Food Chemistry 150 (2014) 80–86

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

Analytical Methods

Coulometric titration with electrogenerated oxidants as a tool

for evaluation of cognac and brandy antioxidant properties
Guzel Ziyatdinova ⇑, Inna Salikhova, Herman Budnikov
Analytical Chemistry Department, Kazan Federal University, Kremlyevskaya, 18, Kazan 420008, Russian Federation

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

Article history: Stoichiometric coefficients for reactions of cognac antioxidants with coulometric titrants (electrogener-
Received 23 May 2013 ated bromine and hexacyanoferrate(III) ions) have been found. Ellagic and gallic acids react with both
Received in revised form 16 September 2013 titrants while aldehydes (vanillin, syringic and coniferaldehyde) – with electrogenerated bromine only.
Accepted 26 October 2013
Furfurals do not show significant reactivity toward both oxidants. Cognac and brandy total antioxidant
Available online 4 November 2013
capacity (TAC) and ferric reducing power (FRP) based on reactions with electrogenerated bromine and
hexacyanoferrate(III) ions, respectively, have been evaluated. Both parameters for cognacs are statisti-
Keywords:
cally significant higher than for brandies and grow with the age increase. Beverages under investigation
Constant-current coulometry
Electrogenerated oxidants
has shown relatively high antiradical activity toward 2,2-diphenyl-1-picrylhydrazyl (7–92% and 5–93%
Antioxidant properties for cognacs and brandies, respectively). Total phenolics content has been evaluated by Folin–Ciocalteu
Total antioxidant capacity method. Older beverages represent the higher phenolics content caused by more time of extraction from
Ferric reducing power oak barrels. Positive correlations (r = 0.8077–0.9617) have been observed for TAC and FRP with antirad-
Total phenolics ical activity and total phenolics content.
Cognac Ó 2013 Elsevier Ltd. All rights reserved.
Food analysis

1. Introduction García-Falcón, Simal-Gándara, and Orriols-Fernández, 2007), only

Cognac is an alcoholic beverage rich in polyphenols and its mod-
erate consumption has shown potential beneficial effects on health.
Cognac has been described to possess antioxidant properties due to
its phenolic constituents and has been established to decrease the
risk of cardiovascular diseases (da Porto, Calligaris, Celotti, & Nicoli,
2000; Goldberg, Hoffman, Yang, & Soleas, 1999). Mechanisms that
have been proposed to explain the prevention of cardiovascular dis-
eases by polyphenols include reduced oxidation of low-density
lipoprotein, inhibition of platelet aggregation and neutrophil adhe-
sion (Carusio, Wangensteen, Filipelli, & Andriantsitohaina, 2008).
Polyphenols have also been reported to affect the activity of en-
zymes critically involved in pathways regulating cell proliferation
and activation (Perez-Vizcaino, Duarte, & Andriantsitohaina, 2006).
Despite the extensive works devoted to the assessment of the
antioxidant properties of several wines and other alcoholic bever-
ages in relation to their phenolic content (de Quirós, Lage-Yusty,
& López-Hernández, 2009; Figueiredo-González, Cancho-Grande,
and Simal-Gándara, 2013; García, Grande, & Gándara, 2004;
Puértolas, Saldaña, Condón, Álvarez, & Raso, 2010; Pérez-Lamela,
⇑ Corresponding author. Address: Department of Analytical Chemistry, A.M.
Butlerov Institute of Chemistry, Kazan Federal University, Kremlyevskaya, 18, Kazan
420008, Russian Federation. Tel.: +7 843 2337736; fax: +7 843 2387901.
E-mail address: Ziyatdinovag@mail.ru (G. Ziyatdinova).
few data have been presented on the antioxidant properties of
cognac (da Porto et al., 2000; Goldberg et al., 1999). This is why,
there is a constant quest to determine cognac antioxidant proper-
ties and associated methods of evaluation.
The most common approaches used for evaluation of antioxi-
dant properties of alcoholic beverages are spectrophotometric
determination of antiradical activity by reaction with 2,2-diphe-
nyl-1-picrylhydrazyl (DPPH) (Aoshima, Tsunoue, Koda, & Kiso,
2004; da Porto et al., 2000) and total phenolics content by Folin–
Ciocalteu method (Alonso, Castro, Rodriguez, Guillen, & Barroso,
2004; Vicente, de Abreu, Goulart, & de Vasconcelos, 2011).
Antioxidants being easily oxidizable compounds are widely
investigated using electrochemical methods. A lot of articles have
been focused on electrochemical evaluation of foodstuff antioxi-
dant properties including alcoholic beverages, namely wines
(Arribas et al., 2013; Šeruga, Novak, & Jakobek, 2011). Polaro-
graphic assay based on hydrogen peroxide scavenging has been
developed for the determination of antioxidant activity of strong
alcoholic beverages (Gorjanovic et al., 2010).
Special attention is paid to cognac and brandy recognition and
classification based on their responses to the voltammetric elec-
tronic tongue analysis (Cetó, Llobet, Marco, & del Valle, 2013),
mid infrared spectroscopy (Picque et al., 2006), front face fluores-
cence spectroscopy (Sádecká, Tóthová, & Májek, 2009) and further
chemometric signals processing.

0308-8146/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.10.133
 G. Ziyatdinova et al. / Food Chemistry 150 (2014) 80–86 81

Coulometry with electrogenerated titrants is characterized by solution (61 lM) were prepared by dissolving a definite amount
high sensitivity, simplicity, accuracy and reliability as well as possi- in methanol (chemical grade purity).
bility of miniaturization. Coulometric generation of the titrant spe- All other chemicals were analytical reagent grade purity and
cies precludes the use of standard solutions. Besides, it is also a very used as received. Double distilled water was used for the measure-
attractive form of providing reagents for systems based on true ments. The experiments were carried out at laboratory tempera-
titration where the sample volume and the amount of reagent ture (20–23 °C). All solutions of compounds under investigation
added up to the end point are the only parameters necessary for were prepared exactly before measurements.
analyte quantification. Constant-current coulometry is successfully
applied for the organic analysis in particular to evaluation of tea and
2.2. Materials
coffee ferric reducing power (Ziyatdinova, Nizamova, & Budnikov,
2011) and total antioxidant capacity of juices, balsams and tinc-
The cognacs and brandies analyzed were commercially avail-
tures (Abdullin, Turova, Budnikov, Ziyatdinova, & Gajsina, 2002).
able samples of different trademarks. A total 11 cognacs of 3 vari-
It should be noted that there is no any information about appli-
ous commercial denominations (VS, VSOP and XO) as well as 18
cation of coulometry for hot spirits antioxidant properties mea-
ordinary and vintage brandies of Russian (Ru), Armenian (Am),
surements. The aim of present work is evaluation of cognac
Ukraine (Ua) and Azerbaijan (Az) origin have been analyzed. The
antioxidants reactivity toward electrogenerated oxidants and
commercial denomination indicates the minimum or average age
development of coulometric methods for cognac and brandy anti-
of spirit which is used in the blend for cognac and brandy,
oxidant properties assay based on sample titration with electro-
respectively. Brandy denomination kV means average age of
generated bromine and hexacyanoferrate(III) ions.
6 years, KS – 10 years and OS – 20 years.

2. Experimental 2.3. Instrumentation

2.1. Chemicals and reagents
Ellagic (95% purity) and gallic acids (99%), vanillin (99%) were
purchased from Sigma (Germany). Syringaldehyde (98%), coniferal-
dehyde (98%), 5-hydroxymethylfurfural (99%) and furfural of 99%
purity were obtained from Aldrich (Germany). Their 0.4–5.0 mM
stock solutions were prepared daily dissolving a definite amount
of the substance in 10.0 mL of ethanol (rectificate).
2,2-Diphenyl-1-picrylhydrazyl (DPPH) and Folin–Ciocalteu
reagent were purchased from Aldrich (Germany). DPPH stock
Coulometric measurements were carried out using P-5827 M
potentiostat (ZIP, Gomel, Belarus) with four-electrode
two-compartment electrochemical cell. A bare platinum foil with
1 cm2 surface area was used as the working electrode, and a
platinum wire separated from the anodic compartment with a
semipermeable diaphragm – as the auxiliary electrode. A pair of
polarized platinum electrodes was used for detection of the
titration end-point (DE = 200 mV). Surface of platinum electrodes
was cleaned by HNO3 and then rinsed thoroughly with double
distilled water.

Table 1
Stoichiometric coefficients of the reactions between cognac antioxidants and electrogenerated oxidants.

Compound Structure m(compound):m(Br2) m(compound):m(FeCN36 )

Ellagic acid O 1:2 1:4
O OH

HO OH

HO O
O
Gallic acid OH 1:2 1:4
HO

OH
HO
O
Syringaldehyde OCH3 1:1 –
O
C OH
H
OCH3
Vanillin OCH3 1:1 –
O
C OH
H
Coniferaldehyde OCH3 1:2.5 –
O
C OH
H
Furfural – –
H
O
O
5-Hydroxymethyl-furfural 1:0.5 –
HO H
O
O
82 G. Ziyatdinova et al. / Food Chemistry 150 (2014) 80–86

Scheme 1. Dehydrodigallic acid oxidation.

Table 2
TAC and FRP of cognacs and brandies (n = 5; P = 0.95).

Beverage Commercial denomination Sample TAC (C/100 mL) RSD (%) FRP (C/100 mL) RSD (%)
Cognac VS F1 86 ± 1 1.0 63 ± 2 2.7
F2 29 ± 1 3.7 23 ± 1 3.7
F3 32.5 ± 0.8 1.9 34 ± 1 3.1
F4 49 ± 2 3.4 44 ± 3 4.8
VSOP F1 112 ± 4 2.7 84 ± 3 2.7
F2 41 ± 3 5.3 36 ± 3 6.6
F4 70 ± 3 3.1 57 ± 3 4.5
F5 51 ± 1 1.6 46.4 ± 0.7 1.2
XO F1 160 ± 2 1.0 136 ± 1 0.7
F2 73 ± 2 2.6 65 ± 1 1.7
F4 94 ± 2 2.0 91 ± 2 2.2
Brandy 3-Star Am1 41 ± 1 2.0 26 ± 1 4.2
Ru1 15.4 ± 0.5 2.7 16 ± 1 5.8
Ru2 29 ± 1 3.7 36.0 ± 0.9 2.0
Ru3 41 ± 1 2.8 36 ± 2 4.7
Ru4 46 ± 2 3.7 45.7 ± 0.3 0.6
4-Star Am2 33 ± 1 3.0 14.0 ± 0.4 2.5
5-Star Am3 43 ± 2 1.8 28 ± 2 5.9
Az 68 ± 3 4.0 29 ± 2 6.4
Ua 30 ± 3 8.5 40 ± 4 8.2
Ru5 60 ± 2 2.6 49 ± 2 3.2
Ru6 33 ± 2 5.4 34 ± 1 3.3
Ru7 24 ± 3 9.1 20 ± 3 10.0
KV Am4 75 ± 2 2.5 55 ± 2 3.0
Ru8 30 ± 1 1.5 25 ± 1 4.0
KS Am5 88 ± 2 1.5 58 ± 2 2.6
Ru9 66.5 ± 0.6 0.8 61.2 ± 0.9 1.2
Ru10 148 ± 3 1.5 132 ± 4 2.5
Ru11 63 ± 2 2.3 55 ± 3 3.5
OS Am6 108 ± 2 1.4 88 ± 3 2.3

Spectrophotometric measurements were performed on spectro- value of the indicator current. The timer was stopped, and the
photometer PE-5300 (NPO Ecros, Russia). generating circuit was turned off. The time of titration were used
for the TAC calculation.
TAC were expressed in units of quantity of electricity
2.4. Determination of cognac TAC (Coulombs (C)) spent for titration on 100 mL of cognac.

Determination of TAC is based on the coulometric titration of

sample by electrogenerated bromine (Nizamova, Ziyatdinova, &
Budnikov, 2011; Ziyatdinova, Budnikov, Pogorel’tzev & Ganeev,
2006).
Electrochemical generation of titrant was carried out from
0.2 M KBr in 0.1 M H2SO4 at a current density 5 mA cm 2 providing
100% current yield. Coulometric titration was carried out in a
50 mL cell containing 20.0 mL of supporting electrolyte. The gener-
ating circuit was switched on and a certain value of the indicator
current was attained. Then an aliquot portion (500 lL) of cognac
was added to the cell and timer was simultaneously started. The
titration end-point was detected by the attainment of the initial
2.5. Determination of cognac FRP
FRP assay is based on coulometric titration of the sample with
electrogenerated hexacyanoferrate(III) ions (Ziyatdinova et al.,
2011).
Hexacyanoferrate(III) ions were generated from 0.1 M
K4Fe(CN)6 in 2 M ROH at the current density of 5 mA cm 2. Coulo-
metric titration was carried out in a 50 mL cell containing 20.0 mL
of the supporting electrolyte. The generating circuit was switched
on and a certain value of the indicator current was attained. Then
an aliquot of cognac (500 lL) was added and timer was started. The
 G. Ziyatdinova et al. / Food Chemistry 150 (2014) 80–86
titration end-point was indicated by the attainment of the initial
value of the indicator current. The timer was stopped, and the gen-
erating circuit was switched off.
FRP of samples was expressed by the quantity of electricity
spent for the titration and recalculated per 100 mL of beverage.
2.6. Antiradical activity assay
Antiradical activity of cognacs was determined using the free
radical DPPH (Brand-Williams, Cuvelier, & Berset, 1995). In its rad-
ical form, DPPH absorbs at 515 nm but upon reduction by an anti-
oxidant or radical species its absorption decreases.
A volume of 3.0 mL of 61 lM DPPH methanol solution was
used. The reaction was started by the addition of 5 lL of cognac
samples. After incubation at room temperature in the dark for
30 min, the remaining DPPH was determined by absorbance at
515 nm, and the radical scavenging activity of each sample was
expressed using the ratio of the absorption decrease of DPPH (%)
to that of the control DPPH solution (100%) in the absence of the
sample. All samples were analyzed in triplicates.
2.7. Total phenolics by Folin–Ciocalteu reagent assay
Total phenolic contents were determined by the Folin–Ciocalteu
colorimetric method with some modifications (Singleton, Orthofer,
& Lamuela-Raventys, 1999). An aliquot (1.0 mL) of cognac or gallic
acid standard solution (20.0, 40.0, 60.0, 80.0, 100.0 and 300 mg L 1)
Fig. 1. Antioxidant parameters for cognac (A) and brandy (B) of different
denominations.
83
was added to 25.0 mL volumetric flask containing 9.0 mL of dis-
tilled water. Folin–Ciocalteu reagent (1.0 mL) was added to the
mixture and shaken. After 5 min, 10 mL of 7% Na2CO3 solution
was added with mixing and solution was immediately diluted to
25.0 mL with distilled water. After incubation at room temperature
for 1.5 h, the absorbance of the solution at 750 nm was measured.
Total phenolic contents were expressed as mg of gallic acid equiv-
alents (GAE) per 1 L of cognac. All samples were analyzed in
triplicates.
2.8. Statistical analysis
All coulometric measurements were performed in five replica-
tions. Statistical evaluation was performed at significance level of
5%. All data are expressed as the X ± DX with X as average value
and DX as confidence interval.
Parameters for different types of cognac and brandy were ex-
pressed as the X ± SD with X as average value and SD as standard
deviation. The difference of parameters was performed by Stu-
dent’s t-test. A p < 0.05 was considered as statistically significant.
Correlation analysis was performed using OriginPro 8.0 (Origin-
Lab, USA) software.
3. Results and discussion
3.1. Reactivity of cognac antioxidants towards electrogenerated
titrants
Cognacs antioxidants properties are caused by presence of phe-
nolic antioxidants and furanic compounds extracted in alcoholic
beverages aged in wood barrels. In accordance to ‘‘Bureau Interpro-
fessionel du Cognac’’, the main antioxidants of cognac are ellagic
and gallic acids, syringaldehyde, coniferaldehyde and vanillin as
well as 5-hydroxymethylfurfural and furfural. Their reactions with
electrogenerated bromine and hexacyanoferrate(III) ions were
investigated. The corresponding stoichiometric coefficients are
presented in Table 1.
In this work, it was shown that the electrogenerated bromine
can react fast and quantitatively with all the compounds under
investigation, discounting furfural. The electrooxidation of bro-
mide ions in acidic medium occurring on the platinum electrode
provides the formation of tribromide anion, bromine and short liv-
ing bromine radicals which are adsorbed on the electrode surface
(Abdullin et al., 2002). The 5-hydroxymethylfurfural is probably in-
volved in the reaction with bromine radicals forming relatively sta-
ble radical. Syringaldehyde and vanillin like ferulic acid (Trabelsi,
Tahar, Trabelsi, & Abdelhedi, 2005) are oxidized to corresponding
o-quinones. Five electrons participate in the reaction of coniferal-
dehyde with electrogenerated bromine. Oxidation of hydroxyl
group as well as electrophilic addition to double bond and substi-
tution to aromatic ring can occur in this case. Ellagic acid is oxi-
dized to corresponding di-o-quinone. Gallic acid undergoes
oxidation to quinone that is unstable and may undergo further
reactions, for instance, condensation and dimerization reactions
(Feldman, Quideau, & Appel, 1996).
Electrogenerated hexacyanoferrate(III) ions react with gallic
and ellagic acids only with participation of 4 electrons. Ellagic acid
is oxidized to di-o-quinone like in reaction with electrogenerated
bromine. In basic medium at pH > 11 under the air oxygen action,
gallic acid undergoes dimerization forming dehydrodigallic acid
(Oniki & Takahama, 2004) which is then oxidized by hexacyanofer-
rate(III) ions to corresponding di-o-quinone (Scheme 1).
The results obtained for individual cognac antioxidants allow
usage coulometric titration with electrogenerated oxidants for
evaluation of cognac antioxidant properties. The different
84 G. Ziyatdinova et al. / Food Chemistry 150 (2014) 80–86

Table 3
Beverages antiradical activity and total phenolics content (n = 3, P = 0.95).
1
Beverage Sample Antiradical activity (%) RSD (%) Total phenolics, GAE mg L RSD (%)
Cognac F1 VS 62 ± 1 1.6 249 ± 6 1.6
F2 VS 17.0 ± 0.9 5.3 103.4 ± 0.8 0.8
F3 VS 23 ± 1 4.2 112 ± 6 3.1
F4 VS 65 ± 2 2.8 198 ± 31 15.0
F1 VSOP 87 ± 3 3.4 342 ± 4 0.8
F2 VSOP 24.0 ± 0.8 3.2 157 ± 3 1.8
F4 VSOP 48 ± 1 1.9 227 ± 12 5.1
F5 VSOP 39 ± 2 5.1 110 ± 4 2.3
F1 XO 92 ± 3 3.2 393 ± 6 1.0
F2 XO 41 ± 1 2.3 244 ± 12 3.1
F4 XO 80 ± 2 2.5 300 ± 13 2.7
Brandy Am1 51 ± 2 3.8 84 ± 1 1.2
Ru1 19 ± 1 5.3 59 ± 2 2.2
Ru2 19.0 ± 0.8 4.1 71 ± 2 2.8
Ru3 51 ± 2 3.9 120 ± 1 0.6
Am2 11.0 ± 0.8 7.3 59 ± 6 7.5
Az 53 ± 3 5.5 137 ± 6 3.3
Ua 20 ± 1 4.9 68 ± 4 4.1
Am3 35 ± 1 2.9 156 ± 5 1.8
Ru5 25.0 ± 0.8 3.2 185 ± 11 3.8
Ru6 6.0 ± 0.5 8.2 151 ± 6 2.7
Ru7 9.1 ± 0.5 5.5 83 ± 3 2.6
Am4 66 ± 2 2.1 228 ± 3 1.3
Ru8 21 ± 1 4.6 112 ± 2 1.2
Am5 60 ± 3 5.0 244 ± 3 0.8
Ru9 55 ± 2 3.6 220 ± 11 3.0
Ru10 93 ± 5 5.3 416 ± 8 1.1
Ru11 47 ± 5 10.2 211 ± 6 1.9
Am 6 85 ± 2 1.6 334 ± 4 1.2

reactivity of phenolic acids and aldehydes toward titrants can be
applied to assay of compounds contribution to common
parameters.
3.2. Coulometric evaluation of cognac and brandy antioxidant
properties
Taking into account the reactivity of the cognac antioxidants,
the TAC and FRP properties were chosen as parameters character-
izing antioxidant properties. These properties are based on the
reactions of antioxidants with electrogenerated bromine and hexa-
cyanoferrate(III) ions, respectively. The corresponding data for real
samples are presented in Table 2.
As Table 2 data show, TAC is statistically significant higher than
FRP for a great part of samples under investigation that is caused
by reactivity of beverage antioxidants toward titrants. Such ap-
proach allows evaluation of aldehydes contribution to common
parameters because aldehydes do not react with electrogenerated
hexacyanoferrate(III) ions. As the age of beverage is risen up, alde-
hydes percent increases from 16% to 19% for cognacs and from 7.7%
to 25% for brandies with further decrease to 11% and 15% for XO
cognacs and brandy of 10 years and older, respectively, although
the difference is statistically insignificant. Decrease of aldehyde
contents is caused by their partial oxidation during aging
processes.
The main contributors to TAC are ellagic and gallic acids that
corresponds well with literature data of their contents in cognacs
(Da Porto et al., 2000; Goldberg et al., 1999). Syringic aldehyde,
vanillin, coniferaldehyde and relative compounds give smaller con-
tribution. FRP is caused by ellagic and gallic acids presence. Furfu-
ral and 5-hydroxymethylfurfural do not contribute to FRP and
negligible to TAC, meaning that the addition of caramel as well
as some aging conditions (i.e., heat treatment of the wood cask,
type of wood, and state and use of the barrel) which can influence
the extent of the extraction of nonenzymatic browning reaction
products (Onishi, Guymon, & Crowell, 1977) do not affect the
antioxidant properties of the samples as was reported earlier (Da
Porto et al., 2000).
The results of coulometric measurements confirm that antioxi-
dant properties of cognacs are mainly caused by lignin-derived
phenolic antioxidants extracted from oak barrels (Goldberg et al.,
1999).
It should be noted that cognac trademark F1 has shown the
highest values of TAC and FRP in comparison with other cognac
samples of the same denominations. FRP of brandy samples Ru2
and Ua is statistically significant higher than TAC indicating the
presence of some components reacting with electrogenerated
hexacyanoferrate(III) ions but not bromine.
In general, TAC and FRP for cognacs are higher than that for
brandies due to different technology of beverage production and
classification. Denomination of cognacs is based on age of youngest
spirit in beverage. Moreover, assemblage based on the addition of
very old (up to 50–70 years old) spirits takes place in cognac pro-
duction (Faith, 2004). Brandies under investigation are denomi-
nated on the basis of the average age of spirits in the beverage
(GOST R 51618-2009, 2009).
TAC and FRP of cognacs showed a trend toward higher values
according to the progression VS, VSOP, XO (Fig. 1A), in line with
increasing quality as reflected by longer wood aging, but this did
not reach statistical significance (p > 0.05) due to strongly different
data for sample F1. The similar relationship has been observed for
brandies (Fig. 1B). However, results for some samples in the group
of the same age are significantly different that is probably caused
by quality of the beverage specified by raw materials used and
accuracy of technological process applied.
So, older beverages shows higher TAC and FRP that agrees well
with the reported earlier data for total antioxidant status of dis-
tilled spirits (Goldberg et al., 1999).
3.3. Antiradical activity of beverages
DPPH test is one of commonly used approach for evaluation of
foodstuff antioxidant properties. Antiradical activity of cognacs
 G. Ziyatdinova et al. / Food Chemistry 150 (2014) 80–86
Fig. 2. Correlation plots for TAC and FRP of cognacs (A and B) and brandies (C and D) vs. antiradical activity.
and brandies has been evaluated (Table 3). Beverages under inves-
tigation show relatively high antiradical activity (7–92% for
cognacs and 5–93% for brandies) depending of the age.
A positive correlations of TAC and FRP with antiradical activity
at P = 0.95 (Fig. 2) have been observed. However, correlation coef-
ficient for FRP of brandies is lower than that one for cognacs.
The main disadvantages of antiradical activity spectrophoto-
metric determination by reaction with DPPH are described in de-
tails in (Karadag, Ozcelik, & Saner, 2009; Magalhães, Segundo,
Reis, & Lima, 2008). In the case of current investigation, the crucial
role play the absorbance of radical after reaction with an antioxi-
dant that is decreased by light, oxygen, and type of solvent. More-
over, water content in solvent effects on the antioxidant capacity
decreasing it, since a part of the DPPH coagulates and it is not eas-
ily accessible to the reaction with antioxidants. Some antioxidants
reacting with oxygen radical species do not interact with DPPH
that leads to falsely low values for antiradical activity of samples.
Coulometric titration with electrogenerated oxidants allows to
avoid the problems noted above.
3.4. Total phenolics content in cognac and brandies
So far as phenolic compounds are the main antioxidants of cog-
nac and brandies, total phenolics content has been evaluated by
Folin–Ciocalteu method (Table 3). As one can see, the total pheno-
lics content is increased with the age of beverages that is caused by
polyphenols extraction time for oak barrels during aging. Total
phenolics content in cognacs is a bit higher than that one in
brandies due to differences in production technology of beverages
and agrees well with reported earlier (Nykänen & Suomalainen,
1983).
85
There are positive correlations of cognac and brandy TAC and
FRP with total phenolics content (r = 0.9617 and 0.9415 at
P = 0.95, respectively).
4. Conclusion
Reactivity of cognac antioxidants toward electrogenerated oxi-
dants (bromine and hexacyanoferrate(III) ions) has been evaluated.
The results obtained allow to use coulometric titration for estima-
tion of cognacs and brandies TAC and FRP. Furfurals presented in
caramel and formed as a consequence of the barrel heat treatment
do not show significant antioxidant properties. FRP is specified by
presence of ellagic and gallic acids in the beverage. The difference
in TAC and FRP makes possible evaluation of aldehydes contribu-
tion to TAC.
Positive correlations of TAC and FRP with antiradical activity
and total phenolics content show that coulometric approaches
developed adequately reflect cognac and brandy antioxidant prop-
erties and can be recommended as alternative methods for their
fast screening. The main advantages of coulometric evaluation
are high reproducibility, simplicity, low cost and rapidity of
determination.
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