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Journal of Cereal Science 54 (2011) 374e379

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Journal of Cereal Science


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

Rheology and texture of starch gels containing iodine


Simarata Dhillon, Koushik Seetharaman*
Department of Food Science, University of Guelph, Guelph, ON, N1G 2W1, Canada

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

Article history: The objective of this study was to investigate the textural and rheological properties of starch gels
Received 3 October 2010 containing different levels of iodine. The research goal is to understand the architectural organization of
Received in revised form granules by utilizing iodine as a marker. Corn (CS), wheat (WS), potato (PS) and tapioca (TS) starch gels
11 February 2011
containing varying concentrations of iodine were prepared in a Rapid Visco Analyser (RVA). The gels
Accepted 8 July 2011
were analysed by using a rheometer for small-deformation properties and also by using a texture ana-
lyser for large deformation properties following storage for 1 or 7 days. With increasing concentration of
Keywords:
iodine, the firmness of gels decreased and the extent of decrease varied for the different starches. The
Starch
Iodine
extent of change in complex modulus (G*) of the gels was highest in the A-type starch, CS, but was
Rheology different from WS, which is also an A-type starch. The G* for PS gels (B-type) decreased with the addition
Texture analysis of 0.1% iodine but there was no significant difference upon increasing the iodine concentration. The G*
for the C-type TS gels was lower than 15 Pa. These observations suggest a difference in the micro-
structure of the starch gels formed, likely resulting from differential leaching of polymers.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction oscillatory strain is increased, the samples maintain their resistance


to deformation until they reach a critical range of strain values,
Starch plays an important role in providing texture to various whereupon they yield to undergo a rapid transition from a high to
food products. Based on the type of starch and processing condi- low modulus. The plateau or the linear viscoelastic region reveals
tions, different interactions occur between the polymers and/or significant differences in the at-rest resistance to deformation i.e.,
added food ingredients, such as lipids or salts. During the process of the strength of the products. The network formed by the leached
gelatinization, the starch granules absorb water and change in polymers determines the strength of the gel and a strong interac-
shape and size due to swelling and crystal melting (Atwell et al., tion between the polymers, resulting in the formation of a matrix, is
1998; Jenkins and Donald, 1997). There is concomitant leaching of required to obtain gels with higher strength (Liu and Lelievre, 1992;
glucan polymers (amylose and amylopectin) from the swollen Lu et al., 2008).
granules, which form a gel network upon cooling (Eliasson, 1986). The glucan polymers in starch are capable of forming a complex
Depending on their structural origins (Rao et al., 1997) chemical with iodine in both solution and vapour form (Rendleman, 2003;
nature of the polymers and the dispersed granule remnants (Atkin Saibene and Seetharaman, 2006, 2008). It is known that pure
et al., 1998; Glenn et al., 2008; Rockland et al., 1977; Stark and Lynn, amylose has higher iodine binding capacity (IBC) as it adsorbs
1992), starch gels from different botanical origins exhibit a wide nearly 20 g iodine per 100 g, and amylopectin adsorbs 1 g iodine
variety of textural properties (Thebaudin et al., 1998). per 100 g (Amari and Nakamura, 1976; Davis et al., 1994). Iodine
The textural properties of starch are usually studied by either ions bind the linear polysaccharide polymer chains and form
measuring the flow behaviour of the starch dispersions or the a helical inclusion complex in which the iodine occupies the central
structural deformation of the gelatinized samples. In a low cavity of the helical polysaccharide (Rundle and French, 1943). The
frequency set, the rheological parameters, such as storage and loss gel obtained after cooking the starches in excess water is a mixture
moduli (G0 /G00 ) depend only on the dimensionless strain; as the of starch granules and the leached polymers; the ratio of which is
thought to impact the rheological characteristics, e.g. pasting
properties of the starches (Inaba et al., 1995). In the previous
studies, the effect of iodine on granular swelling (Dhillon et al., in
* Corresponding author. Department of Food Science, University of Guelph, 116
press; Patel et al., 2006) and pasting properties of starch were
Food Science Bldg, Guelph, ON, N1G 2W1, Canada. Tel.: þ1 519 824 4120x52204;
fax: þ1 519 824 6631. studied (Dhillon, 2009; Saibene and Seetharaman, 2008). It was
E-mail address: kseethar@uoguelph.ca (K. Seetharaman). shown that apart from restricting the granular swelling, iodine

0733-5210/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jcs.2011.07.005
S. Dhillon, K. Seetharaman / Journal of Cereal Science 54 (2011) 374e379 375

complexes with, and inhibits the leaching of polymers. The objec- determine the linear viscoelastic region of the samples along with
tive of this study was to investigate the effect of iodine on the various rheological parameters such as storage modulus, loss
textural and rheological properties of starch gels. modulus, phase angle and critical strain at fracture (strain at which
the gel is disrupted and there is a dramatic decrease in the value of
2. Materials G0 ).

Commercial starches from common corn endosperm (Melojel) 3.3. Texture analysis (large deformation)
[CS], common tapioca endosperm (Tapioca Starch, TS) were
obtained from National Starch and Chemical Company (Bridge- The starch pastes/gels obtained from the RVA were poured into
water, NJ, USA). A commercial starch from potato (Pencook 10) [PS] petri dishes (35 mm  10 mm); aluminium foil was used to raise
was obtained from Penford Food Ingredients Co., Colorado, and the walls of the dishes and cover the top. The samples were then
wheat starch [WS] was from MGP Ingredients Inc., Kansas. Potas- stored at room temperature for 1 day and at 4  C for 7 days. After
sium iodide (ACS reagent) was purchased from Fisher Scientific, removing the aluminium foil, the excess sample above the rim of
Nepean, Ontario and iodine crystals were supplied by Sigma each petri dish was removed with dental floss and the freshly cut
Aldrich, St. Louis. The percentage of amylose in CS, WS, PS and TS surface of the gel was analysed for the textural changes. The stored
was 21.2  0.7, 20.5  0.1, 16.7  0.2 and 17  0.5, respectively. The samples were analysed using a TAXTplus texture analyser (Texture
moisture contents (percentage) of CS, WS, PS and TS were Technologies, Inc.); the gels were measured for their compress-
11.9  0.2, 8.97  0.2, 11.44  0.3 and 9.43  0.5, respectively, as ibility using a spherical compression probe (TA-23, 0.25 inch
measured using a Megazyme Amylose/Amylopectin assay kit diameter). The pre-test, test and post-test speeds were set at 1, 0.2
(Megazyme International Ireland Ltd., Wicklow, Ireland). and 0.2 mm/s, respectively. A force of 5 g was used to compress the
10 mm gels through a depth of 4 mm. The maximum force at 4 mm
3. Methods depth exerted by the sample against the probe was recorded.

3.1. Sample preparation 3.4. Statistical analysis

In the first set of pasting experiments, iodine solution (0.1%e The experimental analyses were conducted at least in duplicate
1.1% dry starch basis) was added to the starches (8% dry basis) at and average values are reported. All statistical analyses were per-
room temperature, with a sample containing distilled water instead formed using StatGraphics Centurion Data Analysis and Statistical
of iodine solution used as control. At the lowest level (0.1%) of I2eKI Software (StatPoint Technologies, Inc., Warrenton, VA).
solution (1:10), there was 4.30  106 mol I2/g starch and 6.59 
105 mol KI/g starch; corresponding to 0.07 mM total ionic
4. Results
concentration of iodine in solution. Whereas at the highest level of
iodine addition (1.1%), there was 4.75  105 mol I2/g starch and
4.1. Rheology
7.27  104 mol KI/g starch; corresponding to 0.77 mM total ionic
concentration of iodine in solution. The starcheiodine solution
Figs. 1e4 show the behaviour of complex moduli of different
mixture (28 g) was heated in a Rapid Visco Analyser (RVA-4,
starch gels prepared with varying concentrations of iodine as
Newport Scientific, Warriewood, Australia) equipped with Ther-
a function of strain. Complex modulus (G*), which is a combination
mocline for Windows (TCW3) software, from 25  C to 95  C at a rate
of the storage (G0 ) and loss (G00 ) moduli, is a measure of the resis-
of 10  C/min with 160 rpm shear. The system was held at 95  C for
tance to deformation by the gels.
3 min before cooling to 25  C at the same rate. The temperature was
When gels containing increasing levels of iodine were subjected
held constant at 25  C before withdrawing the sample.
to small-deformation strains, a decrease in the G* and linear
In the second set of experiments, starch (8% db) and water were
viscoelastic range (LVR) was observed for CS. The addition of 0.1%
mixed in an RVA canister to make up a total of 28 g. The mixture
iodine to CS did not result in any significant difference as compared
was heated in the RVA from 25  C to 95  C at a rate of 10  C/min.
to the control sample. CS gels containing 0.2% and 0.5% iodine
Upon reaching 95  C an additional 5.5 ml of distilled water or iodine
solution (0.1%e4%) was added to the starch slurry, adjusting the
final percentage of solids in the system to 6.7%. The starch slurry
was then held at 95  C for 3 min before cooling to 25  C at the same
rate and holding stable for 3 min. The pH of the samples (7.0  0.1)
before and after the experiment was not controlled. During sample
preparation, the moisture content was taken into account while
calculating the amount of starch to be added on a dry basis.

3.2. Rheology (small deformation)

The small-deformation rheological measurements of the starch


systems were performed by controlled stress dynamic oscillatory
rheometer (AR-2000 Rheometer, TA Instruments, New Castle, DE,
USA) equipped with a parallel plate system (20 mm diameter). The
material obtained at the end of the pasting experiment in the RVA
was poured into moulds (20 mm  3 mm) and stored overnight at
room temperature. The samples, in the form of discs, were sub-
jected to a strainesweep test with the strain varying from 0.1 to Fig. 1. Complex moduli (G*) of control corn starch (CS), wheat starch (WS), potato
500%, at an angular frequency of 1 rad/s (0.16 Hz) and a set starch (PS), tapioca starch (TS), waxy corn starch (WCS) and waxy potato starch (WPS)
temperature of 25  C. The strainesweep tests were conducted to gels (8% dry basis).
376 S. Dhillon, K. Seetharaman / Journal of Cereal Science 54 (2011) 374e379

Fig. 2. Complex moduli of corn starch gels containing varying levels of iodine.
Fig. 4. Complex moduli of potato starch gels containing varying levels of iodine.

underwent a reduction in G* by 23% and 46%, respectively. The LVR


The firmness of the 7 day old starch gels as compared to 1 day
was also observed to shorten with increasing iodine concentration
old gels, both in control gels and in the presence of iodine, was not
(Fig. 2).
significantly different for WS and TS. On the other hand, the control
There was no significant difference between the WS control and
for CS and 0.1% iodine-treated samples of CS and PS were observed
0.1% iodine containing WS gels. With addition of 0.2% iodine, a 10%
to harden upon retrogradation. The firmness of TS control gel, waxy
decrease in the G* was observed (Fig. 3). With PS, the addition of
corn starch (WCS) and waxy potato starch (WPS) gels at all levels
lowest concentration of iodine (0.1%) led to gels with reduced G*,
could not be determined as the gels were too soft, and therefore
but no further reductions were observed in gels with increasing
results are not shown.
levels of iodine (Fig. 4). The G* for TS and waxy starches were below
Moreover, after a day of storage at room temperature, the 0.5%
15 Pa for control and at all levels of iodine in both sets of experi-
iodine-treated samples were 86% less firm compared to the control
ments (results not shown), and no significant differences were
for CS; the same treatment made PS gels only 43% less firm after 1
observed with further increases in iodine concentration.
day of storage. On the other hand, 0.5% iodine-treated CS gels were
68% less firm than the control after 7 days of refrigerated storage,
4.2. Texture analysis while PS gels treated similarly were 46% less firm than the control.
The firmness of starch gels treated with iodine at 95  C is
Table 1 shows the firmness of the starch gels treated with iodine reported in Table 2. Upon addition of iodine at 95  C, the gels
at room temperature. The firmness of all starch gels treated with formed were softer compared to the ones in which iodine was
iodine decreased as a function of increasing iodine concentration, added at room temperature. It should be noted that in the gels
irrespective of the temperature at which it was introduced into the where iodine was added at 95  C, an additional 5.5 ml of water was
system (RT vs. 95  C) or the age of gel (1 day vs. 7 day). involved, and this was likely largely responsible for the softness of
Firmness of 1 day old CS gel did not show a significant difference the starch gels when compared to the ones in which iodine was
from that of control following addition of 0.1% iodine; however, added at room temperature. Firmness of the gels treated with
further addition of iodine resulted in softer gels. WS, PS and TS gels iodine at 95  C decreased as a function of increasing concentration
treated with increasing levels of iodine exhibited a gradual for all starches. Only PS still formed a gel at 4% iodine concentration.
decrease in firmness. However, the gels did not show any significant retrogradation upon
storage after 7 days, except at 0.5 and 1.1% iodine level. A concen-
tration of 1.1% iodine was enough to inhibit gel formation in the rest
of the starches.

5. Discussion

Iodine is well known for its property of forming complexes with


starch polymers (Banks et al., 1971). In previous studies, we
investigated the nuances of granular structure and architecture of
different starch types as classified by their crystallinity (A, B or C-
type) by examining the effect of iodine on their granular swelling,
polymer leaching and pasting properties (Dhillon, 2009; Dhillon
et al., in press). It was observed that addition of iodine to the
starches at room temperature immediately led to the formation of
iodineeglucan polymer complexes, thereby preventing polymers
from leaching out of the granules. When iodine was added at 95  C,
the polymers had already leached out of the starch granules, thus
leading to an extragranular interaction between iodine and glucan
polymers. This prevented the leached polymers from interacting
Fig. 3. Complex moduli of wheat starch gels containing varying levels of iodine. with each other, thus affecting the nature of the network which
S. Dhillon, K. Seetharaman / Journal of Cereal Science 54 (2011) 374e379 377

Table 1
Firmness (in Newton, N) of starches treated with iodine at room temperature.

Iod CS 1d CS 7d WS 1d WS 7d PS 1d PS 7d TS 1d TS 7d
0 0.64c, AB, X 1.03c, Y 0.69d, C, X 0.70c, X 0.56c, A, X 0.71c, X nd 0.35bc
0.1 0.63c, C, X 0.83bc, Y 0.53c, B, X 0.62c, X 0.37b, A, X 0.48b, Y 0.37d, A, X 0.38c, X
0.2 0.35b, B, X 0.50ab, X 0.16a, A, X 0.30a, X 0.44ab, C, X 0.52b, X 0.28c, B, X 0.30b, X
0.5 0.09a, A, X 0.33a, X 0.37b, B, X 0.42b, X 0.32a, B, X 0.38a, X 0.08b, A, X 0.13a, X
1.1 nd nd nd nd nd nd nd nd

CS ¼ Corn starch, WS ¼ Wheat starch, PS ¼ Potato starch, TS ¼ Tapioca starch, 1d ¼ 1 day, 7d ¼ 7 day; nd e not determined.
*Values with the same letter (abcd) are not significantly different (p ¼ 0.05) for the same starch but different levels of iodine.
*Values with the same letter (ABCD) are not significantly different (p ¼ 0.05) for the same iodine level in different starches.
*Values with the same letter (XY) are not significantly different (p ¼ 0.05) for the same iodine level and same starch for 1 and 7 days.

leads to the formation of a gel. This study further investigated the matrix is weakened by the addition of iodine and the application of
gel structure and rheological properties of the iodine-treated gels. stress led to a premature failure of the gel phase. The slope of the G*
curve upon disruption of the gel also increased, suggesting
5.1. Rheology a reduced elastic behaviour of gels containing higher levels of
iodine. Therefore, it is reasonable to expect that a gel with lower G*
The rheological behaviour of starch pastes and gels is a result of will be relatively much weaker.
the combination of various parameters such as volume fraction of CS and WS have higher G* in comparison with the other
swollen granules (swelling capacity), their deformability, and starches, but give way to deforming strains much earlier, thereby
concentration of solids in the system. This behaviour is not gov- suggesting a weaker network (Fig. 1). Since the granules of PS, TS,
erned by the same rules in all starches; the pasting procedure, and WCS and WPS were considerably more solubilised during the
differences in the types and concentrations of the constitutive pasting experiment (Dhillon, 2009), the elasticity of the gels was
polymers play an important role (Doublier et al., 1987). In this much less pronounced. PS, TS and the waxy starches had low G*,
study, a paste/gel may be considered as a composite material with which would suggest that the network formed by the polymers is
the swollen/collapsed starch granules entrapped in a polymer loose, but well-knit (entangled) since it required a relatively higher
solution/matrix. strain to disrupt the gels as compared to CS and WS gels. Therefore,
The technique used for rheological measurement involved the lower values of elasticity in these starches could likely be due to
dynamic oscillations as a function of varying strain, keeping the the lack of rigid, swollen granules, possibly with the polymers
frequency constant. The gradual disruption of the three- inside as in case of CS and WS. Klucinec and Thompson (2002)
dimensional gel network can be detected only under very small- suggested that formation of physical junction zones (PJZ)
deformation conditions (Lapasin and Pricl, 1995); therefore, between amylose and external chains of amylopectin molecules
extremely low frequency was used to determine the transition could possibly occur, hence providing further stability to the gel.
strain between gel and sol state. The angular frequency was chosen Formation of complexes with iodine would lead to formation of
to be 1 rad/s (0.16 Hz) as it was important to observe a net differ- fewer such PJZ and also decreased interactions between the
entiation between the gel and the second state following the phase internal elements, hence lowering the rate and extent of retrogra-
transition. The “second” state in this set up of experiments is ach- dation, apart from having a significant impact on the gel strength.
ieved when recoverable strain, the critical strain at which an elastic Since WS contains shorter chains (Shibanuma et al., 2003), and PS
solid-like material phase transforms into a viscous state due to contains longer chains (Bertoft et al., 2008), one would expect
shear deformity response, is exceeded. Overall, the complex complexation with iodine to have a higher impact on the PJZ
modulus (G*) of the composite gels is a resultant of a combination formation in PS. This is reflected in the lowering of the G* for PS,
of parameters involving elasticity of the continuous phase, the while the same quantity of iodine did not produce a significant
volume fraction of the dispersed phase and the shape and effect on WS. In a previous study (Dhillon, 2009), the effect of
deformability of the swollen particles. A difference in yield stresses iodine was observed only above a critical concentration charac-
(the applied stress, which must be exceeded in order to make teristic for the individual starches, and below this concentration
a structured fluid flow) was observed for the samples containing there was no appreciable variation in the G* values of the starch
different levels of iodine; with increasing concentration having an gels. In some cases, this was the highest level of iodine at which
inverse effect on the relative yield stress. This suggests that the a gel was formed. This hypothesis is based on the postulation that
adhesion between the granule remnants and the extragranular the polymereiodine complex alters the behaviour of gels from

Table 2
Firmness (in Newton, N) of starches treated with iodine at 95  C.

Iod CS 1d CS 7d WS 1d WS 7d PS 1d PS 7d TS 1d TS 7d
0 0.33c*, B**, X***
0.38c, X 0.26b, A, X 0.28b, X 0.39e, B, X 0.43d, X 0.19c, A, X 0.22c, X
0.1 0.29c, B, X 0.39c, Y 0.24b, B, X 0.28b, X 0.25cd, B, X 0.30c, X 0.11a, A, X 0.14a, X
0.2 0.19b, B, X 0.27b, Y 0.12a, A, X 0.17a, X 0.26d, C, X 0.30c, X 0.16bc, AB, X 0.20bc, X
0.5 0.11a, B, X 0.12a, X 0.07a, A, X 0.14a, Y 0.21bc, C, X 0.30c, Y 0.13ab, B, X 0.17ab, X
1.1 nd nd nd nd 0.17b, X 0.27c, Y nd nd
2 nd nd nd nd 0.12a, X 0.17b, X nd nd
4 nd nd nd nd 0.08a, X 0.11a, X nd nd

CS ¼ Corn starch, WS ¼ Wheat starch, PS ¼ Potato starch, TS ¼ Tapioca starch, 1d ¼ 1 day, 7d ¼ 7 day; nd e not determined.
*Values with the same letter (abcd) are not significantly different (p ¼ 0.05) for the same starch but different levels of iodine.
**Values with the same letter (ABCD) are not significantly different (p ¼ 0.05) for the same iodine level in different starches.
***Values with the same letter (XY) are not significantly different (p ¼ 0.05) for the same level, same starch but different days, 1 and 7 day.
378 S. Dhillon, K. Seetharaman / Journal of Cereal Science 54 (2011) 374e379

normal control gels, and may influence the elasticity (solid-like 6. Conclusion
response) of the gel.
While in CS and PS gels, the presence of iodine had an apparent
5.2. Texture analysis effect on G*, the differences could not be detected in WS. Addition
of 0.5% iodine level inhibited gel formation in all starches, except for
The ratio between intact granules and granule remnants has WS, which did not form a gel above 0.2% iodine level. It is therefore
been related to the textural properties of the starch pastes likely that, at a critical concentration, the iodine molecules saturate
(Blennow et al., 2003). The granules of waxy starches and potato the polymer chains by complex formation, thereby preventing
starches are known to form sticky gels upon disruption and sol- them from forming associations in the form of a gel. Below this
ubilisation. The texture analysis of the opaque gels of CS and WS critical concentration of iodine, the differences among the gels are
was performed after 1 day to allow the retrogradation of amylose very well defined by large deformation studies, i.e. measuring
(Miles et al., 1985; Sievert and Wursch, 1993) and after 7 days to firmness using large force compression of gels in a texture analyser
allow the recrystallization (retrogradation) of amylopectin chains but not through small-deformation experiments of varying strain
(Eliasson, 1985). CS seemed to form the firmest gels compared to to measure elasticity using a rheometer. The data presented here
the other starches, which was contrary to the results of Takahashi set the stage for further experimentation to pursue the exploration
and Seib (1988), who stated that at concentrations higher than 1 of the architectural differences among starches and consequent
day old, WS gels (6% dry starch basis) were harder than CS. The impact on starch functionality.
starches behave differently on cooling; while the cereal starch
pastes exhibit a sharp transition upon cooling due to the formation Acknowledgements
of strong gels, PS gels are less affected by cooling. The presence of
distinguishable granular remnants and portions of polymer clusters This work was supported by an endowment from Ontario Cereal
made the CS and WS gels heterogeneous based on microscopic Industry Research Council (OCIRC).
inspection, whereas in PS, TS, WCS and WPS gels, the resulting
network was more homogenous (Dhillon et al., in press). This was
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