Professional Documents
Culture Documents
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.
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.
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.
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.
5. Discussion
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
References
true in the control gels and those containing low concentrations of
iodine where long range ordered sections of polymer chains were Amari, T., Nakamura, M., 1976. Viscoelastic properties of aqueous solutions of
present. Gel firmness had an inverse relationship with iodine amylose-iodine complex at ultrasonic frequencies. Journal of Applied Polymer
Science 20, 2031e2043.
concentration for all starches, with a few exceptions [because of
Atkin, N.J., Abeysekera, R.M., Cheng, S.L., Robards, A.W., 1998. An experimentally-
destabilization of starch granules during gelatinization due to based predictive model for the separation of amylopectin subunits during
increased charge density of iodide ions (Takahashi and Seib, 1988)]. starch gelatinization. Carbohydrate Polymers 36, 173e192.
It is known that for all polysaccharide polyelectrolytes, the pres- Atwell, W.A., Hood, L.F., Lineback, D.R., Varrianomarston, E., Zobel, H.F., 1998. The
terminology and methodology associated with basic starch phenomena. Cereal
ence of low ionic strength leads to stabilization of the system and in Foods World 33, 306e311.
some cases promotes the formation of ordered helical conforma- Banks, W., Greenwood, C.T., Khan, K.M., 1971. The interaction of linear, amylose
tion by screening the repulsion between the charges of the polyion oligomers with iodine. Carbohydrate Research 17, 25e33.
Bertoft, E., Piyachomkwan, K., Chatakanonda, P., Sriroth, K., 2008. Internal unit chain
(Jane, 1993). It can be observed that the retrogradation patterns (gel composition in amylopectins. Carbohydrate Polymers 74, 527e543.
firmness after 1 day vs. 7 days) were different for the starches in the Blennow, A., Hansen, M., Schulz, A., Jorgensen, K., Donald, A.M., Sanderson, J., 2003.
presence of increasing iodine concentrations. The molecular deposition of transgenically modified starch in the starch
granule as imaged by functional microscopy. Journal of Structural Biology 143,
The presence of large numbers of swollen granules with 229e241.
minimal amount of polymer leachate in the extragranular matrix Davis, H., Skrzypek, W., Khan, A., 1994. Iodine binding by amylopectin and stability
was observed in cases where no gel formation took place (Dhillon of the amylopectin-iodine complex. Journal of Polymer Science: Part A: Polymer
Chemistry 32, 2267e2274.
et al., in press). In WS, the formation of a paste instead of a phys-
Dhillon, S., 2009. Use of Iodine as a Marker to Probe Differences in Granular
ical gel at 0.5% iodine level occurred, in spite of the presence of Architecture of Starches from Various Botanical Sources. Thesis (MSc), Univer-
polymer leachate in the extragranular material. The retrogradation sity of Guelph.
Dhillon, S., Abdel-Aal, E.-S.M., Seetharaman, K. Effect of iodine on polymer leaching
of the composite mixture of starch granules, embedded in
and granule swelling of starches from different botanical sources. Journal of
a comparatively lower volume of polymers in the paste, possibly Cereal Science, in press.
lead to an increased firmness compared to the gel formed at the Doublier, J.L., Llamas, G., Lemeur, M., 1987. A rheological investigation of cereal
0.2% iodine level (Section 4.2). This suggests that the presence of starch pastes and gels e effect of pasting procedures. Carbohydrate Polymers 7,
251e275.
the large number of granule remnants inhibited the polymer Eliasson, A.C., 1985. Retrogradation of starch as measured by differential scanning
association. In other words, gel formation was inhibited in such calorimetry. In: Hill, R.D., Munck, L. (Eds.), New Approaches to Research on
a disperse system. However, the physical gels can be categorized Cereal Carbohydrates. Elsevier Science Publishers, Amsterdam, pp. 93e98.
Eliasson, A.C., 1986. Viscoelastic behaviour during the gelatinization of starch I.
into strong and weak gels on the basis of their rheological prop- Comparison of wheat, maize, potato, and waxy-barley starches. Journal of
erties (Lapasin and Pricl, 1995). The results reaffirm that the chain Texture Studies 17, 253e265.
lengths of the polymers in WS are shorter compared to the other Glenn, G.M., Klamczynski, A., Chiou, B.S., Orts, W.J., Imam, S.H., Wood, D.F., 2008.
Temperature related structural changes in wheat and corn starch granules and
starches that were studied. On the other hand, PS, TS and waxy their effects on gels and dry foam. Starch/Stärke 60, 476e484.
starches contain longer chain length polymers with a greater Inaba, H., Hoshizawa, M., Fujiwara, A., 1995. Textural properties of starch gels filled
number of long range ordered sections, possibly containing with collagen and chitin. Journal of Texture Studies 26, 577e586.
Jane, J.L., 1993. Mechanism of starch gelatinization in neutral salt solutions. Starch/
entanglements. Stärke 45, 161e166.
The results from the rheological measurements do not allow Jenkins, P.J., Donald, A.M., 1997. Breakdown of crystal structure in potato starch
much speculation on the microscopic or molecular scale within the during gelatinisation. Journal of Applied Polymer Science 66, 225e232.
Klucinec, J.D., Thompson, D.B., 2002. Amylopectin nature and amylose-to-
same starch treated with different levels of iodine. However, the
amylopectin ratio as influences on the behaviour of gels of dispersed starch.
gels from the different starches show a magnitude of difference in Cereal Chemistry 79, 24e35.
their elasticity. The critical concentration of iodine required for Lapasin, R., Pricl, S., 1995. Rheology of Industrial Polysaccharides e Theory and
saturating the polymers depends on the nature of the polymers Applications. Aspen Publishers Inc., Maryland.
Liu, H., Lelievre, J., 1992. Differential scanning calorimetric and rheological study of
involved, i.e. their length, branching patterns and entanglements the gelatinization of starch granules embedded in gel matrix. Cereal Chemistry
with guest molecules. 69, 597e599.
S. Dhillon, K. Seetharaman / Journal of Cereal Science 54 (2011) 374e379 379
Lu, T.J., Duh, C.S., Lin, J.H., Chang, Y.H., 2008. Effect of granular characteristics on the Rundle, R.E., French, R.R., 1943. The configuration of starch and the starcheiodine
viscoelastic properties of composites of amylose and waxy starches. Food complex. II. Optical properties of crystalline starch fractions. Journal of the
Hydrocolloids 22, 164e173. American Chemical Society 65, 558e561.
Miles, M.J., Morris, V.J., Orford, P.D., Ring, S.G., 1985. The roles of amylose and Saibene, D., Seetharaman, K., 2006. Segmental mobility of polymers in starch
amylopectin in the gelation and retrogradation of starch. Carbohydrate granules at low moisture contents. Carbohydrate Polymers 64, 539e547.
Research 135, 271e281. Saibene, D., Seetharaman, K., 2008. Use of iodine as a tool to understand wheat
Patel, B.K., Saibene, D., Seetharaman, K., 2006. Restriction of starch granule swelling starch pasting properties. Starch/Stärke 60, 1e7.
by iodine during heating. Cereal Chemistry 83, 173e178. Shibanuma, K., Takeda, Y., Hizukuri, S., 2003. Molecular structures of some wheat
Rao, M.A., Okechukwu, P.E., Da Silva, P.M.S., Oliveira, J.C., 1997. Rheological behav- starches. Carbohydrate Polymers 25, 111e116.
iour of heated starch dispersion in excess water: role of starch granule. Sievert, D., Wursch, P., 1993. Thermal behaviour of potato amylose and enzyme-
Carbohydrate Polymers 33, 273e283. resistant starch from maize. Cereal Chemistry 70, 333e338.
Rendleman, J.A.J., 2003. The reaction of starch with iodine vapor. Determination of Stark, J.R., Lynn, A., 1992. Starch granules large and small. Biochemical Society
iodide-ion content of starch-iodine complexes. Carbohydrate Polymers 51, Transactions 20, 7e12.
191e202. Thebaudin, J.Y., Lefebvre, A.C., Doublier, J.L., 1998. Rheology of starch pastes from
Rockland, L.B., Jones, F.T., Hahn, D.M., 1977. Light and scanning electron starches of different origins: application to starch-based sauces. Lebensmittel-
microscope studies on dry beans: extracellular gelatinization of lima bean Wissenschaft und-Technologie 31, 354e360.
starch in water and a mixed salt solution. Journal of Food Science 42, Takahashi, S., Seib, P.A., 1988. Paste and gel properties of prime corn and wheat
1204e1210. starches with and without native lipids. Cereal Chemistry 65, 474e483.