Review

NaturaJ antJoxidants
There is a general trend towards replacing the u~e of synthetic
antioxidants in food processing by the addition of natural oxi-
dation inhibitors or by the preferential use of ingredients that
for food use
naturally possess antioxidant activity. The chemical structures
of natural antioxidants are related to those of synthetic
antioxidants; most phenolic antioxidants are pyrocatechol or Jan Pokorn /
pyrogallol derivatives, dihydrochromanols, or flavonoids. The
most important synergists are polysubstituted organic acids,
antioxidants require expensive testing and theft use
amino acids, phospholipids and Maillard reaction products, might be objected to by consumers3.
which also efficiently chelate heavy metals. Because of their The most readily acceptable oxidation inhibitors are
low solubility, polar compounds or extracts are more suitable common food ingredients, as their use is not limited by
for use in fatty foods than for addition to edible oils. The best legislation. Many foods contain compounds that possess
antioxidant activity (Table 2), but some such foods are
approach may be to produce fatty foods that are oxidatively of limited use as additives as they impart a specific
stable without requiring the addition of antioxidants. flavour, aroma or colour to the finished product; further-
more, those that have low antioxidant activit? or low
solubility in lipids are of limited use in the stabilization
of edible oils and fats, although they may be used in
Edible fats, oils and fatty foods slowly oxidize during fatty foods. Purified 'nature-identical' substances or ex-
storage, and various oxidation products formed cause tracts obtained ffoni foods that have antioxidant activity
randdity and deterioration of the sensory properties of may be used as well.
the products. Foods that may require stabilization Natural oxidation inhibitors may also be prepared
include: most edible oils; lard; fats and oils used for fry- from materials that are not generally used as foods. For
ing; fats and oils used in processed foods; margarines example, nordihydroguaiarefic acid, a pyrocatechol
that contain animal fats; milk fat; fried foods such as derivative isolated from the creosote bush, was one of
potato chips; roasted nuts; dried soups, broths and the first antioxidants kt]own. Both the natural product
seasonings; dried meat; frozen fish and fish oil; dried and the synthetic nature-.ideatical compound have been
milk; potato powder, flakes and granules; cakes; chewing used as food additives; however, doubts about the safety
gum; concentrated vitamin preparations; flavour/_ngs and of the products have resulted in their use being banned
essential oils. in some countries. The safety of all such substances
Lipid autuxidation occurs by a free-radical chain reac- should, therefore, be tested before use.
tion |. In foods, the oxidant is usually molecu!ar oxygen Tire structures of some natural antioxidants that have
from the air; singlet oxygen may also be involved. The been added to foods are given in Fig. 1.
chain reaction may be catalysed by light or by certain
metals. In order to prevent such autoxidation, various Natural antioxidants from vegetable oils
oxidation inhibitors may be added. Inhibitors of autuxi- Tocopherols and related compounds
dation may be classified into groups according to their Tocophemls occm as mil~or constituents in all veg-
mechanism of action (Table 1). etable oils, and are among the best known and most
The first attempts to stabilize food products against widely used antioxidants. The a-, ~-, 7- and 8-
oxidative rancidity occurred 60 years ago. Various natu- tucophemls differ in the degree of methylation of the
ral substances were used, but were soon replaced by
synthetic chemicals, which am cheaper, more easily
Table I. Classificationof inhibitorsof lipid oxidation
available, of consistent quality, and have greater anti-
oxidant activity. Gradually, food safety legislation has Type of inhibitor Mechanismof action
developed to allow only the use of those synthetic
chemicals that have been tested for safety on animals, Antioxidants Reactionwith free radicals, interrupting
and more and more complex, time-consuming and the propagationphaseof the chain
expensive toxicological studies have been required to reaction
guarantee the safety of stabilized foods 2. Synergists Increasingantioxidant activity
During the past two decades, both consumers and legis-
lation officers have become suspicious about synthetic Retarders Reducinghydroperoxideswithout
forming free radicals
chemicals, even chemicals that have been proven by
experiment to be safe, while natural alternatives are Metal scavengers Inhibitingthe ability of heavy metals
considered not to present significant health risks. to catalysethe production of free
Manufacturers also prefer natural products, as synthetic radicals
Singlet-oxygen Deactivatingsingletoxyger.,which may
inn Pokom~/is at the Instituteof ChemicalTechnology,Technick,~1905, quenchers initiate the free-radical chain reaction
CS-16626 Prague6, Czechoslovakia.

Trends in Food Science& Technology September t 991 ©19~i,ElsevierSciencePublishersLid,(UK) 0924-2244/91/$02.00 223

 dihydrochromanol ring. Their antioxidant activities de-
pend very much on the food to which they are added,
the concentration used, the availability of oxygen, and
the presence of heavy metals and various synergists ~. At
high concentrations and in presence of traces of iron and
copper salts, tocopherols may act as pro-oxidants, saris-
factory antioxidant activity is usually achieved only
when they are used in combination with synergists such
as ascorbic acid, citric acid and some amino acids,
o[ wm~ vaiiotis ~.=m..~. agents. Their antioxidant ac-
tivities range in the order: 8-tocopherol (most effective)
> ~tocopherol > 13-toeopherol > ¢t-tocopherol (least
effective).
Synthetic DL-(X-tocopherolor its acetate derivative is
often added to fats and oils, but the addition of natural
tocopherols is preferred because the synthetic prepar-
ations contain biologically inactive stereoisomers. The
natural tocopherols usually consist of mixtures of ct-, 7"
and ~-tocopherols. They are readily available from the
'sludges' formed during the deodorization of refined
vegetable oils4; tocopherol preparations from 'sludges"
have better antioxidant activity than pure ot-tocopheroP
because of their content of 7- and 5-tocopberols. Natural
7-tocopherol efficiently stabilizes stored edible oils 6.
Tocopherol oxidation products also have some anti-
oxidant activity, and the structurally related ¢t-, 13-, 7-
and 6-tocotrienols, which are found in palm oil, have
antioxidant activities similar to those of the respective
tocophe~ls 7.
Antioxidant~,~rom sesameoil and olive oil
The work be Fukuda and co-workers H'~ has signifi-
cantly contributed tc our knowledge of the active anti-
o~id.,~-~,~,npounds of sesame oil, which is quite stable
to oxidation. The active compounds are produced from
lignins in the ~ceds via various precursors such
as sesamolin, which is hydrolysed on heating to form
s0samol ~.
Olive oil is very stable, not only because of its low
content of polyenoic fatty acids, but also due to the
presence of various natural bitter-tasting antioxidants,
mainly derived from hydroxytyrosol (a derivative of
pyrocatechol), which is a produce of tyrosine degradation,
Table 2. Sourcesof the main natural oxidation inbibiton
Sources Oxidation inhibi~on
Oils and oilseeds Tocopherolsand tocotrienols;sesamol
and relatedsubstances;olive oil resins;
phospholipids
Oat and rice brans Variouslignin-derivedcompounds
Fruitsand vegetables
Ascorbicacid; hydrox~carboxylicacids;
flavonoids;carotenoids
Spices,herbs,tea, Phenoliccompounds
cocoa
Proteinsand protein Amino acids;dihydropyridines;
hydrolysates Maillard reactionproducts
224
but also formed from various other polyphenols~°.
During the pressing of olives to make olive oil, the
polyphenol-derived antioxidants pass into the raw oil.
Most other antioxidants remain in the pulp and water
phase and are discarded; they may be recuperated and
used for the stabilization of other oils ~.
Phospholipids
Phospholipids (e.g. lecithin) are present in crude veg-
etable oils; they are removed during the degumming
phase of refining. Phospholipids are often used as syner-
gists in combination with phenolic antioxidants. The
stabilizing effect of the addition of phospholipid prep-
arations is controversial, and is often attributed to the
presence of active minor substances, such as tocoph-
erols, metal chelators and compounds that accelerate the
decomposition of hydreperoxides without producing
free radicals. However, the stabilizing effects of phos-
pholipids increase as their concentrations increase, and
purified phosphorylated acylglycerols containing no
minor active substances have antioxidant activities com-
parable to those of natural phospholipid preparations ~2.
The metal-chelating activity of phospholipids has been
confirmed by comparison of their antioxidant activities
in the presence and absence of iron compounds. The
ethanol-soluble fraction of natural lecithin preparations
is more efficient at chelating metals than the ethanol-
insoluble fractiont3. The antioxidant activity of phos-
pholipids has been attributed to their ability to decom-
pose hydroperoxides, the antioxidant activity appears to
be dependent on the presence of bound choline or
ethanolamine as a constituent of the phospholipids ~4.
Natural antioxidants from cereals
Cereals are among the most common food com-
ponents, and can be added to many food products. Oat
flour and oat extracts were among the first antioxidants
proposed for use tbr the stabilization of fats, oils and
fat-containing foods ~s.
Esters of caffeic and ferulic acids appear to be the
most important antioxidants in oats. Similar compounds,
such as ,lryzanol (an ester of ferulic acid and a triter-
penic alcohol), are found in the brans oi other cereals ~6.
Other active substances identified include fiavonoid gly-
cosides (from rice hulls) and esters of sinapic and proto-
catechuic acids (from rapeseed hulls).
All the above-mentioned antioxidants from cereals
originate from lignins, which are present in many plants.
Their metal-scavenging abilities contribute to their
stabilizing effects.
Natural antioxidants from other sources
Phenolic compounds
Various phenolic compounds, such as hydroxy deriva-
tives of cinnamic and benzoic acids, are common con-
stituents of many plant foods; most possess antioxidant
activity ~7. Esters of caffeic acid (e.g. chlorogenic acids)
are the most important plant-derived phenolic anti-
oxidants, as they have high antioxidant activity at levels
found in natural substances. They are present in many
Trendsin FoodScience& TechnologySeptember1991
 OH

1
R|

vegetables and mushrooms as well as in nuts and o

oilseeds. R H3
R3
Flavonoids
Tooopherol$
Flavones and related compounds occur widely in carnosol
many plant foods. Catechin and quercetin, flavonoid
pyrocatechol derivatives, possess high antioxidant ac- OH
tivity and have been used to stabilize lard. The poly- OH
hydroxydihydrochaleones are efficient antioxidants
found in cabbages and other leafy vegetables, peppers, HO~cHzOH
soybeans, peas, peanuts, cocoa beans, cottonseed, and
many other plants. Some flavonoid pyragailol deriva-
tives, such as tea tannins, also possess antioxidant ac- Rydroxytyroso I
tivity. Ethyl acetate extracts from both green and black Ouercetin
teas have high antioxidant activity when added to lard tS.
o
Tea flavonoids are of practical interest, as dust, II
'grounds' and leaves that are not suitable for drying for H O ~ C ' ~ 0
making tea are available in large quantities for the °
preparation of extracts ~9"2°. n

Antioxidants from herbs, spices and algae Oaf felt acid

The antioxidant activities of various spice extracts
have long been recognized from practical experience.
Kasuga et al. 2t examined extracts from 117 parts of 107
plant species, and detected some antioxidant activity in
more than 50% of the materials examined. Oregano was
shown to contain various antioxidant pyrocatechol de-
rivatives, including 4-(3,4-dihydroxybenzoyloxymethyl)-
phenyl-13-D-glucopyranoside2', and efficient antioxidants
were also found in sage, thyme, clove (in which the main
active component is eugenol), ginger, boldo, catnip,
tonka beans, white oak and ginseng.
The antioxidant activity of rosemary extracts has been
known for about 30 years, and the active compounds
have been elucidated23. The main active substance is
camosol: an active diphenolic diterpene and its quinone
derivative have also been isolated from rosemary
leaves24. The diterpenes epirosmanol and isorosmanol
also have antioxidant activity; the antioxidant activity of
isorosmanol added to lard is comparable with the activi-
ties of the synthetic phenolic antioxidants butylated
hydroxyanisole and butylated hydroxytoluene25.
Extracts from algae such as ChloreUa spp. and
Scenedesmus acutus contain various antioxidant com-
pounds. Fujimoto et al. 2e isolated natural brominated
hydroxylated benzaldehydes and benzylalcohols from
red algae; the compounds had antioxidant activities
comparable to those of synthetic phenolic antioxidants.
Carotenoids
Plant extracts containing carotenes and various
carotenoids are frequently used as natural colouring
materials, but they also possess antioxidant activity,
especially in the presence of light. They act by quench-
ing singlet oxygen produced during photosynthesis27.
The presence of carotcnoids in edible oils may also help
protect against the formation of singlet oxygen by
blocking light transmission through the oil. Owing to
their multiple conjugated double-bond system, the
carotenoids, particularly the 4-oxo derivatives such as
OlI
Chlorogenic acid
HO~j~...-- 0
Nordihydroguaiaretic
acid Sesamol
Fig. 1
Chemical structures of some natural antioxidants. For ot-tocopherot, R1, Rz and
R3,- CH3; R4,- I(CH2hCHICH3)]~Ct-I).
astaxanthin and canthaxanthin, are also able to scavenge
free radicals.
Polysubstituted organic acids
Pol~substituted organic acids, such as citric acid, have
been used for the stabilization of tats and oils for many
decades 28. Decomposition products formed during the
heating of citric acid, and other hydroxycarboxylic acids
such as tartaric, malic and isocitric acids also have some
activity; hydroxycarboxylic acids act as metal scavengers,
and stimulate the decomposition of hydroperoxides by
pathways that do not result in the formation of free rad-
icals. Ascorbic acid and its esters are widely used as
synergists for the stabilization of fats and oils29.
Proteins, peptides, amino acids and Maillard reaction
products
Proteins, peptides and free amino acids decrease the
rate of autoxidation and the hydroperoxide content of
fatty foods. Amino acids are effective synergists in com-
bination with phenolic antioxidants~°, acting both as scav-
engers of heavy metals and as promoters of the decompo-
sition of hydroperoxides, which are otherwise a source of
free radicals. Protein hydroiysates have similar activity3j.

Trends in FoodScience& Technology September1991 225

 benzene ring are substituted with various apolar groups
in both cases.
Natural food components do not possess high acute
toxicity, as highly toxic substances would have been
eliminated from tradition'a] use as foods. However, the
fact that a substance is natural and commonly round in a
food is no guarantee that it is entirely nontoxic. It may
have low toxicity, or be carcinogenic or mutagenic.
Synthetic antioxidants are tested for such effects, but
many natural food components have not yet been tested.
The advantages and disadvantages of natural and syn-
thetic antioxidants are summarized in Box 1. No
rational scientific argument can be given for preferences
During prolonged storage or during the heating of for natural antioxidants; they are more acceptable to
foods, amino acids react nonenzymically with reducing consumers mainly on emotional grounds. While it is
sugars to form brown pigments; the complex sequence important for manufacturers to meet the requirements of
of reactions involved is called the Maillard reaction. It consumers, it is imperative that the safety of additives
has been known for more than 30 years that Maillard that are not 'generally recognized as safe' (GRAS) be
reaction products have antioxidant activity, and their tested before use.
activity in model systems, cookies and meat products Perhaps the safest approach is to avoid the use of both
has been thoroughly studied3z. The main mechanism of synthetic and natural antioxidants by using appropriate
action is the ability of the compounds to bind heavy packaging and storage methods or by avoiding the use
metals, particularly iron~3, to form inactive complexes. of ingredie~at~that are readily oxidized, as summarized
Because of their dark colour and low solubility, Maillard in Table 3. Some consumers will prefer this approach,
reaction products are unsuitable for use in fats and oils, even though it may be more expensive.
but they may be added to improve the oxidative stability
of many foods. References
Low molecular weight carbonyl compounds produced 1 Chan,H.W-S. (1987)Autoxidation of Unsalurated Lipids,
by the Maillard reaction condense with amino acids and AcademicPress
other amine derivatives to form heterocyclic products, 2 Haigh,R. (1986)Food Chem. ToxicoL 24, 1031-1034
such as dihydropyridines, that have been shown to have 3 Haumann,B.F.(1990)AOCSInform 1, 1002-1013
strong antioxidant activity in model systems34, and 4 Liebing, H.andKarw~e,R.(1984)Seifen, Oete, Fette, Wachse110,
which can deactivate singlet oxygen'~'~. 573-575
5 Pokorng,J., Luan,N.T., ~undu, M.K., Domah,M.B., ,~midrkalov,~,E.
and lanf~ek,G, (1974)Nat~run818, 635-643
Conclusions 6 Pongraz,G. (1984)Fet/e.Sei(en,Ansvichm. 86, 455-460
Natural food additives, including antioxidants, are 7 Seher,A. and Ivanov,S.A.(1973) Fette, Seifen, Anstrichm. 75, 606-608
generally preferred by consumers, and more easily gain 8 Fukuda,Y. and Namiki,M. (1988) Nippon 5hokuhin Kogyo Gakkai.shi
legislative approval than synthetic additives, although 35, 552-562
most antioxidants are polysubstituted phenolic com- 9 Fukuda,Y., Nagata,M., Osawa,T. and Namiki,M. (1986)Agric. Biol.
pounds, whether natural or synthetic. Natural anti- Chem. 50, 857-862
oxidants (with the exception of the tocopherols) mostly 10 Vdzquez,R.A.,Graciani,C.E.and Maestro,D.R.(1974) GtasasAceites
contain o-substituted active groups, while the active (Seville125, 269-272
groups of synthetic antioxidants (with the exception of ii 5ervili,M. and Monledoro,G.F. (1989) Ind. Aliment. (Pinerolo, Italy)
the gallates) are p-substituted. Other positions in the 28,14-19
12 Pokorn~/,)., Davfdek,J., Vierecklov.~,M., Rann~,,M. and Sedid~:ek,J.
(1990) Nahrung 34, 719-725
Table 3. Methods of producing stable foods without adding antioxidants 13 Nasner,A. (1985)Fette, 5ellen, Anstrichm. 87,477-481
14 Miyazawa,T., Yamasuchi,M., Lee,J.H., Fujimoto, K. and Kaneda,T.
Technique Methods (1984) Agric. Biol. Chem. 48, 1375-1377
15 Peters,F.N., ir and Mushe':, S. (1937) fnd. Eng. Chem. 29,146-151
Elimination of oxygen Packaging under nitrogen; packaging in vacuum; 16 Endo,T., Naito,S.and Inaba,Y. (1970) Yukagaku19, 298-302
packaging with an oxygen scavenger 17 Herrmann,K. (1973) Felte, Seifen, Anstrichm. 75, 499-504
Elimination of the 18 Pokorng,L, Davidek, L and lani~'ek, G. (t964) Sb. Vys. Sk. Chem.
Replacementof polyunsaturated oils with less
sensitive substrate Technol. Praze,Potrawn. Technol. 8(2),271-292
unsaturated oils, such as olive oil or palm oil, that
are more stable 19 Matsuzaki,T. and Hara,Y. (1985) Nippon Nogei Kagaku Kaishi 59,
129-134
Decreasingthe rate of Storage at low temperatures; storage in 20 Lee,M-H. and Sher,R-L.(1984)]. Chin. Agric. Chem. $oc. 22,
oxidation the dark; use of fats and oils that contain low levels 226-231
of oxidation promoters (e.g. oxidized products and 21 Kasuga,A., Aoyagi,¥. and Sugahara,T. (1988)Nippon Shokuhin
heavy metals); use of ingredients that are naturally Kogyo Gakkai-shi 35, 828--834
rich in antioxidants 22 Naketani,N. and Kikuzaki,H. (1987)Agri¢. Biol. Chem. 51,
2727-2732

226 Trends in Food Science & Technology September 1991

23 Wu, l.W., Lee,M-H., Ho, C-T. and Chap& S.S.(1982)L Am. Oil 30 Seher,A.and L6schner,D.(1986)Fette,Seifen, Anstrichm. 88,1-6
Chem. Soc. 59, 339-345 31 Kim,S-B.,Yeum.D-M.,Yeo,S-G.,Ji,C-I.,Lee,Y-W.and Park,Y-H.
24 Houligan,C.M., Ho, C-T. and Chang,S.S.(1984)J. Am. Oil Chem. Soc. (1989)Korean J. Food Sci. Technol. 21,492-497
61, 1036-1039 32 Lingnert, H. and Edksson, C.E (1980) l. Food Process. Preserv. 4,
25 Nakatani,N. and Inatani,R. (1984) Agric. Biol. Chem.48, 2081-2082 161-181
26 Fujimolo,K., Ohmura, H. and Kaneda,T. (1985) Bull. Jpn Soc. Sci. 33 Einarsson,H., Eklund,T. and Ness,I.F.(1988) Mikrobios 53, 27-36
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Conference Report
Micronutrients and
The future of history will not be decided by the votes of parliament
but by blood and iron

Bismark
The theme of the Micronutrients and Health II confer-
ence was trace minerals and health. The emphasis of the
presentations was on the physiological role of trace min-
erals rather than on their industrial applications. In ad-
dition, several presentations considered the chemical
and analytical aspects of trace minerals.
One of the most stimulating papers of the meeting
was that presented by J. Cook (University of Kansas
Medical Center, KS, USA), which was concerned with
iron deficiency and the measurement of iron status.
Cook reported that the most important consequences of
iron deficiency are impaired learning ability in infants
and children, reduced work capacity in adults, and
increased frequency of premature delivery in pregnant
women. He also focused on the increasing incidence of
chronic iron overload and stated that, while idiopathic
haemochromatosis was once considered rare, it has
recently been shown to be present in 3-5 individuals per
1000 in some Caucasian populations. Cook also ex-
pressed concern that an excess of body iron might en-
hance the survival and proliferation of malignant cells
and promote carcinogenesis. He cited a recent epidemio-
logical study of 14 000 individuals, which showed that
those with high iron stores were three times more likely
to develop malignant disease j.
Cook briefly reviewed the standard methods for
assessing iron status, commented on their limitations,
and stressed the need for sensitive and reliable methods
for measuring iron status in the population. He also
described a new measure of iron status: the serum tmns-
ferdn receptor, which can be quantified by sensitive
immunological techniques. Since the serum transferrin
receptor level reflects the total body concentration of"
* Held in Norwich, UK, 25-26 March 1991
C. 9ho~ is at the Research& TechnicalServiceCentre,ConsumerBrands, of Aberdeen, UK) continued the theme of nutrient
SmithKlineBeecham,51GeorgesAve,WeybridgeK'[13 ODE,UK.
health i[: trace
elements conference'
C. Shortt
transferdn receptor, it indicates the overall need of tis-
sues for iron. It has been used to measure the entire
spectrum of iron deficiency, from storage depletion to
severe iron-deficiency anaemia. An additional advan-
tage of serum transferrin receptor measurement is that it
is able to distinguish between anaemia resulting from
iron deficiency and that due to infection. Cook con-
cluded that wider application of the serum transferrin
recept~,r technique in conjunction with the measurement
of other parameters would provide information that is
required for developing realistic nutritional policies with
regard to iron fortification and supplementation.
R. Whitehead (MRC Dunn Nutrition Centre, UK), cur-
rent chairman of the UK Recommended Daily Amounts
(RDA) Committee, indicated that the panel on Dietary
Reference Values (DRVs) of the Committee on Medical
Aspects of Food Policy (COMA) was close to completing
its review of the current UK RDAs of energy and nutri-
ents. He highlighted that the panel had made fundamental
changes in the derivation of the recommendations, and
had defined a range of reference values for each nutrient.
The new DRVs will include a 'lower reference nutrient
intake', an 'estimated average requirement' and a 'refer-
ence nutrient intake'. While Whitehead discussed the
imnfinent changes in recommendations, he did not give
slsecific details of the DRVs and did not speculate on
the possible interpretation of the new DRVs.
P. Aggett (Foresterhill Medical School, University
recommendations and suggested that, ideally, the

Trends in Food Science & Technology September 1991 ©1991,ElsevierSciencePuh]ishersLtd,[UK)0924 - 2Z44/91/$02.00 227