Professional Documents
Culture Documents
Molecular Basis
and Control
J.A. Gray and J.N. Bemiller
ABSTRACT: The molecular basis of staling is examined by reviewing what is known about the components of wheat flour,
factors that affect staling rate, and the various mechanisms that have been proposed. The conclusion reached is that bread
staling is a complex phenomenon in which multiple mechanisms operate. Polymer crystallizations with the formation of
supermolecular structures are certainly involved. The most plausible hypothesis is that retrogradation of amylopectin
occurs, and because water molecules are incorporated into the crystallites, the distribution of water is shifted from gluten
to starch/amylopectin, thereby changing the nature of the gluten network. The role of additives may be to change the
nature of starch protein molecules, to function as plasticizers, and/or to retard the redistribution of water between
components. Nothing more definite can be concluded at this time.
Introduction
Although it has been studied for more than a century and a
half, bread staling has not been eliminated and remains responsible for huge economic losses to both the baking industry and the
consumer. Bechtel and others (1953) defined staling as a term
which indicates decreasing consumer acceptance of bakery products caused by changes in crumb other than those resulting from
the action of spoilage organisms. While an American Association
of Cereal Chemists Approved Method (AACC Method 74-30;
AACC 2000) quantifies staling organoleptically, many researchers
use the 1953 definition as a general definition and describe specific components of the complex staling process with specific
terms such as crumb firming, crust staling, and organoleptic staling (Kulp and Ponte 1981). In fact, the most widely used indicator
of staling is measurement of the increase in crumb firmness (see
Rheological methods: Uniaxial compression section), which is
the attribute most commonly recognized by the consumer. In this
review, the term bread staling is used to refer to the phenomenon of crumb firming in white pan bread.
Bread is an unstable, elastic, solid foam, the solid part of which
contains a continuous phase composed in part of an elastic network of cross-linked gluten molecules and in part of leached
starch polymer molecules, primarily amylose, both uncomplexed
and complexed with polar lipid molecules, and a discontinuous
phase of entrapped, gelatinized, swollen, deformed (wheat) starch
granules. Neither the bread system nor the staling process is understood well at the molecular level. Even simple bread dough
formulations contain several ingredients, which themselves may
contain several components, each of which may undergo changes during the breadmaking process and during aging of the final
product. And just as bread is a complex, heterogeneous system,
the staling phenomenon seems to be complex, because investigation of hypotheses involving changes in 1 or 2 components have
failed to fully explained the process.
Because the literature on bread staling is so extensive, any re 2003 Institute of Food Technologists
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To understand the mechanism of staling in breads, it is important to understand the natures of the major components that make
up the system. Relationships of these components to staling are
described in Section 2.2. The role of water and additives in staling
are discussed in Sections 3 and 4.
A typical bread formula consists of the following ingredients:
flour (wheat), water, sugar, shortening, nonfat dried milk (or a substitute), salt, yeast, malt, a dough strengthener, a crumb softener, a
mold inhibitor (sodium propionate), and an oxidant (Hoseney
and Seib 1978). Wheat flour consists primarily of gluten, starch,
and pentosans (primarily arabinoxylans), all of which are important contributors to the characteristics of the process and the final
product. Native flour lipids play an important role in breadmaking
(Morrison 1976), especially in their interaction with added shortening (Rogers and others 1988). Wheat flour has considerable amylase activity and a minor amount of -amylase activity.
States of the starch, gluten, and polar lipids in the 3 main stages
in the life of aged bread are outlined in Table 1.
Protein. Hydrated gluten is the continuous phase of wheat flour
doughs (Ponte and Faubion 1985; Davies 1986). During baking,
gluten is denatured, and protein-protein crosslinking occurs via
formation of disulfide bonds (Schofield 1986). The resulting network, combined with partially gelatinized starch granules, is most
certainly responsible for the semirigid structure of baked products
(Blanshard 1988; Hoseney 1989).
Starch. Wheat flour contains 84 to 88% (db) starch. During
baking of bread dough, the starch granules are generally gelatinized (Table 1, footnote c), but little else other than restricted
swelling followed by collapse happens to them because of the
limited amount of water present in the dough system (Schoch
1965), so deformed wheat starch granules can be isolated from
the crumb (Hoseney and others 1978). [Note: When starch granules are heated in excess water, granules swell and some portion
of the amylose diffuses from the granules, concentrates in the interstitial water between granules, and undergoes retrogradation.
The small amount of amylose that leaches from granules during
baking in the limited moisture system of bread dough retrogrades
upon cooling and rapidly becomes unextractable (Kim and
DAppolonia 1977b,c); so even if amylose does leach from granules, by the time bread has completely cooled, any interstitial
amylose will have retrograded (that is, become insoluble) and is
unlikely, therefore, to play a major role in subsequent staling
events.] Even in the presence of excess water, monoglycerides
block the leaching of amylose molecules (Schoch 1965; see Surface-active lipids: Surfactants section), so it can be assumed that
other surfactants would act in the same way, especially in the limited moisture system of bread. Therefore, freshly baked and
cooled bread is an elastic system containing swollen wheat starch
granules that are still largely intact, but may be deformed.
On the other hand, observations made with transmission elec2
Attention is called to another review on the mechanism of staling (Schiraldi and Fessas 2001). Bread staling falls into 2 categories: crust staling and crumb staling. Crust staling is generally
caused by moisture transfer from the crumb to the crust (Lin and
Lineback 1990), resulting in a soft, leathery texture and is generally less objectionable than is crumb staling (Newbold 1976).
Crumb staling is more complex, more important, and less understood. The firmness of bread varies with position within a loaf,
with maximum firmness occurring in the central portion of the
crumb (Short and Roberts 1971).
The key hindrance to development of a preventive strategy for
bread staling is the failure to understand the mechanism of the
process. Many investigations have examined the phenomenon of
crumb-firming, and many theories have been proposed and discussed in previous reviews (Herz 1965; Willhoft 1973; Zobel
1973; Maga 1975; Knightly 1977; Kulp and Ponte 1981; Zobel
and Kulp 1996). A cursory overview of the major theories on the
subject is presented here.
Amylopectin retrogradation. Katz (1928) proposed that starch
polymers retrogradation was responsible for staling of bread because his x-ray diffraction patterns of fresh bread were similar to
those of freshly gelatinized wheat starch, while the patterns of
stale bread were similar to those of retrograded starch. This finding led to the hypothesis that a gradual change in the starch components from amorphous to crystalline forms is important to the
staling process. Hellman and others (1954) provided evidence
that the rate of development of crystallinity in starch gels was similar to the rate of bread firming; but Dragsdorf and Varriano-Marston (1980) obtained evidence that the degree of crystallinity of
bread crumb was inversely related to its firmness and, therefore,
concluded that starch crystallization and bread firming were separate processes.
Vodovotz and others (2002) detected no increase in molecular
rigidity, that is, decrease in molecular mobility, in an aged bread
sample (proton cross-relaxation NMR spectroscopy) that was concurrent with an increase in the amylopectin retrogradation endotherm (DSC). They concluded that differences in molecular mobility could not be, therefore, due to recrystallized amylopectin and
may be attributed to the role of gluten [see Mechanisms of staling: Role of flour protein section] and/or redistribution of water
[see Moisture migration: Moisture redistribution among components section] in the amorphous regions of the samples.
Whether the fraction of starch that contributes to bread firming
is amylose or amylopectin also has been debated. The linear,
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Bread staling. . .
Table 1States of critical components in various stages in the life of breada
Stage
Starch
Gluten
Polar lipid
Dough
Fresh-baked,
but cooled,
bread
a Based on best evidence available. Other views have been stated; see discussion.
bAp = amylopectin, Am = amylose
cGelatinization is the disruption of molecular order within starch granules as they are heated in the presence of water (Atwell and others 1988).
d Both macro-and microscopic redistribution of water occurs during aging.
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Bread staling. . .
mechanism was not affected by protein content, suggesting that
the rate of staling is independent of protein quality. So they concluded that the primary effect of protein in reducing staling is dilution of starch.
Several investigators have concluded that crumb firmness is not
significantly correlated to flour protein type or concentration (Ponte and others 1962; Leon and others 1997; Gerrard and others
2001). By examining a novel starch bread that contained no gluten, Morgan and others (1997) suggested that starch retrogradation alone is sufficient to effect bread firming.
Every and others (1998) suggested that, qualitatively, starchstarch and starch-protein interactions are of equal importance to
the staling mechanism, but that quantitatively, starch-starch interactions are more important since conventional wheat flour contains about 85% starch (db). They hypothesized that gluten is not
essential to the firming process and that increasing bread firmness
results from chains of partially leached amylose and amylopectin
attached to swollen, partially gelatinized starch granules interacting via hydrogen bonds with other starch granule remnants and,
to a lesser degree, with gluten fibrils. Reconstitution experiments
revealed that breads of equivalent specific loaf volume staled at
the same rate irrespective of protein type or concentration, but
other bread properties were altered by changes in the type or
concentration of protein (Gerrard and others 2001), lending support to the above hypothesis.
Maleki and others (1980) postulated that the flour component
primarily responsible for differences in staling rate is gluten and
that its role in staling is something other than dilution of starch.
Furthermore, they proposed that starch and water solubles were
not involved significantly in determining the rate of staling.
Martin and others (1991) proposed that bread firming is a result
of hydrogen bonding between gelatinized (partially pasted) starch
granules and the gluten network in bread tying together the continuous protein network and discontinuous granule remnants.
They theorized that the crosslinking interactions originate during
baking; then during aging, the crumb loses kinetic energy, and
both the number of interactions and their strength increases.
When reheated, bread freshness is restored because the
crosslinks (hydrogen bonds) and entanglements between gluten
and starch polymer molecules are easily broken. This theory is
congruent with results of Dreese and others (1988), who reported
that starch and gluten molecules interact during baking.
Gerrard and others (1997) suggested a modification to the hypothesis of Martin and others (1991). They agreed with the hypothesis that staling is a result of increasing interactions between
swollen starch granules and the gluten network. However, they
put forth the opinion that the decrease in firming rate in breads
made with a-amylase (see Enzymes: -amylases and debranching enzymes section) as a dough additive is not the direct result
of starch hydrolysis products (dextrins and maltooligosaccharides), some of which, they suggest, are nonspecifically associated
with the protein matrix, but a result of modification of swollen
starch granules in such a way that their interaction with the protein network is reduced (presumably either qualitatively or quantitatively).
Rogers and others (1988) reported that, even though shortening
and native lipids have significant effects on bread staling, neither
have major effects on starch retrogradation. They suggested formation of protein-lipid interactions.
Role of pentosans. As mentioned in the Nonstarch polyosaccharides section, the influence of the so-called pentosans on
breadmaking and bread properties is not clear, although the subject has been examined extensively (Kulp 1968; DAppolonia
1971, 1980; Hoseney 1984; Meuser and Sukow 1986; Jankiewicz and Michniewicz 1987; Roels and others 1993: Rattan
and others 1994; Krishnarau and Hoseney 1994; Izydorczyk and
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Bread staling. . .
amylopectin crystallization.
Crumb-crust redistribution of moisture. As baked bread begins to cool, a moisture gradient forms in the loaf (Piazza and
Masi 1995). Differences in vapor pressures between the crust and
the internal region of the loaf result in moisture migration from the
crumb to the crust (Stear 1990). Over time, the moisture content
in the center of the loaf decreases, while that in the external region
increases (Bechtel and others 1953).
Baik and Chinachoti (2000) found that bread stored with its
crust became significantly firmer than bread stored without its
crust and contained more recrystallized amylopectin, indicating
that moisture redistribution from crumb to crust plays a significant
role in firming, a conclusion confirmed by a loss in freezable water in the crumb of bread stored with crust, which correlated with
changes in its thermomechanical profile.
Several NMR parameters correlate with crumb firming and are
believed to be related to both microscopic and macroscopic redistribution of water (Chen and others 1997b). Using NMR techniques, it has been found that, as staling proceeds, the water in
bread becomes less and less mobile (Leung and others 1983;
Wynne-Jones and Blanshard 1986; Kim-Shin and others 1991;
Chen and others 1997a,b; Engelsen and others 2001). However,
Ruan and others (1996), using MRI, found that, as storage time of
sweet rolls increased, mobility of the less-mobile water fraction
decreased, while mobility of the more-mobile fraction increased.
Moisture redistribution among components. Transfer of moisture from one constituent of the bread crumb to another is generally accepted as a contributing factor in staling, possibly being responsible for the perceived dryness of stale bread (Senti and Dimler
1960). Water is a plasticizer, making the bread components more
flexible. Thus, as water is removed (from either gluten or starch or
both), increasing crumb firmness should occur. Whether staling involves dehydration of gluten or starch has been studied extensively,
but is still unclear. However, the majority of evidence suggests a
gluten to starch transfer of water as the starch crystallizes.
Katz (1928) first suggested that, during staling, moisture was released from starch and taken up by gluten. Senti and Dimler (1960),
by studying equilibrium relative humidities, also suggested that
moisture transfer would likely occur from starch to gluten. Cluskey
and others (1959) reported a progressive drop in moisture-sorption
capacity for starch and lack of a change for gluten, indicating a
transfer of moisture from starch to gluten during aging.
In contrast, Alsberg and Griffing (1927) and Alsberg (1936) postulated that it was the gluten that hardened as result of moisture
loss to starch. This concept is supported by data of Bachrach and
Briggs (1947), who observed an increase in moisture-sorption capacity of gelatinized starch upon aging [contrary to the results of
Katz (1928) and Cluskey and others (1959)]. Further evidence
came from investigations by Willhoft and coworkers (Breaden and
Willhoft 1971; Willhoft 1971; Kay and Willhoft 1972), who reported that gluten undergoes a 1st-order transformation resulting
in the release of water from gluten and absorption of this water by
retrograding starch.
The notions of free and bound water have been reported to
be of importance in altering the rate or extent of staling in bread
(Knjaginciev 1970). More recently, the use of NMR and a greater
understanding of the role and mechanism of starch polymer crystallization have led to the conclusion that starch takes up water
from gluten upon aging of bread. Leung (1981) and Leung and
others (1983) proposed that, as starch changes to a more crystalline state, more water molecules become immobilized due to their
incorporation into crystal structures. Chen and others (1997a,b)
reported a decrease in water mobility in bread upon staling, in
agreement with results of others (Wynne-Jones and Blanshard
1986; Slade and Levine 1991), and concluded that the decrease
in water mobility was due to incorporation of water molecules re-
leased from gluten into crystalline structure of starch that developed upon staling. [Note: The B structure has 36 water molecules
in the unit cell, whereas the A structure has only 8 (Sarko and Wu
1978).] Conversely, Kim-Shin and others (1991) proposed that the
redistribution of water occurs in the amorphous phase. The ratio
of starch to gluten (6:1) in bread crumb ensures that moisture
transfer to the starch would result in firming of the continuous gluten phase (Willhoft 1971). It is important to keep in mind at all
times, however, that the change in the state of water cannot be
correlated directly to the retrogradation process (Wynne-Jones
and Blanshard 1986).
Levine and Slade (1990) and Slade and Levine (1991) present
thorough and well-documented evidence for the role of water in
the staling process. Their arguments are based upon the mechanism of polymer crystallization, polymer crystallization kinetics as
a function of glass transition and melting temperatures, water as a
plasticizer, and sugars as antiplasticizers in the system. In their review, Slade and Levine (1991) state essentially that if adequate
packaging prevents simple moisture loss, the predominate mechanism of staling in bread crumb is the time-dependent recrystallization of amylopectin from the completely amorphous state of a
freshly heated product to the partially crystalline state of a stale
product, with concomitant formation of network junction zones,
redistribution of moisture via both microscopic and macroscopic
migration (Czuchajowska and Pomeranz 1989), and increased
textural firmness (Kulp and Ponte 1981; Russell 1983b; Russell
1987). They further point out that there is evidence from studies
of starch gels/pastes that the rate and extent of amylopectin crystallization depends on the mobility of its outer branches (Ring and
others 1987; Russell 1987; Marsh and Blanshard 1988; Slade
and Levine 1989, 1991) and on sample history, since the processes that occur both during heating/baking and during aging/
storage are nonequilibrium processes (Ring and others 1987;
Slade and Levine 1989, 1991). [Note: Slade and Levine refer to
recrystallization of amylopectin, and indeed it is a recrystallization. We have not used the term elsewhere in this review so as to
make it clear that amylopectin molecules do not recrystallize to
the same crystalline state that they were originally in nongelatinized granules.]
Amylopectin crystallization results in a partially crystalline, supermolecular structure containing disperse B-type crystalline regions (Slade and Levine 1987). Incorporation of water molecules
into the crystal lattice occurs during formation of the B-type polymorph (Imberty and Perez 1988) and, thus, a redistribution of
moisture is effected. This process was demonstrated by a progressive decrease in the percentage of freezable water as bread was
stored over 11 d (Slade and Levine 1991). The water molecules
that are part of the crystal lattice are not available for plasticization, so the result is the perceived drier, firmer texture characteristic of stale bread. So, all in all, amylopectin crystallization in bread
requires both microscopic and macroscopic redistribution of water so that there is sufficient moisture present at the locus where
crystallization takes place to plasticize polymer chains so that
they are mobile enough for crystallization to occur and for incorporation into B-type crystal latices (Levine and Slade 1990; Slade
and Levine 1989, 1991).
It seems clear that moisture transfer between bread components, specifically between gluten and starch, occurs as bread
ages. However, like other measurable changes in the nature of
bread components, the role, if any, of moisture and moisture redistribution in the staling process remains undetermined. (See
also Mechanisms of staling: Role of pentosans and Carbohydrate ingredients sections).
Processing factors
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Antistaling Additives
Enzymes
One strategy to reduce the rate of bread staling employs enzymes. The enzyme supplements labeled as amylases and proteases are most commonly used in commercial baking (Miller and
others 1953; Waldt 1968, 1969; Martinez-Anaya 1998; Bowles
1996). The most useful enzymic approach to staling rate reduction has been the use of -amylases, which catalyze a small
amount of hydrolysis of the starch. Proteases depolymerize gluten
proteins and modify baking characteristics. Nonamylolytic enzymes may also be active in the enzyme supplements (van Eijk
and Hille 1996). [Note: While many enzymes are useful in aspects of breadmaking other than in reducing crumb firmness,
only enzymes useful as antistaling agents are discussed below.]
-Amylases and debranching enzymes. Numerous studies
have reported that the rates and degrees of firming in baked
goods can be reduced; and the texture, flavor, aroma, and general
qualities improved; by use of a-amylases. Fungal, cereal, and bacterial -amylases all appeared to improve softness retention of
bread to an extent related to their heat stability (Conn and others
1950; Miller and others 1953). Fungal -amylase was inactivated
by heat before acting on the starch. Although cereal (wheat or barley) a-amylases did not survive the baking process, they had time
to act on the swollen starch. A bacterial a-amylase was able to
partly survive the heat treatment (Amos 1955). [Note: after this
work was reported, intermediate thermostable bacterial -amylases became available. See below.] In any case, major -amylase
activity takes place during baking after the starch is gelatinized
and becomes more susceptible to the enzyme (Ghiasi and others
1979); there is a specific temperature range and time in the breadmaking process when the enzyme is most active in degrading
starch (Martin 1989).
Waldt and Mahoney (1967) reported that, when bacterial aamylase was used, the freshness of 4-d-old bread was equivalent
to that of 2.0 to 2.5-d-old untreated bread, but it has been reported that, when bacterial -amylase derived from Bacillus subtilis is
used in a bread formulation, a gummy texture results (because it
can survive baking) (Hebeda and others 1991). Fungal a-amylases
(such as that from Aspergillus oryzae) are less thermostable than
8
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Bread staling. . .
duced mainly low-molecular-weight, branched dextrins of DP 1924 that either had less ability to retrograde, interfered with amylopectin retrogradation, or interfered with whatever other interactions are responsible for crumb firming.
Duran and others (2001) attributed the antistaling effect of amylases to the production of maltooligosaccharides. Biliaderis
and Prokopowich (1994) found that maltose and maltotriose had
antiretrogradation effects on starch gels and proposed that the
chain ordering of amylopectin in sugar-containing starch gels is a
function of the compatibility of the sugar with the structure of water. Solutes that fit well in the water structure retarded chain reordering. On the other hand, solutes that disturb water structure
promoted ordering and aggregation of starch molecules. Maltotriose, which was reported to be the most effective maltooligosaccharide in impeding retrogradation, disturbs the structure of water
only slightly (Biliaderis and Prokopowich 1994).
Defloor and Delcour (1999) reported that starch hydrolysis
product preparations with average DPs of from 4 to 66 reduced
DSC staling endotherms in baked and stored bread doughs. They
attributed their antistaling effect to a reduction in starch recrystallization but did not speculate about a mechanism.
Martin and Hoseney (1991) proposed that low-molecularweight dextrins (maltooligosaccharides) produced by a-amylases
were directly responsible for the antistaling phenomenon observed by enzyme addition. Their explanation was that the lowmolecular-weight products inhibited cross-link formation between
starch and gluten.
Min and others (1998) studied the effect of 2 novel antistaling
amylases. When added to bread, they produced selectively either
maltose and maltotriose or maltotetraose and maltotriose. Based
on the results, they postulated that maltotriose and maltotetraose
were directly responsible for retarding retrogradation in bread,
suggesting that these oligomers were of the right size to interfere
with starch-gluten interactions [theory of Martin and others (1991)
and Martin and Hoseney (1991) on the mechanism of staling].
Maltose was found to be less effective in bread staling prevention,
and it was suggested that its relatively small size and its ability to
diffuse easily might be the reason why it was less effective than
maltotriose or maltotetraose (Min and others 1998). Donnelly and
others (1973) reported that there is a slight decrease in moisture
adsorptive capacity as the molecular size of maltooligosaccharides increases from DP 3 to DP 11, and that maltose was the exception, being less hygroscopic than was the DP 11 maltooligosaccharide. This led Min and others (1998) to conjecture that
maltotriose and maltotetraose might hold water around starch
molecules and inhibit starch-starch interactions more than maltose does.
Despite conclusions that dextrins directly affect staling in bread,
considerable evidence has been published to the contrary. Salem
and Johnson (1965) found, from experiments in which starch hydrolysis products were added to a bread dough formula, that certain maltooligosaccharides (such as maltohexaose and -heptaose,
as compared to glucose, maltose, and maltotriose, -tetraose, and pentaose) and dextrins increased the rate of crumb firming, in
contrast to results obtained when -amylase was incorporated as
an additive. However, in contrast, Every and others (1992) found
that maltooligosaccharides of DP 3-10 correlated with a reduction
in firming rate, and Akers and Hoseney (1994) implied that starch
hydrolysis products of a size greater than maltoheptaose might
have antifirming properties.
There is a 3rd conclusion. Because added maltooligosaccharides did not survive fermentation and because the presence of
maltooligosaccharides of a specific size class could not be correlated with the firming rate of bread, Gerrard and others (1997)
concluded that maltooligosaccharides (DP 3-8) produced by amylases are not themselves responsible for antistaling, but that
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Bread staling. . .
dition of monoglycerides may counteract staling of breads during
storage, an increased tendency to crumble may result (Malkki and
others 1978).
The mechanism of the antistaling effect of monoglycerides is
still unknown, but it is thought to be different from that of shortening (Rogers and others 1988), for monoacylglycerols can replace
shortening, but shortening cannot replace monoacylglycerols.
Krog and others (1989) concluded that reductions in crumb
firmness brought about by addition of monoglycerides were
probably the result of interactions with amylose rather than with
amylopectin. When relatively large amounts of monoglycerides
are used, essentially all released amylose can be complexed (as
measured by DSC); interactions with amylopectin are also increased. At lower concentrations, monoglycerides interact primarily with amylose because of competition between the 2 polymers.
Polyoxyethylene monostearate (POEMS). POEMS, a reaction
product of ethylene oxide and stearic acid, was one of the first additives reported to retard staling (Maga 1975). Favor and Johnson
(1947) demonstrated that POEMS (0.5 to 1.0%) dramatically reduced the firming rate of bread between the 1st and 3rd d. Other
results (Freilich 1948; Edelmann and Cathcart 1949; Edelmann
and others 1950; Skovholt and Dowdle 1950) confirmed that POEMS was effective in reducing the rate of firming. Carson and others (1950) theorized that POEMS retarded staling by 2 mechanisms: (1) by insolubilizing amylose and (2) by interacting with
starch granules via hydrogen bonding.
Sodium stearoyl lactylate (SSL). Pisesookbunterng and
DAppolonia (1983) found that, among various surfactants studied, SSL had the greatest binding affinity to starch. The anionic surfactant might also prevent protein denaturation. Calcium stearoyl
lactylate is less effective as a crumb softener, but is active.
Glycerol monostearate (GMS). GMS is used in many starchbased food products to improve physical characteristics, including the degree of softness after storage (Krog 1971).
Other surfactants. Other surfactants that are effective as antistaling agents include polyoxyethylene sorbitan monostearate
(Polysorbate 60), succinylated monoglycerides, and glycerol.
Novel surfactants or surfactant blends have been formulated for
use as antistaling agents in bakery products. A blend developed
by Knightly (1987) consisted of a hydrophilic lecithin and at least
one of the following: monoglyceride, lactic acid esterified
monoglyceride, succinic acid esterified monoglyceride, maleic
acid esterified monoglyceride, or edible salts of stearoyl lactylic
acid. This blend was claimed to both inhibit staling and to act as a
dough conditioner. Other antistaling surfactant blends were developed by Vidal and Gerrity (1979).
Mechanism of antistaling effect of surfactants. The mechanism
by which surfactants influence crumb firmness has been debated
and is discussed briefly in the following sections. Amylose-surfactant, amylopectin-surfactant, and protein-surfactant interactions
have all been investigated, as has starch swelling in the presence
of added surfactants. Whether surfactants actually decrease the
rate of firming or produce softer breads that then stale at the same
rate as the control has been debated. Surfactants have multiple
properties, resulting in multiple functionalities, so definitive experiments examining a cause-and-effect relationship with regards to
staling are difficult, if not impossible, to design.
In excess water, surfactants do not change the gelatinization
temperature, but they do delay pasting (Miller and others 1953).
Whether this is related to their functionality in breadmaking is unknown. Knightly (1977) reported that surfactants had little to no
effect on initial crumb firmness, but did affect the firming rate during storage, a finding in agreement with earlier reports (Favor and
Johnson 1947; Skovholt and Dowdle 1950; Hopper 1949; Edelmann and others 1950). Based on unpublished results from in-
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11
mentioned earlier, less swelling means less disruption of crystallinity and other order within the granule, so there is less gelatinized starch to recrystallize, but that which is disordered can recrystallize more easily. Another possible effect is less leaching/migration of amylose so that there is less in the intergranular space
to retrograde. Even in excess water, monoglycerides prevent the
leaching of amylose molecules (Schoch 1965). Surfactants prevent dissolution and leaching of amylose molecules, which may
be the factor responsible for the reduction in granule swelling,
and also complex with amylopectin molecules; and their antistaling effect, which is correlated with a reduction in granule swelling, is likely due to a reduction in starch polymer mobility after
complexation so that less crystallization can occur.
Interaction with protein. Willhoft (1973) hypothesized that the
antistaling effect of monoglycerides might be due to interaction
with gluten, and there is experimental evidence that supports this
hypothesis (Hoseney and others 1969; De Stefanis and others
1977; Quail and others 1991). It has been suggested that surfactant molecules associated with gluten are released during baking
(DeStefanis and others 1977) and complex with leached starch
polymers in intergranular spaces (Conde-Petit and Escher 1994.)
Physical properties of surfactants. According to Kulp and Ponte (1981), the physical state of surfactants is an important factor in
their performance. Krog (1973) reported that amylose-monoglyceride complexation ability decreased in the descending order of
monoglyceride physical states: -type crystalline gel > -type
crystalline hydrate > nonhydrated powder. -Type monoglyceride
crystals pack so that polar groups are exposed to the water phase,
and thus have a greater tendency to form effective aqueous adjuncts (Wren 1968; Larsson 1968). -Type crystals show no
marked antifirming effect unless first hydrated before use. Hydrated -crystals are commonly known as a coagel-foam (Krog
1968).
Shortening
Roles of dextrins and maltooligosaccharides in staling were discussed in the section Enzymes: -amylases and debranching enzymes. Roles of native water-soluble and water-insoluble pentosans were discussed in the section Mechanisms of staling: Role
of pentosans. Use of hydrocolloids and modified starches and
effects of damaged starch are covered in this section. If it is accepted that moisture redistribution is a requirement for staling to
occur (see Moisture migration section), then it follows that any
ingredient that inhibits movement of moisture is a candidate for
reducing staling (Swortfiguer 1971).
Hydrocolloids/gums. Davidou and others (1996) found that,
among locust bean gum, alginate [presumably sodium alginate],
and xanthan, only locust bean gum reduced the rate of dehydration. However, any increased moisture content of breads, if the
moisture is available to the starch molecules, increases the rate of
retrogradation (Rogers and others 1988) (see sections Mechanisms of staling: Role of pentosans and Moisture migration:
Moisture redistribution among components).
Schiraldi and others (1996a) studied the effects of added hydrocolloids (pentosans, modified pentosans, galactomannans, whey
protein) and reported that guar and locust bean gums retarded
starch retrogradation, but did not have any clear antistaling activi-
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Bread staling. . .
ty. They also found that all the hydrocolloids they used generally
improved quality and that those with higher water-holding capacity increased crumb firmness. In contrast, Davidou and others
(1996) reported that both degrees of crumb firmness and the rate
of staling during storage were reduced by addition of locust bean
gum, alginate [presumably sodium alginate], and xanthan. They
proposed that the gums modified the organization of the amorphous part of the crumb, perhaps by inhibiting gluten-starch interactions, perhaps in the same manner as proposed for dextrins
(Martin and others 1991). They also reported that only locust
bean gum (of the 3 gums) effected water retention. Carboxymethylcellulose (CMC) and hydroxpropylmethylcellulose (HPMC)
(0.3%) also decreased initial firmness (Armero and Collar 1998).
No increases in the Avrami value were found. Hydrocolloid-gluten entanglements or linkages were suggested.
Addition of psyllium husk powder/gum (2, 4, or 8%) decreased
the staling rate of bread as measured by compressibility and DSC
(Czuchajowska and others 1992). Moisture content remained
constant. Bread softness improved without increasing the possibility of microbial deterioration. Lent and Grant (2001) found that
bagels containing added xanthan had slightly higher crumb moisture contents and staled at a somewhat reduced rate (DSC). Addition of pectin increased the specific volume of bread and reduced
the rate of firming during storage (Kegoya-Yoshino 1997).
Replacement of 10% of the wheat flour with steamed oat flours
retarded bread staling without adversely affecting the loaf volume
(Zhang and others 1998). The reduction in the rate of staling was
attributed to the high water absorption capacity of the -glucan in
oat flour, but oat starch has been found to retrograde at a slower
rate compared to other starches (White and others 1989).
Patents have been issued for the use of karaya gum (Andt 1966)
and what is called low-molecular-weight amyloses, but which in
reality are the branch chains of amylopectin released by the action of an a-1,6-glucan hydrolase as antistaling agents (Yoshida
and others 1972).
It has also been reported (although not supported in the article
with published experimental data) that methylcellulose and hydroxpropylmethylcellulose extend the shelf life of baked products
via prevention of water loss during baking (Dziezak 1991). The
same report states that guar gum and xanthan gum function as antistaling agents.
Damaged and modified starch. Modified starches have been
investigated as antistaling agents (Maga 1975). Tipples (1969) reported that the use of 25 to 35% damaged wheat starch decreased the rate of staling, especially when malt was added and
the sponge-dough method was used.
On the 4th d of storage, breads containing 5% of a phosphorylated waxy maize starch were as fresh as a 1-d-old control bread
(Bergthaller and Stephan 1970). The water-holding capacity of the
bread was not affected by the starch phosphates.
Miscellaneous
Results of use of dairy ingredients in breads for antistaling purposes have been inconsistent (Mannie and Asp 1999).
DAppolonia (1984) reported that milk solids have little to no effect on bread staling, but do soften the crumb initially. Conversely,
others have suggested that nonfat dry milk solids retard staling
(Dubois and Dresse 1984). Acidic whey (concentrated or unconcentrated) retarded staling in Hamam (French-type) bread at 1%
whey solids (Yousif and others 1998). Neither acid casein or sweet
whey powder were found to reduce staling in bread significantly
(Erdogdu-Arnoczky and others 1996), while acid whey powder
did. Despite its high water-holding capacity, succinylated whey
protein concentrate did not prevent bread staling (Thompson and
Baker 1983).
L-Leucine n-alkyl esters slowed the staling rate of bread more
Flavor Changes
Staled bread is considered unacceptable due to changed flavor.
A review on bread flavor is available (Lorenz and Maga 1972).
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Bread staling. . .
Amylo-Graph, Rapid Visco Analyzer, and related instruments
have been used to measure the extent of starch gelatinization in
bread crumb slurries (Yasunaga and others 1968). Peak viscosity
changes were suggested as an index of staling because it was
thought that peak viscosity would decrease with age due to a
toughening effect on partially gelatinized starch granules during
staling. Based on results in which the outer 1-cm and 2-cm portions of the crumb produced a lower peak viscosity than did the
center portion, it was concluded that starch granules in the crumb
center were less gelatinized than those in the crumb exterior. Despite reporting amylograph data that agreed with those of Yasunaga and others (1968), Varriano-Marston and others (1980) concluded that the amylograph does not indicate the degree of starch
swelling accurately in bakery products, but rather shows the sum
of the contributions of all macromolecules to the viscosity of the
bread slurry. Toufeili and others (1994) found that, as staling increased, pastes made from Arabic bread changed from being viscoelastic solids (G < G) to elastoviscous liquids (G > G).
Thermal analysis
Thermal analysis has been used extensively to study starch retrogradation as well as bread staling (Russell 1983a, b;
Czuchajowska and Pomeranz 1989; Le Meste and others 1992;
Schiraldi and others 1966a,b; Champenois and others 1995;
Vodovotz and others 1996; Baik and Chinachoti 2000), and its
use has been mentioned throughout this review. Of the thermoanalytical methods, differential scanning calorimetry (DSC) and differential thermal analysis (DTA) have proven to be the most useful
in providing basic information on starch retrogradation (Karim
and others 2000). Because both measure the differential temperature or heat flow to or from a sample versus a reference material
as a function of time, both can be used to monitor such changes
as phase transitions, molecular conformational changes, interactions with other components, and pyrolytic degradation of the
sample. Specialized DSC instruments, including modulated DSC
and polarization DSC, are also available (Schenz and Davis
1998).
When aged bread samples are heated in a DSC pan, an endotherm is observed as reordered amylopectin reaches its glass transition and/or melting temperature, and the enthalpy change associated with this transition can be measured. Because the time
scales for endotherm development and for the increase in crumb
firmness are broadly similar in magnitude, DSC can be used to
measure the rate of bread staling quantitatively (Jagannath and
others 1999a). However, there are overlapping transitions over a
wide temperature range because of the variety of components
and range of structures present, which cause difficulty in analysis
(Vodovotz and others 2001).
DTA was used to investigate bread staling by Axford and Colwell (1967). An endotherm peak, which was absent in fresh bread
samples, developed during storage, and the increases in peak
area were proportional to increases in bread firmness (Cornford
and others 1964). Because an increase in glass transition temperature (Tg) of bread crumb stored for different times was correlated
(96.53%) with an increase in the degree of bread staling as measured by compression analysis, it was concluded that the measurement of Tg during storage could be used to quantitatively predict the rate of staling (Jagannath and others 1999a). DSC studies
of starch can approximate gelatinization during baking, since in
both cases the gelatinized starch granules are swollen, but nondisrupted (Jacobson and BeMiller 1998). Thus, the conditions of
gelatinization in the calorimeter more closely approximate those
encountered during baking than those encountered during starch
pasting. Unlike compressibility measurements, endotherm peak
development does not appear to be dependent on specific loaf
volume (Fearn and Russell 1982).
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(Sidhu and others 1997) and used in conjunction with DSC in the
analysis of the effect of various antistaling additives on wheat
bread (Jagannath and others 1998).
It has been concluded that there is not necessarily a cause-andeffect relationship between starch crystallization and bread firming (Dragsdorf and Varriano-Marston 1980; Zobel and Senti
1959), emphasizing the need, when investigating bread staling,
for methods that are not limited to measuring changes in only 1
component.
Jagannath and others (1998) used wide-angle x-ray scattering
(WAXS) to measure the degree of staling.
Conductance and capacitance
Transmitted and polarized light microscopies. Transmittedlight and polarized-light microscopy have been utilized to monitor changes in starch granules from bread before and after staling
(Hug-Iten and others 1999, 2001). Native starch granules are birefringent and possess Maltese crosses when viewed under polarized light. Upon gelatinization, starch crystallites melt and order,
and birefringence is lost. During bread baking, starch granules
lose their Maltese crosses, but retain slight birefringence (Varriano-Marston and others 1980) and granular identity. Upon aging,
the bread crumb regains some birefringence (which is not the
usual native starch granule birefringence, but does indicate
biopolymer ordering in the long, thin birefringent structures) due
to molecular reordering, except in -amylase-containing bread
crumb, which contained more of the birefringent structures (as
compared to a control crumb made without a-amylase) initially,
which changed little with aging (Hug-Iten and others 2001).
Confocal laser scanning microscopy (CLSM). The advantage of
confocal laser scanning microscopy over other microscopies is its
ability to produce an image of the focal plane of interest (optical
section), which can be digitally reconstructed into a 3-dimensional image. CLSM has provided qualitative information about the
crumb structure of bread (Bugusu and others 2002). CLSM has
also been used to investigate changes in starch granules in bread
during staling (Vodovotz and Chinachoti 1998). However, it has
been reported that there were no differences in confocal images
of fresh and 10-d old bread, suggesting that the changes that occur during staling are submicroscopic, that is, molecular only.
[Note: Since, as bread stales, starch molecules become more crystalline and more opaque, reflectance confocal laser scanning microscopy (R-CLSM) might provide more precise 3-D information
on the changes in the starch fraction during staling. R-CLSM offers
the highest resolution of CLSM modes (Hibbs 2000), but to our
knowledge has not been applied to investigations of bread staling.]
Electron microscopy. Electron microscopy has not been used
to study bread staling, but certainly has promise. Both transmission and scanning electron microscopy have been used to investigate doughs (Aranyi and Hawrylewicz 1968; Khoo and others
1975; Bechtel and others 1978; Evans and others 1981), bread
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Bread staling. . .
(Khoo and others 1975; Bechtel and others 1978), and pastes
(Fannon and BeMiller 1992 and references therein).
Sensory/organoleptic tests
Loss of flavor and aroma are among the most noticeable detrimental changes of bread upon staling. Reportedly, the decrease in
the acceptability of bread over 5 d of storage is correlated with a
reduction in aldehydes and an increase in ketones (Lorenz and
Maga 1972). The resulting flavor is one that has been described as
bland (Setser 1996). Changes in texture, of course, also accompany the bread staling phenomenon and can be measured by
both uniaxial compression methods (Section 8.1.1) and sensory
evaluations.
AACC Method 74-30 (AACC 2000) involves panel ratings of a
sum of factors affecting overall staling (appearance or feel of
the crumb/crust, taste and mouthfeel, firmness, flavor, and
texture change, or any other important factor noted by a panelist). A high correlation between measured crumb firmness and
staling as rated by panelists has been found (Cornford and others
1964; Axford and others 1968). Other examples of organoleptic
evaluations are discussed by Pomeranz and Shellenberger (1971)
and Setser (1996).
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Authors Gray and BeMiller are Ph.D. student and Professor, respectively,
with the Whistler Center for Carbohydrate Research, Dept. of Food Science, Purdue Univ., West Lafayette, Ind., U.S.A. Direct inquiries to author
BeMiller (E-mail: bemiller@purdue.edu).
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