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Electrochemical Methods for Antioxidant Activity Detection

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A special issue of Antioxidants (ISSN 2076-3921). This special issue belongs to the section "Methods for Antioxidants Evaluation/Measurement".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 26886

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Dr. Alla V. Ivanova

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Chemical Technological Institute, Ural Federal University Named After the First President of Russia B. N. Yeltsin, 19 Ul. Mira, 620002 Ekaterinburg, Russia
Interests: electrochemical analysis methods; voltammetry; potentiometry; antioxidant capacity; antiradical capacity; sensors; organic electrochemistry
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Dr. Guzel Ziyatdinova

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Guest Editor

Analytical Chemistry Department, Kazan Federal University, Kremleyevskaya, 18, Kazan 420008, Russia
Interests: electroanalytical chemistry; electrochemical sensors; chemically modified electrodes; polymer-based electrodes; coulometric organic analysis; antioxidants, plant polyphenols; colorants and dyes; food analysis; phytochemical and pharmaceutical analysis; biomedical analysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Investigation and quantitative evaluation of the antioxidant properties of various samples (biological fluids, foodstuff, phytochemicals, pharmaceuticals, etc.) are of high importance and interest from both fundamental and practical points of view in life sciences. Free radical reactions and the effect of the antioxidants play a key role in human health and wellbeing. A wide range of antioxidant parameters including individual antioxidant contents and total antioxidant indexes (antioxidant capacity, antioxidant activity, total phenolics, free radical reactions inhibition parameters, etc.) are successfully used for the characterization of antioxidants in modeled and real samples. Traditionally, spectroscopic methods are mainly used for the total antioxidant parameter evaluation, although they have a range of limitations and do not solve all the problems of interest. The electrochemical nature of the antioxidants’ action mechanism allows the application of electroanalytical methods as an alternative.

Contributions to this Special Issue (both original research and review) may cover all aspects of antioxidants research (in vitro or in vivo) using electrochemical methods related to (but not limited to) the following topics: antioxidant recognition, selective determination of individual antioxidants, evaluation of total antioxidant parameters, model oxidant inhibition parameters, investigation of kinetic and thermodynamic characteristics of antioxidant transformation, elucidation of antioxidant mechanisms, development of the sensors and portable devices for total antioxidant parameter evaluation. Novel approaches with improved analytical characteristics and new information about antioxidants are encouraged.

Dr. Alla V. Ivanova
Dr. Guzel Ziyatdinova
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Antioxidants is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

electroanalysis
antioxidants
antioxidant activity
radical/ROS scavenging
total antioxidant parameters
electrochemical sensors
electrochemical portable devices

Related Special Issue

Electrochemical Methods for Antioxidant Activity Detection 2.0 in Antioxidants (4 articles)

Published Papers (10 papers)

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Research

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15 pages, 2103 KiB

Open AccessArticle

Antioxidant Capacity through Electrochemical Methods and Chemical Composition of Oenocarpus bataua and Gustavia macarenensis from the Ecuadorian Amazon

by Carlos Méndez-Durazno, Pablo A. Cisneros-Perez, Bryan A. Loja-Ojeda, Raúl Monge-Sevilla, David Romero-Estévez, Lenys Fernández and Patricio J. Espinoza-Montero

Antioxidants 2023, 12(2), 318; https://doi.org/10.3390/antiox12020318 - 30 Jan 2023

Cited by 3 | Viewed by 4227

Abstract

This study evaluated the antioxidant properties and chemical composition of the seeds, pulp and peels of Ungurahua (Oenocarpus bataua) and Pasu (Gustavia macarenensis)—fruits, native to the Ecuadorian Amazon. The antioxidant capacity was measured by 1,1-diphenyl-2-picrylhydrazyl (DPPH) and cyclic voltammetry (antioxidant index 50 (AI₅₀)) assays; differential pulse voltammetry was used to evaluate antioxidant power using the electrochemical index. The total phenolic content, as well as the yellow flavonoid and anthocyanin content, were quantified via spectrophotometry. In addition, the trans-resveratrol and ascorbic acid content were evaluated through high performance liquid chromatography (HPLC). Ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) was used to identify secondary metabolites with possible therapeutic properties. Results showed that the Pasu peel and seed extracts had the highest antioxidant capacity, followed by the Ungurahua peel; these results were consistent for both spectroscopic and electrochemical assays. HPLC and UPLC-MS analysis suggest that Oenocarpus bataua and Gustavia macarenensis are important sources of beneficial bioactive compounds. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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23 pages, 1574 KiB

Open AccessArticle

Anti- and Pro-Oxidant Activity of Polyphenols Extracts of Syrah and Chardonnay Grapevine Pomaces on Melanoma Cancer Cells

by Ylenia Spissu, Katarzyna Angelika Gil, Antonio Dore, Giulia Sanna, Giuseppe Palmieri, Andrea Sanna, Maurizio Cossu, Feten Belhadj, Boutheina Gharbi, Maria Barbara Pinna, Antonio Barberis, Carlo Ignazio Giovanni Tuberoso and Guy D’hallewin

Antioxidants 2023, 12(1), 80; https://doi.org/10.3390/antiox12010080 - 29 Dec 2022

Cited by 10 | Viewed by 2191

Abstract

The phenolic composition of Syrah and Chardonnay grape pomaces was studied to assess their antioxidant and prooxidant properties. Polyphenols were extracted by a "green" hydroalcoholic solvent (ethanol/water 1:1 v/v), and a detailed chemical and electrochemical characterization of the phenolic compounds was performed. The antioxidant and prooxidant capacity of the pomace was first studied by cyclic voltammetry (CV) and other reference analytical assays, then with biological tests on B16F10 metastatic melanoma cancer cells. Electrochemical data showed that, when a +0.5 V potential was applied, a low to moderate antioxidant capacity was observed. MTT test showed an increasing viability of melanoma cells, after treatments at low concentration (up to 100 μg/mL) and for a short time (6 h), but when cells were treated with higher doses of extract (≥250 μg/mL for 12/24 h), their viability decreased from 25 to 50% vs. control, depending on treatment time, dose, and extract origin. A stronger prooxidant activity resulted when 250 μg/mL of extract was combined with non-toxic doses of H₂O₂; this activity was correlated with the presence of copper in the extracts. This study shows the potential of winemaking by-products and suggests the opportunity to exploit them for the production of cosmeceuticals, or for combined therapies with approved anticancer drugs. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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12 pages, 5120 KiB

Open AccessArticle

In Situ Electrochemical Formation of Oxo-Functionalized Graphene on Glassy Carbon Electrode with Chemical Fouling Recovery and Antibiofouling Properties for Electrochemical Sensing of Reduced Glutathione

by Chunying Xu, Gang Li, Liju Gan and Baiqing Yuan

Antioxidants 2023, 12(1), 8; https://doi.org/10.3390/antiox12010008 - 21 Dec 2022

Cited by 3 | Viewed by 1804

Abstract

Electrochemical detection can be used to achieve intracellular or in vivo analysis of reduced glutathione (GSH) in tissues such as brain by using a microelectrode, which can help to better understand the complex biochemical processes of this molecule in the human body. The main challenges associated with electrochemical GSH detection are the chemical fouling of electrodes, caused by the oxidation product of GSSG, and biofouling due to the non-specific absorption of biological macromolecules. Oxo-functionalized graphene was generated in situ on the surface of a glassy carbon electrode using a green electrochemical method without using any other modifiers or materials in a mild water solution. The fabricated oxo-functionalized graphene interface was characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, electrochemical impedance spectroscopy, and contact angle measurements. The interface showed high electrocatalytic activity towards the oxidation of GSH, and a simple and efficient GSH sensor was developed. Interestingly, the electrode is reusable and could be recovered from the chemical fouling via electrochemical oxidation and reduction treatment. The electrode also exhibited good antibiofouling properties. The presented method could be a promising method used to treat carbon materials, especially carbon-based microelectrodes for electrochemical monitoring of intracellular glutathione or in vivo analysis. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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16 pages, 2477 KiB

Open AccessArticle

Electroanalysis of Naringin at Electroactivated Pencil Graphite Electrode for the Assessment of Polyphenolics with Intermediate Antioxidant Power

by Iulia Gabriela David, Simona Carmen Litescu, Raluca Moraru, Camelia Albu, Mihaela Buleandra, Dana Elena Popa, Sorin Riga, Adela Magdalena Ciobanu and Hassan Noor

Antioxidants 2022, 11(12), 2306; https://doi.org/10.3390/antiox11122306 - 22 Nov 2022

Cited by 5 | Viewed by 1553

Abstract

A simple and rapid differential pulse voltammetric (DPV) method using a single-use electroactivated pencil graphite electrode (PGE*) is proposed for the rapid screening of the total content of polyphenolics (TCP) with intermediate antioxidant power (AOP) in grapefruit peel and fresh juice. The results were compared and correlated with those provided by the HPLC-DAD-MS method. NG voltammetric behavior at PGE* was studied by cyclic voltammetry and an oxidation mechanism was suggested. The experimental conditions (type of PGE, electroactivation procedure, pH, nature and concentration of supporting electrolyte) for NG DPV determination were optimized. The NG peak current varied linearly with the concentration in the ranges 1.40 × 10⁻⁶–2.00 × 10⁻⁵ and 2.00 × 10⁻⁵–1.40 × 10⁻⁴ mol/L NG and a limit of detection (LoD) of 6.02 × 10⁻⁷ mol/L NG was attained. The method repeatability expressed as relative standard deviation was 7.62% for the concentration level of 2.00 × 10⁻⁶ mol/L NG. After accumulation for 240 s of NG at PGE* the LoD was lowered to 1.35 × 10⁻⁷ mol/L NG, the linear range being 6.00 × 10⁻⁷–8.00 × 10⁻⁶ mol/L NG. The developed electrochemical system was successfully tested on real samples and proved to be a cost-effective tool for the simple estimation of the TCP with intermediate AOP in citrus fruits. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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17 pages, 2606 KiB

Open AccessArticle

Carbon Black Functionalized with Naturally Occurring Compounds in Water Phase for Electrochemical Sensing of Antioxidant Compounds

by Filippo Silveri, Flavio Della Pelle, Annalisa Scroccarello, Elisabetta Mazzotta, Tiziano Di Giulio, Cosimino Malitesta and Dario Compagnone

Antioxidants 2022, 11(10), 2008; https://doi.org/10.3390/antiox11102008 - 11 Oct 2022

Cited by 12 | Viewed by 1838

Abstract

A new sustainable route to nanodispersed and functionalized carbon black in water phase (W-CB) is proposed. The sonochemical strategy exploits ultrasounds to disaggregate the CB, while two selected functional naturally derived compounds, sodium cholate (SC) and rosmarinic acid (RA), act as stabilizing agents ensuring dispersibility in water adhering onto the CB nanoparticles’ surface. Strategically, the CB-RA compound is used to drive the AuNPs self-assembling at room temperature, resulting in a CB surface that is nanodecorated; further, this is achieved without the need for additional reagents. Electrochemical sensors based on the proposed nanomaterials are realized and characterized both morphologically and electrochemically. The W-CBs’ electroanalytical potential is proved in the anodic and cathodic window using caffeic acid (CF) and hydroquinone (HQ), two antioxidant compounds that are significant for food and the environment. For both antioxidants, repeatable (RSD ≤ 3.3%; n = 10) and reproducible (RSD ≤ 3.8%; n = 3) electroanalysis results were obtained, achieving nanomolar detection limits (CF: 29 nM; HQ: 44 nM). CF and HQ are successfully determined in food and environmental samples (recoveries 97–113%), and also in the presence of other phenolic classes and HQ structural isomers. The water dispersibility of the proposed materials can be an opportunity for (bio) sensor fabrication and sustainable device realization. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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15 pages, 3175 KiB

Open AccessArticle

The Novel Potentiometric Approach to Antioxidant Capacity Assay Based on the Reaction with Stable Radical 2,2′-diphenyl-1-picrylhydrazyl

by Elena Gerasimova, Elena Gazizullina, Sofya Kolbaczkaya and Alla Ivanova

Antioxidants 2022, 11(10), 1974; https://doi.org/10.3390/antiox11101974 - 1 Oct 2022

Cited by 5 | Viewed by 2145

Abstract

For the first time, new possibilities of using the DPPH^• as a signal-forming oxidant molecule with potentiometric detection are shown. The CV method confirmed the presence of a quasi-reversible potential-determining system DPPH^•/DPPH-H under experimental conditions. This fact makes it possible to use DPPH^• as the model of the oxidizing agent for obtaining an analytical signal by the potentiometry method. The potentiometric approach makes it possible to obtain the value of the Nernst slope and the antioxidant capacity in one experiment. It consists of an antioxidant supplement and two consecutive DPPH^• supplements. In this case, the calculation of the Nernst slope is carried out by introducing the second addition of the oxidizing agent and constructing a calibration curve against the reaction background with an antioxidant. Solutions of individual antioxidants α-tocopherol, quercetin, (±)-catechin hydrate, and α-lipoic acid were studied by the developed approach. A high correlation with the results of spectrophotometric measurements is shown. At the same time, the potentiometry method is devoid of the concentration limitations of the spectrophotometric method, which was confirmed. In the study of plant materials extracts, a high correlation of antioxidant capacity, obtained by potentiometric and spectrophotometric methods, was shown only for objects whose color did not contribute to the DPPH^• absorption. The versatility of the potentiometric method for studying objects of any color was shown. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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19 pages, 1401 KiB

Open AccessArticle

Constant–Current Coulometry with Electrogenerated Titrants as a Novel Tool for the Essential Oils Screening Using Total Antioxidant Parameters

by Guzel Ziyatdinova, Alena Kalmykova and Olga Kupriyanova

Antioxidants 2022, 11(9), 1749; https://doi.org/10.3390/antiox11091749 - 3 Sep 2022

Cited by 4 | Viewed by 1749

Abstract

Essential oils are widely used in aromatherapy, medicine, and food industries due to a wide spectrum of bioactivity. Their antioxidant properties can be considered as markers of therapeutic effect and quality. Constant–current coulometry with electrogenerated titrants has been successfully applied for these purposes for the first time. Fifteen types of essential oils from various plant materials have been studied. Their composition has been identified by gas chromatography with mass-spectrometric detection (GC-MS). The reactivity of individual antioxidants of essential oils towards electrogenerated titrants (bromine and ferricyanide ions) has been estimated. Total antioxidant parameters, in particular total antioxidant capacity (TAC) and ferric reducing power (FRP) based on the reactions of essential oil antioxidants with electrogenerated bromine and ferricyanide ions, respectively, have been evaluated. Positive correlations (r = 0.7051–0.9558) with common antioxidant tests (antioxidant activity by reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH^•) and total phenolic content by the Folin–Ciocalteu method) have been obtained. Coulometric approaches overcome the limitations of spectrophotometry and are applicable to a wider range of essential oils. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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11 pages, 1271 KiB

Open AccessArticle

An Electrochemical Determination of the Total Reducing Capacity of Wheat, Spelt, and Rye Breads

by Danuta Zielińska, Henryk Zieliński and Mariusz Konrad Piskuła

Antioxidants 2022, 11(8), 1438; https://doi.org/10.3390/antiox11081438 - 25 Jul 2022

Cited by 1 | Viewed by 1349

Abstract

The most interesting activities associated with bread components such as phenolic compounds, fibre, tocols, or newly formed compounds in the Maillard reaction, are their reducing properties responsible for the formation of the overall reducing capacity of bread. Among the electrochemical methods, the cyclic voltammetry (CV) technique has been recently adapted for this purpose. In this study, the application of the CV assay for the determination of the total reducing capacity of flours, doughs, and breads as well as their crumbs and crusts, originated from wheat, spelt, and rye formulated on white flours (extraction rate of 70%) and dark flours (extraction rate of 100%) and baked at 200 °C for 35 min and at 240 °C for 30 min was addressed. The reducing capacity of hydrophilic extracts from white flours and breads as well as their crumbs and crusts showed double values when compared to that of lipophilic ones whilst hydrophilic and lipophilic extracts from dark breads and their parts revealed comparable levels. The dark wheat, spelt, and rye breads showed an approximately threefold higher total reducing capacity than white breads. Baking at higher temperature slightly increased the total reducing capacity of breads and the highest value was found for dark rye bread as well as its crust baked at 240 °C for 30 min. The cyclic voltammetry methodology showed to be especially suitable for screening the bread technology and allows for obtaining rapid electrochemical profiles of bread samples. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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14 pages, 2411 KiB

Open AccessArticle

Antioxidant Properties of New Phenothiazine Derivatives

by Olesya Voronova, Sergey Zhuravkov, Elena Korotkova, Anton Artamonov and Evgenii Plotnikov

Antioxidants 2022, 11(7), 1371; https://doi.org/10.3390/antiox11071371 - 14 Jul 2022

Cited by 4 | Viewed by 2760

Abstract

Phenothiazine and its derivatives have a number of properties that contribute to their wider practical use in the production of biologically active substances, drugs, dyes, etc. Therefore, the synthesis and study of new compounds is of great relevance. The aim of this work was to investigate the antioxidant activity of a number of new phenothiazine derivatives. The patterns of electroreduction of oxygen and its radicals in the presence of phenothiazine derivatives in aqueous ethanol media were studied by voltammetry. The influence of various factors on antioxidant activity was considered by the methods of experiment planning. The optimal conditions for the manifestation of the antioxidant activity of phenothiazine derivatives have been found, which seems to be relevant since it opens up new possibilities for their further use as complex preparations with antioxidant activity, including in psychiatric practice. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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Review

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29 pages, 1820 KiB

Open AccessReview

A Review on Electrochemical Sensors and Biosensors Used in Assessing Antioxidant Activity

by Irina Georgiana Munteanu and Constantin Apetrei

Antioxidants 2022, 11(3), 584; https://doi.org/10.3390/antiox11030584 - 18 Mar 2022

Cited by 40 | Viewed by 5772

Abstract

Currently, there is growing interest in screening and quantifying antioxidants from biological samples in the quest for natural and effective antioxidants to combat free radical-related pathological complications. Antioxidants play an important role in human health and provide a defense against many diseases. Due to the valuable dietary role of these compounds, the analysis and determination of their amount in food is of particular importance. In recent years, many attempts have been made to provide simple, fast, and economical analytical approaches for the on-site detection and determination of antioxidant activity in food antioxidants. In this regard, electrochemical sensors and biosensors are considered promising tools for antioxidant research due to their high sensitivity, fast response time, and ease of miniaturization; thus, they are used in a variety of fields, including food analysis, drug screening, and toxicity research. Herein, we review the recent advances in sensors and biosensors for the detection of antioxidants, underlying principles, and emphasizing advantages, along with limitations regarding the ability to discriminate between the specific antioxidant or quantifying total antioxidant content. In this work, both direct and indirect methods for antioxidants detecting with electrochemical sensors and biosensors are analyzed in detail. This review aims to prove how electrochemical sensors and biosensors represent reliable alternatives to conventional methods for antioxidant analysis. Full article

(This article belongs to the Special Issue Electrochemical Methods for Antioxidant Activity Detection)

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