The creation and analysis of a large variety of existing methods for the evaluation of integrated antioxidant properties are quite relevant in connection with a range of biological mechanisms of the antioxidants (AO) action. In this work, the existing methods are correlated with mechanisms of antioxidant action. It is shown that the results obtained by various methods are mainly incomparable. This can be connected with the implementation of various mechanisms of antioxidant action in methods. The analysis of the literature data presented in this review indicates the difficulty of creating a universal method and the feasibility of using integrated approaches based on the use of several methods that implement and combine various mechanisms of the chemical conversion of antioxidants. This review describes methods for studying the chelating ability of antioxidants, except for methods based on electron and hydrogen atom transfer reactions, which are currently not widely covered in modern literature. With the description of each mechanism, special attention is paid to electrochemical methods, as the interaction of active oxygen metabolites of radical and non-radical nature with antioxidants has an electron/proton/donor-acceptor nature, which corresponds to the nature of electrochemical methods and suggests that they can be used to study the interaction.

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.

The synthesis of inhibitors for oxidative stress-associated destructive processes based on 2H-imidazole-derived phenolic compounds affording the bifunctional 2H-imidazole-derived phenolic compounds in good-to-excellent yields was reported. In particular, a series of bifunctional organic molecules of the 5-aryl-2H-imidazole family of various architectures bearing both electron-donating and electron-withdrawing substituents in the aryl fragment along with the different arrangements of the hydroxy groups in the polyphenol moiety, namely derivatives of phloroglucinol, pyrogallol, hydroxyquinol, including previously unknown water-soluble molecules, were studied. The structural and antioxidant properties of these bifunctional 5-aryl-2H-imidazoles were comprehensively studied. The redox transformations of the synthesized compounds were carried out. The integrated approach based on single and mixed mechanisms of antioxidant action, namely the AOC, ARC, Folin, and DPPH assays, were applied to estimate antioxidant activities. The relationship “structure-antioxidant properties” was established for each of the antioxidant action mechanisms. The conjugation effect was shown to result in a decrease in the mobility of the hydrogen atom, thus complicating the process of electron transfer in nearly all cases. On the contrary, the conjugation in imidazolyl substituted phloroglucinols was found to enhance their activity through the hydrogen transfer mechanism. Imidazole-derived polyphenolic compounds bearing the most electron-withdrawing functionality, namely the nitro group, were established to possess the higher values for both antioxidant and antiradical capacities. It was demonstrated that in the case of phloroglucinol derivatives, the conjugation effect resulted in a significant increase in the antiradical capacity (ARC) for a whole family of the considered 2H-imidazole-derived phenolic compounds in comparison with the corresponding unsubstituted phenols. Particularly, conjugation of the polyphenolic subunit with 2,2-dimethyl-5-(4-nitrophenyl)-2H-imidazol-4-yl fragment was shown to increase ARC from 2.26 to 5.16 (10⁴ mol-eq/L). This means that the considered family of compounds is capable of exhibiting an antioxidant activity via transferring a hydrogen atom, exceeding the activity of known natural polyphenolic compounds.

Infusions of medicinal plants are investigated by potentiometry using a system of K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. Models of some flavonoids, phenol carbonic acids, ascorbic acid, and their mixtures are studied. The total polyphenol concentration in these samples is determined by the Folin–Ciocalteu method. Dependences of antioxidant activity on extraction time are obtained.

A comprehensive study of a range of flavonoids and coumarins is presented in this article. The work uses an approach that evaluates the activity of these compounds by various mechanisms: the electron transfer (ET), the hydrogen atom transfer (HAT), and the mechanism of metal chelation. The studies were carried out using the methods of the cyclic voltammetry and the potentiometry. The electrochemical behavior of these compounds was studied by the method of cyclic voltammetry; the main types of voltammograms, depending on the oxidation mechanisms, were identified. Various versions of potentiometric sensor systems have been used to detect analytical signal in approaches implemented in ET, HAT and metal chelation mechanisms. The antioxidant capacity was studied by the electron-transfer mechanism. Compounds with antioxidant properties were selected; half-reaction periods for these compounds have been determined. It has been shown that electron-donating and complexing properties directly depend on the mutual arrangement of hydroxyl groups in the molecule. The antiradical ability of the compounds has been studied. It was shown that all studied compounds inhibit peroxyl radicals. Series on the change in antioxidant and antiradical properties of compounds have been compiled. There is no correlation between the results of the study of antioxidant properties obtained using sensory systems that reveal various antioxidant mechanisms. The need to use an integrated approach in the study of antioxidant properties is shown.