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Fu - 2014 - Additives On Starch Retrogradation

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Starch/Stärke 2014, 66, 1–10 DOI 10.1002/star.

201300278 1

REVIEW

Effect of food additives on starch retrogradation: A review


Zhen Fu, Jun Chen, Shun-Jing Luo, Cheng-Mei Liu and Wei Liu

State Key Laboratory of Food Science and Technology, Nanchang University, Nanchang, P.R. China

Predicting and controlling starch retrogradation is of great interest. Advancements in starch Received: December 11, 2013
retrogradation are relatively slow and many problems remain to be resolved. At present, starch Revised: February 18, 2014
retrogradation can be controlled qualitatively, but not quantitatively, by some techniques. Accepted: February 20, 2014
Constituents or food additives such as proteins, lipids, carbohydrates, and salts play a significant
role in inhibiting the retrogradation of starchy foods. Recent studies concerning the effect of
additives on starch retrogradation are reviewed, and potential mechanisms are discussed.

Keywords:
Additives / Carbohydrates / Lipids / Proteins / Starch retrogradation

1 Introduction starch retrogradation usually decreases the quality of products,


profoundly affects the nutritional properties, and shortens
Starch is the most common storage carbohydrate in plants the shelf-life. Moreover, the phenomenon has drawn great
and the largest source of carbohydrates in human food. It academic attention in the food science industry. A number of
consists of two types of molecules: amylose and amylopectin. techniques have been used to control starch retrogradation;
Starch granules heated in excess water undergo an order– these methods can be conveniently classified as: biotechno-
disorder phase transition called gelatinization. This phase logical modifications, chemical modifications, and physical
transition is a nonequilibrium process associated with the modifications (Fig. 1). Biotechnological modifications are
diffusion of water into the granule, hydration, and swelling of primarily carried out through genetic modifications by
the starch granules, uptake of heat, loss of crystallinity, and controlling the expression of enzymes in starch synthesis
amylose leaching. Upon cooling, the starch chains (amylose and thus changing the structure of starch to influence
and amylopectin) in the gelatinized paste reassociate, leading retrogradation. Chemical modifications change the molecular
to the formation of a more ordered structure. These molecular structure of starch by introducing functional groups to alter
interactions were collectively termed “retrogradation” [1]. retrogradation. Examples of chemical modifications include
Starch retrogradation can be divided into short-term cross-linking, esterification, and oxidation among others.
retrogradation and long-term retrogradation [2]. During the Physical modifications to control or inhibit starch retrograda-
first 2 days of postprocessing, the amylose component tion have been implemented by changing the temperature,
irreversibly and rapidly reassociates to form crystal nuclei, pressure, humidity, shear stress, and storage conditions.
followed by a slower growth of the amylopectin crystalline Addition of food components such as proteins, lipids, and
region around the crystal nucleus and the formation of a nonstarch polysaccharides represents another important
perfect crystal [3–5]. The latter process might proceed for aspect of physical modifications. However, the mechanism
several weeks. of how these additives (such as proteins, lipids, and nonstarch
Starch retrogradation can positively affect the quality of polysaccharides) influence starch retrogradation is not
some extruded products such as rice noodles. Nevertheless, completely understood.
Amylose and amylopectin play different roles during
the retrogradation process [7]. Amylose retrogradation is
Correspondence: Professor Cheng-Mei Liu, State Key Laboratory of
considered to be a fairly fast event and it consists of several
Food Science and Technology, Nanchang University, 235 Nanjing
East Road, Nanchang 330047, P. R. China
E-mail: liuchengmei@aliyun.com
Fax: þ86-791-88334509 Colour online: See the article online to view Figs. 1 and 2 in
colour.
Abbreviations: FFA, free fatty acid; SPI, soy protein isolate; WPI, Additional correspondence: Associate Professor Shun-Jing Luo,
whey protein isolate e-mail: shunjingluo@ncu.edu.cn

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2 Z. Fu et al. Starch/Stärke 2014, 66, 1–10

Figure 1. Effects on starch retrogradation. The blue part of biotechnological modification was redrawn from [6]. GPTI, glucose 6-phosphase
translocator; AGPase, ADP glucose pyrophosphorylase; SS, starch sythases; BE, branching enzymes; DBE, debranching enzymes.

stages [8, 9]. Directly after gelatinization, amylose is in the Several critical reviews have been published on starch
random-coil formation. Then, a fairly rapid reordering occurs retrogradation over the years [1, 7, 14]. They focused on
simultaneously or before phase separation. These helices will amylose and amylopectin crystallization and methodologies,
then aggregate to form crystalline structures [7]. Therefore, but did not provide a comprehensive description of the effects
when additives such as lipids are added, amylose reordering of lipids, proteins, carbohydrates, salts, polyalcohols, and
and aggregation is disturbed because of the formation of polyphenols, emulsifiers, acids, and amylase. This review
complexes between amylose and lipids. Amylopectin retro- performs a comprehensive survey on the effects of additives
gradation occurs over a longer period than that of amylose [3], on starch retrogradation. The factors and potential mecha-
probably because of the branched structure of amylopectin. nisms of additives on starch retrogradation are also analyzed.
Moreover, several researchers proposed that the cocrystalli- Thus, this review serves as a useful complement to existing
zation of amylose with amylopectin could occur during reviews on starch retrogradation.
retrogradation [3, 10]. Vansoest et al. [9] suggested that
amylose could form an ordered matrix and act as a seed nuclei 1.1 Effects of lipids on starch retrogradation
for amylopectin. Schierbaum et al. [11] proposed that the
outer chains of amylopectin molecules could interact with At present, although it is clear that the formation of starch–
amylose to form a network. Klucinec and Thompson [12] also lipid complexes occur in the food industry, their effect on
suggested the existence of amylose–amylopectin interactions. starch retrogradation is less understood. It is generally
Further evidence for the formation of junctions between the believed that amylopectin molecular crystals cause starch
two polysaccharides has been shown and the importance of retrogradation in food, but amylopectin retrogradation is
the nature of the amylopectin molecule, e.g., size and external reversible. As such, starchy foods such as rice and bread can
chain length, as well as the ratio of amylose to amylopectin in be reheated to eliminate the retrogradation of amylopectin
gels, has been emphasized [13]. because amylopectin molecular crystals melt at approximately
Therefore, when the constituents or food additives such as 60°C. Other findings [15] suggested that the melting
proteins, lipids, carbohydrates, and salts are present in the temperature of amylose crystallite was approximately
system, the crystallization of amylose, exterior amylopectin 140°C. Therefore, most research focused on inhibiting the
branched chains, and amylose–amylopectin interactions retrogradation of amylose.
might be influenced due to changes in the intermolecular The amylose chain displays a natural twist providing a
or intramolecular forces such as hydrogen bonding, van der helical conformation with six anhydroglucose units per
Waals, hydrophobic interactions, and steric hindrance. The turn [16]. When lipids are added during starch gelatinization,
subsequent subsections will describe this process in detail. the amylose and lipids interact with each other and

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Starch/Stärke 2014, 66, 1–10 3

what type of outer amylopectin branches can easily interact


with lipids.
The addition of lipids could result in significant changes
in the retrogradation of starch. Starch and lipid formation is a
very complicated process. Therefore, further investigation of
starch–lipid complexes and their antiretrogradation effect on
starch will contribute to novel applications in food processing.

1.2 Effect of proteins on starch retrogradation

In food systems, starch and proteins are biological


macromolecular nutrients that can form different gels. The
interactions of proteins and starch involved in some food
systems affect the quality of the food. In recent years, a
significant amount of research has focused on exploring
protein–starch interactions and the effect on starch retrogra-
dation. Starch–protein interactions could contribute to gel–
Figure 2. Molecular simulation diagram of the interaction between matrix weakening. Specifically, the addition of soy protein
amylose and fatty acids.
isolate (SPI) to starch produced soft gels as measured by
texture profile analysis. SPI–starch gels had a similar
firmness to starch-only gels at the beginning of the storage
simultaneously form amylose–lipid complexes. A diagram of period; additional SPI retarded gel retrogradation during the
the molecular simulation of the interaction between amylose storage period, indicating that proteins might readily interact
and lipids (such as fatty acids) is shown in Fig. 2. The hydroxyl with amylose and exposed branches of amylopectin through
groups of glucose residues are presented on the outer surface noncovalent bonding such as hydrogen bonds [32]. Yang
of the helix, while the internal cavity forms a hydrophobic et al. [33] found that a starch and whey protein isolate (WPI)
tube [17]. Hydrophobic complexing reagents (such as fatty gel had a lower complex modulus and higher phase angle
acids) can remain within the helix through van der Waals value than the starchy food model during the cooling process,
forces between lipids and the adjacent carbon–hydrogen of indicating a lower retrogradation. Additional WPI increased
amylose [18–20]. Meanwhile, the quantity and stability of the gel strength, probably due to the hydrophobic bonds from
starch–lipid complexes might be determined by the starch the protein–protein interactions during cooling and due to
category, amylose chain length, nature of the lipid, solvent, the dilution effect of WPI on the formation of hydrogen
and processing conditions [21–27]. Starch–lipid complexation bonds between starch and water. Nevertheless, the network
might be better assessed by a joint experimental and exhibited a lower strength when the WPI concentration was
molecular mechanics approach because amylose–vanillin decreased because of the inactive filler of WPI that weakened
complexation has been assessed by experimental and the gel structure of the starch–protein mixture [33]. Jimenez
theoretical analysis [28] and computational techniques have et al. [34] investigated the effect of caseinate on the
been employed to fundamentally understand the behavior of retrogradation of corn starch-based films and found that
helically structured amylose in water/DMSO mixtures [29]. the addition of caseinate to starch matrices could lessen the
Because of the formation of strong stable complexes, the degree of crystallinity of starch films and could prevent starch
complexes suppress the cross-linking and formation of recrystallization during film storage. This was because the
double helical structures between amylose molecules. At the rearrangement of starch chains during crystallization in the
same time, the presence of these complexes restricts water presence of sodium caseinate was more difficult. Notably,
penetration and starch granule swelling during gelatiniza- proteins have specific structures that confer a wide range of
tion. Thus, the mobility of amylose molecules is constrained functional properties such as high intermolecular and
in the starch grains and the amylose dissolution in water is intramolecular binding potentials [34]. Therefore, there could
reduced [30]. Therefore, adding lipids to starchy food could also be an indirect influence on starch recrystallization
effectively restrain amylose retrogradation. because of changes in the availability of free water molecules;
In addition, amylose–lipid complexes could prevent this might be associated with the distribution of sodium ions
recrystallization with amylopectin; however, the mechanism in the starch–protein matrix [34].
is unclear and further investigation is needed [31]. Certainly, In addition to added protein, endogenous proteins also
lipids could also interact with the outer branches of have a great influence on starch retrogradation. Before
amylopectin and inhibit retrogradation in a more direct isolation, granule-bound proteins are present in the channels
way [23, 31]. Nevertheless, there are no other reports about of native starch granules of normal and waxy maize,

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4 Z. Fu et al. Starch/Stärke 2014, 66, 1–10

sorghum, and wheat kernels [35]. Gluten represents an starch–polysaccharide systems play a crucial role. Moreover,
important group of wheat proteins that could interact with the interactions between starch and polysaccharides may also
wheat starch during cooking. It is often suggested that gluten be assessed by a combination of experimental investigations
has an antifirming effect on bread. Therefore, hydrogen and molecular mechanics simulations. The possible inter-
bonds could exist between starch and gluten and undergo a actions between rice amylose fraction and mesona blumes gum
transformation resulting in the release of water, which could fragments in water have been illustrated by molecular
be absorbed by retrograding starch [36–38]. However, dynamics simulations [56].
Ottenhof and Farhat [39] found a highly phase-separated During the gelatinization or heating of starch–polysac-
starch–gluten system, and suggested that the phase separa- charide systems, polysaccharides should interact with starch.
tion was due in part to the limited degree of mixing during Moreover, the MW (Mw) of polysaccharides such as guar gum
low shear extrusion and thermodynamic incompatibilities. influenced the interactions between polysaccharides and
Thus, gluten had no effect on the kinetics, extent, or amylose or amylopectin. The higher the Mw of the guar gum,
polymorphism of amylopectin retrogradation. The difference the more facile the interaction between the guar gum and
between the results of these studies is because they used amylopectin, which might be reasonable considering the
different gluten contents [39]. conformationally complicated structure of amylopectin.
Furthermore, potential three-way interactions among However, when the Mw was more than 10  105 g mol1,
starch, protein, and free fatty acid (FFA) have also been the interactions between guar gum and amylose were
suggested [40–42]. Whey protein decreased the enthalpy of independent of the Mw of guar gum, which might be
melting of the starch–lipid complex by 20–30% for FFAs explained by the fixed chain-length of amylose that interacted
except linoleic acid, and increased the reformation exother- with guar gum [57]. Thus, the influence of polysaccharides on
mic enthalpy by 150–350% in the DSC cooling cycle [41]. Teo starch retrogradation can be hypothesized by considering the
et al. [43] compared the rate of retrogradation between rice interactions between polysaccharides and starch components
flour gels and isolated starch gels at a given gel storage (amylose and amylopectin) [45]. Because of the numerous
temperature. They also found that rice flour gels had a hydroxyl groups of polysaccharides and starch, the inter-
considerably lower rate of retrogradation. Therefore, Teo actions between polysaccharides and starch are primarily
et al. [43] proposed that the difference might be due to the based on hydrogen bonding. The strengths of the intermo-
different starch concentrations; however, a more likely reason lecular hydrogen bonds (between polysaccharides, amylose,
was that other flour components such as proteins and lipids and amylopectin) were different, leading to different
might delay retrogradation. However, starch–protein–FFA retrogradation behaviors of amylose and amylopectin.
interactions are not very clear and the effect on starch Simultaneously, the added polysaccharides might change
retrogradation has rarely been discussed. In this regard, the water distribution in the system. Because polysaccharides
further in-depth studies of three-component interactions bind water in aqueous starch systems, it effectively deprives
among starch, proteins, and FFAs should be carried out. the amylose or amylopectin of usable water for crystalliza-
tion [58]. However, in a certain range, the addition of
1.3 Effect of carbohydrates on starch retrogradation polysaccharides accelerates the short-term retrogradation
because polysaccharides increase the effective concentration
Presently, many researchers are developing carbohydrates of amylose and amylose-like components in the continuous
such as monosaccharides, disaccharides, oligosaccharides, phase through thermal thickening [59].
and polysaccharides to control the retrogradation rate of Monosaccharides, disaccharides, oligosaccharides, and
starchy foods. other small sugar molecules were also shown to have a
The effect of polysaccharides on starch retrogradation has significant influence on starch retrogradation. Baek et al. [60]
led to several different conclusions throughout the literature. and Ablett et al. [61] investigated the effects of various
Several reports suggested that polysaccharides could slow or monosaccharides and sugar alcohols on starch retrograda-
prevent retrogradation [44–50]. Other studies reported that tion. They found that fructose and isomaltose produced
polysaccharides might have no effect on starch retrograda- higher degrees of amylopectin recrystallization than other
tion [51–53]. However, there are also some studies that sugars, and sugar alcohols produced a slightly greater
demonstrated that polysaccharides might increase starch recrystallization than the corresponding sugars. Their effects
retrogradation [54]. With such contradicting results, it is on the association of the amylopectin chains followed the
difficult to draw general conclusions about whether poly- order: rhamnose>sucrose>maltose>glucose>fructose. Al-
saccharides retard starch retrogradation or not. This is though the effect of polysaccharides on starch retrogradation
primarily because different paste/gel preparations, storage is in dispute, the mechanism of the effect of small
temperatures, measurement times, and measurement tech- carbohydrates on starch retrogradation is somewhat under-
niques are employed by various research groups [55]. stood. Three mechanisms have been proposed. The first
Nevertheless, in our opinion intermolecular interactions in mechanism is the hydrated layer theory [62], which suggests

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Starch/Stärke 2014, 66, 1–10 5

that hydrated layer formation could indirectly improve the granules was found to be higher than in the water phase [78].
starch paste concentration and may be helpful for starch Therefore, hydrogen ions would migrate from the starch to
chain migration, thus promoting starch recrystallization. water phase because of the concentration gradient. The starch
However, this did not satisfy the reality, because the rate of charge would become negative and the water phase would
amylopectin recrystallization decreased progressively with become positive. The resulting potential between starch and
increasing ribose content [63]. The second mechanism water is called the Donnan potential [78]. The migration of
involves the nonequilibrium behavior of small carbohy- hydrogen ions from the starch to water phase would
drate–water systems [64]. Small-molecule sugars reduce the eventually stop owing to the dynamic equilibrium. Because
molecular chain migration rate, thus inhibiting starch of the potential, starch tends to push cations with a higher
recrystallization. This theory, however, does not fully explain charge density further into the starch. Thus, the intramolec-
why different monosaccharides have different effects on ular repulsive force of starch is changed and starch
recrystallization. The third mechanism is the compatibility retrogradation is probably disturbed. Notably, Ciesielski
theory [65]. This theory suggests that if small-molecule sugars and Tomasik [79] proposed an alternative starch–metal ion
and starch were compatible, the small-molecule sugars would interaction where square planar species of polycentric
form a hydrated layer and reduce the starch molecular chain Werner complexes were formed between starch and metal
rearrangement. Moreover, if the structures were incompati- ions.
ble, small-molecule sugars could accelerate the recrystalliza- Besides the direct effect on starch, salts were shown to
tion process. affect the interactions between starch, nonstarch polysac-
charides, and proteins. Funami et al. [80] investigated the
1.4 Effect of salts on starch retrogradation effect of LiCl, NaCl, KCl, CsCl, CaCl2, and MgCl2 on a starch/
iota-carrageenan composite system. The results indicated that
Salts are of great interest to food scientists because they affect iota-carrageenan increased the rate constant of short
the quality, acceptability, and shelf-life of starch-containing retrogradation and the effect was greater in the presence
foods. The type, valency, as well as concentration have been of monovalent cations, particularly Liþ and Naþ, than divalent
reported to have a significant effect on the gelatinization, cations. Funami et al. [80] also suggested that in the presence
retrogradation, and thermal and rheological properties of of Liþ and Naþ, the number of carrageenan molecules in the
starch [66–74]. random-coil form was larger and more accessible to amylose
Through DSC, dynamic viscoelastic tests, and pulsed because of lower sol-to-gel transition temperatures than other
NMR, the addition of salt was shown to have a pronounced cations. Meanwhile, because the thermal stability of the
effect on enhancing the formation of a rice–starch gel [75]. ligations varied, different salts had different effects on starch
Specifically, a significant reduction in the amount of amylose retrogradation [81]. However, without the addition of salt,
leached out from the starch granules and salt produced a iota-carrageenan had a significant effect on increasing the
charge screening effect, reducing the segmental repul- rate constant of short-term retrogradation. The results
sion [75]. With increasing concentrations of added salt, there suggested that the thermodynamic incompatibility and
was a progressive reduction in the rate of starch retrograda- physical interactions (both molecular complexes and steric
tion [76]. The effect of various chloride salts on starch hindrance) led to a variation in the viscosity during
retrogradation was investigated by Beck et al. [77]. They gelatinization and accelerated the subsequent short-term
suggested that the different cations could significantly retrogradation [81].
influence the starch recrystallization rate. Furthermore,
bivalent cations (such as Ca2þ and Mg2þ) decreased the 1.5 Effect of polyalcohols and polyphenols on starch
starch recrystallization rate more than monovalent cations retrogradation
(Liþ, NH4þ, Naþ, and Kþ) [77]. Salts are a type of strong
electrolyte that can be ionized to anions and cations in water, Polyalcohols and polyphenols may prevent the retrogradation
and these ions affect the hydrogen bonds of water–starch of starch and form stable gel matrices. There are a great
systems and the interactions between starch molecules. number of free hydroxyls in polyalcohols and polyphenols,
Therefore, in starch–water systems, cations replace hydrogen which could form hydrogen bond with starch molecules to
ions inside the starch molecules and the hydrogen ions move restrain starch chain recrystallization.
to the water phase, lowering the pH of the solution. The The influence of polyalcohols varies depending on the
entrapment of larger cations instead of smaller Hþ ions leads number of hydroxyl groups. Polyols were shown to retard the
to less recrystallization of starch and thus to a decreased retrogradation of starch, and might be attributed to the water-
melting enthalpy. Further, starch solubility might change in structure-formation effect of polyols [82]. The more hydroxyl
the presence of ions [77]. Moreover, the interactions between groups the polyalcohol contained, the greater the reduction in
cations and starch hydroxyls leads to different charges. For the recrystallization of granular potato starch [83]. Poly-
example, the hydrogen ion concentration inside the starch phenols are also polyhydroxy compounds, which are found in

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6 Z. Fu et al. Starch/Stärke 2014, 66, 1–10

plant foods such as cocoa, popcorn, tea, soybeans, red wine, emulsifiers adhere to the surface of starch to change the water
fruits, and vegetables and have potential health benefits to distribution. Therefore, interactions with the branched chain
humans [84]. Polyphenols have a great number of free via hydrogen bonding are altered [90, 91].
hydroxyls. These free hydroxyls could form hydrogen bonds
with starch during gelatinization. The hydrogen bond 1.7 Effect of acids on starch retrogradation
formation between polyphenols and starch could retard
starch retrogradation. The number and reactivities of Some organic acids such as citric acid are used as seasoning
hydroxyls in polyphenols have different effects on retarding and to adjust pH values. When citric acid was added to a
starch retrogradation. Smits et al. [83] suggested that the size mixture of starch and a plasticizers, the starch exhibited
and number of hydroxyl groups of polyols had a significant partial esterification, low MW, and a stronger interaction with
influence on the retrogradation of starch, while Wu et al. [85] the plasticizers. These new properties could be expected to
argued that the reactivity of the hydroxyl groups was more prevent retrogradation, promote compatibility with polyes-
important. The stronger the hydrogen bond between starch ters, improve the processing ability, and increase the
and the plasticizer, the more difficult it was for starch to degradation of starch [92]. Furthermore, by adding citric
recrystallize during storage [85]. It is no doubt that during the acid, the pH of the system decreased. Hþ in the solution
starch or starchy food processing, addition of polyphenols would break down the glycosidic bonds between starch
could not only inhibit starch retrogradation but also improve molecules, resulting in smaller starch molecules during the
the nutritional value of products [86, 87]. However, literature gelatinization, which could be expected to prevent
concerning the effect of polyphenols on starch retrogradation retrogradation.
is rare and functional foods incorporated with polyphenols in
the starchy matrix remain scarce [86]. More research is 1.8 Effect of amylase on starch retrogradation
needed to investigate the interaction between polyphenols
and starch, to develop starchy foods fortified with Presently, amylase is often used to advance the processing
polyphenols. properties of dough, improve bread quality, and improve the
taste of rice noodles in the food industry. Additionally, it could
1.6 Effect of emulsifiers on starch retrogradation extent the storage and shelf-life of starchy foods.
Alpha-amylases are used as antiretrogradation agents in
Emulsifiers, as one of the main food additives, play bread. They are obtained from three different sources:
significant roles in the antiretrogradation of starchy foods. bacterial alpha-amylases, cereal alpha-amylases, and fungal
Inhibition of starch retrogradation is determined by the alpha-amylases; each source exhibits different degrees of
emulsifier characteristics [88]. Emulsifiers can interact with effectiveness on bread antiretrogradation. Different alpha-
starch molecules to form stable compounds, which helps amylases had different effects on the quality of bread,
maintain the starchy food quality. During the preparation of probably because of different heat resistances. Generally,
cake, increasing the levels of sodium lauryl sulfate could heat-resistance temperatures of fungi, cereal, and bacteria
prevent starch retrogradation, because sodium lauryl sulfate alpha amylases are 60–63, 74–77, and 93°C, respectively [93].
could lower the specific gravity, surface tension, and Yet, despite the efforts of many investigators, the mecha-
consistency coefficient of the dough [89]. Texture profile nisms of alpha-amylases on stale bread were not completely
analysis of cake crumbs revealed that increasing the levels of unanimous. Conclusions from many studies conducted on
sodium lauryl sulfate lowered crumb firmness and cohesive- bread and starch gels have attributed the lower rates of
ness [89]. The use of 0.2% emulsifier was also successful in retrogradation to an increasing proportion of low-molecular-
retarding the retrogradation of starch and stabilized the gel weight fragments [93–97]. However, other studies pointed out
network. These effects might be attributed to the complex that the antifirming effect of alpha-amylases was not caused
formation of starch chains with emulsifiers [82]. by the presence of low-molecular-weight dextrins, but by the
Emulsifiers bind amylose and amylopectin differently. reduced ability of the degraded starch to retrograde [98–100].
Amylose is generally thought to exist in the linear molecular In addition to amylases, cyclomaltodextrinase is also used
formula, but gelatinized amylose is not linear. Intramolecular to improve starch properties. When rice starch was treated by
hydrogen bonds curl the chains to form an alpha-helix cyclomaltodextrinase, the amylose content of rice starch
structure [16]. A hydrophobic cavity in the internal alpha-helix decreased and the amylopectin content remained almost
structure has a hydrophobic effect. Hydrophobic groups on constant, without a significant change in the chain-length
emulsifiers plug into the alpha helix structure and combine distribution of the side chain. Meanwhile, the retrogradation
with starch hydrophobically, forming strong stable com- rate was significantly retarded than that of the control
plexes. As such, amylose dissolution decreased and prevented sample [101]. The antiretrogradation properties were attrib-
retrogradation [18]. The amylopectin chain is a straight spiral uted to the changed (re)crystallization behavior of the residual
structure and hardly forms complexes with emulsifiers, but amylose and amylopectin populations; the formed dextrins

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Starch/Stärke 2014, 66, 1–10 7

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