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Resistant

Starch
A Review
M.G. Sajilata, Rekha S. Singhal,
and Pushpa R. Kulkarni

ABSTRA
CT
esistant star
ch (RS) has ev
oked new inter
est in the bioav
ailability of star
ch and in its use as
ABSTRACT
CT:: The concept of rresistant
starch
evoked
interest
bioavailability
starch
ce of dietar
y fiber
ticularly in adults
w consider
ed to pr
ovide functional pr
oper
ties and find applicasource
dietary
fiber,, par
particularly
adults.. RS is no
now
considered
pro
proper
operties
a sour
tions in a vvar
ar
iety of foods
mation, consequence of such for
mation, their methods
foods.. Types of RS, factors influencing their for
formation,
formation,
ariety
of pr
epar
ation, their methods of estimation, and health benefits hav
e been br
iefly discussed in this rreview
eview
prepar
eparation,
have
briefly
eview..
Keywor
ds: rresistant
esistant star
ch (RS), functionality
mation, pr
epar
ation, deter
mination, digestibility
eywords:
starch
functionality,, for
formation,
prepar
eparation,
determination,
digestibility,, physiological
effects, applications, commercial sources

Introduction
From the early years of emergence of nutritional science, it has
been recognized that the ingested nutrients in the diet are not
completely utilized in the body. An increasing volume of evidence suggests that with very few exceptions, only a proportion of
the total ingested nutrients in a diet or food is available, and the
term availability has come into use for this proportion (Southgate 1989). The nutrients measured by chemical analysis may not
always be fully utilizable, mainly due to the indigestible cell walls,
a bulky or dense structure, a low solubility, the presence of some
compounds inhibiting the digestion, as well as components
abundantly present in plant foods such as dietary fiber, phytic
acid, and tannic acid, which may significantly reduce the absorption and utilization of some nutrients (Rosado and others 1987).
During food processing, derivatization of nutrients and formation
of cross linkages occur, thereby making the food inaccessible for
digestion or/and metabolism. Such parts of nutrients are also unavailable (Erbersdobler 1989).
Starch, which is the major dietary source of carbohydrates, is
the most abundant storage polysaccharide in plants, and occurs
as granules in the chloroplast of green leaves and the amyloplast
of seeds, pulses, and tubers (Ellis and others 1998). The relatively
recent recognition of incomplete digestion and absorption of
starch in the small intestine as a normal phenomenon has raised
interest in nondigestible starch fractions (Cummings and Englyst
1991; Englyst and others 1992). These are called resistant starches, and extensive studies have shown them to have physiological
functions similar to those of dietary fiber (Asp 1994; Eerlingen
and Delcour 1995). The diversity of the modern food industry and
the enormous variety of food products it produces require starches that can tolerate a wide range of processing techniques and
MS 20050127 Submitted 2/28/05, Revised 8/2/05, Accepted 10/29/05.
The authors are with Food Engineering and Technology Dept., Inst. of
Chemical Technology, Matunga, Mumbai 400 019, India. Email:
rekha@udct.org.

2006 Institute of Food Technologists

preparation conditions (Visser and others 1997). These demands


are met by modifying native starches with chemical, physical, and
enzymatic methods (Betancur and Chel 1997), which may lead to
the formation of indigestible residues. The availability of such
starches therefore deserves consideration. This review therefore
focuses on the availability of the major nutrient, that is, the starch,
with special reference to RS.

Starch and its classification


Chemically, starches are polysaccharides, composed of a number of monosaccharides or sugar (glucose) molecules linked together with -D-(1-4) and/or -D-(1-6) linkages. The starch consists of 2 main structural components, the amylose, which is essentially a linear polymer in which glucose residues are -D-(1-4)
linked typically constituting 15% to 20% of starch, and amylopectin, which is a larger branched molecule with -D-(1-4) and
-D-(1-6) linkages and is a major component of starch (BNF
1990). Amylose is linear or slightly branched, has a degree of polymerization up to DP 6000, and has a molecular mass of 105 to
106 g/mol. The chains can easily form single or double helices
(Takeda and Takeda 1989). On the basis of X-ray diffraction studies on oriented amylase fibers, the presence of type A and type B
amyloe is indicated (Figure 1, Galliard 1987). The structural elements of type B are double helices, which are packed in an antiparallel, hexagonal mode. The central channel surrounded by 6
double helices is filled with water (36 H2O/unit cell). Type A is
very similar to type B, except that the central channel is occupied
by another double helix, making the packing closer. In this type,
only 8 molecules of water per unit cell are inserted between the
double helices. Amylopectin (107 to 109 g/mol) is highly
branched and has an average DP of 2 million, making it one of
the largest molecules in nature. Chain lengths of 20 to 25 glucose
units between branch points are typical. Its structure is often described by a cluster model (Figure 2). The cluster model gained
greater credence when Hizukuri postulated that amylopectin

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chains are either located within a single cluster or serve to connect 2 or more clusters (Hizukuri 1986; Thompson 2000). Short
chains (A) of DP 12-16 that can form double helices are arranged
in clusters. The clusters comprise 80% to 90% of the chains and
are linked by longer chains (B) that form the other 10% to 20% of
the chains. Most B-chains extend into 2 (DP about 40) or 3 clusters (DP about 70), but some extend into more clusters (DP about
110) (Figure 2 and 3) (www.lsbu.ac.uk). On the basis of X-ray diffraction experiments, starch granules are said to have a semicrystalline character, which indicates a high degree of orientation of
the glucan molecules. About 70% of the mass of starch granule is
regarded as amorphous and about 30% as crystalline. The amorphous regions contain the main amount of amylose but also a
considerable part of the amylopectin. The crystalline region consists primarily of the amylopectin.
Various ways to classify native starches

X-ray diffraction. Three types of starches, designated as type A,


type B, and type C, have been identified based on X-ray diffraction

patterns. These depend partly on the chain lengths making up the


amylopectin lattice, the density of packing within the granules, and
the presence of water (Wu and Sarko 1978). Although type A and
type B are real crystalline modifications, type C is a mixed form. The
important features of the types of starches are as follows.
Type A. The type A structure has amylopectin of chain lengths of
23 to 29 glucose units. The hydrogen bonding between the hydroxyl groups of the chains of amylopectin molecules results in
the formation of outer double helical structure. In between these
micelles, linear chains of amylose moieties are packed by forming
hydrogen bonds with outer linear chains of amylopectin. This pattern is very common in cereals.
Type B. The type B structure consists of amylopectin of chain
lengths of 30 to 44 glucose molecules with water inter-spread.
This is the usual pattern of starches in raw potato and banana.
Type C. The type C structure is made up of amylopectin of chain
lengths of 26 to 29 glucose molecules, a combination of type A
and type B, which is typical of peas and beans.
An additional form, called type V, occurs in swollen granules. Xray diffraction diagrams of these starches are shown in Figure 4.
Based on the action of enzymes

According to Berry (1986), starches can be classified according


to their behavior when incubated with enzymes without prior exposure to dispersing agents as follows.
Rapidly digestible starch (RDS). RDS consists mainly of amorphous and dispersed starch and is found in high amounts in
starchy foods cooked by moist heat, such as bread and potatoes.
It is measured chemically as the starch, which is converted to the
constituent glucose molecules in 20 min of enzyme digestion.

Figure 1Unit cells and arrangement of double helices (cross


section) in A-amylose (top) and B-amylose (bottom) (Galliard
1987)
2

Figure 2Cluster model of amylopectin

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Resistant starch - a review


Slowly digestible starch (SDS). Like RDS, SDS is expected to be
completely digested in the small intestine, but for 1 reason or another, it is digested more slowly. This category consists of physically inaccessible amorphous starch and raw starch with a type A
and type C crystalline structure, such as cereals and type B starch,

either in granule form or retrograded form in cooked foods. It is


measured chemically as starch converted to glucose after a further
100 min of enzyme digestion.
Resistant starch. The term resistant starch was first coined by
Englyst and others (1982) to describe a small fraction of starch
that was resistant to hydrolysis by exhaustive -amylase and pullulanase treatment in vitro. RS is the starch not hydrolyzed after
120 min of incubation (Englyst and others 1992). However, because starch reaching the large intestine may be more or less fermented by the gut microflora, RS is now defined as that fraction of
dietary starch, which escapes digestion in the small intestine. It is
measured chemically as the difference between total starch (TS)
obtained from homogenized and chemically treated sample and
the sum of RDS and SDS, generated from non-homogenized food
samples by enzyme digestion.
RS = TS (RDS + SDS)
Based on the nutritional characteristics

Figure 3(a) Shows the essential features of amylopectin.


(b) Shows the organization of the amorphous and crystalline
regions (or domains) of the structure generating the concentric layers that contribute to the growth rings that are visible by light microscopy. (c) Shows the orientation of the
amylopectin molecules in a cross section of an idealized entire
granule. (d) Shows the likely double helix structure taken up
by neighboring chains and giving rise to the extensive degree of crystallinity in granule (www.lsbu.ac.uk).

This classification is based on the extent of digestibility of the


starch as follows.
Digestible starches. These include the starches digestible by
body enzymes, namely the rapidly digestible starches (RDS) and
the slowly digestible starches (SDS). RDS consists mainly of amorphous and dispersed starch, found in high amounts in starchy
foods cooked by moist heat. Like RDS, SDS is expected to be
completely digested in the small intestine, but for 1 reason or another, it is digested more slowly.
Resistant starch. RS is indigestible by body enzymes. It is subdivided into 4 fractions: RS1, RS2, RS3, and RS4. These are also
called as type I, II, III, and IV starches.
RS1 represents starch that is resistant because it is in a physically inaccessible form such as partly milled grains and seeds and in
some very dense types of processed starchy foods. It is measured
chemically as the difference between the glucose released by the
enzyme digestion of a homogenized food sample and that released from a nonhomogenized sample. RS1 is heat stable in most
normal cooking operations and enables its use as an ingredient in
a wide variety of conventional foods.
RS2 represents starch that is in a certain granular form and resistant to enzyme digestion. It is measured chemically as the difference between the glucose released by the enzyme digestion of a
boiled homogenized food sample and that from an unboiled, nonhomogenized food sample. In raw starch granules, starch is tightly
packed in a radial pattern and is relatively dehydrated. This compact structure limits the accessibility of digestive enzymes, various
amylases, and accounts for the resistant nature of RS2 such as,
ungelatinized starch. In the diet, raw starch is consumed in foods
like banana. RS1 and RS2 represent residues of starch forms, which
are digested very slowly and incompletely in the small intestine.
RS3 represents the most resistant starch fraction and is mainly
retrograded amylose formed during cooling of gelatinized starch.
Most moist-heated foods therefore contain some RS3. It is measured chemically as the fraction, which resists both dispersion by
boiling and enzyme digestion. It can only be dispersed with KOH
or dimethyl sulphoxide (Asp and Bjorck 1992). RS3 is entirely resistant to digestion by pancreatic amylases.
Therefore,
RS1 = TS (RDS + SDS) RS2 RS3
RS2 = TS (RDS + SDS) RS1 RS3

Figure 4X-ray diffraction diagrams of starches: type A (cereals), type B (legumes), and type V (swollen starch, Va: water-free, Vh : hydrated) (Galliard 1987)

RS3 = TS (RDS + SDS) - RS2 RS1


RS4 is the RS where novel chemical bonds other than -(1-4) or

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Table 1Classification of types of resistant starch (RS), food sources, and factors affecting their resistance to digestion in
the colon (Nugent 2005)
Type of RS

Description

Food sources

Resistance minimized by

RS1

Physically protected

Milling, chewing

RS2

Ungelatinized resistant granules


with type B crystallinity, slowly
hydrolyzed by -amylase
Retrograded starch

Whole- or partly milled grains and


seeds, legumes
Raw potatoes, green bananas, some
legumes, high amylose corn
Cooked and cooled potatoes, bread,
cornflakes, food products with
repeated moist heat treatment
Foods in which modified starches have
been used (for example, breads, cakes)

Processing conditions

RS3
RS4

Chemically modified starches


due to cross-linking with
chemical reagents

Table 2In vitro digestibility of starch in a variety of foods


(BNF 1990)a
Foods
Flour, white
Short bread
Bread, white
Bread, whole meal
Spaghetti, white
Biscuits made with
50% raw banana flour
Biscuits made with
50% raw potato flour
Peas, chick, canned
Beans, dried, freshly
cooked
Beans, red kidney,
canned

% RDS

% SDS % RS1 %RS 2

%RS 3

38
56
94
90
55
34

59
43
4
8
36
27

38

Traces
Traces
2
2
1
Traces

36

29

35

Traces

56
37

24
45

5
11

Traces

14
6

25

15

60

a Values are expressed as % of the total starch present in the food.

-(1-6) are formed. Modified starches obtained by various types


of chemical treatments are included in this category.
Table 1 outlines a summary of the different types of RS, their
classification criteria, and food sources. In vitro digestibility of
starch in a variety of foods (BNF 1990) is shown in Table 2.

Structure of RS
RS1

RS1 is the physically protected form of starch found in whole


grains (www.cerestarhealthand nutrition.com). Figure 5 shows microscopic view of the physically inaccessible RS1 in cell or tissue
structures of partly milled grains, seeds, and vegetables.
RS2

In raw starch granules, starch is tightly packed in a radial pattern and is relatively dehydrated. This compact structure limits the
accessibility of digestive enzymes and accounts for the resistant
nature of RS2 such as, ungelatinized starch. Figure 6 shows the RS
granules, that is, raw potato, banana, and high-amylose starch
(www.cerestarhealthand nutrition.com).

Food processing and cooking

Less susceptible to digestibility


in vitro

stranded helices. A type A crystalline structure can be obtained if


RS is formed in gelatinized starch stored at high temperature (that is,
100 C) for several hours (Eerlingen and others 1993a). It has a
dense structure and only few water molecules in the monoclinic
unit cell. Upon further retrogradation, the double helices pack in a
hexagonal unit cell. The B form with hexagonal symmetry is more
open. Water molecules (36 to 42 molecules per unit cell) in the B
structure are located in fixed positions within a central channel
formed by 6 double helices. The degree of polymerization (DP) of
amylose also affects the yield of RS3; it rises with DP up to 100 and
thereafter remains constant (Eerlingen and others 1993b). A minimum DP of 10 and a maximum of 100 seems to be necessary to
form the double helix (Gidley and others 1995). Schematic presentation of RS3 formed in aqueous amylose solutions depicted as miscelle and lamella model is shown in Figures 7 and 8.
Structural features of in vivo RS (ingestion of retrograded highamylose maize starch, complexed high amylose maize starch, bean
flakes, or potato flakes) were assessed using the ileal contents of 4
humans (Faisant and others 1993). For all samples, starch fractions,
which escaped digestion in the small intestine, were composed of 3
populations of -glucans with proportions differing according to
the substrate. Small quantities of oligosaccharides made up the 1st
population, illustrating a limitation of absorption in the small intestine. The 2nd population, the main RS, consisted of retrograded
amylose of mean degree of polymerization (DPn) of about 35 glucose units with a melting temperature of 150 C and exhibiting a
type B pattern. Finally high-molecular-weight semicrystalline -glucans were attributed to fragments of starch. This study showed that
some potentially digestible starch could reach the colon and that
crystalline fractions constituted only part of the starch that escaped
digestion in the human small intestine.
RS4

Structure of RS4 includes structures of modified starches obtained by chemical treatments like distarch phosphate ester (Figure 9).

RS3

RS3 represents retrograded starch. Thus, in the formation of RS3,


the starch granule is completely hydrated. Amylose leaches from
the granules into the solution as a random coil polymer. Upon
cooling, the polymer chains begin to reassociate as double helices,
stabilized by hydrogen bonds (Wu and Sarko 1978). The individual
strands in the helix contain 6 glucose units per turn in a 20.8 A repeat. The models for the double helices are left-handed, parallel-

Figure 5Structure of resistant starch type I (RS1)

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Figure 6Structure of resistant starch type II (RS2)

Resistant starch - a review


Functionality of RS
RS has a small particle size, white appearance, and bland flavor.
RS also has a low water-holding capacity. It has desirable physicochemical properties (Fausto and others 1997) such as swelling,
viscosity increase, gel formation, and water-binding capacity,
making it useful in a variety of foods. These properties make it
possible to use most resistant starches to replace flour on a 1-for1 basis without significantly affecting dough handling or rheology.
RS not only fortifies fiber but also imparts special characteristics
not otherwise attainable in high-fiber foods (Tharanathan and Mahadevamma 2003). The functional properties and advantages of
commercial sources of RS 2 and RS3 (Nugent 2005) have been
summarized as follows. They are natural sources, bland in flavor,
white in color, with fine particle size (which causes less interference with texture). They have high gelatinization temperature,
good extrusion and film-forming qualities, and lower water-holding properties than traditional fiber products. They allow the formation of low-bulk high-fiber products with improved texture, appearance, and mouth feel (such as better organoleptic qualities)

compared with traditional high-fiber products; they increase coating crispness of products and the bowl life of breakfast cereals.
They are functional food ingredients lowering the calorific value
of foods and useful in products for coeliacs, as bulk laxatives and
in products for oral rehydration therapy.
Some of these properties of RS have been successfully used in a
range of baked and extruded products as described subsequently.
RS in bread-making for DF fortification
(www.foodinnovation.com/functresist.pdf)

The physical properties of RS, particularly its low water-holding


capacity, allow it to be a functional ingredient that provides good
handling in processing and crispness, expansion, and improved
texture in the final product. Bread is commonly fortified with dietary fiber. However, dark color, reduced loaf volume, poor
mouthfeel, and masking of flavor are all negative attributes that
are often associated with high-fiber breads. A study was conducted at the American Inst. of Baking (AIB) to evaluate the effect of RS
on bread characteristics and to compare their performance to traditional fibers. The study included cellulose, oat fiber, wheat fiber,
and 2 commercially available RS with 23% (Hylon VII starch) and
40% TDF (Novelose 240 starch) and a blend of oat fiber with
Novelose 240 starch in a 50/50 ratio based on TDF contribution.
Compared with oat fiber, cellulose, and wheat fiber, both RS had a
lower water-holding capacity, which is similar to that of flour. Although the water-holding capacity of the RS was lower than that of
the other fiber sources, the quantity required to obtain the same
level of TDF was greater. This raised the total water requirement of
the RS dough. However, absorption of the RS doughs was less
compared with the fiber doughs, despite a larger quantity of water
used. The lower dough absorption consequently had less impact
on dough rheology and was closest to the white pan bread
dough. Bread containing 40% TDF RS had greater loaf volume
and better cell structure compared with traditional fibers tested
(Baghurst and others 1996).

Figure 7Schematic presentation of enzyme resistant starch


type III (RS3) formed in aqueous amylose solutions. Micelle
model. Double helices are ordered into a crystalline structure (C) over a particular region of the chain, interspersed
with amorphous, enzyme degradable regions.

Figure 8Schematic presentation of


enzyme-resistant
starch
type
III
formed in aqueous
amylose solutions.
Lamella
model.
Lamellar structures
are formed by folding of the polymer
chains. The fold
zones are amorphous (A), while the
center of the lamella is crystalline (C).

Figure 9Preparation of cross-bonded starch

Figure 10Behavior of amylose molecules during cooling of


a concentrated aqueous solution
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RS as a texture modifier in baked goods

One way to ensure that the general population receives adequate amounts of fiber in the diet is to fortify good-tasting foods that
normally do not come to mind with fiber fortification but are often
eaten as breakfast items or snacks. RS were incorporated in a variety of baked goods, many of which include batter systems, such as
in cakes, cake-like muffins, or brownies. In general, application
tests showed that RS acts as texture modifier, imparting a favorable
tenderness to the crumb. A low-fat, loaf cake was formulated with
RS and various fibers to obtain approximately 3% TDF or 2.5 g of fiber per 80 g serving. These included a 40% TDF RS (Novelose 240
starch), oat fiber, a blend of oat fiber with Novelose 240 starch in a
50/50 ratio based on TDF contribution, and a 23% TDF RS (Hylon
VII starch). The baked cakes made with RS were similar to that containing oat fiber and the control in the amount of moisture loss after
baking, height, specific volume, and density. A panel rated the 40%
TDF RS loaf cakes as the best for flavor, grittiness, moisture perception, and tenderness 24 h after baking.
RS as a crisping agent

Among other functional properties, RS can be used as an ingredient that improves crispness in foods where high heat is applied
to a products surface during processing. French toast and waffles,
especially frozen reheated types, represent foods in which surface
crispness is desired. Tests were conducted to compare the functionality of RS and various fibers in a buttermilk waffle formulation. Based on the evaluation of the toasted waffles for initial crispness, crispness after 3 min, moistness, and overall texture by a
trained sensory panel RS waffle indicated greater crispness than
control or traditional fiber.
RS as a functional ingredient in other foods

Along with textural enhancement, RS can improve expansion in


extruded cereals and snacks. Various cereals were formulated to
contain 40% TDF RS (Novelose 240 starch) alone and in combination with oat fiber in ratios of 50/50 and 25/75 based on
weight. The cereal with RS and no oat fiber had greater volumetric
expansion than the control. In blends with oat fiber, the cereal
containing 75% of RS had better expansion than the one containing only 50%. Dried pasta products containing up to 15% RS can
be made with little or no effect on dough rheology during extrusion. Although the resultant pasta was lighter in color, a firm al
dente texture was obtained in the same cooking time as a control
that had no added fiber. RS may also be used in thickened,
opaque health beverages in which insoluble fiber is desired. Insoluble fibers generally require suspension and add opacity to
beverages. Compared with insoluble fibers, RS imparts a less gritty
mouthfeel and masks flavors less.

Factors influencing the formation of RS


Several factors influence the formation of RS.
Inherent properties of starch

Crystallinity of starch. One of the causes of resistance to enzymes is the crystallinity of native type B starch granules as observed in the case of amylomaize starch and also the encapsulation of starch within plant cell or tissue structures. X-ray diffraction
and differential scanning calorimetry studies on crystalline residues from amylomaize starch samples have suggested that chain
fragments packed in a type B crystalline structure with a slightly
enlarged crystal lattice contribute to formation of RS from amylomaize starch. Any treatment that eliminates starch crystallinity
(that is, gelatinization) or the integrity of the plant cell or tissue
structure (that is, milling) increases enzyme availability and reduces the content of RS, whereas recrystallization and chemical mod6

ifications tend to increase the RS. The modified food starches are
partially resistant to enzymes as a result of chemical modifications
induced intentionally (Englyst and Cummings 1986; Bjorck and
others 1989; Schweizer and others 1990). Besides these, the cellular structure of plant foods influences the digestibility of starch
in the small intestine as well as the intrinsic digestibility of a particular physical form of starch.
Granular structure. A large variability in susceptibility to amylases shown by raw starch granules also influences RS formation.
Potato starch and high amylose maize starch are known to be
very resistant in vitro and incompletely absorbed in vivo, whereas
most cereal starches are slowly but virtually completely digested
and absorbed in vivo (Holm and others 1987). The smaller surface-to-volume ratio of the large potato granules is probably important. The nature of the granule surface also needs to be considered; an adsorbed layer of non-starch material would effectively
impede the action of the enzyme (Ring and others 1988). Raw
tepary starch is found to be more resistant to hydrolysis than
maize starch, perhaps due to differences in granule structure and
amylose content (Abbas and others 1987).
Amylose:amylopectin ratio. A higher content of amylose lowers
the digestibility of starch due to positive correlation between amylose content and formation of RS (Berry 1986; Sievert and Pomeranz 1989b). The importance of the amylose:amylopectin ratio in
the postprandial glycaemic and insulinaemic responses to corn
was studied in commonly consumed corn products (Granfeldt
and others 1995). The meals containing high amylose (70%) corn
flour had an RS of 20 g/100 g DM than that containing ordinary
corn flour (25% amylose) that had RS of 3 g /100 g DM.
Retrogradation of amylose. When heated to about 50 C, in
the presence of water, the amylose in the granule swells; the crystalline structure of the amylopectin disintegrates and the granule
ruptures. The polysaccharide chains take up a random configuration, causing swelling of the starch and thickening of the surrounding matrix such as, gelatinizationa process that renders
the starch easily digestible. On cooling/drying, recrystallization
(retrogradation) occurs. This takes place very fast for the amylose
moiety as the linear structure facilitates cross linkages by means of
hydrogen bonds. Figure 10 shows the formation of gel and micelle on cooling of a concentrated solution of amylose (Belitz and
Grosch 1999). The branched nature of amylopectin inhibits its recrystallization to some extent and it takes place over several days.
Retrograded amylose in peas, maize, wheat, and potatoes was
found to be highly resistant to amylolysis (Ring and others 1988).
The rate and extent to which a starch may retrograde after gelatinization essentially depends on the amount of amylose present. Repeated autoclaving of wheat starch may generate up to 10% RS.
The level obtained appeared to be strongly related to the amylose
content, and the retrogradation of amylose was identified as the
main mechanism for the formation of RS that can be generated in
larger amounts by repeated autoclaving (Berry 1986; Bjorck and
others 1990). During storage, the dispersed polymers of gelatinized starch are said to undergo retrogradation to semicrystalline
forms that resist digestion by pancreatic -amylase. It forms a major portion of RS in wheat bread and corn flakes (Englyst and
Cummings 1985), whereas only 25% of the RS in cooked, cooled
potatoes can be accounted for as retrograded amylose. The digestibility of legume starch is much lower than that of cereal
starch, which is attributable to higher content of amylose in the
former. The digestibility of high amylose cereal starch is reported
to be significantly lower (Tharanathan and Mahadevamma 2003).
Native high-amylose starch is known to be high in type II RS (RS
2) (Berry 1986), which is defined as starch in its native granular
state that is resistant to digestion in the small intestine. This after
cooking and cooling gives high yields of type III RS (Berry 1986;
Sievert and Pomeranz 1989a) or retrograded starch (Englyst and

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Resistant starch - a review


others 1992). Heating of RS preparation from amylomaize VII resulted in broad endothermic transition, which is ascribed to melting of amylose crystallites (Sievert and Pomeranz 1989, 1990).
Exothermic transitions during controlled cooling of isolated potato amylose fractions have been attributed to amylose chain association. The formation of RS likewise has been attributed to the ordering of amylose chains (Sievert and others 1991). Based on previous studies of amylose behavior, it has been suggested that the
exotherms observed during the cooling of either amylose or a
thermally treated RS preparation reflect chain association, which
may involve amylose aggregation and gelation dominated by formation and subsequent lateral aggregation of type B double helices in crystalline arrays (Gidley 1989; Gidley and Bulpin 1989;
Sievert and Wursch 1993). Gelatinized waxy corn starch stored at
varying temperatures from 6 C to 60 C for 1 to 29 d also
showed reduced enzyme susceptibility to pancreatic -amylase
and amyloglucosidase (Eerlingen and others 1994).
Influence of amylose chain length. Influence of amylose chain
length on enzyme RS formation was studied by Eerlingen and others (1993b) by hydrolyzing potato starch amylose to varying degrees by incubation with barley -amylase for different periods,
and monitored by measuring the number of average chain
lengths or degree of polymerization (DPn). The DPn of RS varied
between 19 and 26 and was independent of the chain length of
the amylose (DP n 40 to 610) from which it was formed. Results
suggested that RS might be formed by aggregation of amylose helices in a crystalline -type structure over a particular region of the
chain (about 24 glucose units).
Linearization of amylopectin. Linearization of amylopectin occurs during the long low-temperature baking process due to the
prolonged activity of intrinsic amylases in the dough, and is
prominent in the presence of certain organic acids that is, in
bread products baked with added lactic acid (Liljeberg and others
1996). It has been reported to significantly increase RS formation
during wet-autoclaving (Berry 1986).
Heat and moisture

Water content is an important factor that affects formation of RS.


Repeated heat/moisture treatment is associated with a decrease in
the hydrolysis limit of pancreatic -amylase and increased formation of RS. Maximum RS yield was obtained at a starch:water ratio
of 1: 3.5 (w/w) (Sievert and Pomeranz 1989b) and a heat treatment
at 18% moisture gave increased levels of the degree of crystallinity of normal and waxy starches and thus reduced enzyme susceptibility. However, at 27% moisture, starch degradation to some
extent made areas of starch more accessible to enzyme attack.
Thus, proper heat treatment could be used as a method of preparation of RS (Franco and others 1995). In addition, higher temperature and less water results in type A configuration, whereas lower
temperature and high water content results in type B configuration
(Wu and Sarko 1978).
Malshick-Shin and others (2003) determined solubility, water
vapor sorption, and swelling characteristics for RS prepared from
wheat starch and linterized wheat starch by autoclaving and cooling and by cross-linking The experimental RS made from wheat
starch contained 10% to 73% RS versus 58% and 40% in commercial sources, Novelose 240 and 330 respectively, produced
from high-amylose maize (corn) starch. In excess water, the experimental RS starches (except for the cross-linked wheat starch)
gained 3 to 6 times more water than the commercial RS starches
at 25 C, and 2 to 4 times more at 95 C. All starches showed similar water vapor sorption and desorption isotherms at 25 C and
aw < 0.8. At aw 0.84 to 0.97, the RS made from wheat starch (except cross-linked wheat starch) showed approximately 10% higher water sorption than the commercial RS.
RS determined in several selected cereals, legumes, and tubers

subjected to dry and wet heat treatment brought out higher RS


contents in foods subjected to dry heat treatment compared with
wet processed ones. Sorghum, green gram dhal, and green plantain showed highest RS content (5.51%, 5.81%, and 10.7%, respectively) (Platel and Shurpalekar 1994).
Interaction of starch with other components

Interactions of starch with different components present in the


food system are known to influence the formation of RS as follows.
Protein. Starch-protein interaction has been believed to reduce
RS contents as observed in case of potato starch and added albumin when autoclaved and subsequently cooled at 20 C (Escarpa and others1997).
Dietary fiber. Insoluble dietary fiber constituents such as cellulose and lignin have been shown to have minimal effects on RS
yields compared with other constituents such as potassium and
calcium ions and catechin (Escarpa and others 1997).
Enzyme inhibitors. Polyphenols, phytic acid, and lectins
present mainly in leguminous seeds, have been reported to inhibit in vitro starch hydrolysis and to lower the glycemic index (Thompson and Yoon 1984). Tannic acid significantly inhibits both
amylases and intestinal maltase activity (Bjorck and Nyman 1987).
Indigestible residues from black beans (Phaseolus vulgaris cv. Tacari gua), green beans (P. vulgaris), carrots (Daucus carota), and
rice bran (Oryza sativa) are all reported to inhibit pancreatic amylase in vitro (Moron and others 1989). Since amylolysis is inhibited by phytic acid, a decrease in phytate content increases
starch digestibility (Thompson and Yoon 1984). Contradictory information exists in the literature on this aspect. The autoclaving
and subsequent cooling of potato starch and catechin was found
to significantly reduce the yields of RS, whereas the addition of
phytic acid to potato starch reduced the RS contents to a minor
extent (Escarpa and others 1997) compared with the RS formed
from potato starch with no added constituent. The reasons for the
same are still not clear.
Ions. The yields of RS in potato starch gels decrease in the presence of calcium and potassium ions compared with those with no
added constituent (Escarpa and others 1997), presumably due to
the prevention of formation of hydrogen bonds between amylose
and amylopectin chains caused by adsorption of these ions.
Sugars. The addition of soluble sugars such as glucose, maltose, sucrose, and ribose has been found to reduce the level of
crystallization and subsequently reduce the yields of RS (Buch
and Walker 1988; IAnson and others 1990; Kohyama and Nishinari 1991). The mechanism of retrogradation inhibition was considered as the interaction between sugar molecules and the starch
molecular chains, which change the matrix of gelatinized starch
(the sugars act as anti-plasticizers and increase the glass transition
temperature).
The role of sugars on the formation of RS in starch gels (RS type
III) was studied by Eerlingen and others (1994). Sugars influenced
the RS levels in starch gels only when added in high concentration (final starch-water-sugar ratio of 1:10:5 w/w). In wheat starch
gels, the RS yields decreased from approximately 3.4% to 2.8% in
the presence of sucrose or glucose, and to 2.5% in the presence
of ribose or maltose. An increase in RS yield was observed with
high-amylose corn starch. The experiments showed that the differences in gelatinization temperature, lipid content, and apparent
amylose content of the 2 starches were not the main causes of the
different impact of sugars on RS yields.
Lipids, emulsifiers. In a study, amylomaize VII starch, autoclaved at 125 C, was reacted during cooling below 100 C with
lysophosphatidyl choline (LPC), sodium stearoyl lactylate (SSL),
and hydroxylated lecithin (OHL) (Czuchajowska and others
1991). Differential scanning calorimetry (DSC) peaks at around

Vol. 5, 2006COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY

CRFSFS: Comprehensive Reviews in Food Science and Food Safety


95 C to 110 C indicated formation of amylose-lipid complexes,
and at about 155 C indicated the presence of enzyme-resistant
starch (RS). Yields of RS from complexed samples isolated by thermostable bacterial -amylase or amyloglucosidase were lower
than yields of RS from the autoclaved and cooled control. Formation of complexes competes with amylose chains involved in generation of RS. Amylose-lipid complexes are enzyme-degradable,
and an increase in complexed amylose reduced yields of RS.
Amylose recrystallization in RS formation is competitively affected
by complexation of amylose with LPC and SSL. Results of X-ray
diffraction powder crystallography were in agreement with DSC
measurements. Complexes of amylose with LPC, SSL, and OHL
gave type V patterns; enzymic hydrolysis of the complexes yielded type B RS structures. However, the viewpoint differs among scientists working in this area. While some workers believe amyloselipid complex to reduce the formation of RS, others believe the
amylose-lipid complex itself to be a form of RS.
From studies on isolated barley starch autoclaved with sodium
stearoyl lactylate (SSL), distilled monoglycerides, diacetyl tartaric
acid esters of mono-diglycerides (DATEM), and ethoxylated monoglycerides (bakery additives), it is postulated that amylose crystallization (as measured by enthalpies of the 158 C endotherm) that is
involved in the formation of RS is competitively affected by its complexation with lipids (Szczodrak and Pomeranz 1992).
Effect of citric acid and 2 emulsifiers SSL and DATEM on formation and structure of RS during extrusion of cornstarch and guar
gum were studied (Adamu 2001). X-ray diffraction of the extruded
starches gave a V-diffraction pattern indicating the formation of
amylose-lipid complexes. Purification of the isolated RS by size
exclusion high-performance liquid chromatography (HPLC) indicated the additives to have a substantial effect on molecular
weight; DATEM and SSL increased molecular weight of RS, while
citric acid decreased it.
The influence of endogenous lipids on the formation of RS from
wheat starch showed defatting to decrease the RS content (Eerlingen and others 1994). When SDS was added to defatted wheat or
amylomaize VII starch, RS yields decreased substantially. X-ray diffraction and DSC showed that amylose-lipid complexes were
formed in the presence of both endogenous and added lipids
(SDS). A similar behavior has been reported on addition of lipids
(Eliasoson and others 1988) such as olive oil (Escarpa and others
1997). Thus, less amylose was available for interactions leading to
the formation of double helices and RS. Adding SDS to the starch
also caused a difference in RS quality.
Amylose-lipid complexes can also be formed during food processing (autoclaving and cooling). Lecithin, palmitic acid, oleic
acid, and soya bean oil affect retrogradation to a lower extent than
monoglycerides. Nevertheless, these authors found that pure potato amylose and oleic acid formed complexes highly resistant to
amylolysis (Mercier 1980).
Processing conditions

Processing techniques may affect both the gelatinization and retrogradation processes, influencing RS formation. This fact is of great
importance for the food industry since it offers the possibility of increasing the RS content of processed foods and foodstuffs. Baking,
pasta production, extrusion cooking, autoclaving, and so forth are
known to influence the yield of RS in foods (Siljestrom and Asp
1985; Bjorck and Nyman 1987; Siljestrom and others 1989; Muir
and ODea 1992; Rabe and Sievert 1992). Highly processed cereal
flours and foods made from the flours, such as pasta, contain much
lower levels of RS, averaging only about 1.5% to 8% RS on a dry
basis. Since the crystalline structure of starch in legumes (type C) is
more stable compared with the crystal structure in cereal grains
(type A) (Ring and others 1988), processing cereal grains results in a
large decrease in RS content, while legumes are excellent sources
8

of RS. Cooking under conditions of high moisture and temperature


can significantly lower the RS content by disrupting crystalline
structure. Increasing the levels of RS can be done in other conditions, such as extrusion followed by cooling to induce crystallization (Haralampu 2000). The RS contents in various processed food
samples have been reported (Siljestrom and Bjorck 1990; Parchure
and Kulkarni 1997; Kavita and others 1998).
Thermal processing

Steam cooking. Steam cooking helps in production of RS. Starches isolated from several steam-heated legumes were rich in indigestible RS (19% to 31%, DM basis), which was not observed in
raw beans (Tovar and Melito 1996). Similarly, RS measured directly
in conventionally and high-pressure steamed beans were 3 to 5
times higher than in the raw pulses, suggesting retrogradation to be
mainly responsible for the reduction in digestibility. Prolonged
steaming as well as short dry pressure heating decreased the enzymically assessed total starch content of whole beans by 2% to 3%
(DM basis), indicating that these treatments may induce formation
of other types of indigestible starch (Tovar and Melito 1996).
Autoclaving. Autoclaving results in increase in RS. Autoclaved
wheat starch has 9% RS compared with less than 1% in uncooked wheat starch (Siljestrom and Asp 1985). Autoclaved
wheat starch contained 6.2% RS (of dm); this increased to 7.8%
after 3 further reboiling/cooling cycles (Bjorck and others 1987).
Quantitative and qualitative influence of incubation time and temperature of autoclaved starch on RS formation was studied by Eerlingen and others (1993a). In another study, white flour subjected
to repeated autoclaving and cooling cycles showed an increase in
total dietary fiber >3 times that of bread flours and 4 times that of
pastry flours (Ranhotra and others 1991b). The increase was primarily due to the formation of RS. Investigations on the formation
of enzyme-resistant starch (RS) during autoclaving and cooling by
Sievert and Pomeranz (1989a) showed highest yield (21.3%) to be
obtained from amylomaize VII starch (70% amylose). Formation of
RS in amylomaize VII starch was affected by the starch/water ratio,
autoclaving temperature and number of autoclaving-cooling cycles. The number of cycles exerted the most pronounced effect on
RS; increasing the number of cycles to 20 raised RS level to
>40%. Furthermore, the thermoanalytical data suggested that
amylose-lipid complexes were not involved in the formation of
RS. Yields in excess of 20% RS can be obtained from autoclaved
amylomaize starch containing 70% amylose. They can be raised
to levels of 40% by increasing the number of autoclaving-cooling
cycles up to 20 (Eerlingen and Delcour 1995).
The extent of RS formation in commercially available autoclaved corn, potato, and leguminous products and in autoclaved
purees intended for consumption by infants aged 3 to 8 mo was
investigated by Siljestrom and Bjorck (1990). RS levels found (g/
100 g DM) were as follows: 0.8 to 2.4 in purees, 0.2 to 3.2 in
canned legumes, 1.9 in canned potatoes, 0.5 and 0.9 in reconstituted dried potatoes, <0.1 in canned corn, and 1.1 in cornflakes.
Native starch (NS) extracted from wheat and subjected to 5 autoclaving and cooling cycles was found to contain 11.5% RS,
which was measured as insoluble fiber; NS contained 0.5% RS
(Ranhotra and others 1991a). Heat-moisture treatment (autoclaving at 121 C) with subsequent cooling was used to produce
amylase-resistant starch (RS) from purified high-amylose starch
samples. The formation of RS in barley starch was strongly affected
by the number of autoclaving-cooling cycles; increasing the number of cycles from 1 to 20 raised the RS yield from 6% to 26%
(Szczodrak and Pomeranz 1991).
Parboiling. Parboiling increases RS production. In studies on 5
rice varieties, differing in amylose content, the in vitro and in vivo
RS levels were low and positively correlated with amylose content
(Eggum and others 1993). Higher RS starch levels were found in

COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 5, 2006

Resistant starch - a review


cooked and parboiled-cooked rice than in raw rice; waxy rice
had very low values. Higher contents of RS have been reported in
parboiled rice than raw white rice, which also increased by cooling or freezing (Marsono and Topping 1999).
Baking. Baking increases RS content. In a study to evaluate the effect of baking on RS formation, white bread was baked and divided
into 3 fractions (crumb, inner crust, and outer crust) (Westerlund
and others 1989). Starch levels were found to be highest in dough
and lowest in outer crust after baking for 35 min. RS levels were
lowest in dough and highest in crumb after baking for 35 min. A
low-temperature, long-time baked product contained significantly
higher amounts of RS than bread baked under ordinary conditions
(Liljeberg and others 1996). Addition of lactic acid increased RS recovery further whereas malt had no impact on RS yield. The highest
level of RS was noted in long-time baked bread based on highamylose barley flour. RS isolated from wheat-based foods such as
chapatti and phulka was structurally characterized as a linear 1, 4linked -D-glucan essentially derived from retrograded amylose
fraction, which was dependent on the severity of the processing
treatments as well as the levels of gluten and damaged starch in the
wheat flour (Tharanathan and Tharanathan 2001).
Extrusion cooking. Effect of extrusion cooking, at different temperatures (90, 100, 120, 140, or 160 C), moisture contents
(20%, 25%, 30%, 35%, or 40%) and screw speeds (60, 80, or
100 rpm), was investigated on the formation of RS of type 3 (RS3)
in hull-less barley flours from CDC-Candle (waxy) and Phoenix
(regular). The RS3 content of the native flours, in general, decreased by extrusion cooking, but not significantly. Storage of extruded flour samples at 4 C for 24 h before oven drying slightly
increased RS3 content (Faraj and others 2004). With pearl barley
used as the primary material in tests designed to optimize the production of RS by extrusion an extrusion temperature of 150 C
and a barley moisture content from 17.5% and 22.5% moisture,
followed by cold storage at 18 C gave the best results (Gebhardt
and others 2001).
Corn starches with and without guar gum [10% (w/w)] and 2%
(w/w) of diacetyl tartaric acid ester of monoglyceride, sodium
stearoyl-2-lactylate or citric acid, respectively, were extrusioncooked in a twin-screw extruder at 18% moisture, 150 C, and 180
rpm screw speed (Adamu 2001). The formation of RS in extruded
corn starch was found to be strongly affected by the addition of
gum and the different food additives. X-ray diffraction of the extruded starches gave a V diffraction pattern indicating the effect of extrusion cooking and amylose-lipid complexes. Enzymatic digestion
did not affect the V structure, which could apparently be attributed
to extrusion cooking. Purification of the isolated RS by size exclusion-HPLC showed a dependence of molecular weight on the added additives. Results of differential scanning calorimetry and X-ray
diffraction suggest that amylose-lipid complexes could also be involved in the formation of RS in extruded cornstarch.
Pyroconversion. Pyroconversion of starch increases RS content. Lima bean (Phaseolus lunatus) starch was modified using pyroconversion, the optimum product being recovered from native
starch treated with a 160:1 starch/HCl ratio, at 90 C for 1 h, resulting in starches containing 49.5% indigestible starch (Tester
and others 2004). Starch pyrodextrinization decreased the
amount of enzymically available starch through formation of atypical glycosidic bonds that are not digested by the amylases and
maltooligosaccharidases in the small intestine of humans.
Microwave irradiation. Microwave irradiation improves the digestibility of tuber starches, which could be accompanied by
physicochemical and structure changes (www.man.poznan.pl).
Microwave cooking of legumes such as chickpeas and common
beans produced a redistribution of the insoluble nonstarch
polysaccharides to soluble fraction, although the total nonstarch
polysaccharides were not affected. This was evaluated by assess-

ing the physicochemical, nutritional, and microstructural modifications in starch and nonstarch polysaccharides (Marconi and
others 2000). The RS level decreased from 32.5% of total starch in
raw chickpeas and beans, respectively, to about 10% in cooked
samples with a concomitant increase in the level of rapidly digestible starch from 35.6% and 27.5% to about 80%.
Studies on effects of different heat treatments (cooking, microwave cooking, pressure cooking) on the rate of hydrolysis, hydrolysis index, and glycaemic index values of kudzu starch and
cornstarch showed increase in digestible starch and decrease in
RS following heat treatment. The rate of hydrolysis of kudzu starch
and cornstarch increased following heat treatment, especially after
microwaving (Geng and others 2003).
Miscellaneous treatments.

Milling. Leguminous seeds, in which cell structures are preserved after cooking (that is, bread with whole seeds); bean flour
with intact cells (Schweizer and others 1990); foods containing
large particles such as bread with whole seeds have lower physical accessibility of starch to amylase action, and thereby contribute to higher RS contents. In some foods, physically inaccessible
starch is likely to be an important fraction of the total starch that is
resistant to digestion in vivo. Schweizer and others (1990) found
evidence of 20% starch malabsorption from a diet containing
bean flour with intact cells. About half of the malabsorbed starch
was retrograded amylose. The precooked flours (PCF) prepared
from dried lentils and beans, rich in intact cells filled with starch
granules, indicated that they contained important quantities of RS,
such as retrograded amylose (3% to 9%, DM).
Germination. Germination is shown to decrease the RS content
in bengal gram, field beans, cow pea, and green gram (Kavita and
others 1998).
Fermentation. Fermentation reduces RS content. Flour from sorghum cv. Tabat was mixed with water and previously fermented
dough starter, and fermented at 37 C for a maximum of 36 h
showed an increase in the in vitro starch digestibility and a decrease in the content of RS and total starch (Abd-Elmoneim and
others 2004). RS formation has also been shown to decrease in the
fermented products, idlis and dhoklas (Kavita and others 1998).
Storage conditions

Generally, RS increases on storage, especially low-temperature


storage. Cold storage seems to support an increase in RS content.
Whole corn bread and corn bread crumb, when stored at different temperatures (20 C, 4 C, or 20 C) for 7 d showed RS contents to reach a maximum between 2 and 4 d at all storage temperatures, after which they decreased (Niba 2003). Lowest RS levels in whole corn bread were found after storage at 20 C (2.18
g/100 g) for 7 d.
A comparison of masa and fresh and stored tortillas from common and Costeno corn varieties showed that Costeno had higher
digestible starch and total dietary fiber contents than its common
counterpart. During storage of both types of tortilla, digestible
starch contents decreased, whereas those of RS starch increased
(Mora-Escobedo and others 2004). Studies on the influence of
cold storage on in vitro starch digestibility of tortillas showed a
decrease in available starch content in tortillas after 48 h of cold
storage, which was concomitant with increased total RS levels
(Agama-Acevedo and others 2004). These changes were due
mainly to retrogradation, as indicated by increased retrograded
resistant starch (RRS) levels which accounted for the major portion
of the total RS. Although amylolysis patterns for fresh and 72 h
stored tortillas were similar, lower digestion rates were observed
for stored samples.
RS contents of gelatinized samples of corn, ragi, rice, sago, and
potato flours increased on low-temperature storage and de-

Vol. 5, 2006COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY

CRFSFS: Comprehensive Reviews in Food Science and Food Safety


creased on reheating the samples. Cooked food samples of rice,
unleavened bread, potato, Bengal gram, and green gram also
showed increased RS formation on storage. There was no significant increase in RS content of stored decorticated legumes (bengal gram, green gram, and red gram), whereas horse gram and
lentils showed lesser RS on storage in comparison with fresh samples. Increase in RS was reported for gelatinized samples of corn,
wheat, ragi, rice, sago, and potato flours on low-temperature storage. A 27% increase in RS of cooked rice was observed when
stored at 4 C (Johansson and Siljestrom 1984). The longer the duration of storage of gelatinized wheat flour, the greater was the formation of RS (Kavita and others 1998). Rice stored at 20 C retrograded more than rice stored in the refrigerator (Mitsuda 1993).

Preparation of RS
RS can be prepared by using heat treatment, enzyme treatment,
combined heat treatment and enzyme treatment, and chemical
treatment.
Heat treatment

Heat treatment of starch to various extents leads to formation of


RS. RS can be obtained by cooking the starch above the gelatinization temperature and simultaneously drying on heated rolls like
drum driers or even extruders. The gelatinization of starch granules by heat processing strongly influences their susceptibility to
enzymatic hydrolysis. In a high-moisture environment, amylose
leaches from the granules, increasing the solubility of starch and
thereby its susceptibility (Holm and others 1988).
Good yields of RS can be obtained by gelatinizing starch at
120 C for 20 min, followed by cooling to room temperature (Garcia-Alonso and others 1999). The starch gels are then frozen overnight at 20 C and dried at 60 C before milling.
Many combinations of time and temperature treatments have
been used to make type III RS from various sources of native
starch. Even for starches with normal amylose levels, it is recognized that cooking at >100 C can increase the yield of type III RS.
The temperature treatments have included autoclaving the starch
at 110 C (Berry 1986), at 121 C (Berry 1986; Bjorck and others
1987; Sievert and Pomeranz 1989; Sievert and Wursch 1993b), at
127 C (Berry 1986; Bjorck and others 1987), at 134 C (Berry
1986; Bjorck and others 1987; Russell and others 1989; Sievert
and Pomeranz 1989), or at 148 C (Sievert and Pomeranz 1989)
for periods ranging from 30 min to 1 h.
An enzyme-RS type III, which has a melting point or endothermic
peak of at least about 140 C, as determined by differential scanning calorimetry (DSC) can be produced in yields of at least 25%
by weight, based on the weight of the original starch ingredient
(Haynes and others 2000). A gelatinization stage, nucleation/propagation stage, and preferably a heat-treatment stage are required to
produce reduced calorie starch-based compositions that contain
the enzyme-resistant starch. It is produced using crystal nucleation
and propagation temperatures, which avoid substantial production
of lower melting amylopectin crystals, lower melting amylose crystals, and lower melting amylose-lipid complexes. The nucleating
temperature used is above the melting point of the amylopectin
crystals. The propagating temperature used is above the melting
point of any amylose-lipid complexes but below the melting point
of the enzyme RS. The high melting point of the enzyme RS permits
its use in baked good formulations.
Partial acid hydrolysis (PAH) of a high-amylose corn starch (aeVII) enhances the effects of hydrothermal treatments used to produce granular RS, which is stable to further heat treatment at atmospheric pressure (Brumovsky and Thompson 2001). PAH of
ae-VII starch involved heating 35% (w/v) starch suspensions with
1% (w/w) HCl at 25 C for up to 78 h. PAH followed by heat mois10

ture treatment tended to increase yield of boiling-stable granular


RS to the maximum of 63.2%.
Selective heat treatment of high amylose starch in the presence
of agents inhibiting the swelling of starch like alkali and alkaline
earth metal salts of halides, sulfates, and phosphates yield granular RS with high dietary fiber.
Recently, pyrodextrinization has been recognized as a way of
producing a RS that is water-soluble and has non-starch linkages
(Laurentin and Edwards 2004). Pyroconversion refers strictly to the
modification of dry starch through heat treatments, with or without
addition of acids. Acids used include hydrochloric acid at 0.15%
(based on starch dry weight) and orthophosphoric or sulfuric acids
at 0.17% (Wurzburg 1995). Commercial pyrodextrins are generally
produced by heating dry, acidified starch in a reactor with agitation.
Acid may be sprayed on the starch to facilitate hydrolysis and transglycosidation. Depending on reaction conditions, pyroconversion
produces a range of products that vary in digestibility, available
starch, viscosity, cold-water solubility, swelling power, color, and
stability (Ohkuma and Wakabayashi 2001). The production of indigestible dextrins or pyrodextrins by heat-treating potato starch in
the presence of an acid and then refining the product has been described (Ohkuma and others 1994, 1995).
Enzymic treatment

The possibility of preparing a RS concentrate from isolated pea


starch was investigated, and sorption of hydrophobic substances
(indicative of health-benefiting properties) by such a concentrate
was studied by Soral and Wronkowska (2000). By use of a thermally stable -amylase, a preparation of up to 70% RS containing a
mixture of mineral and organic N compounds was obtained. The
pea RS concentrate had an affinity to bile acid, deoxycholic, and
cholesterol; however, its affinity to cholesterol was not as efficient as
that of native pea starch. The results concluded that the pea RS concentrate may be potentially used as a food component in special
diets, or for preventive, prophylactic, and therapeutic purposes.
Readily fermentable heat-stable RS of optimal chain length from
poly-1,4--D-glucan useful in various functional foods can be
obtained by in vitro synthesis by adding an enzyme extract containing the amylosucrase of Neisseria polysaccharea to sucrose
solutions, followed by incubation at 37 C over several hours
(Buttcher and others 1997).
A method has been discovered to produce an RS product that
retains the same cooking quality as found in untreated rice starch
or flour, but has a higher percentage of starch resistant to -amylase digestion (King and Tan 2005). This method uses a debranching enzyme, that is, pullulanase, to digest the starch, but does not
require pretreating the starch source before enzymatic treatment.
This method produced RS from low amylose starches, rice starch
(24%), and rice flour (20%). Surprisingly the RS product formed
by this method retained the pasting characteristics of the untreated flour or starch and was heat stable. This method may also be
used to produce RS from other botanical sources, that is, corn,
wheat, potato, oat, barley, tapioca, sago, and arrowroot.
Heat and enzyme treatment

Preparation of RS to be used as a food-grade bulking agent, by


retrogradation of starch followed by enzymatic or chemical hydrolysis to reduce or remove the amorphous regions of retrograded starch (Iyengar 1991). RS can be prepared from high amylose
starch by gelatinization followed by treating the slurry with debranching enzymes like pullulanase and isolating the starch product by drying/extrusion. Controlled heat treatment of starch so as
to achieve swelling and at the same time retain its granular structure followed by enzymatic debranching (Haralampu and Gross
1998) and annealing at suitable temperature followed by drying
produces RS. These RS find applications in a variety of foods and

COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 5, 2006

Resistant starch - a review


beverage products.
Purified RS products having at least 50% RS content can be
produced by forming a water-starch suspension wherein the ratio
of starch to water is approximately 1:2 to 1:20, heating the waterstarch suspension in an autoclave at temperatures above 100 C.
to ensure full starch gelatinization and then cooling to allow amylose retrogradation to take place. It is reported that best results
were obtained at a temperature of 134 C, with 4 heating and
cooling cycles and a starch:water ratio of 1:3.5. The RS was purified by comminuting the starch gel and mixing it with an amylase
to digest non-RS fractions, leaving RS. The amylase is inactivated
by heat treatment above 100 C (Pomeranz and Sievert 1990).
For the preparation of a fragmented starch precipitate for use in
reduced-fat foods, a debranched amylopectin starch is precipitated
and then fragmented. The debranched amylopectin starch may be
derived from a starch that contains amylopectin, for example, common corn starch and waxy maize starch, by gelatinizing the starch,
followed by treatment with a debranching enzyme, such as
isoamylase or pullulanase, and precipitation of the debranched
starch. To form the precipitate, the solution is cooled to ambient
temperature, to reduce the solubility of the debranched starch. The
precipitate may then be heated to about 70 C, while in contact
with a liquid medium, to dissolve at least a portion of the precipitate. Reprecipitation by cooling of the suspension/solution may
then be employed. Repetition of the dissolving and the reprecipitation tends to improve the temperature stability of the resulting aqueous dispersion as was observed on repeating the cycle of heating
and cooling, a total of 8 times (Harris and others 1994, 1995).
A process for increasing the amount of amylase-RS (to a minimum of 15%) in high amylose starch, such as Hylon V or Hylon
VII consisted essentially of gelatinization of a starch slurry, enzymic debranching of the starch, and isolation of the starch product
by extrusion or drying. A further increase in amylase-resistant
starch was obtained by addition of an inorganic salt to debranched starch before isolation (Chiu and others 1994).
Chemical treatment

In type IV RS, the enzyme resistance is introduced by modifying


the starch by crosslinking with chemical agents (Haynes and others
2000). Crosslinked starches are obtained by the reaction of starch
with bi- or polyfunctional reagents like sodium trimetaphosphate,
phosphorus oxychloride, or mixed anhydrides of acetic acid and
dicarboxylic acids like adipic acid. Cross-linking carried out by sulphonate and phosphate groups between various starch molecules
involves their hydroxyl group thus bringing resistance to amylolytic
attack on the starch molecule. Figure 9 shows the preparation of
distarch phosphate ester (Hamilton and Paschall 1967).
Distarch phosphates with 0.4% to 0.5% phosphorus have been
prepared and they contain both slowly digested starch (SDS) and
RS4 (Woo and others 1999). The modified starches were obtained
in quantitative yield, and provided 13% to 69% of SDS and 18%
to 87% RS4. RS4 starches with low swelling power have also been
prepared similarly from wheat, corn, waxy corn, high amylose
corn, oat, rice tapioca, mung bean, banana, and potato starches.
Phosphated di-starch phosphate, a modified RS made from high
amylose maize starch, is currently used as food additive (E1413)
in the EU.

Determination of RS
In vitro methods

The main step of any method to measure the content of RS in


foods must first remove all of the digestible starch from the product
using thermostable -amylases (McCleary and Rossiter 2004). At
present, the method of McCleary and Monaghan (2002) is consid-

ered the most reproducible and repeatable measurement of RS in


starch and plant materials, but it has not been shown to analyze all
RS as defined (Champ and others 2003). It is based on the principle
of enzymic digestion and measures the portions of starch resistant
to digestion at 37 C that are typically not quantitated due to the gelatization at 100 C followed by digestion at 60 C.
Two general methods specifically proposed to determine RS
(Berry 1986; Englyst and others 1992) remove digestible starch
using different amylases, and the residual fraction is quantified after solubilization in 2M KOH.
The Siljestrom and Asp (Siljestrom and Asp 1985) procedure includes preparation and quantification of dietary fiber residue before RS determination. This is usually done by drying the samples
at 105 C. As heating influences the RS content in foods, results
may be modified by this step.
A modified method for measuring RS in dietary fiber residues
from various sources developed by Saura-Calixto and others
(1993) involves mixing fiber residues with KOH, acetate buffer,
and HCl. After incubation with amyloglucosidase samples are
centrifuged and diluted with distilled water. RS is calculated as
glucose (mg) 0.9. Advantages of the method are the use of small
amount of sample, less reagents and elimination of drying.
In vivo methods

Different methods are used to analyze RS in vivo.


One of the ways to assay RS physiologically is to determine
starch in the undigested ileal content. Terminal ileal samples can
be recovered by intubation or from ileostomy bags. The classic
way to substantiate starch digestion is by measuring the glycemic
index as described by Jenkins and others (1981). This implies
measuring the area under the curve (AUC) of the serum glucose
concentration over the first 2 h after administering a starch and dividing this by the serum glucose response after consumption of
an equal amount of glucose.
Determination of breath hydrogen (breath tests) can also be
used as a semiquantitative measurement for RS. In a study on effect of RS on human colon, increased fermentation was verified
by elevated breath hydrogen excretion (Hylla and others 1998).
From the different animal models, the antibiotic-treated rat model
is the one commonly used (Gudmand-Hoyer 1991).

Digestibility, energy value, and RDA of RS


RS is highly resistant to mammalian enzymes. In cereal products,
the RS fraction is not digestible both in vitro and in vivo (Bornet
1993). Four different RS fractions have been identified in cereal
products: native starch, retrograded amylose, the amylo-lipid complex, and encapsulated gelatinized starch. After reaching the large
intestine, the RS fractions are fermented by the colonic flora, resulting in short-chain fatty acids (SCFA). SCFA profiles derived from RS
are lower in acetate and higher in butyrate than those of conventional fibers. The SCFA are an energy source for colonic cells (butyrate) and to the body as a whole (acetate and propionate).
Maize starch acylated with acetic, propionic, or butyric anhydride are also RS and raise large bowel SCFA, apparently through
bacterial release of the esterified fatty acid and fermentation of the
residual starch (Annison and others 2003). Some sources of RS
seem to be less available for fermentation, as has been observed
in some chemically modified starches as well as RS in arepa (high
corn meal bread). Feeding trials on Himalaya 292, a hulless barley
cultivar with a higher RS content, also have resulted in high levels
of SCFA in feces (Bird and others 2004).
Most studies indicate that 30% to 70% of RS is metabolized
(Ranhotra and others 1991a; Behall and Howe 1995; Behall and
Howe 1996; Cummings and others 1996; Ranhotra and others
1996), while the balance is excreted in the feces. The variability is

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CRFSFS: Comprehensive Reviews in Food Science and Food Safety


largely due to effects caused by the malabsorption of the ingested
starch. In human subjects, replacement of 27 g of digestible starch
by RS (raw potato starch) in a single meal lowered diet-induced
thermogenesis by an average of 90 KJ/5 h (Heijnen and others
1995). A study was designed to compare the metabolizable energy of 2 starch sources, standard cornstarch and high amylose
cornstarch (Behall and Howe 1996). Based on energy intake and
fecal excretion from all subjects, the partial digestible energy value
for the RS averaged 11.7 KJ/g RS, which was 67.3% of the energy
of standard cornstarch. Control and hyperinsulinemic subjects
differed in their ability to digest RS, averaging 81.8% and 53.2%,
respectively. RS averaged 2.8 kcal/g for all subjects but only 2.2
kcal/g in the hyperinsulinemic subjects. This enables the use of RS
in reducing the energy value of foods.
Approximately 20 g/d is recommended to obtain the beneficial
health benefits of RS. However, worldwide, dietary intakes of RS
are believed to vary considerably. It is estimated that intakes of RS
in developing countries with high starch consumption rates range
from approximately 30 to 40 g/d (Baghurst and others 2001). Dietary intakes in India and China were recently estimated at 10 and
18 g/d (Platel and Shurpalekar 1994; Muir and others 1998). Intakes in the EU are believed to lie between 3 and 6 g/d (Dyssler
and Hoffmann 1994). Dietary intakes of RS in the U.K. are estimated at 2.76 g/d (Tomlin and Read 1990) and are believed to range
from 5 to 7 g/d in Australia (Baghurst and others 2001). In Sweden, the daily RS intake is estimated to be 3.2 g (Liljeberg 2002).
In New Zealand, RS intakes have been approximated to be 8.5 g/d
and 5.2 g/d in 15- to 18-year-old males and females, respectively
(Baghurst and others 1996).

ing in preventing colonic cancer (Asp and Bjorck 1992).


Significant changes in fecal pH and bulking as well as greater
production of SCFA in the cecum of rats fed RS preparations have
been reported (Ferguson and others, 2000), which have been
suggested to resemble the effects of soluble dietary fiber. However,
when RS was combined with an insoluble dietary fiber like wheat
bran, much higher SCFA levels, in particular butyrate was observed in the feces (Leu and others 2002). In rats, when RS was
combined with psyllium, the site of RS fermentation was pushed
more distally. As the distal colon is the site where most tumors
arise it may be of additional benefit for cancer protection if fermentation is further enhanced within the distal colon (Morita and
others 1999).
Hypoglycaemic effects

A number of physiological effects have been ascribed to RS


(Nugent 2005), which have been proved to be beneficial for
health.

Foods containing RS moderate the rate of digestion. The slow


digestion of RS has implications for its use in controlled glucose
release applications. The metabolism of RS occurs 5 to 7 h after
consumption, in contrast to normally cooked starch, which is digested almost immediately. Digestion over a 5- to 7-h period reduces postprandial glycemia and insulinemia and has the potential for increasing the period of satiety (Raben and others 1994;
Reader and others 1997).
A study using 10 healthy normal-weight males fed test meals
containing either 50 g starch free of RS (0% RS), or 50 g starch
containing a high level of RS (54% RS) proved the ability of high
RS meals to significantly lower the postprandial concentration of
blood glucose, insulin, and epinephrine (Raben and others
1994). Similarly, from a human study (Reader and others 1997),
using a commercial RS3 ingredient (CrystaLean ), the maximum
blood glucose level was found to be significantly lower than that
of other carbohydrates (simple sugars, oligosaccharides, and
common starch). The RS3-containing bar decreased postprandial
blood glucose and may play a role in providing improved metabolic control in type II diabetes (non-insulin dependent).

RS as a component of DF

As a prebiotic

RS appears to be highly resistant to mammalian enzyme and


may be classified as a component of fiber on the basis of the recent definitions of dietary fiber given by AACC (2000) and NAS
(2002). While part of the RS may consist of low-molecular-weight
dextrins, the bulk consists of polymers, of which retrograded amylose often forms the major fraction (Ranhotra and others 1991a).
Although not a cell wall component, RS is obviously nutritionally
more similar to NSP than to digestible starch. There is ample justification that RS behaves physiologically like fiber. RS assays as insoluble fiber, but has the physiological benefits of soluble fiber.
Additionally, RS exhibits a level of slow digestibility and can be
used as a vehicle for the slow release of glucose. Also, like soluble fiber, it has a positive impact on colonic health by increasing
the crypt cell production rate, or decreasing the colonic epithelial
atrophy in comparison with no-fiber diets. There is indication that
RS like guar, a soluble fiber, influences tumorigenesis, and reduces serum cholesterol and triglycerides. Overall, since RS behaves
physiologically as a fiber, it should be retained in the TDF assay
(Haralampu 2000).

RS has been suggested for use in probiotic compositions to


promote the growth of such beneficial microorganisms as Bifidobacterium (Brown and others 1996). Since RS almost entirely
passes the small intestine, it can behave as a substrate for growth
of the probiotic microorganisms.

Beneficial physiological effects of RS

Reduction of gall stone formation

The digestibility of starch in rice and wheat is increased by milling to flour (Heaton 1988). Digestible starch contributes gall stone
formation via a greater secretion of insulin and insulin in turn
leads to the stimulation of cholesterol synthesis. RS is found to reduce the incidence of gallstones (Malhotra 1968). Gallstones are
less in South India where, whole grains are consumed rather than
as flour in Northern India. Notably, dietary intake of RS is 2- to 4fold lower in the United States, Europe, and Australia, compared
with populations consuming high-starch diets, such as India and
China, which may reflect in the difference in the number of gallstone cases in these countries (Birkett and others 2000).
Hypocholesterolaemic effects

Prevention of colonic cancer

Starch unabsorbed in the small intestine is fermented by the microflora of the large intestine. Generally, starch is not present in
the feces of humans or experimental animals, indicating more or
less complete fermentation. In vitro experiments with human fecal
inocula have shown that the butyrate yield from starch is high. As
butyrate is a main energy substrate for large intestinal epithelial
cells and inhibits the malignant transformation of such cells in vitro; this makes easily fermentable RS fractions especially interest12

Hypocholesterolemic effects of RS have been amply proved. In


rats, RS diets (25% raw potato) markedly raised the cecal size and
the cecal pool of short-chain fatty acids (SCFA), as well as SCFA
absorption and lowered plasma cholesterol and triglycerides.
Also, there was a lower concentration of cholesterol in all lipoprotein fractions, especially the HDL1 and a decreased concentration
of triglycerides in the triglyceride-rich lipoprotein fraction.
Results of feeding trials on rats using RS from Adzuki starch (AS)
and tebou starch (TS) suggested that AS and TS had a serum cho-

COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 5, 2006

Resistant starch - a review


lesterol-lowering function due to the enhanced levels of hepatic
SR-B1 (scavenger receptor class B 1) and cholesterol 7-hydroxylase m RNA (Han and others 2003). The bean starches lowered
the levels of serum total cholesterol and VLDL + IDL + LDL cholesterol, increased caecal concentration of short-chain fatty acids
(in particular butyric acid concentration), and increased faecal
neutral sterol excretion.
From studies on hamsters fed diets containing cassava starch
extrudated with 9.9% oat fiber or cassava starch extruded with
9.7% RS, hypocholesterolemic properties of both were demonstrated suggesting their use in foods to improve cardiovascular
health (Martinez and others 2004).

High amylose corn starch (HACS) coatings with RS at 20% to


24% showed excellent properties useful for tablet coatings (Dimantov and others 2004).
Hydrolyzed starches (those which retain their granular structure
and essentially behave like unmodified starches in undergoing
gelatinization on heating), which are also referred to as thin boiling starches, are also a form of RS. The advantage of this starch is
the high concentration, which can be used as a paste of low viscosity and its ability to set as a firm gel (Seib and Kyungsoo 1999).
Cross-linked starches based on maize, tapioca, potato of RS4
type have been useful in formulations needing pulpy texture,
smoothness, flowability, low pH storage, and high temperature
storage (Sajilata and Singhal 2005).

Inhibition of fat accumulation

Replacement of 5.4% of total dietary carbohydrates with RS in a


meal could significantly increase postprandial lipid oxidation suggesting reduction in fat accumulation in the long term (Higgins
and others 2004).
Absorption of minerals

A study to compare the intestinal apparent absorption of calcium, phosphorus, iron, and zinc in the presence of either resistant
or digestible starch brought out that a meal containing 16.4% RS
resulted in a greater apparent absorption of calcium and iron
compared with a completely digestible starch (Morais and others
1996). Thus RS could have a positive effect on intestinal calcium
and iron absorption.

Undesirable manifestations of RS
Some undesirable manifestations of RS are also seen in clinical
studies (Reussner and others 1963). One of the most alarming influences is the cecal enlargement, especially in rats. But, in humans, it is said to be of little relevance because of the considerably smaller size and weight of cecum as well as its smaller role in
the human physiological function. Pelvic nephrocalcinosis is another phenomenon observed in rats especially those fed with
mono substituted cross-linked starches and mono substituted
starches (Baley and others 1973).

Applications of RS
The industrial applications of RS are mainly in the preparation
of moisture-free food products (Yue and Waring 1998). Bakery
products such as bread, muffins, and breakfast cereals can be
prepared by using RS as a source of fiber. The amount of RS used
to replace flour depends on the particular starch being used, the
application, the desired fiber level, and, in some cases, the desired structure-function claims. From a quality standpoint, some
applications are more sensitive to flour replacement than others.
For example, bread and rolls, which generally have a bland flavor,
are low-fat and require a minimum amount of gluten for structure;
the maximum flour replacement is typically 10% to 20% without
noticeably changing the texture.
A type III enzyme-RS with a melting point of at least 140 C,
which could be used as a low-calorie flour replacer in bakery
products exhibits baking characteristics (cookie spread, golden
brown color, pleasant aroma, surface cracking) comparable to
those achieved using conventional wheat flour (Haynes and others 2000).
Excellent quality sponge cakes have been prepared by replacing 30% of flour with 4 cycled autoclaved-cooled RS3 corn starch
(RS3), cross-linked maize starch (RS4) and annealed and crosslinked RS4 maize starch (ARS4) while for yellow layer cake, the replacement level was found to be at 12.5% (Po and others 1994;
Myung-Hee-Kim and others 2001).

Commercial sources of RS
In the commercial development of RS, it is advantageous to start
with a native starch high in amylose. Nearly all patented processes are based on the propensity of high-amylose starch to retrograde, or form highly crystalline regions, which are resistant to enzymatic hydrolysis (Crosby 2001). High-amylose maize starches
have high gelatinization temperatures, requiring temperatures that
are often not reached in conventional cooking practices (154 C
to 171 C) before the granules are completely disrupted. These
starches offer an opportunity to manipulate the amount of RS
present in food products.
The first commercial RS was introduced as Hi-maize in Australia
in 1993 by Starch Australasia, now part of Natl. Starch and Chemical Co. This product is a natural granular form of starch produced
from a corn hybrid containing more than 80% amylose. Hi-maize
analyses as 42% RS and has gained widespread use in Australia
in breads and other baked goods.
Commercial sources of RS (Ranhotra and others 1996), such as
CrystaLean (Opta Food Ingredients, Inc., Bedford, Mass., U.S.A.),
Novelose (Natl. Starch and Chemical Co., Bridgewater, N.J.,
U.S.A.) and Amylomaize VII (Cerestar Inc., Hammond, Ind.,
U.S.A.) are now available to increase the DF content in foods and
provide other functional properties. CrystaLean is a commercial, highly retrograded RS3 based on the aeVII hybrid. It is produced by first fully hydrating and disrupting the starch granules,
followed by an enzymatic debranching of the amylopectin to
yield a low DE maltodextrin mixture, which is almost entirely a
straight chain. Then, the mixture is treated through thermal cycles
to achieve a high level of retrogradation before drying. CrystaLean containing 41% RS is digested slowly, at approximately half
the rate of maltodextrin. The ingredient was introduced in the early 1990s and is now used in products for diabetics.
Shortly after the launch of CrystaLean, Natl. Starch introduced a
very similar product named Novelose 330. More recently, Natl.
Starch Chemical Co. has developed processes for manufacturing
granular forms of concentrated RS containing 47% to 60% RS by
heating and cooling high-amylose corn starch under conditions
of carefully controlled moisture and temperature. These products
are marketed as Novelose 240 and 260. Novelose 240 is a thermally modified RS2 based on ae-VII hybrid of corn (Shi and Trzasko 1997). The modification renders the native granule more stable
by holding the starch at elevated temperature (60 C to 160 C) in
the presence of limited water (10% to 80%). Novelose 260 contains 60% TDF, the highest level available in a RS. It can be formulated into a broad range of foods such as pasta, cereals, and
snack foods that can carry a rich-in-fiber labeling. Novelose 240
(RS2), 260 (RS2), and 330 (RS3) have melting temperatures of
99.7 C, 114.4 C, and 121.5 C, respectively. These products offer medium/high, high, and very high process tolerance and are
therefore suitable for use in a variety of processed foods. Another
player is Cerestar (a Cargill company), which has launched Ac-

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CRFSFS: Comprehensive Reviews in Food Science and Food Safety


tistar containing 58% RS, made by crystallizing hydrolyzed tapioca starch (maltodextrins).
High-amylose corn (amylomaize) is the generic name for corn
that has an amylose content higher than 50%. The endosperm
mutant amylose-extender (ae) increases the amylose content of
the endosperm to about 60% in many dent backgrounds. Modifying factors alter the amylose contents as well as desirable agronomic characteristics of the grain. The amylose-extender gone expression is characterized by a tarnished, translucent, sometimes
semi-full kernel appearance. U.S. production of high-amylose
corn is forecasted at 50000 acres for 2001. 100% of this product
is grown under contract in Indiana for Cerestar and Pioneer. Highamylose corn yields vary, depending upon location, but average
only 65% to 75% of that of ordinary dents. Three types are produced commercially: Class V (50% to 60% amylose) and Class VII
(70% to 80% amylose), and Class IX (90% amylose).
C*ActiStar (Cerestar Food and Pharma Specialties) is made from
native, partially hydrolyzed starch by generating microscopic
structures that are not hydrolyzed by digestive enzymes in the
small intestine (58% RS). The specific structure of C*ActiStar favors
its fermentation to butyrate and helps to reach the lower parts of
the large bowel, which is the most relevant segment of the colon
for the gut health maintenance. It can be used in a variety of foodstuffs such as bread, cereal bars, biscuits/cookies, muesli, low-fat
fermented milk, UHT flavored milk drinks, and ready-to-use powdered mixes such as instant soups and instant chocolate. With
C*ActiStar, each serving can provide a significant amount of RS,
which will contribute to an increase in the pre-existing daily intake of RS. MGP Ingredients, Inc. (Atchison, Kans.) and Cargill
have announced a business alliance for the production and marketing of a new RS product called FibersymTM HA that is derived
from high-amylose corn and ideal for use in a wide array of lower
net carbohydrate food products. Delivering more than 70% dietary fiber, it greatly reduces net carbohydrate levels in foods. Applications cover a wide variety of products, including breads, tortillas, pizza crust, cookies, muffins, waffles, breakfast cereals,
snack products, and nutritional bars. FibersymTM HA joins MGPIs
other resistant starches, which include a wheat-based RS, FibersymTM 70 and a potato-based variety, FibersymTM 80 ST.
Roquette (Roquette, Freres, France) recently developed Nutriose
FB, a new dextrin that offers all the benefits of RS and, in addition, is
a soluble fiber. Because it is only slightly digested in the small intestine and then slowly fermented in the colon, it fits the functional
pattern of RS with a low glycemic response. Fibersol-2, offered
through a joint venture of ADM and Matsutani, is a digestion-resistant maltodextrin. Resistant starches that test high in TDF such as
Roquettes Nutriose FB 06 at 85% fiber content or ADM/Matsutanis
Fibersol-2 at 90% make it possible to enrich products with fiber to
optimum recommended levels and to support label claims.
Research is intensifying regarding RS4 starches created using difunctional phosphate reagents, available for inclusion in foods.
However, as yet there is a lack of information regarding their potential clinical and physiological effects (Brown 2004). As RS is included within the definitions of dietary fiber by the AACC (Anon 2000;
Jones 2000), the Inst. of Medicine of the Natl. Academies (Inst. of
Medicine 2002), and is measured within the remit of the AOAC
method (Prosky and others 1985), which is used in the United
States, U.K., Australia, and Japan, commercially manufactured
sources of RS can be used as vehicles to increase the total dietary fiber content of foods and food products without affecting taste and
texture (Liversey 1994). They may also be used to provide fiber in
some commercially available low-carbohydrate foods marketed for
those following low-carbohydrate dieting regimens.
There are a number of advantages to using commercially manufactured RS in food products. Unlike natural sources of RS (that is,
legumes, potatoes, bananas), commercially manufactured RS are
14

not affected by processing and storage conditions. For example,


the amount of RS2 in green bananas decreases with increasing
ripeness; however, a commercial form of RS2, Hi-maize, does not
experience these difficulties. Among the newest developments in
resistant starches is an RS2 that remains resistant after mild food
processing (Novelose 240). Compared with conventional fibers, it
has many advantageous features. It is white and has a bland flavor
and a fine particle size between 10 and 15 m. It also has a reduced caloric content and may be used as a bulking agent to
complement reduced sugar or reduced-fat formulations. With a
TDF content of approximately 40%, this RS2 can be used alone or
as a functional complement to other fiber sources and can be labeled simply as cornstarch. Most importantly, the commercial
RS has a much lower water-holding capacity than do various traditional fibers. Because it absorbs less water, adjustments in product formulations and processing are substantially minimized.
In general, RS has many properties, which outweigh the disadvantages posed by it. Therefore, for deriving maximum benefits
from RS and minimizing undesirable effects of RS, it becomes essential to regulate the quantity of RS to be used.
Process tolerance needs to be considered when selecting and
using RS for a particular application (www.nstarch.com). The majority of commercial RS on the market will retain their dietary fiber
through typical baking processes and even mild extrusion. However, extreme processing conditions may damage the RS, resulting
in a loss of dietary fiber. Formulators should therefore analyze finished foods made with processes involving extremely high temperatures, pressure, and/or shear to verify the level of dietary fiber.
RS is well-suited for low-moisture food systems where they can
be used at very high levels compared to traditional starches. The
majority of the commercially available RS rely on intact granules or
compact crystalline regions with high melting temperatures to resist
digestion. Therefore, these products generally will not swell or contribute viscosity during most processing. Essentially insoluble, RS
would not replace viscosifying starch in liquid applications.

Conclusions
RS has received much attention for both its potential health
benefits and functional properties. As a functional fiber, its fine
particles and bland taste make possible the formulation of a number of food products with better consumer acceptability and
greater palatability than those made with traditional fibers. RS
shows improved crispness and expansion in certain products and
better mouthfeel, color, and flavor over products produced with
some traditional, insoluble fibers. It is ideal for use in RTE cereals,
snacks, pasta/ noodles, baked goods, and fried foods and permits
for easy labeling as simply starch, conferring additional nutraceutical benefits. Being nondigestible, RS can be used in reduced-fat
and sugar formulations. RS has properties similar to fiber and
shows promising physiological benefits in humans, which may
result in disease prevention. Foods containing high levels of RS
yield fewer calories and lower glycaemic loadsimportant formulation considerations for diabetics as well as the weight-conscious. It is classified as a fiber component with partial or low fermentation. Technically, it is possible to increase the RS content in
foods by modifying the processing conditions such as pH, heating temperature and time, number of heating and cooling cycles,
freezing, and drying. A number of commercially available RS
preparations would make it possible for a wide range of applications with nutraceutical implications.

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