Starch Retrogradation: A Comprehensive Review

Shujun Wang, Caili Li, Les Copeland, Qing Niu, and Shuo Wang

Abstract: Starch retrogradation is a process in which disaggregated amylose and amylopectin chains in a gelatinized
starch paste reassociate to form more ordered structures. Starch retrogradation has been the subject of intensive research
over the last 50 years, mainly due to its detrimental effect on the sensory and storage qualities of many starchy foods.
However, starch retrogadation is desirable for some starchy food products in terms of textural and nutritional properties.
To better understand the effect of starch retrogradation on the quality of starchy foods, measurement methods of starch
retrogradation and factors that influence starch retrogradation have been studied extensively. This article provides a
comprehensive review of starch retrogradation including the definition of the process, molecular mechanisms of how it
occurs, and measurement methods and factors that influence starch retrogradation. The review also discusses the effect
of retrogradation on the in vitro enzyme digestibility of starch. Spectroscopic methods such as FTIR and Raman are
considered to be very promising in characterizing starch retrogradation at a molecular level, although more studies are
needed in the future.
Keywords: additives, amylose, amylopectin, measurement methods, starch retrogradation, starch digestibility

Introduction starch is of nutritional interest in relation to the increasing inci-

The changes that starch undergoes during gelatinization and
retrogradation are major determinants of its functional proper-
ties for food processing, during digestion, and in industrial ap-
plications. These properties determine the quality, acceptability,
nutritional value, and shelf-life of the finished foods (Wang and
Copeland 2013). Starch retrogradation is often considered to have
undesirable effects because of its major contribution to the staling
of bread and other starch-rich foods, which can cause reduced
shelf-life and consumer acceptance and lead to significant waste,
and thereby pose significant challenges to food processors (Collar
and Rosell 2013). However, starch retrogradation is desirable in
some applications, such as in the production of breakfast cere-
als, parboiled rice, dehydrated mashed potatoes, and Chinese rice
vermicelli, due to modification of the structural, mechanical, and
sensory properties (Karim and others 2000). Starch retrogradation
is also desirable in terms of nutritional significance, due to the
slower enzymatic digestion of retrograded starch and moderated
release of glucose into the blood stream (Copeland and others
2009; Wang and Copeland 2013). Starch contributes over 50% of
the average caloric intake in Western countries and up to 90% in
the developing world. How we digest starch as one of the most
important carbohydrate components in many foods has important
health implications. As discussed subsequently, the digestibility of
MS 20150407 Submitted 10/3/2015, Accepted 17/4/2015. Authors Wang, Li,
Niu, and Wang are with Key Laboratory of Food Nutrition and Safety, Ministry of
Education, College of Food Engineering and Biotechnology, Tianjin Univ. of Science &
Technology, Tianjin 300457, China. Author Copeland is with Faculty of Agriculture
and Environment, The Univ. of Sydney, NSW 2006, Australia. Direct inquiries to
authors Wang or Wang (E-mail: sjwang@tust.edu.cn or s.wang@tust.edu.cn).
dence of obesity and diet-related diseases.
Starch retrogradation has been the subject of intensive research
throughout the last half century resulting in a vast body of litera-
ture, which is the subject of this review. After an initial introduc-
tory discussion of starch structure and functionality, this article will
focus on the definition and measurement of starch retrogradation,
factors that influence starch retrogradation, and their impact on
starch digestibility.
Starch Structure and Function
Starch structure and function are very active areas of research
that have been the subject of several recent reviews (for example,
Eliasson and others 2013; Vamadevan and Bertoft 2015; Wang
and Copeland 2015). Only those aspects of this topic relevant
to a discussion of starch retrogradation will be considered here.
Starch is mainly made up of 2 polymers of D-glucose: the lightly
branched amylose with a small number of long glucan chains, and
the highly branched amylopectin, which contains many clusters
of short chains. Native starches generally contain 20% to 30%
amylose, although most pulse starches have higher amylose content
(Hoover and others 2010; Wang and others 2011).
Native starch occurs mostly in the form of semi-crystalline
granules, which have a very complex hierarchical structure
(Figure 1). Starch granules are generally composed of an amor-
phous bulk core area surrounded by concentric semicrystalline
growth rings alternating with amorphous growth rings (Wang and
Copeland 2015). The amorphous core, as observed by scanning
electron microscopy (SEM) and transmission electron microscopy
(TEM), is composed mainly of amylose and amylopectin chains
disordered at the reducing end (Wang and Copeland 2012). The
size of the amorphous core is related to the amylose content of
starch; waxy maize starch granules had the smallest core compared


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568 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015 doi: 10.1111/1541-4337.12143
Starch retrogradation . . .

Figure 1The hierarchical structure of starch granules (I) and a stylized model representing the distribution of amylose and amylopectin molecules
(). (a) Native pea starch granules as viewed by SEM; (b) growth rings as observed by SEM; (c) blocklet structures as revealed by AFM; (dh)
representations of super helix, lamellar, double helical structures and amylopectin and amylose molecules, respectively. The blue lines in () represent
amylose molecules, and the black lines represent amylopectin molecules. The structures in (II) are not represented to scale. Reproduced with
permission from Perez and Bertoft (2010).

to normal and high amylose maize starch, with the latter having
the largest core (Li and others 2003).
Starch granules can be examined on at least 5 levels of structure,
ranging in scale from nano- to micrometer. The largest scale is
the intact granule, which varies in size from 1 to 100 m. At
a level down from this macrostructural scale are the alternating
semicrystalline and amorphous growth rings. The semicrystalline
growth rings are proposed to decrease in thickness from 450 to
550 nm, for those closer to the core, to 80 to 160 nm for rings
near the periphery (Wang and Copeland 2012). The amorphous
growth rings appear to be uniform in width and much thinner
(60 to 80 nm) than the semicrystalline growth rings (Wang and
Copeland 2015).
At the next level down are blocklet structural elements, which
are proposed to vary in size from 20 to 500 nm (Gallant and others
1997). Small blocklets (20 nm) are proposed to be located mainly
in amorphous growth rings, and the large blocklets (50 to 500 nm)
in semicrystalline growth rings (Baldwin and others 1998; Gallant
and others 1997; Perez and others 2009; Perez and Bertoft 2010).
At a smaller size scale than blocklets are the left-handed super-
helices, which are suggested to have a width of approximately 18
nm and a pitch of 10 nm based on electron optical tomography
and cryo-electron diffraction experiments (Oostergetel and van
Bruggen 1993). The structural elements beneath super-helices are
crystalline and amorphous lamellae with a periodicity of 9 nm.
The smallest unit of starch structural organization is the individual
glucosyl unit (0.3 to 0.5 nm; Biliaderis 2009).
Quality and nutritional properties of starch-based foods
are largely determined by the changes that starch undergoes
during processing/cooking and subsequent storage. These
changes, which determine the functional properties of starch, in-
volve water uptake, granule swelling, formation of a viscoelastic
paste during heating, followed by reassociation of dispersed starch
chains on cooling and formation of a gel. Starch functionality
is important for controlling moisture, viscosity, texture, consis-
tency, mouth-feel and shelf-life of the finished products (Wang
and Copeland 2013).
When heated in water, starch granules become hydrated, swell,
and are transformed into a paste. The granule structure collapses
due to melting of crystallites, unwinding of double helices, break-
ing of hydrogen bonds. These changes are collectively referred to
as starch gelatinization and are accompanied by the loss of charac-
teristic birefringence of intact granules. There has been extensive
research on defining and measuring starch gelatinization, including
characterizing phase changes during starch gelatinization, and the
effect of gelatinization on starch digestibility (as reviewed by Wang
and Copeland 2013). On cooling, the disaggregated starch chains
retrograde gradually into partially ordered structures that differ
from those in native granules. As a result of its often detrimental
effects on the quality of starch-rich products, much attention has
focused on reducing or retarding retrogradation (Karim and others
2000; Fu and others 2015).
A functional property of starch that is of great importance for
human nutrition and health is its susceptibility to enzymatic di-
gestion. Starch that is digested rapidly by the human digestive
enzymes in the upper gut causes a rapid release of glucose into the
bloodstream, triggering physiological responses that over time are
associated with increased risks for diabetes, cardiovascular disease,


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Starch retrogradation . . .
and cancer (Brand-Miller 2003). However, starch that is digested
slowly, and starch that passes largely undigested into the colon
(resistant starch) are associated with health benefits through better
blood glucose control and prebiotic effects from promoting the
growth of beneficial colonic microflora (Zhang and Hamaker,
2009; Lee and others 2013). Producing starches with slow-
digesting properties is an important objective for the food industry.
Most starch consumed by humans bas been processed or cooked,
with the exception of a few common starch-rich foods that are
eaten raw, such as bananas. The susceptibility of processed starch
to enzymatic digestion is mainly determined by the extent of
disruption of starch structure that occurred during gelatinization
and aggregates that form during subsequent retrogradation. The
more the starch structure is disrupted during gelatinization, the
greater is the susceptibility of the starch to enzymatic digestion
(Wang and Copeland 2013). Partially gelatinized starch may con-
tain substantial amounts of slowly digested and resistant starch. The
digestibility of retrograded starch is largely related to the extent
of gelatinization and subsequent time and temperature of storage.
Initially there is a rapid decrease in the digestibility of starch due to
the fast retrogradation of amylose molecules. On extended stor-
age there is a further, gradual decrease in digestibility due to the
slower rate of amylopectin retrogradation (Eerlingen and others
1994; Cui and Oates 1997; Chung and others 2006).
Definition of starch retrogradation and molecular
mechanism
When starch is heated in the presence of water and subsequently
cooled, the disrupted amylose and amylopectin chains can grad-
ually reassociate into a different ordered structure in a process
termed retrogradation. A schematic representation of changes that
occur in a starchwater mixture during heating, cooling, and stor-
age is shown in Figure 2. Starch retrogradation is usually accom-
panied by a series of physical changes such as increased viscosity
and turbidity of pastes, gel formation, exudation of water and in-
creased degree of crystallinity with the appearance of B-type crys-
talline polymorphs (Hoover and others 2010). The rearrangement
and association of the outermost short branches of amylopectin
(DP about 15) can result in the formation of some B-type poly-
morphs (Ring and others 1987; Hoover 2001). Dispersed amylose
chains form double-helical associations of 40 to 70 glucose units
through hydrogen bonding (Jane and Robyt 1984; Leloup and
others 1992). Starch retrogradation is not favored by chains that
are too short or too long, with the optimum size range being be-
tween about 14 and 24 (Shi and Seib 1992). The retrogradation of
rice starch may be influenced genetically by Wx and SSIIa genes,
which are responsible for amylose and amylopectin synthesis,
respectively (Yang and others 2014).
For nonwaxy starch, retrogradation results in the transformation
of a starch paste into a firm gel consisting of a 3-dimensional net-
work. Waxy starch pastes on retrogradation form a soft gel, which
contains aggregates but no network (Tang and Copeland 2007).
In general, stronger starch gels are associated with a higher amy-
lose content (Ishiguro and others 2000). Amylose-based networks
are considered to provide starch gels with elasticity and strength
against deformation (Miles and others 1985b; Tang and Copeland
2007), whereas soft gels containing aggregates in the absence of
networks display easier penetrability and greater stickiness and ad-
hesiveness. The reduced availability of amylose for intermolecular
hydrogen-bonding disrupts long-range interactions within the gel
resulting in decreased cohesiveness of the structure.
570 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015
Retrogradation is an ongoing process, which initially involves
rapid recrystallization of amylose molecules followed by a slow re-
crystallization of amylopectin molecules. Amylose retrogradation
determines the initial hardness of a starch gel and the stickiness
and digestibility of processed foods. The long-term development
of gel structure and crystallinity of processed starch, which are
involved in the staling of bread and cakes, are considered to be
due to retrogradation of amylopectin (Tran and others 2001; Gray
and BeMiller 2003; Fadda and others 2014). Because of its indus-
trial significance, methods for monitoring starch retrogradation
and ways to retard it have been investigated extensively, as will be
detailed in the next sections.
Methods Used to Study Starch Retrogradation
As starch retrogradation is a complex process involving a series
of molecular and physicochemical events, a diversity of physi-
cal and chemical methods have been applied to investigate the
changes that take place in starch properties. These methods include
various thermal, rheological, spectroscopic and chromatographic
techniques, X-ray diffraction (XRD) and scattering, mechanical
tests, and microscopic imaging. In addition, the kinetics of re-
crystallization of aging gelatinized starch has been modeled using
the Avrami equation (McIver and others 1968; Mua and Jackson
1998). These various techniques provide information on specific
molecular characteristics or transitions, as well as on changes in
the material as a whole (Karim and others 2000; Bao and others
2007; Yao and Ding 2002; Tian and others 2010a, 2010b). differ-
ential scanning calorimetry (DSC) has proven to be an extremely
valuable and sensitive tool to characterize starch retrogradation,
although no single method can give a complete picture of ret-
rogradation properties at both macroscopic and molecular levels
(Russell 1987; Karim and others 2000). The measurement meth-
ods are summarized in Table 1.
Thermal analysis
When a system is heated, absorption or release of heat or loss of
mass usually occurs as a result of phase transitions (such as melting
or crystallization) or chemical reactions (for example, chemical
decomposition). The realignment of disrupted amylose and amy-
lopectin molecules to form a partially ordered structure and the
exudation of water from starch gels can be monitored by sev-
eral techniques of thermal analysis, including DSC, differential
thermal analysis (DTA), and thermogravimetry (TG). DSC is a
technique that measures energy changes in a material subjected
to programmed heating or cooling. The transition temperatures
(onset, To ; peak, Tp ; and conclusion, Tc ) and enthalpy change
(H) due to crystallite melting or formation of ordered structures
can be derived from DSC thermograms. In the case of retro-
graded starch, the DSC endotherm provides quantitative measures
of enthalpy change and transition temperatures for the melting
of recrystallized amylopectin (Karim and others 2000). DTA and
TG, which measure, respectively, the difference in temperature
between the sample and a reference and the mass loss of a sample
as a function of temperature, have been used to study retrograda-
tion of rice starches differing in amylose content (Tian and others
2011a, 2011b). The degree of retrogradation was characterized by
measuring the mass loss of bound water or the differential tem-
perature (T) of gelatinized and retrograded starch samples (Tian
and others 2011a, 2011b).

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Starch retrogradation . . .
Figure 2Schematic representation of changes that occur in a starchwater mixture during heating, cooling, and storage. (I) Native starch granules;
(II) gelatinization, associated with swelling [a] and amylose leaching and partial granule disruption [b], resulting in the formation of a starch paste; (III)
retrogradation: formation of an amylose network (gelation/amylose retrogradation) during cooling of the starch paste [a] and formation of ordered
or crystalline amylopectin molecules (amylopectin retrogradation) during storage [b]. Reprinted with permission from Goesaert and others (2005).
Rheological methods
Development of viscoelastic properties of starch during ret-
rogradation can be monitored using rheological or mechanical
techniques to measure large or small deformations. Large defor-
mation tests can be conducted using uniaxial compression, texture
profile analysis (TPA), the Brabender Amyloviscograph, or the
Rapid Visco Analyzer (RVA). The application of large forces or
shearing stresses during measurement causes permanent structural
disruption of the material or shear-thinning, making the study of
viscoelastic properties of the system difficult. Hence, the results
may not reflect the actual changes of the gelatinized starch during
retrogradation (Jankowski 1992; Hallberg and Chinachoti 2002;
Vandeputte and others 2003). In many food processing opera-
tions, the viscoelastic materials are often subjected to high shear
conditions that cause varying degrees of deformation, resulting
in nonlinear viscoelastic behavior. To overcome these drawbacks,
small deformation dynamic mechanical devices have been de-
veloped, which allow the viscoelastic properties to be measured
nondestructively. Low-deformation methods include the dynamic
oscillatory test, creep compliance/recovery test, and stress relax-
ation (Biliaderis and Zawistowski 1990; Akuzawa and others 1995;
Shiraishi and others 1995). The last 2 tests are also known as static
procedures. The information obtained by small dynamic rheo-
logical testing is useful to study gelation mechanisms, molecular
interactions during gel formation and development of gel modu-
lus (resistance to deformation) during aging. To fully understand
the viscoelastic properties of starch gels, the combination of 2 or
more methods is usually necessary. However, there have been few
studies aimed at correlating information obtained from large and
small deformation measurements (Karim and others 2000).
Of the rheological methods mentioned, TPA and pasting anal-
ysis are the most commonly used to study starch retrogradation in
model starch gels and food systems. In a TPA test, the sample is
compressed uniaxially, the compressive force is then removed and
the sample is re-compressed. Such a compressive sequence repre-
sents 2 bites. From the output of the instrument, one is able

C 2015 Institute of Food Technologists
to measure 5 primary characteristics of a gel: hardness, cohesive-
ness, adhesiveness, elasticity (also called springiness), and brittle-
ness (also called fracturability). Moreover, several additional texture
characteristics such as gumminess (hardness cohesiveness) and
chewiness (hardness cohesiveness springness) can be derived
(Rosenthal 2010). In general, starch retrogradation contributes to
increase of hardness and decrease of adhesiveness of cooked rice
during storage (Yu and others 2009, 2010).
The tendency of a gelatinized starch to retrograde can also be
studied from its pasting behavior, usually by observing changes in
pasting viscosities during programmed heating and cooling of a
starch suspension using a Brabender Amyloviscograph or RVA.
From the traces of either of these instruments, 5 characteris-
tic parameters can be obtained: peak viscosity, trough viscosity,
breakdown viscosity, final viscosity, and setback viscosity. Of these
parameters, setback is defined as the difference between final vis-
cosity and trough viscosity and its magnitude is considered to
reflect the retrogradation tendency of amylose in a starch paste.
Typically, starch presenting higher setback values has a greater ten-
dency for retrogradation (Zaidul and others 2007).
Spectroscopic methods
Vibrational spectroscopy includes several techniques, the most
important of which are infrared (IR) and Raman spectroscopy.
Both of these complementary techniques are usually required to
fully characterize the vibrational modes of a molecule. Although
some vibrations may give rise to signals in both the Raman and
IR regions of the electromagnetic spectrum, Raman spectroscopy
is best at detecting symmetrical vibrations of nonpolar groups,
whereas IR spectroscopy is best for asymmetrical vibrations of
polar groups (Larkin 2011). IR and Raman spectroscopy have
been used extensively to study the molecular changes during starch
retrogradation, as described in the following sections.
IR Spectroscopy. The technique of Fourier transform mid-
infrared (FTIR) spectroscopy in combination with attenuated total
reflectance (ATR) has been used to follow starch retrogradation.
Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 571
Starch retrogradation . . .

Table 1Methods used to measure starch retrogradation.

Method type Techniques Properties measured References

Thermal analysis DSC Transition temperatures, enthalpy
change (H) of crystallite melting
DTA Temperature differences between the
sample and a reference during a
thermal program
TGA The mass loss of the sample
Rheological analysis RVA Pasting viscosities during programmed
heating and cooling of a starch
suspension
TPA Hardness, cohesiveness, adhesiveness,
elasticity, and brittleness
Spectroscopic analysis FTIR Order in crystalline regions and the state
of organization of the double helices
localized inside crystallites
NIR Molecular changes of starch gel during
retrogradation
Raman Internal vibrations of molecules;
Continuous measurement of starch
retrogradation at the molecular level
NMR 1 H NMR analyzes the mobility of starch
polymer chains
13 C CP/MAS NMR investigates molecular
organization of starch granule at a
shorter distance scale (double helices)
and amorphous single chains
X-ray diffraction WAXD Long-range ordered structure of starch
SAXS Repetitive crystalline and amorphous
lamellae
Microscopic SEM AFM Surface morphology of starch granules
and retrograded starch gels
Physical methods Turbidity Syneresis Changes in density distribution of
gelatinized starch paste
Other methods Blue value determination Retrogradation of amylose during starch
retrogradation
Resistance of starch to hydrolysis Resistance of starch to enzymatic
hydrolysis during retrogradation
Karim and others 2000; Zhou and others
2010; Ambigaipalan and others 2013;
Wang and Copeland, 2013; Chen and
others 2015; Guo and others 2015;
Qiu and others 2015
Tian and others 2011a, 2011b
Wang and others 2006; Tian and others
2011b
Tran and others 2001; Zaidul and others
2007; Zhou and Lim, 2012; Alamri and
others 2013; Chen and others 2015
Perdon and others 1999; Yu and others
2009, 2010; Rosenthal, 2010
van Soest and others 1994; Thygesen
and others 2003; Flores-Morales and
others 2012; Htoon and others 2009;
Ambigaipalan and others 2013; Lian
and others 2013
Cho and others 1998; Bao and others
2007; Mariotti and others 2009
Li-Chan, 1996; Schuster and others 2000;
Kizil and others 2002
Fencher and others 2005; Socrates,
2007; Flores-Morales and others 2012
Ablett, 1992; Teo and others 1992; Wu
and Eads, 1993; Vodovotz and others
2002; Lewen and others 2003;
Bosmans and others 2012; Bosmans
and others 2013
Gidley, Bociek, 1985; Baik and others
2003; Ambigaipalan and others 2013
Gidley and Cooke, 1991; Blazek and
Gilbert, 2011
Ambigaipalan and others 2013; Fu and
others 2013
Tang and Copeland, 2007; Charoenrein
and others 2011; Utrilla-Coello and
others 2013; analysis Putaux and
others 2000; Wu and others 2012
Miles and others 1985a; Wang and
others 2006, 2007; Ambigaipalan and
others 2013; Perera and Hoover,
1999; Miles and others 1985a;
Jacobson and others 1997;
Miles and others 1985a; Jankowski,
1992; Jacobson and others 1997
Sievert and Pomeranz, 1989, 1990;
Eerlingen and others 1994; Wang and
Copeland, 2013

The wavelength range from 800 to 1300 cm1 corresponds mainly
to CO and CC stretching vibrations and is sensitive to changes
in polymer conformation and starch hydration (Htoon and others
2009). The spectral band at 995 cm1 is very sensitive to water
content. Bands at 1047 and 1022 cm1 reflect the amounts of or-
dered and amorphous regions, respectively (van Soest and others
1994; Wang and others 2014). The absorbance ratios of 1047/1022
and 1022/995 cm1 are assumed to represent, respectively, the or-
der in more crystalline regions and the state of organization of
the double helices localized inside crystallites. On retrogradation,
1047/1022 and the 1022/995 cm1 ratios increase, consistent with
an increased organization of structure (Flores-Morales and others
2012; Ambigaipalan and others 2013). Other characteristic bands
were also observed to be affected by retrogradation. A weak shoul-
der at about 2852 cm1 , which overlaps the band for the CH2
symmetrical stretching vibration, was observed to increase with
retrogradation of normal starch. The increased intensity of this
shoulder was attributed to the unwinding of protein (Lian and
others 2013). An alternative explanation is that it may be related
to the formation of amylose-lipid complex during retrogradation
(Wang and others, unpublished data). In addition to the above
well-characterized bands, other bands at 1743, 1650, 1537, 1418,
1373, and 1242 cm1 also change as retrogradation progresses,
although the reasons for this are not well understood. These bands
may be assigned to conjugated carbonyl and carboxyl groups and
CO vibrations (Thygesen and others 2003; Nuoppone and others
2006).
Near-infrared reflectance (NIR) spectroscopy is another tech-
nique for acquiring information on molecular changes during
retrogradation of gelatinized starch (Cho and others 1998; Bao
and others 2007; Mariotti and others 2009). In a study of ret-
rogradation behavior of rice paste (Mariotti and others 2009), the
NIR spectra of rice gels were characterized by small peaks at ap-
proximately 10583 to 10383 cm1 , and by major peaks at 8871
to 8655, 7297, 7097, 5430, 5245, and 4474 cm1 . The peak at
10383 cm1 was attributed to the second overtone of symmetrical

572 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015 
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Starch retrogradation . . .

and asymmetrical stretching of OH of water. Absorbances at 8871 resolution 1 H NMR, which is capable of analyzing the mobility of
and 8655 cm1 are due to the CH stretching vibration of starch starch polymer chains (Ablett 1992). The starch molecules in the
molecules. The peak at 7297 cm1 arises from the CH stretching more mobile liquid (gelatinized) and less mobile solid-like (ret-
vibrations of starch and cellulose molecules, the one at 7097 cm1 rograded) state can be differentiated by the spinspin relaxation
from the first overtone of OH of water. The absorption bands time (T2 ). As retrogradation proceeds, the signal attributed to
at 5245 and 4474 cm1 are due to the combination of water and protons in the solid phase of starch gels increases, whereas the sig-
CH stretching and the bending of starch molecules, respectively nal from the liquid component decreases (Teo and Seow 1992). A
(Cho and others 1998; Barton and others 2002). These major NIR decrease in the T2 value for a population of exchangeable protons
peaks change with retrogradation, reflecting the molecular mod- in a gel network of a crustless crumb stored at 4 C compared to
ifications of starch and water. However, the relationship between 23 C was interpreted as showing that cool storage led to increased
the changes in these NIR spectral bands and structural changes in strength of the starch network (Bosmans and others 2012, 2013).
retrograded starch is not well understood. A decrease in the molecular mobility of the liquid component was
Raman spectroscopy. Raman spectroscopy is used widely to observed by decreases in 17 O T2 (the liquid transverse relaxation
probe molecular vibrations that are sensitive to the chemical en- rate), 1 H D0 (the rate of H1 diffusion coefficient), and T2A (the
vironment around individual atoms (Li-Chan 1996). For starch liquid transverse relaxation time). The value for T2B (the solid
characteristic Raman spectral bands at 3200, 2900, 930, and transverse relaxation time) did not change with concentration or
477 cm1 are associated with amylose and amylopectin molecules. time, indicating that the mobility of the solid component does
The 2 most intense spectral bands, at around 480 cm1 and be- not change over time despite the conversion of the highly mobile
tween 2900 and 3100 cm1 are attributed to vibrations in the starch fraction to the less mobile solid state during retrogradation
pyranose ring of glucose and C-H stretching, respectively. Bands (Lewen and others 2003).
around 860 and 930 cm1 are assigned to the C(1)H and CH2 Wu and others (1992) and Wu and Eads (1993) studied poly-
deformations and COC skeletal mode vibrations of the -1,4 mer immobilization during aging of waxy maize starch gels using
glycosidic linkages. A band at 1127 cm1 is attributed to the 1
H nuclear magnetic cross-relaxation spectroscopy. From the nor-
contribution of 2 main vibrational modes, CO stretching and malized amplitude of the liquid 1 H signal (single resonance), the
COH deformation. The vibrational modes that are dependent Z-spectrum could be obtained, which is a reflection of immobile
upon the crystal structure of amylose occur at approximately 1440, protons in the sample. At the same moisture content, different
1340, and 1200 cm1 . These bands are associated with a complex starch samples showed different Z-spectra, indicative of different
of vibrations among CH2 , COH, and CCH (Schuster and mobilities of protons in the solid fraction (Vodovotz and others
others 2000; Kizil and others 2002; Socrates 2004; Wang and 2002). For example, a narrower line shape is indicative of more
others 2015). mobile protons in the solid phase. An observed increase in the area
Raman spectroscopy is a nondestructive technique that allows and width of the Z-spectral line shape for waxy starch gels during
continuous measurement of starch retrogradation at the molecular aging was dependent on concentration and storage time (Wu and
level. Starch retrogradation can be monitored based on the full Eads 1993; Vodovotz and others 2002).
widths at half-height of peaks (FWHHs), shifts in the position of High-resolution solid-state 13 C NMR has been increasingly
Raman bands at about 480 cm1 and from the spectral features of applied to the study of starch retrogadation using a special tech-
the CH stretching modes between 2800 and 3050 cm1 (Fencher nique referred to as cross-polarization and magic-angle spinning
and others 2005). The FWHH of the spectral feature of the (CP/MAS) NMR spectroscopy. 13 C CP/MAS NMR has been
CH stretching modes between 2800 and 3050 cm1 and shifts used to investigate molecular organization of starch granules at a
of Raman band at 480 cm1 of potato, maize, and wheat starches shorter distance scale than XRD and to obtain information on or-
varied with the storage time of the gel (Fencher and others 2005). dered helices and amorphous single chains. The 2 broad shoulders
Retrogradation of potato starch led to the most remarkable changes at 103.2 and 82.4 ppm are assigned to the amorphous domains for
in the FWHH at 2900 cm1 and shift of the band at 480 cm-1 , C-1 and C-4 (Gidley and Bociek 1985). These 2 domains are gen-
whereas wheat starch showed the least changes on retrogradation. erally used to estimate the proportion of amorphous, single, and
In a study of starch retrogradation in maize tortillas (Flores-Morales
double-helical material in starch samples. On gelatinization, the
and others 2012), the band at 480 cm1 was observed to disap- increase in intensity of the C-4 resonance at 82 ppm was clearly
pear gradually as retrogradation proceeded. Other bands at 1459, evident, reflecting the loss of crystalline structure and increase in
1127, and 856 cm1 were also observed to decrease in intensity proportion of amorphous areas. On retrogradation, the intensity
with ongoing retrogradation, although the significance of these of this peak decreased with aging of a starch gel, indicating the
changes is not known. development of rigid structures due to the interaction of starch
chains. Meanwhile, the double helix content increased with aging
Nuclear magnetic resonance (NMR) spectroscopy of the starch gel (Baik and others 2003; Ambigaipalan and others
NMR as an analytical technique can be dated to the mid-20th 2013).
century, when proton nuclear magnetic resonance (1 H NMR)
was observed in liquid water and paraffin wax (Bloch and oth- X-ray diffraction
ers 1946; Purcell and others 1946). Subsequently, several other XRD techniques are used widely for phase identification of a
magnetically active nuclei such as 13 C, 19 F, and 31 P were used crystalline material and to provide information on crystal struc-
for the analysis of biological and pharmaceutical compounds and ture and unit cell dimensions, as reviewed by Blazek and Gilbert
their mixtures (Malet-Martino and Holzgrabe 2011). As a nonin- (2011). As a semicrystalline material, native starch granules present
vasive and nondestructive technique, NMR has become a central 3 distinct XRD patterns (A, B, and C) and varying degrees of
analytical method in food science (Bertocchi and Paci 2008), in- crystallinity. XRD detects long-range ordered structures involv-
cluding for the study of starch retrogradation. The most frequently ing regular and repeated arrangement of double helices, thereby
used NMR technique in the study of starch retrogradation is low- reflecting the 3-dimensional order of starch crystallinity. The


C 2015 Institute of Food Technologists Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 573
Starch retrogradation . . .
technique is less sensitive to irregularly packed structures, small
chain aggregates, or isolated single helices (Gidley and Cooke
1991). The XRD pattern is an average of many granules and
therefore XRD does not pick up variability between or within
granules. The changes in long-range ordered structure of starch
gels during retrogradation have been studied extensively by XRD.
During gelatinization, the crystalline structure of starch granules
is disrupted, which is usually detected by an amorphous halo in
the XRD patterns of fully gelatinized starch samples. The forma-
tion of new crystallites in freeze-dried retrograded starch can be
distinguished by XRD (Zhou and Lim 2012).
The extent to which crystallites develop, and the type of poly-
morphs formed as a result of retrogradation, are influenced by
many factors, such as storage temperature, water content of gela-
tinized starch samples, extent of gelatinization, and amylopectin
chain length (Ambigaipalan and others 2013; Fu and others 2013).
In most cases, retrograded starch presents a typical B-type XRD
pattern, irrespective of whether it was present as A- or B-type
polymorphs in its native state (Hoover and others 2010). Hellman
and others (1954) found that the type of crystals developed in
aged cereal starch gels depend on water content. Samples contain-
ing more than 43% water presented a B-type pattern on aging,
whereas those containing less than 29% moisture gave an A-type
pattern. Samples with moisture content of between 29% and 43%
displayed a C-type pattern (Osella and others 2005). The develop-
ment of crystalline polymorphs is also influenced by retrogradation
temperature. Storage at low temperature results in the formation
of B-type polymorphs, whereas high temperature leads to the for-
mation of A- and V-type polymorphs (Shamai and others 2004).
Starch retrogradation can also be monitored by small angle X-
ray scattering (SAXS), which is used less often compared to XRD.
SAXS measures variations in the distribution of electron density
between 2 phases, such as amorphous and crystalline lamellae,
or amorphous and crystalline growth rings in starch. The aver-
age total thickness of the crystalline and amorphous lamellae can
be obtained from the SAXS patterns (Blazek and Gilbert 2011).
When re-organization of a starch gel reaches a sufficient level of
ordering, Bragg peaks corresponding to lamellae can be observed
(Suzuki and others 1997; Blazek and others 2011). Retrograda-
tion at low temperature leads to the formation of lamellar peaks of
long-range periodicity, but this peak was not observed for starch
retrograding at high temperature (Shamai and others 2004).
Measurement of turbidity and syneresis
Turbidity, as measured by absorbance of light at 620 nm, may be
used to characterize the retrogradation behavior of dilute starch
pastes (<2%, w/w starch). The changes in density distribution
due to the aggregation of amylose and/or amylopectin chains
reduce the transmission of light (Miles and others 1985). Many
studies have shown that there is a rapid increase in the turbidity
during the early stage of storage of gelatinized starch dispersions,
which remains largely unchanged or increases only slowly after
48 or 72 h storage (Wang and others 2006, 2007). The rapid
increase in turbidity during the first 24 h reflects the formation of
networks resulting mainly from interactions between AM chains
that were leached out of the granules during gelatinization (Perera
and Hoover 1999; Ambigaipalan and others 2013). The changes in
turbidity during storage of starch pastes are consistent with rapid
retrogradation of amylose (Miles and others 1985). The increase
in turbidity of starch pastes during storage has been reported to
be affected by factors such as granule swelling, granule remnants,
574 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015
leached amylose and amylopectin, amylose and amylopectin chain
lengths (Jacobson and others 1997).
Syneresis is a process in which a gel contracts on standing and
exudes liquid. Although syneresis is a physical characteristic of
most gels, it can be used to assess the freezethaw stability of
starch by measuring the water exuded from a gel on standing or
after freezing and thawing (Hoover and Ratnayake 2002). Synere-
sis increases with the number of freezethaw cycles, in part due
to enhanced amylopectin retrogradation in the starch-rich phase
(Yuan and Thompson 1998). A low syneresis value on freezing
and thawing is indicative of slow retrogradation of starch gels due
to strong interactions between dispersed amylose/amylopectin and
water molecules (Liu and others 2014).
Other methods
Blue value determination. Starch can form an inclusion com-
plex with polyiodide ions, which gives rise to a characteristic
deep blue color. Amylose content of native starch is often deter-
mined colorimetrically from the iodine complexation. In amor-
phous domains, the conformation of amylose chains appears to be
mainly in a single helical state or random coil. Dispersed amylose
on retrogradation may form double-helical associations of 40 to
70 glucose units, which cannot accommodate the iodine (Jane and
Robyt 1984). As a result, amylose gradually loses its ability to form
a blue complex with iodine if double-helical associations occur be-
tween amylose chains on retrogradation. The blue value, which
was defined as the absorbance at 635 nm of 10 mg anhydrous starch
in 100 mL diluted I2 -KI solution at 20 C, can be used to monitor
the starch retrogradation progress. As the blue complex is formed
mainly with amylose molecules, the blue value determined dur-
ing starch retrogradation predominantly reflects retrogradation of
amylose. According to the blue value, the amount of soluble amy-
lose in cooked starch decreased rapidly with storage time during
the first 8 h after cooking, and then underwent little change after
24 h at 20 C (Jankowski 1992).
Resistance of retrograded starch to enzymatic hydrolysis. The
resistance of starch to enzymatic hydrolysis can be used as a mea-
sure of starch retrogradation. The formation of ordered structures
such as double helices and/or crystallites as a result of retrogra-
dation increases the resistance of starch to enzymatic hydrolysis
(Eerlingen and others 1994; Cui and Oats 1997). To evaluate
the degree of starch retrogradation by enzymatic hydrolysis, the
selection of enzymes used for starch digestion is very important.
As hydrolytic enzymes differ in specificity and activity towards
retrograded starch (Karim and others 2000), measures of starch ret-
rogradation will depend on the type and amount of the particular
enzymes used. The most commonly used enzymes are pancreatic
-amylase, although Bacillus subtilis -amylase and -amylase and
pullulanase are also used. Heat-stable -amylase at high temper-
ature is not recommended as under these conditions retrograded
starch almost completely hydrolyzed (Sievert and Pomeranz
1989). According to methods developed by Kainuma and others
(1981) and Tsuge and others (1990), nondigestible retrograded
starch can be determined colorimetrically with iodine after
gelatinized starch has been digested by Bacillus subtilis -amylase.
Imaging methods. Microstructures formed by the re-association
of dispersed starch molecules can be distinguished by SEM or
atomic force microscopy (AFM). For starch gels containing amy-
lose, extended molecular networks containing discrete rod-shaped
structures with average dimensions of 52.1 12.4 nm in length,
35.2 6.3 nm in width, and 0.9 0.5 nm in height can be clearly
observed by AFM (Tang and Copeland 2007). In contrast, gels of

C 2015 Institute of Food Technologists
Starch retrogradation . . .
waxy starch and starches mixed with lipids were observed to con-
tain mainly aggregated globular structures with diameter between
20 and 60 nm and height of 0.5 to 1 nm under AFM (Tang and
Copeland 2007).
Retrogradation behavior of starch gels can also be visualized
by SEM and TEM images. Upon storage and dehydration, a
cell-wall structure with fractal-like networks and well-defined
pores in the gel can be observed under SEM or TEM (Putaux
and others 2000; Charoenrein and others 2011; Wu and others
2012; Utrilla-Coello and others 2013). The matrix surrounding
the pores appears increasingly stronger and thicker with longer
storage time. The storage temperature also has important effects
on the apparent fractal microstructure of retrograded starch gels,
with smaller cavities formed at low temperature than at higher
temperatures (Utrilla-Coello and others 2013). This observation
was interpreted in terms of lower temperature reducing mobility of
water and starch, thus yielding an aggregated structure rather than
a globular structure (Utrilla-Coello and others 2013). The aver-
age fractal dimensions of the retrograded starch samples increased
with storage time. Moreover, a good correlation was found be-
tween fractal dimensions and retrogradation enthalpies (Wu and
others 2012; Utrilla-Coello and others 2013). In addition to frac-
tal dimensions, the lacunarity (gaps or holes) can also be used as
an indicator of the homogeneity of retrograded starch gels. The
lacunarity of retrograded maize starch gels increased with stor-
age time and correlated well with the enthalpy of retrogradation
(Utrilla-Coello and others 2013). These results indicated that the
fractal features extracted from SEM images of retrograded starch
gels can be used to characterize the extent of retrogradation (Wu
and others 2012; Utrilla-Coello and others 2013).
In summary, probing changes in a sole parameter over time may
not provide an adequate description of retrogradation. The meth-
ods described for characterizing methods of starch retrogradation
measure different events that occur during the re-association of
amylose and amylopectin chains following starch gelatinization.
The changes involved may not occur simultaneously. For exam-
ple, the development of gel modulus during storage can lag behind
the formation of crystallites as measured by DSC and XRD, de-
pending on starch concentration (Ring and others 1987). The rate
of modulus (G ) development in aging non-waxy starch gels is of-
ten much faster than the rate of increase of retrogradation enthalpy
(H; Biliaderis and Zawistowski 1990). Furthermore, retrograda-
tion kinetics determined by different methods on the same sample
may not be in agreement (Roulet and others 1988). Choosing
the appropriate methods to monitor starch retrogradation in food
products should depend on the physical and/or chemical charac-
teristics of samples, as well as an appreciation of the limitations of
the methods.
Factors Influencing Starch Retrogradation
Starch retrogradation is mostly taken to be an undesirable pro-
cess that occurs during the storage of starchy foods. Retardation
or inhibition of starch retrogradation is of special interest and
a challenge for the food industry, and an area where great ef-
forts have been made to study the influencing factors. As dis-
cussed subsequently, water content, starch source, and storage
conditions are all well-known factors that can greatly influence
starch retrogradation. The presence of food components such as
lipids, carbohydrates, salts, proteins, or peptides have also been
shown to play a significant role in retarding the rate of starch
retrogradation.

C 2015 Institute of Food Technologists Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 575
Water content
In the processing and storage of foods, water plays a crucial
role in starch gelatinization and retrogradation. The effect of wa-
ter content on starch gelatinization has been reviewed by Wang
and Copeland (2013). The rate and extent of starch retrograda-
tion is also largely dependent on water content. The effect of
water content on starch retrogradation, as determined by mea-
suring DSC enthalpy change of recrystallized amylopectin, dis-
played a parabolic shape, with maximum retrogradation occurring
in starch gels at 40% to 45% water content (Zeleznak and Hoseney
1986). However, Jouppila and others (1998) showed that the rate
of retrogradation, as determined by the Avrami equation, was in-
dependent of water content at high temperature; the half-time for
maximum retrogradation was 5.2 days at 60 C, but only 34 min
at 80 C.
The effect of water content on starch retrogradation is influ-
enced by amylose content, which can also affect amylopectin crys-
tallization (Zhou and others 2011). When the water content was
below 20% or above 90%, no retrogradation was observed by DSC
for corn and wheat starch (Longton and Legrys 1981; Zhou and
others 2011). As the water content was reduced to 80%, retrogra-
dation occurred for nonwaxy corn starch, but was not observed
in waxy starch. When the water content was decreased further to
70%, retrogradation occurred for both waxy and nonwaxy starches,
with the former exhibiting smaller enthalpies, indicating that the
retrogradation of starch is facilitated in the presence of amylose
(Sievert and Wursch 1993; Klucinec and Thompson 2002; Zhou
and others 2011). When the water content was 60%, starch ret-
rogradation was not affected by amylose content (Zhou and others
2011).
Storage conditions
Temperature and length of storage are the major determinants
of the extent of starch retrogradation. In general, retrogradation is
rapid initially and then slows down. The onset temperature and
enthalpy change for the melting of retrograded starch molecules
increase with storage time at constant temperature, whereas the
conclusion temperature exhibits little change (Park and others
2009; Zhou and others 2010; Ambigaipalan and others 2013; Fu
and others 2013; Xie and others 2014). These observations in-
dicate that longer storage facilitates the formation of more starch
crystallites with a higher degree of perfection. As was noted for
enthalpy change, the relative crystallinity, double helix content,
and the IR absorbance ratio of 1047/1022 cm1 all increase with
storage time, indicating the increasing formation of starch crystal-
lites and molecular order (Zhang and others 2011; Ambigaipalan
and others 2013; Fu and others 2013; Xie and others 2014). The
hardness and springiness of retrograded starch gels increase dur-
ing the initial stage of storage at a constant temperature, but then
change only slightly on longer storage (Ji and others 2007; Park
and others 2009; Singh and others 2012). In comparison, hold-
ing gels under cycled temperatures of 4/30 C results in hardness
and springiness developing and remaining more or less the same
during the whole process (Park and others 2009).
The most common temperature conditions for studying starch
retrogradation are isothermal storage at 4, 25, or 30 C, or tem-
perature cycling between 4 and 25 C (or 30 C). Generally,
the storage of starch gels at 4 C induces faster crystallization of
amylopectin than at 25 or 30 C. Temperature cycling (4/30 C)
led to smaller melting enthalpy of retrogradation products, higher
melting onset temperatures, and lower melting temperature range,
compared with isothermal storage at 4 C, indicating that
Starch retrogradation . . .
temperature cycles inhibited the formation of crystallites, but en-
hanced their homogeneity and stability (Zhou and others 2010;
Zhou and Lim 2012). Similarly, the DSC melting temperature
range of waxy potato starch products stored at cycles of 4/25 C
shifted toward lower values compared with storage at 25 C, indi-
cating that less perfect crystallites are formed during retrogradation
under temperature-cycled conditions (Mangala and others 1999;
Niba 2003; Zhou and Lim 2012; Xie and others 2014). However,
in another study, storage at 4 C resulted in the lowest To , Tp , Tc ,
Tc To and enthalpy change, compared with storage at 25 C
and temperature cycles of 4/25 C, indicating that storage at 4 C
inhibited generation of crystallites and decreased the perfection
of starch crystallites. Clearly, the type of starch and experimental
conditions will influence how starch retrogrades.
Additives
Many additives are used to retard retrogradation of starch in
foods independent of storage time or temperature. These additives
can be grouped into carbohydrates, salts, amino acids/proteins/
peptides, lipids, and other food components such as polyols,
polyphenols, emulsifiers, citric acid, and amylase. Table 2 sum-
marizes a large number of studies on the effect of additives on
starch retrogradation. The table is included to illustrate the diver-
sity of results, sometimes conflicting, obtained with starches from
different sources under different experimental conditions.
Carbohydrates. Carbohydrates that are widely used as addi-
tives to retard starch retrogradation include: monosaccharides
such as glucose, ribose, and fructose; oligosaccharides such as
sucrose, maltose, lactose; -cyclodextrin and hydroxypropyl--
cyclodextrin; and polysaccharides like crude tea polysaccharide,
-glucan, konjac glucomannan, carboxymethyl cellulose (CMC),
soybean-soluble polysaccharide (SSPS), gum arabic (GA), iota-
carrageenan, pectin, xanthan gum, and guar gum. In most cases,
the addition of carbohydrates can inhibit the extent of retrograda-
tion of starch gels, although exceptions were observed in the pres-
ence of sucrose (Chang and Liu 1991). The extent to which starch
retrogradation is inhibited is largely influenced by the type and
concentration of carbohydrate. The mechanisms for the inhibi-
tion of starch retrogradation are explained in terms of competition
for water between starch and the other carbohydrates.
Glucose, ribose, fructose, sucrose, maltose, and water-soluble
maltodextrins all can retard starch retrogradation. Many studies
have shown disaccharides to be more effective than monosaccha-
rides as inhibitors of starch retrogradation (Kohyama and Nishi-
nari 1991; Katsuta and others 1992a, 1992b; Wang and Jane 1994;
Hoover and Senanayake 1996a, 1996b; Hyang and others 1998;
Smits and others 2003). However, in a few cases disaccharides
increased the rate of starch retrogradation (Germani and others
1983), and sucrose and glucose increased the extent of starch ret-
rogradation (Chang and Liu 1991; Gunaratne and others 2007).
The effect of oligosaccharides on starch retrogradation does not
always follow a consistent trend. In some studies, inhibition of
starch retrogradation decreased with increasing molecular weight
of oligosaccharides (Cairns and others 1991; Katsuta and others
1992c), although this observation was not noted by others (Duran
and others 2001; Rojas and others 2001).
Inconsistent results have also been reported with monosaccha-
rides. In one study, hexoses (with the exception of galactose)
were more effective than pentoses in retarding the retrogradation
of starch (Katsuta and others 1992a), whereas in another study
glucose was less effective than ribose, which almost completely
576 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015
suppressed starch retrogradation (IAnson and others 1990; Cairns
and others 1991).
-Cyclodextrin and hydroxypropyl--cyclodextrin, which are
used widely in the food, cosmetic, and pharmaceutical in-
dustries, have also been used in studies of starch retrograda-
tion. The addition of -cyclodextrin can retard the short- and
long-term retrogradation of amylose-containing starch, which
has been attributed to the interaction between amylose and
-cyclodextrin to form an amylose--cyclodextrin-lipid complex
(Tian and others 2009). -Cyclodextrin did not retard retrogra-
dation of waxy starch. The extent of retrogradation of normal
and high-amylose rice starch decreases with increasing concen-
tration of -cyclodextrin (Tian and others 2009). Hydroxypropyl
-cyclodextrin was more effective in retarding retrogradation of
high-amylose rice starch than was -cyclodextrin (Tian and others
2010b). In another study, hydroxypropyl--cyclodextrin increased
short-term amylose retrogradation, but had little effect on long-
term amylopectin retrogradation (Gunaratne and others 2010).
Nonstarch hydrocolloidal polysaccharides, particularly guar
gum, xanthan gum, and carrageenan and, to a lesser extent, konjac
glucomannan, pentosans, gellan, pectin, pullulan, alginate, inulin,
okra gum, locust bean gum, corn fiber gum, carboxymethyl-
cellulose, hydroxypropylmethylcellulose, and tea polysaccharide,
have all been studied for their effect on starch retrogradation
(Zhou and others 2008; BeMiller 2011; Alamri and others 2013;
Correa and others 2013; Chen and others 2015; Pongsawatmanit
and others 2013; Witczak and others 2014; Qiu and others 2015).
As pointed out by BeMiller (2011), no general conclusions on
the effect of hydrocolloids on starch retrogradation have been
reached. The addition of hydrocolloids can increase, decrease, or
have no effect on the extent of starch retrogradation, depending on
the paste/gel preparation method, storage temperature and time,
and measurement techniques of starch retrogradation. In general,
hydrocolloids seem to promote short-term retrogradation and re-
tard long-term retrogradation, presumably by primarily affecting
amylose-amylose interactions and amylopectinamylopectin asso-
ciations, respectively (BeMiller 2011). The inhibition of starch ret-
rogradation by hydrocolloids is largely concentration dependent.
-Glucan is a food constituent noted for its thickening, gelling,
and stabilizing properties, and for its potential beneficial effects
on human health (Banchathanakij and Suphantharika 2009). The
commonly used -glucans are from cereals such as barley and oats,
and also microbial sources including yeast and bacteria. Similar to
mono- and oligosaccharides, -glucans can also significantly retard
the retrogradation of rice starch gels during refrigerated storage.
Water-soluble oat and barley -glucans were more effective in re-
tarding starch retrogradation than the insoluble curdlan and yeast
-glucans (Banchathanakij and Suphantharika 2009). The retar-
dation effect on starch retrogradation decreased with increasing
ratio of -glucans to starch (Satrapai and Suphantharika 2007).
Salts. Salt, especially sodium chloride (NaCl), is commonly
added to dough formulations at concentrations below 2% (flour
basis) in the preparation of cereal-based products, to improve the
microstructure, physical characteristics, and sensory properties of
the finished products (Miller and Hoseney 2008; Nunez and others
2009; Uthayakumaran and others 2011; Day and others 2013). The
addition of NaCl during processing or storage can alter greatly the
extent of starch gelatinization and retrogradation. In comparison
with gelatinization, the effect of NaCl on starch retrogradation
has attracted relatively little attention. In the presence of NaCl,
the extent of retrogradation is generally decreased when starch
gels are stored at 4 or 25 C (Chang and Liu 1991; Baker and

C 2015 Institute of Food Technologists
 
Table 2Additives used to influence starch retrogradation
Additives Influences
Carbohydrates Monosaccharides Glucose Inhibition of retrogradation of rice, wheat, sweet
potato, oat, corn and tapioca starch
Increased retrogradation of oat starch
Ribose Inhibition of retrogradation of rice and wheat
starch
Fructose Inhibition of retrogradation of rice, wheat, sweet
C 2015 Institute of Food Technologists
potato, oat, corn and tapioca starch
Increased retrogradation of oat starch
Oligosaccharides Sucrose Inhibition of retrogradation of rice, wheat, sweet
potato, oat, corn, acorn and tapioca starch
Increased rate of rice starch retrogradation
Little effect on retrogradation of tapioca starch
Maltose Suppressed retrogradation of rice starch
Lactose Inhibited pastry crumb retrogradation
-Cyclodextrin (-CD) Reduced the rate of retrogradation of amylose
and normal rice starch, but not waxy rice starch
Hydroxypropyl--CD (HP--CD) More effective than -CD in retarding
retrogradation of high amylose rice starch
Low molecular weight dextrins Retarded starch retrogradation
Malto-oligosacchrides Inhibition of rice starch retrogradation and
retarded bread staling
Polysaccharides -Glucan Significant inhibition of retrogradation of rice
starch
Carboxymethyl cellulose (CMC) Concentration dependent inhibition of wheat
and sweet potato starch retrogradation
Tea polysaccharide More effective than CMC in inhibiting wheat
starch retrogradation
Soya-bean soluble polysaccharide (SSPS) Increase the short-term (24h) retrogradation of
wheat starch and retarded long-term
retrogradation more effectively than GA
Gum arabic (GA) Increased short-term (24h) retrogradation of
wheat starch
Retarded retrogradation of sweet potato starch
Xanthan gum Increased retrogradation of wheat starch
Decreased retrogradation of corn, sweet potato
starch and tapioca starch
No effect on retrogradation of corn and wheat
starch amylopectins
Enhanced short-term
Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 577
References
IAnson and others 1990; Kohyama and
Nishinari, 1991; Cairns and others 1991;
Chang and Liu, 1991; Katsuta and others
1992a, 1992b; Wang and Jane, 1994; Baker
and Rayas-Duarte, 1998; Smits and others
2003; Basic and others 2009
Starch retrogradation . . .
Hoover and Senanayake, 1996a
IAnson and others 1990; Cairns and others
1991; Katsuta and others 1992b
Kohyama and Nishinari, 1991; Katsuta and
others 1992a; Katsuta and others 1992b;
Wang and Jane, 1994; Baker and
Rayas-Duarte, 1998; Basic and others 2009
Hoover and Senanayake, 1996a
Cairns and others 1991; Kohyama and Nishinari,
1991; Katsuta and others 1992a; Katsuta and
others 1992b; Wang and Jane, 1994; Hyang
Aee, and others 1998; Basic and others 2009
IAnson and others 1990
Baker and Rayas-Duarte 1998
Germani and others 1983; Chang and Liu, 1991;
Hoover and Senanayake, 1996a
Thirathumthavorn and Trisuth, 2008
Chang and Liu, 1991; Katsuta and others 1992b;
Wang and Jane, 1994; Smits and others 2003
Munzing and Brack 2001
Tian and others 2009
Tian and others 2010b
Wang and Jane, 1994; Duran and others 2001
Katsuta and others 1992c; Rojas and others
2001; Smits and others 2003
Satrapai, and Suphantharika, 2007;
Banchathanakij and Suphantharika, 2009
Lee and others 2002; Zhou and others 2008
Zhou and others 2008
Funami and others 2008
Funami and others 2008
Lee and others 2002
Mandala and Bayas 2004
Lee and others 2002; Muadklay and Charoenrein
2008
Ferrero and others 1993aa, 1993b, 1994
Pongsawatmanit and others 2013
(Continued)
 Table 2Continued

Additives Influences References

Pentosans Water-soluble pentosans slowed the rate of Kim and DAppolonia 1977
amylopectin retrogradation in wheat starch
gels
Starch retrogradation . . .

Water-insoluble pentosans slowed the rate of Kim and DAppolonia 1977

retrogradation of both amylose and
amylopectin in wheat starch gels
Locust bean gum Retarded retrogradation of tapioca, rice, sweet Lee, and others 2002; Funami and others 2005;
potato starch and wheat starch Muadklay and Charoenrein, 2008; Correa and
others 2013
Increased short-term retrogradation of wheat Funami and others 2005
starch
Pullulan Inhibited short-term retrogradation of amylose Chen and others 2015
and long-term retrogradation of amylopectin
Guar gum Inhibited the retrogradation of wheat and sweet Lee and others 2002; Funami and others 2005
potato starch
No effect on retrogradation of tapioca starch Muadklay and Charoenrein 2008
Okra gum Inhibited the retrogradation of wheat and corn Alamri and others 2013
starch
Corn fiber gum Inhibited the retrogradation of Qiu and others 2015
maize starch
Pectin Reduced potato starch retrogradation Witczak and others 2014
Inulin Reduced potato starch retrogradation Witczak and others 2014
Konjac glucomannan Retarded long-term retrogradation of tapioca, Funami and others 2005; Khanna and Tester,
maize, wheat and potato starch 2006; Muadklay and Charoenrein, 2008;

578 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015
Yoshimura and others 1996
Increased short-term retrogradation of wheat Funami and others 2005
starch
Tara gum Increased short-term retrogradation of wheat Funami and others 2005
starch
Inhibit long-term retrogradation of wheat starch Funami and others 2005
Iota-carrageenan Increased short-term retrogradation in the Funami and others 2008
presence or absence of salts
Retarded structural ordering during Lee and others 2002; Funami and others 2008
retrogradation
Alginate Retarded the retrogradation of sweet potato Lee and others 2002
starch
Gellan Retarded the retrogradation of sweet potato Lee and others 2002


starch
Hydroxypropylmethylcellulose Decreased the hardening rate of Barcenas and Rosell 2005
(HPMC) the bread crumb and retarded the amylopectin
retrogradation
Salts Li+ , Mg2 + and Ca2 + Decreased retrogradation of rice starch Beck and others 2011
K+ and Na+ Decreased retrogradation.of amaranth, corn, Chang and Liu 1991; Baker and Rayas-Duarte
wheat, rice, tapioca starch 1998; Thirathumthavorn and Trisuth 2008;
Beck, Jekle and Becker 2011
(Continued)

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Table 2Continued
Starch retrogradation . . .

Additives Influences References

Proteins Soy protein Soybean 7S globulin Retarded retrogradation of corn starch Yu and others 2014

C 2015 Institute of Food Technologists

Soybean 11S globulin Promoted retrogradation of corn starch
Soy protein isolate (SPI) Little effect on retrogradation of corn starch
Wheat protein Gluten Retarded retrogradation of wheat starch
Little effect on wheat starch retrogradation
Glutenin Retard edretrogradation of wheat starch
Albumins, globulins, gliadins Promoted wheat starch retrogradation
Soy or pea protein hydrolysates Retarded maize and corn starch retrogradation
Amino acids Alkaline amino acids (Arg and Lys) Decreased retrogradation of rice, potato and
sweet potato starch
Acidic amino acids (Asp and Glu) Increased retrogradation of potato starch
Decreased retrogradation of sweet potato starch
Lipids Free fatty acids Retarded corn and rice starch retrogradation
Monoglycerides Reduced waxy corn starch and waxy maize starch
retrogradation
Triglycerides No effect on starch retrogradation
Retarded corn and potato starch retrogradation
Other additives Polyols Inhibited retrogradation of potato starch
Polyphenols Tea polyphenols Retarded starch retrogradation of rice starch
Rutin Retarded retrogradation of normal and
high-amylose rice starches
Amylases Retarded starch retrogradation or
bread staling
Emulsifiers/surfactants Cetyltrimethylammonium bromide (CTAB) Retarded starch retrogradation
Sodium dodecyl sulfate (SDS) Retarded starch retrogradation
Sodium stearoyl lactylate (SSL) Retard edstarch retrogradation
Citric acid Increased retrogradtion of low pH starch gels
Yu and others 2014
Yu and others 2014
Eliasson, 1983; Wang and others 2004
Duran and others 2001; Ottenhof and Farhat,
2004
Lian and others 2014
Lian and others 2014
Ribotta and others 2012; Lian and others 2013
An and King, 2009; Chen and others 2015
Chen and others 2015
Lockwood and others 2008
Germani and others 1983; Zhou and others
2007; Copeland and others 2009
Eliasson and Ljunger 1988; Huang and White
1993; Purhagen 2011
Eliasson and Ljunger 1988;
Germani and others 1983; Chiotelli and Meste
2003
Miura and others 1992; Smits and others 2003
Wu and others 2009
Zhu and Wang 2012
Fadda and others 2014
Goesaert and others 2009; Fu and others 2015
Gudmundsson and Eliasson, 1990; Miura and
others 1992; Seyhun and others 2003
Gudmundsson and Eliasson 1990; Gujral and
others 2003
Eliasson 1983; Nunes and others 2009; Fadda
2014
Hirashima and others 2012; Madoka and others
2012

Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 579
Starch retrogradation . . .
Rayas-Duarte 1998; Thirathumthavorn and Trisuth 2008). How-
ever, the addition of 5% NaCl increased the extent of starch
retrogradation of starch gels stored at 20 C (Baker and Rayas-
Duarte 1998).
Proteins/polypeptides/amino acids. Proteins are often key
components of starchy foods and can play an important role in
contributing to their quality and nutrition. Addition of protein
to starchy foods has been shown to influence starch retrograda-
tion. Addition of soybean 7S globulin retarded retrogradation and
decreased retrogradation enthalpy of corn starch gel. In contrast,
addition of soybean 11S globulin promoted starch retrogradation
and increased the retrogradation enthalpy. However, the addition
of soy protein isolate had little effect on retrogradation proper-
ties of corn starch (Yu and others 2014). Wheat gluten protein
has also been investigated but was found to have little effect on
the retrogradation of amylopectin (Ottenhof and Farhat 2004). Of
the albumin, globulin, gliadin, and glutenin fractions from wheat
flour, only glutenin was reported to retard retrogradation of wheat
starch, whereas the other 3 wheat protein fractions promoted starch
retrogradation (Lian and others 2014).
Soy and pea protein hydrolysates have also been shown to retard
maize starch retrogradation (Ribotta and others 2012; Lian and
others 2013), as have free amino acids (Lockwood and others
2008; An and King 2009; Chen and others 2015). The addition
of the alkaline amino acid arginine decreased syneresis of potato
starch, whereas the acidic amino acids aspartate and glutamate
increased it (Chen and others 2015).
Lipids. Lipids are macroconstituents of many cereal and starchy
foods. Although a minor component by weight, lipids can have a
significant role in determining the properties of starch and starch-
based foods. Lipids can interact with starch to form inclusion
complexes by entrapment in the amylose helical cavity (Putseys
and others 2010). The addition of lipids to, or the presence of
free lipids in, starch-based food systems generally retard starch ret-
rogradation after food processing followed by storage (Copeland
and others 2009). For different types of lipids, the shorter the fatty
acid chain, the more effective retardation of starch retrogradation
(Germani and others 1983). The effect of lipids in retarding starch
retrogradation is interpreted in different ways. During starch ret-
rogradation, amylose is more easily retrograded by reassociation
into double helices. The addition of lipid in starchwater systems
can hinder water penetration into granules and granule swelling
and, in turn, amylose leaching during heating. As a result, the
mobility of amylose molecules is constrained, resulting in slower
amylose retrogradation (Becker and others 2001). In addition,
the formation of amylose-lipid complexes during heating and/or
storage could inhibit the cross-linking and formation of double
helical structures between amylose molecules, which would also
slow their retrogradation. The presence of amyloselipid com-
plexes could also hinder the crystallization of amylopectin. Lipids
have also been proposed to complex with the outer branches of
amylopectin and thereby may inhibit starch retrogradation in a
more direct way (Eliasson and Ljunger 1988; Gudmundsson and
Eliasson 1990; Huang and White 1993; Nakazawa and Wang
2004; Putseys and others 2010). However, there is limited exper-
imental evidence for the interaction between lipids and the outer
branches of amylopectin molecules and hence this proposal needs
further investigation for its effect on starch retrogradation.
Other food additives. With the objective of seeking effec-
tive inhibitors of starch retrogradation, other food additives such
as polyols, polyphenols, emulsifiers, citric acid, and amylase
have also been studied for their effect on starch retrogradation.
580 Comprehensive Reviews in Food Science and Food Safety r Vol. 14, 2015
Polyols were shown to inhibit the retrogradation/recrystallization
of starch (Miura and others 1992). The influence of polyols on
starch retrogradation depends on the number of hydroxyl groups,
with more hydroxyl groups exhibiting greater effectiveness in re-
tarding the recrystallization of potato starch (Smits and others
2003). The addition of tea polyphenols to rice starch significantly
retarded starch retrogradation in a concentration-dependent man-
ner (Wu and others 2009). Similarly, addition of the flavonoid
rutin also greatly retarded the retrogradation of normal and high-
amylose rice starches. The retrogradation of normal rice starch
was completely inhibited by the addition of rutin, as measured by
DSC (Zhu and Wang 2012).
Emulsifiers can also retard starch retrogradation and are used as
antistaling agents in starchy foods. The addition of sodium dodecyl
sulfate, cetyltrimethylammonium bromide (CTAB), and mono-
glycerides decreased the retrogradation of starch, which was ex-
plained as being due to complex formation between amylopectin
and the emulsifiers/surfactants (Gudmundsson and Eliasson 1990;
Miura and others 1992). The addition of emulsifiers/surfactants
in the dough can significantly delay the firming of breads or cakes
(Gujral and others 2003; Seyhun and others 2003; Fadda and
others 2014).
Thermostable amylases are used extensively in commercial bread
formulations to retard bread-staling. As reviewed by Fadda and
others (2014) and Fu and others (2015), the retardation of bread-
staling is considered to be due to the formation of low-molecular-
weight dextrins, which reduce the ability of the residual starch
to retrograde by interfering in the reassociation of starch chains
(Goesaert and others 2009). The effect of citric acid on starch
retrogradation has also been studied. Citric acid increased ret-
rogradation of low-pH starch gels, which was attributed to the
promotion of faster reassociation of shorter chains (Hirashima and
others 2012).
The overall picture that emerges on the effect of additives on
starch retrogradation needs considerable refinement. There are in-
consistencies in the literature, which may reflect different experi-
mental materials or conditions. Nevertheless, it seems that agents
that compete with starch for water, or reduce the effectiveness of
leached amylose to form a gel network, are able to retard or inhibit
retrogradation. However, additives that could facilitate the inter-
action of amylose and/or amylopectin chains may induce more
rapid retrogradation of starch.
Effect of Retrogradation on Starch Digestibility
Native starch is digested slowly by enzymes due to the highly
ordered molecular structure in intact granules. Processing or cook-
ing disrupts the ordered structure of granular starch, resulting in
the increased susceptibility of starch to enzymatic digestion (Wang
and Copeland 2013). Subsequent cooling and storage leads to ret-
rogradation, in which starch regains an ordered structure that is
more resistant to enzymatic digestion (Eerlingen and others 1994;
Cui and Oates 1997; Chung and others 2006; Zhou and Lim
2012). The digestibility of retrograded starch is largely dependent
on time and temperature of storage. At constant temperature,
shorter storage induces fast retrogradation of amylose molecules,
which is responsible for the initial decreased digestibility of ret-
rograded starch. Longer storage makes a smaller contribution to
the decreased digestibility of retrograded starch, due to the slower
retrogradation of amylopecitn molecules (Chung and others 2006;
Zhou and Lim 2012). In a study by Cui and Oates (1997), the
degree of digestion of a retrograded sago starch gel (40%, w/w)
dropped rapidly from 78.3% to 45.4% after storage at 5 C for

C 2015 Institute of Food Technologists
Starch retrogradation . . .
1 h. Extending the storage time to over 6 h had little further effect
on the degree of starch digestion. The differences in digestibil-
ity of gelatinized starch stored for different times mainly occur
in the early stage of hydrolysis, but no significant differences are
observed at the later stage of hydrolysis (Chung and others 2006).
As a result of the decreased digestibility of retrograded starch,
there is a decrease in rapidly digested starch (RDS) content and an
increase in slowly digested starch (SDS) content compared with
gelatinized starch. However, little effect was observed for enzyme-
resistant starch (RS) content (Fredriksson and others 2000; Chung
and others 2010; Zhou and Lim 2012), although an increased RS
content was observed in a study by Park and others (2009).
In contrast to storage at a constant temperature, temperature-
cycling during storage can greatly decrease the enzyme digestibility
of retrograded starch (Chung and others 2006; Park and others
2009; Zhou and others 2011; Tian and others 2012; Zhou and
Lim 2012). Temperature-cycling during storage is often used to
increase the RS or SDS content in retrograded starch (Park and
others 2009; Tian and others 2011; Zhou and Lim 2012). The
RS content consistently increased with extended storage time for
16 days at the cycled temperature conditions, along with a decrease
in the proportions of RDS and SDS. In 4 to 16 days of storage,
the cycled temperatures of 4 and 30 C induced a consistently
greater proportion of RS in the starch gel and smaller proportion
of RDS than the constant temperature storage at 4 C (Park and
others 2009). In other studies by Tian and others (2009) and
Zhou and Lim (2012), SDS content of retrograded starch was
increased greatly under temperature-cycled conditions compared
to isothermal storage. Most studies have focused on the effects
on starch digestibility of retrogradation at higher water content;
there is little information on the effect on starch digestibility of
retrogradation at low water content.
Concluding Remarks
Gelatinization and retrogradation are the key functional prop-
erties of starch that determine the quality and nutritional value
of starchy foods. Although many methods are used to character-
ize starch retrogradation during storage, it is clear that no single
method can give a complete picture of the process and its prod-
ucts at both macroscopic and molecular levels. More studies are
needed to reveal the relationship between the changes in FTIR
and Raman bands and starch retrogradation. Starch retrograda-
tion is affected by many factors including water content, storage
temperature, storage time, and additives in the system. Food addi-
tives can greatly alter the rate and extent of starch retrogradation,
by competition for water with starch or by interfering with the
reassociation of starch chains. Food additives that change the wa-
ter activity in starch-water systems may be a key to controlling
retrogradation of starch.
Acknowledgments
The authors gratefully acknowledge the financial support from
the Natl. Natural Science Foundation of China (31401651) and
the Natural Science Foundation of Tianjin (13JCYBJC38100).
Shujun Wang also greatly appreciates the financial support of
Haihe Scholar Program (000050401) and Tianjin 1000 Youth Bosmans GM, Lagrain B, Fierens E, Delcour JA. 2013. The impact of baking
Talents Plan from Tianjin University of Science & Technology.
Authors Contributions
Shujun Wang and Shuo Wang conceived and designed the re-
view. Shujun Wang and Caili Li contributed to the earlier draft
of the manuscript. Shujun Wang and Les Copeland revised and

C 2015 Institute of Food Technologists Vol. 14, 2015 r Comprehensive Reviews in Food Science and Food Safety 581
edited the manuscript; Qing Niu contributed to the drawing of
Table 2 and editing of references.
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