Carbohydrate Polymers 83 (2011) 317–328

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review

Impact of heat-moisture treatment and annealing in starches: A review

Elessandra da Rosa Zavareze ∗ , Alvaro Renato Guerra Dias
Department of Agroindustrial Science and Technology, Federal University of Pelotas, 96010-900, Rua Gomes Carneiro, 1, Centro, Pelotas, RS, Brazil

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

Article history: Heat-moisture treatment (HMT) and annealing (ANN) are physical modifications that change the physic-
Received 5 July 2010 ochemical properties of starch without destroying its granular structure. These hydrothermal treatments
Received in revised form 15 August 2010 are processes in which the starch-to-moisture ratio, temperature, and heating time are critical parameters
Accepted 25 August 2010
that need to be controlled. In HMT, starch is heated to temperatures above the gelatinisation temperatures
Available online 19 September 2010
but with insufficient moisture to gelatinise. In ANN, starch is exposed to excess water for an extended
period of time at a temperature above the glass transition but below the gelatinisation temperature.
Keywords:
The impact of such hydrothermal treatments on starch pasting, morphological, crystalline, thermal, and
Annealing
Heat-moisture treatment
physicochemical properties, as well as on the enzymatic and acid susceptibility of starch will be dis-
Physical modification cussed. The paper also highlights some applications of hydrothermally treated starch. This review is of
Safe food significance not only for the development of novel starches for food and non-food applications, but also
Starch for understanding the impact of HMT and ANN on starch and its functionality.
© 2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
2. Structure and organisation of starch granules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
3. Properties of starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
4. Hydrothermal modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
4.1. Heat-moisture treatment (HMT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
4.1.1. Impact of HMT on starch swelling power and solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
4.1.2. Impact of HMT on starch pasting properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
4.1.3. Impact of HMT on gel texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
4.1.4. Impact of HMT on granule morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
4.1.5. Impact of HMT on starch crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
4.1.6. Impact of HMT on starch gelatinisation characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
4.1.7. Impact of HMT on the susceptibility of starch to enzymatic hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
4.1.8. Impact of HMT on the susceptibility of starch to acid hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
4.1.9. Impact of HMT on slowly digestible starch and resistant starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
4.2. Annealing (ANN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
4.2.1. Impact of ANN on starch swelling power and solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
4.2.2. Impact of ANN on starch pasting properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
4.2.3. Impact of ANN on the gel texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
4.2.4. Impact of ANN on granule morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
4.2.5. Impact of ANN on starch crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
4.2.6. Impact of ANN on starch gelatinisation characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
4.2.7. Impact of ANN on the susceptibility of starch to enzymatic hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
4.2.8. Impact of ANN on the susceptibility of starch to acid hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
4.2.9. Impact of ANN on slowly digestible starch and resistant starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
5. Applications of hydrothermally treated starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327

∗ Corresponding author. Tel.: +55 53 32757258; fax: +55 53 32757258.

E-mail address: [email protected] (E.d.R. Zavareze).

0144-8617/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2010.08.064
318 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328

1. Introduction starch molecules, and amylopectin double helices acquire a more

organised configuration (Gomes, Silva, & Ricardo, 2005).
Starch is a semi-crystalline biopolymer that serves as a carbo- There is currently great interest in using physical modification
hydrate reserve in many plants, including cereals, roots, tubers, techniques, such as HMT and ANN, to alter the physicochemical
seeds, and fruits. Starch granules can vary in shape, size, struc- properties of starches. The extent of modification is influenced
ture, and chemical composition, depending on the origin of the by the starch composition, source, and the ratio of amylose to
starch (Smith, 2001). Starch granules are composed of amylose and amylopectin, as well as by the arrangement of the starch chains
amylopectin macromolecules. The structure of the starch granule within the amorphous and crystalline domains of the native
depends on the way in which amylose and amylopectin are associ- starch granules. Heat-moisture-treated and annealed starches have
ated and distributed throughout the starch granule. Several studies important applications in the food industry, especially due to their
have been conducted to elucidate the location of amylose within improved thermal stability and decreased extent of retrogradation
the granule (Gerard, Colonna, Buleon, & Planchot, 2002; Jane, 2006; (Adebowale et al., 2005). These properties make hydrothermally
Jenkins & Donald, 1995; Jane & Shen, 1993; Tatge, Marshall, Martin, treated starches suitable for utilisation in the canned and frozen
Edwards, & Smith, 1999). Saibene and Seetharaman (2010) most food industries. The decrease in granular swelling and amylose
recently also investigated the location and role of amylose within leaching and the increase in heat and shear stability that result from
the granule. These authors reported that the molecular size distri- HMT and ANN are also desirable properties for noodle manufac-
bution, iodine binding and X-ray diffraction analysis of the potato ture (Hormdok & Noomhorm, 2007). Additionally, these treatments
and corn starches and the respective lintners elucidated differences have been used to enhance resistant starch levels while maintain-
in the location of amylose within the amorphous or crystalline ing granule structure (Brumovsky & Thompson, 2001).
regions. For potato starch, they concluded that there was a par- The physical modification by hydrothermal treatments such as
tial involvement of amylose in the B-type crystallites. For corn HMT and ANN is consistent with societal trends towards natural
starch, the amylose would be located within the amorphous regions products and offers the potential to change starch functionality at a
of the granule, independent of the amylopectin crystallites, free low cost and in an environmentally friendly way. In this review, the
to complex with iodine without disruption of the A-type crys- impact of hydrothermal treatments on starch pasting, morphologi-
tallinity. cal, crystalline, thermal, and physicochemical properties, as well as
Starch, in its native form, does not always have the physical on the enzymatic and acid susceptibility of starch, will be examined.
and chemical properties appropriate for certain types of process- Furthermore, the applications of hydrothermally treated starches
ing. However, modification can increase the use of starch in various in products that require specific properties are also summarised.
industries, such as the food, paper, and textile industries. Starches
are often modified by physical, chemical, and enzymatic processes 2. Structure and organisation of starch granules
to promote specific functional properties. The physical modifica-
tion of starch by moisture, heat, shear, or radiation has been gaining Starch is formed of granules of variable size and is composed
wider acceptance because no by-products of chemical reagents of amylose and amylopectin macromolecules. The amylose and
are present in the modified starch. Modification can achieve func- amylopectin in starch are not free in nature, but compose a semi-
tional properties not found in native starches, which have specific crystalline aggregate organised in the form of granules. The size,
applications in various industries. Chemical modification is widely form and structure of starch granules vary with the botanical
implemented, but there is also a growing interest in the physi- source. The diameter of the granules ranges from 1 to 100 ␮m
cal modification of starch, especially in food applications. A major and their shape can be regular or irregular. Amylose is a linear
advantage of physical modification is that starch is considered to molecule composed of d-glucose units linked by ␣-1,4 glucosidic
be a natural material and a highly safe ingredient, so its presence bonds with a small number of branches (Liu, 2005). According
and quantity in food is not limited by legislation (Bemiller, 1997). to You, Stevenson, Izydorczyk, and Preston (2002), the molecular
Heat-moisture treatment (HMT) and annealing (ANN) are phys- weight of amylose varies from 1 × 105 to 1 × 106 g/mol. Amylose
ical modifications that alter the physicochemical properties of has a helical structure where the interior of the helix contains
starch without destroying its granular structure (Adebowale, hydrogen atoms, while the hydroxyl groups remain on the outside
Afolabi, & Olu-Owolabi, 2005; Hormdok & Noomhorm, 2007; Jacobs (Buléon, Colonna, Planchot, & Ball, 1998). The presence of hydrogen
& Delcour, 1998; Maache-Rezzoug, Zarguili, Loisel, Queveau, & atoms in the interior of the helix makes amylose hydrophobic and
Buléon, 2008). These two related processes both require that the enables it to form complexes with free fatty acids, component glyc-
starch-to-moisture ratio, temperature, and heating time are con- erides of fatty acids, iodine and some alcohols. Amylose complexes
trolled (Chung, Liu, & Hoover, 2009b). However, these treatments with fats and emulsifiers in foods such as mono- and di-glycerides
differ in the amount of water and in the temperature used. HMT is can alter the temperature of gelatinisation and the texture and vis-
carried out under restricted moisture content (10–30%) and higher cosity profile of the paste and can limit retrogradation (Thomas &
temperatures (90–120 ◦ C), while ANN involves a large excess of Atwell, 1999).
water (50–60%) and relatively low temperatures that fall below the Amylose has the ability to form paste after the gelatinisation of
gelatinisation point (Maache-Rezzoug et al., 2008). the starch granules; this behaviour is evident in certain starches
Regardless of the starch’s origin, HMT promotes an increase in that contain higher levels of amylose, such as corn, wheat, rice and
the gelatinisation transition temperature, a widening of the gela- in particular high-amylose corn starch. The paste is mainly formed
tinisation temperature range, a decrease in granular swelling and due to the reassociation (retrogradation) of starch polymers solu-
amylose leaching, and an increase in thermal stability. However, bilised after gelatinisation (Thomas & Atwell, 1999). The amylose
depending on the botanical origin of the starch and the treat- content presented in scientific papers is usually expressed as appar-
ment conditions, changes in the X-ray pattern, the formation of ent amylose content; this is due to the ability of some external
amylose–lipid complexes, the disruption of crystallinity, and either branched amylopectin chains to interact with iodine, thereby over-
increases or decreases in enzymatic susceptibility may occur due to estimating the actual amylose content. However, many authors
HMT (Chung et al., 2009b). In addition, ANN changes the physico- refer to the apparent amylose content as that obtained from
chemical properties of starches by improving crystalline perfection starches that have not previously been defatted because the pres-
and facilitating interactions between starch chains (Jayakody & ence of lipids in starch interferes with iodine affinity (Morrison,
Hoover, 2008). More specifically, ANN leads to a reorganisation of 1995).
 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328 319

Amylopectin is a highly branched macromolecule with linear displacement of the chains by conformational changes, presenting
chains of shorter linked by ␣-1,4 glucosidic bonds containing 10–60 a glassy state. Above the Tg , rotational and diffusional movements
glucose units and side chains with 15–45 glucose units with an of the polymer chains occur. In general, Tg depends on the thermal
average of 5% of links ␣(1–6) in branched points (Van der Maarel, history of the material, the molecular weight of the polymer chains,
Van der Veen, Uitdehaag, Leemhuis, & Dijkhuizen, 2002). The the degree of crystallinity and the composition of the sample. This
molecular weight of amylopectin is about 1000 times the molecular is a reversible transition and occurs prior to gelatinisation.
weight of amylose and ranges from 1 × 107 to 5 × 108 g/mol (You Intact starch granules are not soluble in cold water but can retain
et al., 2002). Amylopectin chains are arranged radially within the small amounts of water, causing a small amount of swelling that
granule with their non-reducing terminal ends oriented towards is reversible by drying. At certain concentrations, starch granules
the surface, and these are arranged with alternating crystalline in solution becomes a dilatant fluid where the flow is inversely
areas (as a double helix) and amorphous areas (with regions of proportional to the pressure that is exerted; the greater the pres-
branching points). sure, the lower the fluidity. The insolubility of starch granules is
The functionality of starch is due to the ratio of these macro- due to strong hydrogen bonds holding the starch chains together.
molecules as well as the physical organisation within the granular However, when starch is heated in excess water above the paste
structure. Starch granules present crystalline and amorphous temperature, the crystalline structure is disrupted due to the relax-
regions. The crystalline regions are formed by branched chains of ation of hydrogen bonds, and the water molecules interact with the
amylopectin molecules and are alternated with amorphous lay- hydroxyl groups of amylose and amylopectin, causing an increase
ers (Liu, 2005). The semi-crystalline structure of starch granules in granule size and partial solubilisation of starch (Hoover, 2001).
is composed of linear and branched macromolecules arranged in The heating of starch suspensions in excess water and above a
the radial direction; the macromolecules form hydrogen bonds certain temperature causes an irreversible transition called gelatin-
because they are associated in parallel, which results in the appear- isation, which can be characterised by an endotherm obtained by
ance of crystalline regions (Gallant, Bouchet, & Baldwin, 1997). differential scanning calorimetry, the loss of birefringence observed
Starch granules are birefringent; however, this birefringence does through polarised light microscopy, and the disappearance of
not necessarily imply a crystalline form, but rather a high degree crystallinity as evidenced by X-ray diffraction (Garcia, Colonna,
of molecular organisation of the granules (Zobel, 1988). According Bouchet, & Gallant, 1997). The gelatinisation of starch results in the
to Billiaderis (1991), the crystalline areas of starch maintain the collapse of its molecular arrangement and irreversible changes to
structure of the granule, control its behaviour in the presence of its properties, including the loss of crystallinity, water absorption,
water and make it more or less resistant to chemical and enzy- the swelling of the granules and the leaching of some compo-
matic attack. The amorphous zone of starch granules is the least nents, mainly amylose (Zhong et al., 2009). Retrogradation is a
dense, is more susceptible to enzymatic attacks and absorbs more phenomenon whereby solubilised amylose molecules and linear
water at temperatures below the gelatinisation temperature. fractions of amylopectin form reassociations by hydrogen bonds.
The different degrees of structural ordering of the granules are This process has been used to describe the changes that occur in
responsible for the properties of birefringence and crystallinity. starch after gelatinisation, from an initially amorphous state to a
The optical birefringence and X-ray diffraction properties provide more ordered or crystalline state (Liu & Thompson, 1998). The pro-
ample evidence of an ordered structure of the starch granule. This cess is accompanied by the loss of water from the gel and is called
structure consists of concentric layers, which can be observed in syneresis.
electron microscope images of granules treated with acid or par- The changes that occur in starch granules during gelatinisation
tially digested by amylases. The crystallinity of the granules is and retrogradation are the main determinants of the behaviours
mainly described as a function of the double helix formed by the of starch paste, which have been quantified mainly by measur-
branches of amylopectin (Hoover, 2001), which ranges between 15 ing changes in viscosity during the heating and cooling of starch
and 45% of relative crystallinity. The crystalline structure is cate- dispersions using a Viscoamylograph. In viscoamylographic anal-
gorised according to its profile from a diffractogram using X-ray ysis, an increase in viscosity is recorded when the granules begin
diffraction. Patterns known as types A, B and C represent spe- to swell during the initial phase of heating a slurry of starch. At
cific diffraction angles caused by the double helix packing of the this point, low molecular weight polymers, particularly amylose
amylopectin branched chains (Parker & Ring, 2001). The pattern molecules, begin to be leached from the granules. Peak viscosity
of crystallinity is defined on the basis of interplanar spaces and is achieved during the formation of paste, when the granules are
the relative intensity of the diffraction lines of the X-ray. The poly- the most swollen (Tsai, Li, & Lii, 1997). Factors such as tempera-
morphic form of type C is considered an arrangement intermediate ture, granule size and concentration and the presence of lipids can
between the types A and B (Fuentes-Zaragoza, Riquelme-Navarrete, influence the behaviour of the starch paste (Jane et al., 1999).
Sánchez-Zapata, & Pérez-Álvarez, 2010). Billiaderis (1991) reported Apparent viscosity curves provide information about the paste
that pattern A is characteristic of cereal starches, pattern B is char- temperature, the peak viscosity, the resistance of the swollen gran-
acteristic of starches from tubers, fruits, and high-amylose corn ules to mechanical action, as well as the influence of cooling on
starch, and pattern C is characteristic of starches of legumes. Amy- viscosity (retrogradation). Amylose molecules reassociate more
lose, when complexed with organic compounds, water or iodine, easily due to their linear structure, and are primarily responsible
may appear as the standard type V. for the occurrence of retrogradation. However, amylose is not the
only component that is involved in starch retrogradation. Studies
by Jaillais, Ottenhof, Farhat, and Rutledge (2006) showed that under
3. Properties of starches certain experimental conditions, the retrogradation of amylopectin
cannot be excluded from the total fraction of retrograded starch.
An important property of partially crystalline materials, such Differential scanning calorimetry, when applied to starch, pro-
as starch granules, is the glass transition of amorphous regions vides quantitative measurements of heat flow associated with
at a certain temperature. The glass transition temperature (Tg ) is gelatinisation, where the endothermic peaks are indicative of melt-
obtained from differential scanning calorimetry (DSC) curves. Dur- ing. To detect the transition phase in starch, DSC methods have
ing heating, the amorphous regions are transformed from a rigid the advantage of being independent of the birefringence of the
glassy state to a mobile rubbery state (Jacobs & Delcour, 1998). granules. This is an important difference when birefringence is
Below the Tg , the polymer has sufficient internal energy to allow the present due to molecular orientation in amorphous regions, or
320 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328

is absent due to the crystals being small or randomly oriented. According to Gunaratne and Hoover (2002), HMT promotes the
The changes in enthalpy observed in DSC are usually related to interaction of polymer chains by disrupting the crystalline struc-
the transition between ordered and disordered crystals presented ture and dissociating the double helical structure in the amorphous
in the form of ordered internal arrangements and in regions of region, followed by the rearrangement of the disrupted crystals.
low order crystalline regions of the granule (Karlsson & Eliasson, Crystalline disruption near the granule’s surface can facilitate the
2003). Lopez-Rubio, Flanagan, Gilbert, and Gidley (2008) pro- attack of ␣-amylase within it. When the crystals are not disrupted
posed that the enthalpy associated with granule gelatinisation by HMT, increased enzymatic susceptibility results due to the dis-
is due to melting of imperfect amylopectin-based crystals, with ruption of the double helices by treatment in amorphous regions.
potential contributions from both crystal packing and helix melt- This disruption facilitates enzymatic access to the sites of interac-
ing enthalpies. The temperature required for the gelatinisation of tion between the amylose chains during the rearrangement of the
starches verified by thermal analysis is important because it defines polymer chains.
the proportion of required energy for cooking. On an industrial
scale, the energy cost of the process must be carefully controlled.
4.1.1. Impact of HMT on starch swelling power and solubility
Thermoanalytical techniques are commonly used in the analysis of
Several researchers have studied the effect of HMT on the
transitions that occur when synthetic polymers are heated. How-
swelling power of potato, cassava (Gunaratne & Hoover, 2002), rice
ever, these techniques are also widely used in the study of starch
(Hormdok & Noomhorm, 2007), sorghum (Olayinka, Adebowale, &
gelatinisation (Leliévre & Liu, 1994).
Olu-Owolabi, 2008), and corn starches (Chung et al., 2009b). In all
of these studies, the authors observed a reduction in the swelling
power of HMT starches. This reduction in swelling power has
4. Hydrothermal modifications also been attributed to increased crystallinity, reduced hydration
(Waduge, Hoover, Vasanthan, Gao, & Li, 2006), increased interac-
4.1. Heat-moisture treatment (HMT) tions between amylose and amylopectin molecules, strengthened
intramolecular bonds (Jacobs, Eerlingen, Clauwaert, & Delcour,
HMT is a physical modification that involves low moisture lev- 1995), the formation of amylose–lipid complexes (Waduge et al.,
els, usually in a restricted range of 10–30%, and heating at high 2006) and changes in the arrangements of the crystalline regions
temperatures (90–120 ◦ C) for a period of time ranging from 15 min of starch (Hoover & Vasanthan, 1994).
to 16 h (Chung et al., 2009b; Maache-Rezzoug et al., 2008). HMT Starch solubility results from the leaching of amylose, which
allows control of molecular mobility at high temperatures by limit- dissociates from and diffuses out of granules during swelling. This
ing the amount of water. HMT-induced changes in starch structure leaching represents a transition from order to disorder within
and properties have been found to vary with starch source and amy- the starch granules that occurs when starch is heated with water
lose content. For instance, tuber starches are more sensitive to HMT (Tester & Morrison, 1990). Adebowale and Lawal (2002), who stud-
than legume or cereal starches (Gunaratne & Hoover, 2002; Hoover ied the effect of HMT on the solubility of bambarra groundnut starch
& Vasanthan, 1994; Jacobs & Delcour, 1998). Significant progress in at 60, 70, 80, and 90 ◦ C, observed a reduction in solubility at all
HMT research has been made over the few last years, as reflected temperatures. Olayinka et al. (2008) also noted a decrease in the
by numerous publications on this subject. The HMT conditions for solubility of hydrothermally treated white sorghum starch com-
starches of different botanical origin are summarised in Table 1. pared to native starch. This solubility decrease was enhanced by

Table 1
Heat-moisture treatment conditions for starches and references.

Starch source Temperature (◦ C) Time Water content (%) Reference

Cassava 110 3–16 h 18–24 Abraham (1993)

100 10 h 30 Gunaratne and Hoover (2002)
Canna 100 16 h 18–25 Watcharatewinkul et al. (2009)
110 5–30 min 20–30 Zhang, Wang, and Shi (2009)
Corn 100–120 2h 30 Chung et al. (2009b)
120 15–60 min 20 Pukkahuta et al. (2008)
120–130 – 13.5 Miyazaki and Morita (2005)
110 16 h 15–27 Kweon et al. (2000)
100 16 h 18–27 Franco et al. (1995)
Pea 120 2h 30 Chung et al. (2009b)
Lentil 120 2h 30 Chung et al. (2009b)
100 16 h 10–30 Hoover and Vasanthan (1994)
Rice 110 1h 15–25 Zavareze et al. (2010)
100–110 0.5–1.5 h 15–25 Hormdok and Noomhorm (2007)
100 16 h 18–27 Khunae et al. (2007)
Potato 100 16 h 24 Varatharajan et al. (2010)
90–130 24 h 17–26 Vermeylen et al. (2006)
100 10 h 30 Gunaratne and Hoover (2002)
100 16 h 10–30 Hoover and Vasanthan (1994)
White sorghum 110 16 h 18–27 Olayinka et al. (2008)
Sweet potato 100 16 h 27 Vieira and Sarmento (2008)
110 4–16 h 25 Collado and Corke (1999)
Sago 100–120 1h 20 Pukkahuta and Varavinit (2007)
Finger millet 100 16 h 20–30 Adebowale et al. (2005)
Wheat and yam 100 16 h 10–30 Hoover and Vasanthan (1994)
Peruvian carrot 100 16 h 27 Vieira and Sarmento (2008)
Ginger 100 16 h 27 Vieira and Sarmento (2008)
Borlotti bean 100 16 h 22 Güzel and Sayar (2010)
Chickpea 100 16 h 22 Güzel and Sayar (2010)
Chestnut 110 3h 25–28 Singh et al. (2009)
 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328 321

increasing the moisture content of the treated starches from 18 to amylose) and concluded that this treatment increased the gel hard-
27%. In contrast, Hormdok and Noomhorm (2007) observed no sig- ness of starch treated with 15 and 20% moisture. For treatments
nificant difference in the solubilities of hydrothermally treated rice under 25% moisture, they found no difference with native starch
and native rice starch. and attributed this fact to a possible partial gelatinisation, result-
The reduction in swelling power and solubility following HMT ing in a less rigid gel due to the partial collapse of the structure
has been attributed to the internal rearrangement of the starch of the granules. During HMT, increase in gel hardness has been
granules, which causes further interactions between the starch’s attributed to the increased cross-linking between starch chains
functional groups (Hoover & Manuel, 1996), the formation of more in the particular amylose portion. These allowed the formation
ordered double helical amylopectin side-chain clusters and the for- of more junction zone in the continuous phase of the gel, result-
mation of amylose–lipid complexes within the granules (Olayinka ing in the increased gel hardness (Liu, Corke, & Ramsden, 2000).
et al., 2008; Tester & Morrison, 1990). Collado and Corke (1999) treated sweet potato starch with HMT
and found that the starch paste became short and stable to shear
4.1.2. Impact of HMT on starch pasting properties and showed a significant increase in gel hardness and adhesive-
HMT promotes intense changes in starches, significantly alter- ness.
ing their pasting profile. Several studies have been conducted to Temperature and moisture content were the dominant factors
investigate the effect of HMT on bambarra groundnut (Adebowale affecting starch granules (Cham & Suwannaporn, 2010). Liu et al.
& Lawal, 2002), white sorghum (Olayinka et al., 2008), rice (2000) reported that the higher the temperature and moisture con-
(Hormdok & Noomhorm, 2007; Zavareze, Storck, Castro, Schirmer, tent, the more perfect the crystalline starch granules. These findings
& Dias, 2010), corn (Chung et al., 2009b), and canna starches suggest that starch granule swelling is restricted by hydrothermal
(Watcharatewinkul, Puttanlek, Rungsardthong, & Uttapap, 2009). treatment. During HMT, the increase in rheological properties was
According to the latter group, HMT (15, 18, 20, 22, and 25% attributed to the increase in cross-linking between starch chains.
moisture/100 ◦ C/16 h) of canna starch altered its pasting profile, This allowed the formation of more junction zones in the continu-
resulting in increased paste temperature and decreased peak vis- ous phase of the gel, resulting in an increase in gel hardness (Hoover
cosity, final viscosity, and breakdown. These authors explained that & Manuel, 1996).
changes in treated starch’s pasting properties are due to associa-
tions between the chains in the amorphous region of the granule 4.1.4. Impact of HMT on granule morphology
as well to changes in crystallinity during hydrothermal treatment. Granule morphology, granule size distribution, and surface
This behaviour intensified as the moisture content of the HMT characteristics play an important role in many food and non-
increased. food applications of starch. HMT did not alter the size or
Olayinka et al. (2008) studied the effect of HMT on white shape of the potato, taro, new cocoyam, true yam, and cassava
sorghum starch and reported that the intensity of its effects on (Gunaratne & Hoover, 2002), maize (Hoover & Manuel, 1996),
starch’s pasting properties depends on the treatment conditions. wheat (Hoover & Vasanthan, 1994), finger millet (Adebowale
As the moisture level increased, paste temperature increased and et al., 2005), rice (Khunae, Tran, & Sirivongpaisal, 2007) and
peak viscosity declined. There was also a significant reduction in canna (Watcharatewinkul et al., 2009) starch granules. However,
breakdown and retrogradation after HMT. As the forces of the intra- Kawabata et al. (1994) observed a formation of cracks on the sur-
granular bonds are strengthened, the starch requires more heat for face of treated maize and potato starches, together with a hollow
structural disintegration and paste formation. A high paste temper- inside the granule. Zavareze et al. (2010) also investigated the
ature thus indicates that more forces and cross-links are present effect of HMT on granule morphology of rice starches with differ-
within the starch granules. ent amylose contents. These authors reported that the HMT (25%
The HMT-induced reduction in breakdown demonstrates that moisture) of the high- and medium-amylose rice starch granules
starches are more stable during continuous heating and agita- slightly affected the format and degree of agglomeration, making
tion, which is supported by Adebowale et al. (2005), Hormdok and the granules more aggregated and the surface of the granules more
Noomhorm (2007), Olayinka et al. (2008) and Watcharatewinkul irregular, as compared with the native starches. However for HMT
et al. (2009). Lan et al. (2008) have shown that retrogradation is (25% moisture) low-amylose rice starch there was signs of the loss
influenced by the amount of leached amylose, granule size, and of physical integrity with distension of the granular surface. This
the presence of rigid, non-fragmented swollen granules. Mean- change in granular morphology of low-amylose rice starch by HMT
while, Chung et al. (2009b) found that HMT reduces amylose is probably due to high moisture content of hydrothermal treat-
leaching from starch granules and that this reduction is more sig- ment, because this condition is more susceptible to the occurrence
nificant in starches containing high levels of amylose. They also of partial gelatinisation and morphological changes.
reported that HMT promotes additional amylose–amylose and/or
amylopectin–amylopectin chain interactions, which reduce amy- 4.1.5. Impact of HMT on starch crystallinity
lose leaching and decrease retrogradation. According to Miao, Zhang, and Jiang (2009), crystallinity dif-
ferences between starches may be attributed to the following:
4.1.3. Impact of HMT on gel texture (1) crystal size; (2) the number of crystalline regions that are
The textural properties of gels depend on the constituents of influenced by amylopectin content and chain length; (3) the ori-
starch and amylose, the volume and deformation of the gran- entation of the double helices within the crystalline area; and
ules and the interaction between the continuous and dispersed (4) the extent of interaction between the double helices. The
phases (Choi & Kerr, 2003). Gel strength has been reported to be effect of HMT on crystallinity depends on the starch’s source
dependent on the binding capacity of starch molecules to water by and treatment conditions. Changes in the X-ray diffraction pat-
hydrogen bonding (Lee & Osman, 1991). The hydrogen bonds that tern from B- to A-type has been noted in heat-moisture-treated
stabilise the double helical structure are broken during gelatinisa- potato (Gunaratne & Hoover, 2002; Vermeylen, Goderis, & Delcour,
tion and replaced by hydrogen bonds with water, where the degree 2006) and yam starches (Gunaratne & Hoover, 2002). However,
of swelling is controlled by the crystallinity of the molecule (Tester according to Jacobs and Delcour (1998), not all temperature and
& Karkalas, 1996). moisture conditions induce a change from B- to A-type crystallinity
HMT affects the textural properties of starch gels. Hormdok and in potato starch. In contrast, other types of starches did not have an
Noomhorm (2007) studied the effect of HMT on rice starch (27% altered X-ray diffraction pattern after HMT, including taro, cassava
322 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328

(Gunaratne & Hoover, 2002), and cereal starches (Jacobs & Delcour, 4.1.7. Impact of HMT on the susceptibility of starch to enzymatic
1998). hydrolysis
As stated by Genkina, Wasserman, Noda, Tester, and Yuryeva Zhang and Oates (1999) reported that the enzymatic suscepti-
(2004), HMT often results in the transformation of the less ther- bility of starch is influenced by several factors, including the ratio
modynamically stable B-polymorphic structure (with hexagonal of amylose to amylopectin, the crystalline structure, and the size of
packing of double helices and about 36 water molecules inside the particles. Among these factors, the crystalline granular struc-
each cell) into a more stable monoclinic structure of A-type poly- ture is perhaps the most important.
morphs (with about six water molecules inside the helices). The HMT-induced changes probably occur in the amorphous regions
HMT-induced changes in the diffraction pattern of starches can be of the starch granules, which are more accessible to hydrolysis.
attributed to dehydration as well as to movement of a pair of double These amorphous areas are more rapidly degraded by ␣-amylases
helices into the central channel. This movement during HMT could than the crystalline areas. According to Gunaratne and Hoover
disrupt starch crystallites and/or change the crystalline orientation (2002), HMT specifically promotes crystalline disruption and the
(Gunaratne & Hoover, 2002). dissociation of double helical structures in the amorphous region,
Some authors have reported an increase in the intensity of the X- which can facilitate the attack of ␣-amylase within the granules.
ray diffraction of corn (Hoover & Manuel, 1996) and sweet potato Based on the hydrothermal treatment (30% moisture/100 ◦ C/10 h)
starches (Vieira & Sarmento, 2008) after HMT. An increase in the of taro, cassava, and potato starches, these authors concluded
X-ray intensity of heat-moisture-treated starches is due to the dis- that the enzymatic susceptibility of starch increases with HMT.
placement of the double helical chains within the starch crystals, Therefore, the structural rearrangement of starch caused by HMT
resulting in a crystalline matrix that is more orderly than in native facilitates enzymatic accessibility to the amorphous areas. Vieira
starch. However, others have identified a reduction in the rela- and Sarmento (2008) studied the effect of HMT in Peruvian carrot,
tive crystallinity of potato (Vermeylen et al., 2006), cassava, true sweet potato and ginger starches and reported that the percentages
yam (Gunaratne & Hoover, 2002), corn (Franco, Ciacco, & Tavares, of hydrolysis after 24 h with ␣-amylase of the heat-moisture-
1995), and Peruvian carrot starches (Vieira & Sarmento, 2008). This treated sample (27% moisture/100 ◦ C/16 h) were 29%, 5% and 22%,
reduction in X-ray intensity due to hydrothermal treatment results respectively; these levels were higher than in native starches.
from either reduced crystallinity or increased amorphous area in Augmented starch digestibility with increased HMT moisture
the semi-crystalline lamella. content was observed by Kweon, Haynes, Slade, and Levine (2000).
Franco et al. (1995) also found that HMT (18% moisture/100 ◦ C/16 h)
enhanced the crystallinity of corn and cassava starches, result-
4.1.6. Impact of HMT on starch gelatinisation characteristics ing in a significant increase in enzymatic susceptibility. According
HMT influences the onset temperature (To ), peak temperature to these authors, the results suggested a rearrangement of starch
(Tp ), conclusion temperature (Tc ), and gelatinisation enthalpy (H) molecules with the strengthening of bonds within the granules.
of starch. This effect is dependent on the moisture level of the treat- Moreover, HMT at a moisture level of 27% led to the disruption
ment, the starch source, and the amylose content. The onset, peak, and subsequent rearrangement of bonds within the granules, caus-
and conclusion gelatinisation temperatures generally rise as the ing starch degradation and thus increasing the number of regions
heat and moisture intensity increase. This increase has been noted accessible to enzymatic hydrolysis.
for potato, cassava, true yam (Gunaratne & Hoover, 2002), corn
(Chung et al., 2009b; Hoover & Manuel, 1996; Maache-Rezzoug
et al., 2008), pea, lentil (Chung et al., 2009b), and canna starches 4.1.8. Impact of HMT on the susceptibility of starch to acid
(Watcharatewinkul et al., 2009). Increased To , Tp , and Tc have been hydrolysis
attributed to structural changes within the starch granules, which The influence of HMT on acid hydrolysis has been shown to
involve amylose–amylose and amylose–lipid interactions (Hoover vary widely among starch sources. In cereal starches, suscep-
& Vasanthan, 1994). Adebowale, Henle, Schwarzenbolz, and Doert tibility towards acid hydrolysis after HMT decreases in wheat
(2009) found that the process of gelatinisation, which involves the (Hoover & Vasanthan, 1994) and maize (Hoover & Manuel, 1996)
melting of crystalline regions and double helices, is determined starches, whereas tuber starches (potato, cassava, and taro) show
by the hydration and swelling of the amorphous regions of starch increased hydrolysis during the first 5 days of hydrolysis on HMT
granules. When the amorphous region swells, it imparts a stress (Gunaratne & Hoover, 2002; Hoover & Vasanthan, 1994). Accord-
on the crystalline regions and polymer chains are stripped from ing to Varatharajan, Hoover, Liu, and Seetharaman (2010), the acid
the surface of starch crystallites. After HMT, the amylose–amylose hydrolysis of potato starch decreased with HMT and this decrease
and amylose–lipid interactions reduce the mobility of the amor- could be explained on the basis of changes in crystalline poly-
phous region. As a result, heat-moisture-treated starches require morphism (B → A + B) and starch chain interactions (amylose and
a higher temperature in order for swelling and disruption of amylopectin). The unit cells of A-type starches are more densely
the crystalline regions to occur, leading to increased To , Tp , and packed than those of B-type starches. This structure suggests that
Tc . closely packed A-type amylopectin chains could hinder the accessi-
The reduction in H promoted by HMT has been reported bility of H3 O + towards the ␣-1,4 and ␣-1,6 glycosidic bonds. These
in potato, cassava (Gunaratne & Hoover, 2002), jackbean (Lawal authors reported that the extent of the decrease in acid suscepti-
& Adebowale, 2005), corn (Chung et al., 2009b; Pukkahuta, bility with HMT is mainly influenced by the extent of polymorphic
Suwannawat, Shobsngob, & Varavinit, 2008), pea, and lentil transformation.
starches (Chung et al., 2009b). However, Hoover and Manuel (1996) According to Gunaratne and Hoover (2002) the changes in the
found no reduction in the H of heat-moisture-treated corn starch extent of acid hydrolysis with HMT can be explained through
at 100 ◦ C. Gunaratne and Hoover (2002) reported that decreased the interplay of the following factors: (1) crystallite disruption
H due to HMT is a result of the disruption of double helices present (increases acid hydrolysis by making more amorphous regions
in the crystalline and non-crystalline regions of the granules. In available); (2) interactions between starch chains (decreases
addition, Hormdok and Noomhorm (2007) argued that the reduc- hydrolysis by reducing chain flexibility and thereby hindering the
tion in H after hydrothermal treatment may be due to the partial conformational change); and (3) disruption of double helices in
gelatinisation of amylose and amylopectin molecules that are less the amorphous region (increases hydrolysis by making glycosidic
stable during heating. oxygen more accessible to protonation).
 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328 323

4.1.9. Impact of HMT on slowly digestible starch and resistant starch than corn starch. These authors studied the effect of HMT
starch (30% moisture/100 ◦ C/24 h) on these starches and found that native
Englyst, Kingman, and Cummings (1992) classified starch into and heat-moisture-treated corn starch had 4.6% and 10.5% resistant
rapidly digestible starch (RDS), slowly digestible starch (SDS), and starch, respectively. Brumovsky and Thompson (2001) found that
resistant starch (RS) based on the rate of glucose released during heat-moisture-treated high-amylose corn starch had 43.9% resis-
starch hydrolysis by digestive enzymes. RDS is the starch fraction tant starch compared to 18.4% in native starch.
that causes a sudden increase in blood glucose level after inges-
tion and SDS is a starch fraction that is digested completely in the 4.2. Annealing (ANN)
small intestine at a lower rate as compared to RDS. RS is repre-
sented by the fraction of starch not digested in the small intestine ANN is the hydrothermal treatment of starch in the presence of
of healthy individuals. SDS is the portion of starch converted to glu- excess water for an extended period of time. This treatment is per-
cose between 20 and 120 min of in vitro enzyme hydrolysis and this formed at a temperature above the glass transition but below the
type of starch predominates in most raw cereal products. Starch not gelatinisation temperature of starch (Gomes et al., 2005; Jayakody
hydrolysed after 120 min of in vitro enzyme hydrolysis is termed & Hoover, 2008). ANN specifically changes the physicochemical
RS. SDS and RS are the starch fractions that have different positive properties of starch by improving its crystalline perfection and
impacts on human health. The main potential health benefits of SDS facilitating interactions between the starch chains. The ANN pro-
are linked to a stable glucose metabolism. According to Lehmann cess leads to a reorganisation of starch molecules and amylopectin
and Robin (2007) the SDS has a medium to low glycemic index double helices such that the structure acquires a more organised
and thus reduces the glycemic load of a food product compared to configuration (Gomes et al., 2005). The extent of starch chain mobil-
RDS with a high glycemic index. Therefore the production of SDS ity and the realignment of double helices on annealing may differ
can have a positive effect in preventing diabetes and cardiovascular between cereal and tuber starches and also among cultivars. The
disease, because it stabilises the rate of glucose in the blood. ANN conditions for starches differ by botanical origin (Table 2).
Shin, Kim, Ha, Lee, and Moon (2005) investigated the formation It has been difficult to define what happens to the internal struc-
and structural characteristics of SDS in sweet potato starch under ture of starch granules in response to hydrothermal treatment. The
various hydrothermal treatments. They reported that depending main changes in annealed starches are as follows: (1) a reorgani-
on the temperature and the moisture content of the hydrother- sation of the granular structure (Gomes et al., 2005; Waduge et al.,
mal treatment, the SDS content could be doubled compared to 2006); (2) an increase in granular stability; (3) an increase in crys-
the native starch. According to Chung et al. (2009b), when the tallinity (Waduge et al., 2006; Lan et al., 2008); (4) an increase in
starch was heat-moisture treated at 120 ◦ C, the RDS decreased by the interactions between starch chains in the amorphous and crys-
10.2%, 14.0%, and 15.1%, the SDS content increased by 2.5%, 2.8% talline regions of the granules; (5) the formation of double helices
and 4.7%, and the RS content increased by 7.7%, 11.2% and 10.4% (Chung et al., 2009b); (6) an elevation in the starch gelatinisation
for corn, pea, and lentil starches, respectively, as compared to gela- temperature and a sharpening of the gelatinisation range (Waduge
tinised unmodified starches. These authors also reported that the et al., 2006; Lan et al., 2008); (7) a reduction in granular swelling
increase in thermo-stable SDS and RS suggests that some interac- and a change in the potential for and extent of amylose leaching
tions formed during hydrothermal treatments may have survived (Gomes, Silva, Ricardo, Sasaki, & Germani, 2004; Gomes et al., 2005;
after gelatinisation, thereby partly restricting accessibility of starch Lan et al., 2008; Waduge et al., 2006); (8) a reduction in peak viscos-
chains to the hydrolysing enzymes. Niba (2003) also investigated ity and retrogradation (Gomes et al., 2004, 2005); (9) an increase
the effect of heat treatment, storage temperature and time on in enzymatic susceptibility (Serrano & Franco, 2005; Wang, Powel,
digestibility of maize, potato, cocoyam, yam, plantain, and rice & Oates, 1997); and (10) the formation of resistant starch (Chung
flours. This author reported that the SDS content for all flours were et al., 2009b). However, the presence and degree of these changes
increased compared to the native flours. depend on the source of the starch (Chung et al., 2009b).
RS is fermented in the large intestine and its properties are sim- Jayakody and Hoover (2008) referred to the two main models of
ilar to those of dietary fibre; it has a prebiotic effect, acts on lipid the ANN process in semi-crystalline polymers as “sliding diffusion,”
metabolism, reduces cholesterol and reduces the risk of ulcerative in which complete molecular sequences move within a crystalline
colitis and colon cancer (Walter, Silva, & Denardin, 2005). The for- lattice (a mechanism that is favoured by the high mobility of the
mation of resistant starch usually involves partial acid hydrolysis chains in the crystals) and/or “complete or partial fusion” of the
and hydrothermal treatments, heating, retrogradation, extrusion crystals and a subsequent re-crystallisation of the melted materials
cooking, and chemical modification. Resistant starch has been clas- at the ANN temperature.
sified into four general subtypes called RS 1–4. The four distinct
classes of RS in foods are (1) RS 1: physically inaccessible starch, 4.2.1. Impact of ANN on starch swelling power and solubility
which is entrapped within whole or partly milled grains or seeds; ANN generally reduces the swelling power of starch. This
(2) RS 2: some types of raw starch granules such as banana, potato reduction is largely influenced by the interplay between the
and high-amylose corn starch; (3) RS 3: retrograded starch either extent of crystalline perfection and the amylose–amylose and/or
processed from unmodified starch or resulting from food process- amylose–amylopectin interactions. Both crystalline perfection and
ing applications; and (4) RS 4: starches that are chemically modified amylose-chain interactions decrease the hydration of the amor-
to obtain resistance to enzymatic digestion, such as some starch phous regions of starch, thereby decreasing granular swelling.
ethers, starch esters, and cross-linked starches (Fuentes-Zaragoza This reduced granular swelling due to ANN has specifically been
et al., 2010; Ratnayake & Jackson, 2008; Sanz, Salvador, Baixauli, & observed in potato starch (Hoover & Vasanthan, 1994).
Fiszman, 2009). Gomes et al. (2005) explained that an increase in molecular
Physical methods to raise resistant starch content include organisation is responsible for the reduction in the swelling power
hydrothermal treatments such as heat-moisture treatment and and solubility of starch. ANN has also been reported to reduce
annealing (Jacobs & Delcour, 1998; Kurakake, Tachibana, Masaki, swelling power in barley (Waduge et al., 2006), fermented cassava
& Komaki, 1996). HMT may be used to increase resistant starch (Gomes et al., 2005), unfermented cassava (Gomes et al., 2004),
content in starch without the disruption of granular structure. bambarra groundnut (Adebowale & Lawal, 2002), and wheat (Lan
According to Chung et al. (2009b), pea and lentil starches, which et al., 2008) starches. Specifically, swelling power has been shown
have higher amylose contents, showed higher levels of resistant to be influenced by amylopectin structure (Sasaki & Matsuki, 1998),
324 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328

Table 2
Annealing conditions for starches and references.

Starch source Temperature (◦ C) Time Water contenta Reference

Potato 50 24 h 1:2 (w/w) Jacobs et al. (1995)

20 and 50 72 h 1:10 (w/w) Kohyama and Sasaki (2006)
48 and 53 24 h 1:2 (w/w) Jacobs et al. (1998a)
Bambarra groundnut 50 24 h 1:2 (w/v) Adebowale and Lawal (2002)
Corn 30–50 72 h Excess Liu et al. (2009)
10 and 15 24 h Excess Chung et al. (2009a, 2009b)
25–65 72 h Excess Tester et al. (2000)
20 and 50 72 h 1:10 (w/w) Kohyama and Sasaki (2006)
Waxy maize 55 168 h Excess Qi, Tester, Snape, and Ansell (2005)
Fermented cassava 50 72–240 h 1:5 (w/w) Gomes et al. (2005)
Unfermented cassava 50 24–192 h 1:5 (w/w) Gomes et al. (2004)
50–60 48 h 1:2 (w/v) Serrano and Franco (2005)
Barley 29–31 0.5–4 h Excess Kiseleva et al. (2004)
50 72 h Excess Waduge et al. (2006)
Pea 10 and 15 24 h Excess Chung et al. (2009b)
50 24 h 1:2 (w/w) Jacobs et al. (1995)
Lentil 10 and 15 24 h Excess Chung et al. (2009b)
Rice 45–55 16 h 1:3 (w/w) Dias et al. (2010)
45–55 8–24 h 1:3 (w/w) Hormdok and Noomhorm (2007)
55 24 h 1:2 (w/w) Jacobs et al. (1995)
Wheat 45 24 h 1:2 (w/w) Jacobs et al. (1995)
20 and 50 72 h 1:10 (w/w) Kohyama and Sasaki (2006)
48 and 53 24 h 1:2 (w/w) Jacobs et al. (1998a)
Navy bean 50 24 h Excess Chung et al. (2010)
Yam bean 50 24 h 1:2 (w/v) Adebowale et al. (2009)
Black bean 50 24 h 1:3 (w/w) Hoover and Manuel (1996)
Sago 60 5h 1:5 (w/w) Wang et al. (1997)
a
w/w: starch:water.

amylose content, and the extent of amylose–amylose- and/or tends to increase the region of crystallinity as a result of the reori-
amylopectin–amylopectin-chain interactions (Tester, Debon, & entation of the starch granules. The strengthening of intragranular
Sommerville, 2000). The reduced solubility of annealed starch is bonded forces results in starch requiring more heat before struc-
due to a strengthening of the bonds between amylose and amy- tural disintegration and paste formation occurs. Along these lines,
lopectin or between amylopectin molecules, preventing leaching a reduction in retrogradation due to ANN was noted by Gomes et
out of the granules (Gomes et al., 2005). al. (2004), although Hormdok and Noomhorm (2007) found that
According to Waduge et al. (2006), the swelling power of retrogradation actually increased in annealed rice starch. In any
annealed barley starches was lower than their native counterparts. case, ANN promotes a reorganisation of starch molecules, caus-
These authors reported that the extent of this reduction depended ing them to occupy a more stable conformation and decreasing
on the amylose content of barley starches and followed the order: amylose leaching.
normal > waxy > high amylose. The reduction in swelling power in
the waxy starches on annealing is mainly due to the perfection of
4.2.3. Impact of ANN on the gel texture
starch crystallites because crystallite perfection reduces the extent
Using ANN, temperature and time are the dominant factors
of hydration of the amorphous regions. In contrast, in the normal
affecting gel hardness. According to Cham and Suwannaporn
and high-amylose starches, the interplay of crystallite perfection
(2010), the increase in crystalline perfection of granules by the
and amylose–amylose interactions on annealing may have been
ANN technique affected starch gel properties. Crystalline perfection
responsible for the reduction in swelling power.
resulted from an increase in mobility of the amorphous part, which
facilitated the ordering of double helices and probably greater
ordering in the amorphous regions (Lin, Wang, & Chang, 2008).
4.2.2. Impact of ANN on starch pasting properties
Chung, Moon, and Chun (2000) reported that ANN causes a
The impact of ANN on the pasting properties of starch is very
rearrangement of starch molecules, resulting in the reduction of
controversial. According to Stute (1992) and Jacobs et al. (1995),
swelling power and solubility; this reduction in the volume of gel
ANN increases the paste temperature and final viscosity of potato
promotes an increase in gel hardness. Hormdok and Noomhorm
starch and decreases its peak viscosity. Meanwhile, others (Jacobs,
(2007) also found an increase in gel hardness of rice starch sub-
Eerlingen, & Delcour, 1996) have found that ANN increases the peak
jected to annealing.
and final viscosities of wheat, pea, and rice starches. Taken together,
published results suggest that the effect of ANN on starch pasting
properties mainly depends on the structural characteristics of the 4.2.4. Impact of ANN on granule morphology
starch and the analysis conditions. According to Jacobs et al. (1996), Several authors (Adebowale et al., 2005; Hoover & Vasanthan,
the influence of ANN on the pasting profile of starch varies with 1994; Jacobs, Eerlingen, Spaepen, Grobert, & Delcour, 1998b;
the heating and cooling rates applied during analysis. Depending Jayakody, Hoover, Liu, & Donner, 2009; Stute, 1992) have found
on the rate of heating, annealed starches can better resist heat and no changes to granule morphology on annealing of wheat, oat,
mechanical stirring than native starches (Serrano & Franco, 2005). lentil, potato, finger millet, and yam starches. However, Kiseleva
Based on the work of Gomes et al. (2004), the bond strengthen- et al. (2005) observed that the granules of high amylose and waxy
ing promoted by ANN indicates that a higher temperature will be wheat starches were slightly deformed on annealing and the extent
required to gelatinise starch granules. Adebowale et al. (2009) also of this deformation was greater in the waxy starch. According to
reported that the increase in pasting temperature after hydrother- Dias, Zavareze, Spier, Castro, and Gutkoski (2010), the annealed
mal treatments supports the fact that the modification process high-amylose rice starch granules presented pores on the surface,
 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328 325

as compared with the native high-amylose starch granules. These The increase in gelatinisation temperatures is associated with a
authors also reported that the annealing slightly affected the mor- decrease in swelling power, provided that some granular structure
phology of medium- and low-amylose rice starches; the granules is retained. This is reflected in a higher temperature for the onset
were more agglomerated compared to the native starches. of swelling and reduced swollen volume (Tester & Debon, 2000).
Liu, Yu, Simon, Dean, and Chen (2009) reported that all sam- Adebowale et al. (2005) reported that an increase in To , Tp , and
ples of corn starches annealed at 30 ◦ C showed a similar thermal Tc reflects the melting of crystallites that are formed as a result
behavior as their corresponding native samples, indicating that this of amylose–amylose and amylose–amylopectin interactions along
temperature was not high enough to affect the microstructures. the chains. These interactions suppress the swelling of the granule,
However, the annealing treatment at 50 ◦ C increased the granule leading to delayed gelatinisation and higher To , Tp , and Tc val-
sizes in all samples of corn starches with different amylose content, ues. According to Kohyama and Sasaki (2006), the DSC endotherm
and the average rate of size change was increased with increas- associated with the gelatinisation of amylopectin shifted to a
ing amylopectin content. According to Waduge et al. (2006), the higher temperature and became narrower after ANN at 50 ◦ C. These
pore size of some barley cultivars also have been shown to increase authors reported that the treatment increased the To and Tp values
slightly on annealing. The increase in granule size can be explained of gelatinisation, while the Tc and H values were not changed by
by the ingress of moisture through the amorphous regions of the ANN.
starches during annealing. Waduge et al. (2006) studied the effect of ANN on barley
starches and reported that the treatment increased To , Tp , and Tc
4.2.5. Impact of ANN on starch crystallinity and decreased the temperature range (Tc –To ). They also attributed
The effects of ANN on crystallinity and X-ray diffraction pat- such changes to the perfection of the crystalline structure and
terns are dependent on the type of starch. The diffraction patterns amylose–amylose and/or amylose–amylopectin interactions, lead-
of starch granules result from the parallel packing of left-handed, ing to the formation of new double helices.
co-axial double helices in extended regular arrays (Lan et al., 2008).
ANN is a condition in which granules assume a more stable con- 4.2.7. Impact of ANN on the susceptibility of starch to enzymatic
figuration due to realignment of the polymer chains within the hydrolysis
non-crystalline and crystalline regions of the granule, enhancing Some studies have indicated that annealed wheat, sago and rice
crystallinity. Lan et al. (2008) observed an increase in wheat starch starches are more easily hydrolysed by ␣-amylases than native
crystallinity, while Waduge et al. (2006) demonstrated a similar starches (Dias et al., 2010; Jayakody & Hoover, 2008; Wang et al.,
increase in high-amylose barley starch after ANN treatment. Aug- 1997). These findings have been contradicted by other research
mented crystallinity due to ANN may arise from the interplay of on wheat, lentil and potato starches, although small starch gran-
several factors, such as increased crystalline perfection, the gen- ules (oat) have been reported to be much more easily hydrolysed
eration of new crystallites formed by interactions between starch post-annealing (Hoover & Vasanthan, 1994). The increase in hydrol-
chains, and increased crystalline size and reorientation. However, ysis with ANN has been attributed to an increase in granule
Jayakody and Hoover (2008) found that a slight reduction in potato porosity (O’Brien & Wang, 2008). A decrease in enzyme suscep-
starch crystallinity due to ANN may be a reflection of crystalline tibility with ANN has been attributed to crystallite perfection
disruption or reorientation, as reported by Vermeylen et al. (2006). and amylose–amylose and/or amylose–amylopectin interactions
According to Gomes et al. (2004), all annealed starches exhibit a (Hoover & Vasanthan, 1994; Hoover & Zhou, 2003).
reduced intensity of the crystallinity peak. These authors reported ANN promotes changes in the amorphous areas of granules,
that the increase in helical order is not induced by the formation of making them more accessible to enzymatic activity. Jayakody
amylose–lipid complexes, but rather by interactions between amy- and Hoover (2008) reported that ANN increased the susceptibil-
lose and amylopectin chains. Reduced intercrystalline spacing may ity of wheat starch to fungal and bacterial enzymes. Meanwhile,
indicate that helical packing becomes more compact and organised. Nakazawa and Wang (2003) observed that ANN promotes the for-
Small-angle X-ray scattering peak positions after ANN of wheat mation of pores on the surface of starch granules. This porous
and potato starches were unchanged, indicating that the repeat dis- structure could alter the enzymatic hydrolysis of starch depend-
tance of crystalline and amorphous lamellae was not altered by ing on the type of starch and enzyme (O’Brien & Wang, 2008). For
the treatment (Jacobs et al., 1998a). According Jacobs and Delcour example, the enzymatic susceptibility of waxy, normal, and high-
(1998), ANN may affect the individual lamellar sizes and the more amylose corn starches specifically increases after ANN.
pronounced peaks for the annealed starches, indicated by higher Because ANN promotes the formation of pores or fissures on
electron-density contrast between the amorphous and crystalline the granular surface, the hydrolysis profile of the starch changes
regions. Jenkins and Donald (1995) have also shown that amylose and ␣-amylase enters the granules more easily (Wang et al., 1997).
disrupts the packing of amylopectin crystallites by small-angle X- According to Serrano and Franco (2005), despite the fact that the
ray scattering of normal, waxy, and high-amylose corn and barley amorphous and crystalline lamellae of the granules become more
starches. These data suggest that because structural changes due ordered with ANN, the enzyme makes the amorphous areas more
to ANN occur within starch crystallites, the extent of these changes accessible. They also reported that although ANN increased the
may be influenced by the number of crystalline defects (high amy- crystallinity of cassava starch, when evaluated by X-ray diffraction
lose > normal > waxy) in native starches. the annealed starch was found to be more susceptible to the action
of ␣-amylase than the native starch.
4.2.6. Impact of ANN on starch gelatinisation characteristics
Stute (1992) suggested that changes in DSC curves are sensi- 4.2.8. Impact of ANN on the susceptibility of starch to acid
tive indicators of the type of hydrothermal treatment that a starch hydrolysis
underwent. He emphasised that narrower peaks after ANN indicate When a starch granule is treated with acid, the amorphous
greater homogeneity during melting of the crystallites and swelling regions of the granule are preferentially hydrolysed, leaving intact
and hydration of the starch granules. the more resistant crystalline regions (Gallant et al., 1997). The
The effect of annealing on gelatinisation characteristics is well amorphous regions of starch granules are less dense and therefore
established, particularly using DSC, where there tends to be an more susceptible to modifications than the more highly organised
increase in To and Tp , a decrease in the gelatinisation range (Tc –To ) crystalline regions. The susceptibility of starch to acid hydrolysis
and either no change or an increase in gelatinisation enthalpy. depends of reaction time and the degree of hydrolysis.
326 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328

The impact of ANN on the susceptibility of starch to acid hydrol- tion and retrogradation, although its content in food depends of
ysis has been shown to be influenced by the method used for the type of processing, the amylose/amylopectin ratio, the storage
annealing (single step, double step, or multistep), the starch source, time and the temperature and the amount of water used in pro-
and the ANN temperature (Hoover & Vasanthan, 1994; Nakazawa & cessing. However, the change in resistant starch content promoted
Wang, 2003). According to Hoover and Vasanthan (1994), annealing by ANN is not related to gelatinisation and retrogradation because
in a single step has been reported to decrease the acid suscep- the annealed starch does not gelatinise. The changes in resistant
tibility of wheat, potato and lentil starches. However, Nakazawa starch content are therefore related to structural changes, such as
and Wang (2003) showed that multistep ANN of wheat, tapioca, molecular reorganisation and changes in the crystallinity of starch.
potato, maize, waxy maize and high amylomaize increased acid
susceptibility during both phases of acid hydrolysis.
5. Applications of hydrothermally treated starches
According to Jayakody et al. (2009), ANN reduced susceptibility
to acid hydrolysis in yam starch. They also reported that varia-
Hydrothermal modifications (HMT and ANN) of starches
tion in the extent of reduction in hydrolysis among the starches
promote increased thermal stability and reduced retrograda-
may reflect differences in the size and/or number of crystallites.
tion (Adebowale et al., 2005). Therefore, hydrothermally treated
These authors also reported that the perfection of starch crystal-
starches could be utilised in the canned and frozen food indus-
lites during annealing cannot be considered as a factor influencing
tries due to these respective advantages (Jayakody & Hoover, 2008).
hydrolysis of the annealed starches.
Collado and Corke (1999) studied some industrial applications of
Various theories have been advanced to explain the suscepti-
hydrothermally treated starches, including in their use in infant
bility of annealed starches to acid hydrolysis. The decrease in acid
food, the processing of potato starch to replace corn starch in times
hydrolysis with ANN has been attributed to the perfection of starch
of shortage, the production of starches with excellent freeze–thaw
crystallites, the formation of double helical structures between
stability, and the improvement of the baking quality of potato
amylose chains, and the formation of V-amylose–lipid complexes
starch.
(Hoover & Vasanthan, 1994; Jacobs et al., 1998a).
The decrease in swelling power and amylose leaching and the
elevation in heat and shear stability that result from HMT and
4.2.9. Impact of ANN on slowly digestible starch and resistant
ANN are all desirable properties for noodle manufacture. Hormdok
starch
and Noomhorm (2007) evaluated the quality of noodles when rice
According to Guraya, James, and Champagne (2001), the slowly
flour was substituted for rice starch modified by HMT and ANN.
digestible starch (SDS) can be produced by physical, chemical and
This study showed an improvement in the texture (adhesiveness,
enzymatic treatments. These authors reported that each produced
chewiness, and tensile strength) of the noodles prepared with
SDS in different level and form depends upon the treatment con-
hydrothermally modified rice starch. Miyazaki and Morita (2005)
dition. The annealing is hydrothermal method that has been used
also investigated the properties of dough and bread made from
to modify starch digestibility. Chung et al. (2009b) investigated the
wheat flour partially replaced by heat-moisture-treated corn starch
effect of ANN on digestibility of corn, pea, and lentil starches and
to improve bread quality. Suzuki and Sekiya (1994a, 1994b) studied
reported that the ANN increased the RDS and decreased SDS levels
functional properties of industrialised HMT maize starch in search
in all native granular starches. O’Brien and Wang (2008) explained
of an application for processed foods, such as pouch-packed food,
that the increase in RDS levels on ANN is probably due to the for-
canned food and for fillings.
mation of a more porous structure and the formation of a porous
Brumovsky and Thompson (2001) and Chung et al. (2009b)
structure would allow greater accessibility of hydrolytic enzyme
found that HMT and ANN may be used to enhance resistant
into the granular interior. Chung, Hoover, & Liu (2009a), in study
starch levels while maintaining granular structure. According
with corn starch ANN at 50 ◦ C, also found an increase in the RDS
to Brumovsky and Thompson (2001), high-amylose corn starch
level and a decrease in SDS level.
treated by HMT or ANN was composed of 43.9% or 28.1% resis-
Annealing has been used to enhance resistant starch (sum of
tant starch, respectively, compared to 18.4% in native starch. These
starch and starch-containing products not absorbed in the small
authors also demonstrated that partial starch hydrolysis with
intestine) levels while maintaining granule structure (Brumovsky
hydrochloric acid followed by hydrothermal treatment intensified
& Thompson, 2001). The initial temperature of gelatinisation in
the increase in resistant starch content. Acid hydrolysis may thus
ANN should not be exceeded; therefore, there is no change in
increase the mobility of starch chains. Finally, Jayakody and Hoover
molecular structure due to the gelatinisation process. This modi-
(2008) reported that resistant starch can be incorporated into foods
fication makes the starch granule more organised and more stable,
without altering their appearance and texture, partly due to its
strengthening the links between the molecules of amylose and
bland taste and white colour, allowing it to be used as a fat mimetic
amylopectin. Brumovsky and Thompson (2001) studied the effect
or to increase the dietary fibre content of food.
of ANN on high-amylose corn starch and reported that there is
HMT also has been used to prepare biodegradable films. Singh,
an increase of 53% in resistant starch compared to native starch.
Bawa, Riar, and Saxena (2009) characterised biodegradable films
High-amylose maize starch has been used for enhancing resistant
from native and HMT chestnut starches. The film elaborated with
starch because it is digested very slowly. Chung, Liu, and Hoover
HMT starch presented higher peak force, puncture energy and
(2010) found a reduction in the resistant starch content of annealed
tensile strength and lower solubility as compared to the native
pea, lentil and navy bean starches compared to native starches, and
starch. These authors reported that the film forming ability of native
they reported that the crystalline perfection and amylose–amylose
and heat-moisture-treated starches showed a promising future for
and/or amylose–amylopectin interactions should have theoret-
exploration as packaging material.
ically increased the resistant starch level. However, increased
granule porosity caused by ANN may negate the effect of crystalline
perfection and starch chain interactions on enzyme susceptibility. 6. Conclusion
These authors studied the effect of dual modification (ANN–HMT
and HMT–ANN) in gelatinised samples, which resulted in further Among the known starch modifications, hydrothermal treat-
increases in resistant starch levels. ments are highly promising for generating food additives or
Pomeranz (1992) and Kutos, Golob, Kac, and Plestenjak (2003) ingredients that require specific properties. In the literature, there
reported that the resistant starch content is related to gelatinisa- is a broad description of the physicochemical changes in starches
 E.d.R. Zavareze, A.R.G. Dias / Carbohydrate Polymers 83 (2011) 317–328 327

of different botanical origins that result from hydrothermal treat- Garcia, V., Colonna, P., Bouchet, B., & Gallant, D. J. (1997). Structural changes of cas-
ments. The extent of these changes is influenced by the starch sava starch granules after heating at intermediate water contents. Starch/Stärke,
49, 171–179.
composition and source, the ratio of amylose to amylopectin, and Genkina, N. K., Wasserman, L. A., Noda, T., Tester, R. F., & Yuryeva, V. P. (2004).
treatment conditions (temperature, time, and moisture levels). Effects of annealing on the polymorphic structure of starches from sweet pota-
However, the exact molecular mechanisms of these treatments toes (Ayamurasaki and Sunnyred cultivars) grown at various soil temperatures.
Carbohydrate Research, 339, 1093–1098.
remain poorly characterised. Therefore, it would be interesting to Gerard, C., Colonna, P., Buleon, A., & Planchot, V. (2002). Order in maize mutant
have more studies to investigate the effects of hydrothermal treat- starches revealed by mild acid hydrolysis. Carbohydrate Polymers, 48, 131–141.
ments on molecular structure of starches from different sources, Gomes, A. M. M., Silva, C. E. M., & Ricardo, N. M. P. S. (2005). Effects of annealing on
the physicochemical properties of fermented cassava starch (polvilho azedo).
such as location of amylose, amorphous zone size, amylose and Carbohydrate Polymers, 60, 1–6.
amylopectin conformation and their interactions, as well as the Gomes, A. M. M., Silva, C. E. M., Ricardo, N. M. P. S., Sasaki, J. M., & Germani, R. (2004).
interactions with water molecules intra and intermolecular before Impact of annealing on the physicochemical properties of unfermented cassava
starch (polvilho doce). Starch/Stärke, 56, 419–423.
and after hydrothermal treatments. The study of hydrothermal
Gunaratne, A., & Hoover, R. (2002). Effect of heat-moisture treatment on the struc-
treatment for starch modification is of interest due to its possible ture and physicochemical properties of tuber and root starches. Carbohydrate
applications in the food industry, either for use alone or in combi- Polymers, 49, 425–437.
nation with other types of starch modifications. There are studies Guraya, H. S., James, C., & Champagne, E. T. (2001). Effect of enzyme concentra-
tion and storage temperature on the formation of slowly digestible starch from
that show that acid modifications in combination with hydrother- cooked debranched rice starch. Starch/Stärke, 53, 131–139.
mal modifications (HMT and ANN) have important properties such Güzel, D., & Sayar, S. (2010). Digestion profiles and some physicochemical properties
as the formation of RS. Furthermore, the combination of HMT with of native and modified borlotti bean, chickpea and white kidney bean starches.
Food Research International, doi:10.1016/j.foodres.2010.07.025
ANN can also change the SDS and RS contents. Therefore it would be Hoover, R. (2001). Composition, molecular structure, and physicochemical proper-
interesting to study the effects of HMT and ANN with other physical ties of tuber and root starches: A review. Carbohydrate Polymers, 45, 253–267.
and chemical modifications. Hoover, R., & Manuel, H. (1996). Effect of heat-moisture treatment on the structure
and physicochemical properties of normal maize, waxy maize, dull waxy maize
and amylomaize V starches. Journal of Cereal Science, 23, 153–162.
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