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Instituto de la Grasa, Consejo Superior de Investigaciones Cientcas, Avenida Padre Garca Tejero 4, 41012 Seville, Spain
Centro de Investigacin y de Estudios Avanzados del I.P.N., Unidad Quertaro, Libramiento Norponiente # 2000, Fraccionamiento Real de Juriquilla,
76230 Quertaro, Quertaro, Mexico
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Instituto de Ciencias Bsicas, Universidad Veracruzana, Av. Dr. Rafael Snchez Altamirano s/n, Col. Industrial Animas, Carretera Xalapa-Las Trancas Km. 3.5,
91192 Xalapa, Veracruz, Mexico
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Facultad de Ciencias Agrcolas, Campus El Cerrillo, Universidad Autnoma del Estado de Mxico, Piedras Blancas, Carretera Toluca Ixtlahuaca Km. 15.5,
5020 Toluca, Estado de Mxico, Mexico
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a r t i c l e
i n f o
Article history:
Received 24 March 2014
Received in revised form 11 June 2014
Accepted 20 June 2014
Available online 27 June 2014
Keywords:
Acrylamide
Tortilla chips
Minimum integral entropy
a b s t r a c t
The objective of this study was to relate the tortilla minimum integral desorption entropy with acrylamide content during processing of tortilla chips. Tortilla pieces were stored at 30 C at aw of 0.110.84 for
4 days and fried later in soybean oil at 180 C for 25 s. The lowest acrylamide content was observed in
tortilla chips made of non-stored tortilla (aw = 0.98) as well as in those prepared from tortilla stored in
the minimum integral entropy (aw = 0.53). In addition, the color and texture values were similar in both
cases. These results suggest that the reduction of the acrylamide content during processing of tortilla
chips and other tortilla based foods thermally processed might be modied by factors such as moisture
content, aw, and the physical state of water in the tortilla. Thus, the minimum integral entropy showed to
be a reliable indicator to establish the most appropriate moisture conditions to obtain tortilla chips with
reduced level of acrylamide when tortilla is dehydrated.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The Maillard reaction is the main responsible of the generation
of avor and color in thermally processed foods (Ames, 1990).
However, this reaction has been also linked to the acrylamide
formation, specically with the presence of carbonyl compounds
with groups capable of forming a Schiff Base with the amino acid
asparagine (Hidalgo et al., 2009; Mottram et al., 2002; Stadler
et al., 2002). Acrylamide, a neurotoxic compound (Spencer and
Schaumburg, 1974) and probable human carcinogen (IARC,
1994), has attracted the attention of the scientic community in
recent years due to it has been found in high concentrations in
thermally processed foods (Tareke et al., 2002).
The effect of water activity (aw) on acrylamide formation has
been widely studied. Depending on the water activity range
studied, positive or negative correlations between water activity
and acrylamide content have been observed. De Vleeschouwer
et al. (2007) showed very slight promoting effect of water activity
Corresponding author. Tel.: +52 442 211 9900; fax: +52 442 211 9938.
E-mail address: rsalazar@qro.cinvestav.mx (R. Salazar).
http://dx.doi.org/10.1016/j.jfoodeng.2014.06.029
0260-8774/ 2014 Elsevier Ltd. All rights reserved.
2.1. Materials
Labeled [2,2,3-2H3]acrylamide was purchased from Sigma
Aldrich (St. Louis, MO). All other chemicals were analytical grade
and purchased from Sigma (St. Louis, MO) or Merck (Darmstadt,
Germany). Soybean oil was obtained from local supermarkets in
Quertaro, Mxico.
2.2. Elaboration of nixtamalized corn our and tortilla chips
Nixtamalized corn our was prepared with commercial corn
variety named Pioneer 30P16 and commercial lime (Ca(OH)2) (El
Topo, Monterrey, N.L. Mexico), commonly used in the tortilla
industry. This our was prepared by cooking (8 kg) of whole corn
kernels in a solution of 16 l of water with 80 g of Ca(OH)2, corresponding to 1.0 g/100 g of lime relative to the corn weight used.
The corn was boiled in an aluminum pan for 25 min and steeped
for 16 h at room temperature (22 1 C). The steep liquor was
removed. The cooked corn was washed with 16 l of water, then
ground into corn dough (FUMASA, M100, Quertaro, Mxico),
and nally dehydrated using a ash type dryer (Cinvestav-AV,
M2000, Quertaro, Mxico). The drying conditions were adjusted
to have 250 C inlet air temperature and 90 C to the exhaust air
to avoid burning the material. Before storage, the nixtamalized
corn our was milled using a hammer mill (PULVEX 200, Mxico
DF) equipped with a 0.5 mm screen.
For tortilla chips elaboration, nixtamalized corn our (100 g)
was rehydrated with enough water (118 mL) to provide fresh
dough with proper consistency to make tortillas. The dough was
shaped into thin disks (11 cm diameter and 1.0 mm thickness)
using a commercial tortilla roll machine (Casa Herrera, Mxico,
D.F.). The dough shaped into tortillas were cooked on both sides
for around 1.0 min by using an iron hot plate (270 10 C) named
comal. The resulting tortillas were cut into circular pieces with
an average area of 10 cm2 and its aw and pH value (AACC
International, 2010) determined. Two set of tortilla pieces were
obtained. The rst set was fried immediately in soybean oil at
180 C for 25 s (control). The second set was used in the construction of desorption isotherms. After frying, tortilla chips were
cooled on a paper towel to remove supercial oil and the color,
fracture force and acrylamide content determined.
2.3. Water desorption isotherms
Water desorption isotherms were determined using a static
equilibrium method. Tortilla samples (4.0 g) (aw = 0.98) were
weighed in triplicate into standard weighing dishes with a circular
M 0 Ckaw
1 kaw 1 kaw Ckaw
P %
where Mei is the moisture content at observation i; Mci is the predicted moisture content at that observations; and N is the number
of observations. It is generally assumed that a good t is obtained
when P < 10% (Lomauro et al., 1985).
2.4. Determination of minimum desorption integral entropy
The determination of the integral (enthalpy and entropy) thermodynamic properties, and the water activity-temperature conditions where the tortilla minimum integral entropy occurred,
considered as the point of maximum storage stability (monolayer
value), was established as indicated by Pascual-Pineda et al.
(2013) and Vigan et al. (2012). These authors have provided a
thorough description of the procedure followed and equations
used for this purpose. Briey, the integral enthalpy changes
(DHint)T (J/mol) at the watertortilla interface and, at different
stages of the adsorption process, were determined using the equation of Othmer (1940).
d ln Pv
d ln P0v
Hv T
Hov T
ln Pv
Hv T
Hov T
ln P 0v A
/
DHint T
Hv T
1
Hov T
Hov T
/
/ lap la RT
W ap
Wv
aw
Md ln aw
Using the values obtained for (DHint)T changes, the molar integral entropy (DSint)T can be estimated using the following
equation:
DHint T
R ln aw
T
The fracture force of the tortilla chips was evaluated using the
Texture Analyzer TA-XT2 (Texture Technologies Corp., N.Y.). Fracture force was evaluated in freshly prepared samples. The test
was carried out using a 2.03 mm diameter stainless-steel probe
and a platform accessory with a hollow cylindrical base with
33.5 and 10 mm external and internal diameters, respectively.
The probe traveled at a velocity of 10 mm/s until it cracked the
sample (distance 6 mm).
2.8. Acrylamide determination in tortilla chips
DSint T S1 SL
2:03 104 T 3
20
15
10
40
20
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
aw (-)
Fig. 1. Moisture desorption isotherms of tortilla used to make tortilla chips at 25
(d), 30 (h) and 35 (4) C. The continuous lines are the tted points using the GAB
model.
-20
-40
Table 1
Estimated GAB parameters for tortilla desorption isotherms.
Mo (g H2O/100 g d.s.)
C
k
r2
P (%)
25
the energy value of the molecules in the monolayer and the liquid
water. When k = 1, the properties of the water present in the multilayer are similar to those of the free water (Prez-Alonso et al.,
2006).
Variations in the differential and integral entropy with respect
to aw of the tortilla used to make tortilla chips are represented in
Fig. 2. The intersection of the curves is found in the water content
and aw corresponding to the minimum integral entropy. It could be
observed that as tortilla desorbed moisture, their integral entropy
fell to a minimum. Integral entropy can be directly related to the
orderdisorder of water molecules sorbed on food, and therefore
it is a useful function to study the effect of drying method on the
stability of the product. The minimum integral entropy is expected
where strong bonds between the adsorbate and the adsorbent are
(Nunes and Rotstein, 1991), and hence water molecules are less
available to participate in spoilage reactions. This point has been
proposed as the most suitable for storage and it is considered as
the water content corresponding to the monolayer (Domnguez
et al., 2007; Hill et al., 1951).
Although the value of minimum entropy may be unique, there
are food products with zones in which this minimum does not vary
appreciably in a dened range of moisture. As it can be observed in
Fig. 2, the minimum integral entropy at 30 C for tortilla corresponds to aw value of 0.53 (13.20 g water/100 g dry solids). It
should be noted that although the minimum integral entropy
occurs in a given aw, this minimum does not vary appreciably in
a dened range of water activities (0.450.62). Differential entropy
had a minimum at 7.3 g water/100 g dry solids (aw = 0.18). This
parameter does not mean order or disorder of the total system.
The differential entropy represents the algebraic sum of the integral entropy at a particular hydration level, plus the change of
order or disorder after new water molecules were desorbed by
the system at the same hydration level. If the values of moisture
content corresponding to minimum integral entropy and minimum differential entropy are different, this particular hydration
level at the minimum differential entropy cannot be considered
as the maximum stability point, because not all available active
sites have been occupied at that particular water content, and
therefore it is possible to obtain after this point lower differential
changes that provide a better ordering of the water molecules desorbed on food (Beristain et al., 2002).
The minimum integral entropy approach has been veried in
several studies (see for example: Beristain et al., 1994; Bonilla
et al., 2010; Carrillo-Navas et al., 2011; Rascn et al., 2011).
25 C
30 C
35 C
10.11
14.67
0.66
0.99
0.96
9.46
15.72
0.67
0.99
1.36
8.96
14.26
0.70
0.99
1.58
-60
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
aw (-)
Fig. 2. Differential (j) and integral (s) entropy changes as a function of water
activity for tortilla at 30 C.
60
54
E (-)
48
42
900
600
300
0
0.0
1200
Acrylamide ( g/kg)
1500
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
aw (-)
Fig. 3. Effect of tortilla water activity on acrylamide content in tortilla chips fried at
180 C for 25 s.
0
0.0
b
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
aw (-)
Fig. 4. Effect of tortilla water activity on: color (a) and fracture force (b) in tortilla
chips fried at 180 C for 25 s.
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