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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
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.
Table 1
Explanation of the novel model parameters for the first part of pasting curves.
Table 2
Damaged starch contents and some properties of starches.
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
Table 3
Pasting properties of starches.
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.
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
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