Nutritional Aspects and Safety of Modified Food Starches
Otto B. Wurzburg
The term “modified starches” covers a wide
variety of starch-derived products. A number of
techniques, such as those involved in bleach-
ing, enzymic digestion, dextrinizing, and hy-
drolysis, have either no effect on the starch or
are used to reduce the size of the starch mole-
cule. The latter process is similar to the diges-
tive process, as well as such common food-
processing techniques as toasting or baking
bread. Starch modifications in these catego-
ries are widely accepted as being similar to
unmodified starches for use in foods. For this
reason, no further attention will be given to this
type of modification.
Chemical Starch Modification
This paper is devoted to those modified
starches made by treating starch with agents
that introduce substituent chemical moieties
into the starch granule through reaction with
hydroxyl groups in the starch molecule. These
chemically modified starches have been used
as food ingredients for over 45 years. All are
cleared for use in the US, Canada, and the UK,
and have been accepted by the Joint Expert
Committee on Food Additives of the FAO/
WHO. They impart to food systems valuable
functional properties that cannot be realized
with unmodified starches. They provide tex-
ture, thicken, suspend solids, stabilize emul-
sions, facilitate processing by protecting foods
during processing, or protect finished foods
during distribution and storage.
Within the broad category of chemically
modified starches there are wide variations in
Mr Wurzburg is past Vice President of Natural Poly-
mer Research at National Starch and Chemical
Company, Bridgewater, NJ, USA.
74 NUTRITION REVIEWSNOL. 44, NO. ZFEBRUARY 1986
the extent to which the starch has been chemi-
cally altered. Many such starches contain only
infinitesimal amounts of substituent groups
and might be considered 99.9 percent pure
starch. The presence of the added chemical
groups is not readily detected except by so-
phisticated analytical methods or by physical
characterization. Others contain sufficient
amounts of substituent chemical moietiesto be
easily detected.
There are two major ways to modify starch
chemically: crosslinking, and introduction of
monosubstituent groups. Most of the modified
food starches used in the food industry are
made either by crosslinking or by combining
crosslinking and introducing monosubstituent
groups. Limited amounts of starches contain-
ing only monosubstituent groups are used in
foods.
Unmodified or native starch occurs in the
form of minute granules that are insoluble in
cold water. They owe their integrity to crystal-
lites formed by hydrogen bonds between hy-
droxyls on adjacent molecules. When heated
in the presence of water, the hydrogen bonds
holding the granule together weaken, permit-
ting the granules to imbibe water, swell, and
thicken to form colloidal dispersions. Such dis-
persions have limited value in most food sys-
tems because of the sensitivity of the hydrogen
bonds responsible for the integrity of the swol-
len granule to thermal and mechanical break-
down.
Crosslinking as a Chemical Modification
Crosslinking reinforces starch granules with
intermolecular chemical bonds that keep the
swollen starch granules intact after the hydro-
gen bonds have been ruptured. The technique

imparts to the dispersions of starch resistance
to thermal, chemical, and mechanical break-
down.
Two types of crosslinked starches are used
in foods: distarch adipates, made by treating
starch with a mixed anhydride of adipic and
acetic anhydride; and distarch phosphates,
made by treating starch with either phosphorus
oxychloride or sodium trimetaphosphate.
Since the granule contains a tremendously
large number of anhydroglucose units in the
molecules, relatively few chemical crosslinks
are required to reinforce the granule and pro-
duce a marked effect on the physical proper-
ties of the starch dispersion. In most cross-
linked food starches there is one substituent
crosslinking group per 1,000 or more anhy-
drogIucose units.
Since the substituent groups present in
crosslinked food starches may be metabo-
lized, and in view of the extremely low levels at
which they are present, the impact of cross-
linking on the nutritional value of starch and on
physiologic behavior is minimal or undetect-
able.
Numerous in vitro studies indicate that low
levels of crosslinking have little effect on en-
zyme digestibility. Thus, in vitro digestibility
studies on distarch adipates containing low
levels of acetyl groups and on distarch phos-
phates indicate that starches crosslinked
within the limits set by regulation approach
native starches in digestibility.
In vitro amyloglucosidase digestibility of
acetylated distarch adipate, made by treating
waxy maize starch with 0.15 percent adipic
acid in a 1:3 adipic-acetic mixed anhydride,
was 98 percent of the digestibility of unmodi-
fied waxy maize starch.’I2 Under these condi-
tions; the level of adipic treatment was 20 per-
cent higher than the maximum approved for
use in making modified food starch.
In vitro enzyme digestibility studies on di-
starch phosphate also show in vitro digestibili-
ties approaching or comparable to those ob-
tained with unmodified starch. Thus, in vitro
amyloglucosidase digestibility of waxy maize
starch, crosslinked by reaction with 0.035,
0.070 and 0.100 percent phosphorus oxychlo-
ride, ranged from 98 to 96 percent that of un-
modified waxy maize starch.’I2 In vitro digesti-
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bility by pancreatin of corn or potato starch
crosslinked with 0.05 or 0.1 percent phospho-
rus oxychloride was similar to that of unmodi-
fied starch.l”
While in vitro studies indicate the suscepti-
bility of modified starches to digestion by spe-
cific enzymes, the digestion and absorption of
carbohydrates is an integrated rather than se-
quential process. As a result, in vivo studies
provide a better picture of the digestibility and
nutritive value of modified food starches.
The caloric value of acetylated distarch adi-
pate, prepared by treating an acid hydrolyzed
waxy maize starch with a mixed anhydride
containing 0.2 percent adipic acid and 5.5 per-
cent acetic anhydride in an adipic-acetic mixed
anhydride, was equal to that of control starch in
28-day feeding studies. Groups of ten weanl-
ing male albino rats were fed a basal diet con-
taining 1.5 or 3.0 g of modified or control
starch, or 0.75 to 4.5 g of sucrose supple-
ment.ls2s4 In these studies, the level of adipic
acid treatment was 67 percent higher than that
permitted in making crosslinked distarch adi-
pate for food use.
Studies of the caloric value of distarch phos-
phates prepared by treating waxy maize starch
with 0.03 or 0.1 percent phosphorus oxychlo-
ride, as well as of distarch phosphate made by
treating milo starch with trimetaphosphate,
showed that distarch phosphates are compa-
rable to unmodified control starches in caloric
value. s2s5
Since the level of crosslinking substituents is
extremely low, it is questionable whether ca-
loric determinations reflect the presence of
substituents even if they are indigestible. To
determine the metabolic fate of the adipate
crosslink, young male adult rats were given by
stomach tube a suspension of acetylated di-
starch adipate prepared using 14C-labeledadi-
pic acid. A physical mixture of 14C-labeledadi-
pic acid and unmodified starch was
administered as a control. After 25 hours, 99.3
percent of the activity of the free adipic acid
had been recovered in the respired air com-
pared to 70.5 percent of the activity of the
labeled starch. Most of the balance of the activ-
ity had been recovered in the feces and the
rest in the urine.1,2,6
Other studies included investigations by An-
NUTRITION REVIEWSNOL. 44, NO. 2/FEBRUARY 1986 75

derson et a17 in which 3-day-old Pitman-Moore
miniature pigs were fed for 25 days formulated
diets containing either acid hydrolyzed waxy
maize starch as the control, or acid hydrolyzed
waxy maize starch crosslinked with 0.08 per-
cent phosphorus oxychloride as the test
starch. Starch provided 24 percent of the calo-
ries in the diet. Body weight gains of the ani-
mals fed the distarch phosphate were similar to
those fed the control starch. There were no
statistically significant differences in the organ
weights expressed as percentage of body
weight. Serum cholesterol, triglyceride, cal-
cium, phosphorus, alkaline phosphatase, urea
nitrogen, total protein, albumin, and globulin
levels were similar in both groups of animal^.^
Starches resistant to attack by digestive en-
zymes are subject to increased microbial activ-
ity in the gut when fed to rats at high dietary
levels, resulting in flatulence and enlarged
caeca. When waxy maize distarch phosphate
containing levels of crosslink within the legal
range was fed to rats at a dietary level of 16
percent there was no evidence that such levels
of crosslinking caused caecal enlargement.* In
view of these and other studies, it appears
reasonable to conclude that crosslinking
starch within the limits allowed by regulation
provides a modified food starch comparable to
unmodified starch in nutritive value and safety.
Substitution of Monosubstituent Groups
The second major approach to chemical
starch modification is through the introduction
of monosubstituent groups of acetate, phos-
phate, octenyl succinate half ester, and hy-
droxypropyl groups. These may represent the
sole modification or, in the case of all but the
octenyl succinate half ester, part of a dual
modification involving introduction of adipate
or phosphate crosslinks. Since crosslinks per
se have no significant effect on nutrition and
safety, and since most of the commercial food
applications for modified food starches con-
taining monosubstituent groups also require a
crosslinking treatment, nutrition and safety
studies on acetates, phosphates, and hydroxy-
propyl derivatives have frequently been based
on monosubstituent modifications that have
also been crosslinked.
The level of monosubstitutent groups intro-
76 NUTRITION REVIEWSNOL. 44, NO. 2/FEBRUARY 1986
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duced in the production of modified food
starches is relatively low. In the case of ace-
tates, the maximum level of substitution by
regulation is 2.5 percent. This corresponds to
one acetate group for roughly every 10 to 11
anhydroglucose units. The maximum level for
phosphates is 0.4 percent phosphorus which
corresponds to one phosphate group for
roughly 47 to 48 anhydroglucose units. The
treatment level of propylene oxide permitted in
making hydroxypropyl starches varies among
regulatory agencies. However, the typical
maximum level is 10 percent, corresponding to
a maximum of one hydroxypropyl substituent
for about every 5 anhydroglucose units. In the
case of octenyl succinate half esters, there is
at most about one substituent group for every
50 anhydroglucose units.
There are two objectives in modifying starch
by introducing monosubstituent groups. One is
to stabilize the starch so its sols will not thicken
or gel on cooling (in the case of cereal
starches), and to maintain hydrating ability,
syneresis and gelling ability when holding at
low temperatures or repeatedly freezing and
thawing (waxy maize, tapioca, and potato
starches). This is accomplished by interrupting
the linearity of the amylose component or of
the outer branches of the amylopectin, reduc-
ing the tendency for intermolecular association
via hydrogen b ~ n d i n gThe
. ~ other objective is
to introduce new or added functions into the
starch molecules. This is the primary objective
in making octenyl succinate half esters of
starch. These substituents impart emulsion
stabilizing properties to starch.
Substituent groups introduced at significant
levels will affect the in vitro enzymic digestibi-
lity of starch.l0S1lAn approximation of the influ-
ence of the degree of substitution on the in
vitro digestibility of cooked cereal starch with
pancreatin or amyloglucosidase is illustrated in
Figure 1. The nature of the substituent group
and type of starch will vary this pattern.
An in vitro study showed that acetate ester
linkages are cleaved by pancreatic juices6
This finding was based on the isolation and
detection of 14C-labeled acetic acid from the
pancreatic digest of acetylated distarch adi-
pate containing 14C-labeled acetate groups.
The conditions for the in vitro study, however,

looti
0 005 01 015 02
D.S.
Figure 1. Percentage of in vitro enzymic digestibility
relative to that of unmodified cereal starch as func-
tion of degree of substitution (D.S.).
_ _ _ _ _ _ ~
were such that some hydrolysis of the starch
acetate possibly occurred during the study, so
that the observation may have been based on
an artifact due to hydrolysis rather than evi-
dence of enzymatic removal.
As noted p r e v i ~ u s l yinl ~the
~ ~discussion
~ on
starches crosslinked with adipate groups, in
vivo feeding studies of rats fed acetylated di-
starch adipate made by treating with a mixed
anhydride containing 0.2 percent adipic acid in
5.5 percent acetic anhydride showed that the
caloric value of the modified starch, which had
an acetate degree of substitution of 0.07, was
comparable to that of unmodified starch. Thus,
even though this starch had an in vitro digesti-
bility of about 80 percent that of the control, its
in vivo digestibility was essentially 100 percent
that of the control, indicating that in starch
stabilized with ester groups there are digestive
mechanisms for removing stabilizing ester
groups, probably through hydrolysis.
The hydroxypropyl substituent groups in hy-
droxypropylated starches, however, are not
susceptible to hydrolysis as are ester groups.
Leegwater studied the digestion of a hydroxy-
(2-14C) propylated starch having a degree of
substitution of 0.12 in rats, and found that over
95 percent of the radioactivity administered to
the rats was detected in the feces.’* In subse-
quent studies using hydroxypropyl starches
with varying degrees of substitution ranging
from 0.025 to 0.106, the major components
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were tentatively identified as hydroxypropyl
maltose, dihydroxypropyl maltotriose, and di-
hydroxypropyl malt~tetraose.’~ The digestibi-
lity of the series decreased with increasing
substitution.
Rats fed substituted and substituted cross-
linked starches, depending upon the degree of
substitution and nature of substituent group,
and unlike those fed crosslinked starches
treated in accordance with regulations for
modified food starches, tended to develop en-
larged caeca at high feeding levels. Such en-
largements are an adaptive change involving
the proliferation within the large intestine of
microorganisms capable of degrading food
constituents not degraded by enzymes such
as amylases, glucosidases, maltases, etc,
present higher up in the gastrointestinal tract.*
They are associated with feeding slowly di-
gested materials and formation of hyperosmot-
ically active substances in the caecum. They
are not of toxicological significance. The cae-
cum returns to normal size when the slowly
digestible material is removed from the diet.**
Long-term Toxicity Studies of Modified
Starches
Long-term studies in rats fed various modi-
fied starches14-15gave negative results in re-
spect to carcinogenesis, but rats fed high di-
etary levels of some substituted or crosslinked
substituted modified starches exhibited an in-
creased incidence of mineral deposits in the
pelvic region of the kidney along with caecal
enlargement. Concern over the etiology of
these deposits by regulatory authorities led to
extensive studies by Feron et a1,16 Newberne
et aI,l7,l8 and Hodgkinson et aI.l9 The conclu-
sions drawn from these studies and literature
investigations were that:
1) Rats are far more sensitive than mice to
the development of pelvic nephrocalcinosis,
and the phenomenon has no apparent human
counterpart;
2) pelvic nephrocalcinosis is commonly seen
in aging rats fed regular laboratory diets. Its
incidence is enhanced by incorporating a wide
range of substances other than modified
“FJC Roe, unpublished data.
“DC Leegwater, unpublished data.
NUTRITION REVIEWSNOL. 44, NO. UFEBRUARY 1986 77

starches in the diets. Lactose in the diet is far
more effective in enhancing the incidence of
pelvic nephrocalcinosis than are modified
starches;
3) all carbohydrates increase calcium ab-
sorption in rats, but some sugars, including
lactose, increase it markedly.20The increased
absorption of calcium leads to its increased
urinary excretion, and it is this increased uri-
nary excretion that predisposes the animals to
pelvic nephrocalcinosis;
4) the problem tends to be exacerbated in
rats by including too much calcium and phos-
phorus and too little magnesium in the diet. Of
special importance, too, is a low Ca:P ratio;
and
5) the effects of excessive calcium absorp-
tion in rats are more severe in older than in
younger ones, because calcium retention as-
sociated with bone growth ceases after matur-
ity is reached.
The picture that emerges is that when sub-
stituted starches are fed at abnormally high
dietary levels, the rate of digestion in the upper
gastrointestinal tract is insufficient to handle all
the carbohydrate. Consequently, unabsorb-
able substituted di- and trisaccharides enter
the caecum where they accumulate pending
possible degradation by bacterial enzymes
and, in the meantime, increase the osmotic
pressure and cause caecal enlargement.
These changes in the gut are associated with
increased calcium absorption, and increased
calcium levels in renal tissue and in the urine,
which lead to calcium deposition in the kidney.
These effects are related to the type and level
of substitution. Hydroxypropyl derivatives
show them to a greater extent than ester deriv-
atives and the effects correlate positively with
the level of substitution.
The effects observed in rats fed high dietary
levels of modified starches are of no relevance
to human beings, for two reasons. First, human
beings, unlike rats, are not sensitive to the
development of any form of nephrocalcinosis
as a consequence of dietary mineral imbal-
ance or excessive intake of lactose. Second,
the dietary levels of modified starches required
to enhance pelvic nephrocalcinosis in rats far
exceed those to which humans are exposed.
In those foods containing modified food
78 NUTRITION REVIEWSNOL. 44. NO. Z/FEBRUARY 1986
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starches with significant levels of monosubsti-
tuents, the amount rarely exceeds 5 to 6 per-
cent in the food. In terms of daily intake it is well
below 1 percent. In infant foods, modified
starches, including simple crosslinked
starches, rarely account for more than 10 per-
cent of the caloric intake.21 An unpublished
survey in 1970 showed that the ratio of cross-
linked to esterified crosslinked, and to esteri-
fied crosslinked starches in baby foods was
10:5:1. Since then, esterified crosslinked
starches have been dropped from most infant
foods. Thus, the level of modified food
starches containing monosubstituents rarely
accounts for more than about 3.3 percent of
the caloric intake in infant foods.
In 25-day-long studies on miniature pigs fed
modified food starches, including hydroxypro-
pylated crosslinked starch, in formulas in
which the modified and control starches were
about 25 percent of the diet, no significant
treatment-relatedeffects were observed on the
growth, biochemical values of blood or serum,
or on carcass or liver comp~sition.~
Ninety-day-long studies on rats, using hy-
droxypropyl distarch phosphate and a control
starch fed at dietary levels of 5, 10, and 25
percent, showed no deviations from the control
with respect to growth, gains in body weight,
food intake, or efficient food utilization at the 5
or 10 percent
Controlled human studies have been limited.
However, one by Pieters et al involving feeding
12 volunteers a 60-g diet containing starch
acetate with 1.98 percent acetyl (degree of
substitution of about 0.075) for 4 days, pro-
duced no gastrointestinal e f f e ~ t s . ~ ~ , ~ ~
Summary
From these observations, it appears that
simple crosslinked starches are indistinguish-
able from unmodified starches in their nutri-
tional characteristics because of the extremely
low level of crossbonds in the starch. Modified
food starches containing monosubstituent
groups alone or in combination with crosslinks,
depending upon the level of substitution, may
show slightly slower rates of digestion at high
feeding levels, but this is of no significance at
the levels of daily intake found in the human
diet. 0

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