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Food Chemistry 172 (2015) 175182

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

Anthocyanin and antioxidant activity of snacks with coloured potato


Agnieszka Nems a,, Anna Peksa a, Alicja Z. Kucharska b, Anna Sok-etowska b, Agnieszka Kita a,
_ z_ a, Karel Hamouz c
Wioletta Drozd
a

Department of Food Storage and Technology, Faculty of Food Science, Wroclaw University of Environmental and Life Sciences, Poland
Department of Fruit, Vegetable and Cereals Technology, Faculty of Food Science, Wroclaw University of Environmental and Life Sciences, Poland
c
Department of Plant Production, Faculty of Agrobiology, Food and Natural Resources, Czech University of Life Sciences Prague, Czech Republic
b

a r t i c l e

i n f o

Article history:
Received 2 July 2014
Received in revised form 5 September 2014
Accepted 6 September 2014
Available online 16 September 2014
Keywords:
Coloured potatoes
Snacks
Antioxidant activity
Polyphenols
Anthocyanins

a b s t r a c t
Coloured-eshed potatoes of four varieties were used as raw material for coloured our and fried snack
production. The effects of thermal processes traditionally used in dried potato processing and in snack
pellet manufacturing on anthocyanin proles, total polyphenols and antioxidant properties of obtained
half- and ready products were studied. There was a signicant inuence of potato variety on the experimental our and snack properties. Flours with the highest antioxidant activities were obtained from
Salad Blue and Herbie 26 potatoes; however, the our prepared from the Blue Congo exhibited a much
higher total polyphenol and anthocyanin content. Snacks produced with coloured our had 23 times
higher antioxidant activities, 40% higher contents of polyphenols, attractive colour and better expansion
compared to control samples. The lowest losses of anthocyanins during snack processing were in snacks
with our from the purple-eshed Blue Congo and red-eshed Herbie 26.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Pellet snacks are well-known within the world market of food
products for having huge versatility regarding taste, raw materials
used and some sensory characteristics. Pellet snacks are typically
small, have large expansion, a porous structure and a crispy texture; however, these properties can differ depending upon the
raw material used. The specic physical and sensory features of
these popular snacks are the effect of starch transformation during
processing. In the manufacturing of pellet snacks, a raw material
containing starch, such as potato starch, akes, granules or grits,
are mixed with water, salt and optionally with other dough components, such as vegetable, cereal or legume our, semolina or
grits, and pellets are formed, usually with the use of low shear
extrusion technology. Pellets of approximately 2030% moisture
content are subjected to a drying process under mild temperature
conditions to obtain a half-product of approximately 1112% moisture equally dispersed throughout the pellets volume. To obtain
ready-to-eat products a thermal process, such as frying or baking,
is necessary. During that process, the pellets expand, increasing
their volume 38 times and the typical porous, light structure
and crispy texture of the nal product is created (Lusas &
Rooney, 2001).
Corresponding author.
E-mail address: agnieszka.nems@wnoz.up.wroc.pl (A. Nems).
http://dx.doi.org/10.1016/j.foodchem.2014.09.033
0308-8146/ 2014 Elsevier Ltd. All rights reserved.

There is suggested by different authors (Brown, 2005; Lachman,


Hamouz, Orsk, & Pivec, 2000; Yen & Chen, 1995) that antioxidants
naturally presented in food have health-promoting and antiaging
effects in the human body. However, depending on the type of bioactive compounds they can be well absorbed and act as antioxidants within the organism or can be abolished during rst-pass
metabolism in the intestine and liver. Among antioxidants ascorbic
acid and a-tocopherol preserve their properties in the organism
but another phytochemicals, like polyphenols lose this function
as a result of the attachment of a functional group at exactly those
positions of the molecule that are responsible for its antioxidant
activity. This is one of the reason why the referring total antioxidant capacity (TAC) of food, measured by different in vitro assays,
to its importance for human health is to be discouraged
(Pompella et al., 2014). However, antioxidants can also play an
important role in food technology by contributing to food quality,
for instance by the preventing fat deterioration in fried products.
Potatoes are known as one of the richest sources of antioxidant
compounds in the human diet. The main antioxidants are polyphenols, ascorbic acid, a-tocopherol and b-carotene. In addition, the
antioxidant activity of patatin, a tuber storage protein, has been
investigated (Hillebrand, Naumann, Kitzinski, Kohler, &
Winterhalter, 2009; Lachman, Hamouz, Orsk, Pivec, & Dvorak,
2008). Polyphenols are the largest group of plant components
and can be divided into phenolic acids, avonoids, stilbenes and
lignans (Manach, Scalbert, Morand, Remesy, & Jimenez, 2004). In

176

A. Nems et al. / Food Chemistry 172 (2015) 175182

potatoes, the major antioxidants are phenolic acids, such as chlorogenic acid that comprises approximately 80% of the total phenolic
acids (Brown, 2005), caffeic acid, cinnamic acid, p-coumaric acid,
ferulic acid and sinapic acid (Friedman, 1997), and other compounds, such as ascorbic acid, carotenoids, tocopherols, lipoic acid
and selenium (Lachman et al., 2009). As stated by Brown (2005),
coloured potatoes contain twice as much phenolic acid as yellow-eshed potatoes. However, these potatoes contain large
amounts of avonoids, particularly catechin, epicatechin and
anthocyanidins.
In recent years, there has been an increasing interest in potato
varieties with coloured esh (Manach et al., 2004; Nicoli, Anese,
& Parpinel, 1999; Perla, Holm, & Jayanty, 2012; Peksa et al.,
2011; Tajner-Czopek, Rytel, Kita, Peksa, & Hamouz, 2012), mainly
because of the high anthocyanin content of the raw material. The
authors emphasise the importance of anthocyanin stability during
food processing and discuss changes in the overall antioxidant
activity due to thermal processing of potato tissue and preservation procedures.
The aim of the present experiment was to study how thermal
processes necessary for potato our and nal snack processing
affect particular anthocyanins, total phenolic content and antioxidant properties of the extruded material and ready snacks enriched
with coloured potato our.
2. Materials and methods
2.1. Raw material
Dried potato products, such as starch obtained from Pepees SA
_ and trade grits produced by a potato facpotato factory in omza
tory in Lublin, Poland, were used as the main components of pellet
snacks in the experiment. Samples of coloured potato our were
obtained from four varieties of red and purple eshed potatoes
supplied by the Czech University of Life Sciences, Prague. Redeshed Herbie 26 and the following three purple-eshed potato
varieties were used: Val, Blue Congo and Salad Blue. Corn semolina, salt and oil purchased from the trade were used as additives.
2.2. Preparation of coloured potato our
Eight randomly selected tubers of each potato variety were
washed with tap water, strained with the use of paper towels,
mechanically peeled and cut into slices of approximately 10 mm
thick. Two simultaneous samples of tubers were prepared. Approximately 500 g samples of slices were blanched in a 1 L solution of
0.5% NaHSO3 at 80 C for 15 min, strained in a sieve and paper,
cooled at room temperature and frozen at 20 C. The samples
were then freeze-dried at 30 C. Dried slices were ground in a knife
grinder, sieved through a sieve of 1 mm mesh size, packed in plastic boxes and stored under refrigeration until further investigation.
Additionally, slices of raw tubers not blanched were freeze-dried to
obtain samples of raw material for analysis.
2.3. Preparation of dough for pellet extrusion
Fifty percent of trade potato grits in a pellet recipe were
replaced by coloured our from four coloured-eshed potato varieties. For the control sample of snacks, 335 g of starch and 130 g of
potato grits were mixed with corn semolina, salt and rape seed oil
to obtain 500 g of dough mixture. The moisture content of the
dough for extrusion was established at 4045% by adding a suitable quantity of water. The moistened mixture was pressed by a
sieve and placed in sealed polyethylene bags under refrigeration
for 12 h to equilibrate the moisture in the dough.

2.4. Pellet extrusion


Material for pellets was extruded in a single-screw extruder
(Brabender DN 20, Germany). The following extrusion parameters
were kept constant: die size (0.5 mm  80 mm), speed of dough
supplier (38 rpm), screw speed (120 rpm), screw loading (2.8 A)
and barrel temperature distribution (60 C/70 C/80 C). Strands
that had previously been subjected to extrusion but were not
expanded were cut into pellets of ca. 27  27 mm and dried at
room temperature for 12 h to ca. 1213% moisture content and
sealed in polyethylene bags to equilibrate moisture until frying.
2.5. Preparation of fried snacks
Snacks were obtained from pellets following 48 h of storage at
room temperature. The samples were fried in hot (180 C) rapeseed
oil for 1520 s (3 s after expanded product appears on the oil surface). The product to oil ratio was kept at 1:20 w/v.
2.6. Analysis
2.6.1. Proximate chemical analysis
The dry weight of the dough, the dough components and snacks
were determined by drying at 102 C until constant weight was
achieved (AOAC, 2000). In the raw material and snacks, the total
phenolics, anthocyanin content and anti-oxidant activity, as
di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH), 2,20 -azinobis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) and the ferric
reducing ability of plasma (FRAP), were also determined.
2.6.2. Extraction of polyphenols
The freeze-dried potato samples and the defatted samples of
snacks were extracted by 70% aqueous acetone (0.1% acetic acid)
in a graduated tube. The mixture was homogenised using a vortex
for 30 s and allowed to stand for 2 h at room temperature. The acetonewater solution was partitioned with chloroform to remove
the lipophilic compounds. Next, the acetonewater fraction was
collected and placed on a Bchi rotary evaporator until all residual
acetone was evaporated. The remaining aqueous extract was
brought to a known volume with distilled water and stored at
20 C until analysis. The samples were ltered with 0.2 lm lters
before HPLC-MS analysis.
2.6.3. Determination of total polyphenols
The total polyphenolic content of the extracts was determined
using the FolinCiocalteu colorimetric method, as described by
Gao, Bjork, Trajkovski, and Uggla (2000). Potato extract (0.1 ml)
and FolinCiocalteu reagent (0.2 ml) were pipetted into cuvettes.
After 3 min, 1 ml of a 20% aqueous solution of sodium carbonate
(Na2CO3) and 2 ml of distilled water were added. The absorbance
at 765 nm was measured after 1 h, and the results were expressed
as mg of gallic acid equivalents per 1 g of dry matter (DM). Data are
reported as the mean value for four measurements.
2.6.4. HPLC analysis of anthocyanins
Anthocyanins were determined using a Dionex (USA) HPLC
system equipped with a model Ultimate 3000 diode array detector,
a LPG-3400A quaternary pump, a EWPS-3000SI auto sampler and a
TCC-3000SD thermo stated column compartment, controlled by
Chromeleon v.6.8 software. A reverse phase Atlantic T3
(250 mm  4.6 i.d., 5 lm) column (Waters, Ireland) and an Atlantis
T3 (20  4.6 i.d, 5 lm) guard column (Waters, Ireland) were used.
The following solvents constituted the mobile phase: A. 4.5% formic acid and B. acetonitrile. The following elution conditions were
applied: 01 min, 5% B isocratic; 16 min, linear gradient from
510% B; 626 min, linear gradient 1020% B; 2633 min, linear

A. Nems et al. / Food Chemistry 172 (2015) 175182

gradient from 20100% B; and then the initial conditions. The ow


rate was 1 mL/min, and the injection volume was 40 lL. The column was operated at 30 C. Anthocyanins were monitored at
520 nm.
2.6.5. LCMS/MS analysis of anthocyanins
Compound identication was performed on an Acquity ultraperformance liquid chromatography (UPLC) system coupled with
a quadrupole-time of ight (Q-TOF) MS instrument (UPLC/Synapt
Q-TOF MS, Waters Corp., Milford, MA, USA) with an electrospray
ionisation source (ESI). Separation was achieved on an Acquity
TM BEH C18 column (100 mm  2.1 mm i.d., 1.7 lm; Waters).
The detection wavelength was set at 520 nm. The mobile phase
was a mixture of 4.5% formic acid (A) and acetonitrile (B). The gradient program was as follows: initial conditions 99% (A), 12 min
75% (A), 12.5 min 100% (B), 13.5 min 99% (A). The ow rate was
0.45 mL/min, and the injection volume was 5 lL. The column was
operated at 30 C.
Major operating parameters for the Q-TOF MS were set as follows: capillary voltage, 2.0 kV; cone voltage, 45 V; cone gas ow,
11 L/h; collision energy, 50 eV; source temperature, 100 C; desolvation temperature, 250 C; collision gas, argon; desolvation gas,
nitrogen; ow rate, 600 L/h; data acquisition range, m/z 100
1000 Da; ionisation mode, positive. The data were collected by
Mass-Lynx TM V 4.1. software.
2.6.6. Determination of antioxidant activity
The antioxidant activity of aqueous extracts was determined
using the Trolox equivalent antioxidant capacity (TEAC) with ABTS
and DPPH radicals and the FRAP method. The TEAC assay with
ABTS radicals was carried out according to Re et al. (1999), and
the TEAC assay with DPPH radicals was carried out according to
a procedure described by Yen and Chen (1995). The antioxidant
activity measured using FRAP was performed according to a
method by Benzie and Strain (1996). TEAC results are expressed
as lmol of Trolox equivalents per 1 g of dry matter (DM). Data
are reported as the mean of four measurements.
2.6.7. Physical properties of snacks
The texture of the obtained snacks was determined by using an
Instron type 5544 texture-measuring device with Merlin software.
The minimal force (N) necessary to break up a snack was measured
using a share blade at a displacement rate of 250 rpm. The expansion ratio of the snacks was calculated as a quotient of snack size to
pellet size. The colour of snacks (Hunter lab scale) was measured
using a Minolta CM-5 chromameter against a white reference standard. Hue angle and chroma colour space parameters were calculated from a and b values.
Hue angle = Arctan (b/a).
Chroma = ((a^2) + (b^2))^0.5 (Wrolstad, Durst, & Lee, 2005).

177

2.7. Statistical analysis


Statistical analyses of all data were performed using a one-way
analysis of variance (ANOVA). Duncans range test was used to
determine the differences among samples with a probability level
of 0.05. Statistical analyses and standard deviations were determined using Statistica v. 9.0 software (StatSoft Inc., Tulsa, OK, USA).
3. Results and discussion
3.1. The effect of processing coloured potatoes for our on
anthocyanins, total polyphenol content and antioxidant activity
Blanching coloured-esh potatoes during our processing
resulted in a decrease in anthocyanins, total polyphenols and antioxidant capacity of the obtained our in an amount dependent on
the potato variety.
3.1.1. Anthocyanins
The main anthocyanins found in the purple-eshed varieties of
potatoes studied were petunidin and malvidin. In the red-eshed
potatoes, pelargonidin derivatives were the most abundant anthocyanin (Table 2). In the tubers Blue Congo and Val, the presence of
anthocyanins such as petunidin-3-rutinoside-5-glucoside, petunidin-3-feruloylrutinoside-5-glucoside and malvidin-3-feruloyrutinoside-5-glucoside were detected. Additionally, differences in the
content of petunidin-3-caffeoylrutinoside-5-glucoside, petunidin2-p-coumaroylrutinoside-5-glucoside
and
malvidin-3-p-coumaroylrutinoside-5-glucoside were found between the samples
of raw potatoes examined, and higher levels of those anthocyanins
were found in the Blue Congo variety of potato. In tubers of the
Salad Blue variety, the same derivatives were detected; however,
in distinctly lower quantities than in the Blue Congo or Val potatoes, a decrease that was particularly notable for petunidin-2-pcoumaroylrutinoside-5-glucoside. The red-eshed Herbie 26 potatoes had the highest level of pelargonidin-3-p-coumaroylrutinoside-5-glucoside and also contained notable quantities of
pelargonidin-3-rutinoside-5-glucoside, pelargonidin-3-feruloylrutinoside-5-glucoside and pelargonidin-3-caffeoylrutinoside-5glucoside.
The current results are in agreement with reports of other
authors (Rodriguez Saona, Giusti, & Wrolstad, 1998) who proved
that the dominant anthocyanins in potatoes with red-coloured
esh were acylated glucosides of pelargonidin, such as pelargonidin glycosides-3-O-p-coumaroylrutinoside-5-O-glucoside. Lewis.
C.E. (1996) identied 5-glucoside-3-rahmnosyl glucoside derivatives of all common anthocyanidins acylated by p-coumaric or
ferulic acids in red-eshed potatoes. Alcade-Eon, Saavedra, de
Pascual-Teresa, & Rivas Gonzalo, 2004 showed that acylated glucosides of anthocyanins are present in potatoes with coloured esh,
of which the aglycons were pelargonidin, malvidin, petunidin,

Table 1
Total polyphenols content [mg * g1 DM] and antioxidant activity [lmol Trolox * g1 DM] of dried potatoes of four varieties and obtained our.
Potato Variety

Total polyphenols

Antioxidant activity
DPPH

Salad Blue
Blue Congo
Val
Herbie 26
LSD
P Potatoes.
PF Potato our.

ABTS

FRAP

PF

PF

PF

PF

3.34 0.14
4.27 0.14
3.01 0.14
2.47 0.12
0.21

1.81 0.09
1.36 0.11
1.19 0.12
1.57 0.14
0.18

7.81 0.46
15.68 0.52
10.29 0.65
4.38 0.40
0.80

22.53 0.70
14.28 1.26
7.09 0.97
20.67 1.69
1.87

5.81 0.34
9.01 0.39
6.97 0.55
6.27 0.34
0.64

36.10 2.32
24.62 1.58
14.95 9.50
35.07 3.23
8.04

5.57 0.34
13.31 0.54
7.16 0.41
1.74 0.06
0.59

29.45 1.89
17.78 1.93
27.39 2.32
26.83 2.87
3.53

A. Nems et al. / Food Chemistry 172 (2015) 175182

178

Table 2
Mass spectrometric properties of anthocyanins found in studied coloured eshed potatoes of 4 varieties.
Nr of pik

[M]+ (m/z)

MS/MS (m/z)

Compound

1
2
3
4
5
6
7
8
9
10
11
12

787,229
801,245
949,265
933,266
963,275
947,282
977,296
741,224
579,172
903,258
887,261
917,271

317,066/479,117/625,177
331,081/493,144/639,195
317,067/479,114/787,205
317,066/479,119/771,214
317,067/479,120/801,224
331,082/493,137/785,229
331,083/493,195/815,241
271,061/433,113/579.171
271,061/433,113
271,061/433,112/741,203
271,061/443,113/725,208
271,061/443,112/755,218

Petunidin-3-rutinoside-5-glucoside
Malwidin-3-rutinosside-5glucoside
Petunidin-3-caffeylrutinoside-5-glucoside
Petunidin-2-p-coumarylrutinoside-5-glucoside
Petunidin-3-feruloylrutinoside-5-glucoside
Malwidin-3-p-coumarylrutinoside-5-glucoside
Malwidin-3-feruloyrutinoside-5-glucoside
Pelargonidin-3-rutinoside-5-glucoside
Pelargonidin-3-rutoside
Pelargonidin-3-caffeoylrutinoside-5-glucoside
Pelargonidin-3-pcoumaorylrutinoside-5-glucoside
Pelargonidin-3-feruloylrutinoside-5-glucoside

peonidin and delphinidin acylated by hydrocynamic acid found in


the skin and esh. Burnmeister et al. (2011) and Hillebrand et al.
(2009) proved that potatoes with coloured esh contained two
main and several lateral pigments identied by HPLC-ESI-MS and
HPLC-DAD methods as petunidin-3-p-coumaroylrutinoside-5-glucoside and peonidin-p-coumaroylrutinoside-5-glucoside. Fossen
and Andersen (2000) determined the prole of anthocyanins in
purple-eshed potatoes and found feruloyl-glyco and rhamno-pyranosides of malvidin and petunidin. The same authors (Fossen,
Ovstedal, Slimestad, & Andersen, 2003) stated that anthocyanins
in purple-eshed potatoes were acylated with caffeic acid. Other
authors (Lachman et al., 2012) have indicated that individual cultivars of potatoes differ signicantly in their relative proportions of
anthocyanidins and anthocyanins, showing a dominance of one or
more acylated glucosides of pelargonidin, cyanidin, peonidin,
delphinidin, petunidin and malvidin.
The content of total anthocyanins in raw material ranged from
38.7 mg/100 g DM (Salad Blue) to 96.7 mg/100 g DM (Herbie 26)
(Table 3). The process of our manufacturing and potato variety
affected the anthocyanins content. The anthocyanin content of
the our from purple-esh potatoes of the Blue Congo and Val
varieties decreased compared to raw material, from 72.2% to
68.8%; and in particular, the dominant anthocyanin, petunidin2-p-coumaroylrutinoside-glucoside, was lost. Nonetheless, the
total anthocyanin content and the basic pigment, petunidin-3-caffeylrutinoside-5-glucoside, did not change signicantly in the
product from Salad Blue potatoes (also purple-eshed) but other
anthocyanins present in the our from this variety showed slight
variations.

Results suggest that anthocyanins in the Salad Blue potatoes


were better stabilised than in the other tuber varieties. Notable
losses of anthocyanins (approximately 58%) were observed in the
our of Herbie 26, a red-eshed potato, because of raw material
processing (mainly the blanching stage), mainly affected by
changes in the content of pelargonidin-3-p-coumaorylrutinoside5-glucoside (a 62.9% loss). From the results, it can be observed that
the highest losses of anthocyanins were in the our prepared from
tubers of the Blue Congo variety and the lowest in the our from
red-eshed potatoes of the Herbie 26 variety. Lachman et al.
(2012) stated that the total anthocyanin contents and their proles
were strongly associated with potato cultivars of red, purple or
blue-coloured esh.
3.1.2. Total polyphenols
Of the coloured-esh tuber varieties studied, the samples contained from 2.47 to 4.27 mg GA/g DM of total polyphenols (Table 1).
The highest content of those compounds was found in tubers of the
Blue Congo variety and the lowest content in Herbie 26 potatoes.
Experimental our manufactured from purple and red-eshed
potatoes of the four varieties studied contained from 36% (Herbie
26) to 68% (Blue Congo) less total polyphenols compared to the
raw material, and the highest loses were found in the our from
the purple-eshed Blue Congo and Val varieties.
Polyphenolics are soluble in water but susceptible to thermal
processes. This may be the reason for the distinct loses of those
natural compounds during blanching, which is the typical process
in the industry for potato grit production. They are lost by washing
out of the potato and undergoing thermal degradation. Perla et al.

Table 3
Pigments [mg cyanidin-3-glucoside * 100 g1 DM] in coloured eshed potatoes and obtained ours.
Nr of pik

Potato variety
Salad Blue

Blue Congo

Val

Herbie 26

PF

PF

PF

PF

1
2
3
4
5
6
7
8
9
10
11
12

1.77 0.084
0.263 0.172
1.71 0.604
28.34 9.30
2.07 0.385
3.97 1.125
0.617 0.104
n.d.
n.d.
n.d.
n.d.
n.d.

2.58 0.345
Traces
2.12 0.760
30.92 9.72
2.09 0.417
1.97 0.270
0.137 0.083
n.d.
n.d.
n.d.
n.d.
n.d.

2.33 0.475
0.116 0.051
4.02 0.611
75.97 12.38
3.52 0.155
7.03 1.389
0.72 0.052
n.d.
n.d.
n.d.
n.d.
n.d.

1.74 0.498
Traces
1.34 0.097
20.85 3.546
0.98 0.095
1.04 0.080
0.035 0.003
n.d.
n.d.
n.d.
n.d.
n.d.

1.96 0.048
0.353 0.107
2.73 1.542
57.77 28.75
3.64 1.343
3.75 1.713
0.521 0.139
n.d.
n.d.
n.d.
n.d.
n.d.

1.13 0.401
Traces
1.09 0.255
18.38 4.55
0.89 0.141
1.00 0.412
0.024 0.006
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
1.76 0.217
0.439 0.164
1.78 0.778
86.70 33.62
5.99 1.830

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
3.01 0.622
0.894 0.156
2.31 0.515
32.20 6.970
2.21 0.455

Sum

38.73

39.81

93.70

25.98

72.06

22.50

96.66

40.63

P Potatoes.
PF Potato our.

A. Nems et al. / Food Chemistry 172 (2015) 175182

179

Table 4
Total polyphenols content [mg * g1 DM] and antioxidant activity [lmol Trolox * g1 DM] of dough and snacks enriched with coloured potato our obtained from potatoes of 4
varieties.
Potato Variety

Total polyphenols
Douhg

Control
Salad Blue
Blue Congo
Val
Herbie 26
LSD

0.276 0.046
0.344 0.030
0.436 0.018
0.370 0.049
0.321 0.025
0.054

Antioxidant activity
Snacks

0.157 0.012
0.261 0.014
0.290 0.078
0.244 0.019
0.240 0.069
0.073

DPPH

ABTS

FRAP

Douhg

Snacks

Douhg

Snacks

Douhg

Snacks

0.61 012
0.26 0.05
1.12 0.19
0.83 0.34
0.27 0.05
0.28

0.22 0.03
0.60 0.06
0.68 0.18
0.59 0.04
0.46 0.13
0.16

1.08 0.16
0.57 0.04
2.18 0.76
1.85 0.67
0.52 0.11
0.81

0.67 0.07
1.16 0.07
1.34 0.28
1.16 0.24
1.17 0.07
0.26

0.75 0.19
0.26 0.05
1.63 0.63
1.25 0.56
0.26 0.04
0.59

0.48 0.06
0.80 0.07
0.96 0.26
0.89 0.09
0.73 0.20
0.24

Control Products without presence of coloured potato our.

(2012) studied the effect of different methods of thermal treatment


on potatoes with differing esh colour and found that cooking in
water affected total polyphenols, resulting in losses from 33% to
62% depending on potato variety and the content of these compounds in the raw material. Friedman (1997) stated that losses
of polyphenols during cooking are mainly connected to losses of
phenolic acids, and Blessington (2005) showed that cooking in
water caused higher losses of total polyphenols compared to microwaving, baking or frying.

3.1.3. Antioxidant activity


Differences in the proles of anthocyanins contained in raw
material and in the our could contribute to the differences in antioxidant activity. It has been suggested by some authors (Hamouz,
Lachman, Vokl, & Pivec, 1999; Lachman et al., 2000) that the antioxidant activity of potatoes depends on the composition and on the
content of particular anthocyanins and also on phenolic acids,
mainly chlorogenic acid and its isomers. The antioxidant activity
of anthocyanins is mainly determined by the number of free
hydroxyl groups in their structure. This may be the reason why
petunidin has a higher antioxidant activity when compared to malvidin, peonidin or pelargonidin derivatives.
The antioxidant activity of the studied raw material and the
our manufactured as a supplement of trade grits in snack pellets
in the conditions related to proceeded in potato industry, was
expressed as ABTS and DPPH and by a method utilising the reduction properties of ferric ions (FRAP). As shown in Table 1, the antioxidant and antiradical activity of the potatoes depended on the
variety. The highest activity was observed in tubers of the Blue
Congo potato variety and signicantly lower activity, expressed
as FRAP and DPPH, in the red-eshed potatoes of Herbie 26. Similarly, other authors (Lachman et al., 2008; Lachman et al., 2009)
proved that the antioxidant activity of coloured-esh potatoes
depends on the variety and on the place of their cultivation and
weather conditions during the growing of the potato plant.
Experimental potato our obtained from coloured-eshed
tubers that had previously been blanching in a solution of SO2
had higher antioxidant activity than the raw material. The presence of SO2, which is reductive, caused an increase in the reductive
power (FRAP) of the experimental our and the activity was conrmed by the ABTS and DPPH tests. The highest increase of FRAP
antioxidant activity was observed in our from Herbie 26 potatoes
(15 times as much as raw material) and the lowest in our from
Blue Congo potatoes (13 times higher). Experimental our manufactured from tubers of the purple-eshed Salad Blue variety and
the red-eshed Herbie 26 had much higher antioxidant activity
than the raw material and also had higher or similar activity compared to the our prepared from the remaining 2 potato varieties.
According to Brown (2005) and Brown, Culley, Yang, Durst, and
Wrolstad (2005), the antioxidant activity of potatoes with coloured
esh is affected mainly by polyphenols in tubers and in particular

anthocyanins. Quantity differences and the proles of anthocyanins can signicantly affect the antioxidant activity of manufactured ready products from this type of raw material. Nayak,
Berrios, Powers, Tang, and Ji (2011) showed that steam blanching
potatoes with purple esh preserved the colour of the product after
drying.
3.2. The effect of pellet snack processing on anthocyanins, total
polyphenol content and antioxidant activity of ready-to-eat products
3.2.1. Anthocyanins in snacks
There was a signicant decrease in the anthocyanin contents in
snacks compared to the dough, which is later fried to make the
snacks (Table 5). The lowest losses were observed in products supplemented with the our from purple-eshed tubers of the Blue
Congo variety (37.5%). In the remaining snack samples, much
higher losses were observed, ranging from 60% (Herbie 26) to
70% in snacks with our from Val potatoes. Kita, BakowskaBarczak, Hamouz, Kuakowska, and Lisinska (2013) fried chips
from tubers of the same potato varieties and reported lower contents of anthocyanins in the chips, from 22% to 81%, compared to
the raw material. In addition, they showed that the lowest losses
of anthocyanins were observed when Herbie 26 potatoes had been
used for crisps processing, and the highest losses were found with
the use of Blue Congo as a raw material. Lachman et al. (2012) stated that thermal processes, when related to particular potato varieties, showed a preservation of, or even a slight increase in, the
anthocyanin content and that this was dependent on the type of
process used: baking, microwaving, steaming or boiling.
In potatoes with purple esh, the most thermal stabile anthocyanin was petunidin-3-rutinoside-5-glucoside. Losses of this pigment in snacks containing our from purple-eshed potatoes
ranged from 30% (Blue Congo) to 61% (Val). The most stabile
anthocyanin in red-eshed potatoes was pelargonidin-3-rutinoside-5-glucoside. The lowest losses of this pigment (33%) were
found in snacks supplemented with our from Herbie 26 potatoes.
The resistance of 3-rutinoside-5-glucoside of petunidin and pelargonidin could be an effect of phenolic acid separation from related
acylated anthocyanins, which most likely increased the concentration of 3-rutinoside-5-glucosides.
The basic factors that decrease the anthocyanin content in food
products are the conditions of the thermal processes and extrusion,
particularly when conducted at high temperatures and pressures
(Camire, Chaovanalikit, Dougherty, & Briggs, 2002). According to
these authors, extrusion cooking at a temperature of 130 C
degraded 7490% of the anthocyanins in the unheated dough prepared from corn meal and fruit concentrates or powders, such as
grape, blueberry, cranberry, concord grape and raspberry.
3.2.2. Total polyphenols in snacks
Dough destined for pellet extrusion and subsequently snack frying, enriched with coloured-potato our, had higher contents of

A. Nems et al. / Food Chemistry 172 (2015) 175182

180

Table 5
Pigments [mg cyanidin-3-glucoside * 100 g1 DM] in dough and snacks enriched with coloured potato our obtained from potatoes of 4 varieties.
Nr of pik

Potato variety
Salad Blue

Blue Congo

Val

Herbie 26

Dough

Snacks

Dough

Snacks

Dough

Snacks

Dough

Snacks

1
2
3
4
5
6
7
8
9
10
11
12

0.420 0.028
Traces
0.316 0.053
4.084 0.661
0.229 0.022
0.299 0.040
0.027 0.005
n.d.
n.d.
n.d.
n.d.
n.d.

0.182 0.066
Traces
0.119 0.014
1.387 0.195
0.063 0.005
0.096 0.014
0.011 0.002
n.d.
n.d.
n.d.
n.d.
n.d.

0.272 0.026
Traces
0.254 0.015
3.597 0.171
0.118 0.018
0.207 0.007
0.021 0.004
n.d.
n.d.
n.d.
n.d.
n.d.

0.191 0.069
Traces
0.162 0.101
2.229 1.198
0.156 0.108
0.106 0.062
0.009 0.005
n.d.
n.d.
n.d.
n.d.
n.d.

0.256 0.080
Traces
0.228 0.021
3.573 0.234
0.110 0.005
0.219 0.005
0.019 0.000
n.d.
n.d.
n.d.
n.d.
n.d.

0.098 0.036
Traces
0.072 0.017
1.112 0.262
0.051 0.014
0.054 0.006
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.520 0.056
0.178 0.019
0.343 0.043
4.880 0.536
0.3801 0.047

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.347 0.118
0.065 0.0347
0.141 0.064
1.811 0.912
0.189 0.068

Sum

5.375

1.858

4.469

2.853

4.405

1.387

6.301

2.533

total polyphenols than dough containing only industry made


potato grits. The highest quantity of polyphenols was found in
dough prepared with our from tubers of the purple-eshed Blue
Congo potato variety.
Dough processing, with low shear extrusion, drying at room
temperature and frying in oil at 180 C for 20 s, caused a stated
decrease in polyphenol content. Snacks manufactured with the
addition of coloured our had similar contents of total polyphenols, from 0.240 (Herbie 26) to 0.290 mg GA/g DM (Blue Congo)
and higher values than snacks made with trade potato grits (control sample), which contained 0.157 mg GA/g DM total
polyphenols.
As shown in Table 4, the highest losses of polyphenolic compounds were observed in snacks produced without the experimental our (43% loss compared to the dough before extrusion). The
total losses of polyphenols in snacks enriched with our from coloured-eshed potatoes, as a result of dough extrusion and frying,
ranged from 25% (Salad Blue and Herbie 26) to 34% (Val). The
most polyphenols were found in the products supplemented with
our from Blue Congo potatoes. These results suggest that the
polyphenols present in tubers of coloured-eshed varieties are better stabilised during thermal processes than polyphenolic compounds in potatoes of traditional coloured esh. These
differences also depended on potato variety and on the polyphenolic prole.
Brown, Durst, Wrolstad, and De Jong (2008) stated that the
polyphenols in tubers of red and purple-coloured esh are better
preserved in ready-to-eat products after processing by various
methods, including frying, compared to potatoes of traditional
white, crme or yellow esh that mainly contain the polyphenol
chlorogenic acid.

3.2.3. Antioxidant activity of snacks


The production conditions of pellet snacks signicantly contributed to changes in the antioxidant activity of the nal product,
compared to the dough (Table 4). The direction of those changes
depended on the potato variety used for our production.
From the data in Table 4, it appears that the antioxidant activities of snacks obtained with our from the Blue Congo and Val
potatoes and products that were not supplemented with coloured
our were signicantly lower compared to the antioxidant activity
of the dough. In contrast, a 50% increase in antioxidant capacity was
observed in snacks after the addition of our from Salad Blue and
Herbie 26 potatoes. These differences could be due to a higher degradation of total polyphenols in snacks supplemented with Blue
Congo and Val potato our (approximately 35% of total phenolics)

than in snacks supplemented with our from Salad Blue and Herbie
26 potatoes (approximately 25% of total phenolics) (Table 4).
The increase in antioxidant activity could also result from the
presence of Maillard reaction products, most likely created during
extrusion and frying of dough that contains suitable quantities of
necessary substrates, such as reducing sugars and amino acids.
Thermal processes can contribute to the creation of browncoloured complex polymeric compounds known as melanoidin
pigments, which can show antioxidant capacity, such as hydroxymethyl furfural. Similarly, other authors (Nicoli et al., 1999) have
noted an increase in antioxidant activity as a result of vegetable
and fruit processing and explained this increase as the effect of
Maillard reactions and fermentation processes or protein hydrolysis. According to Blessington (2005), thermal processes, such as
frying and microwaving, can increase the antioxidant activity of
potatoes. In addition, Dewanto, Wu, and Liu (2002) stated that
heating process increased the antioxidant activity of vegetable
products. They found increases of 44% in the phytochemical content, such as ferulic acid and total phenolics, present in sweet corn
subjected to 115 C for 25 min. Other authors (Turkmen, Sari, &
Velioglu, 2005) have suggested that the changes in total antioxidant activity depend on the type of vegetable but not on the type
of cooking process. Generally, thermal stages of food processing
are suggested to be one of most important factors affecting the
destruction or changes in the phytochemicals naturally present
in raw material and therefore change the antioxidant capacity of
the processed food (Nayak et al., 2011; Nicoli et al., 1999).
3.3. The effect on physical properties of pellet snack enrichment with
coloured potato our
3.3.1. Colour
As can be observed from the data presented in Table 6, snacks
supplemented with the our from coloured esh potatoes had
novel visual characteristics not found in traditional snacks. They
displayed an interesting colour that was affected by the anthocyanins present in the purple and red-eshed potatoes that were used
as the raw material.
These compounds did not undergo total destruction during
snack processing, and this could have affected the resulting colour.
All of the snacks that were obtained using coloured our had lower
lightness (L in the range 64.2366.90) than control samples. The
addition of our from red-eshed Herbie 26 potatoes resulted in
a pink colour (Hue = 29.55) that was attractive to the consumer.
The saturation of the colour (Chroma) of snacks supplemented
with our from the red-eshed potato variety was more distinct
(C = 15.55) than the colour of snacks produced with the our from

A. Nems et al. / Food Chemistry 172 (2015) 175182

181

Table 6
Physical properties of snacks enriched with potato our obtained from potatoes of 4 coloured eshed varieties.
Control

Feature

Colour (Hunter Lab)

LSD

Salad Blue

Blue Congo

Val

Herbie 26

65.24 1.13
4.76 0.39
4.62 0.25

64.23 0.21
4.98 0.15
347.47 0.82

64.56 0.19
4.90 0.15
357.55 10.02

66.90 1.12
15.55 0.29
29.55 0.66

L
C
H

80.56 0.84
20.01 0.46
83.17 0.35
3.83 0.41

5.59 0.49

4.86 0.12

5.40 0.46

5.50 0.56

0.52

[N]

29.04 9.49

31.09 17.36

35.69 15.49

29.52a 10.43

35.94 19.47

7.57

Expansion index
Texture

Potato variety

0.72
0.29
98.06

Control Snacks without the presence of coloured potato our.

the purple-eshed potatoes (C coordinate values between 4.34 and


4.90). Snacks made using a traditional recipe, without the addition
of coloured our, had a more intense crme-yellow colour
(C = 20.01, Hue = 83.17). All of the snacks that were supplemented
with the our from potatoes with purple esh (independent of the
potato variety) were a grey colour with a light blue shade (values
of Hue coordinate closed to 0).
Processing can change the anthocyanin content and the colour
in fruits and vegetables. The overall colour changes could be due
to a number of factors such as pigment degradation, pigment
polymerisation, reactions with other components of the formulation, non-enzymatic browning, oxidation of tannins, and other
reactions completely unrelated to the added coloured our
(Wrolstad et al., 2005).
Phenolics, such as phenolic acids and anthocyanins, can be destructed by physical factors during food processing or enzyme activity in vegetables and fruits stored in different conditions (Kader,
Irmouli, Nicolas, & Metche, 2002; Rossi et al., 2003). The conditions
of food processing can cause a discoloration of polyphenols present
in raw material into yellowish or brownish pigments (Clifford,
2000) found in the colour of ready-made products.
3.3.2. Texture and expansion index
Incorporation of the experimental our into the pellet snack
recipe did not signicantly change their texture. Similar to the control sample, snacks supplemented with coloured-eshed potato
our had a hardness of 30 N (Table 6). These results are similar
to the data presented by Peksa, Kita, & Zieba, 2004, who measured
the texture of potato snacks supplemented with dietary bre and
Peksa, Miedzianka, Kita, Tajner-Czopek, and Rytel (2010) who
determined the texture of snacks with added potato proteins.
The texture of expanded snacks is dependent on the content of gelatinised starch, its chemical composition and is correlated with the
expansion index of the nal product (Lusas & Rooney, 2001).
Experimental our used as a component of pellet snacks
improved their expansion ratio, independent of the tuber esh colour and potato variety. Snacks supplemented with coloured our
were noticeably more expanded than control snacks. The expansion index of snacks with experimental our ranged from 4.86 to
5.59 and was approximately 40% higher compared to traditional
snacks (on average 3.83). The greatest expansions were observed
from the addition of our from Salad Blue, Herbie 26 and Val
potato varieties.
The texture of pellet snacks and their expansion indexes are
directly dependant on the degree of starch gelatinisation, which
is the main component of potato snacks. Only products that have
almost all of the starch in the gelatinised form expand properly
(Lusas & Rooney, 2001). The carbohydrate composition and
changes of these compounds in potatoes of coloured esh are not
well recognised but can have an important inuence on the creation of physical features and sensory properties of expanded
snacks manufactured with their addition.

4. Conclusions
The antioxidant activity of ours from coloured-eshed potatoes and the pellet snacks produced with the coloured our serving
as one of the dried components varied depending on the potato
variety. Blanching in a solution of SO2 during potato our production was the most important factor affecting the antioxidant and
antiradical activity of coloured our and increased the antioxidant
activity from 2 to 15 times, dependant on the potato variety and
method of determination. However, this increase was not found
in the ours obtained from the Blue Congo and Val varieties of
purple-eshed potatoes. Flour with the highest antioxidant activity
was prepared from Salad Blue and Herbie 26 potato varieties, and
Val potatoes had the lowest activity. Blue Congo potatoes had
much greater total polyphenols and anthocyanins compared to
purple-eshed Salad Blue and red-eshed Herbie 26 potatoes. In
purple-coloured our, petunidin-2-p-coumarylrutinoside-5-glucoside dominated; and in red-coloured our, pelargonidin-3-pcoumaorylrutinoside-5-glucoside dominated. Thermal process
applied in experimental our production caused a 3868%
decrease in polyphenols and a 5872% decrease in anthocyanins
and was particularly high in products prepared from tubers of
the purple-eshed Blue Congo and Val varieties. The compounds
in the dry matter of purple-eshed Salad Blue and, to a lower
degree, present in red-eshed Herbie 26 affected the higher stability of the anthocyanins present in tubers during the blanching
process. The least stabile anthocyanins were found in the purpleeshed potatoes, malwidin-3-p-coumarylrutinoside-5-glucoside
and petunidin-2-p-coumarylrutinoside-5-glucoside, and the most
stable were petunidin-3-rutinoside-5-glucoside. In Herbie 26 our,
pelargonidin-3-rutinoside-5-glucoside, pelargonidin-3-caffeoylrutinoside-5-glucoside and pelargonidin-3-rutinoside anthocyanins
were present in lower quantities but were better stabilised during
thermal processes than the same anthocyanins in the other potatoes varieties examined.
Snacks produced with coloured potato our had 23 times
higher antioxidant activity, particularly when measured by DPPH,
compared to control samples with commercial potato grits as the
our component and contained on average 40% more of polyphenols. The processes of low shear extrusion and frying utilised for
snack production affected a decrease in the antioxidant activity of
products with our from the Blue Congo and Val varieties but an
increase in activity in snacks with our from the Salad Blue and
Herbie 26 varieties. The anthocyanin content in snacks depends
on the variety of potato used for coloured our production. The
highest content of these compounds and the lowest losses during
snack processing were in snacks with our from the purple-eshed
Blue Congo and the red-eshed Herbie 26 potatoes. The utilisation
of experimental, coloured potato ours favourably affected the colour and expansion index of the obtained snacks and did not changed their texture. In particular, the red-coloured our from Herbie
26 potatoes resulted in an attractive snack colour.

182

A. Nems et al. / Food Chemistry 172 (2015) 175182

Acknowledgements
The authors would like to acknowledge the Wrocaw University
of Environmental and Life Sciences for nancial support of the doc_
toral Grant NOZ/85/2013/SC.

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