Free Radical Biology & Medicine, Vol. 8, pp. 61-69, 1990 0891-5849/90 $3.00+ .

00
Printed in the USA. All rightsreserved. © 1990 PergamonPressplc

Review Article
ANTIOXIDANT FUNCTIONS OF PHYTIC ACID

ERNST GRAF*'t and JOHN W. EATON:~

tThe Pillsbury Company, Technology Center, 311 Second Street S.E., Minneapolis, MN 55414, U.S.A. ;
~tUniversity of Minnesota, Department of Laboratory Medicine and Pathology, Dight Institute, 400 Church Street S.E.,
Minneapolis, MN 55455, U.S.A.

(Received 17 January 1989; Revised and accepted 27 April 1989)

Abstract--Phytic acid is a natural plant antioxidant constituting 1-5% of most cereals, nuts, legumes, oil seeds,
pollen and spores. By virtue of forming a unique iron chelate it suppresses iron-catalyzed oxidative reactions and
may serve a potent antioxidant function in the preservation of seeds. By the same mechanism dietary phytic acid
may lower the incidence of colonic cancer and protect against other inflammatory bowel diseases. Its addition to
foods inhibits lipid peroxidation and concomitant oxidative spoilage, such as discoloration, putrefaction, and
syneresis. A multitude of other industrial applications are based on the antioxidant function of phytic acid.

K e y w o r d s - - F r e e radical, Colonic cancer, Phytic acid, Iron, Chelating agent, Antioxidant, Ferroxidase, Myo-
inositol phosphate esters

I. INTRODUCTION Partial protection against o x i d a t i v e d a m a g e is likely

conferred by the severe d e h y d r a t i o n o f seeds during
The seeds of certain plants m a y remain viable 400
storage which decreases the kinetic m o b i l i t y o f reac-
years.~ The reasons for this r e m a r k a b l e l o n g e v i t y are
tants and catalysts. Slight increases in the ambient rel-
largely unknown. These hardy properties are particu-
ative h u m i d i t y are k n o w n to increase their v u l n e r a b i l i t y
lary puzzling considering that seeds contain a poten-
to o x i d a t i v e stress and decrease their survival rate. ~
tially reactive mixture of large amounts of highly un-
A d d i t i o n a l p r o t e c t i o n is afforded by natural antioxi-
saturated lipids, iron, and o x y g e n . Clearly, elements
dants, such as a - t o c o p h e r o l and a wide range of phe-
within seeds must conspire to p r e v e n t the occurrence
nolic c o m p o u n d s present in m a n y seeds. 2
of extensive o x i d a t i v e injury which w o u l d l o w e r their
A third m e c h a n i s m for extending seed v i a b i l i t y - - a
germinability.
part of the subject of this r e v i e w - - m a y be iron che-
lation by phytic acid. This recently d e v e l o p e d hypoth-
esis asserts that phytic acid maintains iron in the Fe(III)
Ernst Graf is a senior scientist in the Technology Center at the oxidation state and obstructs generation of h y d r o x y l
Pillsbury Company in Minneapolis, Minnesota. He received his un- radical and other activated o x y g e n species by occu-
dergraduate education in Switzerland, and in 1981 he earned his
PhD degree in Biochemistry from the University of Minnesota. His p y i n g all of the available iron coordination sites. 3-5
primary research interests include the chemistry and biochemistry In this r e v i e w , we shall discuss the k n o w n antiox-
of activated oxygen species, i.e., their formation, reactivity, effects idant effects o f phytic acid and, in addition, e x a m i n e
on biological and food systems, and chemical means of mitigating
the consequences of these oxidative events. He is particularly in- the p r o p o s i t i o n that this substance m a y play an im-
terested in the influence of iron and iron chelates, such as Fe(IlI)- portant role in the natural and artificial preservation o f
phytate, on oxygen-mediated reactions. He has participated in sev- o x i d i z a b l e materials and, perhaps, in the prevention
eral symposia and has authored a book and over a dozen publications
on various aspects of phytic acid. In his spare time he likes to camp and treatment o f a n u m b e r o f human disorders.
with his family and run marathons.
John Eaton is Professor of Laboratory Medicine/Pathology and 2. STRUCTURE AND CHEMICAL PROPERTIES OF
Medicine at the University of Minnesota, Minneapolis. He was trained
in Anthropology (PhD, University of Michigan, 1969) and his re- PHYTIC ACID
search interests include biological redox chemistry and pathogen-
host interactions. The Iron Bolt Award was inflicted on him by the A. Occurrence
Oxygen Radicals Gordon Conference in 1987. In his spare time he
avoids exertion. Phytic acid or m y o - i n o s i t o l h e x a p h o s p h o r i c acid is
*Author to whom correspondence should be addressed. a ubiquitous plant c o m p o n e n t that constitutes 1 - 5 % by

61
62 E. GRAF and J. W. EATON

weight of most cereals, nuts, legumes, oil seeds, spores, in solution as the chair conformation of hexaphos-
needles and pollen (Table 1). It typically accounts for phorylated myoinositol as shown in Figure 1.J5-~7
60-90% of the total seed phosphorus 6 and usually oc- Despite the tremendous potential energy inherent in
curs as a mixed calcium-magnesium-potassium salt in the six phosphoric ester linkages, phytic acid is inert
discrete regions of the seeds, such as the aleurone layer and very stable. It can be stored as a solid for years
of wheat and rice. 7 In the past its primary functions and in neutral or alkaline 50% aqueous solutions at 5°C
during dormancy have been believed to be 1) for the for several months before generating any decomposi-
storage of cations 8 and phosphorus, 9 2) a cell wall tion products. The release of 50% of the phosphorus
precursor,I° and 3) as storehouse for potential energy. ~1 requires acid hydrolysis in 5N HC1 at 100°C for at least
In view of its newly discovered antioxidant potential, 6 h, while refluxing at 100°C for 6 h at pH 12 releases
however, phytic acid has been proposed to serve a vital no measurable phosphorus at all. 12Both acid hydrolysis
role in protecting the seeds against the deleterious ef- and enzymatic treatment with phytase result in a mix-
fects of oxygen and iron. ture of myo-inositol, inorganic phosphate and myo-
Elsewhere in nature, phytic acid comprises up to inositol mono-, di-, tri-, tetra-, penta- and hexaphos-
50% of the total weight of the larva of the mesozoan phate. 12 Similarly, during germination of seeds phytic
Dicyemid tyous, a 28-cell organism, where it is stored acid becomes successively dephosphorylated to yield
as a hydrated magnesium salt in the 2 apical cells. Its myoinositol and inorganic phosphate.I°
role in these amoebae is unknown, but it is believed The energetically unfavorable biosynthesis of this
to bind cations that stimulate pinocytosis.12 Myo-ino- compound requires 5 sequential phosphorylation steps
sitol pentaphosphate, a lower phosphate homologue of of myo-inositol monophosphate. In suspension-cul-
phytic acid, is present in both avian and amphibian tured rice cells each successively phosphorylated in-
erythrocytes. This substance binds avidly to hemoglo- termediate was produced until, at 7 days, phytic acid
bin, reducing its affinity for oxygen and causing release was the major form. 9.18 A number of distinct synthetic
of oxygen at higher 02 tensions, a function served by pathways have been identified in different seeds.l°
diphosphoglycerate in mammalian red blood cells.~3 Most qualitative and quantitative analyses for phytic
acid are based on the extreme insolubility of Fe(llI)4-
phytate and the determination of either residual or com-
B. Structure and chemical properties
plexed iron as described in a previous review. 19A more
The structure and chemical properties of phytic acid sensitive and specific method employs reverse phase
have been extensively reviewed in a prior mono- HPLC separation and refractive index detection. 2°
graph. ~2X-ray crystallographic analyses of crystalline
sodium phytate have revealed its exact structure as the
C. Interaction with proteins
hexaorthophosphate ester of myo-inositol, with the
phosphates at positions C1, 3, 4, 5 and 6 in the axial Phytic acid forms strong electrostatic linkages with
position and that at C2 equatorial. 14 Attempts at crys- basic amino acyl residues at low pH and thereby pre-
tallizing other metal salts of phytic acid have failed
and therefore the conformation of iron phytate is un-
known. Several NMR and Raman spectroscopic stud-
ies, however, have deduced the structure of phytic acid
4
Table 1. Phytic Acid Content of Various Seeds 2
Sample Phytic Acid (% w/w) 3

Wheat 1.1
Wheat bran 4.8
Corn 0.9
Corn bran 0 5 I
Corn germ 6.4
Soy beans
Sesame seeds
1.4
5.3 0
Peanuts 1.9 U
Dehydrated peas
Lima beans
0.9
2.5 ® - -o-P-OM
Barley 1.0
Oats
Wild rice
0.8
2.2 OH
Sunflower seeds 1.9
Fig. 1. Structure of phytic acid in solution? S
 Antioxidant functions of phytic acid 63

cipitates most proteins below pH 5.0. At neutral and shown to contain some phytase activity, 3° the majority
alkaline pH both phytate and proteins have a net neg- of the ingested phytate passes through the gastroin-
ative charge which leads to their dissociation from each testinal tract undegraded. 31 Therefore, it is believed to
other. Polyvalent cations, however, form metal bridges interfere with mineral bioavailability in humans and,
between phytic acid and proteins and promote their over the past 30 years, has been the topic of numerous
association at neutral pH. By virtue of binding to pro- research papers, symposia and review papers. 24~32-3s
teins, phytic acid has been found to inhibit polyphenol This subject is highly controversial; many investiga-
oxidase, 5 e~-amylase, 2~ alcohol dehydrogenase, 22 tryp- tions have shown no effect or even enhancement of
sin,23 and other enzymes. These protein-phytate interac- cation uptake. 35
tions were reviewed previously in detail] 4 The effect of dietary phytic acid on mineral bio-
A unique type of protein-phytate interaction is the availability depends on a number of experimental fac-
high affinity of phytic acid for the 2,3-diphosphogly- tors discussed previously. 36 One of these factors is the
cerate site in hemoglobin. In human hemoglobin A, ratio of metal-to-phytate. Although most cation-phy-
eight basic amino acyl residues form electrostatic bridges tate solutions are insoluble, complexes containing only
and two hydrogen bonds with the six phosphate moie- 1 cation (or possibly 2) per phytate molecule are very
ties of phytic acid. The dissociation of this complex is soluble at any pH. 35This stoichiometry can be obtained
6 x 10 -8 M for deoxygenated and 1 x 10 -6 M for by adding excess phytic acid. Figure 2 shows the bi-
oxygenated hemoglobin. Therefore, the binding of phytic phasic effect of phytic acid on calcium solubility. The
acid modifies the heme iron-O2 interaction which fa- same relationship holds for all other soluble polyvalent
cilitates dissociation of oxygen from hemoglobin. The cations tested. Therefore, the solubility of monocat-
chemistry and physiological implications of this site- ionic phytate may provide an explanation for the ap-
specific protein binding are discussed in a previous parent controversy of past nutritional investigations.
review. 25 Phytic acid can be incorporated into eryth-
rocytes irreversibly to give functionally intact cells with
improved 02 transport capabilities. 26 These phytate-
3. ANTIOXIDANT PROPERTIES OF PHYTIC ACID
laden erythrocytes may prove useful in the treatment
of organ ischemia, hemolytic anemia, pulmonary in- Many antioxidants function by reacting with acti-
sufficiency and hypererythropoiesis. 27 vated oxygen species, thereby being consumed. Phy-
tate, in contrast, is remarkably unreactive and extraor-
D. Chelation of metals dinarily stable. All of the antioxidant properties of phytic
The unique structure of phytic acid suggests tremen- acid likely derive from its relatively high binding af-
dous chelation potential. Indeed, phytic acid exhi- finity for iron.
bits a high affinity for all polyvalent cations in the fol-
100
lowing decreasing order of stability: Cu 2÷ > Zn 2+ >
Ni 2+ > Co 2+ > Mn 2÷ > Fe 3+ > Ca 2+. By virtue of
its high calcium affinity, phytic acid also adsorbs tightly ,.-.,. 80
to hydroxyapatite, a complex crystalline calcium phos-
phate (Cas[POa]3OH), which is the chief structural ele-
ment of vertebrate bone and tooth. 28 However, disso- ~ 60
ciation constants (Ka's) are not known due to the
complexity of these electrostatic interactions, that is,
1 phytate molecule can bind up to 6 divalent cations
and the metal could possibly bridge at least 2 phytate
molecules depending on the redox state. All of these
complexes are coexistent and have different Ka's. Fur- 20
thermore, metal chelates of high metal-to-phytate ra-
tios precipitate due to their pronounced insolubility.
0 '
Potentiometric measurements at 20°C estimated the Ka's o 1: lo-' 1: lo -2 10-1
of the first 2 calcium ions bound to phytate to be [Phytic Acid] (M)
44 x 10-6 M at pH 7.2 and <1 x 1 0 - r M a t p H 8 . 4 . 29
Metal phytate complexes have long been known to Fig. 2. Effectof phytic acid on calcium and iron solubilities. The
be highly insoluble over a wide pH range, which forms solubility of 10 mM Ca2. (squares) and 0.7 mM Fe3÷ (circles) was
determined in 100 mM Hepes at pH 7.4 and 25°C. Solublecalcium
the basis for the highly publicized concern over dietary and iron were measured radiometrically. Redrawn from Graf and
phytate. While intestinal mucosa and bacteria have been Eaton, 1984. 35
64 E. GRAFand J. W. EATON

A. Iron catalysis 100

\1
w w v

As has been very thoroughly reviewed in this journal

and elsewhere, 37-39 iron-catalyzed reactions play a cru- 80
cial role in the oxidative damage to biological mate-
rials. These reactions most often involve activation of v

oxygen and subsequent reaction with iron, generating 60

even more reactive species. The reaction product most
often invoked to explain the damaging effects of iron O
m 40
is the dread hydroxyl radical, -OH. It should, however, e.-

be mentioned that several lines of evidence suggest

that free .OH may not be as important as ferryl and
20
perferryl ions that selectively oxidize substrates to which
iron is bound. 4°'41 Several iron chelators have been
found to suppress this activity. 4
0
-9 -8 -7 -6 -5 -4 -3
log [Iron] (M)
B. Iron-phytate chelate
Fig. 3. Effect of phytic acid on iron solubility. The solubility of
In contrast to calcium, Fe 3+, in the absence of phy- Fe3+ at pH 7.4 in the absence (squares) and presence of 1.15 mM
tate, is completely insoluble at neutral or higher pH phytate (circles) was determined radiometricallyafter incubation for
24 h. Redrawn from Graf and Eaton, 1984.35
due to the formation of large polynuclear iron-hydrox-
ide complexes (Fig. 2). High concentrations of phytic
acid solubilize iron in the form of Fe(III)l-phytate,
C. Inhibition of oxidative reactions
whereas low concentrations evidently precipitate iron
as Fe(III)3- and Fe(III)4-phytate complexes. The degree As is well-known free iron and certain iron chelates
of solubility of Fe(III)2-phytate is difficult to ascertain greatly facilitate the production of radical species with
since its formation invariably also entails the presence reactivities similar to that of .OH. Iron-catalyzed for-
of insoluble species. Only Fe(III)wphytate can be pre- mation of .OH requires the availability of at least one
pared in relatively pure form by adding a large excess reactive iron coordination site 4 as well as iron solu-
of phytic acid as shown in Figure 2. bility. In fact, by virtue of maintaining the solubility
The dissociation constants for the various iron-phy- of iron many chelators enhance this catalytic function
rate complex species are not known. From radioactive of iron.
iron solubility studies it is evident, however, that phy- There are, however, a few chelators which, while
tic acid exhibits a tremendous affinity for iron. Figure preserving the solubility of iron, make the metal totally
3 shows the effect of phytic acid on iron solubility at unreactive. Phytic acid is one of these rare chelators;
pH 7.4. Chelation of iron by phytic acid prevents the in molar ratios of 0.25 phytate-to-iron and above the
formation of polynuclear insoluble aggregates even at superoxide-driven generation of .OH is almost com-
iron concentrations as low as 6 riM. pletely blocked (Fig. 4). Similar results are obtained
The six coordination sites of trivalent iron are oc- when ascorbate is used as the reducing agent. Inter-
cupied by water and hydroxide ions in aqueous solu- estingly, not all six phosphate moieties are required
tion. Most chelating agents displace five of these li- for this inhibition. Myo-inositol tri-, tetra- and pen-
gands and form a pentadentate chelate with H20 taphosphate are also effective (Graf, unpublished re-
occupying the sixth coordination site. EDTA forms a sults).
hexadentate chelate but due to its small size distorts Phytate also decreases the rate of lipid peroxidation
the chelate and makes a seventh site available for H20. catalyzed by iron and ascorbate as shown in Figure 4. 4
Phytic acid, however, is unique in occupying six co- This latter may be due, in part, to the diminished reac-
ordination sites and displacing all of the coordination tivity of phytate-bound iron with ascorbate (cf. Fig. 5)
water in the Fe(III)rphytate complex. 4 This chelate and may also be related to the ferroxidase activity of
lacks an aquo coordination site as determined by spec- phytate discussed below.
trophotometric titration with azide (which will displace Many important iron-driven oxidative reactions re-
the water).4 The validity of this competitive displace- quire ferrous ions as a necessary intermediate. Indeed,
ment assay has been confirmed by IH-NMR relaxation the ferroxidase activity of ceruloplasmin (which ca-
measurements.4 talyzes spontaneous oxidation of ferrous to ferric) has
 Antioxidant functions of phytic acid 65

60

"~ 6

o t-
40
E .o
.5
:3
c-
"0
o
o n
"o
"-r
2 0

0. 20
"0
"~. 2
"1

0 0
Fe FeADP FePhy Fe FeADP FePhy
Fig. 4. Effect of phytic acid and ADP on iron-catalyzed lipid peroxidation (A) and .OH generation (B). Formation of hydroxyl
radical (-OH) during 30 min in 50 #M Fe ~+, 500 ,aM chelating agent, 50 mM Tris, pH 7.4, 50 mM dimethyl sulfoxide, 300
#M hypoxanthine, and 10 milliunits of xanthine oxidase at 37°C was determined as previously described. ~ Lipid peroxidation
was measured by incubating 160 pM arachidonic acid, 150 #M Fe 3÷ , 1.0 mM ascorbate, 240 #M chelating agent, and 100 mM
NaHCO3, pH 7.4, at 30°C for 60 min and determining malondialdehyde (MDA) with thiobarbituric acid spectrophotometrically# 2
Redrawn from Graf, 1986. 43

been invoked to explain certain antioxidant character-

istics of this copper-bearing plasma protein. 45,46 We
find that phytic acid is also a potent ferroxidase as
shown in Figure 6. Whereas the spontaneous oxidation
of Fe 2+ in neutral pH is relatively slow, the addition
250 of phytic acid causes a greatly accelerated rate of ox-
idation of Fe 2+ to Fe 3+.
Blank In sum, there are at least 3 ways in which iron-
200
~ a t e driven oxidative reactions might be interdicted by a
chelator. First, the chelator may occlude all reactive
,--,150
coordination positions, thereby making the iron cata-
"lO lytically inert. Second, because many iron-mediated
reactions require redox cycling of the metal, chelators
0
which enforce one exclusive oxidation state will block
0
0
this cycling. Third, certain " t a r g e t e d " iron reactions
& (such as the scission of DNA 47'48) may require direct
50 juxtaposition of the reactive metal with the substrate.
Some chelators may slow these reactions by preventing
binding of iron to the host molecule. There is evidence
0 i i i i l

10
, i i , I

20
¢ , , ,

30
I , , , ,

40 that phytate exerts antioxidant functions in all three

ways.
Time (min)
Fig. 5. Effect of 240 g M phytic acid on iron-catalyzed oxidation 4. B I O L O G I C A L EFFECTS AND APPLICATIONS OF
of 200/zM ascorbic acid. The reaction was carried out in 150 #M
Fe 3+ and 50 mM Tris buffer, pH 7.4, at 25°C. Oxidation of ascorbic PHYTIC ACID
acid to dehydroascorbic acid was estimated from the decrease in
absorbance at 260 nm" using a differential molar extinction coef- Some potential uses of phytic acid presently being
ficient of 1.5 x 104 M - ' c m - L explored have nothing to do with the antioxidant ca-
66 E. GRAF and J. W. EATON

180 diet. It was earlier hypothesized that diets which are

,JW Addition of Fe2+ high in fiber content are protective by virtue of accel-
160
erating the movement of food through the gastro-in-
140 testinal tract. We have proposed the alternative inter-
pretation that it is the phytate content of the diet, rather
120 than the fiber, which is most important. 53 This prop-
-I-
osition is, at least indirectly, supported by several ob-
E 100
E servations.
80 First, carcinogenesis may importantly involve metal-
0
60 mediated catalysis of activated oxygen formation and
D N A scission. 47'48'54 As earlier reviewed, phytate, by
40 binding free iron, will suppress a number of iron-driven
oxidative reactions. Because the intestine may contain
20
large amounts of potentially reactive iron (particularly
0 in the case of populations which eat diets rich in red
0 5 10 15 20
meat), the simultaneous presence of phytate may act
"lime (rain) to suppress iron-driven steps in carcinogenesis.
Fig. 6. Effect of phytic acid on the oxidation of Fe2+ by 02 at pH Second, close inspection of the available epidemi-
7.4. Oxygenconsumptionat 25°C was measured using a Clark elec- ologic data reveals that the correlation between high
trode following the addition of 500 pM Fe2~ (A) or 500 ,uM Fe-~+ phytate intake and low incidence of colonic cancer is
with 2 mM phytic acid (B). Redrawn from Graf et al., 19877
much better than the correlation between high fiber
diets and lowered cancer rate. s3
Finally, there is now some experimental support for
pacity of this very stable seed constituent. The very
the antineoplastic effects of phytate. Shamsuddin et al.
high affinity of phytate for hydroxyapatite is being
have recently found that the carcinogenic effects of
exploited in the design of new cariostatic and plaque-
azoxymethane are significantly offset when experi-
arresting oral care products .28 The adsorption onto cal-
mental animals are given drinking water containing 1%
cium-based crystals also checks bone resorption and
sodium phytate? 5 Furthermore, Jariwalla et al. have
the growth of renal calculi. 28 A high phytate diet has
found that the tumor-promoting effects of magnesium
been used effectively to treat hypercalciuria and kidney
oxide are suppressed in rats fed a diet containing over
stones in humans 49 and dietary phytate has been shown
12% phytate by weight. 56 Interestingly, the inclusion
to be inversely correlated with the incidence of renal
of this very large amount of phytic acid in the food
stones in epidemiological studies. 5° Phytate has also
had no perceptible adverse effects on the animals even
been found to inhibit platelet aggregation, s~ Important
after 6 months of continuous feeding.
clinical uses of phytate-laden erythrocytes are currently
under development to treat disorders arising from poor
2. Additional biological effects. The presence of high
local tissue oxygenation, such as organ ischemia, he-
concentrations of phytate (actually, myoinositol pen-
molytic anemia, pulmonary insufficiency and erythro-
taphosphate--IP5) in the erythrocytes of birds and am-
cytosis.27 Inhibition of a-amylase also lowers the blood
phibians has already been noted. Within the erythro-
glucose response and may prove useful in the clinical
cytes of these species, the IP5 has profound effects on
management of hyperlipidemia and diabetes. 2~ Appli-
the oxygen binding characteristics of hemoglobin, al-
cations based on phytate's hypocholesterolemic effect,
lowing improved delivery of oxygen at higher oxygen
antidote activity against acute lead poisoning and oth-
pressures. We should point out an additional, but un-
ers have been reviewed elsewhere. 43'52 But the most
tested, possibility--that the IP5 also acts to suppress
important applications of phytate may derive from its
adverse iron-driven reactions within the red cell. In
marked antioxidant capabilities.
certain hemoglobinopathies such as sickle cell disease,
enhanced oxidation of the cell membrane--evidently
A. Biomedical Applications mediated by hemoglobin-derived iron--may be im-
1. Suppression of colonic carcinogenesis. We earlier portant in the accelerated erythrocyte destruction char-
proposed that the dietary intake of phytate might ex- acteristic of these disorders. 57-59Similar, but less marked,
plain some of the well-known variations in the inci- iron-driven oxidative events may occur within normal
dence of colonic cancer. 53 Human populations show red cells. If so, the presence of high concentrations of
large differences in the frequency of colonic cancer IP5 within an erythrocyte would be a great advantage,
and these differences are likely related to variations in giving the cell a large reserve of chelation capacity to
 Antioxidant functions of phytic acid 67

neutralize the effects of any iron released from intra- Phytic acid was found to significantly decrease the
cellular hemoglobin. consumption of headspace oxygen by cooked minced
Many of the above effects are mediated not only by chicken breasts stored in sealed O2-impermeable con-
phytic acid, but also by myo-inositol tri-, tetra-, and tainers at 4 ° C . 62 Furthermore, it substantially sup-
pentaphosphate. A myo-inositol phosphate isomer of pressed MDA generation by cooked whole chicken
particular interest is a recently isolated hydrolysis product breasts (Fig. 7). A trained sensory panel affirmed a
from yeast fermentation which was identified as D- concomitant decrease in the development of WOF.
myo-inositol 1,2,6-triphosphate (PP56). 6° It is biolog- Similar antioxidant effects of phytic acid on cooked
ically quite different from the well known second mes- ground beef were reported previously. 66 Presumably
senger, D-myo-inositol 1,4,5-triphosphate. This com- phytic acid removes myoglobin-derived iron from neg-
pound exhibited profound antiinflammatory effects in atively charged phospholipids and prevents their au-
foot pad edema and adjuvant arthritis (Persson, per- toxidation and off-flavor formation.
sonal communication). Several additional pharmaco-
logical actions of PP56 have been demonstrated, such C. Corrosion inhibition
as inhibition of ADP-induced thrombus formation in
the microcirculation of the hamster cheek pouch. 61 Two past reviews summarize the extensive body of
patent literature on the anticorrosive properties of phy-
t i c a c i d . 3,43 By virtue of chelating and inactivating iron,
B. Food preservation phytic acid coating of metals and alloys imparts to them
long-lasting corrosion inhibition, scratch resistance,
Many foods are extremely sensitive to air oxidation
good solderability, superior appearance, and improved
due to their high level of iron and unsaturated fats in
adhesion to organic finishes. Anticorrosive primers and
close proximity. Oxygen levels above 1% in the head-
paint additives containing phytic acid produced films
space of food containers may cause undesirable texture
of improved hardness, flexibility, adhesion, and cor-
changes, discoloration, flavor changes, nutritional losses
rosion resistance. Gypsum containing phytic acid was
and microbiological safety hazards. Therefore, a num-
found to prevent the corrosion of the steel frames that
ber of food industries undertake painstaking efforts to
it was poured into. Additional applications based on
reduce these effects by eliminating oxygen from the
package and/or adding antioxidants, such as radical
scavengers or metal sequestrants.
The antioxidant properties of phytic acid make this
ubiquitous plant seed constituent an effective natural 8
food preservative. 3 Studies on water-in-oil emulsions
have demonstrated marked antioxidant effects of phytic
acid at room temperature for at least 12 months. 62 Al-
though it is not affirmed GRAS (Generally Recognized
As Safe) by the United States Food and Drug Admin- t3n
istration, it is employed extensively as a food additive E
v 4
in several foreign countries. Commercial aspects of 00
phytic acid were reviewed previously63 and it is cur- <
rently being manufactured in large-scale quantities by m
~- 2
Tsuno Rice Fine Chemicals for the preservation of soy-
bean oil, meat, fish meal pastes, coloring agents, cav-
iar, fresh vegetables, and various other f o o d s . 64 0
A very sensitive model for testing the efficacy of 0 5 10 15 20 25 30
food antioxidant systems is uncured cooked meat, Time (days)
poultry, or fish. During the cooking process iron is Fig. 7. Effect of phytic acid on TBARS generation in whole chicken
liberated from myoglobin which interacts with phos- breasts. Chicken breast strips were defatted and 100 g samples with
pholipids to catalyze lipid peroxidation and the devel- 10 g water (circles) or 1.5 mM phytic acid (squares) were added to
a small microwave baking dish. The samples were soaked for 2 min
opment of WOF (warmed-over flavor) during refrig- at room temperature and them cooked in a Litton Generation II
erated storage for as little as 24 h . 65 The inhibition of microwave oven on high for 3 1/2 min (in a separate experiment
WOF development (rancid or stale flavors) is of great the water absorption by chicken breasts was determined to be 11 -+
1% by weight). All samples were stored in O2-impermeable vacuum
economic importance and represents a major technical pouches at 4°C. TBARS were distilled from entire samples and
challenge to a broad spectrum of the food industry. determined using TBA.
68 E. GRAF and J. W. EATON

iron chelation are the formulation of active cleaners inositol hexakis(phosphate) in aqueous solution. A carbon-13
NMR, phosphorus-31 NMR, and Raman spectroscopic inves-
and rust removers useful for automobile radiators.
tigation, J. Am. Chem. Soc. 102:3144-3148; 1980.
18. Igaue, I.; Shimizu, M.; Miyauchi, S. Formation of a series of
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