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Antioxidants in
the Oxidation
of Foods
Eunok Choe and David B. Min
ABSTRACT: Antioxidants delay or inhibit lipid oxidation at low concentration. Tocopherols, ascorbic acid,
carotenoids, flavonoids, amino acids, phospholipids, and sterols are natural antioxidants in foods. Antioxidants in-
hibit the oxidation of foods by scavenging free radicals, chelating prooxidative metals, quenching singlet oxygen and
photosensitizers, and inactivating lipoxygenase. Antioxidants show interactions, such as synergism (tocopherols
and ascorbic acids), antagonism (-tocopherol and caffeic acid), and simple addition. Synergism occurs when one
antioxidant is regenerated by others, when one antioxidant protects another antioxidant by its sacrificial oxidation,
and when 2 or more antioxidants show different antioxidant mechanisms.
Figure 1 ---
HO HO Structures of
tocopherols and
tocotrienols.
CH2[CH2CH2CH(CH3)CH2]3H CH2[CH2CH2CH(CH3)CH2]3H
O O
-tocopherol -tocopherol
HO HO
CH2[CH2CH2CH(CH3)CH2]3H CH2[CH2CH2CH(CH3)CH2]3H
O O
-tocopherol -tocopherol
HO HO
CH2[CH2CH=C(CH3)CH2]3H CH2[CH2CH=C(CH3)CH2]3H
O O
-tocotrienol -tocotrienol
HO HO
CH2[CH2CH=C(CH3)CH2]3H CH2[CH2CH=C(CH3)CH2]3H
O O
-tocotrienol -tocotrienol
Flavonoids are major plant polyphenols and are derivatives and others 1986; Dachtler and others 2003). Concentration of
of diphenylpropanes and a heterocyclic 6-membered ring with sesamol is increased to higher than 36 ppm by roasting the
oxygen. They include flavanols (catechins, naringin), flavanones sesame seeds due to hydrolysis of sesamolin to sesamol (Kim
(hesperidin, naringenin), flavones (apigenin, luteolin), flavonols and Choe 2005). Sesamin and sesamolin extracted from roasted
(kaempferol, quercitrin, myricetin, quercetin), anthocyanins, and sesame oil and sesaminol in bleached sesame oil are more
leucoanthocyanidins. The glycosylation of flavonoids results heat-resistant than -tocopherol (Fukuda and others 1986; Lee
in lower antioxidant activity than the corresponding aglycons and others 2007). Secoisolariciresinol and secoisolariciresinol
(Shahidi and Wanasundara 1992). The solubility of flavonoids in diglucoside (14.1 to 30.9 mg/g, dry basis) are found in flaxseed
fats and oils is very low and their role in the oxidation of oil is (Eliasson and others 2003).
not significant; however, they can contribute to decreasing the
oxidation of oil in food emulsions (Zhou and others 2005). Ascorbic acid
Phenolic acids. Phenolic acids are closely related to flavonoids. Ascorbic acid, sodium ascorbate, and calcium ascorbate are
They include hydroxycinnamic acids (coumaric, ferulic, caffeic, water soluble and have a limitation as antioxidants for fats and
chlorogenic, and sinapic acids), hydroxycoumarin (scopoletin), oils. Ascorbyl palmitate is used in fat-containing foods to decrease
and hydroxybenzoic acids (ellagic, gallic, gentisic, salicylic, and their oxidation.
vanillic acids). Chlorogenic and caffeic acids are present in sun-
flower oil, and sinapic and ferulic acids are present in rapeseed Carotenoids
(Leonardis and others 2003) and defatted rice bran oils (Devi and Carotenoids are polyenoic terpenoids having conjugated trans
others 2007), respectively. Olive oil contains vanillic, syringic, double bonds. They include carotenes (-carotene and ly-
caffeic, and cinnamic acids (Servili and Montedoro 2002). Phe- copene), which are polyene hydrocarbons, and xanthophylls
nolic acids as antioxidants in oils are also limited due to solubility (lutein, zeaxanthin, capsanthin, canthaxanthin, astaxanthin, and
problems. violaxanthin) having oxygen in the form of hydroxy, oxo, or epoxy
Lignans. Lignans are phenylpropanoids derived from pheny- groups (Figure 3). Carotenoids are fat soluble and play an impor-
lalanine as shown in Figure 2. They include sesamol, sesamin, tant role in the oxidation of fats and oils.
sesamolin, sesaminol, sesamolinol, pinoresinol, and secoisolari- Carotene is the major carotenoid in oils, and -carotene is the
ciresinol. The major lignans in unroasted sesame oil are sesamin most studied. Palm oil is one of the richest sources of carotenoids.
(474 ppm), sesamolin (159 ppm), and sesamol (<7 ppm) (Fukuda Crude palm oil and red palm olein contain 500 to 700 ppm
346 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 8, 2009
Reaction mechanism of antioxidants . . .
O
Figure 2 --- Structures of lignans.
O
HO
O
O
O O
O sesamol
O
O O
O
sesamin
O
O
O
HO
O
O O
O O
O
O sesamolin
O O
sesaminol O
O HO
O
O
O OH
OH
sesamolinol O
OCH3 OH
H3CO pinoresinol
OH
HO
OCH3
OH
secoisolariciresinol
carotenoids (Bonnie and Choo 2000), but refined plam oil is not Maillard reaction products
a good source of carotenoids. Virgin olive oil contains 1.0 to Maillard reaction products from amines and reducing sugars or
2.7 ppm -carotene, as well as 0.9 to 2.3 ppm lutein (Psomiadou carbonyl compounds from lipid oxidation slow down lipid oxi-
and Tsimidou 2002). Corn, soybean, and peanut oils contain dation (Kumari and Waller 1987; Saito and Ishihara 1997). There
lower amounts of -carotene at 1.2, 0.28, and 0.13 ppm, respec- are a number of Maillard reaction products, but the responsi-
tively (Parry and others 2006). ble compounds for the antioxidant activity have not been clearly
determined to date.
Protein-related compounds
Hypoxanthine, xanthine, glycine, methionine, histidine, tryp- Phospholipids
tophan, proline, lysine, ferritin, transferritin, and carnosine show Crude oil contains phospholipids such as phosphatidyletha-
their antioxidant activities in the oxidation of lipid-containing nolamine, phosphatidylcholine, phosphatidylinositol, and phos-
foods (Reische and others 2002). Enzymes such as glucose oxi- phatidylserine, but most of them are removed by oil process-
dase, superoxide dismutase, catalase, and glutathione peroxidase ing such as degumming (Jung and others 1989). Oils that are
are known to decrease the oxidation of foods (Yuan and Kitts consumed without refining contain higher amounts of phos-
1997). Application of enzymes and proteins as antioxidants is pholipids. Crude soybean oil contains phosphatidylcholine and
limited to unprocessed oil because oil processing denatures the phosphatidylethanolamine at 501 and 214 ppm, respectively;
enzymes and proteins. however, RBD soybean oil contains only 0.86 and 0.12 ppm
Vol. 8, 2009COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 347
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
-carotene
lycopene
OH
lutein
OH
HO capsanthin
O
OH
HO
astaxanthin
O
OH
O
HO
violaxanthin
phosphatidylcholine and phosphatidylethanolamine, respec- phosphatidylcholine (Sugino and others 1997). Although phos-
tively (Yoon and others 1987). Unroasted sesame oil contains pholipids are generally known as antioxidants, they can increase
690 ppm phospholipids (Yen 1990). Extra virgin olive oil con- lipid oxidation depending on the environment such as presence
tains 34 to 156 ppm phospholipids and filtration of the oil lowers of iron (Yoon and Min 1987). Lee (2007) reported that phos-
the contents to 21 to 124 ppm (Koidis and Boskou 2006). phatidylcholine and phosphatidylethanolamine increased the ox-
Phosphatidylcholine decreased the oxidation of docosahex- idation of tocopherol-stripped canola oil with added chlorophyll
aenoic acid (DHA) and soybean oil in the dark (Koo and b under light.
Kim 2005; Lyberg and others 2005). Egg yolk phospholipids
at 0.031% to 0.097% decreased the autoxidation of DHA- Sterols
rich oil and squalene, and the antioxidant activity of egg Sterols are steroid alcohols with an aliphatic hydrocarbon side
yolk phosphatidylethanolamine was higher than that of chain of 8 to 10 carbons at the C17-position and a hydroxy
348 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 8, 2009
Reaction mechanism of antioxidants . . .
Autoxidation
Fats and oils should be in radical forms to react with triplet
oxygen in autoxidation. Lipids are normally in nonradical sin-
glet state and heat, metals, or light accelerates their radical for-
mation. Allylic hydrogen, especially hydrogen attached to the
carbon between 2 double bonds, is easily removed due to low
bond dissociation energy (Min and Boff 2002; Choe and Min
2005). The carbon and hydrogen dissociation energies are the
lowest at the bis-allylic methylene position (Wagner and others
1994). Bis-allylic hydrogen at C11 of linoleic acid is removed
at 75 to 80 kcal/mol. The energy required to remove allylic hy-
drogen in C8 or C14 of linoleic acid is 88 kcal/mol, and 101
kcal/mol is necessary to remove alkyl hydrogen from C17 or C18
-sitosterol (Wagner and others 1994; Min and Boff 2002; Choe and Min
HO
2005). Upon formation of lipid radicals by hydrogen removal,
the double bond adjacent to the carbon radical in linoleic and
linolenic acids shifts to the more stable next carbon, resulting
in conjugated diene structures. The shifted double bond mostly
takes the more thermodynamically stable trans form.
The lipid radical reacts with triplet oxygen very quickly at nor-
mal oxygen pressure (2 to 8 109 /M/s; Zhu and Sevilla 1990)
and forms lipid peroxy radical. The lipid peroxy radical abstracts
hydrogen from other lipid molecules to form lipid hydroperoxide
and another lipid radical. The radicals automatically catalyze the
reaction and the autoxidation is called free radical chain reac-
stigmasterol tion. When radicals react with each other, nonradical species are
HO produced to stop the reaction.
Photosensitized oxidation
Light accelerates lipid oxidation, especially in the presence
of photosensitizers such as chlorophylls. Chlorophylls in singlet
state become excited upon absorption of light energy in pico
second (Choe and Min 2006). Excited singlet state chlorophylls
become excited triplet state via intersystem crossing (k = 1 to
20 108 /s; Min and Boff 2002). Excited triplet state chlorophylls
react with triplet oxygen and produce singlet oxygen by energy
sitostanol transfer, returning to their ground singlet state. Singlet oxygen
HO
is able to diffuse over larger distances, about 270 nm (Skovsen
and others 2005), to react with electron-rich compounds. Since
Figure 4 --- Structures of sterols. singlet oxygen is electrophilic due to a completely vacant 2 p
orbital, it directly reacts with high-electron-density double bonds
via 6-membered ring without lipid radical formation (Gollnick
1978; Choe and Min 2005). The resulting hydroperoxides by
group at the C3-position (Figure 4). -Sitosterol, stigmasterol, and singlet oxygen are both conjugated and nonconjugated (Frankel
sitostanol are present in edible oils, with the highest amount of 1985; Figure 5). Production of nonconjugated hydroperoxides
-sitosterol. Corn and rapeseed oils have 8000 ppm sterols, and does not occur in autoxidation. The oxidation of linoleic acid by
palm and coconut oils have 600 to 1000 ppm sterols (Verhe and singlet oxygen produces C9- and C13-hydroperoxides, as well as
others 2006). Virgin and refined olive oils contain -sitosterol at C10- and C12-hydroperoxides (Frankel 1985).
667 and 898 ppm, respectively (Canabate-Diaz and others 2007). The reaction rate of lipid with singlet oxygen is much higher
Antioxidant activity of -sitosterol was lower than those of ferulic than that with triplet oxygen; the reaction rates of linoleic acid
acid and tocopherol in the autoxidation of soybean oil (Devi and with singlet oxygen and triplet oxygen are 1.3 105 and 8.9
others 2007). Solubility of plant sterols in corn oil is 2% to 3% at 101 /M/s, respectively (Rawls and Van Santen 1970).
25 C (Vaikousi and others 2007).
Thermal oxidation
Heating of oil produces various chemical changes including
oxidation. The chemical mechanism of thermal oxidation is basi-
Oxidation Mechanisms of Fats and Oils cally the same as the autoxidation mechanism. The rate of thermal
Different chemical mechanisms are responsible for the oxi- oxidation is faster than the autoxidation, and the unstable primary
dation of fats and oils during processing, storage, and cooking. oxidation products, hydroperoxides, are decomposed rapidly into
Two types of oxygen, atmospheric triplet oxygen and singlet oxy- secondary oxidation products such as aldehydes and ketones
gen, can react with fats and oils. Triplet oxygen, having a radical (Choe and Min 2007). Specific and detailed scientific informa-
character, reacts with radicals and causes autoxidation. The non- tion and comparisons of the oxidation rates between thermal
radical electrophilic singlet oxygen does not require radicals to oxidation and autoxidation are not yet available.
react with; it directly reacts with the double bonds of unsaturated Thermal oxidation of oil produces many volatiles and non-
fats and oils with high electron densities, which is called type II volatiles. Volatiles such as aldehydes, ketones, short-chain hy-
photosensitized oxidation (Choe and Min 2005). drocarbons, lactones, alcohols, and esters are produced from
Vol. 8, 2009COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 349
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
3
light O2
Chlorophyll Chlorophyll* 1
O2 + Chlorophyll
OOH
13 12 10 9 13 12 10 9 13 12 10 9
1
O2
11 11 11
O (CH2)7COOH
CH3(CH2)4 CH3(CH2)4
CH3(CH2)4 (CH2)7COOH H (CH2)7COOH
O
Conjugated
OOH
13 12 10 9 13 12 10 9
1 11
O2 11
O
CH3(CH2)4 (CH2)7COOH CH3(CH2)4 CH(CH2)6COOH
O H
Nonconjugated
OOH
13 12 10 9 13 12 10 9
1
O2
11 11
O
CH3(CH2)4 (CH2)7COOH CH3(CH2)3CH (CH2)7COOH
H O
Nonconjugated
OOH
13 12 10 9 13 12 10 9
1
O2
11 11
O
CH3(CH2)4 (CH2)7COOH CH3(CH2)4 (CH2)7COOH
O H
Conjugated
(T)
O
O
+ ROOH
O C16H33
O C16H33
(T )
+ R'OO + T
tocopherol dimer
O
CH2 + R'OOH
O C16H33
tocopherol semiquinone
have reduction potentials of 500, 330, and 330 mV (Steenken and others 2002). Reaction rates of peroxy radical of unsaturated
and Neta 1982; Jovanovic and others 1996), respectively, which fatty acids with -tocopherol are 1.85 106 /M/s (Kamal-Eldin
are lower than peroxy, alkoxy, and alkyl radicals. This enables for and others 2008). Tocopherols slowly and irreversibly react with
tocopherol and ascorbic acid to donate hydrogen to the peroxy, superoxide anion radicals in organic solvents and produce toco-
alkoxy, and alkyl radicals to slow down the formation of food pherol radical, but the reaction is insignificant in aqueous solu-
radicals. Phenolic compounds can donate hydrogen to alkyl per- tion (Arudi and others 1983; Halliwell and Gutteridge 2001).
oxy radicals and the resulting phenolic radicals do not catalyze Tocopherol radical sometimes reacts with lipid peroxy radi-
the oxidation of other molecules due to the low reduction po- cals at their very high concentration and produces tocopherol
tential (Shahidi and Wanasundara 1992). The phenolic radicals peroxide. Tocopherol peroxide produces 2 isomers of epoxy-
react with each other to form hydroquinone with regeneration of 8-hydroperoxytocopherone by elimination of an alkoxy radical
phenolic antioxidants or to form phenolic dimers. The phenolic followed by oxygen addition and hydrogen abstraction. Epoxy-
radical can react with lipid peroxy radicals to form phenolic- 8-hydroperoxytocopherone becomes epoxyquinones upon hy-
peroxy species adducts that undergo the degradation reactions drolysis (Liebler and others 1990). This reaction produces alkoxy
(Reische and others 2002). radicals, instead of peroxy radicals, and loses only tocopherol.
-Tocopherol reacts with alkyl peroxy radicals more rapidly Since there is no net decrease in free radicals in the system,
than alkyl radicals since the difference in reduction potential be- tocopherol does not act as an antioxidant; however, reducing
tween tocopherol radicals and alkyl peroxy radicals (500 mV) is agents such as ascorbic acid can regenerate tocopherols from
higher than that between tocopherol radicals and alkyl radicals tocopherylquinone.
(100 mV). Tocopherol donates hydrogen at the 6-hydroxy group Tocopherol radical at high concentration sometimes abstracts
on a chromanol ring to alkyl peroxy radical, and alkyl hydroper- hydrogen from lipids having very low concentration of per-
oxide and tocopherol radical are formed. Tocopherol radical is oxy radical and produces tocopherol and lipid radical; how-
relatively stable due to a resonance structure (Figure 8). Toco- ever, the rate is very low (Kamal-Eldin and others 2008). The
pherol radical can react with lipid peroxy radical to produce resulting lipid radical can increase the lipid oxidation by re-
tocopherol semiquinone having no vitamin E activity, or react acting with triplet oxygen, and tocopherol acts as prooxidant
with each other for the formation of tocopherol dimer (Reische instead of antioxidant (Bowry and Stocker 1993; Yamamoto
352 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 8, 2009
Reaction mechanism of antioxidants . . .
9
O 2 5' backbone.
7 Figure 11 --- Hydrogen release from carotenoids (CarH) via
electron donation (E; reduction potential).
6'
A C
6 3 Reduction potential for sequential transferring 2 electrons are
10
4 different in canthaxanthin and astaxanthin, generally E1 < E2,
5 while lycopene, -carotene, and zeaxanthin have similar E1 and
O
E2 values (Jeevarajan and Kispert 1996; Liu and others 2000).
Electron donation of carotenoids containing terminal electron
acceptor group is difficult and the 2nd electron donation oc-
2001). Tocopherol-mediated peroxidation is prevented by ascor- curs at quite a different potential to the 1st oxidation step. As the
bic acid since ascorbic acid quickly reduces tocopherol radicals electron-accepting strength of the end groups decreases, E (E1
to tocopherols (Yamamoto 2001). E2) decreases or cation radical can be reduced to carotenoid
Tyrosol and hydroxytyrosol in olive oil (Chimi and others 1991) radical with a reduction potential E3 which is generally much
and sesamol and sesaminol in sesame oil (Dachtler and others lower than E1 (Jeevarajan and Kispert 1996). The standard re-
2003; Suja and others 2005) scavenge free radicals by a simi- duction potential of carotenoid radical cation (700 to 1000 mV;
lar mechanism as tocopherols due to the presence of phenolic Jeevarajan and Kispert 1996; Liu and others 2000; Niedzwiedzki
hydrogen. Phenolic hydrogens of tyrosol and hydroxytyrosol are and others 2005; Han and others 2006) is not low enough that
transferred to food radicals with the production of semiquinone carotenoid cation donates hydrogen to alkyl (E = 600 mV)
radicals. The semiquinone radical of tyrosol or hydroxytyrosol or peroxy radicals of polyunsaturated fatty acids (E = 770 to
may scavenge another radical to give a quinone, disproportion- 1440 mV). It is easier for carotenoids to give hydrogen to hy-
ate with another semiquinone radical to give the parent com- droxy radicals having a high reduction potential (2310 mV) than
pound and quinone, or react with oxygen to produce quinone to alkyl peroxy radicals. The energy required to remove hydrogen
and hydroperoxy radical (Niki and Noguchi 2000). from carbons in carotene cation is about 65 kcal/mol (Zhou and
Flavonoids should have special structural features for scaveng- others 2000). Lycopene radical cation has the lowest reduction
ing free radicals as shown in Figure 9: the ortho-dihydroxy or potential (748 mV) followed by the radical cations of -carotene
catechol group in the B-ring, the conjugation of the B-ring to the (780 mV), zeaxanthin (812 mV), and canthaxanthin (930 mV)
4-oxo group (Rice-Evans and others 1995; Van Acker and oth- (Jeevarajan and Kispert 1996). Astaxanthin is a weaker antioxi-
ers 1996; Pietta 2000; Silva and others 2002). Quercetin, rutin, dant than zeaxanthin (Mortensen and Skibsted 1997a; Edge and
and luteolin satisfy the requirements and are known as some of others 1998).
the most efficient radical scavengers among the nonvitamin plant -Carotene may donate hydrogen to lipid peroxy radical with
phenols (Rice-Evans and others 1995). Catechin, an efficient rad- some limitations and produce carotene radical (Edge and others
ical scavenger, does not have a 2,3-double bond and 4-carbonyl 1998). Carotene radical is a fairly stable species due to delocal-
group, but it has many hydroxy groups to donate hydrogen (Rice- ization of unpaired electrons in its conjugated polyene, and has
Evans and others 1996). Catechol-structured flavonoids scavenge enough lifetime for a reaction with lipid peroxy radicals at low
lipid peroxy radicals by donating hydrogen and become more sta- oxygen concentration and forms nonradical carotene peroxides
ble phenoxy radicals. Phenoxy radicals undergo disproportion- (Burton and Ingold 1984; Beutner and others 2001). Carotene rad-
ation and produce phenolic quinone and a dihydroxy phenolic ical can also undergo oxygen addition, and subsequent reaction
compound, as shown in Figure 10 (Shahidi and Wanasundara with another carotene molecule, and produce carotene epoxides
1992). and carbonyl compounds of carotene (Beutner and others 2001)
Carotenoids can give electrons and then donate hydrogen as as shown in Figure 12.
shown in Figure 11. Two electrons rather than 1 are transferred In addition to the radical scavenging activity of carotenoids by
per carotenoid with 2 reduction potentials, E1 and E2. Ease donating hydrogen to lipid peroxy radicals, carotenoids can en-
of electron donation of carotenoids depends on the nature of hance lipid oxidation (Lee and others 2003). Lipid peroxy radicals
substituents on the carotenoids (Jeevarajan and Kispert 1996). (ROO r) from the oxidation of oils may be added to -carotene
O OH Figure 10 ---
OH OH Reactions of
catechol-
structured
flavonoid with
OH O OH X X O lipid peroxy
OH OH radicals.
OH O
ROO R
X X X
dicarbonyls
(Car) and produce carotene peroxy radical (ROOCar r), espe- Metals catalyze food radical formation by abstracting hydrogen.
cially at oxygen pressure higher than 150 mm Hg (Burton and They also produce hydroxy radicals by catalyzing decomposi-
Ingold 1984). -Carotene peroxy radical reacts with triplet tion of hydrogen peroxide (Andersson 1998) or hydroperoxides
oxygen to form peroxy radical of carotene peroxide (ROO (Benjelloun and others 1991). Ferric ions decrease the oxidative
CarOO r), which then abstracts hydrogen from another lipid stability of olive oil by decomposing phenolic antioxidants such
molecule and produces lipid radicals (R r). The resulting lipid as caffeic acid (Keceli and Gordon 2002).
radicals propagate the chain reaction of lipid oxidation (Iannone Crude oil contains transition metals such as iron or copper,
and others 1998), thus -carotene acts as a prooxidant: often existing in chelated form rather than in a free form (Decker
2002). Oil refining decreases metal contents. Edible oils manu-
Car + ROO r ROO Car r factured without refining, such as extra virgin olive oil (9.8 ppb
copper and 0.73 ppm iron) and roasted sesame oil (16 ppb copper
ROO Car r + 3 O2 ROO Car OO r and 1.16 ppm iron), contain relatively high amounts of transition
metals (Choe and others 2005).
ROO Car OO r + R H ROO Car OOH + R r Metal chelators decrease oxidation by preventing metal re-
dox cycling, forming insoluble metal complexes, or providing
steric hindrance between metals and food components or their
-Carotene may donate electrons to free radicals and become oxidation intermediates (Graf and Eaton 1990). EDTA and citric
-carotene radical cation (Liebler 1993; Mortensen and others acid are the most common metal chelators in foods. Most chela-
2001). -Carotene radical cation is stable due to resonance, and tors are water-soluble, but citric acid can be dissolved in oils
the reaction rate with oxygen is very low (Edge and Truscott 2000; with some limitation to chelate metals in the oil system. Phos-
Decker 2002). However, -carotene radical cation can easily pholipids also act as metal chelators (Koidis and Boskou 2006).
oxidize tocopherols and ubiquinones (Liebler 1993) as well as Flavonoids can also bind the metal ions (Rice-Evans and others
tyrosine and cystein (Burke and others 2001). Hydrogen or elec- 1996) and the activity is closely related with the structural fea-
tron transfers from carotenoids to food radicals depend on the tures: 3 , 4 -dihydroxy group in the B ring, the 4-carbonyl and
reduction potentials of food radicals and chemical structures of 3-hydroxy group in the C ring, or the 4-carbonyl group in the
carotenoids, especially the presence of oxygen-containing func- C ring together with the 5-hydroxy group in the A ring (Hudson
tional groups (Edge and others 1997). Electron-transfer reaction and Lewis 1983; Feralli and others 1997). Lignans, polyphenols,
from carotenoids to free radicals is favored when the alkyl peroxy ascorbic acid, and amino acids such as carnosine and histidine
radicals contain electron withdrawing R groups (Edge and others can also chelate metals (Decker and others 2001).
1998).
Ascorbic acid and glutathione scavenge free radicals by do- Singlet oxygen quenching
nating hydrogen to food radicals, producing more stable ascor- Singlet oxygen having high energy of 93.6 kJ above the ground
bic acid and glutathione radicals than food radicals (Buettner state triplet oxygen (Korycka-Dahl and Richardson 1978; Girotti
1993). Ascorbic acid radicals become dehydroascorbic acid by 1998) reacts with lipids at a higher rate than triplet oxygen. Toco-
loss of proton (Decker 2002). Amino acids containing sulfhydryl pherols, carotenoids, curcumin, phenolics, urate, and ascorbate
or hydroxy groups such as cystein, tyrosine, phenylalanine, and can quench singlet oxygen (Lee and Min 1992; Das and Das
proline also inactivate free radicals (Gebicki and Gebicki 1993). 2002; Choe and Min 2005). Singlet oxygen quenching includes
Inactivation of food radicals by proteinaceous compounds might both physical and chemical quenching. Physical quenching leads
be a result of competition between proteinaceous compounds to deactivation of singlet oxygen to the ground state triplet oxy-
and lipid for high-energy food radicals, rather than an actual gen by energy transfer or charge transfer (Min and others 1989).
chain breaker (Decker 2002). There is neither oxygen consumption nor product formation. Sin-
glet oxygen quenching by energy transfer occurs when the en-
Metal chelating ergy level of a quencher (Q) is very near or below that of singlet
Metals reduce the activation energy of the oxidation, especially oxygen:
in the initiation step, to accelerate oil oxidation (Jadhav and oth-
ers 1996). The activation energies for the autoxidation of refined 1
O2 + Q 3 O2 + 3 Q
bleached and deodorized soybean, sunflower, and olive oils were
17.6, 19.0, and 12.5 kcal/mol, respectively (Lee and others 2007). 3
Q 1 Q (no radiation)
354 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETYVol. 8, 2009
Reaction mechanism of antioxidants . . .
HOO O O HO OOH
HO OH OH
Carotenoids with 9 or more conjugated double bonds are good electron to the triplet oxygen to form a superoxide anion radical,
singlet oxygen quenchers by energy transfer. The singlet oxy- and these reactive oxygen species react with food components
gen quenching activity of carotenoids depends on the number to produce free radicals (Min and Lee 1988). Carotenoids having
of conjugated double bonds in the structure (Beutner and oth- fewer than 9 conjugated double bonds prefer the inactivation
ers 2001; Min and Boff 2002; Foss and others 2004) and the of photosensitizers instead of singlet oxygen quenching; singlet
substituents in the -ionone ring (Di Mascio and others 1989). - oxygen quenching is preferable by carotenoids with 9 or more
Carotene and lycopene which have 11 conjugated double bonds conjugated double bonds (Viljanen and others 2002). Energy of
are more effective singlet oxygen quenchers than lutein which the photosensitizer is transferred to the singlet state of carotenoids
has 10 conjugated double bonds (Viljanen and others 2002). The to become a triplet state of carotenoids, which is changed to
presence of oxo and conjugated keto groups, or cyclopentane the singlet state by transferring the energy to the surrounding or
ring in the structure increases the singlet oxygen quenching ability emitting phosphorescence (Stahl and Sies 1992). The edge-to-
(Di Mascio and others 1989); however, -ionone ring substituted edge distance for a direct quenching of triplet state of chlorophyll
with hydroxy, epoxy, or methoxy groups is less effective (Viljanen by carotenoids must be less than the van der Waals distance
and others 2002). The rate constants for singlet oxygen quenching (0.36 nm), which enables some overlap between electron orbitals
by canthaxanthin, -apo-8 -carotenal, all trans -carotene, and of these 2 pigments (Edge and Truscott 1999).
ethyl -apo-8 -carotenate are 1.45 1010 , 1.38 1010 , 1.25
1010 , and 1.20 1010 /M/s, respectively (Min and others 1989). Inactivating lipoxygenase
When a quencher has high reduction potential and low triplet Lipoxygenase is a catalytic enzyme in the oxidation of lipids
energy, it quenches singlet oxygen by a charge transfer mecha- and is inactivated by tempering, which is heat treatment with
nism. These types of quenchers are amines, phenols (including moisture. Steaming of ground soybeans at 100 C for 2 min or
tocopherols), sulfides, iodide, and azides, which all have many 116 C under 44.5 N for 1 min decreases the lipoxygenase activity
electrons (Min and others 1989). The quencher donates electron by 80% to 100%, with a decrease in peroxide values, which
to singlet oxygen to form a singlet state charge transfer complex improves the sensory quality of crude soybean oil (Engeseth and
and then changes the complex to the triplet state by intersys- others 1987).
tem crossing. Finally, the triplet state charge transfer complex is
dissociated into triplet oxygen and a quencher:
Interactions of Antioxidants in the Oxidation of Foods
1
O2 + Q [O2 Q+ ]1 [O2 Q+ ]3 3 O2 + Q Interactions among antioxidants can be synergistic, antagonis-
tic, or merely additive. Synergism is a phenomenon in which a
Chemical quenching of singlet oxygen is a reaction in- net interactive antioxidant effect is higher than the sum of the
volving the oxidation of a quencher rather than a quench- individual effects. A typical example of antioxidant synergism is
ing, thus producing breakdown or oxidation products of a between -tocopherol and ascorbic acid in autoxidation (Liebler
quencher. -Carotene, tocopherols, ascorbic acid, amino acids 1993) and photooxidation of lipids (Van Aardt and others 2005).
(such as histidine, tryptophan, cysteine, and methionine), pep- Antagonism is a phenomenon in which a net interactive antiox-
tides, and phenolics are oxidized by singlet oxygen, and they idant effect is lower than the sum of the individual antioxidant
are all chemical quenchers of singlet oxygen (Foote 1976; effects, and the additive interaction means that a net interac-
Michaeli and Feitelson 1994; Halliwell and Gutteridge 2001). tive antioxidant effect is the same as the sum of individual ef-
-Carotene reacts with singlet oxygen at a rate of 5.0 fects. Polyphenolic compounds such as epigallocatechin gallate,
109 /M/s (Devasagayam and others 1992) and produces 5,8- quercetin, epicatechin gallate, epicatechin, and cyanidin showed
endoperoxides of -carotene (Stratton and others 1993). Re- additive effects on free radical scavenging activity with ascorbic
action of ascorbic acid with singlet oxygen produces an acid or -tocopherol (Murakami and others 2003).
unstable hydroperoxide of ascorbic acid as shown in Figure 13.
Tocopherol reacts irreversibly with singlet oxygen and pro- Synergism
duces tocopherol hydroperoxydienone, tocopherylquinone, and Several mechanisms are involved in synergism among antioxi-
quinone epoxide (Decker 2002). The reaction rates of tocopherols dants: a combination of 2 or more different free radical scavengers
with singlet oxygen are different among isomers: -tocopherol in which one antioxidant is regenerated by others, a sacrificial
shows the highest reaction rate of 2.1 108 /M/s, followed by - oxidation of an antioxidant to protect another antioxidant, and a
tocopherol with 1.5 108 /M/s, -tocopherol with 1.4 108 /M/s, combination of 2 or more antioxidants whose antioxidant mech-
and -tocopherol with 5.3 107 /M/s (Mukai and others 1991). anisms are different (Decker 2002). Regeneration of a more effec-
tive free radical scavenger (primary antioxidant) by a less effective
Photosensitizer inactivation free radical scavenger (coantioxidant, synergist) occurs mostly
Foods contain sensitizers such as chlorophylls and riboflavin when one free radical scavenger has a higher reduction poten-
(Jung and others 1989; Salvador and others 2001), which are tial than the other. The free radical scavenger having a higher
activated by light. Photoactivated sensitizers transfer the energy to reduction potential acts as a primary antioxidant. Regeneration
triplet atmospheric oxygen to form singlet oxygen, or transfer an of primary antioxidants contributes to a higher net interactive
Vol. 8, 2009COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 355
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
antioxidant effect than the simple sum of individual effects synergism (Decker 2002). A combination of metal chelators and
(Decker 2002). The antioxidant system of ascorbic acid and to- free radical scavengers is a good example. They show synergism
copherols is an example, in which tocopherols (E = 500 mV) in inhibiting the oxidation of food components, mainly due to
are primary antioxidants and ascorbic acid (E = 330 mV) is a the sparing action of free radical scavengers by chelators. Metal
synergist (Liebler 1993). Tocopherols (TH) act as antioxidant by chelators such as phospholipids inhibit metal-catalyzed oxidation
donating hydrogen to alkyl (R r) or alkyl peroxy (ROO r) radi- (Koidis and Boskou 2006), producing lower levels of radicals to
cals in foods and become tocopherol radical (T r) which does be reduced by the antioxidants acting as free radical scavengers.
not have antioxidant activity. Ascorbic acid (AsH) gives hydrogen Metal chelators mainly act during the initiation step of lipid oxi-
to tocopherol radical to regenerate tocopherols and it becomes dation and free radical scavengers do so at the propagation step
semihydroascorbyl radical (As r), and then dehydroascorbic acid (Choe and Min 2006). Phosphatidylinositol acts as a synergist
(DHAs; Buettner 1993): with tocopherols in decreasing lipid oxidation, mainly by in-
active complex formation with prooxidative metals (Servili and
TH + R r T r + RH Montedoro 2002). Quercetin and -tocopherol show a synergism
in decreasing the oxidation of lard by the mechanism in which
TH + ROO r T r + ROOH -tocopherol acts as a free radical scavenger while quercetin acts
as a metal chelator (Hudson and Lewis 1983).
T r + AsH TH + As r Antagonism
Antagonism has been observed between -tocopherol and ros-
As r DHAs + H r marinic acid or caffeic acid (Peyrat-Maillard and others 2003;
Samotyja and Malecka 2007), between catechin and caffeic acid,
Interaction between tocopherols and carotenoids for their and between caffeic acid and quercetin (Peyrat-Maillard and oth-
regeneration is another example of synergism, although it is ers 2003). Plant extracts rich in polyphenols showed strong an-
more complicated. Carotenoids are regenerated by tocopherols tagonism with -tocopherol in lard (Banias and others 1992) or
and tocopherols are regenerated by carotenoids (Mortensen and sunflower oil (Hras and others 2000).
Skibsted 1997b, 1997c). But the carotenoid regeneration by to- Antagonism among antioxidants in the oxidation of food com-
copherols is more preferable (Kago and Terao 1995; Thiyam and ponents can arise by regeneration of the less effective antioxi-
others 2006), partly because of the higher standard reduction dant by the more effective antioxidant (Peyrat-Maillard and others
potential of the carotenoid radical cation (700 to 1000 mV; 2003), oxidation of the more effective antioxidant by the radicals
Jeevarajan and Kispert 1996; Liu and others 2000; Niedzwiedzki of the less effective antioxidant, competition between formation
and others 2005; Han and others 2006) than that of the to- of antioxidant radical adducts and regeneration of the antioxi-
copherol radical (500 mV). -Carotene (0.75 M) was shown dant (Mortensen and Skibsted 1997a, 1997c), and alteration of
to sharply disappear from the beginning of oleic acid oxida- microenvironment of one antioxidant by another antioxidant. An-
tion and then mostly disappeared within 100 h in the absence tagonism of antioxidants in the oxidation of foods has not yet been
of tocopherols. But the co-presence of -tocopherol at 3.8 described in detail.
103 M increased the time from 100 to 1500 h (Przybylski
2001). -Tocopherol regenerates the carotenoid by reducing the Conclusions
carotenoid radical cation (Mortensen and Skibsted 1997c; Edge
Reaction mechanisms and the type of natural antioxidants in
and others 1998; Mortensen and others 1998). However, Henry
foods, tocopherols, ascorbic acid, carotenoids, flavonoids, amino
and others (1998) showed that there was no cooperative interac-
acids, phospholipids, and sterols were reviewed kinetically and
tion between -tocopherol and -carotene in delaying the onset
thermodynamically. They inhibit the oxidation of useful food
of safflower seed oil oxidation at 75 C.
components by inactivating free radicals, chelating prooxida-
Two antioxidants whose bond dissociation energy difference
tive metals, and quenching singlet oxygen and photosensitizers.
is high exert a synergistic antioxidant effect (Decker 2002). Re-
When there are 2 or more antioxidants together, interaction oc-
generation of the antioxidant is fast when a synergist has a higher
curs such as synergism, antagonism, and simple addition.
bond dissociation energy than the primary antioxidant (Pedrielli
and Skibsted 2002). Also, the primary antioxidant can be regen-
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