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Analysis of commercial grape raisins: Phenolic content, antioxidant capacity and radical scavenger activity

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Seven different commercial grape raisins from the Spanish market were evaluated for total phenolic composition, antioxidant potential and scavenger activity. Commercial red raisins (from the Cardinal grape variety) generally had the significantly highest content of total phenolic compounds (406.9 mg/100 g raisin) and antioxidant capacity (27.88 mM Fe(II) and 10.73 mM trolox, respectively by applying FRAP and ABTS methods) while commercial white raisins had the lowest content for the parameters analyzed, especially for commercial Moscatel of Alexandria and Sultana raisins (ranging from 110.8 to 284.4 mg/100 g raisin for total phenolic compounds and ranging from 6.0 to 17.04 mM Fe(II) and from 2.43 to 8.94 mM trolox, respectively for antioxidant capacity by applying FRAP and ABTS methods). Finally, the Pearson test shows a very high correlation (0.95 and 0.97, α<0.05) between total phenolic content and antioxidant capacity. Results prove that all commercial raisin samples studied constitute a natural source of polyphenols and antioxidants, especially raisin samples obtained from the red grape variety.
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Ciência Téc. Vitiv. 29(1) 1-8. 2014
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ANALYSIS OF COMMERCIAL GRAPE RAISINS: PHENOLIC CONTENT,
ANTIOXIDANT CAPACITY AND RADICAL SCAVENGER ACTIVITY
ANÁLISE DE UVAS PASSAS COMERCIAIS: CONTEÚDO FENÓLICO, CAPACIDADE
ANTIOXIDANTE E ACTIVIDADE SEQUESTRADORA DE RADICAIS LIVRES
Susana Sério1, Maria D. Rivero-Pérez2, Ana Cristina Correia1, António Manuel Jordão1*,
Maria L. González-San José2
1 Polytechnic Institute of Viseu (Centre for the Study of Education, Technologies and Health), Agrarian Higher School, Estrada de Nelas, Quinta
da Alagoa, Ranhados, 3500-606 Viseu, Portugal.
2 University of Burgos, Department of Biotechnology and Food Science, Plaza Misael Bañuelos s/n 09001, Burgos, Spain.
* corresponding author: António Manuel Jordão, Polytechnic Institute of Viseu (Centre for the Study of Education, Technologies and Health),
Agrarian Higher School, Estrada de Nelas, Quinta da Alagoa, Ranhados, 3500-606 Viseu, Portugal email: antoniojordao@esav.ipv.pt
(Received 07.05.2013. Accepted 08.04.2014)
SUMMARY
Seven different commercial grape raisins from the Spanish market were evaluated for total phenolic composition, antioxidant potential and
scavenger activity. Commercial red raisins (from the Cardinal grape variety) generally had the significantly highest content of total phenolic
compounds (406.9 mg/100 g raisin) and antioxidant capacity (27.88 mM Fe(II) and 10.73 mM trolox, respectively by applying FRAP and ABTS
methods) while commercial white raisins had the lowest content for the parameters analyzed, especially for commercial Moscatel of Alexandria
and Sultana raisins (ranging from 110.8 to 284.4 mg/100 g raisin for total phenolic compounds and ranging from 6.0 to 17.04 mM Fe(II) and from
2.43 to 8.94 mM trolox, respectively for antioxidant capacity by applying FRAP and ABTS methods). Finally, the Pearson test shows a very high
correlation (0.95 and 0.97,
α
<0.05) between total phenolic content and antioxidant capacity. Results prove that all commercial raisin samples
studied constitute a natural source of polyphenols and antioxidants, especially raisin samples obtained from the red grape variety.
RESUMO
Efetuou-se o estudo de 7 amostras diferentes de uvas passa comerciais disponíveis no mercado espanhol, ao nível dos compostos fenólicos totais,
do potencial antioxidante e ainda da atividade sequestradora de radicais livres. As uvas passa tintas (variedade Cardinal) apresentaram no geral
valores significativamente mais elevados de compostos fenólicos totais (406.9 mg/100 g uva passa), capacidade antioxidante (27.88 mM Fe(II) e
10.73 mM trolox, respetivamente pela aplicação das metodologias FRAP e ABTS) enquanto que as uvas passa brancas apresentaram valores mais
baixos, em particular as amostras das variedades Moscatel de Alexandria e Sultanas (variando os valores entre 110.8 e 284.4 mg/100 g uva passa,
para os compostos fenólicos totais, entre 6.0 e 17.04 mM Fe(II) e entre 2.43 e 8.94 mM trolox, respetivamente para a capacidade antioxidante pela
aplicação dos métodos FRAP e ABTS). Finalmente, através da aplicação do Teste de Pearson observou-se a existência de elevada correlação (0.95
e 0.97, α<0.05) entre os compostos fenólicos totais e a capacidade antioxidante. Os resultados obtidos, provam que as amostras comerciais de
uvas passa estudadas constituem uma fonte natural de compostos fenólicos e de antioxidantes, em especial as uvas passa tintas obtidas a partir da
variedade Cardinal.
Key words: antioxidant activity, grape raisins, phenolic compounds.
Palavras-chave: capacidade antioxidante, uvas passa, compostos fenólicos.
INTRODUCTION
Food preservation methods have been applied for
many years. One example is fruit drying. Dried fruits
represent a relatively concentrated form of fresh fruit
whereby moisture removal confers increased shelf
life. These fruits are commonly consumed in large
quantities in different countries, and raisins are
consumed very often, especially in Mediterranean
countries. For fresh consumption as well as for use in
baking and confectionery, raisins are produced by
dehydrating grapes using the heat of the sun, natural
air drying, or a mechanical process of oven drying,
artificially dried (dipped), and sulfur dioxide-treated
(golden) raisins (Mary and Michael, 2003; Fadhel et
al., 2005).
The United States is the world’s leading raisin
producer, producing 317.51 tons in 2007/2008.
However, there are other important producers, such as
Turkey, China, Iran, Chile, South Africa, Greece,
Australia, Uzbekistan and Tunisia (Chiou et al., 2007;
Andrew et al., 2010; Gary and Arianna, 2010; Ghrairi
et al., 2013).
During the drying process changes occur in the grape
composition, particularly increased sugar
concentration due to the grape dehydration (Franco et
al., 2004). In addition, there is an increase in total
energy, nutrient density, fibre content, and often a
Article available at http://www.ctv-jve-journal.org or http://dx.doi.org/10.1051/ctv/20142901001
2
significant increase in antioxidant activity compared
to fresh fruit as a consequence of this concentration.
The elevated antioxidant activity and browning index
were related to the increase in polyphenol
concentration during drying, and potentially the
generation of Maillard reaction products, such as
hydroxymethylfurfural (Sanz et al., 2001;
Çağlarirmak, 2006), favoured by the high sugar
concentration and the temperatures reached during the
drying process which can enhance antioxidant activity
(Yilmaz and Toledo, 2005; Moreno et al., 2007).
However, the drying process can also lead to losses in
total polyphenolic compounds and changes in free to
total polyphenol ratios, as shown by Vinson et al.
(2005) in six types of dried fruit.
The health benefits associated with fresh grape
consumption are broadly known and linked to the
richness of phenolic compounds such as gallic acid,
catechin, anthocyanins and resveratrol, and a wide
variety of procyanidins. These compounds have been
demonstrated to have a wide range of biochemical
and pharmacological effects, including
anticarcinogenic, and antiatherogenic, anti-
inflammatory, antimicrobial, and antioxidant
activities (Simonetti et al., 1997; Dell’Agli et al.,
2004; Darra et al., 2012).
In recent years several authors have reported the
phenolic composition and antioxidant capacity of
different varieties of raisins, namely from Tunisia
(Ghrairi et al., 2013), China (Meng et al., 2011), the
United States (Parker et al., 2007; Zhao and Hall,
2008) and Australia (Bennett et al., 2011). However,
the effects of industrial drying practices on
polyphenolic content, antioxidant capacity and radical
scavenger activities have not been systematically
studied, especially in commercial raisin samples from
the Iberian Peninsula. For this reason, the purpose of
this study was to determine, total phenolic content,
antioxidant capacity and scavenger activity and the
relationship between them from a selection of
commercial raisins produced from different grape
varieties.
MATERIAL AND METHODS
Raisin samples
A total of 7 commercial raisin samples (from Vitis
vinifera L. species) purchased at a local Burgos city
market (Spain) were studied. One commercial raisin
sample from the red grape variety (Cardinal) and
three different commercial white raisin samples from
Moscatel of Alexandria, Moscatel of Málaga and
Sultana grape varieties were analyzed. For the Sultana
grape variety four different commercial samples were
analyzed. Visual appearance of the commercial raisin
samples studied is shown in Figure 1.
Figure 1 - Visual appearance of the commercial raisin samples studied. C - Cardinal; MO - Moscatel of Alexandria; MA – Moscatel of Málaga; SI,
SII, SIII and SIV - Sultanas.
Aspeto visual das amostras de uvas passa estudadas. C - Cardinal; MO - Moscatel de Alexandria;
MA – Moscatel de Málaga; SI, SII, SIII e SIV - Sultanas.
Sample preparation
The sample preparation method was based on what
was described by Izcara and González-San José
(2001), consisting of extracting phenolic compounds
from raisins by a methanol:formic acid (97:3, v/v)
solution as an extracting solvent. A first extraction
was carried out adding 25 mL of extracting solvent to
each set of 20 g of ground raisins. This first extraction
was performed while stirring for 24 hours at room
temperature and protected from light. After the first
extraction, the supernatant was collected and a second
extraction was carried out for 6 hours under the same
conditions. In the end the two supernatants were
collected. The process was carried out in triplicate for
each commercial type of raisins under analysis.
Total phenolic content
The total phenolic content of the raisin samples was
determined with a Folin Ciocalteu reagent, using
gallic acid as the standard. The Singleton and Rossi
(1965) improved method was applied. The results
3
were expressed as gallic acid equivalents (mg/100 g
raisin).
Antioxidant capacity
ABTS method: This assay is based on discolouration
which occurs when the radical cation ABTS+ is
reduced to ABTS (2,2’-azinobis-3-
ethylbenzothiazoline-6-sulfonic acid) (Re et al.,
1999). The radical was generated by the reaction of a
7 mM solution of ABTS in water with 2.45 mM
potassium persulphate (1:1). The radical solution
shows stable absorbance values up to 16 h from the
time of mixture. This reaction time takes place in
darkness at room temperature. According to previous
papers (Rivero-Pérez et al., 2007), the assay was
made up with 980 μL of ABTS+ solutions and 20 μL
of the raisin extract sample (at a dilution of 1:50 in
water). Absorbance measurements at 734 nm were
made after 15 min of reaction time.
FRAP method: This method was used to measure the
reductive power of a sample (Benzie and Strain,
1996). It is based on increased absorbance at 593 nm
due to the formation of tripyridyl-s-triazine
complexes with iron(II) (TPTZFe(II)) in the presence
of a reductive agent. The reactive mixture was
prepared by mixing a 25 mL sodium acetate buffer
solution (0.3 mol/L, pH 3.6), 2.5 mL TPTZ (10
mmol/L), 2.5 mL FeCl3 (20 mmol/L) and 3 mL water.
30 μL of diluted raisin extract sample (diluted in
water at 1:10) was added to 970 μL of the latter
reactive mixture and incubated at 37 ºC for 30 min.
The results were expressed as mM FeII, using linear
calibration obtained with different concentrations of
FeSO4.
Radical scavenger activity
Radical scavenger activities toward hydroxyl radical
(HRSA) and superoxide radical (SRSA) were
measured, because they are two of the most
biologically active reactive oxygen species.
Hydroxyl radical-scavenging activity (HRSA):
Deoxyribose (2-deoxy-D-ribose) decays when
exposed to hydroxyl radicals generated by the Fenton
reaction (Halliwell et al., 1987). The hydroxyl
radicals (HO•) were generated through the following
system: 10 μL of FeCl3 (0.1 mmol/L), 10 μL of
ascorbic acid (0.1 mmol/L), 10 μL of H2O2 (1
mmol/L), and 10 μL of EDTA (0.1 mmol/L). Raisin
extract samples (15 μL at a dilution of 1:50 in
distilled water) were incubated at 37 ºC for 1 h, with
20 μL of desoxyribose (1 mmol/L final concentration)
in the presence of FeCl3, ascorbic acid, H2O2, and
EDTA. 1.5 mL of trichloroacetic acid (28 %, w/v)
and 1 mL of thiobarbituric acid (1 %, w/v, 0.05 mol/L
NaOH) were added to 1 mL of the raisin extract
sample under incubation and held for 15 min at 100
ºC, after which it was left to cool down to room
temperature. The malondialdehyde formed from the
decay of desoxyribose was evaluated by reaction with
thiobarbituric acid and measured at 532 nm. The final
results were expressed as inhibition percent in relation
to a control test (without the sample).
Superoxide radical-scavenging activity (SRSA):
The superoxide radical reacts with 4-nitroblue
tetrazolium chloride to generate a coloured compound
with absorbance to 560 nm (Liu et al., 1997). The
antioxidant scavenging superoxide radical values are
associated with the colouration formed during the
reaction process. The reactive solution was made with
50 μL of nicotinamide (77 μmol/L), 50 μL of 4-
nitroblue tetrazolium chloride (50 μmol/L), and 5 μL
of phenazin methosulfate (3.3 μmol/L final
concentration) in a medium of 16 mmol/L Tris–HCl,
pH 8, and 10 μL of the raisin extract sample. The
results were expressed as a percentage of inhibition in
relation to a control test (without the sample).
Statistical analysis
All data are expressed as the mean ± standard
deviation from three replicates (i.e., data from three
different extracts obtained from a given sample of
commercial raisins). In order to determine whether
there was a statistically significant difference between
the results obtained for the different analytical
parameters studied from the commercial raisin
samples analysed, an analysis of variance and
comparison of treatment means (ANOVA, one-way)
were carried out with SPSS software (version 20.0).
Differences between means were tested using
Scheffler’s test (
α
< 0.05). In addition, Pearson
coefficients of correlation values were also
determined using the same statistical software.
RESULTS AND DISCUSSION
Total phenolic content
The data reported in Figure 2 show total phenolic
compounds of the different commercial raisins
analysed. The results show that the levels of total
phenolic compounds in the commercial raisin samples
differed significantly (
α
<0.05) between all samples
produced from the different grape varieties (Cardinal,
Moscatel of Alexandria, Moscatel of Málaga and
Sultana). However, for the commercial raisins
produced from the Sultana variety, no significant
difference was found among three of the samples
analysed (SII, SIII and SIV). Thus, total phenolic
compound values ranged from 110.8 to 406.9 mg/100
g raisin (average value of 215.8 mg/100 g raisin) for
all raisin grapes analysed. As expected, commercial
white raisin samples having the lowest phenolic
concentration (ranging from 110.8 to 284.1 mg/100 g
raisin) while commercial red raisin grapes (Cardinal
variety) had the highest phenolic concentration (406.9
mg/100 g raisin) which may be related to the presence
of several phenolic compounds in high quantity, such
as procyanidins in their skins. According to
Williamson and Carughi (2010), the most abundant
phenolic compounds in raisins are usually quercetin
and kaempferol, and phenolic acids, as well as
4
caftaric and coumaric acids. Compared to the total
phenolic concentrations reported for other raisins,
values found in the commercial raisin samples tested
were comparable to concentrations found by other
authors in other raisin varieties (Pastrana-Bonilla et
al., 2003; Chiou et al., 2007). However, the values
obtained in this study were lower than the values
quantified by Meng et al. (2011) in several raisins
produced in a Chinese province.
Figure 2 - Total phenolic compounds of the commercial raisin samples studied. C - Cardinal; MO - Moscatel of Alexandria; MA – Moscatel of
Málaga; SI, SII, SIII and SIV - Sultanas. Different letters indicate statistically significant differences between the different samples tested
according to the Scheffler’s test (
α
< 0.05). Result expressed in fresh weight.
Compostos fenólicos totais das amostras comerciais de uvas passa estudadas. C - Cardinal; MO - Moscatel de Alexandria; MA – Moscatel de
Málaga; SI, SII, SIII e SIV - Sultanas. Letras diferentes indicam valores estatisticamente diferentes entre as diferentes amostras estudadas de
acordo com o teste de Scheffler (
α
< 0.05). Resultado expresso em peso fresco.
Most of the phenolic compounds during drying
process as a result of the concentration effect
resulting from the loss of water in grapes. However,
processing grapes into raisins may also result in the
loss of phenolic compounds resulting from enzymatic
and air oxidation which occurs during the drying
process (Breksa et al., 2010; Bennett et al., 2011).
According to Figueiredo-González et al. (2013), some
phenolic fractions such as hydroxycinnamic acids,
anthocyanins and flavan-3-ol derivatives are involved
in oxidative reactions by enzymatic pathways, which
contribute to degrading them and to the browning of
grapes. Karadeniz et al. (2000) studied raisin samples,
including sun-dried, dipped, and golden raisins, and
found that flavonols were not influenced by
processing while procyanidins and flavan-3-ols were
completely degraded in all raisin samples. This
problem could be partially circumvented by if
producers utilize varieties with increased phenolic
concentrations to produce raisins, because we know
that genetic factors (other than skin colour) are key
influencers of a grape cultivar’s phenolic content
(Jordão et al., 2001; Gatto et al., 2008; Costa et al.,
2014).
Antioxidant capacity and scavenger activity
For a more comprehensive and accurate evaluation of
the antioxidant capacity and scavenger activity of
commercial raisins samples, four antioxidant activity
assays (ABTS, FRAP, SRSA and HRSA) were
selected for their different functions. The antioxidant
capacity and scavenger activity of all commercial
raisin samples are shown in Figures 3 and 4.
Generally, it was clear that the antioxidant capacity
results of the 7 commercial raisin samples analysed
show a dispersion of the values between all of the
samples tested (Figure 3). This result was
independent of the two antioxidant methods used.
Thus, antioxidant capacity values ranged from 6.0 to
27.88 mM Fe(II) for the FRAP method and from 2.43
to 10.73 mM trolox for the ABTS method. Of the 7
commercial grape raisin samples, red grape raisin
samples produced from the Cardinal variety had a
significantly (
α
< 0.05) higher antioxidant capacity
(27.88 mM Fe(II) and 10.73 mM trolox, for the FRAP
and ABTS methods, respectively). In contrast to their
antioxidant capacity, white commercial raisin samples
had the lowest antioxidant capacity, especially the
commercial raisin samples of the Sultana variety
(ranging from 6.0 to 9.56 mM and from 2.43 to 4.57
mM for the FRAP and ABTS methods, respectively).
The commercial raisin sample produced from the
Moscatel of Alexandria grapes also had a low level of
antioxidant capacity. It is important to note, that, as
for total phenol content, it was also observed that the
commercial raisin samples obtained from red and/or
seed-containing berries (Cardinal and Malaga
Muscatel varieties) showed a higher antioxidant
capacity than the samples produced from the seedless
grape variety (Sultana variety). Recently, Costa et al.
5
Figure 3 - Antioxidant capacity (FRAP and ABTS methods) of the commercial raisin samples studied. C - Cardinal; MO - Moscatel of
Alexandria; MA – Moscatel of Málaga; SI, SII, SIII and SIV - Sultanas. Different letters indicate statistically significant differences between the
different samples tested according to the Scheffler’s test (
α
< 0.05).
Capacidade antioxidante (métodos FRAP e ABTS) das amostras comerciais de uvas passa estudadas. C - Cardinal; MO - Moscatel de Alexandria;
MA – Moscatel de Málaga; SI, SII, SIII e SIV - Sultanas. Letras diferentes indicam valores estatisticamente diferentes entre as diferentes
amostras estudadas de acordo com o teste de Scheffler (
α
< 0.05).
(2014) analysed 24 different grape varieties
cultivated in two Portuguese wine regions and
concluded that seeds were the grape berry fraction
with the highest antioxidant capacity followed by the
skins and pulp, irrespective the grape variety studied.
In addition, there are other factors that could affect
the polyphenolic and antioxidant capacity of this type
of natural products such as the specific effects of
drying (Bennett et al., 2011) and storage conditions
(Sanz et al., 2001). On the other hand, the antioxidant
capacity of a certain material such as grapes is nearly
always associated with the quality and quantity of
phenolics in the samples (Rodríguez-Bernaldo de
Quirós et al., 2009; Costa et al., 2014). In addition,
for Jayaprakasha et al. (2001), the antioxidant
capacity of raisins is associated, not only with
experimental materials, but also with extraction
solvents, extract concentration, and the reaction time
of the methodologies used.
The data in Figure 4 show the scavenger activity
results quantified in the commercial raisin samples
tested. As shown in Figure 4, through the SRSA
method, the results obtained ranged from 14.94 to
36.47% (average value of 23%), while as a result of
using the HRSA method, the values ranged from
33.75 to 53.59% (average value of 44%). For the
HRSA method, these results are slightly lower than
those obtained by Meng et al. (2011) in 9 different
raisin varieties from China and that ranged from
53.07 to 81.16%. In addition, according to Sun et al.
(2010) polysaccharide compounds that are abundantly
found in raisins also contribute to the scavenger
activity of raisins.
As for the individual scavenger activity of the
different commercial raisin samples tested,
superoxide radical scavenger activity (SRSA) data
revealed that the scavenger activity tendencies were
similar to those obtained for total phenolic
compounds and antioxidant capacity values. Thus, the
Cardinal variety commercial red grape raisin sample
had a significantly higher scavenger activity value
(36.47%) than commercial white grape raisin samples
6
Figure 4 - Scavenger activity (SRSA and HRSA methods) of the commercial raisin samples studied. C - Cardinal; MO - Moscatel of Alexandria;
MA – Moscatel of Málaga; SI, SII, SIII and SIV - Sultanas. * Different letters indicate statistically significant differences between the different
samples tested according to the Scheffler’s test (p < 0.05).
Atividade sequestradora de radicais livres (métodos SRSA e HRSA) das amostras comerciais de uvas passa estudadas. C - Cardinal; MO -
Moscatel de Alexandria; MA – Moscatel de Málaga; SI, SII, SIII e SIV - Sultanas. * Letras diferentes indicam valores estatisticamente diferentes
entre as diferentes amostras estudadas de acordo com o teste de Scheffler (p < 0.05).
from other grape varieties (Moscatel of Alexandria,
Moscatel of Malaga and Sultana). However, for
radical scavenger activities through the hydroxyl
radical (HRSA), no significant differences were
detected between the scavenger activities of the
different commercial raisin samples tested. From
these results it becomes clear that the scavenger
activity values depend on the method used. This
divergence is probably due to the different reactivates
of the polyphenols with each method applied. Thus,
one single method cannot comprehensively
demonstrate the scavenger activity of substances.
First, organisms have more than one antioxidant
system and second, different free radicals have
different antioxidant clearance mechanisms (Meng et
al., 2011). Finally it is important to note, that the
potential differences in drying and storage conditions
that induce, for example, a potential polyphenolic and
enzymatic composition could also determine different
raisin compositions and consequently generate
different radical scavenger activities toward hydroxyl
radicals. For Noda et al. (1997) the solubilisation of
the components of natural extracts is another factor
that must be taken into consideration when evaluating
the results of hydroxyl and superoxide radical
scavenging activities of natural products. In addition,
the use of treatments such as heat, filtration, and
enzymatic treatments will help clarify the relative
contribution of components to radical scavenging
activity.
Correlation between the different variables
Table I shows the Pearson correlation coefficients
between total phenolic content, different antioxidant
capacity methods, and different radical scavenger
methodologies. The Pearson test shows a very high
correlation (0.97 and 0.95,
α
< 0.05) between total
phenolic content and antioxidant capacity (measured
by the ABTS and FRAP methods). These high
correlation results between total phenolic content and
antioxidant capacity quantified by two methodologies
are in accordance with those reported by other authors
7
in raisins obtained from different grape varieties
(Borbolan et al., 2003; Orak, 2007; Breksa et al.,
2010). In addition, it is important to note that when
we used the Folin-Ciocalteu reagent for total phenol
determination (such as was used in this study), we not
only measure polyphenols but also the total reducing
substances from the sample. A high correlation value
(0.94,
α
< 0.05) was also obtained between the two
antioxidant capacity methodologies (ABTS and
FRAP). The SRSA method exhibited a weaker
correlation with total phenol content (0.47,
α
< 0.05)
and with the other antioxidant methodologies (0.56
and 0.47,
α
< 0.05, for FRAP and ABTS,
respectively). Finally, as for the HRSA method, the
results showed that this method did not have any
correlation with total phenolic content and the
different antioxidant methodologies. This result is
similar to what was obtained by Meng et al. (2011),
who reported a negative correlation between HRSA
and other phenolic parameters, such as total
polyphenol and total flavanoid compounds. The low
correlation or uncorrelated values (especially for
HRSA) probably imply that, generally, the raisin
extracts with the greatest ability to transfer hydrogen
atoms are the least effective at stabilizing the
hydroxyl radical.
TABLE I
Pearson coefficients of correlation values (
α
<0.05) calculated for commercial raisin samples studied.
Valores do coeficiente de correlação de Pearson (
α
<0.05) calculados para as amostras comerciais de uvas passa estudadas.
Variables
Commercial raisin samples (n = 21)
TPC FRAP ABTS SRSA HRSA
TPC --- 0.97 0.95 0.47 n.c.
FRAP --- --- 0.94 0.56 n.c.
ABTS --- --- --- 0.47 n.c.
SRSA --- --- --- --- n.c.
HRSA --- --- --- --- ---
TPC = total phenolic compounds; FRAP and ABTS = antioxidant capacity methods; SRSA and HRSA = scavenger activity methods; n.c.= not
correlated.
TPC = compostos fenólicos totais; FRAP e ABTS = métodos de capacidade antioxidante; SRSA e HRSA = métodos de atividade sequestradora de
radicais livres; n.c.= não correlacionados.
Thus, it was clear that HRSA and SRSA showed
different correlations, which is in line with the results
obtained by Rivero-Pérez et al. (2007) when these
authors studied the profiles of the antioxidant capacity
and radical scavenger activity of red wines through
various methods. In addition, these results confirm the
hypothesis that different mechanisms are involved in
capturing both types of radicals or their related
compounds. These factors may contribute to the
differences in correlation coefficients between the
different methodologies and between the different
studies carried out on this subject matter.
CONCLUSIONS
Raisins from 7 different commercial samples were
studied for their antioxidant capacity, scavenger
activity and total phenolic content in this study. The
red, Cardinal variety raisin sample had the
significantly highest total phenolic compound
content (average value of 406.9 mg/100 g raisin) and
antioxidant capacity (average value of 27.88 mM
Fe(II) and 10.73 mM trolox, respectively by applying
the FRAP and ABTS methods). In contrast,
commercial white raisin samples showed the
significantly lowest total phenolic compound content
(average value of 719.9 mg/100 g raisin) and
antioxidant capacity (average value of 8.98 and 4.52
mM trolox, respectively by applying the FRAP and
ABTS methods). In addition, high correlation
coefficient values between total phenolic content,
antioxidant capacity and among the different
methods for quantifying antioxidant capacity were
obtained.
Thus, the results obtained confirm that commercial
raisins constitute a natural source of polyphenols and
antioxidants. However, the comparison of these
values should be conducted with caution since they
are obtained from a limited number of commercial
raisin samples and the results could vary notably
with respect to others.
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... Generally, the dried seedless grape cultivars where the internal moisture is reduced to around 15% are known as raisins (Karimi and Mirzaei, 2018). Raisins are a good source of nutritive elements, including of potassium, iron, flavonoids and organic acids, and their health benefits have been documented by many researchers (Karadeniz et al., 2000;Sério et al., 2014;Restani et al., 2016). Today the global production of industrial dried grape as raisins reached 1.21 million tons based on the final report of the United States Department of Agriculture (USDA, 2019). ...
... 'Red Sultana' is a main grape (Vitis vinifera L.) cultivated variety in Iran and many grapeproducing countries of the world and consumed mainly as table grape, juice and raisins (Ghrairi et al., 2013;Karimi and Mirzaei, 2018). However, improper fertilization condition could negatively influence its raisin phenolic compounds and antioxidant capacity (Sério et al., 2014;Ghrairi et al., 2013). Therefore, application of proper treatments that increase the nutritional value and further accumulation of secondary metabolites in this cultivar may increase the quality of raisins. ...
... Iron has a key role in tree fruit carbohydrate metabolism and quality. Glucose and fructose are two main soluble sugars in raisin (Ghrairi et al., 2013) with an inherent low glycemic index which can enter in blood stream without digestion and provide energy immediately for those persons subjected to stress (Sério et al., 2014). Moreover, potassium and iron have different physiological functions in grape nutritional profile (Karimi and Mirbagheri, 2018) and in our study their application improved the quality of raisins as a functional food. ...
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Article type: Raisins are good sources of bioactive compounds with beneficial effects on human health. Mineral nutrition is one of the main viticultural practices affecting grape and raisin phytochemical compositions. In this study, the effect of preharvest foliar application of potassium (K2SO4; 0, 1.5 and 3%) and iron (Fe-EDDHA; 0, 0.5 and 1%) was evaluated on some nutritional and biochemical properties of raisins produced from ripped 'Red Sultana' grape (Vitis vinifera L.). The experiment laid on a factorial arrangement of variables using a completely randomized block design. The highest soluble sugars of fructose and glucose were related to raisin produced from the vines treated with 3% potassium in combination with 0.5% iron fertilizers. However, 3% K2SO4-treated vines in combination with 1% Fe-EDDHA showed a considerable increase in raisin sucrose and also putrescine concentration. The raisin organic acids of succinic acid, fumaric acid, citric acid, and malic acid increased significantly in treated vines with both fertilizers at final doses; however, tartaric acid showed the highest amount in 3% potassium in combination with 0.5% iron treatments. The vines treated with a high level of potassium in combination with moderate level of iron produced raisin with the highest phenolic acids of kaempferol, quercetin, chlorogenic acid and resveratrol and also showed the lowest polyphenol oxidase activity. Furthermore, raisin cinnamic acid, rutin and catechin concentration showed a peak in vines sprayed with a high level of potassium and iron and also most anthocyanidins such as petunidin-3-glucoside, peonidin-3-glucoside, cyanidin-3-glucoside and delphinidin-3-glucoside reached their highest concentration by this treatment. Likewise, the highest antioxidant capacities (measured by FRAP, DPPH and ABTS methods) were achieved in 3% potassium-treated vines in combined with iron at a moderate level. In conclusion, results indicated that preharvest application of potassium and iron are highly effective to improve the Red Sultana raisin bioactive compositions.
... Moreover, t cell uptake ratios of Urumqi berries were higher than Turpan berries. There was a very high correlation between phenolic compounds and antioxidant c pacity [26]. Grape berries have been shown to have antioxidant activity by the DPPH a say [27]. ...
... The antioxidant activity of grape berries planted in Urumqi w better than in Turpan in both the ORAC assay and the CAA assay. It was speculated th There was a very high correlation between phenolic compounds and antioxidant capacity [26]. Grape berries have been shown to have antioxidant activity by the DPPH assay [27]. ...
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As popularly consumed fruit berries, grapes are widely planted and processed into products, such as raisins and wine. In order to identify the influences of different climatic conditions on grape coloring and quality formation, we selected two common varieties of grape berries, ‘Red Globe’ and ‘Xin Yu’, for investigation. Grapes were separately grown in different climates, such as a temperate continental arid climate and a temperate continental desert climate, in Urumqi and Turpan, China, for five developmental stages. As measured, the average daily temperature and light intensity were lower in Urumqi. Urumqi grape berries had a lower brightness value (L*) and a higher red-green value (a*) when compared to Turpan’s. A RT-qPCR analysis revealed higher transcriptions of key genes related to anthocyanin biosynthesis in Urumqi grape berries, which was consistent with the more abundant phenolic substances, especially anthocyanins. The maximum antioxidant activity in vitro and cellular antioxidant activity of grape berries were also observed in Urumqi grape berries. These findings enclosed the influence of climate on anthocyanin accumulation and the antioxidant capacity of grapes, which might enlarge our knowledge on the quality formation of grape berries and might also be helpful for cultivating grapes with higher nutritional value.
... μmol Fe/g for grapes grown in Poland. Sério et al. (2014) showed that FRAP values ranged between 6.0 FeSO4/g and 17.4 FeSO4 g. Guo et al. (2003) reported that the FRAP value was as follows: seed > peel > pulp, respectively. ...
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This study aimed to investigate the effects of altitude and ripening stage on the total fat content and fatty acid composition, antioxidant properties, and phenolic profiles of the seed, skin, and pulp of the ‘Karaerik’ grape. Amounts of gallic acid, catechin and total monomeric anthocyanin contents, as well as metal chelation properties and antioxidant activity (FRAP and DPPH●) of ‘Karaerik’ grape samples were found to be statistically significant (p < 0.01). On the other hand, total fat, altitude, ripening groups, and years were found to be statistically insignificant (p > 0.05). While altitude and ripening did not show an effect on total fat, a significant effect was found for the core part. Palmitic and stearic acid from saturated fatty acids and linoleic acid from unsaturated fatty acids were determined as major fatty acids. K, Mg, Ca, P, Zn, Cu, and Fe were found to be the main minerals in seeds.
... Seeded raisin varieties (Ekşi Kara and Gök Üzüm) showed the lowest activity of all the studied enzymes. Sério et al. [14] reported that the raisins produced from the white Sultana seedless grape variety showed a lower antioxidant capacity than the commercial raisin samples obtained from red and/or seed-containing berries. Costa et al. [44] reported that the seeds, rather than skins and pulps in different grape varieties, had the highest antioxidant capacity. ...
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... Türkiye produces 3.67 million tons Mehmet Settar Unal munal62@hotmail.com M. S. Unal Fig. 1 Local grape varieties used as plant material in the study content, and drying time (Sério et al. 2014;Keskin et al. 2022). During the drying process, there is a significant concentration difference in total antioxidant activity, volatile compounds, vitamins, minerals, and fiber content compared to fresh grapes (Franco et al. 2004). ...
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... Raisin production is generally followed by three stages, namely pretreatment, drying, and post-drying. Drying processes considerably affect the raisin quality due to their impact on the duration of dried, sugar concentration and enzymatic activity [4]. During the drying process of grapes, there is a significant concentration in the fiber content, total carbohydrates, minerals, vitamins, fruity volatile compounds, and general antioxidant activity compared to non-dried grapes [5]. ...
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... According to Zhang and Tsao (2016), these substances, present in some types of foods act in the prevention of chronic diseases and can contribute to minimize oxidative stress, which occurs in metabolic reactions, for example. When the grapes are inserted in the daily diet, essential nutrients such as fiber are obtained in values that contribute to health benefits, such as antioxidant, cardioprotective, anticancer, antiaging and antimicrobial effects (SÉRIO et al., 2014). ...
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The effects of sun drying, shielding film drying and room drying on the quality of seedless purple and green raisins were analyzed. We determined the phenolic substances and antioxidant capacity of raisins. The results showed that: the contents of total phenolic and total flavonoid of raisins in room drying were higher compared with the other two drying methods and had a better antioxidant activity. Overall, the peroxyl radical scavenging capacity and the cellular antioxidant activity of purple seedless raisins were higher than green seedless raisins. The correlation analysis showed that the phenolic substances were related to the antioxidant capacity. The findings illustrated that room drying is suitable for making seedless raisins, which can retain its phenolic substances and antioxidant activity.
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A method for the screening of antioxidant activity is reported as a decolorization assay applicable to both lipophilic and hydrophilic antioxidants, including flavonoids, hydroxycinnamates, carotenoids, and plasma antioxidants. The pre-formed radical monocation of 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS*+) is generated by oxidation of ABTS with potassium persulfate and is reduced in the presence of such hydrogen-donating antioxidants. The influences of both the concentration of antioxidant and duration of reaction on the inhibition of the radical cation absorption are taken into account when determining the antioxidant activity. This assay clearly improves the original TEAC assay (the ferryl myoglobin/ABTS assay) for the determination of antioxidant activity in a number of ways. First, the chemistry involves the direct generation of the ABTS radical monocation with no involvement of an intermediary radical. Second, it is a decolorization assay; thus the radical cation is pre-formed prior to addition of antioxidant test systems, rather than the generation of the radical taking place continually in the presence of the antioxidant. Hence the results obtained with the improved system may not always be directly comparable with those obtained using the original TEAC assay. Third, it is applicable to both aqueous and lipophilic systems.
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Natural sweet wines are mainly characterised by their high sugar concentration which can be achieved by over-ripening of grapes and/or a previous process of grape dehydration. Although the quality of these sweet wines is determined essentially by aroma compounds, few reports on phenolic compounds and colour of sweet wines have been published. Phenolic composition and colour of natural sweet wines are described now in this review from two points of view: influence of drying or dehydration process on colour and phenolic composition of grapes for producing natural sweet wines; and also, influence of grape sugar process on colour and phenolic composition of their respective sweet wines. Grapes and wines are simultaneously grouped according to the dehydration -on or -off-vine. The grape drying process should be studied in greater depth to know mechanisms involving phenolic compounds that directly affect the colour, stability and ageing of natural sweet wines.
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Raisins of 9 grape genotypes from Xinjiang Province were evaluated for phenolic composition and dietary antioxidant potential by using several assays, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging capacity, cupric reducing antioxidant power (CUPRAC), nitrite scavenging capacity (NTSC), potassium ferricyanide reducing power (PFRAP), and hydroxyl radical scavenging capacity (HRSC). Desert king had the highest content of total phenolics, total flavonoids, oligo proanthocyanidin, and total flavanols. Significance analysis demonstrated that Desert king had the highest antioxidant capacity in DPPH, CUPRAC, NTSC, and PFRAP. In HRSC, red manaizi showed the highest antioxidant capacity. 3,4-Dihydroxybenzoic acid was the predominant phenolic compound in the majority of raisin samples.
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The total antioxidant activity (TAA) of 13 typical Italian wines was determined (average 12.3 and 1.6 mM Trolox equivalents for red and white wines, respectively), and the resulting values were correlated with total phenols (1365-3326 and 96-146 mg/L for red and white wines, respectively), flavanols (203-805 and 11-49 mg/L, for red and white wines, respectively), and flavonols. Only the red wines contained appreciable amounts of flavonols (average 15.3 mg/L), with quercetin and rutin being the most abundant, followed by myricetin, kaempferol, and isorhamnetin accounting for only 0.7-3% of TAA. The TAA of investigated wines are well correlated with phenol (r = 0.9902) and flavanol (r = 0.9270) content. These results confirm that red wine polyphenols are in vitro significant antioxidants and may explain the beneficial effects of a moderate daily intake of red wines, probably through a sparing action of highly bioavailable vitamins C, E, and beta-carotene.
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Currant (Vitis vinifera L.) is a dried vine product, produced almost exclusively in Southern Greece and used in the Mediterranean diet. The three different commercial sub-varieties of currants, namely Vostizza, Gulf, and Provincial were investigated for their total polyphenol content, individual phenolic compounds, and total antioxidant capacity. Total polyphenol content was estimated with the Folin-Ciocalteau assay while identification and quantification of individual target polyphenolic compounds was performed by gas chromatography/mass spectrometry. Total polyphenol content ranged between 151mg/100g and 246mg/100g currants. Among the polyphenols studied, 17 were identified in Gulf and Provincial currants and 16 in Vostizza currants. The predominant polyphenolic compound in all currants was vanillic acid at mean concentration 1.21±0.23mg/100g currants. Caffeic acid, gallic acid, syringic acid, p-coumaric acid, protocatechuic acid, ferulic acid, and quercetin also predominated. The antioxidant activity of currants was assessed by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay. The amount of currants needed to scavenge 50% of DPPH radical (EC50) was similar for all sub-varieties ranging from about 4mg to 6.5mg. Total antioxidant capacity is in descending order Vostizza>Provincial>Gulf. By the present work, the consumption of currants is considered to contribute to the intake of antioxidants.
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The objective of this work is to analyse the drying of the Sultanine grape variety by three different solar processes. Three drying kinetics have been established respectively in a natural convection solar drier, under a tunnel greenhouse and in open sun. These tests show that the solar tunnel greenhouse drying is satisfactory and competitive to a natural convection solar drying process.
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A high-performance liquid chromatographic method coupled with UV and fluorescence detectors for the determination of polyphenols in white wines samples is reported. The proposed method was validated regarding linearity, repeatabilities within day and between days, recoveries and polyphenol stabilities.Eleven phenolic compounds including, flavanols and flavanols dimmers (procyanidins), hydroxycinnamates, flavonols and stilbene derivatives were identified and quantified. Samples were injected into the chromatograph directly without previous treatment.The in-house method validation provided good results with respect to repeatabilities (within day (RSD⩽4%) and between days (RSD⩽5%)) and recoveries (⩾97.3%).In the second part of the work the antioxidant activity of the wine samples was determined by 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay. The correlation between specific polyphenols and the antioxidant activity in samples was also investigated.