Application of the Stripping Voltammetry Method for the Determination of Copper and Lead Hyperaccumulation Potential in Lunaria annua L.

by Maša Buljac, Josip Radić, Marijo Buzuk, Ivana Škugor Rončević, Nives Vladislavić, Denis Krivić and Ana Marijanović

Chemosensors 2022, 10(2), 52; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors10020052 - 29 Jan 2022

Viewed by 2104

Abstract

Various species of the Brassicaceae family are known to hyperaccumulate metals. Lunaria annua L., a plant from the Brassicaceae family, is an oilseed crop known for its pharmaceutical and nutraceutical applications. In this work, Lunaria annua L. was investigated for its accumulation potential in copper and lead-contaminated soil. Concentrations of copper and lead were measured before planting (in seeds and soils) and after the plant was harvested (in soils and plant). Two types of soils were used: a soil sample collected from the Botanical Garden of the Faculty of Science, University of Split (soil 1, S1) and a commercially available organic mineral substrate (soil 2, S2). Measured pH values showed that the S1 (pH = 8.58) was moderately alkaline soil. On the other hand, the purchased organic soil, S2 (pH = 6.35), was poorly acidic to neutral. For the determination of copper (Cu) and lead (Pb), square wave anodic stripping voltammetry (SWASV), using a glassy carbon electrode modified with mercury film, was applied. The concentrations of Pb and Cu were determined and calculated in the sample using the standard addition method. Obtained results have shown that Lunaria annua L. is a lead hyperaccumulator (4116.2 mg/kg in S1 and 3314.7 mg/kg in S2) and a potential copper accumulator (624.2 mg/kg in S1 and 498.9 mg/kg in S2). Likewise, the results have shown that the higher the pH is, the lower the possibility that metal accumulation exists. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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17 pages, 3872 KiB

Open AccessArticle

Glassy Carbon Electrode Modified with C/Au Nanostructured Materials for Simultaneous Determination of Hydroquinone and Catechol in Water Matrices

by Samuel Piña, Christian Candia-Onfray, Natalia Hassan, Paola Jara-Ulloa, David Contreras and Ricardo Salazar

Chemosensors 2021, 9(5), 88; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors9050088 - 24 Apr 2021

Cited by 13 | Viewed by 3058

Abstract

The simultaneous determination of hydroquinone and catechol was conducted in aqueous and real samples by means of differential pulse voltammetry (DPV) using a glassy carbon electrode modified with Gold Nanoparticles (AuNP) and functionalized multiwalled carbon nanotubes by drop coating. A good response was obtained in the simultaneous determination of both isomers through standard addition to samples prepared with analytical grade water and multivariate calibration by partial least squares (PLS) in winery wastewater fortified with HQ and CT from 4.0 to 150.00 µM. A sensitivity of 0.154 µA µM⁻¹ and 0.107 µA µM⁻¹, and detection limits of 4.3 and 3.9 µM were found for hydroquinone and catechol, respectively. We verified the reliability of the developed method by simultaneously screening analytes in spiked tap water and industrial wastewater, achieving recoveries over 80%. In addition, this paper demonstrates the applicability of chemometric tools for the simultaneous quantification of both isomers in real matrices, obtaining prediction errors of lower than 10% in fortified wastewater. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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13 pages, 3155 KiB

Open AccessArticle

Paracetamol Sensing with a Pencil Lead Electrode Modified with Carbon Nanotubes and Polyvinylpyrrolidone

by Piyanut Pinyou, Vincent Blay, Kantapat Chansaenpak and Sireerat Lisnund

Chemosensors 2020, 8(4), 133; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors8040133 - 15 Dec 2020

Cited by 15 | Viewed by 3320

Abstract

The determination of paracetamol is a common need in pharmaceutical and environmental samples for which a low-cost, rapid, and accurate sensor would be highly desirable. We develop a novel pencil graphite lead electrode (PGE) modified with single-wall carbon nanotubes (SWCNTs) and polyvinylpyrrolidone (PVP) polymer (PVP/SWCNT/PGE) for the voltammetric quantification of paracetamol. The sensor shows remarkable analytical performance in the determination of paracetamol at neutral pH, with a limit of detection of 0.38 μM and a linear response from 1 to 500 μM using square-wave voltammetry (SWV), which are well suited to the analysis of pharmaceutical preparations. The introduction of the polymer PVP can cause dramatic changes in the sensing performance of the electrode, depending on its specific architecture. These effects were investigated using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The results indicate that the co-localization and dispersion of PVP throughout the carbon nanotubes on the electrode are key to its superior electrochemical performance, facilitating the electrical contact between the nanotubes and with the electrode surface. The application of this sensor to commercial syrup and tablet preparations is demonstrated with excellent results. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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14 pages, 4339 KiB

Open AccessArticle

A Simple but Efficient Voltammetric Sensor for Simultaneous Detection of Tartrazine and Ponceau 4R Based on TiO₂/Electro-Reduced Graphene Oxide Nanocomposite

by Zirong Qin, Jinyan Zhang, Ying Liu, Jingtao Wu, Guangli Li, Jun Liu and Quanguo He

Chemosensors 2020, 8(3), 70; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors8030070 - 19 Aug 2020

Cited by 25 | Viewed by 3129

Abstract

In this work, we report a simple but efficient voltammetric sensor for simultaneous detection of ponceau 4R and tartrazine based on TiO₂/electro-reduced graphene oxide nanocomposites (TiO₂/ErGO). TiO₂/ErGO nanocomposites were prepared by ultrasonically dispersing TiO₂ nanoparticles (TiO₂ NPs) into graphene oxide (GO) solution followed by a green in-situ electrochemical reduction. TiO₂ NPs were uniformly supported on ErGO nanoflakes, which provides a favorable interface for the adsorption and subsequent oxidation of target analytes. TiO₂/ErGO showed remarkable electrocatalytic capacity for the oxidation of ponceau 4R and tartrazine, with minimized oxidation overpotentials and boosted adsorptive striping differential pulse voltammetric (AdSDPV) response peak currents. Under the optimal experimental conditions, the anodic peak currents of ponceau 4R and tartrazine increase linearly with the respective natural logarithm of concentrations from 0.01 to 5.0 μM. The detection limits (LOD = 3σ/s) for ponceau 4R and tartrazine are 4.0 and 6.0 nM, respectively. The extraordinary analytical properties of TiO₂/ErGO/GCE are primarily attributed to the synergistic enhancement effect from ErGO nanoflakes and TiO₂ NPs. Moreover, the proposed TiO₂/ErGO/GCE achieves reliable determination of ponceau 4R and tartrazine in orange juice with excellent selectively, reproducibility and stability. Together with simplicity, rapidness, and low cost, the proposed sensor demonstrates great potential for on-site detection of azo colorants. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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17 pages, 1597 KiB

Open AccessArticle

Voltammetric Sensors Based on Nanomaterials for Detection of Caffeic Acid in Food Supplements

by Alexandra Virginia Bounegru and Constantin Apetrei

Chemosensors 2020, 8(2), 41; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors8020041 - 18 Jun 2020

Cited by 26 | Viewed by 4209

Abstract

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

(This article belongs to the Special Issue Voltammperometric Sensors)

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14 pages, 2696 KiB

Open AccessArticle

Electrochemical Sensing of Caffeic Acid Using Gold Nanoparticles Embedded in Poly(3,4-ethylenedioxythiophene) Layer by Sinusoidal Voltage Procedure

by Davide Bottari, Laura Pigani, Chiara Zanardi, Fabio Terzi, Sanda Victorinne Paţurcă, Sorin Dan Grigorescu, Cristian Matei, Cecilia Lete and Stelian Lupu

Chemosensors 2019, 7(4), 65; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors7040065 - 12 Dec 2019

Cited by 17 | Viewed by 3147

Abstract

The increasing demand for sensitive electrochemical sensors in various medical and industrial applications promotes the fabrication of novel sensing materials with improved electrocatalytic and analytical performances. This work deals with the development of a composite material based on gold nanoparticles (AuNPs) embedded in poly(3,4-ethylenedioxythiophene) (PEDOT) layer for electrochemical determination of caffeic acid (CA). CA is a phenolic compound with excellent antioxidant properties that is present in vegetables, fruits, and alcoholic and non-alcoholic beverages. Its analytical quantification is of great interest in food production monitoring and healthcare applications. Therefore, the development of sensitive analytical devices for CA monitoring is required. The AuNPs have been prepared in situ onto PEDOT coated glassy carbon electrode (GC) by means of an innovative procedure consisting on the use of a sinusoidal voltage (SV) superimposed on a constant potential. The physico-chemical properties of the PEDOT-AuNPs composite material were investigated by a range of techniques including cyclic voltammetry, electrochemical quartz crystal microbalance, and scanning electron microscopy. The glassy carbon electrode/poly(3,4-ethylenedioxythiophene)-gold nanoparticles-sinusoidal voltage (GC/PEDOT-AuNPs-SV) sensor exhibited good analytical performance toward the CA quantification with a linear response over a wide concentration range from 10 µM to 1 mM. In addition, the proposed GC/PEDOT-AuNPs-SV sensor was successfully applied in the determination of total polyphenols content expressed as equivalents of CA in juice samples. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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Review

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16 pages, 1795 KiB

Open AccessReview

Application of Voltammetric Sensors for Pathogen Bacteria Detection: A Review

by Jorge Lopez-Tellez, Sandra Ramirez-Montes, T. Alexandra Ferreira, Eva M. Santos and Jose A. Rodriguez

Chemosensors 2022, 10(10), 424; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors10100424 - 17 Oct 2022

Cited by 7 | Viewed by 3037

Abstract

In recent years, new strategies for bacteria determination have been developed in order to achieve rapid detection and adequate limits of detection for quantification of microorganisms. This review classifies voltammetric sensors according to whether the bacteria are directly or indirectly detected. Direct methods are based on the recognition of the bacteria themselves, either in labeled or label-free mode. In contrast, indirect methods detect a metabolite produced by the bacteria. New trends in bacteria sensors involve DNA analysis, which makes it possible to improve the sensitivity and specificity of measurements. Voltammetric sensors provide good linear ranges and low limits of detection and are useful for analysis of food and clinical and environmental samples. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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23 pages, 3676 KiB

Open AccessReview

Nanomaterials Based Electrochemical Sensors for Serotonin Detection: A Review

by Dorin Dăscălescu and Constantin Apetrei

Chemosensors 2021, 9(1), 14; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors9010014 - 14 Jan 2021

Cited by 30 | Viewed by 6485

Abstract

The present review deals with the recent progress made in the field of the electrochemical detection of serotonin by means of electrochemical sensors based on various nanomaterials incorporated in the sensitive element. Due to the unique chemical and physical properties of these nanomaterials, it was possible to develop sensitive electrochemical sensors with excellent analytical performances, useful in the practice. The main electrochemical sensors used in serotonin detection are based on carbon electrodes modified with carbon nanotubes and various materials, such as benzofuran, polyalizarin red-S, poly(L-arginine), Nafion/Ni(OH)₂, or graphene oxide, incorporating silver-silver selenite nanoparticles, as well as screen-printed electrodes modified with zinc oxide or aluminium oxide. Also, the review describes the nanocomposite sensors based on conductive polymers, tin oxide-tin sulphide, silver/polypyrole/copper oxide or a hybrid structure of cerium oxide-gold oxide nanofibers together with ruthenium oxide nanowires. The presentation focused on describing the sensitive materials, characterizing the sensors, the detection techniques, electroanalytical properties, validation and use of sensors in lab practice. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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19 pages, 1409 KiB

Open AccessReview

Electrochemical Sensors Coupled with Multivariate Statistical Analysis as Screening Tools for Wine Authentication Issues: A Review

by Elisabeta-Irina Geană, Corina Teodora Ciucure and Constantin Apetrei

Chemosensors 2020, 8(3), 59; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors8030059 - 30 Jul 2020

Cited by 24 | Viewed by 3856

Abstract

Consumers are increasingly interested in the characteristics of the products they consume, including aroma, taste, and appearance, and hence, scientific research was conducted in order to develop electronic senses devices that mimic the human senses. Thanks to the utilization of electroanalytical techniques that used various sensors modified with different electroactive materials coupled with pattern recognition methods, artificial senses such as electronic tongues (ETs) are widely applied in food analysis for quality and authenticity approaches. This paper summarizes the applications of electrochemical sensors (voltammetric, amperometric, and potentiometric) coupled with unsupervised and supervised pattern recognition methods (principal components analysis (PCA), linear discriminant analysis (LDA), partial least square (PLS) regression, artificial neural network (ANN)) for wine authenticity assessments including the discrimination of varietal and geographical origins, monitoring the ageing processes, vintage year discrimination, and detection of frauds and adulterations. Different wine electrochemical authentication methodologies covering the electrochemical techniques, electrodes types, functionalization sensitive materials and multivariate statistical analysis are emphasized and the main advantages and disadvantages of using the proposed methodologies for real applications were concluded. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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39 pages, 6082 KiB

Open AccessReview

Progress in Electrochemical (Bio)Sensors for Monitoring Wine Production

by Alina Vasilescu, Pablo Fanjul-Bolado, Ana-Maria Titoiu, Roxana Porumb and Petru Epure

Chemosensors 2019, 7(4), 66; https://0-doi-org.brum.beds.ac.uk/10.3390/chemosensors7040066 - 16 Dec 2019

Cited by 29 | Viewed by 6644

Abstract

Electrochemical sensors and biosensors have been proposed as fast and cost effective analytical tools, meeting the robustness and performance requirements for industrial process monitoring. In wine production, electrochemical biosensors have proven useful for monitoring critical parameters related to alcoholic fermentation (AF), malolactic fermentation (MLF), determining the impact of the various technological steps and treatments on wine quality, or assessing the differences due to wine age, grape variety, vineyard or geographical region. This review summarizes the current information on the voltamperometric biosensors developed for monitoring wine production with a focus on sensing concepts tested in industry-like settings and on the main quality parameters such as glucose, alcohol, malic and lactic acids, phenolic compounds and allergens. Recent progress featuring nanomaterial-enabled enhancement of sensor performance and applications based on screen-printed electrodes is emphasized. A case study presents the monitoring of alcoholic fermentation based on commercial biosensors adapted with minimal method development for the detection of glucose and phenolic compounds in wine and included in an automated monitoring system. The current challenges and perspectives for the wider application of electrochemical sensors in monitoring industrial processes such as wine production are discussed. Full article

(This article belongs to the Special Issue Voltammperometric Sensors)

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