Food Chemistry 221 (2017) 1371–1381

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Review

Electrochemical methods as a tool for determining the antioxidant

capacity of food and beverages: A review
Jorge Hoyos-Arbeláez a, Mario Vázquez a, José Contreras-Calderón b,⇑
a
Interdisciplinary Group of Molecular Studies (GIEM), Chemistry Institute, School of Exact and Natural Sciences, University of Antioquia, Medellín, Colombia
b
BIOALI Research Group, Food Department, Faculty of Pharmaceutical and Food Sciences, University of Antioquia, Street 67 No. 53-108, Medellin, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: The growing interest in functional foods had led to the use of analytical techniques to quantify some
Received 25 July 2016 properties, among which is the antioxidant capacity (AC). In order to identify and quantify this capacity,
Received in revised form 2 November 2016 some techniques are used, based on synthetic radicals capture; and they are monitored by UV–vis spec-
Accepted 2 November 2016
trophotometry. Electrochemical techniques are emerging as alternatives, given some of the disadvan-
Available online 4 November 2016
tages faced by spectrophotometric methods such as the use of expensive reagent not environmentally
friendly, undefined reaction time, long sample pretreatment, and low precision and sensitivity. This
Keywords:
review focuses on the four most commonly used electrochemical techniques (cyclic voltammetry, differ-
Antioxidant capacity
Electrochemical methods
ential pulse voltammetry, square wave voltammetry and chronoamperometry). Some of the applications
Cyclic voltammetry to determine AC in foods and beverages are presented, as well as the correlation between both spec-
Differential pulse voltammetry trophotometric and electrochemical techniques that have been reported.
Square-wave voltammetry Ó 2016 Elsevier Ltd. All rights reserved.
Chronoamperometry

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
2. Electrochemical techniques as alternative for the determination of AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
2.1. Electrochemical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
2.1.1. Cyclic voltammetry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
2.1.2. Differential pulse voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
2.1.3. Square-wave voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
2.1.4. Amperometric method (Chronoamperometry) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1375
3. Electrochemical methods applied to determine AC in food and beverages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1375
3.1. Application of cyclic voltammetry for determining AC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1375
3.2. Application of Differential Pulse Voltammetry for determination of AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1377
3.3. Application of square wave voltammetry for determination of AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1377
3.4. Application of chronoamperometry for determination of AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1378
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
Conflict of interest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379

1. Introduction diseases, neurodegenerative disorders, aging, hypertension,

Parkinson, Alzheimer, acute respiratory distress syndrome
The discovery of the role of free radicals in diseases and other diseases (Ratnam, Ankola, Bhardwaj, Sahana, &
such as cancer, diabetes, cardiovascular disease, autoimmune Kumar, 2006) has produced a revolution in research in
order to identify synthetic compounds or molecules
⇑ Corresponding author. present in foods that may combat the activity of free
E-mail address: jose.contrerasc@udea.edu.co (J. Contreras-Calderón). radicals.

http://dx.doi.org/10.1016/j.foodchem.2016.11.017
0308-8146/Ó 2016 Elsevier Ltd. All rights reserved.
1372 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
Free radicals are species that have one or more unpaired elec-
trons, which makes them highly reactive and cause oxidative
stress, which is defined as an ‘‘unbalance between oxidants and
antioxidants in favor of oxidants, which can lead to damage”
(Sies, 1997).
Oxidative stress can damage lipids, oxidizing polyunsaturated
fatty acids; proteins, oxidizing the amino acids, enzymes, carbohy-
drates and DNA in cells and tissues resulting in membrane damage,
fragmentation or crosslinking of molecules such as DNA and even
cause DNA fragmentation-induced cell death and lipid peroxida-
tion (Beckman & Ames, 1998).
Antioxidants are molecules that counteract free radicals and
prevent the damage caused by them. These substances may reduce
oxidative damage by reacting with free radicals before they reach
biological targets, preventing chain reactions or preventing oxygen
activation to more reactive forms (Ratnam et al., 2006). Depending
on the access and diversity of natural products present in an envi-
ronment, and also on eating habits, the use of natural or synthetic
supplements is necessary to guarantee the daily needs of such
compounds in the body (Guan, Chu, Fu, & Ye, 2005).
Fruits and vegetables contain several antioxidants like vitamin
C, whose importance is due to its capacity to reduce the incidence
of chronic and degenerative diseases; it can be found in apples,
bananas, broccoli, orange juice, peppermint, among others. Vita-
min E is one of the major membrane protectants against reactive
oxygen species and lipid peroxidation; it is present in grains, green
tea, olives and olive oil, and sunflower seeds (Oroian & Escriche,
2015). On the other hand, Carotenoids are associated with a posi-
tive influence on certain types of cancer, and can be found in
orange juice, sweet potatoes, and red carrots, among other vegeta-
bles. Polyphenols are the major class of antioxidants derived from
the diet, and it has been reported that the intake of polyphenols is
important due to their activity preventing cardiovascular disease,
anti-inflammatory and anti-viral activity; they are also said to pre-
vent diabetes among other health benefits. Polyphenols can be
found in several fruits and vegetables like onions, lemons, citrus
peel, honey, wine, grapes, red cabbage, dried ginger, mango, straw-
berries, whiskey, chocolate and cocoa, among others (Oroian &
Escriche, 2015).
Usually, the identification and quantification of these substances
in foods are performed by using analytical techniques such as HPLC
coupled with different detection systems, gas chromatography,
micellar electrokinetic capillary chromatography, capillary elec-
trophoresis, UV–visible spectrophotometry, potentiometry, in vitro
and in vivo analyses (André, Castanheira, Cruz, Paseiro, & Sanches-
Silva, 2010; Hernández-Borges, González-Hernández, Borges-
Miquel, & Rodríguez-Delgado, 2005; Pinelli et al., 2008; Wang,
Melnyk, Tsao, & Marcone, 2011; Ćavar, Kovač, & Maksimović, 2012).
For the evaluation of the AC (ability to capture a radical or
reduce an agent antioxidant), methods based on the spectrophoto-
metric monitoring of formation or disappearance of radical nature
chromogenic compounds are often used. Among them are DPPH
(2,2-diphenyl-1-picrylhydrazyl), ABTS 2,20 -azino-bis(3-ethylbenzo
thiazoline-6-sulphonic acid), ORAC (Oxygen radical Absorbance
Capacity), FRAP (Ferric reducing ability of plasma), DCFH-DA (dich
lorofluorescein-diacetate). As the presence of polyphenols is related
to the AC of vegetables and fruits, the determination of total
polyphenols in a sample is a good indicative of the AC of the food.
These methods are usually monitored by UV–Visible spectropho-
tometry and some of them give a direct measurement of AC (ABTS
and DPPH) because they are based on a direct capture of the radical
by the sample, and the others (FRAP and Folin) give an indirect
measurement of the AC because they are based on the ability of
the sample to reduce an Fe-complex (in the case of FRAP
assay), or to reduce the Folin-Ciocalteu reagent (a mixture of
phosphomolybdate and phosphotungstate) in the case of total
polyphenols determination (Arab, Alemzadeh, & Maghsoudi,
2011; Brand-Williams, Cuvelier, & Berset, 1995; Contreras-
Calderón, Calderón-Jaimes, Guerra-Hernández, & García-Villanova,
2011; Mantle et al., 1998; Prior & Cao, 1999; Vassalle et al., 2004).
Electrochemical techniques emerge as an alternative strategy
for a quick, precise, and economic measurement of the AC of foods
and beverages when we consider some of the characteristics of
conventional spectrophotometric methods for determining their
AC, like long analyses and sample preparation time, expensive
equipment, use of expensive reagents unfriendly to the environ-
ment, and undefined reaction times (Alam, Bristi, &
Rafiquzzaman, 2013; Bors, Michel, & Saran, 1984; Huang, Boxin,
& Prior, 2005; Kabouche, Kabouche, Öztürk, Kolak, & Topçu,
2007; Kooy, Royall, Ischiropoulos, & Beckma, 1994; Miller,
Rice-evans, Davies, Gopinathan, & Milner, 1993; Ordoudi &
Tsimidou, 2006; Prior, Wu, & Schaich, 2005; Robak & Gryglewski,
1988; Singleton, Orthofer, & Lamuela-Raventós, 1998). Other
advantages of these techniques will be discussed further in this
review.
Currently a review of such methods applied to food does not
exist in the literature. Therefore the goal of this work is to present
to the scientific community the advantages of using alternative
electrochemical methods to determine AC compared with the con-
ventional spectrophotometrical methods.
2. Electrochemical techniques as alternative for the
determination of AC
An alternative for the experimental determination of the AC of
foods and beverages is presented here by using electrochemical
tools which have gained interest in recent years, in order to deter-
mine the total reducing power, especially of low molecular weight
antioxidants (Piljac-Žegarac, Valek, Stipčević, & Martinez, 2010).
The total reducing power is defined as the ability of certain mole-
cules to act as electron donors or protons receptors in oxidation-
reduction reactions. An advantage of these electrochemical meth-
ods is that they allow quick, simple and inexpensive determina-
tions; and in some cases, they allow measurements in the
presence of compounds that interfere other methods such as the
case of ascorbic acid in juice, which can mask the existence of other
organic acids in lower concentrations (Sousa, da Rocha, Cardoso,
Silva, & Zanoni, 2004), or when working with colored samples that
do not allow direct measurement by spectrophotometric tech-
niques, like in the case of as wine and fruit juice with high content
of anthocyanins (Lino et al., 2014).
Another benefit of electrochemical techniques is that they allow
a large number of experimental parameters to be obtained that
help to characterize the phenolic compounds present in the sam-
ples. This is of relevance for assigning which species have greater
contribution to AC. Among these parameters may be mentioned
the half-wave potential, the voltammetric charge, and peak current
(Piljac-Žegarac et al., 2010). Still another possibility offered by
electrochemical techniques is to quantify the antioxidant com-
pounds with very good detection limits (Ceballos & Fernández,
2000; Medeiros, Rocha-Filho, & Fatibello-Filho, 2010). This allows
to perform analyses both of AC determination and quantification
of these compounds in the same equipment.
2.1. Electrochemical techniques
Among the several electrochemical techniques that exist, the
most commonly used and reported are cyclic voltammetry, square
wave voltammetry, differential pulse voltammetry and chronoam-
perometry (André et al., 2010; Prior & Cao, 1999). The electrochem-
ical techniques that will be discussed in the present work are the
following:
 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381 1373

Fig. 1. (i) Potential-time excitation signal in cyclic voltammetry. (ii) Typical cyclic voltammogram for a reversible redox process (O + ne
R). (iii) Voltammogram for Quasi-
reversible system (Curve B) and irreversible system (Curve A). (iv) Potential-time excitation signal in differential pulse voltammetry. (v) Potential-time excitation signal in
square wave voltammetry. (vi) Square wave voltammogram for reversible process. Curve A: Forward current. Curve B: Reverse current. Curve C: net current. (vii) Potential-
time waveform in a chronoamperometric experiment. (viii) Current-time response in a chronoamperometric experiment (Bagotsky, 2006; Bard & Faulkner, 2001; Wang,
2001).
1374 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
It is worth noting that the theoretical foundations presented
below apply to reversible electrochemical reactions, which differ
from chemical reversibility in that the first occur on the surface
of an electrode. It is also important to clarify that the mathematical
developments presented in the text refer to processes of oxidation
on the electrode governed by diffusion of the species to be oxidized
from the bulk of the solution to the electrode surface (Bard &
Faulkner, 2001).
2.1.1. Cyclic voltammetry
Cyclic voltammetry (CV) is the most widely used techniques for
acquiring qualitative information about the properties and charac-
teristics of the electrochemical processes. This technique provides
considerable information on the thermodynamics of redox pro-
cesses and kinetics of heterogeneous electron-transfer reactions,
as well as on coupled chemical reactions or adsorption processes
(Sawyer, Sobkowiak, & Roberts Jr, 1995; Wang, 2001).
Cyclic voltammetry consists of scanning linearly the potential of
a stationary working electrode (WE) (in an unstirred solution)
using a triangular potential waveform as seen in Fig. 1-i. Depend-
ing on the information sought, single or multiple cycles can be
used. The potentiostat/galvanostat measures the current generated
by the redox process resulting on a plot of current vs applied
potential.
Considering the reversible system O + ne
R, where O is an potential.
oxidized specie, R is the reduced form of the same species, and
ne is the number of electrons needed for the reaction to take place,
when the potential-time perturbation is applied to the system. The
expected response is shown in Fig. 1-ii for a single potential cycle.
It is assumed that initially, only the R form is present. A positive-
scanning potential is chosen for the first half of the cycle, starting
from a potential value where no reaction occurs. As the applied
potential approaches to the characteristic standard reduction
potential (E°) for the redox process, an anodic current begins to
increase until a peak is reached. After passing the potential region
where the oxidation process takes place, the potential sweeping
direction is reversed. During the reverse scan, the O molecules
(generated in the forward scan, and accumulated near the
electrode surface) are reduced back to R and a cathodic peak is
observed.
For reversible systems, the peak current, ip, will be proportional
to the concentration of the analyte in the solution bulk, according
to the Randle-Sevcik equation:
ip ¼ ð2:69  105 Þn3=2 ACD1=2 m1=2 ð1Þ
where n is the number of transferred electrons, A is the electrode’s
electroactive area (in cm2), C is the analyte’s bulk concentration (in
mol L1), D is the analyte’s diffusion coefficient (in cm2 s1), and v is
the scan rate (in V s1).
The separation between peak potentials, expressed in volts, for
reversible systems, is given by:
0:059
DEp ¼ Ep;a ¼ Ep;c ¼ ð2Þ
n nF
where Ep,a is the anodic peak’s potential, Ep,c is the cathodic peak’s
potential, n is the number of transferred electrons.
Thus, the peak separation can be used to determine the number
of electrons transferred, and also as a criterion for a Nernstian
behavior, understood as the conditions on which the potential var-
ies linearly with the logarithm of the activity of the species
(Bagotsky, 2006; Bard & Faulkner, 2001).
For quasi-reversible systems, the current is controlled by both
the charge transfer and the mass transport of the analyte from
the solution’s bulk towards the electrode surface. The voltammo-
grams for quasi-reversible systems are more drawn-out and exhi-
bit a large separation between peak potentials compared to those
of a reversible system (Fig. 1-iii, curve B)
For irreversible systems (those in which the electron transfer is
slow) the individual peaks are widely separated and reduced in
size as shown in Fig. 1-iii, curve A.
Among the main uses of cyclic voltammetry are studies of reac-
tion mechanisms, studies of adsorption processes, quantitative
applications, stability of reaction products, determining the pres-
ence of intermediates in redox reactions, reaction kinetics,
reversibility of a reaction, and electron transfer kinetics (Wang,
2001).
The benefits of the cyclic voltammetry improved remarkably
when pulse techniques were introduced. This way, greater sensi-
tivity was achieved by discounting the influence of capacitive cur-
rent (Bard & Faulkner, 2001).
2.1.2. Differential pulse voltammetry
Differential pulse voltammetry (DPV) is a technique where
fixed-magnitude pulses are superimposed on a linear potential
ramp. Fig. 1-iv shows the typical potential-time excitation signal
for DPV, where the response current is sampled twice, just before
the pulse application (at 1 in Fig. 1-iv) and again late in the pulse
life (at 2 in Fig. 1-iv). The first current is subtracted from the
second and the current difference is plotted versus the applied
The pulse length usually takes values between 40 and 60 ms,
and the interval between pulses varies from 0.5 to 5 s. By sampling
the current just before the potential is changed, the amount of
capacitive current (from the charging of the electrochemical dou-
ble layer) is minimized in the current measurement (Sawyer
et al., 1995).
The typical response for this technique is a voltammogram that
presents current peaks, where the peak’s height is directly propor-
tional to the concentration of the analyte according to:
 
nFADa=2 C 1  r
ip ¼ pffiffiffiffiffiffiffiffiffi ð3Þ
ptm 1 þ r
where tm is the time after application of the pulse at which the cur-
rent is sampled, r = exp [(nF/RT)(DE/2)], R is the ideal gas constant
(8.314 J mol1 K1), T is the temperature in Kelvin, n is the number
of transferred electrons, F is the Faraday constant
(96485.4 C mol1), A is the electrode’s electroactive area, D is the
analyte’s diffusion coefficient, and C is the bulk’s concentration of
the analyte (Wang, 2001).
The peak potential can be used to identify species. The peak-
shaped response obtained in DPV results in improved resolution
between two species with similar redox potentials. In different sit-
uations, peaks separated by 50 mV may be measured. Such quanti-
tation depends not only upon the corresponding peak potentials
but also on the widths of the peaks. The width of the peak (at half
height) is related to electrons transferred in the process:
3:52RT
W 1=2 ¼ ð4Þ
where R is the gas constant, T is the system’s temperature in Kelvin
scale, n is the number of transferred electrons, and F is the Faraday
constant (96485.4 C mol1).
2.1.3. Square-wave voltammetry
Square Wave Voltammetry (SWV) is a large-amplitude differen-
tial technique in which a wave form composed of a symmetrical
square wave, superimposed on a base staircase potential, is applied
to the working electrode (Osteryoung & Osteryoung, 1985).
Fig. 1-v shows the typical potential-time excitation signal
for SWV, where the current is sampled twice during each
 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
square-wave cycle, once at the end of the forward pulse (at 1 in
Fig. 1-v) and once at the end of the reverse pulse (at 2 in Fig. 1-v).
DE corresponds to step height; Esw, pulse amplitude; s, square-
wave period; Td, delay time before the first pulse is applied to
the working electrode.
Fig. 1-vi shows the typical voltammogram obtained for a rever-
sible electron transfer, where curve A corresponds to the current
measured at 1 along the potential sweep, or forward current; curve
B corresponds to the current measured at point 2 along the poten-
tial sweep, or reverse current; and C corresponds to net current,
calculated by subtracting reverse current from forward current
(Mirceski, Komorsky-Lovric, & Lovric, 2007; Osteryoung &
Osteryoung, 1985; Wang, 2001).
Excellent sensitivity accrues from the fact that the net current is
larger than either the forward or the reverse components (since it
is the difference between them); the sensitivity is higher than that
of differential pulse voltammetry (in which the reverse current is
not used). Very Low detection limits near 1  108 M, can be
attained (Wang, 2001) coupled with the effective discrimination
against the charging background current.
In SWV the response current is directly proportional to the ana-
lyte concentration according to:
nFAD1=2 C b
i¼ pffiffiffiffiffiffi WðDE; Esw Þ ð5Þ
ps
i is the measured current on each pulse, n is the number of elec-
trons transferred, F is the Faraday constant, A is the electrode’s
electroactive area, D is the analyte’s diffusion coefficient, Cb is the
bulk concentration of the analyte, s is the pulse width, and W is
the dimensionless current function, which depends on step height,
DE, and square wave amplitude, Esw (Bard & Faulkner, 2001).
2.1.4. Amperometric method (Chronoamperometry)
Chronoamperometry (CA) involves stepping the potential of the
WE from a value at which no faradaic reaction occurs to a potential
at which the surface concentration of the electroactive species is
effectively zero. The response current is recorded as function of
time.
Fig. 1-vii shows a typical potential-time wave and Fig. 1-viii
shows the typical response of a chronoamperometric experiment.
As mass transport under these conditions is solely by diffusion,
the current-time curve reflects the change in the concentration
gradient in the vicinity of the electrode surface (Wang, 2001). At
the beginning of the experiment, a large current is observed, which
is due to the charging of the electrode’s Electrical Double Layer
(EDL) as required by the potential change. The maximum current
and the EDL charging depend on the electrode’s system, size, and
parameters used (Potential, time, etc). When this process has
ended, the faradaic component of current remains and it in turn
will reflect the changes in concentration near the electrode’s sur-
face (Bagotsky, 2006). This involves a gradual expansion of the dif-
fusion layer associated with the depletion of the reactant, and
hence the decreased slope of the concentration profile as time
progresses.
Accordingly, the current (at a planar electrode) decays with
time as given by Cottrell equation (Wang, 2001):
1=2
nFACD 1=2
iðiÞ ¼ pffiffiffiffiffiffi ¼ kt ð6Þ
ps
where n is the number of electrons transferred, F is the Faraday con-
stant, A is the electrode’s electroactive area, C is the bulk concentra-
tion of the analyte, D is the analyte’s diffusion coefficient. This
expression can be simplified as the right member of the equation,
where k is the collection of constants for the given system (n, F,
A, C, D), and t is time expressed in seconds.
1375
3. Electrochemical methods applied to determine AC in food
and beverages
This review presents some applications of the electrochemical
methods described above in order to determine the AC of different
samples.
Table 1 shows some of the advantages and disadvantages of the
electrochemical methods used for determining the AC (Ceballos &
Fernández, 2000; Hart & Wring, 1994, 1997; Jin, Kwon, Park, Kim, &
Jung, 2008; Medeiros et al., 2010; Novak, Šeruga, & Komorsky-
Lovrić, 2010; Piovesan, Jost, & Spinelli, 2015).
3.1. Application of cyclic voltammetry for determining AC
Cyclic voltammetry has been widely used for the determining
the total AC of low-molecular weight antioxidants present in ani-
mal plasma, biological fluids, edible plants and fruits (Chevion,
Roberts, & Chevion, 2000).
Table 2 shows some works that have used cyclic voltammetry
to determine the AC of samples or standards using different elec-
trodes and monitoring several parameters.
From the data obtained in CV, it follows that the most important
parameters are the peak potential and the peak current. The peak
potential correlates with the type of reductant; low oxidation
potentials are associated with a greater facility or strength of a
given molecule for the electron donation and, thus, to act as
antioxidant (Prior & Cao, 1999); peak current is directly propor-
tional to the antioxidant concentration according to Randles-
Sevcik equation (Eq. (1)).
In the work presented by (Piljac-Žegarac et al., 2010), the
authors report the determination of the AC of 10 different fruit
tea infusions using the frequent spectrophotometric methods,
ABTS, FRAP, DPPH and Folin; and they correlate the results with
the ones obtained by applying the electrochemical approach of
Cyclic Voltammetry. For all the tea samples, they determine the
area underneath the bigger anodic peak, the one that appears
around 440 mV, and the value of the area is called Q600, charge
up to a potential of 600 mV. The correlation of all the methods is
carried out through the AC Index (ACI), which was determined
by assigning an equal weight to all the assays. An index value of
100 was assigned to the best score for each test, and the corre-
sponding index score was calculated for each sample. The Index
score was calculated using the formula ACI = (sample score/best
score)  100. For all the samples analyzed in this work, sample
FT3, which is composed of Hibiscus flower (25%) and Rose hip fruit
(75%), showed the higher score in all the assays including the Q600.
This fact confirms that the results derived from CV are reliable and
comparable to the results of other commonly employed methods.
The main reason for the correlation obtained for the spec-
trophotometric methods mentioned above (ABTS, DPPH, FRAP
and Folin) and the electrochemical ones is that both the
spectrophotometric and electrochemical are based on a single
Table 1
Some advantages and disadvantages of the electrochemical methods applied to the
determination of AC.
Advantages Disadvantages
Quick and simple measurements Total reducing power (including
interferent molecules with no
antioxidant capacity)
Good detection limits Not selective to a family of molecules
(1  1007 M) (i.e. carotenoids, polyphenols) unless
the electrode is modified
Small amount of sample (up to
50 lL using screen printed
electrodes)
Easy sample preparation
1376 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381

Table 2
Cyclic voltammetry applied to the determination of AC.

Working electrode Parameter Sample or standard References

MWCNT/GCE Ip Quercetin Abdel-Hamid, Rabia, and Newair (2013)
Au & Cysteamine/Au Ipa Quercetin, daizeol, plant extracts Wang et al. (2007)
GCE Ipa Commercial orange juice, caffeic, chlorogenic Sousa et al. (2004)
and ascorbic acid
GCE Ep2, Ipc/Ipa, Q600 Fruit tea infusions Piljac-Žegarac et al. (2010)
CPE EI Coffee samples Oliveira-Neto et al. (2016)
GCE I DPPH, trolox, orange juice, red wine, black Milardovic, Ivekovic, and Grabaric (2006)
currant juice
BDD Qp Commercial margarine and mayonnaise Medeiros et al. (2010)
GCE Ipa2 Sauvignon blanc juice Makhotkina et al. (2012)
GCE Epa, Ipa, Q Grape pomace, Gallic acid, catechin, quercetin José Jara-Palacios et al. (2014)
PBHR-MWCNT CPE Ip Wine, tea, t-resveratrol, caffeic acid Granero, Fernández, Agostini, and Zón (2010)
BDD Polarizability (a), QC3 Quercetin, morin, catechin, chrysin, fisetin, Ferreira, Greco, Delarmelina, and Weber (2015)
luteolin, kaempferol, apigenin
GC disk, Pt disk Ip BHA, TBHQ, BHT dos Santos Raymundo, da Silva, Paula, Franco, and Fett (2007)
GCE Ep , I p Ginger infusion Chaisuksant, Damwan, and Poolkasem (2012)
CF-UME Ip Vegetable oils Ceballos and Fernández (2000)
GCE Epa, Ipa, ARP DPPH, Gallic acid, Eugenol, Coumarin Arteaga et al. (2012)

MWCNT: Multi-walled Carbon nanotubes, Au: Gold electrode, GCE: Glassy Carbon Electrode, CPE: Carbon paste electrode, BDD: Boron-doped diamond, PBHR: Brassica napus
hairy roots, CF-UME: Carbon fiber ultra-microelectrode, Ip: Peak current, Ipa; Anodic Peak Current, Ipc: Cathodic peak current, Ep2: Second peak potential, Qp: Peak charge, Q600:
Charge of the anodic peaks under 600 mV, EI: Electrochemical index, QC3: Carbon 3 charge, ARP: anti-radical power, BHA: Butyl hydroxyanisole, TBHQ: tert-butylhydro-
quinone, BHT: Butyl hydroxytoluene.

electron transfer mechanism (Benzie & Strain, 1996; Brand-
Williams et al., 1995; Miller et al., 1993; Singleton et al., 1998).
Regarding those works reported in the Table 2, some interesting
facts about application of the electrochemical technique are
highlighted.
There are reports in which different materials are used as work-
ing electrodes, whether they are unmodified (e.g. Pt, Glassy Carbon
Electrode (GCE), and Boron-doped Diamond electrode (BDD)) or
modified (Arribas, Martínez-Fernández, & Chicharro, 2012;
Chevion et al., 2000; Masek & Chrzescijanska, 2015; Masek,
Chrzescijanska, & Zaborski, 2014; Masek, Chrzescijanska,
Zaborski, & Maciejewska, 2012; Procházková, Boušová, &
Wilhelmová, 2011). From an instrumental point of view, some-
times the electrochemistry tool is applied prior to the use of other
instrumental techniques such as HPLC-MS (Makhotkina &
Kilmartin, 2012), and sometimes the determination of the AC is
obtained indirectly by considering the reducing properties of flavo-
noids when they affect metallic nanoparticles, together with its
UV–Visible spectrum (Wang, Zhou, Zhu, Huang, & Li, 2007).
Another study that proposed an amperometric method using the
same reagent employed in the spectrophotometrically determina-
tion of AC, has showed interesting results with several samples of
tea, wine, and juice (Milardovic, Ivekovic, & Grabaric, 2006).
While most of the research in antioxidant properties is nor-
mally based on a particular family of food products, and makes it
possible to compare the various analyzed responses from a quanti-
tative point of view, it is necessary to define specific parameters,
such as the case of ACI proposed by Piljac-Žegarac et al. (2010).
From the standpoint of products to which it is possible to deter-
mine its AC we can note that even in the case of relatively complex
matrices, as is the case of pomaces, the CV electrochemical tech-
nique is shown suitable to quantify phenolic compounds from
the analysis of the peak currents obtained in the study (José Jara-
Palacios, Hernanz, Luisa Escudero-Gilete, & Heredia, 2014). In the
case of activated glassy carbon working electrode, this advantage
is based on the fact that, in some potentially interfering cases like
ascorbic acid, it is not deposited on the surface of the modified
electrode (Sousa et al., 2004).

Table 3
Differential Pulse Voltammetry applied to the determination of AC.

Working electrode Parameter Sample or standard References

Ir, Rh, Pt, Au, Ag, Cu, Co, Ni Ep, Ip Tumbo (Passiflora mollisima), Camu-camu (Myrciaria Baldeón et al. (2015)
dubia) juices
Hg Film Ip Green tea, ascorbic acid, citric acid, glucose, Korotkova, Karbainov, and Shevchuk (2007)
polyvinylpyrrolidone
CPE EI Red, white, rose, sparkling, fortified wine, grape juice, Lino et al. (2014)
nectar juice
BDD Ep, Ip Commercial margarine and mayonnaise Medeiros et al. (2010)
CPE EI Coffee samples Oliveira-Neto et al. (2016)
GCE TAP Melissa officinalis L., Fragaria L., Origanum majorana L., Głód, Kiersztyn, and Piszcz (2014)
Salvia officinalis L., Equisetum arvense L., Tussilago farfara
L., Hyssopus L., Urtica L., Mentha arvensis L., Calendula L.,
Alcea rosea L., Melilotus officinalis L. extracts
GCE Ep, Ip Cabernet Sauvignon wine, V. vinifera grapes, raspberry Aguirre et al. (2010)
fruits
NiO-graphene/GCE Ep, Ip Ascorbic acid Liu et al. (2014)
GCE Ep, Ip Croatian red wines Šeruga et al. (2011)
MWCNT/GCE Ep, Ip Commercial brandy and cognac Ziyatdinova et al. (2014)
GCE Ep, Ip Cytisus multiflorus, Filipendula ulmaria and Sambucus Barros, Cabrita, Boas, Carvalho, and Ferreira (2011)
nigra
CS-Fe2O3-GO/GCE Ep, Ip Gallic acid, Red and white wine Gao et al. (2015)
Poly-CDDA/GCE Ep, Ip Ascorbic acid, dopamine, uric acid, Ensafi, Taei, and Khayamian (2009)

MWCNT: Multi-walled Carbon nanotubes, GCE: Glassy Carbon Electrode, CPE: Carbon Paste Electrode, Ip: Peak Current, Ep: Peak potential, EI: Electrochemical index, TAP:
Total Antioxidant Power, CS: Chitosan, GO: Graphene oxide, CDDA: 3-(5-chloro-2-hydroxyphenylazo)-4,5-dihy- droxynaphthalene-2,7-disulfonic acid).
 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
While this review is specifically oriented to the study of antiox-
idant properties in food and beverages, AC can be evaluated by
electrochemical methods in clinical studies evaluating the pres-
ence of compounds with AC in different biological means
(Chevion et al., 2000).
3.2. Application of Differential Pulse Voltammetry for
determination of AC
Differential Pulse Voltammetry (DPV) has been applied to
antioxidant quantification due to the good detection limits
achieved through it. Gao et al. (2015) reported a detection limit
by using DPV of 1.5  107 M for Gallic Acid by using a modified
electrode.
Table 3 shows some works where DPV has been applied to
determine AC and to quantify antioxidant’s concentration in
diverse samples.
Now, concerning previously reported research on the subject,
the use of different types of electrodes is verified. Glassy carbon,
carbon paste, and modified glassy carbon are some of the most
used. The first two kinds are reported in the study of wine samples
for catechin quantitation with detection limits of 1.77 mg L1
(Šeruga, Novak, & Jakobek, 2011), as well as for the analysis of
anthocyanins in the same drink, directly over a simple dilution
with no need of buffer addition (Aguirre et al., 2010).
Carbon paste electrodes have been used directly over coffee
infusions for determining their electrochemical index (EI) obtained
from the current, and peak’s potential resulting from these samples
(Oliveira-Neto et al., 2016).
Glassy carbon electrodes can be used after surface modifica-
tions which improve their sensitivity. These modifications can be
achieved through different ways; for instance, by applying other
materials to the electrode’s surface, as in the case of carbon nan-
otubes for determining the AC in cognac and brandy
(Ziyatdinova, Salikhova, & Budnikov, 2014), or using the synergy
created with several modification agents to build a multiple
system. The latter has been verified by analyzing the response of
gallic acid (Gao et al., 2015).
It is worth noting the work carried out by Lino et al. (2014),
where the AC of different types of wines like red, white, rose, for-
tified and sparkling wines was determined. They show an interest-
ing correlation between the electrochemical method applied to
determine AC (EI) and the conventional method of DPPH radical,
expressed in EC50 (this represents thereby the amount of wine nec-
essary to produce 50% of decolorization of DPPH in relation to
blank control). The Pearson’s correlation was 0.9110, and the
Table 4
Square Wave Voltammetry applied to the determination of AC.
Working electrode Limit of Detection
GCE 4.2 ng mL1 for trans-resveratrol
Guanine/GCE, Adenine/GCE 0.29 mg L1, 0.99 mg L1 for AA
BDD 1 lM for BHA
0.68 lM for BHT
CF-UME, Pt Band-UME N. R.
GCE 0.04 lM for EGCG
2.48 lM for EGC
GCE 0.326 lM for ECG
4.27 lM for EC
PVP/CPE 0.04 lM for Kaempferol
Guanine/GNR/GCE 0.05 mg L1 for AA
MWCNT/GCE 2.36 lM for Quercetin
Carbohydrate/GCE
GCE: Glassy Carbon Electrode, AA: Ascorbic acid, BDD: Boron-doped diamond, BHA: Butyl hydroxyanisole, BHT: Butyl hydroxytoluene, CF-UME: Carbon fiber ultra-micro-
electrode, N. R.: Not reported, EGCG: Epigallocatechin gallate, EC: Epicatechin, ECG: Epicatechin gallate, PVP/CPE: Carbon paste electrode modified with poly(vinylpyrroli-
done), Guanine/GNE/GCE: Guanine on graphene nano ribbon-modified glassy carbon electrode, MWCNT: Multi-walled carbon nanotubes.
1377
authors conclude that the results obtained reinforce the use of
the electroanalytical method, which in turn is less expensive, sim-
pler and, at least two times faster.
The EI concept was first proposed by the Escarpa group (Blasco,
González, & Escarpa, 2004; Escarpa, 2012), by taking into account
the voltammetric parameters, the anodic peak potential (Epa) and
the anodic peak current (Ipa) independently. Thus, since the lower
is the potential (thermodynamic parameter), the higher is the elec-
tron donor ability; likewise, the higher is the peak current (kinetic
and concentration parameter), the higher is the electron transfer
rate and/or the amount of electroactive species (Escarpa, 2012;
Makhotkina & Kilmartin, 2009), the EI was calculated by using
the Eq. (7).
Ipa1 Ipa2 Ipan
EI ¼ þ þ  þ ð7Þ
Epa1 Epa2 Epan
where Ipa1 is anodic current of peak 1, Epa1 is the anodic potential of
the same peak.
3.3. Application of square wave voltammetry for determination of AC
Like in the case of the DPV, SWV has been used to identify and
quantify antioxidants within a different food-and-beverage’s
matrix, obtaining thereby very good detection limits as reported
by Novak et al. (2010). They achieved a detection limit of 40 nM
for Epigallocatechin gallate in green and black teas. Table 4 shows
some works where SWV has been applied to quantify antioxidant’s
concentration in diverse samples by using the peak current as a
working parameter.
When we consider the characteristics of this technique in rela-
tion to the elimination of the capacitive current, it has been used in
different food matrixes. In some cases, using GC as working elec-
trode, it has been verified the possibility of studying products that
are not electrochemically active if CV is used, due to the formation
of polymeric films that block the electrode’s surface (Novak et al.,
2010).
GC electrodes have also been used to electrochemically adsorb
compounds of interest previous to the anodic scan, e.g. trans-
resveratrol. By using this stripping procedure very low detection
limits have been achieved (Airado-Rodríguez, Galeano-Díaz, &
Durán-Merás, 2010).
Similar to what has been done with other techniques; some
studies modifying the electrode’s surface have been carried out.
For example, in the case of carbon paste, poly (vinylpirrolidone)
has been incorporated into the paste to take advantage of the
Sample or standard References
Red wine and trans-Resveratrol Airado-Rodríguez et al. (2010)
Flavor and flavored waters Barroso et al. (2012)
Mayonnaise and margarine Medeiros et al. (2010)
Edible oils Noel Robledo, Alicia Zón, Daniel Ceballos, and
Fernández (2011)
Green and black teas Novak et al. (2010)
EC and ECG Novak, Seruga, Komorsky-Lovric, Šeruga, and
Komorsky-Lovrić (2009)
Spinach, Cabbage, Broccoli, Chicory Piovesan et al. (2015)
Fruit juices Yang et al. (2013)
Quercetin Jin et al. (2008)
1378 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
extracting power that this polymer exhibits towards phenolic com-
pounds. This procedure has been tested in edible plant extracts
(Piovesan et al., 2015).
Another interesting modification is that in which antioxidant
activity is evaluated through analyzing the protective power of
antioxidants against hydroxyl radical attack on purine bases.
These bases, e.g. guanine, are immobilized upon the surface of
GC electrodes and then submitted to the radical attack in pres-
ence or absence of different extracts, i.e. fruit juices, which con-
tain the antioxidant compounds (Barroso, Delerue-Matos, &
Oliveira, 2012).
In the work realized by Medeiros et al. (2010) a comparison
between the electrochemical method and the usual analytical
method (HPLC) was performed. As mentioned before, HPLC is
one of the most used analytical tools for quantifying the antiox-
idants in foods and beverages. Through a cathodic pretreatment,
the authors carried out an analysis of the peak potential vs the
logarithm of the frequency in order to determine the number of
transferred electrons. After the mathematical treatment of the
data, the number of transferred electrons for both BHA and
BHT was 2. This is helpful in order to propose an oxidation
mechanism. Besides this mechanism, the authors compared
the efficiency of the electrochemical method to detect and
quantify these antioxidants in commercial mayonnaise and mar-
garine by comparing it with an HPLC analysis of the same sam-
ples; it was found that the electrochemical method presented a
very good correlation by using the Error calculated as: Error (%)
= 100  (SWV value  HPLC value)/HPLC value. For BHA, the
greatest Error was 5.0% and for BHT was 7.7%. Based on this
information, the authors concluded that very low detection lim-
its were obtained for the simultaneous determination of BHA
and BHT (0.14 lmol L1 and 0.25 lmol L1 respectively); these
values were lower than the other reported previously by using
voltammetric methods. Also, the concentration values obtained
for BHA and BHT were similar to those obtained when using
a HPLC method. Therefore, the SWV method used in their work
is effective for the simultaneous determination of BHA and BHT
in food products; furthermore, it is a very simple, inexpensive,
and rapid method.
3.4. Application of chronoamperometry for determination of AC
Table 5 shows some works where CA has been applied to quan-
tify antioxidant’s concentration by combining both electrochemi-
cal and spectrophotometrical assays.
In order to study the AC, it turns out to be important to evaluate
the stationary current obtained at working potential. In some cases
this option allows to obtain different results for different products,
Table 5
Chronoamperometry applied to the determination of AC.
Working electrode Parameter Sample or standard
GCE I, Q Gallic Acid
MWCNT/GCE Iss Commercial Brandy and Cognac
TFG, Pt Iss Uric and Ascorbic acid, cysteine, glutathione
PCDDA/GCE Iss Dopamine, Ascorbic acid, Uric acid
BDD Iss Quercetin, rutin, catechin, phenolic acids, BHA.
BDD Iss Quercetin, morin, catechin, chrysin, fisetin, luteolin, kaempferol, apigenin
GCE Iss Commercial juices
GCE I Trolox, Orange juice, red wine, black currant juice
Ti/Pt microband Iss Trolox, ascorbic acid, gallic acid, caffeic acid
GCE, Au, Pt I 20 -Hydroxy-chalcones
GCE Iss Dry red wines
MWCNT/GCE Iss Brandy
GCE: Glassy Carbon Electrode, I: Current, Q: Electric Charge, TFG: Thick-film graphite, Iss: Current in the steady state, PCDDA/GCE: poly 3-(5-chloro-2-hydroxyphenylazo)-
4,5-dihy- droxynaphthalene-2,7-disulfonic acid), GCE: Glassy Carbon Electrode, BDD: Boron-doped Diamond, BHA: Butyl hydroxyanisole, MWCNT: Multi-walled carbon
nanotubes.
e.g. wines; even when these samples do not show important result
signals when cyclic voltammetry studies are realized carried out
(Zikos, Karaliota, & Liouni, 2011). From a mechanistic point of view,
this technique allows to determine parameters as diffusion coeffi-
cient by using the current value corresponding to a diffusional con-
trol of the reaction (Abdel-Hamid & Newair, 2011).
From the electrode perspective, GC is often reported, but mod-
ified electrodes have also been used to perform several studies, for
instance, one modified with multi-walled carbon nanotubes which
allows to identify adulterations in brandy in a fast way by deter-
mining the stationary current value after 75 s of initiated the
chronoamperometric experiment (Ziyatdinova, Salikhova,
Skorobogatova, Chibisova, & Budnikov, 2015).
Other works of particular interest are those carried out by de
León et al. (2011) and Milardović et al. (2006) where the conven-
tional spectrophotometric assay is combined with the electro-
chemical approach. In the first one, the authors compare the
differences between monitoring the DPPH radical capture reac-
tion by using spectrophotometry and chronoamperometry. They
found that it is possible and adequate to monitor the reaction
advance through the electrochemical approach, obtaining thereby
a very good detection limit for trolox (1.5 lM) when employing
the same procedure of the spectrophotometric assay. This tech-
nique combines the radical and the sample before the measure,
and incubates the mixture for 30 min. According to the authors,
one of the advantages of combining both methods is that the con-
centration of the DPPH radical can be increased in order to avoid
dilution as sample pretreatment; otherwise, in the spectrophoto-
metric assay, greater concentrations of DPPH would result in big
values of absorbance that may show uncertainty depending on
the equipment.
On the other hand, Milardović et al. (2006) propose an inge-
nious method that combines the features of one of the most com-
monly used reagents for quantifying antioxidants, e.g. DPPH
radical, with chronoamperometry in order to determine the scav-
enging capacity by applying trolox as a standard, and also deciding
to realize the chronoamperometric experiments at a working
potential of 140 mV. The latter was determined by using cyclic
voltammetry of the working solutions. This potential was chosen
because, at that value, no electrochemical reaction occurs; there-
fore, the current registered in the experiment is the result of either
the chemical reaction that took place with the trolox or between
the sample and the DPPH radical, due to diffusion processes. When
using this method, the authors make small additions of 10 lM
DPPH solution and register the response current until they have
enough point to build a calibration curve; then, at the same DPPH
solution, they perform additions of 2.5 lM of trolox until the
current returns to the initial value. After these experiments, they
References
Abdel-Hamid and Newair (2011)
Ziyatdinova et al. (2014)
Ensafi et al. (2009)
Ferreira and Avaca (2008)
Ferreira et al. (2015)
de León et al. (2011)
Milardović, Iveković, and Grabarić (2006)
Oliveira, Bento, Sella, Thouin, and Amatore (2013)
Serifi et al. (2013)
Zikos et al. (2011)
Ziyatdinova et al. (2015)
 J. Hoyos-Arbeláez et al. / Food Chemistry 221 (2017) 1371–1381
correlated their results with those obtained through the spec-
trophotometric assay, and found out an R value of 0.9996, indicat-
ing therefore a very good correlation between both methods. They
conclude that under the same conditions both methods have the
same advantages and disadvantages; however, spectrophotometric
method can be easily affected by the color and turbidity of a sam-
ple, hence demanding sample pretreatment. The amperometric
method showed a good chemical stability, and no-transparent or
turbid samples did affect the response of the detector. The good
agreement between the results obtained by the proposed ampero-
metric methods and the classic spectrophotometric method con-
firmed the usefulness of the amperometric method for
determining the AC of a wide variety of samples.
It is important to note that AC of a sample, composed of several
electroactive molecules, is not given by the sum of the individual
antioxidant capacities of its components, it also depends on the
microenvironment in which the compound is. The electroactive
compounds can interact with each other resulting in a synergic
or inhibitory effect (Kuskoski, Asuero, Troncoso, Mancini-Filho, &
Fett, 2005).
4. Conclusions
Electrochemical methods have been used for a while to deter-
mine the AC of different samples of foods and beverages; they have
proved to have an excellent correlation with other analytical
approaches. This allows their implementation as a tool for fast,
easy, and economic determination of AC in them. Also, due to the
high sensitivity achieved through these techniques, it prompted
researchers to begin using this approach, not only because of the
very good detection limits that can be achieved but also because
in the same equipment (potentiostat/galvanostat), and with few
resources (a set of electrodes), several methods can be applied,
and it is therefore easier to obtain diverse information; also, this
way, both analytical and physicochemical parameters can help to
propose reaction mechanisms, and a better understanding of the
system under study.
Conflict of interest
The authors declare that they do not that have any conflict of
interest.
Acknowledgments
The authors would like to thank the Committee for the Develop-
ment of Research-CODI-University of Antioquia and its strategy for
Sustainability of Research Groups 2014-2015.
JHA and MVV would like to thank the Committee for the Devel-
opment of Research-CODI-University of Antioquia, for the support
in the project CPT-1233.
JHA would like to thank Departamento Administrativo de Cien-
cia, Tecnología e Innovación – COLCIENCIAS for the doctoral
scholarship.
The authors would like to thank Ramiro Restrepo Marin for
assisting with the English version.
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