International Journal of Biological Macromolecules 113 (2018) 443–449

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Starch hydrogels: The influence of the amylose content and

gelatinization method
Bárbara Biduski a,b, Wyller Max Ferreria da Silva a, Rosana Colussi a, Shanise Lisie de Mello El Halal a,
Loong-Tak Lim b, Álvaro Renato Guerra Dias a, Elessandra da Rosa Zavareze a,⁎
a
Departamento de Ciência e Tecnologia Agroindustrial, Universidade Federal de Pelotas, Rio Grande do Sul, Pelotas, RS 96010-900, Brazil
b
Department of Food Science, University of Guelph, Guelph, Ontario N1G 2W1, Canada

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

Article history: Gelatinization and retrogradation, influenced by amylose and amylopectin ratio, are important characteristics for
Received 26 October 2017 starch hydrogels elaboration. The objective of this study was to evaluate the influence of amylose content and the
Received in revised form 18 January 2018 gelatinization method on the physicochemical characteristics of native and cross-linked rice starch hydrogels.
Accepted 22 February 2018
The native and cross-linked starches were gelatinized with heating or alkaline solution, added polyvinyl alcohol,
Available online 24 February 2018
frozen and then freeze-dried. The cross-linked starch had a low final viscosity (101.38 RVU), which made the
Keywords:
heat-induced gelatinized hydrogel readily disintegrated in water. However, modified starch hydrogels obtained
Rice starch by alkaline-induced gelatinization resulted in a more rigid structure than the native starch hydrogels. In addition,
Cross-link the starch sample with high amylose content had lower water absorption (322.2%) due to the greater stiffness of
Hydrogel the hydrogel structure that resisted swelling. The alkaline-gelatinization resulted in stiffer hydrogels with lower
Amylose water absorption (322.2 to 534.8%), while the heat-gelatinized behaved as a superabsorbent (658.7 to 1068.5%).
Gelatinization process The variability of the hydrogels properties of this study can enable a range of applications due to different amy-
lose contents and gelatinization methods.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction Researchers have developed hydrogels based on potato, corn, and

Hydrogels are physical or chemical cross-linked macromolecules
forming a three-dimensional network capable of retaining water
without disintegrating. Therefore, they are ideal carriers for bioactive,
as in drug delivery applications [1]. Hydrogels derived from synthetic
polymers, such as polyvinyl alcohol (PVA), are stable against disintegra-
tion and have a high mechanical strength. On the other hand, natural
polymers, such as starch, have weaker mechanical properties but high
biocompatibility and biodegradability [2]. Blending starch with PVA is
promising to form functional hydrogels due to intra- and intermolecu-
lar hydrogen bonding interactions between these polymers [3]. In addi-
tion, PVA is a water-soluble, degradable and non-toxic polymer [4].
Besides blending, covalent cross-linking in the starch chain can further
enhance the mechanical stability of the hydrogels [5]. The sodium
trimetaphosphate (STMP) is one of the reagents allowed by the Food
and Drug Administration (FDA) as a food grade for cross-linking since
the residual phosphate in food starch-modified do not to exceed 0.04%
[6].
⁎ Corresponding author.
E-mail addresses: bbiduski@uoguelph.ca (B. Biduski), llim@uoguelph.ca (L.-T. Lim),
alvaro.guerra@pq.cnpq.br (Á.R.G. Dias), zavareze@pq.cnpq.br (E.R. Zavareze).
soluble starches [7–9]. The formation of starch-based hydrogels in-
volves first starch gelatinization and then retrogradation to form a
three-dimensional network. The first step is needed to disrupt the crys-
talline structure of starch to facilitate polymer chain-chain interaction.
The typical approach involves solubilization and heating in water [10].
However, the starch can also be gelatinized chemically through an alka-
line solution.
Rice (Oryza sativa L.) is one of the most produced and consumed
grains in the world [11]. During processing, drying and prolonged stor-
age, rice grains can develop defects due to chemical, physical, and bio-
logical phenomena [12,13]. Thus, starch isolated from defective rice
grains can add value to this crop [14]. Starch is the major component
in rice grains (around 90%) with a wide range of amylose content (1
to 37%) [15]. The amylose content can influence gelatinization and ret-
rogradation properties of starches, thereby defining their end use appli-
cation [16]. High amylose content tends to promote retrogradation,
forming a more organized and more rigid crystalline structure, while a
low amylose matrix can result in a more open structure that tends to
disintegrate in water.
Researchers have been reported on the starch hydrogel elaboration
focusing on different chemical cross-linking such as acrylic acid [1], alu-
minum chloride and glutaraldehyde [17] or by esterification with

https://doi.org/10.1016/j.ijbiomac.2018.02.144
0141-8130/© 2018 Elsevier B.V. All rights reserved.
444 B. Biduski et al. / International Journal of Biological Macromolecules 113 (2018) 443–449

succinic anhydride [10]. Besides that, starch-PVA hydrogel has been suc-
cessfully produced [9]. However, the influence of the amylose content
from a different source of starch has not been reported. Furthermore,
the gelatinization method may influence in the retrogradation process
of the gelatinized starch. Based on the importance of the gelatinization
and retrogradation characteristics in the hydrogel process, understand-
ing how the amylose content as well, the gelatinization method can in-
fluence the hydrogel elaboration allows creating a material with the
desired properties, depending on its application. Besides no data were
found in the literature, this knowledge could increase the range of appli-
cation for food or non-food applications.
Thus, the objective of this study was to evaluate the influence of the
amylose content and starch gelatinization method on the physical and
chemical characteristics of native and cross-linked rice starch hydrogels.
2. Materials and methods
2.1. Materials
Rice grains cultivars from Motti, IRGA-406, and IRGA-417, with 8%,
20%, and 32% amylose content, respectively, were used. The amylose
content was determined by a colorimetric method with iodine accord-
ing to McGrane, Cornell, and Rix [18]. All the chemical reagents used
were of analytical grade.
2.2. Starch isolation
The rice grains were ground and the starch isolation from rice flour
was performed by the alkaline method as described by Colussi et al.
[19].
2.3. Cross-linking of starch
The cross-linking of the starch was performed by using sodium
trimetaphosphate (STMP), according to Woo and Seib [20], with some
modifications. Rice starch (50 g) was stirred at 45 °C in distilled water
(100 mL) containing 4.5 g of STMP (9 g STMP/100 g starch) and 1 g of
the sodium sulfate catalyst (2 g reagent/100 g starch) at pH 11 (by the
slow addition of 0.5 mol·L−1 NaOH). After 2 h, the solution was filtered,
washed with distilled water and dried in an air circulation oven at 40 °C
for 16 h. After the modification, the starches were dialyzed to remove
the unbound phosphorus salts. The dialysis was carried out by dispers-
ing 15% the starch in water within dialysis bags submerged in distilled
water. At the beginning of the dialysis process (initial 6 h), the water
was changed every 2 h. After 24 h, the dialyzed starches were filtered
and dried in an air circulation oven at 40 °C.
2.4. Starch properties
The phosphorus contents of the native and cross-linked starches
were quantified according to Smith and Caruso [21]. The degree of sub-
stitution (DS) was determined by the equation below using the phos-
phorus content (P):
162P
DS ¼
3100−102P
The pasting properties of the starch were analyzed by Rapid Visco
Analyzer (model RVA-4, Newport Scientific, Australia) using profile
Standard Analysis 1, according to Colussi et al. [19].
The thermal properties of starch were analyzed by differential scan-
ning calorimetry (DSC, TA-60WS, Shimadzu, Kyoto, Japan). A starch
sample of 2.5 mg was weighed in an aluminum pan and added with dis-
tilled water (1:3, w/w). The pan was hermetically sealed and allowed to
equilibrate for 24 h before analysis. The sample pans were heated from
30 to 120 °C at a rate of 10 °C·min−1. An empty pan was used as a
reference.
2.5. Hydrogels synthesis
Rice starch hydrogels were prepared according to Zhu et al. [4], with
modifications. The starches were gelatinized by alkaline or heating
methods, as described below.
2.5.1. Hydrogels synthesis by alkaline-gelatinization
A starch solution (3 g) in distilled water (20 mL) was heated to 55 °C
and gelatinized by NaOH 50% (0.5 mL). Then a 10% PVA solution (1 g re-
agent/10 mL water) was added to the gelatinized starch. The tempera-
ture was maintained for 30 min. The paste was placed in molds of
20 mm diameter and 10 mm height and freeze-dried.
2.5.2. Hydrogels synthesis by heat-gelatinization
A starch solution (3 g) in distilled water (20 mL) was heated to 90 °C
for 20 min. Then, the solution was cooled to 55 °C and a 10% PVA solu-
tion (1 g reagent/10 mL water) was added to the gelatinized starch.
The temperature was maintained for 30 min. The paste was placed in
molds of 20 mm diameter and 10 mm height and freeze-dried.
2.6. Macro and microscopic analysis of the hydrogels
The lyophilized and swollen hydrogels were photographed and eval-
uated for structural integrity after immersion in distilled water for 24 h.

Table 1
Phosphorus content, degree of substitution, and pasting properties of the native and cross-linked starches with different amylose contents.

Parameters1 Starch Amylose content

Low Medium High

Phosphorus content (%) Native 0.023 ± 0.002b⁎ 0.049 ± 0.002a ns 0.046 ± 0.001a⁎
Cross-linked 0.064 ± 0.002a 0.058 ± 0.000b 0.054 ± 0.001b
Degree of substitution Native 0.002 ± 0.000a⁎ 0.002 ± 0.000a⁎ 0.002 ± 0.000a⁎
Cross-linked 0.003 ± 0.000a 0.003 ± 0.000a 0.003 ± 0.000a
Pasting temperature (°C) Native 62.35 ± 0.00c ns 69.23 ± 0.25b ns 77.73 ± 0.39ª
Cross-linked 64.45 ± 0.49 + 68.75 ± 0.35 –
Initial viscosity (RVU) Native 316.88 ± 3.47a⁎ 284.54 ± 3.24b⁎ 236.33 ± 1.06c
Cross-linked 78.09 ± 0.94+ 10.13 ± 0.53 –
Final viscosity (RVU) Native 215.75 ± 0.24c⁎ 349.59 ± 0.23a⁎ 315.96 ± 2.65b
Cross-linked 101.38 ± 2.06+ 10.96 ± 0.53 –
Breakdown (RVU) Native 123.54 ± 3.48a⁎ 56.42 ± 6.13b⁎ 14.59 ± 0.47c
Cross-linked 3.75 ± 0.71+ 0.13 ± 0.18 –
Setback (RVU) Native 22.42 ± 7.19c ns 121.46 ± 3.13a⁎ 94.21 ± 1.39b
Cross-linked 27.04 ± 0.41+ 0.92 ± 0.23 –
1
Different letters in the same row, differ statistically (p ≤ 0.05) the averages submitted by Tukey test. ⁎ or ns means significant and not significant, respectively, by the t-test between the
native and modified starches for each parameter. + and NS means significant and not significant, respectively, by the t-test between the cross-linked starches in the same row.
 B. Biduski et al. / International Journal of Biological Macromolecules 113 (2018) 443–449 445

Table 2 resilience was measured as how the sample recovers in terms of

Thermal properties of native and cross-linked rice starches with different amylose speed and force derived.
contents.

Amylose content Modification T0 (°C)a Tp (°C) Tf (°C) ΔT (°C) ΔH (J·g−1) 2.9. Statistical analysis
Low Native 60.49 67.45 74.41 13.92 6.73
Cross-linked 62.02 67.78 73.01 10.99 4.64 Analytical determinations were performed in triplicate, except for
Medium Native 61.76 67.41 72.47 10.71 8.51 the thermal analysis, and standard deviations were reported. Means
Cross-linked 61.69 67.83 73.03 11.34 8.95
were compared by Tukey's test at 5% level of significance by analysis
High Native 59.77 66.55 70.95 11.18 5.32
Cross-linked 62.54 65.97 70.92 8.38 2.05 of variance (ANOVA). The comparison of two groups was compared
a
by the t-test at 5% significance.
T0: onset temperature; Tp: peak temperature; Tf: final gelatinization temperature; ΔH:
gelatinization enthalpy.
3. Results and discussion

The hydrogels internal morphology was evaluated using a scanning
electron microscope (SEM, JEOL JSM-6610LV, Kyoto, Japan). The
hydrogels were fractured with liquid nitrogen and fixed to the surface
of the stub with a double-sided carbon tape. The samples were
sputtered coated with gold using a vacuum metallizer (Denton Desk
V, Denton Vacuum, USA).
2.7. Water absorption of hydrogels
Water absorption capacity of the starch hydrogels was performed by
immersing samples in distilled water according to the method D570
[22]. The measurement was performed by weighing the lyophilized
samples after immersion for 24 h in water at ambient temperature.
The absorption capacity was measured gravimetrically:
Swollenweight −Dryweight
Absorption capacity ð%Þ ¼  100
Dryweight
2.8. Texture profile analysis (TPA)
The TPA of the swollen hydrogels was determined using a Texture
Analyzer (TA.XTplus, Stable Micro Systems, UK). Two-cycle of compres-
sion was applied and the samples were compressed to 50% of their ini-
tial height at a 5 mm·s−1 by a cylindrical probe with 36 mm diameter.
Hardness was considered as the first peak height in the force-time
curve; the springiness was measured as the height that the sample re-
covers during the time between the end of the first cycle and the start
of the second cycle; cohesiveness was measured as the ratio of the pos-
itive force area during the second and the first compression; gumminess
is the energy required to disintegrate a semi-solid material; and
3.1. Starch properties
The phosphorus content and degree of substitution for the native
and cross-linked starches are shown in Table 1. The presence of phos-
phorus in the native rice starches was due to the residual ash from phos-
pholipids, which are proportional to the amylose content [23]. In
general, rice starches show higher phosphorus content when compared
with others starches sources [24]. The amylose content affects the
chemical modification process, as reported in several studies [25,26].
In general, starches with a lower amylose contents are more susceptible
to chemical and/or physical modifications than the higher amylose
counterparts. The cross-linked starch with low amylose content showed
a higher phosphorus content than the other modified starches. The in-
clusion of functional groups during chemical modification occurs
mainly in the amorphous lamellae of the starch granules, as with
starches modified by oxidation [27]. Similar behavior is expected in
the cross-linked starches, due to the greater susceptibility of the amor-
phous areas to chemical modification.
Characteristics such as initial and final viscosity, paste temperatures,
breakdown, and setback are influenced by the amylose and amylopectin
ratio as summarized in Table 1. The final viscosity and retrogradation of
the native starches showed a positive linear trend with the amylose
content. The short-term increase of final viscosity can be attributed to
the retrogradation of the leached out amylose [28]. Starch samples
with higher amylose content had a higher final viscosity and pasting
temperature values, probably due to the greater hydrogen bonding in-
teractions. In addition, amylose molecules tend to re-associate easier
than amylopectin due to their linear molecular morphology, which
also promotes retrogradation [28].
The cross-linked rice starches show lower peak viscosity, final vis-
cosity, breakdown, and setback values than the unmodified starches.

Low Amylose Medium Amylose High Amylose

Native Cross-linked Native Cross-linked Native Cross-linked

a b c d e f
Freeze-Dried

g h i j k l
Swollen

Fig. 1. Freeze-drying hydrogels of native (a, c, e) and cross-linked starches (b, d, f), with low (a, b), medium (c, d) and high (e, f) amylose content, and swollen hydrogels of native (g, i,
k) and cross-linked starches (h, j, l), with low (g, h), medium (i, j) and high (k, l) amylose content, by alkaline-gelatinization.
446 B. Biduski et al. / International Journal of Biological Macromolecules 113 (2018) 443–449

Low Amylose Medium Amylose High Amylose

Native Cross-linked Native Cross-linked Native Cross-linked
a b c d e f
Freeze-Dried

g h i j k l
Swollen

Fig. 2. Freeze-drying hydrogels of native (a, c, e) and cross-linked starches (b, d, f), with low (a, b), medium (c, d) and high (e, f) amylose content, and swollen hydrogels of native (g, i,
k) and cross-linked starches (h, j, l), with low (g, h), medium (i, j) and high (k, l) amylose contents, by heat-gelatinization.

For high amylose starch samples, due to their low viscosity, pasting pa-
rameters could not be determined. Wongsagonsup et al. [29] reported
that cross-linked cassava starches showed a higher stability at high tem-
peratures, observing low viscosity, breakdown and setback values in
their samples. The authors attributed the phenomenon to the formation
of covalent cross-links that strengthen the granules against breakage
under high temperature and shear. Similarly, Hirsch and Kokini [30] re-
ported that increasing the degree of cross-linking of their corn starch
lowered the peak viscosity due to lowered inter granular interaction.
Therefore, the observed low viscosity in the present study for the
cross-linked rice starches could be due to the formation of covalent
bonds between the starch molecules.
The gelatinization temperature and energy required to disrupt the
crystalline structure are presented in Table 2. After the modification,
an increase in the onset gelatinization temperature of the starches
was observed and a decreased in the gelatinization temperature
range, although the peak gelatinization temperatures were similar to
those of the native starches (Table 2). A similar observation was re-
ported by Wongsagonsup et al. [29], who studied the physical proper-
ties of cross-linked cassava starch. These authors reported that some
cross-linked starch granules had intact structure after heated at a high
temperature (around 90 °C), as reflected by the presence of Maltese
cross observed under a polarized light microscope. According to Liu
et al. [31], the introduction of cross-links may enhance the hydrogen
bond interactions, and therefore gelatinization must be carried out at
a higher temperature. However, thermal analysis of the swollen hydro-
gel showed no peak of gelatinization, which may indicate that the
starches have been completely gelatinized (data not shown).
The gelatinization enthalpy (ΔH) mainly reflects the molecular
order loss [32], related to the energy required to disrupt the starch gran-
ule crystalline structure [33]. The ΔH values of the cross-linked starches
from low and high amylose content were lower than the native starches
(Table 2). Liu et al. [31], Jyothi et al. [34], and Carmona-Garcia et al. [35]
reported similar decreases in ΔH of the corn, cassava and banana
starches, respectively, modified by sodium trimetaphosphate when
compared to the native starches.
3.2. Macro and microscopic analysis of hydrogels
The macroscopic analysis of the native and cross-linked starch
hydrogels with different amylose contents, alkaline- or heat-
gelatinized, are shown in Figs. 1 and 2. Insoluble hydrogels were ob-
tained from the cross-linked low and medium amylose rice starches
by alkaline-induced gelatinization (Fig. 1h and j). The alkaline-
gelatinized hydrogels of the native medium amylose starch were partial
soluble (Fig. 1i), while those derived from the native high amylose
starch were more stable and remained intact structure after swelling
(Fig. 1k and l). These observations indicate that amylose content has af-
fected the water absorption capacity of the hydrogels, as well as their
solubility and structural integrity.
The hydrogels of the low amylose native starch obtained by alkaline
gelatinization were completely soluble (Fig. 1g), so as those of the cross-
linked starches by heat-gelatinization (Fig. 2h, j, and l). Considering that
no gel formation was observed (i.e., no viscosity change) for the cross-
linked starches during the heating treatment (Table 1), it is fair to as-
sume that retrogradation during cooling might not have occurred. The

a b

Fig. 3. Internal hydrogel structures of the high amylose starches: (a) native; and (b) cross-linked by alkaline-gelatinization.
 B. Biduski et al. / International Journal of Biological Macromolecules 113 (2018) 443–449 447

lack of retrogradation, because of the low amylose content, might be the In some applications, a rigid water-insoluble hydrogel is required,
reason for the disintegration of the low amylose native starch hydrogels and in other applications such as controlled release of compounds,
via the alkaline-gelatinization process. This problem was solved by the hydrogels with partial solubility and high water absorption may be use-
starch modification, the low amylose starch showed the more intense ful to control the release of bioactive agents such as drugs.
modification (nearly 3 times higher than the native starch). After the
modification, the cross-linking bonds formation allowed the develop- 3.4. Texture profile analysis of hydrogels
ment of an insoluble hydrogel by alkaline-gelatinization.
Hydrogels derived from native and cross-linked high amylose The texture profile analysis of the starch hydrogels is shown in
starches by alkaline-gelatinization showed increased structural integ- Table 3. Alkaline-gelatinization allowed the formation of more rigid
rity after swelling. On the other hand, when the gels were fractured, yel- structure (673.17 g) than the hydrogel from the heating-induced
lowish continuous internal structures were observed (Fig. 3). This
observation may be due to the high amylose content of the starch that
promoted the formation of stronger gels. In addition, this can hypothe-
size that the increase in the hydrogen bonding interactions between the
starch chains may hind the release of water during the freeze-drying
process. Moreover, the high amylose content also increased the ten-
dency of retrogradation, forming pores only in the exterior of the hydro-
gel structure.
The hydrogels showed porous morphology (Fig. 4), except the
hydrogels of the native and cross-linked high amylose starches obtained
by alkaline-gelatinization, which showed continuous internal structure
(Fig. 4e and f). The hydrogels of the low and medium amylose alkaline-
gelatinized starches showed micropores within the large pores (Fig. 4a
and c). The larger pores facilitate the water penetration into the hydro-
gel structure, increasing its swelling capacity [36]. The hydrogels of the
cross-linked medium amylose starch, alkaline-gelatinized had homoge-
neous and small pores in through the internal morphology (Fig. 4d). The
hydrogels of the high amylose content did not allow the formation of
pores in their internal structure (Fig. 4e and f) and the swelling and
the capacity of water absorption were lower. This can hypothesize
that the starch solution has a greater cryo-protectant property, which
inhibited the formation of large ice.
Comparing between gelatinization methods, the alkaline-
gelatinization allowed the formation of rounded and larger pores
when compared to the heat-gelatinized hydrogels. The heat-
gelatinization resulted in hydrogels with tubular pores through the hy-
drogel network.

3.3. Water absorption of hydrogels

The water absorption and structural integrity are important to de-

fine the end-use applications. The hydrogels by alkaline-gelatinized
from the native low amylose starch, as well the modified samples by
heat-gelatinized were completely water-soluble; therefore, water ab-
sorption capacity was not quantified (Figs. 1 and 2).
Medium and high amylose starch hydrogels by alkaline-
gelatinization showed similar water absorption capacity (Table 3). The
leaching of the amylose from the granule increases starch solubility.
On the contrary, increased interaction between amylose-amylose and
amylose-amylopectin will reduce polysaccharide chain leaching. This
phenomenon may explain the water solubility characteristics of starch
with medium and high amylose contents [37]. Moreover, retrogradation
process will also affect the solubility of the starch. According to Liu et al.
[31], the starch retrogradation is influenced by the amylose content and
the chain length of the molecules. In some cases, the high absorption
and low retrogradation tendency may fragment and solubilize the
starch and the hydrogels, such as occurred to the low amylose starch hy-
drogel by alkaline-gelatinization. Similarly, the fragmentation of the
heat-gelatinization starch may be related to the low retrogradation ca-
pacity, as well as the low paste viscosity.
Cross-linking modification in the starch could also interfere the
starch-PVA interaction. As the interaction between the starch and PVA
is only by hydrogen bonds, the ionization by alkaline-gelatinization Fig. 4. Hydrogel morphologies of the native (a, c, e, g, i, l) and cross-linked starches (b, d, f,
may increase the hydrogen bond number improving the stability of h, j, m), with low (a, b, g, h), medium (c, d, i, j) and high (e, f, l, m) amylose content by
the hydrogel network, even in the cross-linked starches. alkaline- (a–f) or heat-gelatinization (g–m).
448 B. Biduski et al. / International Journal of Biological Macromolecules 113 (2018) 443–449

Table 3
Water absorption capacity and texture profile of the native and cross-linked rice starches hydrogels, with different amylose contents, by alkaline- or heat-gelatinization.

Parameter1 Gelatinization method Amylose content

Low Medium High

Native Cross-linked Native Cross-linked Native Cross-linked

a b⁎ b bc⁎
Water absorption capacity (%) Alkaline N.A. 534.8 ± 19.5 410.8 ± 4.1 393.2 ± 18.2 365.8 ± 9.1 322.2 ± 13.2c
Heating 658.7 ± 53.4c N.A. 1068.5 ± 39.7a N.A. 851.0 ± 1.7b N.A.
Hardness (g) Alkaline N.A. 609.98 ± 71.55b 41.29 ± 0.31c ns 563.24 ± 211.65b 673.17 ± 8.42b⁎ 1277.99 ± 62.98a
Heating 50.67 ± 0.41b N.A. 41.94 ± 4.08b N.A. 82.46 ± 2.30a N.A.
Springiness Alkaline N.A. 0.92 ± 0.01a 0.71 ± 0.02a ns 0.82 ± 0.17a 0.85 ± 0.19a ns 0.84 ± 0.04a
Heating 0.99 ± 0.01a N.A. 0.77 ± 0.00c N.A. 0.87 ± 0.01b N.A.
Cohesiveness Alkaline N.A. 0.76 ± 0.02a 0.47 ± 0.01b ns 0.71 ± 0.04a 0.65 ± 0.02a⁎ 0.68 ± 0.03a
Heating 0.77 ± 0.02a N.A. 0.56 ± 0.04b N.A. 0.75 ± 0.02a N.A.
Gumminess (g) Alkaline N.A. 485.71 ± 34.46b 19.71 ± 0.17c ns 401.52 ± 171.95b 440.18 ± 17.70b⁎ 862.85 ± 3.68a
Heating 38.78 ± 0.57b N.A. 23.33 ± 0.42c N.A. 61.95 ± 3.54a N.A.
Resilience Alkaline N.A. 0.53 ± 0.03a 0.10 ± 0.00b ns 0.50 ± 0.02a 0.43 ± 0.03a ns 0.41 ± 0.08a
Heating 0.47 ± 0.01a N.A. 0.11 ± 0.05c N.A. 0.29 ± 0.01b N.A.
1
Different lowercase letters in the same row differ statistically (p ≤ 0.05) among the averages submitted by Tukey test. * or ns means significant and not significant, respectively, by the t-
test (p ≤ 0.05) between gelatinization methods. N.A. = not analyzed due to its complete solubilization in water.

gelatinization (82.46 g) with high amylose content. During the alkaline-
gelatinization, the alkali is partially absorbed by the starch hydroxyl
groups; besides that, most hydroxyl groups of the glucose units of the
starch structure are ionized at high pH by increasing the starch affinity
with water [38]. Thus, the higher amylose content allowed a greater
ionization of the hydroxyls, resulting in firmer and stronger gels
influencing the hardness of the hydrogels. There was no difference in
the hardness between the gelatinization methods for the native me-
dium amylose hydrogels.
Regarding the other textural properties, the gelatinization using
heating formed hydrogels with lower gumminess values (23.33 to
61.95 g) when compared to the hydrogels obtained by alkaline-
induced gelatinization (19.71 to 862.85 g). The cohesiveness is the mea-
sure of the strength of the internal bonds making up. Thus, the low co-
hesiveness from hydrogel obtained of native medium amylose starch
can be due to the poor inter-chain association. The hydrogel obtained
of low amylose starch showed the higher springiness than the others
starch hydrogel in the heat gelatinization, indicating a reduced rigidness
and a non-elastic material. The amylose content had no influence in the
springiness when the hydrogel was elaborate by alkaline gelatinization.
The cross-linking allowed the formation of more rigid hydrogels
when alkaline-gelatinization was applied. This may have occurred due
to the formation of crosslinks in the starch, which together with the ion-
ization of the hydroxyls caused by the alkaline solution, resulted in a
more structured and resistant three-dimensional network.
4. Conclusion
The starch gelatinization method influences the characteristics of
the hydrogels, causing the formation of the firmer gels. When
performed by the alkaline method, insoluble hydrogels with higher
compressive strength were obtained. In addition, the amylose content
influenced the hydrogels properties, since low amylose content starches
produced hydrogels that were partially (heat-gelatinization) or
completely water-soluble (alkaline-gelatinization). High amylose
starches changed the microstructures structure of the hydrogels by
alkaline-gelatinization, with lower water absorption, and higher me-
chanical strength. The choice of the starch, as well as the gelatinization
method, will depend on its end-use application.
Acknowledgment
We would like to thank CAPES (88887.124727/2014-00), CNPq
(448800/2014-4) and FAPERGS-PRONEM-2014 (16/2551-0000250-9)
for project financing; CEME-Sul, FURG and the University of Guelph
for the analyses.
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