Eur. J. Lipid Sci. Technol.

2015, 117, 1095–1137 1095

Review Article
The supramolecular chemistry of lipid oxidation and
antioxidation in bulk oils

Elizabeth S. Budilarto and Afaf Kamal-Eldin

Department of Food Science, United Arab Emirates University, Al-Ain, United Arab Emirates

The microenvironment formed by surface active compounds is being recognized as the active site of lipid
oxidation. Trace amounts of water occupy the core of micro micelles and several amphiphilic minor
components (e.g., phospholipids, monoacylglycerols, free fatty acids, etc.) act as surfactants and affect
lipid oxidation in a complex fashion dependent on the structure and stability of the microemulsions in a
continuous lipid phase such as bulk oil. The structures of the triacylglycerols and other lipid-soluble
molecules affect their organization and play important roles during the course of the oxidation reactions.
Antioxidant head groups, variably located near the water-oil colloidal interfaces, trap and scavenge
radicals according to their location and concentration. According to this scenario, antioxidants inhibit
lipid oxidation not only by scavenging radicals via hydrogen donation but also by physically stabilizing
the micelles at the microenvironments of the reaction sites. There is a cut-off effect (optimum value)
governing the inhibitory effects of antioxidants depending inter alias on their hydrophilic/lipophilic
balance and their concentrations. These complex effects, previously considered as paradoxes in
antioxidants research, are now better explained by the supramolecular chemistry of lipid oxidation and
antioxidants, which is discussed in this review.

Keywords: Antioxidants / Amphiphilic compounds / Bulk oils / Critical micelle concentration / Lipid oxidation
Received: April 26, 2014 / Revised: December 20, 2014 / Accepted: January 8, 2015
DOI: 10.1002/ejlt.201400200

1 Introduction and sensory properties such as texture and flavor [1–3].

Specifically, the highly unsaturated omega-3 fatty acids of
Unsaturated fatty acids play important roles as food fish lipids undergo instantaneous oxidation, which limits
components and nutrients, and contribute to food’s stability their shelf-lives and restricts their applications as health
promoting fatty acids in the diet [4–8]. Attempts have
continuously been made to find ways to protect unsaturated
Correspondence: Afaf Kamal-Eldin, Department of Food Science, United
fatty acids from oxidative deterioration but no satisfactory
Arab Emirates University, P.O. Box 15551, Al-Ain, United Arab Emirates
E-mail: [email protected]
solutions have been found [9].
Tel.: þ971-3-7136563 Lipid oxidation is known to occur in three phases: initiation,
propagation, and termination [4, 9, 10]. The theory that was
Abbreviations: BHA, butylated hydroxyanisole; BHT, butylated hydrox- developed in the 1940s [11] about the autocatalysis of lipid
ytoluene; CMC, critical micelle concentration; CPP, critical packing oxidation by-produced hydroperoxides (LOOH) is largely
parameter; DAG, diacylglycerol; DHA, docosahexaenoic acid; DOPC, acceptable and provides logical description of the chemical
dioleoylphosphatidyl-choline; DPPC, dipalmitoylphosphatidyl-choline;
reactions involved in the oxidative changes of fatty acids during
DPPE, dipalmitoylphosphatidyl-ethanolamine; DPPS, dipalmitoylphos-
phatidyl-serine; EDTA, ethylenediaminetetraacetic acid; EGCG, epigallo- the propagation and termination periods [6, 12–14] as well as
catechin gallate; EPA, eicosapentaenoic acid; FFA, free fatty acid; HLB, the products of oxidation and their significance especially as off-
hydrophilic lipophilic balance; IP, induction or initiation period; LOOH, lipid flavor compounds [3, 6, 15–17]. The hydroperoxide theory
hydroperoxide; LOO•, lipid peroxyl radical; MAG, monoacylglycerol; OO, outlined by Farmer et al. [11] provides a general description of
olive oil; OSI, oil stability index; o/w, oil in water emulsion; p-AV, para- the role of antioxidants in inhibiting lipid oxidation. However,
Anisidine value; PUFA, polyunsaturated fatty acids; PV, peroxide value; this description is often not precise and sometimes suffers from
SAXS, small angle X-ray scattering; SBO, soybean oil; SDS, sodium
inconsistencies and paradoxical outcomes when it comes to
dodecyl sulfate; SFO, sunflower oil; SMILES, simplified molecular-input
line-entry specification; TAG, triacylglycerols; TBARS, thiobarbituric acid certain details [1, 3, 18–20]. Knowledge that was accumulated
reactive substances; TBHQ, tert-butylhydroquinone; w/o, water in oil during the last two decades emphasize that lipid oxidation
emulsion cannot be explained merely by chemical reactions but also by

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This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which
permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no
modifications or adaptations are made.
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1096 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

considering molecular positions in space, especially at the primary antioxidants, decomposing LOOH to nonradical
interfaces of nanoemulsions. This paper reviews the current species, scavenging ground state and singlet oxygens, and
knowledge of lipid oxidation with emphasis on the effects of absorbing UV light [22]. It has been debated by Brim-
antioxidants and the physical microenvironments on the berg [26, 27] that the role of these retarders relies on their
oxidation of bulk oils. Bulk oils are considered as water-in-oil effects on micellization but unfortunately this work has not
nanoemulsions rather than pure lipid phases. been noticed in time.
Combinations of primary and secondary antioxidants are
often found more effective in retarding lipid oxidation than
2 Antioxidants and their mechanisms the sum of their single actions [1, 3, 28]. It was shown that the
synergism between these two classes of antioxidants
An antioxidant is defined as “Any substance that, when effectively increases the length of the IP and reduces reaction
present at low concentrations compared with those of an rates [13, 29]. This synergism has been shown, for example,
oxidizable substrate, delays or prevents the oxidation of that between tocopherols and ascorbic acid and between mixtures
substrate” [21]. Two kinds of antioxidants, primary and of natural tocopherols and citric acid [19]. A good method to
secondary antioxidants, have been classified based on their evaluate the efficiency of inhibitors and retarders, according
mechanisms of action in inhibiting lipid oxidation reaction to which the “antioxidant” efficacy can be measured by
[6, 20, 22]. considering the length of the IP as well as the rate of oxidation
during the IP was presented by Yanishlieva and Marinova [29
2.1 Primary antioxidants (mainly phenolic and references cited therein]. Three descriptive parameters
compounds) are considered:
(1) Effectiveness, which is the ability of an antioxidant to
They react with lipid hydroperoxyl radicals producing lipid
inhibit the oxidation chain reaction by donating hydro-
hydroperoxides and more stable, low energy, antioxidant
gens and inactivating RO2 during the IP. Effectiveness
radicals (A•) [22, 23], which are significantly much less
is measured by stabilization factor, F ¼ IPinh/IPo,
reactive in propagation reactions [19]. By acting as hydrogen
where IPinh is the IP of an inhibited oxidation (with
donors or radicals scavengers, primary antioxidants prolong
an antioxidant), and IPo is the IP of the uninhibited
the IP and delay the propagation period [3, 22]. Primary
oxidation (no antioxidant present).
antioxidants (e.g., BHA, BHT, TBHQ, tocopherols, and
(2) Strength, which is the inverse measure of the partic-
flavonoids) are generally mono- or polyhydroxy phenols with
ipation of an antioxidant in the side reactions that
hydrogen-donating substitutions on the ring [6, 19, 24]. It is
may results in the change of oxidation rate during the
currently believed that the most important factor governing
IP. The oxidation rate ratio ORR ¼ Winh/Wo, where
the antioxidant potency of phenolic compounds relates to
Winh is the rate of oxidation of an inhibited oxidation
their hydrogen donating powers, that is, to the number of
(with an antioxidant) and Wo is the rate of oxidation of
O–H groups in ortho and para positions, their bond
an uninhibited oxidation (no antioxidant present) is an
dissociation enthalphies (BDE), and whether these phenolic
inverse measure of strength, ORR > 1 indicates that an
hydrogens are hydrogen bonded [4, 14, 25]. Some primary
antioxidant causes a faster oxidation rate than the rate
antioxidants, called multiple-function antioxidants, combine
without antioxidant.
more than one of the following antioxidant functionalities;
(3) Antioxidant activity (A ¼ F/ORR), which indicates the
free radical scavenging, oxygen sequestering, metal chela-
capability of an antioxidant in terminating autoxidation
tion, and light energy absorption. Examples of these
chain and in affecting the rate of oxidation during IP [13, 29].
antioxidants include propyl gallate, proanthocyanidins, and
ascorbic acid [14].

2.2 Secondary antioxidants (or retarders) Until recently, most of the explanations given for
observed synergistic interactions have been based mainly
These are preventive antioxidants that enhance the inhibitory on unfounded assumptions related to possible chemical
activity of primary antioxidants. This class of antioxidants interferences of primary and secondary antioxidants. The
includes sequestrants or chelating agents (e.g., phytic acid, addition of primary antioxidant and synergists often increase
EDTA, and citric acid), oxygen scavengers, and reducing the IP and decrease the rate of oxidation during the IP (Winh),
agents (e.g., ascorbates), and other factors whose effect is not for example, the inhibition of autoxidation of fish oil at 20°C
completely explained (e.g., amino acids and phospholi- by 1000 ppm ascorbyl palmitate and 5 ppm lecithin [28]
pids) [6, 19]. The exact mechanism of action of the wide (Fig. 1) of fish oil at 20°C with 500 ppm ascorbyl palmitate
variety of secondary antioxidants have not been properly and 2000 ppm lecithin [30], of soybean oil at 110°C
understood but some of their speculated activities include with 4000 ppm a-tocopherol and 15 000 ppm phospho-
chelating prooxidants or catalysts, providing hydrogen to lipids [31], and of peanut oil at 110°C with 1000 ppm

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 O O

CH3 O
Ascorbic acid, ascorbyl Trolox and α-tocopherol Gallic acid, octyl gallate Cinnamic acid derivatives Epi-catechins and derivatives
OH
palmitate
CH3 OH OR3
2+ H3CO OCH3
OH OH OH
HO HO OH OH
RO O O OH
CH3

HO O
H3C O
R1
R Epigallocatechin, R1 = OH, R2 = H,R3 = H
CH3 Epigallocatechin gallate (EGCG), R1 = OH, R3 = H,
HO OH
OH
Ascorbic acid, R = H; RO O OR2
Alpha tocopherol, R = C16 H33 ; Gallic acid, R = H;
Ascorbyl palmitate, R = Trolox, R = -COOH
CH3 (CH2)13CO- Octyl gallate, R = -(CH2 )7-CH3 O OH
OR
Sinapic acid, R = H; R2 = CO OH

Sinapine, R = -(CH2)3N(CH3)3
Epicatechin, R1 = H, R2 = H, R3 = H
Epicatechin gallate, R1 = H, R3 = H,
OH
Caffeic acid and its derivatives Chlorogenic acid and its derivatives OH
OH OH
EGCG ester (stearate), R1 = OCOR4, R3 = OCOR4, where R4 = (CH2)16CH3
OCOR 4

HO HO
CO OH
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

R2 =
OOR R2 = C OH
O
R OH
O
OH OCOR 4
O
Caffeic acid, R = -CH2 =CH2-COOR1 where R1 = H; HO Carnosic acid and derivatives Hydroxytyrosol Resveratrol
Caffeic acid phenethyl ester, R = -CH2=CH2 -COOR1 OH CH3 OH OR2
where R1 = -CH2 -CH2-Phe; OH
Dihydrocaffeic acid, R = -CH2-CH2-COOH; Chlorogenic acid, R = H HO OH
Propyl caffeate, R = -CH=CH2 -COO-(CH2 )2-CH3; Chlorogenic acid esters: CH3 R1 O
Propyl hydrocaffeate, R = -CH2-CH2 -COO-(CH2)2-CH3 Butyl chlorogenate, R = -(CH2)3 -CH3 COOR
Dodecyl chlorogenate, R = -(CH2)11-CH3
Hexadecyl chlorogenate, R = -(CH2)15-CH3

OR1
Ferulic acid and derivatives Propyl isoferulate OR3
O O
H 3C CH3
HO
Hydroxytyrosol, R1 = H;
H3CO
O Carnosic acid, R = H Hydroxytyrosol acetate, R1 = COR2 , where Resveratrol, R1 = H, R2 = H, R3 = H
OR
Methyl carnosate, R = CH3 R2 = -CH3; Acylated resveratrols:
Hydroxytyrosol butyrate, R1 = COR2, 3-stearoylresveratrol, R1 = -CO(CH2)16CH3, R2 =
Carnosol where R2 = -(CH2 )2-CH3; H, R3 = H
HO H3CO
Ferulic acid, R = H; OH CH3 Hydroxytyrosol laurate, R1 = COR2, where 4’-stearoylresveratrol, R1 = H, R2 = -
Ferulic acid phenetyl ester, R = -(CH2)3 -Ph; R2 = -(CH2 )10-CH3; CO(CH2)16 CH3’ R3 = H
Alkyl ferulates: HO Hydroxytyrosol palmitate, R1 = COR2,
1-pentyl ferulate, R = -(CH2)4 -CH3 O CH3 where R2 = -(CH2 )14-CH3; Glucosylated resveratrols, has the same
1-hexyl ferulate, R = -(CH2 )5-CH3 Hydroxytyrosol stearate, R1 = COR2, backbone structure as resveratrol but with
1-heptyl ferulate, R = -(CH2)6 -CH3 where R2 = -(CH2 )16-CH3;
Propyl ferulate, R = -(CH2 )3-CH3 Hydroxytyrosol oleate, R1 = COR2 , where OH
R2 = -(CH2 )7-CH=CH-(CH2 )7-CH3;
O
Hydroxytyrosol linoleate, R1 = COR2 , R1 = HO
where R2 = HO

Quercetin and its derivatives H3 C CH3

-(CH2 )7-CH=CH- CH2-CH=CH-(CH2)4-CH3;
OH
Hydroxytyrosol octanoate, R1 = COR2 ,
OH HO
where R2 = -(CH2)6-CH3 Resveratrol-3-β-glucopyranoside, R2 = H
O
OH R3 = H;
Quercetin-3-O-glucoside, R= Resveratrol-3,5-di-β-glucopyranoside, R2 = H
OH
HO R3 = β-glucose;
HO O Resveratrol-3,4’-di-β- glucopyranoside, R2 = β-
OH glucose, R3 = H

OR
Rutin, R =
OH O

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Quercetin, R = H

Figure 1. Structures of antioxidants with different polarity discussed in this paper.

Supramolecular chemistry of lipid oxidation

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1098 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

a-tocopherol and 1500 ppm phospholipids [32]. Some acids [46]. Similarly, alkylation of ferulic acid [48] and
indogenous minor components in refined bulk oils, such hydroxytyrosol [51, 52], and methylation of carnosic acid [42,
as phospholipids, can act as synergists to tocopherols and 43] cause their lipophilicity to increase and their antioxidant
contribute to protecting the oils against oxidation while effectiveness in bulk oil to decrease. In addition, the presence of
others, such as monoacylglycerols, may act as prooxidants a double bond in the acyl substituent reduces the polarity and
and decrease the IP and/or increase the rate of oxidation antioxidant capacity of propyl caffeate compared to hydro-
during the IP [8, 14, 20, 33–35]. Besides synergism, there are caffeate and of ferulate compared to isoferulate [47]. Catechin,
more examples of unexplained phenomena related to with a trans configuration, has a better antioxidant activity
reaction rates of inhibited oxidations. One permanent case than epicatechin, with a cis configuration [50]. However, it was
is the loss of antioxidant efficacy with increased primary shown with epigallocatechin-gallate (EGCG) and its esters and
antioxidant concentration [4, 25], which is well known, for with the glycosylation of quercetin (quercetin-3-O-glucoside
example, a-tocopherol [18]. The concept of side reactions and rutin) [25, 44, 49] that this effect is variable, that is,
was used to account for such paradoxical outcomes of lipophilic antioxidants are sometimes more active in bulk oils
antioxidants such as the loss of efficiency at increased (at lower levels) because the effects of lipid solubility on the
concentrations [9 and references cited therein]. antioxidant efficiency are stronger than those caused by
the interfacial phenomenon. This suggests that the polar
paradox might be applied only when antioxidant is added
3 The polar paradox and interfacial at high concentrations (above a critical concentration) where
phenomena the interfacial phenomenon is dominant over solubility
effects [53]. This controversy is discussed below.
It is clear from the previous section that the pure chemical
model failed to adequately describe the effects of primary and
secondary antioxidants on the rates of lipid oxidation reactions 4 The role of micelles and association
and their synergistic interactions. Knowledge has gradually colloids
developed to strongly suggest that effects related to molecular
orientation and self-assembly of different molecular species are Koga and Terao [54] suggested that phospholipids enhance the
important and can help explain phenomena that are not yet well antioxidant activity of a-tocopherol in bulk lipids because they
understood. The historical developments in the understanding aggregate to form microemulsions thus bringing the tocopherol
of the role of physical location of lipid-soluble components on closer to the oxidation site (or increased partition in the water
lipid oxidation are presented in (Table 1). phase of reversed micelles). Accordingly, the phenolic group of
The initial observations related to the effects of molecular a-tocopherol and the polar head of the phospholipids are
properties other than BDE were presented in the break through positioned near the polar region of the reversed micelles where
papers by late William Porter [36–38]. He explained the role of radicals are formed and trapped while the nonpolar acyl chains
a polar paradox by stating that polar (hydrophilic) antioxidant are located in oil phase. Thus, these authors recognized the lipid
(e.g., Trolox C, ascorbic acid, propyl gallate, and TBHQ) are oxidation reaction sites as the interfaces formed between traces
more effective in bulk lipids with a low surface/volume ratio of water and the continueous lipid phase rather than the air-oil
whereas nonpolar (lipophilic) antioxidants (e.g., a-tocopherol, interfaces suggested by Frankel et al. [39–41]. It has also already
ascorbyl palmitate, BHA, and BHT) are more effective in oil- been evident for Ulla Brimberg [26, 27] that the transition of
in-water emulsions (o/w) having a high surface/volume ratio. lipid oxidation from the initiation to the propagation phase is
Shortly after, Frankel et al. [39–41] explained the polar governed by the critical micelle concentration (CMC) of
paradox by the interfacial phenomena that hydrophilic hydroperoxides and its modification by other amphiphiles
antioxidants were more oriented at the air-oil interfaces in acting as antioxidants, prooxidants, or modifiers (synergists or
bulk lipids, while lipophilic antioxidants had more affinities antagonists). Brimberg proposed a set of empirical equations
toward water-oil interfaces in o/w. The interfacial phenom- that was also able to successfully describe the oxidation of
enon was first studied in o/w emulsions because of the wide different oil/additive combinations [26, 27]. Brimberg and
availability of the methods needed to characterize these Kamal-Eldin [56] proposed that lipid oxidation in bulk oil starts
emulsions [14]. Table 2 presents results of investigations of by pseudo-first order slow build-up of hydroperoxides until
the antioxidant potency of pairs of antioxidants shown in Fig. 1 these reach their CMC and start aggregation to form reversed
having different polarities and effectiveness in bulk lipids micelles. At this point, the reaction rate change to a second
confirming the polar paradox theory (e.g., carnosic acid vs. order reaction and the oxidation enters the propagation phase
methyl carnosate [42, 43], and quercetin vs. rutin [25, 44]). (Fig. 2). Accordingly, the main effects of anti- and prooxidants
Examples for the effects of antioxidant polarity and steric depend on their modulation of the CMC of lipid
hindrance on their effectiveness in bulk oils include the hydroperoxides.
decrease in radical-scavenging activity by esterification of It started to become clear that lipid oxidation is affected
sinapic acid [45] and caffeic, dihydrocaffeic, and rosmarinic by several properties of emulsion droplets and interface

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1099

Table 1. Historical developments in the understanding of the physical effects of components and additives on lipid oxidation in bulk oils

References Observations Conclusions

Porter [36, 37] and Porter The general rule of the polar paradox was proposed and confirmed stating The antioxidant activity is
et al. [38] that polar antioxidants (e.g., propyl gallate, tert-Butylhydroquinone oppositely related to the
(TBHQ), and Trolox C) are more effective in food systems with low surface- polarity of antioxidants in
to-volume ratio or nonpolar lipids such as bulk vegetable oils while nonpolar relation to food lipids
antioxidants (e.g., BHA, BHT, and a-tocopherol) work better in foods with
high surface-to-volume ratio or polar lipid emulsion such as o/w emulsion
Brimberg [26, 27] Lipid hydroperoxides (LOOH) are surface-active agents that form micelles Micelles formed by
at above their critical micelle concentration (CMC). O2 is maximumly hydroperoxides are the site
solubilized in lipids when hydroperoxide CMC is attained of lipid oxidation reaction
Frankel et al. [39–41] The interfacial phenomenon was proposed to explain the polar paradox. Interfacial phenomenon is
Lipophilic antioxidants (e.g., a-tocopherol and ascorbyl palmitate) were related to the kinds of
more effective in o/w emulsion system than in bulk oil because they had interfaces at which the
more affinities toward water-oil interface, while the opposite was true for antioxidants are more
hydrophilic antioxidants (Trolox, ascorbic acid, rosmarinic acid, carnosic oriented, which may
acid, and rosemary extract), which were more oriented in air-oil interfaces in explain the polar paradox
bulk oil. Mixtures of a-tocopherol and ascorbic acid were more active in
bulk oils than in o/w emulsions
Koga and Terao [54] In the aqueous microenvironments in bulk lipids (15:85 by mol/mol mixture Interfacial
of methyl linoleate and methyl laurate), phospholipid aggregates enhanced microenvironment is the
the accessibility of a-tocopherol to radicals and hence the interruption of place where interactions
chain initiation. The polar OH group of a-tocopherol is located not too among surfactants,
deeply in hydrophobic region of phospholipid bilayer membrane but just antioxidants, and radicals
near by the membrane surface take place
Huang et al. [60] Linoleic acid competed with Trolox for Tween 20 in the polar region of the Micelle is where the
micelles and at the o/w interface. Trolox diffused in the water phase and the oxidation and interactions
mixed micelles and thus was a better antioxidant than a-tocopherol that was of antioxidants and
diffused in the oil phase surfactants take place
Carlotti et al. [123] An emulsion was known to contain micellar structure. L-tryptophan was a Micelle core and interface
very effective synergist with a-tocopherol because it was distributed in the have different roles in
micellar core or in the o/w interface autoxidation
Endo et al. [106, 116, 118] A mixture of trieicosapentaenoylglycerol and tripalmitoylglycerol (2:1, mol/ Physical structures, such as
mol) was most susceptible to oxidation than other ratios. The triacylglycerol the position of fatty acids
(TAG) structure affected the oxidation rate of unsaturated fatty acids. TAGs on TAG, have an effect on
with unsaturated fatty acids at sn-2 positions were more stable than those lipid oxidation
having unsaturated fatty acids at sn-1 and sn-3 positions
Hamilton et al. [28] Lecithin solubilizes ascorbyl palmitate and enhances its physical interactions Reversed micelles are
with a-tocopherol which form reversed micelles. This versatile network had formed in w/o emulsions
an ability to interrupt free-radical propagation by inhibiting the participation
of ascorbyl radical in promoting LOOH scission
Frankel and Meyer [124] The effectiveness of antioxidants in a system is influenced by several factors O/w partition coefficient
including the partitioning behavior of antioxidants between lipid and can explain the affinity of a
aqueous phase, the oxidation conditions, and the physical state of the compound in lipid and
oxidizable substrate. Surface-active substances influence the interfacial aqueous phase
interactions between the system and antioxidant. The oil-water partition
coefficients influence the distribution of relatively polar antioxidants in the
lipid and aqueous phase of a food emulsion. Trolox, which is very polar,
works very well in bulk oil and is more effective in o/w emulsions of linoleic
acid compared to those of TAG. Unlike TAG, linoleic acid is more polar
and forms micelles in aqueous system. Micelle-forming substrates enhance
the activity of hydrophilic and polar antioxidant
Khan and Shahidi [84] The synergistic interactions of tocopherols and phospholipids in borage and Phospholipid synergists
evening primrose TAG can be explained partly by phosphatidylcholine support antioxidants by
increasing the accessibility of a-tocopherol in the aqueous modifying the reaction
microenvironment where the induction of lipid oxidation occurs environment

(Continued)

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1100 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

Table 1. (Continued)

References Observations Conclusions

Schwarz et al. [43] Antioxidants (Trolox, propyl gallate, gallic acid, methyl carnosoate, and The activity of antioxidants
carnosic acid) had either moderate or higher activity in bulk oil than in can be enhanced or
emulsions. The most polar antioxidants (propyl gallate and gallic acid) reduced by emulsifiers.
exhibited either prooxidant or no antioxidant activity in polar medium (i.e., Mesophase structures
o/w emulsions). Emulsifiers (Cetheareth-15, glyceryl stearate, and depend on molecular
polyglyceryl glucose methyl distearate) form lamellar structure in bulk oil structure and critical
causing a higher solubilization of polar antioxidants in nonpolar medium. packing parameter (CPP)
Antioxidant actions in bulk oil, except gallic acid which was not influenced of the compound
by polysiloxan polyalcohol polyether copolymer, are enhanced by emulsifiers
including a-tocopherol

Gupta et al. [87] Inverse micellar structures (~60 A in diameter) were formed by Reversed micelles are
phospholipids in a hexane-oil mixtures containing <0.3% water. The formed in w/o
principal domains of the phase behavior include micellar solution, two phase nanoemulsions. The size of
dispersion, and dense micellar solution. A smooth transition to dense aggregates depends on the
micellar phase was observed with increased phospholipids concentration. amount of surfactants and
Dynamic light scattering measurements showed that aggregate sizes were water
affected by the amount of phospholipids and >1.5% water, below which the
available water is very limited to significantly affect core sizes
Kortenska et al. [81] Polar products of lipid oxidation with oxygen containing groups (e.g., Polar products of lipid
LOOH, fatty alcohols, acids, and water) tend to associate in non-polar oxidation affect the
media to form complexes and aggregates. Fatty alcohols may play a role as oxidation rate by
an initiation of formation of these aggregates and hence influence lipid modulating the reaction
oxidation rate environment
Kortenska et al. [68] Relatively high concentrations of polar compounds (e.g., LOOH, lipid Fatty alcohols or BHT
peroxyl radical [LOO], and BHT) form microaggregate (micelles) in the might act as surfactants and
presence of fatty alcohols. This leads to an increase of the rate of termination form microaggregates
and causes a decrease in the efficiency of BHT to protect purified sunflower (micelles) in the w/o system
oil (SFO) as LOOH decompose faster inside the polar interior of the micro
aggregate
Velasco and Cloudy OO was more oxidatively stable than filtered OO. Suspended and Polar constituents in oils,
Dobarganes [12] dispersed materials in cloudy olive oil (OO) play a physical stabilization role for example, unsaponifiable
by acting as antioxidants and/or as a buffer and preventing acidity increases materials, may play a
physical role in oil
solubilization
Brimberg and Kamal- LOOH formed during methyl linoleate oxidation are surface-active and can CMC of hydroperoxides
Eldin [125] form micelles. When LOOH concentration reaches CMC, lipid oxidation marks the beginning of
enters the propagation period propagation period
Brimberg and Kamal- The amount of oxygen solubilized in lipid is comparative to the number of Organic peroxides (not
Eldin [55] micelles formed during oxidation. When lipid medium has conjugated hydroperoxides) are not
double bonds is oxidized, no hydroperoxides are formed but instead cyclic surface active and do not
peroxides that are not surface-active and do not form micelles, hence there is atfect the oxidation rate
no propagation period
El-Shattory et al. [69] Reversed micelles were formed with surfactant aggregates in organic Reversed micelles are
solvents, for example, LOOH, methylglucose dioleate, polyglyceryl-3-oleate, formed in organic system in
and lecithin the presence of surfactants
Kiokias and Gordon [71] The activity of norbixin as antioxidant in bulk oil is consistent with the polar Norbixin is an example to
paradox. Norbixin is soluble in water as aggregates and is probably oriented supports the polar paradox
at the oil-water interface in the emulsion due to its massive hydrocarbon
backbone but it is insoluble in oil
Decker et al. [72] Differences in the effectiveness of the antioxidants in oil systems are mainly Antioxidant effectiveness
due to their physical location in the system, namely the antioxidant paradox. depends on how and where
Polar (hydrophilic) antioxidants are more effective in bulk oil because they they are partitioned in the
can accumulate at the air-oil interface or in reversed micelles within the oil, system. In bulk oil, lipid
where lipid oxidation occurs. On the other hand, nonpolar (lipophilic) oxidation occurs at the air-

(Continued)

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1101

Table 1. (Continued)

References Observations Conclusions

antioxidants are more effective in o/w emulsions because they accumulate in oil interface as well as in the
the oil droplets and/or may accumulate at the oil-water interface, where reversed micelle (oil-water)
interactions between LOOH at the droplet surface and pro-oxidants (e.g., interface
transition metals) take place
Calligaris and Nicoli [126] Salts with the antichaotropic anionic species were able to form weak bonds Hydrophobic structure
may form a “hydrophilic” structure around them and inhibit the solubility of formed by the salts might
other substances with lower polarities. Thus, these salts may enhance the salt-out amphiphilic
activity of certain antioxidants molecules and affect lipid
oxidation
Becker et al. [44] Antioxidant activity in bulk oil was related to the polarity of the antioxidants, Hydrophilicity (or
within the order: quercetin >a-tocopherol  astaxanthin ¼ rutin. Rutin lipophilicity) do not always
was an exception in that it is relatively hydrophilic but had the lowest activity correlate with the
in bulk oil. This indicated that it is not only the polarity that govern the antioxidant effectiveness in
effectiveness of antioxidants. Poor solubility of rutin in bulk oil or bulk oil
degradation of its glycoside at high temperature also influenced its effects
Chaiyasit et al. [14] Edible oils contain polar lipids (e.g., monoacylglycerol (MAG), The term association
diacylglycerol (DAG), free fatty acid (FFA), phospholipids, sterols, colloids, include geometric
cholesterols, phenolic compounds, aldehydes, and ketones), which have forms such as lamellar
amphiphilic nature. Components with especially low HLB can self-assemble structures and reversed
due to hydrophobic interactions and form association colloids, including micelles, which are formed
lamellar structures and reversed micelles. These surface active molecules by surfactants was
partition at the o/w interface and induce the concentration of antioxidants at proposed
the surface of colloids, thus increasing interactions between antioxidants
and/or prooxidants with metal at the interface or water core
Chaiyasit et al. [33] Edible oils contain surface-active compounds and water that can form More examples on the
physical structures such as reversed micelles. Both phosphatidylcholine and effects of surface-active
oleic acid were suggested to be located at the o/w interface by 5- compounds and reversed
dodecanoylaminofluorescein probe measurement, and phosphatidylcholine micelles on lipid oxidation
was found to increase the accessibility of a-tocopherol to radicals while oleic were presented
acid acted as prooxidants
Kasaikina et al. [70] LOOH do not form classical micelles but form associates (1–500 nm in size) Associates rather than
alongside water, surfactants, alcohols, acids, ketones, and other oxidation micelles were suggested.
products. LOOH is amphiphilic and concentrates on the boundary of Charges of surfactants
micelle and water. In a natural olefin (limonene), cationic surfactant affect the role of the
promotes oxidation, whereas anionic and nonionic surfactants did not have surfactants as antioxidant
any influence or prooxidant
Koprivnjak et al. [73] Bipolar molecules such as lecithin form reversed micelle where their polar On the role of
groups are pointed toward the interior and their nonpolar tails are directed phospholipids as stabilizers
toward the exterior (oil). Lecithin ability to increase oxidative stability was of reversed micelles
due to its bipolar character and its ability to entrap hydrophilic antioxidants
to concentrate on the micellar interface
Laguerre et al. [17] Not all nonpolar antioxidants behave as antioxidant in polar medium; the The Polar Paradox is not
antioxidant capacity of homologous series of chlorogenic acid esters in o/w linear. As the alkyl chain
emulsions increased as the alkyl chain length increased until dodecyl chain. length increase, the
Further chain extension caused a drastic drop of antioxidant capacity (a cut- hydrophilicity and the
off effect) antioxidant activity in o/w
emulsions increase to a
certain extent, but further
increase reduces the
antioxidant activity (a cut-
off effect)
Belhaj et al. [103] The size of nanoemulsions was influenced by the pressure, oil composition, The importance of
and the surface-active properties of surfactants. Changes of a-tocopherol nanoemulsions in lipid
antioxidative effect in bulk oil was more significant than that in emulsions oxidation was proposed

(Continued)

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1102 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

Table 1. (Continued)

References Observations Conclusions

Bendini et al. [127] When virgin OO was subjected to temperature close to 0°C, changes in the At lower temperatures
physical state happened leading to destabilization of the microdroplets of (close to 0°C), destabilized
water and the concentration of polar phenolic compounds and finally the microdroplets in bulk oils
lost of antioxidant activity may accelerate the rate of
lipid oxidation
Chen et al. [7] When the phospholipid concentration exceeds their CMC, reversed micelles As amount of surfactant
were formed. Dioleoylphosphatidylcholine and water formed spherical increased, CMC was
association colloids in SBO, and they were prooxidative because more affected and so the
(small) non-scattering association colloids were formed. 1,2-dibutyryl-sn- formation of reversed
glycero-3-phoshocholineformed cylindrical structures and had no impact on micelle. The kinds of
oxidation rates physical structures affect
oxidation differently.
Spherical shapes of
association colloids were
prooxidants, while
cylindrical shapes had no
impact on oxidation rates
Gramza-Michalowska and Astaxanthin causes no protection of bulk oils, which indicates that Lipophilic compounds do
Stachowiak [128] antioxidant activity was correlated with its polarity. Astaxanthin is not affect the oxidation in
hydrophobic, it is located in the oil not at the air-oil interface protecting o/w bulk oils
emulsions but not bulk oils and liposome
Kasaikina et al. [86] Primary amphiphilic products of the oxidation of LOOH and lipids, and Mixed micelles with
cationic surfactants form mixed micelles, which accelerated the different geometric forms
decomposition of LOOH and other polar components (e.g., metal- were detected in w/o
containing compounds, inhibitors etc.) emulsions that enhance the
decomposition of LOOH
Medina et al. [104] The effectiveness of antioxidants relies on its chemical reactivity (as radical On the importance of
scavenger or metal chelator), its interaction with other food components, physical effects of
their concentration and physical location in homogeneous or heterogeneous antioxidants
system. For instance, resveratrol had a low activity in inhibiting lipid
autoxidation in w/o emulsions and bulk oil because it has a low
incorporation in the droplet interface and its poor solubilty in water, thus
probably located far away from the air-oil interface
Chen et al. [7] Amphiphilic surface active compounds, which exist after oil refining (such as Different surfactants form
MAG, DAG, phospholipids, sterol, and FFA), interact with water to form different kinds of
association colloids (in the forms of reversed micelles, microemulsions, mesophase structures that
lamella, and cylindrical aggregates). Increasing water concentration had very affect lipid oxidation.
little impact on the IP of lipid oxidation (by hexanal) at 55°C. MAG formed Water concentration had a
ordered lamellar structures in hazelnut oil. Association colloids impact on limited effect on oxidation
lipid oxidation depends on the additives ability to form the colloids and how at 55°C
the additives are partitioned in the micelles
Chen et al. [20] Lipid oxidation is not only influenced by the traditional chemical factors, Physical structures are
such as lipid compositions, transition metals; but also by the existence of important affectors of lipid
physical structures. Phospholipids formed microstructures known as oxidation
association colloids within soybean oil (SBO). Reversed micelle of
dioleoylphosphatidylcholine shorthened the IP of SBO at 55°C
An et al. [129] Antioxidative and prooxidative properties are determined by internal factors Changes in the
(i.e., the oxidation substrates, structural organization and the hydrophilicity of an
microenvironment for the bioactive compound) and external factors (i.e., antioxidant affect its
heat, pressure, and exposure to light). Hydrophobic alkyl chain increased inhibitory activity of lipid
water insolubility of 7-n-alkoxydaidzeins: daidzein, 7-n-butyloxy-daidzein, oxidation
7-n-octyloxy-daidzein, 7-n-dodecyloxy-daidzein, and 7-n-hexadecyloxy-
daidzein. Daidzein increased membrane fluidity, but 7-n-butyloxy-daidzein
until 7-n-hexadecyloxy-daidzein decreased fluidity. The compounds were

(Continued)

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1103

Table 1. (Continued)

References Observations Conclusions

suggested to present in the central domain of the liposome bilayer in the

order 7-n-dodecyloxy-daidzein > 7-n-octyloxy-daidzein > 7-n-butyloxy-
daidzein > 7-n-hexadecyloxy-daidzein > daidzein, leaving 7-n-dodecyloxy-
daidzein as the most effective antioxidant, as monitored by fluoresence
spectroscopy using a fluorescence probe
Shahidi and Zhong [53] In this review, the polar paradox was re-examined. The distribution of polar A cut-off effect was found
antioxidants at the oil-air interface was questioned because air is much less for hydrophilic antioxidant
polar than oil. Antioxidants action was influenced by various micro- or in nonpolar medium
nanoenvironments (such as lamellar and reversed micelles) which are
formed by water, amphiphilic compounds, and oxidation products (e.g.,
LOOH, aldehydes, and ketones) alter the physical location of antioxidants.
The association colloids are the site of lipid oxidation in bulk oil. A cutoff
effect was observed, a non-linear phenomenon occurred wherein antioxidant
activity increases as the alkyl chain lengthens until a threshold is achieved,
then further increased of chain length caused a drastic collapse on activity.
Molecular size also influenced antioxidant effectiveness and causing a cutoff
effect, antioxidants with bulky structures (e.g., phenolic derivatives with long
alkyl chains) have steric hindrance thus lower mobility than those of smaller
size, therefore lower diffusibility toward reactive centers
Sorensen et al. [61] W/o emulsion resemble bulk oil, of which water is located in micelles and W/o emulsions resemble
aqueous phase is surrounded by emulsifier. The efficacy of antioxidants in bulk oils in their response
emulsions of water in omega-3 lipids follow polar paradox hypothesis, but to the polarity of
not for the o/w emulsion. In the case of w/o, at pH7, ascorbic acid had compounds
negative charges and repulsive forces existed between the interface and
ascorbic acid, thus it was located away from the interface. The polar paradox
was insufficient to explain antioxidant effects in multiphase systems such as
emulsions, as there are interactions between iron, emulsifiers, and
antioxidants
Sun et al. [23] Polar antioxidants with higher affinity were known to concentrate on oil/air Polar paradox is affected by
or oil/water interface of the reversed micelle. Thus the antioxidant polar other factors contributing
paradox does not always prevail, as some research found different results. to non-linearity in the effect
Thus the influencing factors of antioxidant activity in reversed micelle were of antioxidants in lipid
not solely based on antioxidant polarity oxidation
Sun-Waterhouse et al. [74] Caffeic acid and p-coumaric acid are hydrophilic. They tend to partition into Antioxidants may cause
the water phase, locate outside of the oil droplets and chelate metal ions other adverse effects, for
which exist in the oils. Both antioxidants stabilized oil against autoxidation example, hydrolysis of
but facilitated the hydrolysis of TAG in the oils TAG
Chen et al. [34] Soybean oil is found in seeds inside micro-sized oil bodies, which consist of a Natural organization
central neutral lipid core (94–98% w/w) and is surrounded by phospholipids protects unsaturated fatty
monolayer (0.5–2% w/w) and a coat of strong amphiphilic oleosin (0.5– acids. Water exists as nano-
3.5% w/w). These soybean oil bodies had a better physicochemical stability scale droplets in w/o
than emulsified soybean oil. Heat treatment (up to 55°C) did not affect the emulsions
LOOH and hexanal content of oil body suspensions (2% wt at pH 3).
Rukmini et al. [130] W/o microemulsion exist in bulk oil with nano-scale droplets of water inside. Nonionic surfactants offer
Formulation and stabilization of water-in-virgin coconut oil were prepared an alternative solution as it
with food grade nonionic surfactants (Span 80, Span 20, and Tween 20). stabilizes w/o emulsions
Cosurfactants may not be suitable for foods because of the toxicity and and do not contribute to
irritation induced by short- and medium-chain alcohols. Nonionic surfacts oxidation
permitted stabilization of such w/o emulsion without the use of
cosurfactants, but phase separation was observed when the microemulsion
was heated at 70°C or higher

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 Table 2. Results on antioxidants potency of pairs of antioxidants of similar structure and different hydrophilicity in bulk oil 1104

References Antioxidants Substrates and conditions Results

Frankel et al. [39] Ascorbic acid vs. ascorbyl Stripped corn oil, added antioxidant Ascorbic acid was a more potent antioxidant than ascorbyl
palmitate (232 and 1161 mM), 60°C palmitate based on LOOH and hexanal formation
Carelli et al. [131] SFO; each additive is at 200, Ascorbic acid was a more effective antioxidant than
400, 600, and 800 ppm; 30 and ascorbyl palmitate, according to Rancimat, and
68°C (Oven); and 130°C (Rancimat) peroxide value (PV) (30°C), para-anisidine value
(p-AV), total content, and distribution of polar
compounds and residual a-tocopherol
Sorensen et al. [61] W/o emulsion (98% of 1:1 fish oil:rapeseed oil, Ascorbic acid was more effective antioxidant than
stripped), 1% polyglycerol ascorbyl palmitate on the basis of LOOH and
polyricinoleateemulsifier; propanal formation. Ascorbyl palmitate exhibited
E. S. Budilarto and A. Kamal-Eldin

antioxidants added at 100 mM; 37°C pro-oxidative effects toward the end of storage period
Frankel et al. [39] Trolox vs. a-tocopherol Stripped corn oil, antioxidants added at Trolox was a better antioxidant than a-tocopherol on
232 and 1161 mM, 60°C the basis of LOOH and hexanal formation. At the
high concentration, a-tocopherol had a prooxidant
effect
Schwarz et al. [43] Stripped corn oil; w/o emulsion; Trolox had higher activity than a-tocopherol based
cetheareth-15 and glyceryl stearate, polyglyceryl on LOOH and hexanal formation in both bulk oil
glucose methyl distearate, polysiloxan and w/o emulsion with and without emulsifers. With
polyalcohol polyether copolymer and a few exceptions, a-tocopherol showed better activity
polyglyceryl-3 oleateas emulsifers each for w/o polysiloxan polyalcohol polyether copolymer
at 20% level; antioxidants added at 100 emulsion based on LOOH and w/o polyglyceryl-3
mM (based on the oil phase), 37 and 60°C oleate emulsion based on hexanal formation at 37°C.
a-tocopherol showed a prooxidative effect in bulk
oil with polyglyceryl-3 oleate at 60°C
Huang et al. [60] Linoleic acid, methyl linoleate, corn oil TAG, Trolox was a better antioxidant than a-tocopherol,
a-tocopherol are at 65 and 130 ppm and in terms of LOOH and hexanal formation. With a few
Trolox are at 38 and 76 ppm, 37 exceptions, a-tocopherol showed a better activity than
or 60°C in a shaking water bath Trolox (38 ppm), at 37°C, in bulk methyl linoleate
and corn oil TAG based on hexanal formation;
and at 60°C in bulk corn oil TAG, Trolox caused
a pro-oxidative effect by hexanal results
Chen et al. [20] Stripped SBO; 1,2-dioleoyl-sn-glycero- Trolox was a more effective antioxidant than
3-phosphocholine, a-tocopherol with and without the addition of
1,2-dibutyryl-sn-glycero-3-phosphocholine phospholipids (except 1,2-dibutyryl-sn-glycero-3-
each at 1000 mM; antioxidants phosphocholine). 1,2-dioleoyl-sn-glycero-3-
at 10 and 100 mM; 55°C phosphocholine improved, while 1,2-dibutyryl-sn-

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glycero-3-phosphocholine decreased the a-
tocopherol and Trolox activity
Thiyam et al. [45] Sinapic acid and sinapine Purified rapeseed oil, sinapic acid, Sinapic acid was better in reducing LOOH and
and sinapine at 50 and propanal compared to its derivatives sinapine
500 mmol/kg oil, 40°C

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 Table 2. (Continued)

References Antioxidants Substrates and conditions Results

Chen and Ho, [132] Caffeic acid vs. caffeic acid Lard and corn oil each at In lard, caffeic acid had better activity in extending
phenethyl ester 2 mM, Rancimat (110°C and 20 mL/min) the IP than caffeic acid phenethyl ester did. In corn
oil, the activities of both antioxidants were the same
Nenadis et al. [46] Caffeic acid vs. dihydrocaffeic acid Triolein, each additive Based on the PV, the activity dihydrocaffeic acid was
is at 10 ppm, 45°C in the dark higher than caffeic acid and control. The presence of
the conjugated double bond in the side chain of
caffeic acid, makes its less polar and also decrease its
hydrogen-donating properties, compared to
dihydrocaffeic acid
Silva et al. [47] Propyl caffeate and hydrocaffeate Refined SFO, propyl hydrocaffeate, and The antioxidant effectiveness of propyl hydrocaffeate
propyl caffeate each at 160 and 200 ppm, was higher than that of propyl caffeate
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

Rancimat 110°C and 20 L/h

Leonardis et al. [133] Caffeic acid vs. chlorogenic acid Cod liver oil, antioxidants added Caffeic acid was a better antioxidant compared to
(ester of caffeic acid and quinic acid) at 0.005–0.05% by weight, Rancimat chlorogenic acid. The later exhibited weak antioxidative
at 80 and 100°C and 20 L/h effects
Laguerre et al. [134] Chlorogenic acid and its esters Stripped corn oil, each additive is at Hydrophobicity of chlorogenic acid and its butyl,
200 mmol/kg, 55°C in the dark dodecyl, and hexadecyl esters did not correlate well with
their antioxidant capacity in bulk oil. With and without
dioleoylphosphatidylcholine, conjugated dienes test
showed longer IP as the akyl chain increased
Chen and Ho [132] Ferulic acid vs. ferulic Lard and corn oil, 2 mM, Rancimat In lard, ferulic acid and ferulic acid phenetyl ester had
acid phenetyl ester (110°C and 20 mL/min) the same activity in extending the IP. In corn oil, both
compounds had no significant effects in improving the
oxidative stability
Fang et al. [48] Ferulic acid vs. alkyl ferulates: Linolec acid; each additive is at Alkyl ferulate (1-pentyl, 1-hexyl and 1-heptyl ferulates)
1-pentyl, 1-hexyl, 1-heptyl ferulates 1.0  104, 3.0  104, slightly increased the antioxidant activity compared to
1.0  103, 3.0  103 molar ratios of the ferulic acid but their activities were not significantly
additive to linoleic acid; 37, 50, 65, different
and 80°C in the dark
Silva et al. [47] Propyl ferulate and isoferulate Refined SFO, propyl isoferulate, and Propyl isoferulate had a better antioxidant activity than
propyl ferulate each at 160 and 200 ppm, propyl ferulate
Rancimat 110 °C and 20 L/h
Huber et al. [49] Quercetin and quercetin Fish oil without antioxidant; each additive Quercetin-3-O-glucoside had a higher antioxidant
-3-O-glucoside is at 100, 500, 1000, and 5000 mM; 70°C activity than quercetin at 100 and 500 mM. At
1000 mM, their activities were equal
Becker et al. [44] Quercetin vs. rutin Purified high-oleic SFO; each additive is at The antioxidant activity of quercetin was higher

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0.25, 0.5, 1.0, and 2.0 mmol /kg oil; than rutin
Rancimat 100°C and 20 L/h
Wanasundara and Shahidi [25] Refined-bleached and deodorized seal The antioxidant activity of quercetin was higher than
Supramolecular chemistry of lipid oxidation

blubber oil and menhaden oil, each rutin in all substrates, as monitored by weight gain, PV,
additive is at 200 ppm, 65°C in Schaal oven and thiobarbituric acid reactive substances (TBARS)

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1105

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 Table 2. (Continued) 1106

References Antioxidants Substrates and conditions Results

Huang and Frankel [50] Catechins Corn oil TAG, each additive is According to LOOH formation: gallic acid had more
at 140 mM, 50°C antioxidant activity than epicatechin gallate and
epigallocatechin gallate (EGCG) had more antioxidant
activity than epigallocatechin
Shahidi and Zhong [53] EGCG and its esters Stripped corn oil; 1 mL/3 g, At lower concentrations, the antioxidant activity of
Rancimat (100°C and 20 L/h) EGCG was lower than its lipophilic ester derivative
(stearate); but the effects were reversed at higher
concentrations
Huang et al. [42] Carnosic acid and methyl carnosate Corn oil TAG, each additive is The antioxidant activity of methyl carnosate was higher
at 150 and 300 mM, 60°C than carnosic acid on basis of LOOH and hexanal
formation
E. S. Budilarto and A. Kamal-Eldin

Schwarz et al. [43] Tocopherol-stripped corn oil; w/o Methyl carnosate had higher antioxidant activity
emulsion; cetheareth-15 and glyceryl stearate, compared to carnosic acid in both bulk oil and w/o
polyglyceryl glucose methyl distearate, emulsions according to LOOH and hexanal formation,
polysiloxan polyalcohol polyether copolymer, which does not agree with the polar paradox
and polyglyceryl-3 oleate emulsifers each is
at 20% level; antioxidants added at 100 mM
(based on oil phase), 37 and 60°C
Frankel et al. [40] Carnosic acid and carnosol Stripped corn oil, each additive is at 50 ppm, Carnosic acid had a higher antioxidant activitiy than
60°C in a shaker oven carnosol in bulk oil on the basis of LOOH and hexanal
formation
Frankel et al. [41] Corn oil, SBO, peanut oil, and fish oil. Carnosic acid had a higher antioxidant activitiy than
Each additive is at 30 and 50 ppm, 60°C carnosol in bulk corn oil, SBO, peanut oil, and fish oil
on the basis of conjugated dienes and hexanal formation
Hopia et al. [59] Methyl linoleate, linoleic acid, corn oil TAG, Carnosic acid was a better antioxidant than carnosol in
additives at 150 and 300 mM, 37 and 60°C methyl linoleate and corn oil but not in bulk linoleic
acid where carnosol had better activity than carnosic
acid. The substrate seems to affect the performance of
antioxidants
Trujillo et al. [51] Hydroxytyrosol and its Glyceridic matrix, each additive is at Hydroxytyrosol had higher antioxidant activity than
fatty acid esters 1 and 5 mM, Rancimat 90°C hydroxytyrosyl acetate, palmitate, oleate, and linoleate
Medina et al. [52] Fish oil, each additive is at Hydroxytyrosol had better antioxidant activity than its
10, 25, 50, 100, 150, and esters with increasing size of alkyl chain (i.e.,
200 ppm, 40°C hydroxytyrosol acetate, butyrate, octanoate, laurate, and
octyl gallate)
Medina et al. [104] Resveratrol vs. acylated and Cod-liver oil, each additive Resveratrol fatty acid esters with increasing size of alkyl

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
glucosylated resveratrol is at 100 ppm, 40°C chain (i.e., 3-stearoylresveratrol, 3-stearoylresveratrol,
and 40 -stearoylresveratrol) and glucosylation
(i.e., resveratrol-3-b-D-glucopyranoside, resveratrol-3,
5-di-b-D-glucopyranoside, and
resveratrol-3,40 -di-b-D-glucopyranoside)
had reduced antioxidant effectiveness compared
to original phenol

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1107

protecting o/w emulsions because they orient more at the

water-oil interface [33, 39, 61, 169].
Table 3 presents collated results on the effect of different
additives on lipid oxidation in bulk oil. The more hydrophilic
Trolox was found to be a better antioxidant than a-tocopherol
because it concentrates in the water phase of the mixed
micelles [7, 65]. On the other hand, trace metal ions act as
prooxidants by migrating to the oil-water interface of the
micelles [57, 66, 67]. Similarly, free fatty acids and mono-
acylglycerols act as prooxidants by a “micellar effect” by
concentrating at the oil-water interface and accelerating the
decomposition of hydroperoxides [33, 39, 61, 169]. On
Figure 2. Peroxide value (PV) evolution during the autoxidation of the other hand, phospholipids act as synergists by enabling
flaxseed oil at 40°C. The first period (lag phase or induction period) the antioxidants at the interface [14, 33], where the polar heads
is dominated by reactions between unsaturated fatty acids (LH) and of the antioxidants are located at the water-oil interface and
low concentrations of hydroperoxides (LOOH). This reaction is first their hydrogen atoms are donated to the radicals. Thus, the
order with respect to LH and LOOH but because of the relatively antioxidants and phospholipids (synegist) trap the radicals in a
very high concentration of LH and the very low concentration of cage (i.e., microenvironment) [54] and prevent their diffusion
LOOH, it is often described as zero order. When the concentration into the bulk oil; the so called volume cage effect [68]. The
of LOOH reaches its critical micelle concentration (CMC), formation combination of antioxidants and surfactants can act synergisti-
of micelles become significant and the reaction enter the cally or antagonistically depending on their types (Fig. 3) and
bimolecular phase with respect to hydroperoxides. Attainment of concentrations [69]. The effects of surface-active agents are
CMC marks the end of the induction period (IP). influenced by their hydrocarbon chain length, hydrophilic
lipophilic balance, and concentrations [63, 64].
In summary, microemulsions are the site of oxidation and can
be considered as microreactors for autocatalysis by hydro-
properties including droplet size, interfacial area, charge, peroxides. The oxidation is prevalent at the water-oil interface
thickness, and permeability [14, 57, 160]. For example, and the antioxidants positioned near the polar region will
cationic charge caused transition metals to be excluded from scavenge radicals in this region [70–74]. The nature of micro-
the interface hence lessening oxidation rates in o/w [14]. This environments is affected by and affects the physical location of
finding was later verified in bulk oils when the research group prooxidants (including oxidation products), antioxidants, and
of Decker et al. studied these phenomena in depth and secondary modifiers, and thus the rate of lipid oxidation [14].
reported several supporting findings [14, 22, 160]. The
conclusion is that compounds that are surface active change
the physical location or the state of other compounds that 5 The supramolecular chemistry of lipid
form reversed micelles in bulk oils such as hydroperoxides oxidation
and metals [20, 33]. When water, other polar compounds,
and amphiphilic molecules (e.g., lecithin) coexist in oil, Micelles are formed in a heterophase system in order to
association colloids (e.g., reversed micelles) are formed achieve a minimum free energy state with the driving force is
providing a reaction site for oxidation to take place [14, 33]. the increase of entropy that accompany the withdrawal of
Oxygen, the primary catalyst of lipid oxidation, is 3–10 times hydrophobic regions of surfactants from water and the
more soluble in oil than in water and in fact, air (dielectric accompanying disorder. In the microemulsions, the hydro-
constant ¼ 1.0) is much nonpolar than oil (dielectric philic head groups of antioxidants and surfactants are
constant ¼ 3.0). Thus hydrophilic antioxidants are more oriented towards the water and the hydrophobic hydro-
likely to partition at the oil-water interface than at the air-oil carbon tails are more oriented towards the oil [7, 14, 75]. In
interface supporting the assumption that the microemulsions bulk lipids (Fig. 2), trace amounts of water and other polar
in the oil are the site of oxidation [14, 42, 53, 59–61]. These compounds like salts and acids are located in the core of
polar antioxidants aggregate to form microemulsions and the micelles, while surfactants occupy the interface as a
create a shield to protect micelles [14, 62]. In the same way, monolayer and is separated from the core of the micelle by a
emulsifiers enhance the formation of micelles that entrap depletion layer, that is, a layer of water of a few molecular
amphiphilic antioxidants and bring them to the inter- diameter that almost does not contain surfactants, occurs
phase [63, 64]. On the other hand, lipophilic antioxidants next to the monolayer [75]. The microemulsion is defined as
are less effective in retarding oxidation in bulk lipids because a thermodynamically stable single phase system of water, oil,
they disperse in the continuous oil phase far away from the and an amphiphile, which varies in size and is capable of
catalytic sites of the micelles while they are effective in solubilizing significant amount of polar and non-polar

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 Table 3. The effects of different types of additives on the stability of bulk lipids 1108

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Fatty alcohols
Yanishlieva and SFO, OO, lard, tristearin, 1-Tetradecanol, 1-hexadecanol, The pro-oxidative effects of fatty Fatty alcohols antagonized
Kortenska [135] olive oil methyl esters, 1-eicosanol (5–80 mmol/kg) alcohols depend on the type, the antioxidant effect of
70–135°C concentration, valency of the phenolic inhibitors
alcohols and LOOH, and the
degree of unsaturation of the lipid
media. The pro-oxidative effect
was less in TAG than in fatty acid
methyl esters
E. S. Budilarto and A. Kamal-Eldin

Kortenska et al. [136] SFO, methyl ester, 50°C p-Methoxyphenol (0.1 M), 1-Octadecanol and 1- Fatty alcohols inhibited
1-octadecanol (0.1 M), and palmitoylglycerol acted as inhibitor by formation of
1-palmitoylglycerol (0.1 M) prooxidant, by decreasing the rate H-bonds and complex
constant of chain termination, in formation with the
the presence of inhibitor (p- inhibitor. 1-
methoxyphenol) palmitoylglycerol had a
stonger effect because of its
two hydroxyl groups
Yanishlieva and TAG of SFO and TAG Hydroquinone (1  104 mol/L), Fatty alcohols accelerated the Shorter chain alcohols
Kortenska [137] of OO, 23 and 110°C 1-tetradecanol, 1-octadecanol oxidation of lipids (in the presence caused stronger complex
([0.59.0]  102 mol/L) of hydroquinone). Increasing formation (H-bond) with
unsaturation of substrate caused a hydroquinone. However,
lesser prooxidative effect of the longer chain alcohols had a
alcohols higher prooxidative activity
in the propagation,
branching, and termination
reactions
Kortenska and TAG of SFO, 80°C Hydroquinone, BHT, a-tocopherol Fatty alcohols acted as There was no interaction
Yanishlieva [138] (each at 0.1 mM); prooxidants. A linear dependence between 1-octadecanol and
1-tetradecanol, of oxidation of oil was seen, with BHT, because 1-
1-octadecanol (5, 20, 40, and hydroquinone, in the presence of octadecanol participates in
60 mM) 1-tetradecanol, a-tocopherol þ 1- the process only by
tetradecanol þ 1-octadecanol. No accelerating the
interactions between BHT and 1- decomposition of LOOH
octadecanol in inhibiting
oxidation

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
Kortenska et al. [68, 81] TAG of SFO, 80°C 2,6-Di-tert-butyl-4-methylphenol Fatty alcohols decreased the IP, as Polar compounds such as
(0.1 mM), 1-tetradecanol (40 mM), measured by LOOH. 1- fatty alcohols and oxidation
1-octadecanol (40 mM), and monopalmitoylglycerol caused a products associate in non-
1-monopalmitoylglycerol (40 mM) further reduction of IP. polar medium. LOOH
BHT þ fatty alcohols also decomposed faster inside

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

exhibited prooxidative effects, the polar interior of the

with no improvement on the IP micro emulsion. Fatty
alcohols alone and
combined with BHT were
prooxidants
Kortenska et al. [68] SFO and lard, 100°C a-Tocopherol (1.3 mM), The higher the 1-octadecanol Fatty alcohols acted as
1-octadecanol (5, 40, and 80 mM) level, the more the reduction of IP prooxidant and inhibited a-
and increase of oxidation rate in tocopherol activity
both medium. The relative
increase of oxidation rate in SFO
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

was more than in lard

Free Fatty Acids (FFA)
Miyashita and Takagi [115] Oleic acid, methyl oleate, No additives Methyl esters are more stable than FFAs are more susceptible
linoleic acid, methyl their corresponding FFA (longer to oxidation than
linoleate, linolenic acid, IP and have lower PV) corresponding esterified
methyl linolenate; 50°C in fatty acids. The catalytic
the dark effect of the carboxyl
Methyl linoleate and SBO; Stearic acid (0, 0.5, 1, 3, and 5%) The addition of stearic acid to groups of FFA on the
50°C in the dark methyl linoleate or SBO did not formation of free radicals
affect the IP but increased the and decomposition of
oxidation rate during this IP LOOH was thought to be
Methyl linoleate Stearic acid (0, 0.2, 0.5, and 1%) Hydroperoxides (PV and the reason. According to
hydroperoxides; 50°C in conjugated diene content), the current theory a bulk of
the dark decomposed faster in the presence FFAs is different from a
of stearic acid bulk of TAGs in the
Mistry and Min [139] SBO, forced air oven 55°C Stearic, oleic, linoleic, linolenic, or FFA, but not octadecane, showed molecular assembly of the
octadecane (0, 0.5, and 1%) prooxidant activity in SBO (PV, substrate itself and of any
volatile compounds, and oxygen in added additive. FFAs are
the headspace) surface active and
Hamam and Shahidi [140] Doxosahexaenoic acid Capric acid (not added but due to Acidolysis of the single cell oil, contribute to micelle
single cell oil; Schaal oven acidolysis) with capric acid, decreased the formation when added to
60°C oxidative stability of the oil TAGs
(Conjugated dienes and TBARS)
compared to unmodified
doxosahexaenoic acid single cell

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
oil
Frega et al. [141] Virgin OO; Rancimat 110° Oleic acid or methyl oleate (0–3%) Methyl oleate but not oleic acid The prooxidant effect of
C, 20 L/h; OO (cloudy (% acidity) decreased the IP of FFA is dependent on the
Supramolecular chemistry of lipid oxidation

untreated, cloudy paper- virgin OO. Oleic acid (% acidity) matrix. For example, oleic
filtered, cloudy membrane- increased the IP of cloudy acid had a prooxidant

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 Table 3. (Continued) 1110

Substrates and oxidation

References conditions Additive(s) Results Conclusions

filtered, and cloudy untreated oil, did not affect the IP activity in membrane-
bleached with clay); of cloudy paper-filtered oil, and filtered and bleached OO
Rancimat 110°C, 20 L/h decreased the IP of cloudy but not in cloudy oils; and
membrane-filtered and cloudy methyl oleate but not oleic
bleached oils acid had a prooxidant effect
on virgin OO
Chaiyasit et al. [14] Methyl linolenate in model Oleic acid (0, 25, 50, and Oleic acid reduced the reversed The prooxidant effect of
oil system containing 100 mmol/kg lipid) micelle size and accelerated lipid FFA seems to be related to
sodium bis(2-ethylhexyl) oxidation (LOOH and TBARS) their action as surfactants
sulfosuccinate, water- compared to a control and added (increasing the number of
E. S. Budilarto and A. Kamal-Eldin

hexadecane; ferrous sulfate, phosphatidylcholine small micelles)

24°C in the dark
Monoacylglycerols (MAG) and diacylglycerols (DAG)
Mistry and Min [142] Refined, bleached, and 1-Monolinolein (0.01%) MAG (1-monolinolein) had MAG and DAG showed
deodorized SBO, forced-air prooxidant activity in SBO (PV prooxidant effects in pure
oven 55°C and volatile compounds) (but not unpure TAG)
Mistry and Min [143] SBO, forced-air oven 55°C Monostearin, monolinolein, distearin, Monostearin, monolinolein, depending on polarity,
and dilinolein (0, 0.25, and 0.5%) distearin, and dilinolein acted as concentration, and
prooxidants in SBO (decrease of temperature
headspace oxygen) in a
concentration-dependant manner
Caponio et al. [144] Purified SBO, oven 60°C; Unnamed MAG (0, 0.5, 1, 2, and The effect of MAG in the
measured at 4, 6, 9, 14, and 3%) oxidation of purified SBO is
18 days concentration-dependent. At low
amount (0.5 and 1%), MAG
increased the oxidation rate while
at higher concentrations the IP
was reduced
Aubourg [65] Cod liver oil containing Unnamed MAG (0.1, 0.5, 2, and 5%) MAG (2 and 5%) caused an MAG and DAG enhanced
citric acid; 15, 30, and inhibitory effect on the protective the oxidation of cod liver oil
50°C effect of citric acid at 50, but not at containing citric acid,
15 and 30°C which functions as a metal
Cod liver oil containing Monolauroyl-glycerol, The prooxidant effect of MAG chelator. A longer chain
citric acid; 50°C monomiristoyl-glycerol, increased as the chain length of length increased the
monopalmitoyl-glycerol, and MAG increased prooxidant effect possibly

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
monostearoyl-glycerol (3.78 mM) because of increased
Cod liver oil containing Unnamed diacylglycerols (0.1, 0.5, 2, DAG showed an inhibitory effect surfactant activity
citric acid; 30 and 50°C and 5%) on the protective effect of citric
acid at 50 but not 30°C. There
was no difference in effect between
different DAG concentrations

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Wang et al. [145] Purified and natural corn 1-Monolinoleoyl-rac-glycerols (0, 0.1, MAG decreased the IP for MAG may contribute
oil; 28°C 0.25, and 0.5%) purified but not for unpurified oil pro-oxidant effect(s) in the
Natural and randomized 1-Monolinoleoyl-rac-glycerols and MAG showed a higher prooxidant oxidation of bulk oils
corn oil, Oxidative Stability 1,3-dilinoleoyl-rac-glycerol (conc. activity than DAG (reduced OSI
Index (OSI), 28°C unknown) IP)
Natural and randomized 1,3-Dilinoleoyl-rac-glycerol (5%) There was an increase in the
corn oil; 28°C oxidation rate of purified oil with
5% DAG but the increases were
not as great as that of randomized
oil
Phospholipids (PL)
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

King et al. [146] Salmon oil, Fischer forced- Phosphatidylcholine (0.01, 0.1, Phosphatidylcholine improved the The amine group of
draft oven, 180°C and 1%) oxidative stability of the oil in a phosphatidylcholine and
concentration-dependant manner phosphatidylethanolamine
(as measured by TBARS and and the reducing sugar of
polyene index) phosphatidylinositol can
Salmon oil, Fischer forced- Phosphatidylglycerol, Nitrogen-containing facilitate hydrogen or
draft oven, 180°C phosphatidylinositol, phospholipids electron donation by
phosphatidylserine, (i.e., phosphatidylethanolamine, a-tocopherol at 180°C.
phosphatidylethanolamine, phosphatidylcholine, Nitrogen-containing
phosphatidylcholine, lysophosphatidylcholine, and phospholipids perform
lysophosphatidylcholine, and sphingomyelin showed higher better in improving the
sphingomyelin (1% each) antioxidant acitivity than oxidative stability of oil
phosphatidylglycerol and than those that do not
phosphatidylinositol (yielded the contain nitrogen
least activity). The slope of
oxidation rate showed that
sphingomyelin was the most
effective and phosphatidylinositol
was the least effective
Methyl linoleate, methyl Dipalmitoylphosphatidylcholine Without a-tocopherol, DPPC and DPPE act
laureate, 50°C in the dark, (DPPC, 100 nM), Dipalmitoylphosphatidylcholine synergistically with
continuous shaking at dipalmitoylphosphatidylethanol- gave a slower oxidation rate than a-tocopherol, but the effect
120 rpm amine (DPPE, 100 nM), a- dipalmitoylphosphatidylethanol- is insignificant
tocopherol (10 nM) amine. With a-tocopherol, IP was

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
prolonged and methyl linoleate-
OOH accumulated after a-
tocopherol was consumed. DPPC
and DPPE showed an insignificant
Supramolecular chemistry of lipid oxidation

effect in oxidation rate, in the

presence or absence of a-
tocopherol

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 Table 3. (Continued) 1112

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Koga and Terao [54] Methyl linoleate; methyl Dipalmitoylphosphatidylcholine, With the use of 2,20 -azobis(2- Phospholipids accelerated
laureate; 2,20 -azobis(2- dibutyrylphosphatidylcholine, amidinopropyl) dihydrochloride, the consumption of a-
amidinopropyl) dicaprylphosphatidylcholine, and phospholipids caused a more rapid tocopherol when radicals
dihydrochloride (AAPH) dimyristoylphosphatidylcholine (each consumption of a-tocopherol. are generated from water-
(water soluble radical 100 nM), a-tocopherol (10 nM) With 2,20 -azobis(2,4- soluble radical generators
initiator); 2,20 -azobis(2,4- dimethylvaleronitrile), with a trace of water
dimethylvaleronitrile) phospholipids did not affect the
(AMVN) (lipid soluble consumption of vit E. The IP
radical initiator), 50°C in increased with increasing
the dark, continuous hydrocarbon chain length of acyl
E. S. Budilarto and A. Kamal-Eldin

shaking at 120 rpm moieties of phospholipids

Khan and Shahidi [84] Borage oil TAG, dark, in a Phosphatidylcholine (500 ppm), Phosphatidylcholine lengthened Phosphatidylcholine is
Schaal oven at 60°C phosphatidylethanolamine the oxidation time more than more effective than
(500 ppm), a-tocopherol (500 ppm), phosphatidylethanolamine (based phosphatidylethanolamine
d-tocopherol (500 ppm) on conjugated dienes). alone and in combination
Combinations of with a-tocopherol in
phosphatidylcholine þ a- borage oil TAGs.
tocopherol., Phosphatidylethanolamine
phosphatidylcholine þ d- was more effective than
tocopherol, phosphatidylcholine in
phosphatidylethanolamine þ a- evening primose TAGs.
tocopherol, Phospholipids increase the
phosphatidylethanolamine þ d- accessibility of the
tocopherol (500 ppm tocopherols to the aqueous
phospholipids and 500 ppm environment (the micellar
tocopherol) lengthened the phase)
oxidation time than individually
added phosphatidylcholine,
phosphatidylethanolamine, a-
tocopherol, and d-tocopherol.
Combination of a-tocopherol with
each phospholipid was more
effective than combination of d-
tocopherol. The most effective
combination was that of

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
phosphatidylcholine and a-
tocopherol (on basis of TBARS)
Evening primrose oil TAG, Phosphatidylcholine (500 ppm), Phosphatidylethanolamine
dark, in a Schaal oven at phosphatidylethanolamine lengthened the oxidation time

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

60°C (500 ppm), a-tocopherol (500 ppm), more than phosphatidylcholine

and d-tocopherol (500 ppm) (based on conjugated dienes).
Combinations of
phosphatidylcholine þ a-
tocopherol,
phosphatidylcholine þ d-
tocopherol,
phosphatidylethanolamine þ a-
tocopherol,
phosphatidylethanolamine þ d-
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

tocopherol (500 ppm

phospholipids and 500 ppm
tocopherol) with the combinations
with phosphatidylethanolamine
being more effective than those
with phosphatidylcholine (on basis
on TBARS)
Hidalgo et al. [147] Refined SBO, heated in the Phosphatidylethanolamine, Phospholipids lengthened the IP Phosphatidylcholine,
dark under air at 60°C phosphatidylcholine, and (phosphatidylcholine > phosphatidylethanolamine,
phosphatidylinositol (each 200 ppm) phosphatidylethanolamine and phosphatidylinositol
> phosphatidylinositol) and the improved the oxidative
protection was better with stability of the oil. Lysine
oxidized activity as antioxidant was
phosphatidylethanolamine, improved in combination
phosphatidylcholine, and with
phosphatidylinositol (by polymeric phosphatidylethanolamine
pyrroles). or phosphatidylcholine
Phosphatidylethanolamine (synergism). No synergism
showed max. antioxidative activity was observed for
when the pyrrole content was phosphatidylcholine plus
between 800–1400 nmol of phosphatidylethanolamine
pyrrole/mmol of
phosphatidylethanolamine
Refined OO (ROO), Phosphatidylethanolamine, Phosphatidylethanolamine,
Rancimat 110°C phosphatidylcholine, lysine, and BHT phosphatidylcholine, lysine, and

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
(each added at 4 levels: 100, 200, BHT increased oxidative stability
300, and 400 ppm) of the oil at 200 ppm or more. The
IP of oil with 400
Supramolecular chemistry of lipid oxidation

phosphatidylethanolamine had
similar stability as that of oil with

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 Table 3. (Continued) 1114

Substrates and oxidation

References conditions Additive(s) Results Conclusions

200–400 ppm BHT

Phosphatidylethanolamine and/or Phosphatidylethanolamine and
lysine (combinations at 100/300,200/ lysine showed a better protection
200, and 300/100 ppm) to the oil than when each was
added alone. The IP increased in
the following sequence 100/
300 < 200/200 < 300/100 ppm
Phosphatidylcholine and/or lysine Phosphatidylcholine and lysine
(combinations at 100/300, 200/200, showed a better protection to the
and 300/100 ppm) oil than when each was used alone.
E. S. Budilarto and A. Kamal-Eldin

The IP increased in the following

sequence 200/200  300/
100 < 100/300 ppm
Phosphatidylcholine and/or Phosphatidylcholine and
phosphatidylethanolamine phosphatidylethanolamine did not
(combination at 100/300, exhibit any synergism
200/200, and 300/100 ppm)
Koprivnjak et al. [73] Filtered virgin OO, Phospholipids (lecithin) (0, 2.5, 5, As the amount of lecithin
Rancimat, 120°C 7.5, and 10 g/kg) increased, IP lengthened. The
addition of lecithin also increased
total tocopherols but decreased
the a/g tocopherol ratio
Lee and Choe [148] Tocopherol-stripped SFO; Phosphatidylcholine (0, 250, and Phosphatidylcholine extended the
Water in oil emulsion 1000 ppm) IP of the oil. Different
consists of methylene phospholipids concentrations have
chloride, n-butanol, the same effects
Na2MoO42H2O, sodium
dodecyl sulfate; rubrene (a
singlet oxygen quencher);
25°C for 24 h
Chen et al. [7] Stripped SBO, 25°C for Dioleoylphoshatidylcholine, The association colloids formed by The structure of association
24 h dibutyrylphosphatidylcholine, (each 0 dioleoylphoshatidylcholine and colloids may influence lipid
–1270 mmol/kg) water were prooxidative, while oxidation in bulk oils.
those formed by Dioleoylphoshatidylcholine
dibutyrylphosphatidylcholine were and dibutyrylphosphatidyl-

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
comparable to control choline have identical
Chen et al. [20] Stripped SBO, 50°C Dioleoylphoshatidylcholine Dioleoylphoshatidylcholine choline groups but different
(1000 mM), a-tocopherol (10 and formed reversed micelles in oil and physical structure in oil.
100 mM), and Trolox (10 and shortened the IP. SAXS measurement
100 mM) Dioleoylphoshatidylcholine revealed that

(Continued)

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

improved the activity of low a- dioleoylphoshatidylcholine

tocopherol or Trolox formed spherical structures
concentrations (10 mM) but while dibutyrylphos-
decreased the activity at high phatidyl choline formed
concentrations (100 mM) cylindrical structures
OH-containing carotenoids
Haila et al. [149] TAG from low-erucic acid Lutein (5, 20, 30, and 40 ppm), Lutein caused more LOOH. Lutein was prooxidant both
rapeseed oil, under dark at lycopene (20 ppm), annatto (20, 30, Lutein (20 ppm) þ g-tocopherol in the dark and light. When
40°C and 60 ppm as bixin), b-carotene (15 ppm) were antioxidants. lutein is combined with
(20 ppm), g-tocopherol (10 and Lutein was consumed faster and tocopherol, they
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

15 ppm), lutein þ g-tocopherol slower (higher retention), without significantly increase

(20 þ 15 ppm, 1:1 in molar ratio), or and with g-tocopherol, oxidative stability.
lutein þ g-tocopherol (20 þ 10 ppm, respectively. The consumption of Lycopene and b-carotene
1.5:1 in molar ratio) g-tocopherol was not affected by were prooxidants
lutein. Total of 30 and 60 ppm
bixin (annatto) was significantly
reduced LOOH levels
Henry et al. [150] Purified safflower seed oil, Lycopene (35 mM), lutein (66 mM), The orders of the rate of Geometric configurations
OSI, 75°C for 24 h, 85°C 9-cis-b-carotene (54 mM), and all- degradation were lycopene >9-cis- do not effect the
for 12 h, 95°C for 5 h trans-b-carotene (150 mM) b-carotene ¼ all-trans-b- decomposition rate, as in 9-
carotene > lutein cis and all-trans carotene.
OSI in hours and lipid
oxidation measurements (e.
g., PV, TBARS) need to be
performed to study the
effects of carotenoids on
safflower oil oxidation
Subagio and Morita [151] Purified corn-oil TAG, a-Tocopherol, b-carotene, and lutein Lutein increased the amount of The antioxidative effect of
paraffin, 40°C, dark (each at 5, 10, and 30 ppm and LOOH. b-carotene þ lutein b-carotene was dose-
combination of 30 and 30 ppm) caused more degradation of b- dependent, at higher
carotene. Lutein was more concentration it became
unstable than b-carotene in prooxidant. When
paraffin (medium similar to TAG) combined, b-carotene
protected lutein, as b-
carotene degraded more

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
than lutein in oil. But in
paraffin it is the opposite
Kiokias and Gordon [71] Purified OO, oven, 60°C b-carotene (1 g/L), annatto oil- Norbixin showed synergisms with The presence of polar
Supramolecular chemistry of lipid oxidation

soluble (bixin; 1 g/L), and annatto ascorbic acid, ascorbyl palmitate, carboxylic acid groups in
water-soluble (norbixin) (1 and and tocopherols, which were the norbixin molecule may

(Continued)

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 Table 3. (Continued) 1116
Substrates and oxidation
References conditions Additive(s) Results Conclusions

2 g/L), virgin olive oil polar extract beyond the effect of phenolic contribute to chelation of
(0.2 g/L), a-tocopherol (0.1 mM), antioxidants in oils and emulsions. metal ions or other polar
g-tocopherol (0.1 mM), ascorbic acid These effects are better than that initiating species, thus
(0.1 mM), and ascorbyl palmitate of b-carotene or b-carotene and retarding autoxidation of
(0.1 mM) polar extract oil
Becker et al. [44] Purified SFO; Rancimat a-Tocopherol, rutin, astaxanthin, The antioxidant ranking in bulk Astaxanthin exerts
(OSI), 100°C, 20 L/h quercetin (each at 0.25, 0.5, 1.0, and oil: quercetin > a-tocopherol  antioxidant activity in bulk
2.0 mmol antioxidant/g oil, and their astaxanthin ¼ rutin oil
combination of 1.0 þ 1.0, 0.5 þ 0.5,
and 0.25 þ 0.25 mmol/g)
E. S. Budilarto and A. Kamal-Eldin

Zeb and Murkovic [152] Refined OO, Rancimat, b-Carotene, E-astaxanthin E-astaxanthin protected olive oil 9-Z-astaxanthin showed a
110°C, 1–14 h (300 0.5 ppm) in olive oil from oxidation (reduced epoxides) higher antioxidant effects
and inhibited b-carotene among E and Z-
degradation astaxanthin. b-Carotene
acted as prooxidant after
prolonged heating
Amino acids
Ahmad et al. [153] Safflower oil, a mixture of Cysteine, proline, tryptophan, Cysteine and glutamic acid were Antioxidative activity of
sunflower and cottonseed methionine, glutamic acid, lysine, and prooxidants in the oil mix, and amino acids in such oils
oil, active oxygen method arginine (each at 0.01, 0.02, 0.04, glutamic acid was prooxidants in was low. It could be that
at 97.8°C 0.07, 0.10, 0.40, 0.70, and 1.00%) the safflower oil. The highest they do not contribute as
protection activity in the safflower antioxidant by themselves,
oil was due to methionine, proline, but requiring primary
lysine, and cysteine. The highest antioxidants
protection activity in the mix was
due to lysine, arginine, glutamic
acid, methionine, and
hydroxyproline. However the
amino acid protection activities
were very low, low, or medium
Alaiz et al. [154] SBO, air in the dark at N-(Carbobenzyloxy)-1(3)-[10 - The order of stability: Compound Reactions of products from
60°C (formylmethyl)hexyl]-L-histidine 1 > Z-Hitidine > Control. The lipid oxidation (aldehydes)
dihydrate (compound 1) formed from protection index of compound 1 and amino acids exhibited
reaction of histidine and (E)-2- and Z-histidine increased with an antioxidant property.
octenal (50, 100, and 200 ppm), concentration The polymerization of

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
Z-histidine (50, 100, and 200 ppm) these compounds produces
melanoidin-like polymers
which cause changes in
color and fluorescence

(Continued)

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Carlotti et al. [123] Linoleic acid in sodium a-Tocopherol (1.06.0  106 M), Glutathione, L-tryptophan, L- Amino acids exhibited
dodecylsuphate micellar a-tocopherol: 5.0  106 M, and alanine, L-cysteine, and glycine antioxidative effects, either
solutions (with ascorbic acid: 0.41.0  104 M, a- prolonged the IP of micellar added alone or
ethylenediaminetetraacetic tocopherol: 5.0  106 M, and solution (containing combination with other
acid (EDTA) and azo- ascorbic acid: 0.5  104 M, L- 5.0  106 M a- amino acids or a-
initiator added), pH 5.0 tryptophan tocopherol þ 5.0  106 M vit tocopherol
and 7.0, 45 and 56°C (8.5  105 M  1.0  104 M), L- C) at pH 5.0 and 7.0 (at 45°C).
alanine (1.0  1.2  104 M), L- The synergistic action was
cysteine particularly significant for L-
(8.5  104 M  1.0  104 M), cysteine, L-tryptophan, and
glycine (1.0  1.5  104 M), and Glutathione
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

gluthathione reduced form

(7.5  8.5  105 M)
Hidalgo et al. [155] Refined OO, Rancimat, Phosphatidylethanolamine, Lysine (200 ppm or more) Lysine and
110°C phosphatidylcholine, lysine, BHT increased IP, which was superior phosphatidylethanolamine
(each 0, 100, 200, 300, and 400 ppm to those of oil with or phosphatidylcholine
and combination of phospholipids of phosphatidylethanolamine, exhibited synergism. The
100, 200, or 300 ppm with amino phosphatidylcholine, and BHT of amino group of lys reacted
acid of 100, 200, or 300 ppm) the same concentration. A total of with oxidized lipids to form
300 ppm hydrophilic pyrroles, which
phosphatidylethanolamine þ are good for oil (polar
100 ppm lysine caused 185% paradox)
increase of IP compared to
control, and when both were used
alone. Phosphatidylcholine and
lysine increased the IP
Papadopoulou and Roussis [156] Corn oil; 50, 120, and N-acetyl cysteine and gluthathione N-acetyl cysteine and gluthathione N-acetyl cysteine and
180°C (10, 20, and 40 mg/L),butylated reduced the formation of gluthathione are
hydroxyanisole (BHA; 200 mg/L) conjugated dienes, trienes, and PV hydrophilic compounds,
at 50, 120, and 180°C. The which have more affinities
antioxidative ranking were toward the air-oil interface
BHA > N-acetyl in bulk oil, thus more
cysteine > gluthathione; except effective than lipophilic
that at 180°C, N-acetyl cysteine ones in bulk oil
were more effective than BHA
Hidalgo et al. [157] Stripped virgin OO, b- Phosphatidylethanolamine (0, 100, Phosphatidylethanolamine, Amino groups of lysine

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
sitosterols added stripped 200, 300, and 400 ppm), phosphatidylcholine, lysine, and react with oxidized lipids to
virgin OO, Rancimat, phosphatidylcholine (0, 100, 200, their combinations cause a form hydrophilic pyrroles,
90°C, 10 L/h 300, and 400 ppm), lysine (0, 100, significantly higher antioxidative which may contribute to
Supramolecular chemistry of lipid oxidation

200, 300, and 400 ppm), and b- effects in b-sitosterol added virgin the stabilization of oil
sitosterols (1500 mg) OO, compared to virgin OO. The
combined

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 Table 3. (Continued)
1118
Substrates and oxidation
References conditions Additive(s) Results Conclusions

phosphatidylethanolamine/
phosphatidylcholine gave a shorter
IP but phosphatidylethanolamine/
lysine and phosphatidylcholine/
lysine increased the IP, more than
when the components were added
alone
Citric acid and ethylenediaminetetraacetic acid (EDTA)
Hras et al. [158] Stripped SFO, oven, 60°C Rosemary extract (0.02%), a- Citric acid alone reduced peroxide Citric acid is a chelating
tocopherol(0.01%), ascorbyl value (PV) and anisidine value agent, by forming bonds
palmitate (0.01%), citric acid (AV), but the activity was lower between the metal and the
E. S. Budilarto and A. Kamal-Eldin

(0.01%), and their combinations than the extract and ascorbyl carboxyl or hydroxyl
palmitate. The order of groups of the citric acid
antioxidant activity: extract þ molecule. Citric acid alone
ascorbyl palmitate > extract þ had antioxidant role. The
citric acid > extract > extract þ effect was greater when
AT > control citric acid was combined
with extract
Jaswir et al. [159] Fresh, cold-pressed, Oleosin rosemary extract (0, 0.05, Antioxidants (extracts and their Antioxidants added to the
unrefined, and antioxidant- and 0.1%) , sage extract (0, 0.05, and combinations) significantly oil before frying were
free flaxseed oil, heated to 0.1%), and citric acid (0, 0.025, and reduced PV, p-AV, FFA, color effectively retarding lipid
frying temp. 165 5°C for 0.05%) yellow, C18:1, C18:2, and C18:3, oxidation and reducing oil
3.5 min, then 165°C for reduced some of absorbances at hydrolysis during deep
6 min., and allowed to 232 and 268 nm, but increased frying
reach 60°C at room T, C16:0 and C18:0
flushed with N2 gas and
kept in a cold room at 4°C
until analysis
Wang et al. [145] Natural and randomized Citric acid (100 and 200 ppm) Randomized corn oil had a much Citric acid protective effect
corn oil; OSI, 100°C lower OSI than natural corn oil is not related to chelation of
does. Citric acid (200 ppm) transition metals
partially restored the OSI of
randomized oil
Drusch et al. [32] Stripped refined fish oil, a-Tocopherol (100 ppm), d- 500 ppm ascorbyl palmitate þ Citric acid effects are due
20°C tocopherol (1000 ppm), ascorbyl 500 ppm citric acid reduced to its metal ions chelation
palmitate (50 and 500 ppm), lecithin LOOH compared to control and ability, the action is greater

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
(500 and 2000 ppm), and citric acid sample with 500 ppm ascorbyl when trace metal content is
(100 and 500 ppm) palmitate þ 200 ppm lecithin þ high and is trivial when
(100 or 500 ppm) citric acid trace metal content is low.
Citric acid showed a more
synergism with ascorbyl
palmitate, but less with
lecithin

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Yi et al. [160] Mixture of yellow palm Ascorbyl palmitate (200 and Citric acid and ascorbyl palmitate Citric acid did not show
olein/fish oil, mixture of red 500 ppm), citric acid (50 ppm), displayed a pronounced inhibiting synergisms with
palm olein/fish oil, 30°C in phosphatidylethanolamine effect on the formation of radicals, phospholipids
the dark (500 ppm), and phosphatidycholine IP, PV, and TBARS
(500 ppm) (Phosphatidylethanolamine or
phosphatidylcholine) þ (ascorbyl
palmitate þ citric acid), the
phospholipids exhibited a
prooxidant effect
Wang et al. [145] Natural and randomized EDTA (100 ppm) Randomized corn oil had a much The protective effect of
corn oil; OSI, 100°C lower OSI than natural corn oil EDTA is not related to
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

does. EDTA (100 ppm) chelation of transition

completely restored the OSI of metals
randomized oil
Ascorbyl palmitate
Frankel et al. [39] Stripped corn oil, 60°C in a a-Tocopherol, trolox, ascorbic acid, a-Tocopherol and ascorbyl Lipophilic antioxidants (a-
shaker oven and ascorbyl palmitate (each at 100 palmitate were more effective in o/ tocopherol and ascorbyl
and 500 ppm) w emulsion than in bulk oil. palmitate) were more
Ascorbic acid, Trolox and a- effective in o/w emulsions
tocopherol þ ascorbic acid, or a- than bulk oil (or w/o
tocopherol þ ascorbyl palmitate emulsions). The opposite
were more active in bulk oil, but exists for hydrophilic
ascorbic acid alone was better than antioxidants (ascorbic acid
a-tocopherol þ ascorbic acid. and Trolox). There is a
LOOH and hexanal were strong synergism between
measured a-tocopherol þ ascorbyl
palmitate and a-
tocopherol þ ascorbic acid,
but a-
tocopherol þ ascorbic acid
were not significantly better
than ascorbic acid alone
Gordon and Kourkimska [161] Rapeseed oil, heating at 80° TBHQ (0.2 g/kg), lecithin (1 g/kg), Rancimat results gave the order of The effect on
C, deep fat frying, ascorbyl palmitate (0.2 g/kg), antioxidant activity: microenvironment
Rancimat 100°C rosemary extract (1 g/kg), BHT TBHQ > lecithin > ascorbyl modulation may sometimes

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
(0.2 g/kg), BHA (0.2 g/kg), and D-d- palmitate > rosemary be more important than
tocopherol (0.2 g/kg) extract > BHT, BHA, and d- hydrogen donation
tocopherol
Supramolecular chemistry of lipid oxidation

(Continued)

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 Table 3. (Continued) 1120

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Hamilton et al. [28] Refined-deodorized a-Tocopherol, d-tocopherol, g/d- Ascorbyl palmitate and lecithin Ascorbyl palmitate
Chilean anchovy fish oil, tocopherols (each was 0.006, 0.2, 1, alone gave a small improvement in promotes LOOH scissions.
20°C, free access to air, RH and 2%), ascorbyl palmitate (0.1 %), oxidative stability (unlike The function of lecithin is
45% and lecithin (0.5%) tocopherols). Ascorbyl palmitate merely for solubilizing
exhibited a pro-oxidant effect in ascorbyl palmitate, which
the presence of 0.2 and 2% d- causes ascorbyl palmitate to
tocopherol or g/d-tocopherol. partition in the o/w
Ascorbyl palmitate þ lecithin and interface. The action of
ascorbyl palmitate þ 0.2 or 1% a- lecithin as an antioxidant is
tocopherol (not at other level) due to its phosphatidyl part
E. S. Budilarto and A. Kamal-Eldin

displayed strong synergy which sequesters trace of

heavy metals, its ability to
inhibit ascorbyl palmitate
in hydroperoxide scission
and to react with free
ascorbyl radicals
Hras et al. [158] a-Tocopherol free SFO, Rosemary extract (0.02%), a- Ascorbyl palmitate significantly Rosemary extract contains
oven, 60°C tocopherol (0.01%), ascorbyl reduced PV and p-AV, compared phenolic diterpenes such as
palmitate (0.01%), citric acid to other additives and control, but carnosic acid, carnosol,
(0.01%), and their combinations lower than extract. Combination rosmanol; and other
of extract and ascorbyl palmitate phenolic acid such as
resulted in the lowest PV and p- rosmarinic acid. Extract
AV and tocopherol act as
radical scavengers.
Ascorbyl palmitate is
ascorbic acid derivative that
is oil-soluble. Ascorbyl
palmitate plays a role as
oxygen scavenger. Ascorbyl
palmitate alone acted as
antioxidant but not when
combined with extract
Frankel et al. [162] Algal oil containing 5.1– Ascorbyl palmitate (0.025%) Ascorbyl palmitate caused an Ascorbyl palmitate might
12.7% eicosapentaenoic increase in the oxidative stability have an antioxidant
acid (EPA), 10.5–52.4% (PV and propanal) of the oil. synergism with tocopherols

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
docosahexaenoic acid Carotenoids at high concentration
(DHA), 11–19.37% a- may have pro-oxidant effect by
tocopherol, and lowering the relative stability of
carotenoids (577– certain algae oil
2823 ppm); 40, 50, and
60°C in a shaker oven

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Kiokias and Gordon [71] Tocopherol-stripped OO, b-Carotene (1 g/L), annatto oil- Ascorbyl palmitate reduced PV of Ascorbyl palmitate
oven, 60°C soluble (bixin; 1 g/L), and annatto oil. Ascorbyl palmitate showed significantly modulates the
water-soluble (norbixin; 1 and 2 g/L), synergism with norbixin, which antioxidant activity of
virgin OO polar extract (0.2 g/L), a- were beyond the effect of phenolic phenolic inhibitors
tocopherol (0.1 mM), g-tocopherol antioxidants, but lower than
(0.1 mM), ascorbic acid (0.1 mM), ascorbyl palmitate alone
and ascorbyl palmitate (0.1 mM)
Carelli et al. [131] SFO; stored at 30°C, Ascorbic acid, d-tocopherol, ascorbyl Ascorbic acid, ascorbyl palmitate, There was an absence of
Rancimat 130°C palmitate, a-tocopherol, and citric and d-tocopherol significantly linearity of OSI and
acid (each at 0, 100, 200, 400, 600, increased IP. Ascorbic acid gave concentration of ascorbic
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

and 800 ppm) the most effect. Samples acid and ascorbyl
containing 100 ppm of each palmitate, because they are
additive and control had similar consumed or participated
PV, p-AV, and residual in chain termination
tocopherol. Polar compound reactions and in one or
showed an antioxidative synergism more side reactions. a-
with ascorbic palmitate and d- tocopherol showed the
tocopherol greatest efficacy at
<700 ppm but not at
higher level because of its
participation in side
reactions
SFO; stored at 68°C; Ascorbic acid, d-tocopherol, ascorbyl Results of rancimat test of IP were At high temperature,
Rancimat 130°C palmitate, a-tocopherol, and citric the same as above. No significant oxygen has lower solubility
acid (each at 0, 100, 200, 400, 600, differences in p-AV of all in oil thus autoxidation rate
and 800 ppm) treatments. Antioxidant is lower and becomes
effectiveness in terms of PV and gradually replaced with
phosphatidylcholine was d- polymerization, showed by
tocopherol > ascorbyl formation of triglyceride
palmitate > ascorbic acid > citric dimer (At 68°C). Ascorbyl
acid. d-Tocopherol was the only palmitate and d-tocopherol
antioxidant present. Oxidized protect the oil at higher
triglyceride monomers were lower temperatures
from oil with d-tocopherol, at a
longer storage time

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
SFO; stored at 130°C; Ascorbic acid, d-tocopherol, ascorbyl Results of rancimat test of IP were Ascorbic acid could
Rancimat 130°C palmitate, a-tocopherol, and citric the same as above. The p- deteriorate at high
acid (each at 0, 100, 200, 400, 600, AVshowed antioxidant effects of temperature, which lessens
Supramolecular chemistry of lipid oxidation

and 800 ppm) ascorbyl palmitate and d- its antioxidant activity.

tocopherol. Ascorbyl palmitate Both oxidative and thermal
spared the highest tocopherol degradation took place at

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 Table 3. (Continued) 1122

Substrates and oxidation

References conditions Additive(s) Results Conclusions

residual. Ascorbyl palmitate and 130°C, as shown by a

d-tocopherol gave the lowest polar significant increase in polar
compounds. d-tocopherol showed triglyceride and triglyceride
lower oxidized triglyceride dimer
monomers
Olsen et al. [163] Refined and deodorized Tocopherol concentrate (800 ppm), The order of decreasing PV was Tocopherol þ ascorbyl
cod liver oil, 25°C in dark, ascorbyl palmitate (200 ppm) tocopherol concentrate > palmitate can be used to
Rancimat is done at control > tocopherol stabilize cod liver oil, in
20 mL/min and 80°C concentrate þ ascorbyl palmitate. terms of odor and flavor,
The p-AV increased significantly when the oil is stored in the
E. S. Budilarto and A. Kamal-Eldin

with time. Tocopherol dark at 25°C. Volatile

concentrate þ ascorbyl palmitate compounds and IP did not
caused a more grass/cucumber- give useful information
like, than herring oil and paint about the resistance of the
odor and flavor, which was oils to autoxidation at 25°C
perceived as more acceptable by
consumers. Tocopherol
conc. þ ascorbyl palmitate
inhibited the formation of most
volatile oxidation products, except
hexanal groups. IP did not
significantly changed during
storage, compared to initial IP
Drusch et al. [32] Stripped refined fish oil, a-Tocopherol (100 ppm), d- Order of reduction of LOOH: The synergisms of ascorbyl
20°C tocopherol (1000 ppm), ascorbyl 500 ppm ascorbyl palmitate, lecithin, and a-
palmitate (50 and 500 ppm), and palmitate > 2000 ppm tocopherol are owing to the
lecithin (500 and 2000 ppm) lecithin > 500 ppm antioxidative effect of
lecithin > 50 ppm ascorbyl lecithin (by regeneration of
palmitate. 500 ppm ascorbyl a-tocopherol from its
palmitate þ 2000 ppm oxidized radical or by
lecithin þ (100 ppm a-tocopherol interaction with ascorbyl
and 1000 ppm d-tocopherol) gave radicals), a chelating effect
the most effect in LOOH of lecithin, or physical
reduction, but increased propanal phenomena that might
content. 500 ppm lecithin used in occured (better

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
combination with others caused a solubilization of ascorbyl
lower effect than a single effect of palmitate and formation of
lecithin reversed micelles of lecithin
with tocopherol and
ascorbyl palmitate)

(Continued)

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

Karabulut [164] Butter oil TAG, oven, 60° Ascorbyl palmitate (5, 50, 100, and b-car. and ascorbyl palmitate had The synergism of a-
C 200 ppm), a-tocopherol (10, 25, and higher oxidation rate (no IP) than tocopherol and ascorbyl
50 ppm), and b-carotene (5, 10, 25, that with a-tocopherol, but lower palmitate was due to a-
and 50 ppm) than control; measured by PV and tocopherol that was spared
p-AV. There was synergism at the expense of ascorbyl
between ascorbyl palmitate þ palmitate during oxidation
a-tocopherol, but not ascorbyl or ascorbyl palmitate is
palmitate þ b-car. (had no used to regenerate
effects) tocopherols. Ascorbyl
palmitate donates hydrogen
to tocopheroxyl radical
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

Sorensen et al. [61] Water in oil emulsion Ascorbic acid, ascorbyl palmitate, The IP as measured by LOOH Ascorbic acid, ascorbyl
containing 98% oil (fish oil ascorbyl conjugated linoleic acid showed that all additives acted as palmitate, and ascorbyl
and rapeseed oil, 1:1), 37° (ascorbyl conjugated linoleic acid), antioxidants. Propanal and conjugated linoleic acid
C in the dark and conjugated linoleic acid, each hexanal concentration results owing their antioxidative
additive at 50, 100, 150, 200, and were: ascorbyl palmitate > properties mostly due to
250 ppm; polyglycerol polyricinoleate ascorbyl conjugated linoleic their ascorbyl group.
(1%) acid > ascorbic acid > Ascorbic acid is known as a
conjugated linoleic acid radical scavenger of
hydrophilic radicals and to
have a reducing power due
to its ability to donate an
electron to reactive free
radicals
Yi et al. [160] Mixture of yellow palm Ascorbyl palmitate (200 and Ascorbyl palmitate (200 and Ascorbyl palmitate
olein/fish oil, mixture of red 500 ppm), citric acid (50 ppm), 500 ppm) alone or with citric acid synergists with citric acid,
palm olein/fish oil, 30°C in phosphatidylethanolamine displayed a pronounced inhibiting but not with
the dark, 100°C (500 ppm), and phosphatidylcholine effect on the formation of radicals, phosphatidylethanolamine
(500 ppm) lengthening IP, PV, and TBARS and phosphatidylcholine
in both oil.
(Phosphatidylethanolamine or
phosphatidylcholine) along with
(ascorbyl palmitateorcitric acid),
the phospholipids exhibited a
prooxidant effect
Sterols

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
Soupas et al. [165] Tripalmitin, 80°C for Stigmasterol, sitostanol (each 1%) Stigmasterol and sitostanol oxides At high temperature, the
1–8 wk, 100°C for 3–48 h, (formed more) increased during unsaturated matrix is more
140°C for 0.5–6 h, 180°C all heat treatments in both readily oxidized than the
Supramolecular chemistry of lipid oxidation

for 0.5–6 h; purified medium, except stigmasterol stigmasterols, thus

rapeseed oil, 60°C for oxides during heating at 100°C for protecting the sterols; while
1–7 days, 100°C for 0–6 h and sitostanol oxides during saturated matrix forces the

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(Continued)

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 Table 3. (Continued) 1124

Substrates and oxidation

References conditions Additive(s) Results Conclusions

3–48 h, 140°C for 0.5–24h, heating at 80°C for 0–4 wk. At low stigmasterols to react.
180°C for 0.5–6 h T., the stigmasterol oxides had There is no relationship
lower oxidation in tripalmitin than between sitostanol, matrix,
in the rapeseed oil. At all T., and temperatures, as
sitostanol was oxidized more at sitostanol oxidized faster
both matrix than both matrix
Soupas et al. [166] Rapeseed oil, hydrogenated Microcrystalline phytosterol 30% phytosterol caused more The differences in the
coconut oil, and refined suspensions contains of 77% phytosterol oxides than that of susceptibility of phytosterol
palm kernel oil, 4°C for sitosterol and 8% campesterol (18 18% phytosterol. 18 and 30% oxidation in different
12 months and 30%) phytosterol, caused the sitosterol matrix are due to initial
E. S. Budilarto and A. Kamal-Eldin

to be more oxidized in oxide contents in

hydrogenated coconut oil and phytosterol preparation and
refined palm kernel oil, and lipid matrix. A higher level
rapeseed oil, respectively. The sitosterol is oxidized more
phytosterol content at the readily than the
beginning and after 12 months of unsaturated matrix (at 4°C)
cold storage did not change
significantly
Cercaci et al. [167] Corn oil, 55°C in the dark; Cholesterol, stigmasterol, b-sitosterol, 7-keto derivatives of phytosterols Oxidation of phytosterols
phytosterol-oxide was 5-alfa-cholestane (1, 2, 3, 4, and increased with time, the most results in ketones, alcohols,
made at 150°C for 2 h in 5 mmol/kg hexadecane) being 7-ketositosterol. The ability epoxides and dienes. The
an oven; hexadecane, 30°C of sterols to reduce interfacial 7-keto derivative is the
for 24 h tension was in the order: major phytosterol oxidation
stigmasterol > cholesterol > b- product. Sterols have a
sitosterol > 5a-cholestane planar rigid structure which
causes them to pack
together tightly, and with
their ability to be surface
active, they can concentrate
at o/w interface
Winkler-Moser et al. [102] SBO, high-oleic SFO, Mixed phytosterols consist of Phytosterol was prooxidants, by At lower temperature and
stripped SBO, stripped brassicasterol (3.8%), campesterol increasing dimers and polymerized in less unsaturated matrix
high-oleic SFO, Rancimat (26.9%), campestanol (0.6%), triacylglycerol in stripped SBO (e.g., stripped high oleic
(OSI), 110°C stigmasterol (17.2%), b-sitosterol and high-oleic SFO, but not after SFO), phytosterols
(48.2%), sitostanol (1.1%), D5- 4 h. In stripped oil, phytosterol oxidized quicker than the

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
avenasterol (1.3%), D7-stigmastenol caused lower OSI matrix, causes higher
(0.8%) (0.25, 0.5, 1, and 2.5%) dimers and polymerized
TAG formation. But at
higher T and in more
unsaturated matrix (e.g.,

(Continued)

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 Table 3. (Continued)

Substrates and oxidation

References conditions Additive(s) Results Conclusions

stripped SBO),
polyunsaturated fatty acids
(PUFA) are oxidized
preferentially over sterols
and protect the sterols from
oxidation
Hidalgo et al. [157] Stripped virgin OO, b- Phosphatidylethanolamine (0, 100, Phosphatidylethanolamine, There was a synergism
sitosterols added stripped 200, 300, and 400 ppm), phosphatidylcholine, lysine, and among b-sitosterol and
virgin OO, Rancimat, 90° phosphatidylcholine (0, 100, 200, their combinations caused a phosphatidylethanolamine;
C, 10 L/h 300, and 400 ppm), lysine (0, 100, significantly higher antioxidative b-sitosterol and
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

200, 300, and 400 ppm), and b- effects in phytosterol added OO, phosphatidylcholine; b-
sitosterols (1500 mg) compared to stripped OO. sitosterol and lysine; b-
Phosphatidylethanolamine/lysine sitosterol and phosphatidyl-
and phosphatidylcholine/lysine ethanolamine þ lysine; and
increased the IP compared to b-sitosterol and
when they are added alone, but phosphatidylcholine þ
not phosphatidylethanolamine/ lysine
phosphatidylcholine. The effects
were higher for lysine (200 ppm or
more) and
phosphatidylethanolamine/lysine
(300/100 ppm) in stripped OO
and phytosterol added OO
Soupas et al. [166] Heat treated non-fat milks, Phytosteryl esters containing 45% Phytosteryl esters oxidized more As phytosteryl esters
long term storage at room sitosterol, 25% campesterol, and 18% than phytostanyl esters. oxidized more than
T. and 4°C stigmasterol; phytostanyl esters Temperature did not influence the phytostanyl esters, it could
containing 65% sitostanol and 33% oxidation effects of both be that if phytosteryl esters
campestanol (the sterol ester were antioxidants were used as antioxidant
added at 0.5%) then it will protect the
matrix more. The effects on
oil matrix must be
investigated
Salts
Calligaris and Nicoli [126] SBO; Rancimat, 120°C at Potassium carbonate, potassium Potassium carbonate and The antioxidant activity
20 L/h acetate, acetic acid, sodium acetate, potassium acetate significantly was attributed to the

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
sodium chloride, and potassium reduced PV and hexanal. Others antichaotropic anionic
chloride (all salts were added at 10% (acetic acid, sodium acetate, species, of which could
w/w) sodium chloride, and potassium interact and form H bonds
Supramolecular chemistry of lipid oxidation

chloride) reduced hexanal and with LOOH

increased IP by Rancimat

(Continued)

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1126 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

depend on the type of fluid

Salt decreased CMC. The
70

size and other parameters

surface coverage did not

need to be studied. The
of nanoemulsions might

interface (air/water, oil/

hydrocarbons) and salt

60
Conclusions

water with different

50

concentration

PV (mg/kg)
40

30

20

10
150 mM NaCl had a lower surface

tension of SBO/water than in C16/

water. The coverage of interface of

hexadecane (with SDS and NaCl).

saturation of the ionic surfactants

and NaCl caused a lower surface
tension than 10 mM NaCl. SDS

coverage of SBO (with SDS and

the nanoemulsions at CMC was

NaCl) was lower than that of

0
lower than 90%. The surface

0 5 10 15
There was an absence of

Time (weeks)
Results

Figure 3. Synergistic effects of binary mixtures of ascorbyl

palmitate and lecithin on the autoxidation of fish oil at 20°C;
^: no antioxidant, &: 0.1% ascorbyl palmitate, D: 0.5% lecithin,
at the CMC

^: 0.1% ascorbyl palmitate þ0.5% lecithin. Data from [28].

compounds [56, 76–80]. The model in Fig. 4 considering

bulk oil as a nanoemulsion would better explain available
Sodium dodecyl sulfate (SDS) (105,
104, 103, and 102), NaCl (10 and

results on lipid oxidation [53, 68, 81].

Water activity influences lipid oxidation rates due to its
relation to metal reactivity and hydroperoxide stability [82].
In food products, the rate of lipid oxidation is lowest at
Additive(s)

water activity of 0.2–0.4 and it increases with increased

water activity [14, 69]. When water activity is increased,
metals are mobilized and oil viscosity is reduced hence
oxidation is accelerated [69]. Different water types or
150 mM)

concentrations and levels of emulsifiers produce different

shapes of association colloids and affect lipid oxidation
differently [20, 83]. It was found that phospholipids
Water/air and water/oil (n-
Substrates and oxidation

hexadecane and SBO)

conditions

emulsions
Table 3. (Continued)

Figure 4. Schematic representation of the distribution of hydro-

Gurkov et al. [168]

philic and hydrophobic antioxidants in bulk oil and the

microenvironment with hydroperoxides and water as explained by
Frankel et al. in 1994 [39] by the antioxidant partitioning at the oil-air
References

interface (left) and later modified by Chaiyasit et al. in 2007 [14] to

antioxidant and surfactant partioning at the oil-water interface of
micelles/association colloids (right).

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1127

synergize the activity of a-tocopherol only in the presence of The effect of antioxidants and other surface-active
small amounts of water and catalysis by water-soluble additives on microemulsion formation depends on their
radical generators [54]. It was also found that as an hydrocarbon chain length, that is, their hydrophilic lip-
increase of the length of the acyl moieties of phospholipids ophilic balance (HLB) [54] and quantities [146, 151]. From
increases the induction period [54, 84]. The kinds of the empirical point of view, the term HLB is used to indicate
fatty acid composition and functional groups of the the solubility of an antioxidant in lipid systems [88].
phosphate groups of phospholipids also influence oxidation Surfactants with low HLB (3–6) favor the formation of w/o
differently [20]. This research implies that the aqueous emulsions whereas those with high HLB (8–18) enhance
microenvironment influences lipid oxidation and must be o/w emulsions [90, 91]. Free fatty acids, mono- and
controlled [85] as discussed in the previous part. It is diacylglycerol have low HLBs (1.0, 3.4–3.8, and 1.8,
possible that water causes some hydrolysis of triacylglycerols respectively) and, thus, prefer to form and stabilize reversed
(TAG) resulting in the formation of mono- and diacylgly- micelles in w/o [14]. Phospholipids with intermediate HLB
cerols and free fatty acids, which would influence the (around 8.0) can form variety of structures; spherical
microemulsion in a negative way and act as prooxidants as in reversed micelles in bulk oil with small amount of water
many studies (Table 3). (<0.3%) and lamellar structures in combination with other
At low levels (e.g., in the range of 230–240 ppm) water surfactants [7, 14].
seem to have no effects on the oxidation of an oil despite a Another factor that determines surfactants activity is
high interfacial tension and more oxidation [33]. The same the surfactant packing parameter (Sp) which use a more
results was found when the amount of water is increased quantitative approach, relates to the geometry of the
(up to 1000 ppm) possibly because water here is bound to surfactant and determines the curvature preference of a
polar compounds and is trapped in multilayer association surfactant molecule (particularly when co-surfactant is used)
colloids [20]. Water in refined oils (approximately 300 ppm) [76, 78, 91]. Sp is related to solubilization of micro-
originates from the water present in oilseeds, and the emulsions in the solvent [78, 170]. Additional information of
water used during neutralization and degumming processes additives, such as log P, topological polar surface area and
[7, 14, 20]. Throughout oxidation, more water is formed by volume are presented in (Table 4). In summary, the octanol-
the bimolecular decomposition of hydroperoxides during water partition coefficient (or log P), which is a measure of
the propagation phase. the lipophilicity of a compound, can be used to estimate
The minor components of vegetable oils (such as transport properties of a compound across an interface [171]
FFA, MAG, and phospholipids) and lipid oxidation and to predict the structure-activity relationship of com-
products (e.g., hydroperoxides, aldehydes, ketones, and pounds [172]. Molecular volume, the volume of 1 mol of
epoxides) are amphiphilic and surface active. In the a substance at a specific temperature and pressure, also
presence of small amounts of water and/or surfactants, predicts the transport characteristics of substances across
these minor constitutents will be able to form micro- an interface [173]. Another property that is used to
emulsions or association colloids, which influence oxida- predict the transport characteristics of a molecule is
tion [7, 14, 20, 33, 70]. Stripped corn oil had higher topological or molecular total polar surface area (TPSA)
interfacial tension (31.5 0.68 mN/m) than original corn [174], which is the quantity of surface contributions of
oil (20.1 0.09 mN/m) indicating that minor components polar atoms, such as oxygens, nitrogens, and hydrogens in a
act as surfactants by reducing the interfacial tension and molecule [175].
the overall energy of the system [14, 33, 80]. The size of A co-surfactant is a compound that can physically
the reversed micelles in bulk oils is in the range of 1– synergize the dissolution of surfactants in the organic solvent
500 nm [70, 86]. Refining of vegetable oils effectively (increasing the solubility of surfactant) and facilitate the
removes minor components (some minor components are formation of reversed micelles and the stabilization of
undesireable such as free fatty acids, and cause foaming and the microemulsions [92, 93]. Examples of co-surfactants
reduce smoke point of oils and chlorophyll, which acts as commonly used in pharmaceutics include short-chain
photosensitizers) but increases the rate of lipid oxidation in alcohols C3–C6, medium chain length alcohols C6–C12,
bulk oils because antioxidants such as tocopherols and glycerol, sorbitol, geraniol, and fatty acid sucrose esters [78,
emulsifiers are removed [14, 20, 33]. Although refining 80]. The location of cosurfactants in micelles is not clear, but
removes minor components to a significant extent, there are they are also in the interface as they can partition between oil
still traces of these compounds in the refined oil that can still and water phase [21]. In addition, co-surfactants can be
affect oxidation in oil [20]. Techniques commonly used to located in the oil phase close and in between surfactant
investigate the structure of microemulsions include cryo- molecules (Fig. 5), and forms complex with surfactants [93].
transmission electron microscopy (cryo-TEM), dynamic Co-surfactants are weak amphiphiles [94], that exert their
light scattering (DLS), small-angle neutron scattering effects by reducing electrostatic repulsion between surfactant
(SANS), wide-angle X-ray scattering (WAXS), and small- head groups and causing weak hydrophobic interactions
angle X-ray scattering (SAXS) [87]. between surfactant tails leading to a modulated packing of

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 Table 4. Structural feature of selected additives (polarity, volume, and topological polar surface area) 1128

Topological
M.Wt LogP Volume polar surface

Compound Molinspirationsmiles (miSmiles)a CAS# (Da) (miLogP) (cubic A) area (TPSA)

Dipalmitoylphosphatidyl CCCCCCCCCCCCCCCC(¼O)O[C@H](COC(¼O) 5681-36-7 691.96 9.647 721.801 134.400

ethanolamine (DPPE) CCCCCCCCCCCCCCC)COP(O)(¼O)OCCN
Dipalmitoylphosphatidyl CCCCCCCCCCCCCCCC(¼O)O[C@H](COC(¼O) 40290-42-4 757.94 9.111 748.828 171.699
serine (DPPS) CCCCCCCCCCCCCCC)COP(O)(¼O)OC[C@H](N)C(O)¼O
Dipalmitoylphosphatidyl CCCCCCCCCCCCCCCC(¼O)OC[C@H](COP([O-])(¼O) 2644-64-6 734.04 6.383 773.671 111.206
choline (Lecitin) OCC[Nþ](C)(C)C)OC(¼O)CCCCCCCCCCCCCCC
Ascorbylpalmitate CCCCCCCCCCCCCCCC(¼O)OC[C@H](O)[C@H]1OC 57233-83-7 414.5 6.284 411.443 113.294
(¼O)C(O)¼C1O
E. S. Budilarto and A. Kamal-Eldin

Glycerol-1,3-dipalmitate CCCCCCCCCCCCCCCC(¼O)OCC(O)COC(¼O) 502-52-3 568.91 9.913 630.593 72.838

CCCCCCCCCCCCCCC
Glycerol-1,2-dipalmitate CCCCCCCCCCCCCCCC(¼O)OCC(CO)OC(¼O) 40290-32-2 568.91 9.913 630.593 72.838
CCCCCCCCCCCCCCC
Glycerol monopalmitate CCCCCCCCCCCCCCCC(¼O)OCC(O)CO 26657-96-5 330.50 6.090 358.856 66.761
Astaxanthin CC2¼C(\C¼C\C(C)¼C\C¼C \C(C)¼C\C¼C\C¼C(C)\C¼C\C¼C 472-61-7 596.85 8.596 612.415 74.598
(C)\C¼C\C1¼C(C)C(¼O)C(O)CC1 (C)C)C(C)(C)CC(O)C2¼O
b-Carotene CC2¼C(\C¼C\C(C)¼C\C¼C \C(C)¼C\C¼C\C¼C(C)\C¼C\C¼ 7235-40-7 536.88 9.843 591.964 0
C(C)\C¼C\C1¼C(C)CCCC1(C)C)C(C) (C)CCC2
Stigmastanol CCC(CCC(C)C3CCC4C2CCC1CC(O)CCC1(C)C2CCC34C)C(C)C 19466-47-8 416.72 8.714 462.730 20.228
b-Sitosterol CCC(CCC(C)C3CCC4C2CC¼C1CC(O)CCC1(C)C2CCC34C)C(C)C 83-46-5 414.72 8.620 456.517 20.228
D5—Avenasterol CC¼C(CCC(C)C3CCC4C2CC¼C1CC(O)CCC1(C) 481-14-1 412.69 7.688 450.304 20.228
C2CCC34C)C(C)C
Palmitic acid CCCCCCCCCCCCCCCC(¼O)O 9006-59-1 256.42 7.059 291.422 37.299
Oleic acid CCCCCCCC/C¼C\CCCCCCCC(O)¼O 112-80-1 232.50 7.583 318.839 37.299
Methyl linoleate CCCCC/C¼C\C/C¼C\CCCCCCCC(¼O)OC 112-63-0 294.47 7.165 330.18 26.305
Linoleic acid CCCCC/C¼C\C/C¼C\CCCCCCCC(O)¼O 60-33-3 280.45 6.858 312.652 37.299
a-Linolenic acid CC/C¼C\C/C¼C\C/C¼C\CCCCCCCC(O)¼O 463-40-1 278.43 5.840 306.466 37.299
Eicosapentaenoic acid CC/C¼C\C/C¼C\C/C¼C\C/C¼C\C/C¼C\CCCC(O)¼O 10417-94-4 302.45 5.399 327.696 37.299
Docosahexaenoic acid CC/C¼C\C/C¼C\C/C¼C\C/C¼C\C/C¼C\C/C¼C\CCC(O)¼O 24880-45-3 330.50 5.684 355.112 37.299
b-Sitosteryl palmitate CCCCCCCCCCCCCCCC(¼O)O[C@H]4CC[C@]3(C)[C@H]2CC 2308-85-2 653.14 10.256 728.254 26.305
[C@@]1(C)[C@@H](CC[C@@H]1 [C@H](C)CCC(CC)C(C)C)C2CC¼C3C4
b-Sitosteryl ferulate CCC(CCC(C)[C@H] 5CCC4C3CC¼C2CC(OC(¼O)\C¼C/c1ccc – 590.87 9.397 608.856 55.767
(O)c(OC)c1)CC[C@]2(C) C3CC[C@@]45C)C(C)C
Squalene CC(C)¼CCCC(C)¼CCCC(C)¼CCCC¼C(C)CCC¼C(C)CCC¼C(C)C 111-02-4 410.72 9.622 477.642 000
Squalane CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C 111-01-3 422.81 9.568 514.918 000

ß 2015 The Authors. European Journal of Lipid Science and Technology Published by Wiley-VCH Verlag GmbH & Co. KGaA
Chlorophyll a CCc2c(C)c3cc6[n-]c(cc1nc ([C@@H](CCC(¼O)OC/C¼C(\C)CCC 479-61-8 893.51 9.149 864.172 123.665
[C@H](C)CCC[C@H](C)CCCC(C)C) [C@@H]1C)c4[C@@H](C(¼O)OC)C
(¼O)c5c(C)c(cc2n3)[n-]c45)c(C) c6C¼C.[Mgþ2]
Chlorophyll b CCc2c(C¼O)c3cc6[n-]c (cc1nc([C@@H](CCC(¼O)OC/C¼C(\C)CCC 519-62-0 907.47 8.915 866.594 140.736
[C@H](C)CCC[C@H](C) CCCC(C)C)[C@@H]1C)c4[C@@H](C(¼O)OC)C

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 Table 4. (Continued)

Topological
M.Wt LogP Volume polar surface

Compound Molinspirationsmiles (miSmiles)a CAS# (Da) (miLogP) (cubic A) area (TPSA)

(¼O)c5c(C)c(cc2n3)[n-] c45)c(C)c6C¼C.[Mgþ2]
a-Tocopherol CC(C)CCC[C@@H](C)CCC [C@@H](C)CCC[C@]2(C) 59-02-9 430.71 9.043 474.499 29.462
CCc1c(C)c(O)c(C)c(C)c1O2
b-Tocopherol CC(C)CCC[C@@H](C)CCC [C@@H](C)CCC[C@]2 54-28-4 416.68 8.982 457.938 29.462
(C)CCc1cc(O)c(C)c(C)c1O2
d-Tocopherol CC(C)CCC[C@@H](C)CCC [C@@H](C)CCC[C@]2 119-13-1 402.65 8.602 441.377 29.462
(C)CCc1cc(O)cc(C)c1O2
Linoleic acid-9-hydroperoxide CCCCC/C¼C\C¼C/C(CCCCCCCC(O)¼O)OO – 313.45 6.004 329.681 66.761
Linoleic acid-13-hydroperoxide CCCCCC(OO)C¼C/C¼C\CCCCCCCC(O)¼O – 313.45 6.004 329.681 66.761
Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

BHT Cc1cc(C(C)(C)C)c(O)c(C(C)(C)C)c1 128-37-0 220.35 5.435 240.996 20.228

BHA COc1ccc(O)c(C(C)(C)C)c1.COc1ccc(O)cc1C(C)(C)C 25013-16-5 180.24 3.617 183.794 29.462
TBHQ CC(C)(C)c1cc(O)ccc1O 1948-33-0 166.24 3.081 166.266 40.456
Trolox Cc2c(C)c1OC(C)(C(O)¼O)CCc1c(C)c2O 53188-07-1 250.29 3.071 233.557 66.761
Curcumin COc2cc(/C¼C/C(¼O)CC(¼O)\C¼C\c1ccc(O)c(OC)c1)ccc2O 458-37-7 366.38 2.303 332.182 93.066
Ferulic acid COc1cc(/C¼C/C(O)¼O)ccc1O 1135-24-6 194.18 1.249 172.025 66.761
Caffeic acid OC(¼O)\C¼C\c1ccc(O)c(O)c1 331-39-5 180.16 0.941 154.497 77.755
Vanillin COc1cc(C¼O)ccc1O 121-33-5 152.15 1.067 136.591 46.533
Ascorbic acid OC[C@H](O)C1OC(¼O)C(O)¼C1O 50-81-7 176.12 1.402 139.707 107.217
EDTA C(CN(CC(¼O)O)CC(¼O)O)N(CC(¼O)O)CC(¼O)O 60-00-4 292.24 5.193 247.019 155.672
Phytic acid [C@@H]1([C@@H]([C@@H] ([C@@H]([C@H]([C@@H]1OP 83-86-3 660.04 5.547 422.961 400.566
(¼O)(O)O)OP(¼O)(O)O)OP(¼O)(O)O)OP (¼O)(O)O)OP
(¼O)(O)O)OP(¼O)(O)O
Citric acid C(C(¼O)O)C(CC(¼O)O)(C(¼O)O)O 77-92-9 192.12 1.983 151.764 132.125

a
Simplified molecular-input line-entry specification (SMILES). Data on log P values, volume, and topological polar surface area are from www.molinspiration.com (accessed 1
November 2012).

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Supramolecular chemistry of lipid oxidation

www.ejlst.com
1129

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1130 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

ogous series of chlorogenic acid esters increased with alkyl

chain length increased (lipophilicity increased), but up to
C12 while further chain extension, starting from C16, caused
a drastic drop of antioxidant capacity [17]. In another study
in o/w emulsions, the effect of hydroxytyrosol fatty acid esters
on antioxidant capacity (measured by surfactant effective-
ness) increased until hydroxytyrosol decanoate (C12) with
further increase of chain length caused a drop in surfactant
effectiveness [62]. The cut-off effects are related to the
molecular size of antioxidants and their mobility with bulkier
structures compounds (i.e., compounds with long alkyl
chain) having reduced mobility due to steric hindrance and
lower diffusability in oxidation sites [100, 101].
As mentioned above, the general rule described in the polar
paradox is that “polar (hydrophilic) antioxidant are more
effective in bulk oil with a low surface/volume ratio whereas
nonpolar (lipophilic) antioxidants are more effective in oil in
water emulsions.” However, lately it was discovered that there
is a certain non linearity in this effect. Using EGCG and its
esters as examples, Shahidi and Zhong [53] explained that as
lipophilicity increases, the antioxidants are more active at lower
levels in bulk oils because their effects on their solubility in
lipids are stronger than those of interfacial phenomenon. So, it
is possible that the polar paradox is applicable only when
antioxidant is added at high concentration (reaching a critical
Figure 5. Structure representation of a reversed micelle stabilized
by surfactants and co-surfactants. Symbols: A ¼ monolayer of
concentration) making its effects on interfacial phenomena to
surfactants, B ¼ depletion layer, and C ¼ core (water). dominate over solubility effects. These phenomena were also
observed for Trolox/a-tocopherol, ascorbic acid/ascorbyl
palmitate, and gallic acid/propyl gallate [53].
surfactants in micelles because of the increased volume and Thus, the polar paradox is influenced not only by the
mobility of surfactant tails (v) and reduced interfacial surface HLB of the antioxidants but also by their molecular size and
area (ao) [80, 95, 96]. Co-surfactants, whose effects are configuration (Table 4), and indeed concentrations. There-
dependent on their size and chain length [97, 98], keep water fore, polar paradox does not always prevail and can explain
in the micelles and reduce the size of these micelles [93]. antioxidant effectiveness in the system from only a general
System conditions and molecular geometry of molecular perspective. Moreover, previous experimental inferences
aggregates in o/w and w/o emulsions, when surfactants and/ were the outcome of “pure chemical thinking” in the absence
or co-surfactants are employed, are illustrated in (Fig. 5). So of the understanding of supramolecular chemistry.
far, the existence of molecules with co-surfactant properties
and their role in lipid oxidation have not been discussed but it
might explain the synergistic effect of compounds such as 7 Seeking further explanations in
citric acid and amino acids [99]. supramolecular chemistry
The antioxidant mechanisms of some secondary anti-
oxidants and minor components are not well known. It could It is well understood that besides the degree of fatty acid
be that they act as synergists by affecting the physical unsaturation, several other factors influence antioxidant
structures of the microemulsions, which are the site of effectiveness in bulk oil, for example, diffusion of oxygen,
oxidation. The historical developments in understanding temperature and light [6, 18], interaction with prooxidants,
the physical effects of components on lipid oxidation are amphiphilic minor components (e.g., phospholipids, MAG,
presented in (Table 1). FFA [7], the presence of compounds which act as surfactants
(their HLB, nature, and ratio) [56], lipid composition-
structure-position [102, 103], other food components [104],
6 Hydrophilic–lipophilic balance and the physical structures [20], pH [34, 105], interfacial character-
cut-off effect istics [22, 57, 67], stability of EPA and DHA [3], and
position of fatty acids on glycerol [106]. A global conceptual
In a study in o/w emulsified systems, the antioxidant capacity framework has, however, never been reached due to frequent
(tested by conjugated autoxidizable triene assay) of homol- inconsistencies and paradoxes. It is clear from the above

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Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137 Supramolecular chemistry of lipid oxidation 1131

discussions that these effects should be revisited and may be but fine tuning of the concept is still needed. This gives
explained by the new paradigm of supramolecular inter- possibilities for molecular modifications, for example, by
actions and effects.This new paradigm needs to recognize esterifying free –OH group(s) MAG or DAG with other
and consider molecular shapes and the relative positions of molecules such as citric acid.
hydrophilic and lipophilic regions. The position of double bonds of unsaturated fatty acids
In bulk lipids, several components are often surface active also has an effect in oxidation of colloidal dispersions [112]
and form, together with water, many kinds of association with more stability when the double bond is closer to the
colloids that affect oxidation by modulating prooxidative or methyl end of the molecule [22]. Trans fatty acids, with a
antioxidative effects [33]. These effects may be very sensitive straight configuration causing their molecules to be tightly
to structural details. For example, 1,2-dioleoyl-sn-glycero-3- packed with higher melting points, are more stable than cis
phosphocholine (DOPC) and 1,2-dibutyryl-sn-glycero-3- fatty acids [113]. The pH also has an impact on oxidative
phosphocholine (DC4PC) increased and reduced the stability of lipid. A study of oil/water emulsions showed that
oxidation rate of stripped soybean oil with Trolox added when the lipid droplets were coated with proteins, at pH
due to influences on the size and shape of micelles [20, 107]. lower than the isoelectric points of amino acids, droplets had
DOPC formed reversed micelles and caused a prooxidative cationic surface which repel transition metals thus lessening
effect in stripped soybean oil while DC4PC formed the oxidation [34, 105]. High pH causes precipitation of
cylindrical structures (not reversed micelles) and had no iron onto emulsion surface and increases the lipid oxidation
effect on oxidation in the same oil [7, 8, 20]. Therefore, rates [23, 57].
surfactants also affect antioxidant effectiveness. The reasons The discussion of lipid oxidation in fish oils requires
could be due to phospholipids aliphatic chain which special considerations because of the high degree of
influences the size and shape of micelles [107] and DOPC unsaturation as well as the highly bended structure of their
reversed micelle which may had negatively charged very long-chain omega-3 polyunsaturated fatty acids,
surface thus attracted metals [20]. Similarly, phosphatidyl- namely eicosapentaenoic acid (EPA) and docosahexaenoic
choline (1,2-dibutyl-sn-glycero-3-phosphocholine) does acid (DHA) [114]. The autoxidation rate of these PUFAs
not form reversed micelles and is not prooxidative while depends not only on their degree of unsaturation but also
the reversed micelles formed by DOPC lead to the on the position of the fatty acids in the triacylglycerols [115].
concentration of endogenous iron and lipid hydroperoxides It should be mentioned here that sea mammalian oils,
at the water-lipid interface and enhancement of the such as seal and whale oils, are more stable than fish
decomposition of the hydroperoxides [35]. In addition, oils because of different location of the fatty acids in
charge-related interactions with metals [20] where the their triacylglycerol molecules, that is, at sn-1 and sn-3
zwitterionic effects of the phospholipid surfactants may have positions [106, 116, 117]. In these mamalian oils, EPA
significant relevance [80]. and DHA are distributed mainly in the sn-1 and sn-3
Interfacial characteristics due to ionic surfactants can have positions while they are mainly in the sn-2 position in
variable impacts on oxidation. Anionic surfactants (e.g., fish oils [176]. In another study, it was shown that the
sodium dodecylsulfate [SDS] and sodium dioctyl sulfosucci- stability of triacylglycerols is compromised when EPA was
nate or [AOT]) form large micelles [68] and create negatively highly concentrated within rather than between the
charged interfaces causing metals to bind to reversed micelles triacylglycerol molecules [118]. However, in the case of
and increase the oxidation rates in o/w [14, 33] but showed soybean oil, it had achieved a higher oxidative stability
no effects on oxidation in lipophilic substrates (e.g., limo- when its unsaturated fatty acids are at sn-2 position [106].
nene) [86]. Cationic surfactants, such as cetyltrimethylam- This shows that the type of the unsaturated fatty acids
monium bromide (CTAB) and quaternary ammonium and substrate/lipid system also influence the oxidation. The
alkyl salts, form many very small micelles [20, 70, 86] and bent structure of fish/mammalian fatty acids affects
promote oxidation in bulk oil and limonene while reducing it the interfacial space and the molecular distribution of lipids
in o/w [70, 78]. The addition of a cosurfactant that increases in a way different from that in other oils and fats. In
the micelle sizes will mitigate these effects and improve dispersed systems, such as bulk lipids adopting a nano-
stability [110]. In bulk oils, cationic surfactants affect emulsion structure, the size of the micelles and dispersion
oxidation at the initiation phase but not at the propagation phase is critical with more stability for systems containing
and termination phases [70]. Nonionic surfactants (e.g., smaller particles [119]. Certain kinds of fish lipids (such
polyoxylene lauryl ether [Brij 35], sorbitan oleate [Span 80], as fish roe lipids) with high amounts of EPA and DHA
sugar surfactants such as alkyl glucosides and sucrose fatty acid were more stable against oxidation than other kinds
esters, mono- and diacylglycerol, medium chain triacylgly- of fish lipids because their EPA and DHA present
cerides, fatty acid esters such as isopropyl myristate) may together with a-tocopherol and phospholipids. Similar
increase the oxidative stability of emulsions [23, 64, 80] but observation was also found in perilla oil. Thus phospho-
these findings are not consistent and are in contradiction with lipids act synergistically with a-tocopherol in protecting the
results of other studies [23, 111]. The trend seems to be clear oil [3, 120–122].

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1132 E. S. Budilarto and A. Kamal-Eldin Eur. J. Lipid Sci. Technol. 2015, 117, 1095–1137

Indeed, there is a correlation between the chemical properties

relevant to primary antioxidants, mainly BDE, and important
physical properties, such as HLB, as both are influenced by
the substitution in the antioxidant phenolic ring(s). This
indirect correlation might have concealed the physical factors
governing antioxidant activity. It is now time to reconsider
the antioxidant structure-activity relationships as a first step
to design more effective antioxidants for future applications.

This work was supported by the United Arab Emirates University

PhD study grant to the first author.

The authors declare no conflicts of interest.

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