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Electrochemical Methods for Total Antioxidant Capacity and Its Main Contributors Determination: a Review Open Chem., 2015; 13: 824–856 Review Article Open Access Aurelia Magdalena Pisoschi*, Carmen Cimpeanu, Gabriel Predoi Electrochemical Methods for Total Antioxidant Capacity and its Main Contributors Determination: A review Abstract: Backround: The present review focuses on molecules at various electrodes, as well as the influences electrochemical methods for antioxidant capacity and on the electroactive properties are discussed. The its main contributors assessment. The main reactive characteristics of the developed methods are viewed from oxygen species, responsible for low density lipo- the perspective of the antioxidant molecule structure protein oxidation, and their reactivity are reminded. influence, as well as from the importance of electrode The role of antioxidants in counteracting the factors material and/or surface groups standpoint. leading to oxidative stress-related degenerative diseases The antioxidant molecule-electrode surface occurence, is then discussed. Antioxidants can scavenge interaction, the detection system chosen, the use of free radicals, can chelate pro-oxidative metal ions, or modifiers, as well as the nature of the analysed matrix are quench singlet oxygen. When endogenous factors (uric the factors discussed, which influence the performances acid, bilirubin, albumin, metallothioneins, superoxide of the studied electrochemical techniques. dismutase, catalase, glutathione peroxidase, glutathione Conclusions: The electrochemical methods reviewed reductase, glutathione-S-transferase) cannot accomplish in this paper allow the successful determination of the their protective role against reactive oxygen species, total antioxidant capacity and of its main contributors in the intervention of exogenous antioxidants (vitamin C, various media: foodstuffs and beverages, biological fluids, tocopherols, flavonoids, carotenoids etc) is required, pharmaceuticals. The advantages and disadvantages as intake from food, as nutritional supplements or as of the electrochemical methods applied to antioxidant pharmaceutical products. content and antioxidant activity assay are treated and Literature study: The main advantages of interpreted, in the case of various analysed matrixes. electrochemical methods with respect to traditional, Combining advanced materials with classical electrode more laborious instrumental techniques are described: construction, provides viable results and can constitute sensitivity, rapidity, simplicity of the applied analytical an alternative for the future. procedure which does not require complicated sample pre-treatment etc. Keywords: antioxidant activity, voltammetry, The paper reviews minutiously the voltammetric, amperometry, potentiometry, foodstuffs, biological fluids. amperometric, biamperometric, potentiometric and coulometric methods for total antioxidant capacity DOI: 10.1515/chem-2015-0099 estimation. For each method presented, the electroactivity received November 16, 2014; accepted February 2, 2015. and the mechanism of electro-oxidation of antioxidant 1 Introduction to oxidative stress *Corresponding author: Aurelia Magdalena Pisoschi: University of Agronomic Sciences and Veterinary Medicine of Bucharest, Faculty and antioxidants of Veterinary Medicine, 105 Splaiul Independentei, 050097, sector 5, Bucharest, Romania, E-mail: [email protected] Oxidative stress was defined as the organism’s status Gabriel Predoi: University of Agronomic Sciences and Veterinary Medicine of Bucharest, Faculty of Veterinary Medicine, 105 Splaiul involving cell damage, by enhanced release of radical Independentei, 050097, sector 5, Bucharest, Romania or non-radical oxygenated species [1]. Oxidative stress, Carmen Cimpeanu: University of Agronomic Sciences and representing a disproportion between oxidative and Veterinary Medicine of Bucharest, Faculty of Land Reclamation reductive factors in living organisms, has been more and Environmental Engineering, 59 Marasti Blvd, 011464, sector 1, rigorously reconsidered as an interruption of the redox Bucharest, Romania © 2015 Aurelia Magdalena Pisoschi, Carmen Cimpeanu, Gabriel Predoi, licensee De Gruyter Open. This work is licensed under the Creative CommonsBrought Attribution-NonCommercial-NoDerivs to you by | University of Georgia 3.0Libraries License. Authenticated Download Date | 5/24/15 7:42 PM Electrochemical Methods for Total Antioxidant Capacity and its Main Contributors Determination 825 circuits which are part of signaling transduction pathways, chain oxidation, and, to achieve this goal, they intervene such as the cysteine moieties regulated by glutathione or in the initiation or propagation steps [7,13,14]. thioredoxins. Taking over such a definition, led to methods Antioxidants represent a wide class of chemical for distinguishing disruptions of redox signaling and compounds that fight against the oxidative processes, control. Hence, this is an answer to the requirement for including the degradation of nutrients found in diet, of uncomplicated and viable markers for the investigation materials such as rubber or plastic, of essential molecules and treatment of diseases, reactive oxygenated and found in biological media, etc [15,16]. nitrogenated species are responsible for [2,3]. Newly, with the continuously growing preoccupation During cellular respiration, the transfer of unpaired for distinguishing secure food antioxidants, the choice single electrons towards molecular oxygen may occur is represented by natural antioxidants, especially plant- resulting in free radical generation [4]. Reactive oxygen sourced. The reverse relationship between the consumption species may also result in some cell-mediated immune of fruits and vegetables and the development of oxidative functions [5]. These may be represented by either very stress-related disorders, confirmed by epidemiological unstable radicals containing a minumum of one unpaired studies, has been attributed to the presence of compounds electron, or by oxidizing non-radical species, that can endowed with high antioxidant activity [17-20]. The main promote the peroxidation of membrane lipids with biocompounds found in natural sources are phenolics accumulation of lipid peroxides [6,7]. Reactive oxygen (flavonoids or non-flavonoids), associated to health species are present at physiological levels during normal benefits resulted from the inhibition of low-density cell functioning. If the respective amounts are exceeded, lipoprotein oxidation [19,21-25]. these oxidative species are capable of attacking vital To accomplish their protective role, antioxidants biological molecules such as nucleic acids, lipids, proteins, act as free radical captors, metal chelating agents and polyunsaturated fatty acids or carbohydrates. It is known singlet oxygen quenchers [26]. They can be classed as that namely, DNA damaging, is associated with mutations, primary (named also long-term) antioxidants and as thus being the cause of the genesis and pathophysiology secondary (called also processing) antioxidants. Primary of numerous diseases: atherosclerosis, type 2 diabetes, antioxidants are mainly represented by hindered phenols neurodegeneration (Alzheimer, Parkinson, amyotrophic and secondary aryl amines, whereas the secondary lateral sclerosis), infections, cardiac impairment and antioxidants’ class contains organophosphites and cancer [8]. thioesters [27]. The primary antioxidants behave mainly as Different types of oxygen-centred free radicals, called radical captors, hydrogen donors or chain breakers, while reactive oxygen species (ROS), comprise superoxide secondary antioxidants are mainly known as peroxide - anion radical (O2· ), hydroxyl (HO·), peroxyl (ROO·) and decomposers or singlet oxygen quenchers [25-27]. alkoxyl (RO·) radicals, and nitric oxide (NO). Hydroxyl Endogenous antioxidants (part of the organism’s (half-life of nanoseconds) and alkoxyl (half-life of complex defense system) are uric acid, bilirubin, seconds) free radicals are endowed with high reactivity albumin, metallothioneins, as well as enzymes towards biomolecules, whereas, superoxide anion, lipid superoxide dismutase, catalase, glutathione peroxidase, hydroperoxides and nitric oxide were reported as having glutathione reductase, glutathione-S-transferase. lower reactivity [9]. Alongside the afore-mentioned Exogenous antioxidants are natural (vitamin C, vitamin radicalic oxygenated species, nonradicalic reactive oxygen E, carotenoids, phenolic compounds such as flavonoids, species are also known, such as singlet oxygen, hydrogen phenolic acids, anthocyanins, proteins such as transferrin, peroxide, or hypochlorous acid [10]. ceruloplasmin or albumin, some minerals like Se) or During normal biological processes, reactive oxygen synthetic compounds, such as butylated hydroxyanisole, species are formed in small amounts, and the antioxidant butylated hydroxytoluene, gallates, etc. It is recognized systems of the organism can effectively deplete them. that vegetables, fruits, grains and beverages such as tea, However, it has been confirmed that, under stress juice and wine constitute significant sources of natural conditions such as the intake of drugs, the action of exogenous antioxidants [25,28,29]. Their intake has been UV radiation or metabolic dysfunctions, these ROS can confirmed to lower the oxidative stress [30-32]. Another be generated in sufficient amounts, as to exceed the adequate manner to fight against the deleterious action normal antioxidant defense capabilities of the organism, of free radicals is represented
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