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Journal of Cereal Science 74 (2017) 272e278

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Journal of Cereal Science


journal homepage: www.elsevier.com/locate/jcs

A modeling approach in the interpretation of starch pasting properties


_
Ibrahim €
Palabiyik a, *, Omer Said Toker b, Safa Karaman c, Onder Yildiz d
a
Namik Kemal University, Agricultural Faculty, Food Engineering Department, 59030, Tekirdag , Turkey
b _
Yildiz Technical University, Chemical and Metallurgical Engineering Faculty, Food Engineering Department, 34210, Istanbul, Turkey
c
Erciyes University, Engineering Faculty, Food Engineering Department, Kayseri, Turkey
d  dır, Turkey
Igdır University, Engineering Faculty, Food Engineering Department, 76000, Ig

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

Article history: In this work, starch pasting curves were reinterpreted with suitable models to show deficiency of widely
Received 20 December 2016 used starch pasting parameters in the literature. The aim was to attract scientific attentions to the
Received in revised form behavior and dynamics of the curve with respect to process parameters instead of values on the curve.
19 February 2017
Mainly, pasting curve was separated into four parts combining sigmoidal gelatinization model, expo-
Accepted 20 February 2017
Available online 21 February 2017
nential thinning model and Arrhenius temperature model. For the gelatinization part, starch swelling
rate, water binding capacity and starch resistivities to heat and shear might be compared by the pro-
posed model parameters. Amylose and damaged starch contents of starches had a good relation with
Keywords:
Hill model
Arrhenius and exponential model parameters. Activation energy values gave clues about retrogradation
Starch rate of starches and changed between 7142 and 17,327 kJ/mol.
Viscosity © 2017 Elsevier Ltd. All rights reserved.
Pasting parameters

1. Introduction limited their usage in the food industry. Therefore, investigation of


those characteristics of the starches is required.
Starch is a plant-based polysaccharide widely used in the food Determination of pasting properties of starches gives informa-
industry. Easy availability, cheapness, abundant sources, biocom- tion about gel viscosity, shear resistance and retrogradation
patibility, biodegradability and non-toxic characteristics (Yuliana behavior. There are different methods for pasting analysis which
et al., 2012) enable them to be also used in many industries such can be carried by differential scanning calorimetry, rapid visco
as pharmaceutical, biomedical, and polymer industries (Afolabi analyzer (RVA), rheometer and amilograph. RVA is one of the
et al., 2012). Amylose and amylopectin composed of glucosyl mostly used methods which include heating/shearing/cooling
units are major constituents of the starches. Moreover, they also parts, in turn. During these steps, viscosity of the slurry is measured
include minor components such as protein, phosphorus, lipids and with respect to time and the pasting parameters (peak viscosity,
ash (Pe rez and Bertoft, 2010). Starches are added in the food for- trough viscosity, breakdown viscosity, final viscosity, setback vis-
mulations due to their influence on texture, viscosity, gel formation, cosity, peak temperature and pasting temperature) are obtained.
adhesion, binding, moisture retention, film formation and product However, unlike well-known and every time used models for
homogeneity (Kaur et al., 2012). From those properties, starches are rheological behaviors of shear thinning and yield stress fluids, there
widely used in formulations of soups, sauces and gravies, bakery is no any model used for pasting curves in the literature concerning
products, dairy confectionery, snacks, batter and coatings and meat pasting properties of starches. Instead, values on pasting curve
products (Davies, 1995). The amylose-to-amylopectin ratio of were given in the literature, which is generally inconclusive for
starches is important for functional (Jane et al., 1999) and techno- comparing and interpreting data. For instance, how fast peak vis-
logical properties of the starches, determining usage area of them. cosity is attained is generally not studied so far due to absence of a
Low solubility, high viscosity, shear resistance, thermal resistance, model, which is actually valuable in understanding gelatinization
thermal decomposition and retrogradation are drawbacks of (granule swelling) kinetics, determining processing times of foods
starches (Gul et al., 2014; Liu et al., 2012; Wani et al., 2014), which or selecting appropriate starch for an intended food product.
Therefore, using a rational model will shed light not only on un-
derstanding of relation between starch constituents and pasting
behavior but also on developing food product with desired features.
* Corresponding author.
_ Palabiyik).
E-mail address: ipalabiyik@yahoo.com (I.
Moreover, a model may help to study the effects of various

http://dx.doi.org/10.1016/j.jcs.2017.02.008
0733-5210/© 2017 Elsevier Ltd. All rights reserved.
_ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I. 273

parameters and explain texturizing effects of starches. Also exis- used in pasting analyses was adjusted to 14%. The initial tempera-
tence of a model which can predict rheological behavior of a ture was set to 50  C. In order to distribute starch particles, the
product during production is precious for process design and slurries were mixed at 960 rpm for 10 s. Then the shearing speed
quality control purposes. was reduced to a moderate value of 160 rpm. Temperature was
Therefore, the aim of this work is to analyze each stage of a increased from 50  C to 95  C in 4 min. The starch gels were mixed
typical starch pasting curve by using appropriate empirical models at 160 rpm and 95  C for 5 min. Then the temperature was reduced
which is believed to help understanding, interpreting and to 50  C at a rate of 15  C/min. Pasting parameters, namely peak
comparing data among future starch pasting properties related viscosity (PV), trough viscosity (TV), breakdown viscosity (BV), final
studies. viscosity (FV), setback viscosity (SV), peak time (PeT) and pasting
temperature (PaT) were calculated using pasting curve obtained
2. Materials and methods from analysis.

2.1. Determination of amylose content


2.5. Modeling of pasting curve
The amylose levels of the starch samples were determined ac-
cording to the methodology described by Mohammadkhani et al.
As seen from Fig. 1, the typical pasting curve was separated into
(1999). For this purpose, 5 mg of each starch sample was
four parts:
weighed into a glass tube and 1 ml of ethanol and 2.7 ml of NaOH
First Part: Temperature increased at constant rpm (160 rpm in
(1 N) were added to the glass tube. Then, the samples were kept at
this study) up to peak viscosity, where modified Hill model, gela-
175  C for 15 min to provide a complete gelatinization. The tube
tinization model (Eq. (2)), was applied to the data present in this
was then cooled, mixed on a vortex and filled with 25 ml of distilled
part.
water. Two and half ml of sample was taken from the stock solution
Second Part: Temperature also increased at constant rpm after
and neutralized with 2 ml of citric acid solution (0.15% w/v) and
peak viscosity value, where Arrhenius equation (Eq. (3)) was per-
then 1 ml of fresh iodine solution (0.2 g I2þ2 g KI þ250 ml distilled
formed to determine relation between viscosity and temperature at
water) and 14.5 ml of distilled water were added and the final
constant shear rate.
samples were kept at 4  C for 20 min. At the end, the absorbance of
Third Part: Constant temperature and speed was applied to
the samples was recorded at 620 nm using a spectrophotometer
slurry and in this part exponential model was used (Eq. (4)).
(Agilent 8443 spectrophotometer, USA). The amylose levels of the
Fourth Part: Temperature decreased at constant shear rate,
samples were determined using a calibration curve using amylose
where Arrhenius equation was used (Eq. (3)).
standard from corn (Sigma Aldrich Chemical Co, Steinheim, Ger-
First part;
many). The analyses were performed triplicate with two
The first part of a typical pasting curve is identified as the region
repetitions.
between the start of the curve and peak viscosity. It is an “S” shape
(sigmoid) curve which can be fitted to a logistic function. This curve
2.2. Determination of damaged starch content
can be fitted to a novel model which has similar roots with Hill
model (Hill, 1910).
The content of damaged starch was determined according to the
AACC 76-30A method (2000). A fungal enzyme from Aspergillus
Ln
oryzae (A6211, Sigma Chemical Co., St. Louis, MO, USA) was used. q¼ (1)
Kd þ Ln
Determinations were made in triplicate.
where q is the fraction of the ligand-binding site on the receptor
2.3. Determination of syneresis
protein; Kd is equilibrium constant for dissociation.
Hill model has been widely used in biochemistry and pharma-
Syneresis of the starch was determined according to the method
cology (Csajka and Verotta, 2006), explaining the binding of a
reported by Mali et al. (2003). For this purpose, the starch pastes
ligand to a macromolecule especially with cooperative binding. The
were prepared by the mixing of starch and water to obtain 6/100 g
novel model, Eq. (2), can be constructed as follows and definition
suspension. Starch suspensions were gelatinized under constant
and importance of the model parameters are shown in Table 1.
stirring in a thermostatic bath at 95  C and once attained this final
temperature, systems remained at 95  C during 20 min. Samples
Vpeak t S
were cooled at room temperature in a controlled temperature V¼ (2)
cabinet (20  C), prior to performing the tests. A homogeneous RS þ t S
system was obtained it was gelatinized (thermostatic bath at 95  C, Second and fourth part;
held at 95  C for 20 min), divided into plastic tubes (2.5 cm diam- Second part is the region between peak viscosity and beginning
eter, 1.5 cm height), allowed to cool at room temperature (20  C) of the third part. Common Arrhenius equation was used for these
and stored in a controlled temperature chamber at 4  C for 0, 7 and parts to determine relation between temperature and viscosity at
14 days. At different times (0, 7, 14 days) during refrigerated storage, constant shear rate.
starch systems were allowed to attain room temperature; exudates
was decanted from the samples and weighed. Exudates were h ¼ A0 expðEa =RTÞ (3)
calculated as the weight of exudate per 100 g of sample. Three
replicates were used. where A0, is the constant parameter of the model, h is viscosity (cP),
Ea is the activation energy, R is gas constant and T is temperature (in
2.4. Pasting properties Kelvin).
Third part;
Pasting properties of the pea, corn, waxy maize, wheat and The relation between time and viscosity at constant tempera-
tapioca starches were determined using rapid visco analyzer ture and shear rate was expressed by the following exponential
(Perten RVA 4500, Australia). Starch concentration of the slurry equation.
274 _ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I.

Fig. 1. Schematic diagram of pasting curve parts used in each model.

Table 1
Explanation of the novel model parameters for the first part of pasting curves.

Parameters Definitions Importance

V viscosity during processing help to predict viscosity during processing


Vpeak peak viscosity help to compare starch swelling extent or free water binding capacity
t processing time parameter help to determine processing time for the intended viscosity
R the time that gives rise to 50% of peak viscosity help to compare starch resistivities to heat and shear
S starch coefficient a kind of swelling rate and help to compare interior (granule architecture, amylose-amylopectin
ratio, damaged granules, compositions) or exterior (heating, shearing rates) effects on starch
swelling. It can be speculated due to nature of the model that if S ¼ 1, penetration of water into
starch granule does not affect penetration of other incoming water molecules; if S < 1, penetration of
water into starch granule negatively affect penetration of other incoming water molecule so its
affinity for other water molecules decreases; if S > 1, penetration of water into starch granule
positively affects penetration of other incoming water molecules so other water molecules easily
enter to the granule, therefore granule swelling rate increases by water penetration.

(6.62%) and corn (5.03%) starches, respectively. Starch granular


h ¼ K expðntÞ (4) structure and rheological and functional properties of starches are
markedly influenced by starch damage (Faridi, 1990); therefore,
where h represents viscosity (cP), K and n model parameters and t is damaged starch content is significant for the products where
the time in the third part of the curve. starches are used in the formulation. Barrera et al. (2013) reported
that damaged starch content was associated with the wheat
3. Results and discussion hardness and conditions and techniques used in the milling
process.
3.1. Damaged starch, amylose contents and syneresis of starches Amylose content of the starches varied between 0.28 and
36.61%. Waxy maize starch had the lowest amylose content
Damaged starch and amylose contents of the starches analyzed whereas it was found as highest in pea starch. Amylose contents of
in this study are presented in Table 2. As seen from the Table, the starches were found to be similar with the compositions re-
damaged starch content of waxy maize starch was found to be ported by Belitz et al. (2009). Genetics and growing conditions of
33.86%, which was followed by tapioca (8.92%), pea (7.38%), wheat starch source are known as important factors affecting chemical

Table 2
Damaged starch contents and some properties of starches.

Starch Damaged Starch (%) Amylose content (%) Syneresis (%) BV % SV %

Waxy maize 33.86 ± 1.35A 0.28 ± 0.08D 0.15 ± 0.00D 73.1 52.6
Wheat 6.62 ± 0.32CD 20.78 ± 1.57C 1.22 ± 0.11D 32.0 33.3
Tapioca 8.92 ± 0.25B 19.67 ± 0.47C 6.25 ± 0.07C 71.2 64.8
Corn 5.03 ± 0.15D 24.33 ± 0.16B 12.62 ± 0.87B 43.8 48.7
Pea 7.38 ± 0.22BC 36.61 ± 0.86A 14.72 ± 0.96A 59.3 115.0

Different uppercase superscript letters within same column show significant differences between samples (p < 0.05).
_ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I. 275

composition of starches (Gregori and Kreft, 2012; Gao et al., 2016).


The percentage of syneresis ranged between 0.15 and 14.72% PV  TV
BV% ¼  100 (5)
(Table 2). The highest syneresis was observed in pea starch and the PV
lowest was in waxy maize starch. As seen from the findings, posi-
By using this formula, the magnitude of peak viscosity and
tive correlation was observed between amylose content and syn-
trough viscosity could be eliminated and the decreasing percentage
eresis percentage (r ¼ 0.8262). The deviation from this relation
of the viscosity due to applied shear and temperature could be
between amylose content and syneresis might have resulted from
calculated. Table 2 presents the BV% values calculated for the
variation in damaged starch content and other chemical composi-
starches analyzed in the present study. BV% values of the starches
tions (trace compounds) of the starches. Charoenrein et al. (2008)
changed between 32.0% and 73.1%. According to the %BV values, the
found that the syneresis of medium-amylose rice flour was lower
most stable sample was found to be wheat starch and the least
than that of high-amylose rice flour. Retrogradation occurred dur-
stable was waxy maize. Therefore, the decreasing rate did not
ing freezing and thawing was affected by amylose content of the
correlate with the BV value. When comparing BV values of the waxy
starches (Charoenrein et al., 2011).
maize and tapioca starches, BV value of tapioca was higher, which
indicated waxy maize starch was more stable. However, as
3.2. Pasting properties of starches
considering BV% tapioca starch was found to be more stable since
its viscosity decreasing rate was lower.
Pasting curves of the starches are presented in Fig. 2. Pasting
FV values of the starches were found to change between 1572
parameters of the starches were calculated by a traditional method
and 3567 cP. Pea starch had the highest FV, followed by wheat, corn,
and their magnitudes were summarized in Table 3. Weaknesses of
tapioca and waxy maize starches, respectively. FV of the starches
dealing with only these parameters were discussed. As seen PV of
could be taken into consideration during formulation of the prod-
the starches changed between 2468 and 4569 cP. Peak viscosity of
uct since FV represents the gel or paste forming capability of the
starches is correlated with the swelling power of the starch (Kong
starches after cooking and cooling. However, since gel forming
et al., 2015). However without mentioning about viscosity
capacity of starches depends on time, FV value is also insufficient
increasing rate and giving only PV value were inconclusive when
for data comparison among different studies and inconclusive
processing times were concerned. Peak time (PeT) is the time when
when real products are concerned.
the starch gel reaches to peak viscosity value, which can also be
Another problematic parameter obtained from RVA analysis is
understood from the slope of the curve up to peak viscosity. PeT of
SV which calculated from subtraction of TV from FV. Therefore, the
the starches changed between 3.77 and 6.90 min. The starches
magnitudes of FV generally results in higher SV. If the FV and TV of
having the sharp curve up to peak viscosity had low PeT. However,
starch sample were 1000 cP and 500, respectively its SV was 500 cP.
this parameter fell short of comparing swelling rate or starch re-
For another starch FV and TV were 2000 and 1000 cP, respectively
sistivity to shear and heat among starches.
and SV was 1000 cP according to these values. When considering SV
Trough viscosity values of the samples were found to change
values, the former starch had lower SV and therefore, it was more
between 1030 and 1678 cP and breakdown viscosity equaled to
stable against syneresis since SV value is wrongly associated with
difference between magnitudes of peak and trough viscosity of the
the syneresis phenomena. However, by using the following formula
samples which varied between 790 and 3252 cP. Both parameters
similar to BV% to calculate increasing rate of viscosity, it can be
cannot result in detailed comparison about viscosity decreases or
concluded that their SV% values were equal and therefore, their
granule integrity. When considering the RVA analysis during the
stabilities against syneresis were also almost equal. Therefore, us-
step where peak viscosity reduced to trough viscosity, the gel was
ing the following formula to compare stability of the starches
sheared at constant temperature. Therefore, breakdown viscosity
against cooling and shear can be more logical.
represented the stability of the sample against applied shear and
temperature. According to the breakdown viscosity values, the
FV  TV
most stable sample was wheat starch and the least stable one was SV% ¼  100 (6)
tapioca starch. However, interpreting of this value by this way can TV
result in mistake since the sample having high peak viscosity value SV% values of the starches are also presented in Table 2 and
also generally has high breakdown viscosity value. Therefore, in varied between 115 and 33.25%. According to the SV values, pea
order to eliminate this, relative viscosity decreasing rate of the starch was found as the least stable starch, which was also suitable
starches (BV%) was calculated in the present study. The BV% was for the SV% values. Regarding SV values the most stable starches
calculated using the following formulation: were waxy maize and wheat starches; however, for SV% values
wheat starch was more stable than waxy maize starch.
The last parameter obtained from RVA analysis was pasting
temperature which ranged between 69.43 and 85.90  C. As wheat
starch had the highest PaT value, pea and tapioca starches had the
lowest. PaT of the starches is important for energy consumed dur-
ing cooking; therefore, it should be considered during production.
Considering the pasting parameters, there are significant dif-
ferences among starches and giving parameter values without
models is inadequate for data interpretation and may cause
misleading results. Pasting properties of the starches are affected
from many factors simultaneously. Amylose and lipid contents and
branch chain-length distribution of amylopectin influences the
pasting properties (Jane et al., 1999). As amylopectin enables the
swelling of the starches, amylose and lipid contents decreased
swelling capacity (Tester and Morrison, 1990). Chain-length of
amylopectin and molecular size of amylose have synergistic effect
Fig. 2. Pasting curves of the starches. on the viscosity of the starch pastes (Jane and Chen, 1992).
276 _ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I.

Table 3
Pasting properties of starches.

Starch PV (cP) TV (cP) BV (cP) FV (cP) SV (cP) PeT (min) PaT ( C)

Waxy maize 3834 ± 16C 1030 ± 13D 2804 ± 2.8B 1572 ± 17C 543 ± 30C 3.77 ± 0.04D 72.9 ± 0.6C
Wheat 2468 ± 21E 1678 ± 25A 790 ± 45E 2236 ± 33B 558 ± 58C 6.90 ± 0.04A 85.9 ± 0.0A
Tapioca 4569 ± 34A 1317 ± 9.9C 3252 ± 24A 2171 ± 55B 854 ± 65B 4.13 ± 0.00C 70.6 ± 0.6D
Corn starch 2664 ± 30D 1498 ± 70B 1165 ± 40D 2227 ± 1.2B 728 ± 72B 5.42 ± 0.04B 76.9 ± 0.0B
Pea starch 4068 ± 17B 1657 ± 49A 2412 ± 32C 3567 ± 9.2A 1910 ± 58A 4.23 ± 0.05C 69.4 ± 0.0E

PV: Pasting viscosity, TV: Trough viscosity, BV: Breakdown viscosity, FV: Final viscosity, SV: Setback viscosity, PeT: Peak time, PaT: Pasting temperature.
Different uppercase superscript letters within same column show significant differences between samples (p < 0.05).

3.3. Modeling of the pasting curve and corn starch. “S” value can be used to analyze the effect of po-
tential factors on the gelatinization dynamics by investigating one
As mentioned in materials and methods section, the obtained kind of starch at a constant process heating rate.
pasting curve was separated in four parts (Fig. 1) and each part was The second part covers the duration which is between peak
described with suitable models. viscosity and the beginning of temperature stability at maximum
In the first part, pasting curves generally exhibit a sigmoidal temperature (95  C). For corn and wheat starches, the second re-
behavior. This natural behavior has been seen in various fields and gion was not observed since they reached their peak viscosities
specific modified models accommodating this behavior have been during temperature stability. Regarding the pasting analyses
used in ecology for modeling growth of population, in medicine for method, in this part the gel was stirred at constant shear and gel
modeling growth of tumors, in chemistry for modeling autocata- temperature was increased to 95  C. Therefore, in addition to
lytic reactions, etc. Similarly, in this work the novel model (Eq. (2)) shearing factor, the effect of temperature increase on viscosity is
was proposed and parameters were described in Table 1. Three dominated here and viscosity as a function of temperature was
important kinetic parameters: Vpeak, R and S (see Table 1) were modeled with Arrhenius equation (Eq. (2)). As seen from Fig. 2,
revealed by fitting the model to viscosity change against processing viscosity of the gels decreased with increasing temperature.
time curve. In the literature, PV value has been used in this region Reduction of viscosity is associated with the decreasing intermo-
and there is no any interpretations exist about how fast peak vis- lecular forces due to the increasing distances between molecules,
cosity was reached. Peak times (PeT) was also used however the which resulted from increasing thermal energy of the molecules
beginning of gelatinization was not considered therefore this (Arslan et al., 2005). Also, temperature increase might enhance
parameter should not be used to compare swelling rate or starch granule rupture. The Arrhenius equation model parameters and the
resistivity against heat and shear. Considering the novel parame- calculated R2 values are presented in Table 4. Ea values of the waxy
ters, tapioca starch had the highest Vpeak as 4650 cP and wheat had maize, tapioca and pea starches were calculated to be 33,391,
the lowest as 2620 cP. It was found that damaged starch content or 29,632 and 15,882 kJ/mol, indicating that the pea starch gel is the
amylose content had no clear effect on the maximum paste vis- most stable starch against temperature change. By using Arrhenius
cosity. This showed that granule architecture and interaction be- model, excellent correlation between amylose content and Ea
tween granule components might have the biggest role in peak values were revealed which was not possible to determine with
viscosity and water binding capacity same as found by generally used pasting parameters in the literature. This showed
Raghunathan et al. (2017). The parameter “R” in the model which is that amylose content increased temperature stability of the gel
the time that gives rise to 50% of peak viscosity can be used to most probably due to formation of complex structure between
compare starch resistivities against process conditions. R value of granule and leached amylose in the gel phase.
wheat starch (327 s) was the highest followed by corn, waxy maize, In the third region, the obtained gels were sheared at 95  C. In
tapioca and pea starches with 250, 205, 202 and 200 s, respectively. this part, different time-dependent models, namely Weltman and
The results showed that the granule structure of wheat starch was structural models were tried but they could not satisfactorily
the most durable against heat and shear. As Tester and Morrison describe the relation between time and viscosity. The decreasing
(1990) reported that larger phospholipid content and amylosee- behavior of the third region data were fitted to exponential type
phospholipid complex restricted swelling of wheat starch granules. model and corresponding model parameters were summarized in
Nevertheless, tapioca, pea and waxy maize starch could be used as Table 4. As seen, R2 values calculated changed between 0.9465 and
thickening agent without causing more power consumption. The 0.9942, indicating that the established model satisfactorily
other novel dimensionless parameter is “S” which can be a starch described the relation between time and viscosity. The model
coefficient showing a kind of swelling rate. Waxy maize had the constant equal to slope of time versus ln h changed between
highest “S” value as 42 followed by pea, tapioca, corn and wheat 0.00222 and 0.00283. As seen damaged starch contents were
starches as 18, 16, 12 and 12, respectively. Since S > 1 for all starches, generally correlated with BV% values except for corn and wheat
penetration of water into starch granule increased granule swelling starches, however the proposed model parameter h in the third
rate. Again there is no any relation found about amylose and region was perfectly correlated with damaged starch content.
damaged starch content with the parameter “S” among different When damaged starch content increased, h value increased. The
starches. However, when amylose content was lower, the param- results showed that model parameters provide understanding
eter S increased dramatically. In fact, S value increased from 12 to about the interior structure of the granule and its technological
42 by using waxy maize instead of corn starch. Gelatinization can property. High h can be explained as the fragile structure of the gel
be accepted as a 2-step process, containing breakage of hydrogen against shear. Therefore, damaged starch content is very important
bonds in the amorphous portions of the starch and hydration and for stability of the starch against shearing. If damaged starch con-
swelling of these regions (Wani et al., 2012). Different “R” values tent increases, stability of the starches decreases. From this fact, in
and the same “S” values observed for corn and wheat starch may order to improve stability of the starch gels against applied shear,
indicate stronger hydrogen bonds of the wheat starch and the same the production process of the starch could be carefully organized.
hydration and swelling rates of the amorphous regions of wheat Otherwise, the starch used in the formulation of the product can
_ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I. 277

Table 4
Model parameters calculated for the pasting data of the starches.

1st part 2nd part 3rd part 4th part

Vpeak R S R2 A0 (cP) Ea (kJ/mol) R2 K (cP) n*100 R2 A0 (cP) Ea (kJ/mol) R2

Pea 4068 200 18 0.9986 20.42 15,882 0.9799 3380 0.247 0.9874 5.98 17,237 0.9939
Corn 2750 250 12 0.9946 N.A.a 3623 0.222 0.9779 70.52 9268 0.9946
Waxy maize 3900 205 42 0.9975 0.04 33,391 0.9437 2194 0.283 0.9543 57.09 9021 0.9588
Wheat 2620 327 12 0.9993 N.A.a 2517 0.225 0.9942 149.9 7142 0.9372
Tapioca 4650 202 16 0.9965 0.22 29,632 0.9091 2602 0.253 0.9465 29.64 11,618 0.9975
a
Corresponding region was not observed in these starches.

deteriorate the quality which may negatively influence consumer parameter in the fourth part could be used as a retrogradation rate
acceptability. in starches.
In the fourth part, as seen from Fig. 1, the starch gels were cooled
from 95  C to 50  C at constant shear. Similar to 2nd region, the Conflict of interest
obtained data were modeled with Arrhenius equation and corre-
sponding model parameters are also summarized in Table 4. R2 There are no financial disclosures or conflict of interest for any of
values calculated varied between 0.9372 and 0.9975. Ea values of the authors.
the starch gels were found to between 7142 and 17,327 kJ/mol. As
pea starch had the highest Ea value, wheat starch had the lowest. Ea
References
values generally correlated with SV% values calculated except corn
and waxy maize starch. The model parameter Ea in the fourth re- Afolabi, T.A., Olu-Owolabi, B.I., Adebowale, K.O., Lawal, O.S., Akintayo, C.O., 2012.
gion could be interpreted as a kind of retrogradation rate since Functional and tableting properties of acetylated and oxidised finger millet
amylose leached from starch granules during gelatinization forms a (Eleusine coracana) starch. Starch-Starke 64 (4), 326e337.
American Association of Cereal Chemists, 2000. Approved Methods of the AACC.
rigid structure by interacting with amylopectin chains of swollen American Association of Cereal Chemistry, St. Paul, MN.
starch granules and firmness of cooked food increased due to this Arslan, E., Yener, M.E., Esin, A., 2005. Rheological characterization of tahin/pekmez
recrystallization of starch molecules. When Ea was high, retrogra- (sesame paste/concentrated grape juice) blends. J. Food Eng. 69, 167e172.
Barrera, G.N., Bustos, M.C., Iturriaga, L., Flores, S.K., Leo n, A.E., Ribotta, P.D., 2013.
dation rate increased. This might depend on amylose content which Effect of damaged starch on the rheological properties of wheat starch sus-
was free and not bounded with lipids. Without using models, SV pensions. J. Food Eng. 116, 233e239.
value was used in the literature to interpret and compare retro- Belitz, H.-D., Grosch, W., Schieberle, P., 2009. Food Chemistry. Springer-Verlag,
Berlin Heidelberg.
gradation rates of starches. However, waxy maize had the lowest SV
BeMiller, J., Whistler, R., 2009. Starch: Chemistry and Technology, third ed. Aca-
value whereas wheat starch had the lowest Ea.. Therefore, it can be demic Press, Burlington, MA01803, USA.
postulated that SV value might show the retrogradation extent, on Charoenrein, S., Tatirat, O., Muadklay, J., 2008. Use of centrifugation-filtration for
determination of syneresis in freezeethaw starch gels. Carbohyd. Polym. 73,
the other hand, model parameter Ea showed retrogradation rate.
143e147.
Phospholipids are present more in wheat starch compared to the Charoenrein, S., Tatirat, O., Rengsutthi, K., Thongngam, M., 2011. Effect of konjac
other starches (BeMiller and Whistler, 2009). Although amylose glucomannan on syneresis, textural properties and the microstructure of frozen
content was the lowest in waxy maize starch, retrogradation rate in rice starch gels. Carbohyd. Polym. 83, 291e296.
Csajka, C., Verotta, D., 2006. Pharmacokinetic-pharmacodynamic modelling: history
wheat starch was lower than waxy maize since amylose formed a and perspectives. J. Pharmacokinet. Pharm. 33, 227e279.
complex with phospholipids in this starch and this even further Davies, L., 1995. Starch-composition, modifications, applications and nutritional
decreased recrystallization rate of starch molecules. However, value in foodstuffs. Food Technol. Eur. 6/7, 44e52.
Faridi, H., 1990. Applications of rheology in the cookies and cracker industry. In:
when enough time was given, retrogradation extent was lower in Faridi, Faubion (Ed.), Dough Rheology and Baked Product Texture. Van Nostrand
waxy maize starch compared to wheat starch as it had very low Reinhold, New York, pp. 363e384.
amylose content and it was hard for branched amylopectin mole- Gao, J., Kreft, I., Chao, G., Wang, Y., Liu, X., Wang, L., Wang, P., Gao, X., Feng, B., 2016.
Tartary buckwheat (Fagopyrum tataricum Gaertn) starch, a side product in
cules to form highly packed ordered structure. functional food production, as a potential source of retrograded starch. Food
Chem. 190, 552e558.
4. Conclusions Gregori, M., Kreft, I., 2012. Breakable starch granules in a low-amylose buckwheat
(Fagopyrum esculentum Moench) mutant. J. Food, Agric. Environ. 10, 258e262.
Gul, K., Riar, C.S., Bala, A., Sibian, M.S., 2014. Effect of ionic gums and dry heating on
Starch specific physicochemical properties determine its func- physicochemical, morphological, thermal and pasting properties of water
tionality therefore finding a model predicting product viscosity by chestnut starch. LWT-Food Sci. Technol. 59, 348e355.
Hill, A.V., 1910. The possible effects of the aggregation of the molecules of hae-
process parameters will be useful for understanding pasting moglobin on its dissociation curves. J. Physiol. 40 (iv-vii).
properties, quality control and process design perspectives. A novel Jane, J., Chen, J.F., 1992. Effects of amylose molecular size and amylopectin branch
approach for the interpretation of pasting curve was proposed by chain length on paste properties of starch. Cereal Chem. 69, 60e65.
Jane, J., Chen, Y.Y., Lee, L.F., McPherson, A.E., Wong, K.S., Radosavljevic, M.,
using suitable models. The pasting curve was divided into 4 parts Kasemsuwan, T., 1999. Effects of amylopectin branch chain length and amylose
and described by different models. Various parameters were ob- content on the gelatinization and pasting properties of starch. Cereal Chem. 76
tained and showed inadequacy of widely used pasting parameters (5), 629e637.
Kaur, B., Ariffin, F., Bhat, R., Karim, A.A., 2012. Progress in starch modification in the
in the literature. For the first part, gelatinization model parameters last decade. Food Hydrocoll. 26, 398e404.
might be used to compare starch resistivities, swelling extent or Kong, X., Zhu, P., Sui, Z., Bao, J., 2015. Physicochemical properties of starches from
free water binding capacity and swelling rates among different diverse rice cultivars varying in apparent amylose content and gelatinisation
temperature combinations. Food Chem. 172, 433e440.
starches at a constant heating rate. Negative relation was found by
Liu, T., Ma, Y., Xue, S., Shi, J., 2012. Modifications of structure and physicochemical
activation energy and amylose contents in the second part showing properties of maize starch by g-irradiation treatments. LWT-Food Sci. Technol.
temperature stability by increasing amylose content of starches. 46, 156e163.
Positive relation was found by model parameter and damaged Mali, S., Ferrero, C., Redigonda, V., Beleia, A.P., Grossmann, M.V.E., Zaritzky, N.E.,
2003. Influence of pH and hydrocolloids addition on yam (Dioscorea alata)
starch in the third part indicating fragile structure of the gel against starch pastes stability. LWT-Food Sci. Technol. 36, 475e481.
shear due to high damaged starch content. Activation energy Mohammadkhani, A., Stoddard, F.L., Marshall, D.R., 1999. Amylose content in
278 _ Palabiyik et al. / Journal of Cereal Science 74 (2017) 272e278
I.

segregating populations of einkorn, emmer, and rye. Starch/St€ arke 51, 66e73. Wani, A.A., Singh, P., Shah, M.A., Schweiggert-Weisz, U., Gul, K., Wani, I.A., 2012. Rice
rez, S., Bertoft, E., 2010. The molecular structures of starch components and their
Pe starch diversity: effects on structural, morphological, thermal, and physico-
contribution to the architecture of starch granules: a comprehensive review. chemical propertiesda review. Compr. Rev. Food Sci. Food Saf. 11 (5), 417e436.
Starch/Sta€rke 62, 389e420. Wani, I.A., Jabeen, M., Geelani, H., Masoodi, F.A., Saba, I., Muzaffar, S., 2014. Effect of
Raghunathan, R., Hoover, R., Waduge, R., Liu, Q., Warkentin, T.D., 2017. Impact of gamma irradiation on physicochemical properties of Indian Horse Chesnut
molecular structure on the physicochemical properties of starches isolated from (Aesculus indica Colebr.) starch. Food Hydrocoll. 35, 253e263.
different field pea (Pisum sativum L.) cultivars grown in Saskatchewan, Canada. Yuliana, M., Huynh, L.-H., Ho, Q.-P., Truong, C.-T., Ju, Y.-H., 2012. Defatted cashew nut
Food Chem. 221, 1514e1521. shell starch as renewable polymeric material: isolation and characterization.
Tester, R.F., Morrison, W.R., 1990. Swelling and gelatinization of cereal starches. I. Carbohyd. Polym. 87 (4), 2576e2581.
Effects of amylopectin, amylose, and lipid. Cereal Chem. 67, 551e557.

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