Chemistry and Physics of Lipids 165 (2012) 662–681

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Chemistry and Physics of Lipids

journal homepage: www.elsevier.com/locate/chemphyslip

Review

Chemical alterations taken place during deep-fat frying based on certain reaction
products: A review
Qing Zhang, Ahmed S.M. Saleh, Jing Chen, Qun Shen ∗
National Engineering and Technology Research Center for Fruits and Vegetables, College of Food Science and Nutritional Engineering,
China Agricultural University, Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: Deep-fat frying at 180 ◦ C or above is one of the most common food processing methods used for preparing
Received 17 April 2012 of human kind foods worldwide. However, a serial of complex reactions such as oxidation, hydrolysis,
Received in revised form 9 June 2012 isomerization, and polymerization take place during the deep-fat frying course and influence quality
Accepted 5 July 2012
attributes of the final product such as flavor, texture, shelf life and nutrient composition. The influence of
Available online 16 July 2012
these reactions results from a number of their products including volatile compounds, hydrolysis prod-
ucts, oxidized triacylglycerol monomers, cyclic compounds, trans configuration compounds, polymers,
Keywords:
sterol derivatives, nitrogen- and sulphur-containing heterocyclic compounds, acrylamide, etc. which are
Deep-fat frying
Triacylglycerol
present in both frying oil and the fried food. In addition, these reactions are interacted and influenced
Chemical alteration by various impact factors such as frying oil type, frying conditions (time, temperature, fryer, etc.) and
Reaction product fried material type. Based on the published literatures, three main organic chemical reaction mecha-
Formation mechanism nisms namely hemolytic, heterolytic and concerted reaction were identified and supposed to elucidate
the complex chemical alterations during deep-fat frying. However, well understanding the mechanisms
of these reactions and their products under different conditions helps to control the deep-fat frying pro-
cessing; therefore, producing healthy fried foods. By means of comprehensively consulting the papers
which previously studied on the chemical changes occurred during deep-fat frying process, the major
reaction products and corresponding chemical alterations were reviewed in this work.
© 2012 Elsevier Ireland Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
2. Major reaction products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
2.1. TAG degradation products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
2.1.1. Oxidized volatile products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
2.1.2. Hydrolysis products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
2.2. Oxidized TAG monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
2.3. Nonpolar TAG derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
2.3.1. Cyclic fatty acid monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
2.3.2. Trans isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669

Abbreviations: AA, acrylamide; Ag-HPLC, silver ion-high performance liquid chromatography; APCI, atmospheric pressure chemical ionization; ATR, attenuated total
reflection; BHA, butylated hydroxyanisole; BHT, butylated hydroxytoluene; C=C, carbon-carbon double bond; CFAMs, cyclic fatty acid monomers; CLA, conjugated linoleic
acid; DAD, diode array detection; DAG, diacylglycerol; DPPH, 1,1-diphenyl-2-picrylhydrazyl; ECD, electron capture detector; EPR, electron spin resonance; ESI, electrospray
ionization; GC×GC, comprehensive two-dimensional gas chromatography; GC-MI-FTIR, gas chromatography-matrix isolation-Fourier transform infrared spectroscopy;
GLC, gas-liquid chromatography; GPC, gel permeation chromatography; HAAs, heterocyclic aromatic amines; HPLC, high performance liquid chromatography; HPSEC,
high performance size exclusive chromatography; HPTLC-UV-FLD, high performance thin layer chromatography-ultraviolet-fluorescence detection; ITMS, ion trap mass
spectrometry; MAG, monoacylglycerol; NIR-PLS, near infrared spectroscopy-partial least squares regression; NMR, nuclear magnetic resonance; RI, refractive index; RPLC-
TSP-MS, reverse-phase high-performance liquid chromatography–thermospray-mass spectrometry; SP(M)E, solid-phase (micro-) extraction; TAGs, triacylglycerols; TD-GC-
MS, thermal desorption-gas chromatography-mass spectrometry; TOFMS, time-of-flight mass spectrometry.
∗ Corresponding author. Tel.: +86 10 62737524; fax: +86 10 62737524.
E-mail address: shenqun@cau.edu.cn (Q. Shen).

0009-3084/$ – see front matter © 2012 Elsevier Ireland Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemphyslip.2012.07.002
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681 663

2.4. TAG polymerized products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670

2.5. Sterol derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
2.6. Antioxidant alterations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
2.7. Products derived from interactions between frying oil and food material constituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
2.7.1. Nitrogen- and sulphur-containing heterocyclic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
2.7.2. Acrylamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676

1. Introduction The chemical reactions occurred during deep-fat frying roughly

involved in hydrolysis, oxidation, isomerization and polymeriza-
tion (Choe and Min, 2007; Velasco et al., 2009) resulted in the
It is well known that deep-fat frying is a prevalent and old food
cooking method which can go back to 1600 BC. Although 180 ◦ C generation of free fatty acids, small molecular alcohol, aldehyde,
ketone, acid, lactone and hydrocarbon (Pokorný, 1989), diglyceride
is usually recommended for frying foods, it is always higher than
and monoglyceride, cyclic and epoxy compounds (Rojo and Perkins,
180 ◦ C in the practical deep-fat frying (Firestone, 1993). Fast food
1987), trans isomers (Martin et al., 1998a,b,c), TAG monomer, dim-
processing, palatable taste of fried food and considerable economic
mer, oligomer (Martin et al., 1998a,b,c). Besides, these reactions
benefit make the deep-fat frying become one of the most pop-
interact and impact each other during the treatment at high-
ular food cooking methods used in household kitchen, fast-food
temperature. As a result, when the deep-fat frying excessively
restaurant and instant noodles industry. Furthermore, the sale of
proceeded, the phenomena of off-flavor, foaming, color deep-
pre-cooked and ready-to-eat products which also refer to the deep-
ening and the increase of viscosity would appear in the frying
frying process has dramatically increased in the western world and
oil.
is rapidly expanding throughout the developing countries. In other
Polar compounds and TAG oligomers which produced during
words, fried food has become an industry chain in catering industry.
The fried food is endowed with attractive flavor, golden pellicle and deep-fat frying course with content range of 20–27% and 10–16%
respectively have been proposed to determinate the rejection of
crisp texture or mouth feel when it is fired under the appropriate
conditions (Rossell, 2001; Warner, 2008). used frying oil (Bastida and Sánchez-Muniz, 2002; Paul and Mittal,
Under the established conditions of fried material’s natural 1997). However, the measurement of polar compounds doesn’t
properties and corresponding sample handling, frying can involve represent the whole content of reaction products formed during
all of the components to participate in a series of physical and chem- the deep-fat frying and the reaction products are not detailed
ical alterations. These changes not only include the decomposition in these indices. Some products were considered as potential
reactions of the constituents such as the nutrients of raw material detrimental substances to the human body from the nutritional
and triacylglycerols (TAGs) of frying oil, but also include the inter- aspect (Lamboni and Perkins, 1996; Saguy and Dana, 2003; Totani
actions among these constituents (Chu and Luo, 1994; Dobarganes et al., 2008). Therefore, it is quite necessary and useful to know
et al., 2000a,b). Moreover, deep-fat frying is a complicated physic- more systematic precise information about the nature and quan-
ochemical processes which is simultaneously influenced by many tity of the new compounds formed during the deep-fat frying
factors such as the nature of fried material and frying oil, time, tem- course.
perature, intermittent or continuous heating, fresh oil complement, Although the chemical alteration pathways occurred during
fryer model and use of Filters (Chatzilazarou et al., 2006; Kalogianni deep-fat frying are complex and not well understood, some reac-
et al., 2010; Rojo and Perkins, 1987). Therefore, many products are tion pathways and the resulted reaction products have the same
formed due to these complex substrates and chemical conditions. characteristics and could be analyzed and classified as one class.
Furthermore, frying with food and frying without food have a sig- Therefore, the major reaction products which have been previ-
nificant different chemical in reaction pathways (Barrera-Arellano ously identified and reported to be elucidated by category and their
et al., 1997; Houhoula et al., 2002). corresponding chemical reaction pathways are presented in this
On the other hand, deep-fat frying is a process of drying and work.
cooking in hot oil at high-temperature with simultaneous heat and
mass transfer (Ahromrit and Nema, 2010; Dincer, 1996; Ni and 2. Major reaction products
Datta, 1999). Oil and fat is an excellent heat-transfer medium, thus
the material is quickly heated and cooked when it is immersed Analysis of substrate-known reaction products is not an easy
into the oil (Alvis et al., 2009). Mass transfer involves the loss of work to analysts due to the quantity and characteristic of the
moisture, oil and fat, carbohydrate, protein and vitamins and other products, not to mention the reactions involved in the deep-fat fry-
components from fried material and the oil uptake of material ing process. However, with a combination of developed analytical
from frying oil (Krokida et al., 2000; Sosa-Morales et al., 2006). instrument and chemometrics, the determination of the reaction
Therefore, both fried material and frying oil influence on each products with similar configuration or trace quantity has become
other and collectively promote the occurrence of complex chemical possible and practical. Given that TAGs are the major kind of con-
reactions. stituents existing in frying oil, the probable emerging products and
Based on published data, there are few systemic and compre- their possible formation routes which have been investigated were
hensive studies to investigate the specific pathways of chemical reviewed as following details according to the alterations of TAGs.
reactions taken place during the deep-fat frying course. Among Moreover, being viewed as the major impact factor to the chemical
these reactions and products, some are expected to occur alterations, food material was also considered in term of the inter-
such as the desirable color and attractive flavor resulted from actions between food material components and TAGs. The major
maillard reaction and some are undesired outcomes due to los- reaction products and their characteristics are shown in Table 1
ing of nutrients, producing of aldehyde, acrylamide and trans for direct and systematic understanding of the whole deep-fat fry-
configuration-contained substances which are prejudicial to the ing course. The specific product types and their possible formation
quality of fried food and health of people (Boskou, 2003). mechanisms are elucidated as follows.
664
Table 1
The major reaction products formed during deep-fat frying, their characteristics and proposed formation mechanism and identifying methods according to the previously
reported studies.
Main products
Oxidized decomposition
compounds
Hydrolysis products
Oxidized TAG monomers
Cyclic fatty acid monomers
Trans isomers
TAG polymerized products
Sterol derivatives
Antioxidant alterations
Heterocyclic compounds
Acrylamide
Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
Characteristics
Degradation product; volatility; alcohol,
aldehyde, ketone, acid, lactone and
hydrocarbon etc.; short-chain compounds
(saturate or unsaturate); depending on the
number and position of C C, extra oxygen
etc.; molecule weight lower than that of
parent TAGs
Degradation product; polar; diacylglycerol
(DAG), monoacylglycerol (MAG), glycerol
and free fatty acids; depending on the
presence of water; molecule weight lower
than that of parent TAGs
Oxidized TAGs with keto, epoxy, hydroxyl,
aldehyde and epoxy groups (saturate or
unsaturate); extra oxygen-containing
groups may simultaneously exist in one
molecule; polar; core aldehydes; cis and
trans configuration; depending on the
number and position of C C, extra oxygen
etc.; molecule weight approximately
equals to that of parent TAGs
Nonpolar; low concentration and latent
biological hazard; five- or six-membered
ring structures (saturate or unsaturate);
monocyclic and bicyclic rings; cis and trans
configurations; depending on the number
and position of C C; molecule weight
lower than that of parent TAGs
Nonpolar; trans fatty acids, conjugated
linoleic acids; adverse effects on human
health; one more trans configurations may
simultaneously exist; depending on the
number and position of C C; molecule
weight lower than that of parent TAGs
Dimmers, trimers and oligomers, etc.; with
the linkages of –C–C–, –C–O–C– and
–C–O–O–C– among the TAG molecules;
Nonpolar and polar; acyclic and cyclic
polymers; depending on the number and
position of C C, extra oxygen etc.; can be
polymerized by both abovementioned
products and parent TAGs; molecule
weight higher than that of parent TAGs
Formed mainly result in special molecule
structure; Hydroxy, keto and epoxy
group-contained compounds; sterol
dimmers, trimers and oligomers also
present; homologous
Rooted in natural and synthetic
antioxidants or called free radical
scavengers; accompany with many
changes (i.e. the decrease of some
undesirable products) during the deep-fat
frying course; possess the quinine
structure
Nitrogen- and sulphur-containing
heterocyclic compounds; volatility; latent
mutagenicity and carcinogenicity; derived
from interactions between frying oil and
food material constituents or their reaction
products; formed from the interaction
between lipid oxidation and maillard
reaction
Possesses neurotoxicity, genetic toxicity
and carcinogenicity; depending on the
oxidability of frying oil and the type of fried
food; formed from the interaction between
lipid oxidation and maillard reaction;
acrolein has been proposed as its precursor
Proposed formation mechanism
Oxidation
Homolytic reaction (Free radical
reaction)
Hydrolysis
Heterolytic reaction (nucleophilic
reaction)
Oxidation
Epoxidation
Free radical reaction
Cyclization
Intramolecular rearrangement
catalyzed by free radicals
Concerted reaction
([1,j]-prototropic migrations)
Free radical reaction
(Addition-elimination mechanism)
Heat-induced isomerization
Concerted reaction
([1,j]-sigmatropic rearrangements)
Oxidized polymerization and
thermal polymerization
Free radical reaction
Concerted reaction (Diels-Alder
reaction)
Oxidation (Free radical reaction)
Polymerization
Free radical reaction
Esterification
Dimerization
Free radical reaction
Maillard reaction
Electrocyclic and aromatization
reaction
Nucleophilic reaction
Oxidation (Free radical reaction)
Maillard reaction (Strecker
degradation)
Identifying methods
TD-GC-MS (Fullana et al., 2004; Overton
and Manura, 1995), SPME-GC-MS
(Mildner-Szkudlarz and Jeleń, 2008), 1 H
NMR (Guillén and Uriarte, 2009), EPR
(Roman et al., 2012)
GC (Lee et al., 2002), GC and HPSEC
(Romero et al., 1998; Houhoula et al., 2003)
GLC (Velasco et al., 2002), HPLC (Schulte,
2002), HPSEC (Caldwell et al., 2011),
GC-MS (Kamal-Eldin et al., 1997),
RPLC–TSP-MS (Yamane, 2002);
RPLC-ESI-MS (Giuffrida et al., 2004a,b), 1 H
NMR (Aerts and Jacobs, 2004; Guillén and
Ruiz, 2008)
Ag-HPLC and GC-MS (Dobson et al., 1995),
GC-EI-MS (Berdeaux et al., 2007),
GC-MI-FTIR and GC-EI-MS (Mossoba et al.,
1996a,b)
GC (Aro et al., 1998), GC-MS (Kandhro
et al., 2008) and Ag-HPLC (Yurawecz et al.,
1999; Eulitz et al., 1999), ATR-FTIR (Cho
et al., 2011; Mossoba et al., 2007)
HPSEC (Dobarganes et al., 2000a,b;
Caponio et al., 2007), on-line LC-EI-MS
(Byrdwell and Neff, 2004), ATR-FTIR
(Kuligowski et al., 2010a), On-line
GPC-FTIR (Kuligowski et al., 2010b),
NIR-PLS (Kuligowski et al., 2012)
GC-MS (Soupas et al., 2004); LC-APCI-MS
(Kemmo et al., 2008); SEC-APCI-MS
(Rudzińska et al., 2010);
HPLC-RI/UV/APCI-MS (Saldanha et al.,
2006); SPE-HPSEC (Lampi et al., 2009)
HPLC (Rennick and Warner, 2006);
HPLC-NMR (Verleyen et al., 2001a,b)
GC-MS (Horiuchi et al., 1998; Van Loon
et al., 2005), Alternative GC–MS
approaches: GC–ITMS, GC–TOFMS,
GC × GC–TOFMS (Lojzova et al., 2009);
HPTLC-UV-FLD (Jautz et al., 2008)
GC-ECD (Zhang et al., 2006), GC-MS/MS
(Hoenicke et al., 2004), HPLC-UV (Wang
et al., 2008), LC–DAD (Gökmen et al.,
2005), LC-MS/MS (Carrieri et al., 2010;
Pedreschi et al., 2007; Viklund et al., 2007),
NIR-PLS (Pedreschi et al., 2010)
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
2.1. TAG degradation products
Oil and fat is a mixture of TAGs which are composed of one
glycerol and three groups of saturated or unsaturated fatty acids
with different carbon numbers. Not only the natures of fatty acid,
but also the various combination positions of fatty acids to glyc-
erol molecule would impact the reaction activity of TAG. Therefore,
the TAG degradation products mainly result from the breakages
occurred in the carbon-carbon double bond (C C) of aliphatic
chains and ester bond. These compounds have a smaller molecular
weight compared with that of the parent TAG and almost possess of
volatility such as the decomposition compounds of lipid oxidation
and TAG hydrolysis.
2.1.1. Oxidized volatile products
It is well known that autoxidation is an important degradation
reaction which is attributed to the rancidity of oil and fat. It is
as well the major reaction occurred during frying along with the
increase of temperature. The mechanism of thermal oxidation is
principally similar with the autoxidation mechanism, the different
only in the reaction speed (Houhoula et al., 2003). During the fry-
ing treatment, except the absorbed parts by both fried material and
frying oil, these compounds volatilize out of the frying system due
to the high-temperature and their volatility. On the other hand, the
oxygen content decreases with the proceeding of high temperature
treatment. In addition, when the state of oxygen-free occurs, many
other thermal reactions would take place. However, the reaction
speed of oxidation increases during the frying treatment under the
condition of high temperature.
A classic peroxidation kinetic model of unsaturated fatty acids
which is regarded as three steps (i.e. initiation, propagation and
termination) has been generally accepted to elucidate free radical
reaction pathways of lipid oxidation. The initiation step is catalyzed
by many factors such as light, heat and metal ions. Propagation
step involves the production of peroxyl radicals (ROO• ) which then
abstract hydrogen from other organic substrates to form hydroper-
oxides. Along with the decrease of lipid radicals (R• ) during the
ROO• ·formation course, an increase of R• also occurs in the pro-
cedure of formation of hydroperoxides. Therefore, the role of R
during the propagation step is both reaction substrate and prod-
uct. In addition, the formed hydroperoxides are very unstable and
easy to give rise to ␤-scission homolytic cleavage of the O O, C C
and C O around peroxide group to decompose into short-chain
compounds (Porter et al., 1995). The decomposition of hydroper-
oxides promotes the proceeding of propagation step and this step
is a circulatory continuous reaction from reversibility point of view.
The final step includes the combination of free radicals which pre-
vent the proceeding of propagation step (Frankel, 1980; Schaich,
2005). As shown in Fig. 1-1, these compounds include a homolo-
gous series of small molecular alcohols, aldehydes, ketones, acids,
lactones, etc. One result of thermal oxidation is the occurrence of
volatile compounds which is the main cause of the favorable odor
and off-flavor of fried material and frying oil.
In a recent study, another alternate kinetic model has been pro-
posed to explain the formation of aldehydes directly from peroxyl
radicals through an independent pathway during thermal treat-
ment of peanut oil at 180 ◦ C (Silvagni et al., 2010). As shown
by the dashed arrows reactions in Fig. 1-1, two peroxyl radicals
combined to form two alkoxyl radicals and a molecular oxygen
by a bimolecular termination reaction. Actually, an intermediate
tetraoxide which is unstable and easily decomposes to the alkoxyl
radical and molecular oxygen at high temperature exist in this reac-
tion. In addition, this proposed mechanism was verified by the
results of reaction kinetics analysis and reaction products identifi-
cation by means of NMR and EPR and had the same accordance with
the classical aldehydes formation from hydroperoxides. Under the
665
condition of high temperature, lipid peroxidation becomes more
complex compared to the condition of ambient temperature, thus
the exhaustive elucidation of lipid peroxidation should be paid
more comprehensively consideration in further studies.
Studies on volatile compounds have been greatly reported
in the last century and mainly the odor constituents formed
during deep-fat frying with food material and without food mate-
rial were investigated extensively (Brewer et al., 1999; Macku
and Shibamoto, 1991a; Wu and Chen, 1992). Volatile products
formed from corn oil (Kawada et al., 1967), hydrogenated cotton-
seed oil (Yasuda et al., 1968), trilinolein (Thompson et al., 1978),
and triolein (May et al., 1983) during simulated deep-fat fry-
ing were initially studied under well controlled frying conditions
and a total of 220 volatile compounds such as acids, hydrocar-
bons, alcohols, aldehydes, ketones, esters, lactones and aromatic
compounds were detected (Chang et al., 1978). In addition, 140
volatile constituents were detected and identified from used fry-
ing oils which were collected from large-scale commercial meat
and poultry processing plant and the typical volatile constituents
were 1-pentanol, hexanal, furfuryl alcohol, (E)-2-heptenal, 5-
methylfurfural, 1-octen-3-ol, octanal, 2-pentylfuran, (E)-2-octenal,
nonanal, (E)-2-nonenal, hexadecanoic acid and pyrazines (Takeoka
et al., 1996). According to these studies, though there are many
degradation products, they could be classified into a number of
categories based on similarity of structure or property.
Volatile short-chain aldehyde compounds such as acrolein
(2-propenal) have been detected in several cooking oils under
different conditions of frying oil type and frying temperature
and time (Katragadda et al., 2010; Osório and de Lourdes,
2011). Unfortunately, these volatile aldehyde compounds are
not just small part of the degradation products but most of
them have been found to have certain potential threat to health
of consumer (Kamal-Eldin and Appelqvist, 1996; Seppanen and
Csallany, 2002), especially the genotoxic and cytotoxic properties
of ␣,␤-unsaturated aldehydes (Guillén and Goicoechea, 2008). The
genotoxic and cytotoxic olefine aldehyde-contained compounds
such as 4-hydroxy-2-trans-hexenal, 4-hydroxy-2-trans-octenal,
4-hydroxy-2-trans-nonenal and 4-hydroxy-2-trans-decenal are
produced and have been reported to be absorbed by the fried
material (Seppanen and Csallany, 2004; Seppanen and Csallany,
2006). The saturated and monounsaturated FAMEs such as methyl
stearate and methyl oleate model systems heated at 185 ◦ C for 0
to 6 h did not generate any of the four ␣,␤-unsaturated 4-hydroxy-
aldehydes, but 4-hydroxy-2-trans-hexenal existed in the products
of both methyl linoleate and methyl linolenate model systems due
to heat treatment (Han and Csallany, 2009; LaFond et al., 2011).
4-oxo-trans-2-decenal, 4-oxo-trans-2-undecenal, 4-oxo-trans-2-
nonenal, 4-hydroxy- trans-2-nonenal, 4-hydroxy-trans-2-hexenal,
and trans-4,5-epoxy-trans-2-decenal were detected in extra vir-
gin olive, sunflower and virgin linseed oils which were subjected
to 195 ◦ C for prolonged periods of time in a discontinuous indus-
trial fryer (Guillén and Uriarte, 2012). In combination with the
instability of hydroperoxides, an important fragmentation of the
peroxide bond to produce two carbonyl fragments, which named
as Hock-cleavage, could be used to explain the formation mecha-
nism of these oxidized aldehyde compounds (Schneider et al., 2005;
Schneider et al., 2001).
The remarkable products of short-chain compounds formed
during deep-fat frying or just oil heating have also been inves-
tigated and identified. Short-chain fatty acids decomposed from
the carbon-carbon bond scission of alkoxy radical were detected in
frying oil without food materials and used to well indicate the all
alterations and early quality of used frying oil (Brühl and Matthäus,
2008; Berdeaux et al., 1999a; Márquez-Ruiz and Dobarganes, 1996).
Fig. 1-2 shows the formation pathways of typical short-chain
glycerol-bound compounds from the 9-hydroperoxide of oleyl,
666 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681

1 Initiation: R (CH2)6 CH2 CH CH R' + O2 Catalyst R (CH2)6 CH CH CH R' + OOH

R (CH2)6 CH2 CH CH R' Catalyst R (CH2)6 CH CH CH R' + H

Propagation: R (CH2)6 CH CH CH R' + O2 R (CH2)6 CH CH CH R'

OO + R (CH2)6 CH CH CH R'
O2 OO
R (CH2)6 CH CH CH R' + R (CH2)6 CH2 CH CH R'
2R (CH2)6 CH CH CH R'
OO
O
R (CH2)6 CH CH CH R' + R (CH2)6 CH CH CH R'
OOH
R (CH2)6 CH CH CH R' Scission, Rearrangement, etc. Acids, Olefine acids
Alcohols, Enol
OOH
Aldehydes, Olefine aldehydes
Degradation
Ketones, Ketenes
compounds
Lectones
Furans
Etc.

Termination : 2R (CH2)6 CH CH CH R' R (CH2)6 CH CH CH R'

R' CH CH CH (CH2)6 R R (CH ) CH CH CH R'
26

R (CH2)6 CH CH CH R' + R (CH2)6 CH CH CH R' O

OO O
R' CH CH CH (CH2)6 R
OOH HO O
2 R (CH2)6 CH2 CH CH CH R' R (CH2)6 CH2 CH CH CH R'

O O
R: R''-C R'' : Glyceridic backbone R (CH2)6 CH2 R (CH2)6 CH2 C H
R': (CH2)7-CH3 oleic
[H ] [O2]
CH2-CH=CH-(CH2)5-CH3 linoleic O
CH2-CH=CH-CH2-CH=CH-CH2-CH3 linolenic R (CH2)6 CH3 R (CH2)6 CH2 C OH

Fig. 1. The possible mechanisms for formation of degradation compounds by the free radical reaction pathways of thermal oxidation (1) and the formation of typical
short-chain compounds from 9-hydroperoxide of major fatty acyl groups (2).

linoleyl and linolenyl groups (Velasco et al., 2004a,b). The same
alterations would occur at C C in other aliphatic chain, conse-
quently producing glycerides with more than one short carbon
chains. Monoacid TAGs (i.e. triolein and trilinolein) and FAME (i.e.,
methyl oleate and linoleate) were selected as model compounds
to undergo 180 ◦ C for different time periods and six compounds
which included methyl heptanoate, methyl octanoate, methyl 8-
oxo-octanoate, methyl 9-oxononanoate, dimethyl octanodiate and
dimethyl nonanodiate were identified (Berdeaux et al., 2002). In
addition, the ratio between the compounds from 9-hydroperoxide
and those from 8-hydroperoxide provided a good indication of the
degree of unsaturation of the frying oil irrespective of the total
alteration level (Velasco et al., 2005).
2.1.2. Hydrolysis products
Another source of decomposition products is the hydrolysis
of TAG which results in the production of diacylglycerol (DAG),
monoacylglycerol (MAG) and glycerol (Dobarganes et al., 2000a,b).
Generally, TAG hydrolysis is a reversible reaction course which is
promoted by heat or some catalysts and involves three steps. Out
of the feature of reversible reaction, the characteristic of this reac-
tion is that the speed is slow in the first step, fast in the second
step and slow in the third step. The key phase is the water with
weak nucleophilicity to react with the protonated ester with strong
electrophilicity (Gillatt, 2001). However, it is hard to figure out the
breakage of specific ester bond position on the status of nonenzy-
matic hydrolysis. The breakage sequencing of ester bond at Sn-1,
Sn-2 and Sn-3 might be influenced by the position and num-
ber of C C, length of carbon chain, steric hindrance among the
aliphatic chains, moister content, temperature or other unknown
factors.
When water and heat simultaneously exist, the decomposi-
tion of ester linkage easily takes place. MAGs and DAGs initially
increased and reached a plateau when potato chips fried in refined
cottonseed oil by heating from 155 to 195 ◦ C though it was not
significant (p < 0.05) (Houhoula et al., 2003). The water would be
evaporated and the moisture content decrease along with the
increase of temperature, which could slow down the proceeding
of hydrolysis. However, the formed glycerol volatilizes away above
150 ◦ C which is in favor of the conduct of hydrolysis (Naz et al.,
2005). Oil replenishment during deep-fat frying might minimize
the producing of DAGs or MAGs and slow down the hydrolytic
changes (Romero et al., 1998). With the increase of frying time, the
content of the formed fatty acids increased. The important result of
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
hydrolysis is the increase of the content of free fatty acids, which is
broadly used as an index for monitoring the quality of frying oil.
According to above-mentioned degradation compounds and
their possible formation pathways, there are various impact factors.
Frying with food material which refers to the type and moisture
content of the material (Yu et al., 1993; Chyau and Mau, 1999;
Ramírez et al., 2004) and just heating frying oil (Fullana et al.,
2004) have the different composition of degradation products. Fur-
thermore, different frying oil types and their composition (Chyau
and Mau, 2001; Özyurt et al., 2011), frying temperature and time,
aerobic or anaerobic frying significantly influence the chemical
alterations resulting in production of degradation compounds.
Degradation products mainly stem from ␤-scission cleavage of
hydroperoxides and TAG hydrolysis according to previous studies.
The deep-fat frying is indeed a complex physicochemical pro-
cess which involves many substrates and reaction mechanisms
and is affected by various external contributors. The formed com-
pounds with small molecular not only volatilize away, but also are
absorbed in the frying system for participating in or promoting
further sophisticated reactions.
2.2. Oxidized TAG monomers
Structure of fatty acids impacts the chemical reactions hap-
pened in TAGs during deep-fat frying. The number and position of
C C are the most important structural factors. Oxidation occurred
in the place of C C is the important and easy-to-happen reaction
during the deep-fat frying course. Oxidized TAG monomers involve
many classes of variations which are originated from hydroper-
oxides with extra oxygen. These compounds mainly include the
oxidized TAG monomers with keto, epoxy, hydroxyl and aldehyde
groups supporting the modified ester acyl chains linked to the back-
bone of glycerol (Giuffrida et al., 2004a,b; Guillén and Ruiz, 2008;
Kalogeropoulos et al., 2007; Marmesat et al., 2008).
Oxo-fatty acids, monohydroxy-fatty acids and polyhydroxy-
fatty acids were periodically analyzed and identified in the frying
fat of fast-food (mostly tallow), olive oil and safflower oil (Schwartz
et al., 1994). Similar to the formation mechanism of short aliphatic
chain glycerides, the producing of oxidized TAG monomers with
keto and hydroxyl group also involves free radical reaction of 9-
hydroperoxide, which are shown in Fig. 2-1 (Velasco et al., 2004a,b).
From the pathway, it could be observed that thermal-oxidation ini-
tiated the alterations. The hydroperoxide then changed into alkoxyl
radical to absorb another hydrogen atom to form oxidized TAG
monomers with hydroxyl group (route A) and react with other
changed alkoxyl radical to form oxidized TAG monomers with
keto and hydroxyl group on the basis of radical disproportiona-
tion (route B). In other words, the number and position of these
two function groups in the carbon chains were determined by the
number and position of C C in the original fatty acyl chains.
Another common oxidized TAG monomers are epoxy-TAGs
which are produced by epoxidation of C C in the fatty acyl chains.
Olive oil and sunflower oil were heated and different monoepoxy
products were identified. The results indicated that frying oil with
different unsaturated degrees led to produce monoepoxides with
different amounts (Velasco et al., 2004a,b). The formation pathway
of these products and some typical of them which were detected
from fatty acid methyl esters (FAMEs) heated by frying conditions is
shown in Fig. 2-2 (Berdeaux et al., 1999b; Giuffrida et al., 2004a,b;
Marmesat et al., 2008). From the proposed mechanism, a direct
attack on the alkenyl in fatty acyl chains by a hydroperoxyl radical,
resulting in the formation of an epoxy compound and an alkoxyl
radical. In addition, in conjunction with the typical epoxy com-
pounds, the position of epoxy group may present in any of the
original C C position in case of high unsaturated degree. Con-
version of C C into epoxy group is one of the most alterations
667
happened during the deep-fat frying course, which has been con-
firmed by detection of the resulted epoxy-TAGs using different
instrumental approaches (Aerts and Jacobs, 2004). It is worth not-
ing that the occurrence of cis and trans configuration under the
formation of epoxy group, which increases the diversity of reaction
products.
Except for the above-mentioned short-chain aldehyde com-
pounds, the higher carbonyl compounds, called as core aldehydes
(Kamal-Eldin et al., 1997), were also detected in deep-fat frying
oils. Generally, these products originate from the oxidation of an
unsaturated fatty acid of a triglyceride and the subsequent cleavage
of the double bond. Used frying fats samples mixed with 2,4-
dinitrophenylhydrazine to detect the content of core carbonyl has
been investigated and the results showed that the method was
helpful and could be used to well judge the quality of frying oil
(Schulte, 2002).
It is interesting that these oxidized groups were not only inde-
pendently present in the fatty acyl chains, but also simultaneously
exist in the same carbon chain or different carbon chains in the
glycerol backbone. On the other hand, the unsaturated degree of
the fatty acyl groups affect the finally products and their composi-
tion. That’s to say, more than one oxygenated function group may
be present in the same fatty acyl chain and more than one oxi-
dized fatty acyl group may be present in one TAG molecule, such
as the trilinolein and trilinolenin, which have higher unsaturated
degree.
2.3. Nonpolar TAG derivatives
Some non-altered TAGs which showed the nonpolar property
can present after the deep-fat frying treatment, but it can not fully
reflect the whole components of the nonpolar part. Many other
nonpolar compounds could be formed during the high temperature
treatment. Nonpolar TAG derivatives mainly include the reaction
products without extra oxygen formed during the deep-fat frying
course. According to this definition, cyclic compounds and trans
isomers which contain the compounds of carbon chains with cyclic
and trans configuration attached to the glycerol backbone or the
cyclic and trans monomers are the typical nonpolar TAG deriva-
tives. It is worth noting that some extra oxygen-free TAG polymers
and nitrogen-containing compounds such as heterocyclic amines
which also belong to this kind of nonpolar products would be intro-
duced in the later sections.
2.3.1. Cyclic fatty acid monomers
Cyclic fatty acid monomers (CFAMs) are a category of cyclization
products intramolecularly or intermolecularly formed by alter-
ations occurred at C C in the aliphatic chains under condition
of frying or refining at 200 ◦ C or above (Sébédio et al., 1987).
Cyclization can occur in both the fatty acyl chains in TAG and the
decomposed fatty acids, as long as the occurrence of C C. Apart
from previously discussed epoxy-TAGs, CFAM ring with only carbon
atom also present in the deep-fat frying system. In spite of the low
concentration of these cyclic monomers present in the frying prod-
ucts (Romero et al., 2000a), the suspicious latent biological hazard
to the health of consumer is a topic of worth exploring (Flickinger
et al., 1997; Martin et al., 2000; Sébédio and Grandgirard, 1989).
Several vegetable oils have been used to investigate the influ-
ence thereof on the formation amount of CFAMs and the results
indicated that frying oil with high oleic acid had well frying effect
and lower CFAMs yield (Romero et al., 2003, 2006). Fatty acid
positional distribution in glycerol backbone has also been con-
sidered to impact the cyclization rate in model system and come
to the conclusion that the influence of TAG structure was hia-
her than that of TAG composition on the formation tendency
of CFAMs, and the C18 polyunsaturated fatty acid in the Sn-2
668 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681

OOH
1 R (CH 2 )6 CH 2 CH CH CH R'

HO
O
R (CH 2 )6 CH 2 CH CH CH R'
A B O
+ RH + R (CH 2 )6 CH 2 CH CH CH R'
OH R O
R (CH 2 )6 CH 2 CH CH CH R' R (CH 2)6 CH 2 C CH CH R'
+
OH
R (CH 2)6 CH 2 CH CH CH R'

ROO RO O
2 R (CH 2 )7 CH CH CH 2 R' R (CH 2 )7 CH CH CH 2 R'
O

CH 3 O O C CH HC CH3
(CH 2)7 O (CH 2)7 A: cis-9, 10 -epox ystea rate

CH 3 OOC CH HC B: tran s-9, 10 -epox ystearate

(CH 2 )7 CH 3
O (CH 2 )7
CH HC
CH 3 OOC
(CH 2 )7 CH CH C: cis-9, 10 -epox yoleate
O CH 2 (CH 2 )4
CH 3
CH HC
CH 3 OOC
(CH 2 )7 CH CH D: tran s-9, 10 -epox yolea te
CH 2 (CH 2 )4
O CH 3

CH 3OOC CH CH CH HC E: cis-12, 13 -epox yoleate

(CH 2 )7 CH 2 O (CH 2)4
CH 3
CH 3OOC CH CH CH HC F: tran s-12, 13 -epox yolea te
(CH 2 )7 CH 2 (CH 2)4
CH 3
O
R: R''-C R'' : Glyce ridic backbon e
R': (CH 2 )7 -CH 3 oleic
CH2-CH=CH-(CH2) 5-CH 3 linoleic
CH2-CH=CH-CH 2-CH=CH-CH2-CH 3 linolenic

Fig. 2. The possible formation pathways of oxidized TAG monomers with keto and hydroxyl group from 9-hydroperoxide of major fatty acyl chains (1) (Velasco et al., 2004a,b)
and epoxy-TAGs (2) (A-F are the typical epoxy compounds produced by fatty acid methyl esters.).

position of TAG made the oil easily undergo the cyclization reac-
tion upon heat treatment (Martin et al., 1998a,b,c). It is well known
that C C is the essential for cyclization; however, the degree of
cyclization, content and composition of the formed CFAMs dur-
ing the deep-fat frying course could be varied according to the
unsaturation degree, position and configuration of C C in differ-
ent unsaturated aliphatic chains of frying oil (Christie et al., 1993;
Dobson et al., 1997). After cyclization, one C C would be lost, so
most of the formed cyclic fatty acid monomers were mono-olefinic
structure when sunflower oil undergone small-scale frying opera-
tions (Dobson et al., 1996a) but diene is the main structure of the
formed CFAMs when evening primrose oil (Dobson and Sébédio,
1999) and linseed oil were heated at 275 ◦ C under nitrogen (Dobson
et al., 1996b). In addition, the present of monocyclic, dicyclic and
even polycyclic monomers also constitute the cyclic compounds
(Chen and Chen, 2003; Mossoba et al., 1996a,b). Therefore, the type
and content of unsaturated fatty acids of frying oil could be reflected
in the composition of the formed CFAMs.
According to previous studies, the formed CFAMs were all five-
or six-membered ring structures with a carboxyl-contained car-
bon chain and a hydrocarbon chain. That’s to say, a wide variety of
different cyclopentenyl, cyclopentyl, cyclohexenyl and cyclohexyl
fatty acids would emerge in the frying products (Mossoba et al.,
1995). If the cyclic compounds have C C, C C may exist in both
the ring’s interior and the alkyl chains. The existence of C C and its
stereomutation make these cyclic compounds have certain basic
carbon skeleton, consequently producing the cis and trans config-
urations with equal extent (Christie and Dobson, 2000).
The formation mechanism of CFAMs could be explained by
intramolecular rearrangement catalyzed by free radical intermedi-
ate, as shown in Fig. 3-1 (Christie and Dobson, 2000; Mossoba et al.,
1994). The first step of this consecutive reaction is the combination
of aliphatic chain with an allylic hydrogen radical, and sequen-
tially comes about a ring closure by reaction of an ethylenic bond
with a secondary carbon radical. Afterwards, the formed CFAM
radical reacts with hydrogen radical to produce a stable cyclic struc-
ture (A). Another pathway is that the formed CFAM radical loses a
hydrogen radical to form a new C C structure, thereby producing
another kind of product (B). However, this kind of C C positional
isomerization has been seldom reported in the investigated CFAMs.
Thus, this radical catalysis of cyclization should be verified in future
studies.
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681 669

1 R1 R2
R , RO
R1 R2

R1 R
R2
R1 A
R2
RH

R1
R2
R1
H R2
B
R1
R2

2 HOOC 9 10
H 14 HOOC 1014 B

HOOC H 9 10 HOOC 5 9 C
5

H 15 15
HOOC 9 HOOC E
10

HOOC HOOC
4 H 10 4 F
9
9 H
HOOC HOOC 9 10 12 G
12
H
9
HOOC
H
H HOOC 10 H
13 9

Fig. 3. The formation mechanism of cyclic fatty acid monomers (CFAMs) by free radical catalyzation (1, A is the typical formed CFAM and B has seldom been observed in
previous reports) and [1,6]- and [1,7]-prototropic migrations (2) from unsaturated fatty acid (Destaillats and Angers, 2005a).

Another convincible mechanism for interpreting the forma-
tion of CFAM is the thermally induced [1,6]- and [1,7]-prototropic
migrations cooperated with cycloaddition (Destaillats and Angers,
2005a; Spangler, 1976). Eight monocyclic saturated fatty acids
which comprised four basic structures: cyclopentyl fatty acids with
rings from C-5 to C-9 and C-10 to C-14, and cyclohexyl fatty acids
with rings from C-4 to C-9 and C-10 to C-15 of the original fatty acid
chain, were identified from oleic acid and high-oleate sunflower oil
during small-scale frying (Dobson et al., 1996a). According to Fig. 3-
2 and by observation of the linkage of carbon atoms, vinylic C-9 was
involved to form C and D under the induction of [1,6]-prototropic
migration and vinylic C-10 was involved to form E and F under
the induction of [1,7]-prototropic migration. In addition, the size of
the formed ring is feasible by the principal of Baeyer strain theory.
On one hand, due to the discrepancies between bond angles and
109.5◦ value of “normal” tetrahedrold and the certain steric hin-
drance between C-9 and C-12 or C-13, the formation of cyclopropyl
(G) or cyclobutyl (H) is limited. In the second hand, the carbon
band angle values of five-membered and six-membered rings are
similar to tetrahedral angle value, hence no angle strain exist and
their formations are possible, consequently only the four cyclic
products were detected. According to this mechanism, the for-
mations of bicyclic fatty acid monomers, cyclopentenyl and
cyclohexenyl CFAMs from linolein (Dobson et al., 1997) and
linolenic (Dobson and Sébédio, 1999) were also reasonable and
corresponded to the product analysis.
2.3.2. Trans isomers
In fact, some of the aforementioned cyclic monomers referred
to cis/trans isomerization belonged to the trans isomers category.
Except the trans cyclic compounds, there were several other kinds
of trans isomers. It is well known that trans isomers of fatty acid
have many adverse effects on human health such as coronary heart
disease (Willett et al., 1993), sudden cardiac death (Kummerow,
2009) and systemic inflammation (Mozaffarian, 2006). However,
the source of trans isomers is very extensive in terms of both
raw food materials and food products (Ledoux et al., 2007; Craig-
Schmidt, 2006). Hydrogenated vegetable oil was widely applied
on shortening or margarine, but the content of trans isomers was
very considerable (Romero et al., 2000b). In addition, small amount
of trans fatty acid also can be observed during edible oil refining
(Mezouari and Eichner, 2008; Schwarz, 2000).
670 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
During the deep-fat frying, all the breakage, shift and formation
of C C involve the presence of trans configuration. Therefore, it is
inevitable that the formation of trans fatty acid during vegetable oil
heating or frying. Trans, trans-2,4-decadienal which related to the
induction of low density lipoprotein oxidation was by-produced
in fried potatoes (Boskou et al., 2006; Andrikopoulos et al., 2004).
Fortunately, an ordinary frying process in suitable time using un-
hydrogenated edible oils has little impact on intake of trans fatty
acid from edible oils (Tsuzuki et al., 2010).With the increase of fry-
ing time, the amount of trans fatty acid increased but decreased
when the frying system was added with butylated hydroxyanisole
(BHA) or phenolic extracts of dry rosemary (Gamel et al., 1999;
Tsuzuki et al., 2008). In addition, to select appropriate kind of fry-
ing oil (Martin et al., 1998a,b,c; Ribeiro et al., 2009) which also refers
to the fatty acid composition of frying oil is a good strategy to avoid
the formation of trans fatty acid in conventional life.
As a kind of isomerized products, trans configuration-contained
compounds were produced from cis-polyunsaturated fatty acids
during thermal treatment. Generally, lipid oxidation leads to the
isomerization of cis-polyunsaturated structure to trans configura-
tion and very low content of trans fatty acid was produced (Liu
et al., 2007). The mechanism is illustrated by free radical chain
reaction of methyl oleate oxidation as shown in Fig. 4-1 (Porter,
1986). Electron rearrangement and migration of C C were rec-
ommended to form the elaidic acid and other trans octadecenoic
acids when the triolein was isothermally heated at 280, 300, and
325 ◦ C (Christy et al., 2009). Addition-elimination mechanism has
also been used to interpret the isomerization induced by radical
species (Chatgilialoglu et al., 2006; Jiang et al., 1999). Therefore,
the oxidation supplied free radicals to add with the C C to form a
radical-adduct, which then underwent ␤-elimination of the radi-
cal and formed the thermodynamically stable trans configuration
(Fig. 4-2). On the other hand, thermally induced isomerization of
C C in unsaturated fatty acids also exist during deep-fat frying
(Christy, 2009a). Arrhenius plot was used to investigate the thermo-
dynamics of the heat-induced isomerization of triolein (9-cis, 18:1)
and trielaidin (9-trans, 18:1) and the results indicated that heat-
induced cis/trans isomerization of triolein and trielaidin occurred
mainly through the formation of radical species (Tsuzuki, 2010).
It is worth mentioning the formation of conjugated fatty acid
isomers, like conjugated linoleic acid (CLA) by linoleic acid during
heat treatment at 180 and 220 ◦ C (Juanéda et al., 2003). Geometri-
cal isomerization of linoleic (9-cis, 12-cis, 18:2) acid into conjugated
C18:2 acids which were mainly composed of all-trans and cis/trans
CLA isomers has been investigated (Sébédio et al., 1988). 9t,12t fatty
acid-contained TAG and its methyl ester also led to form conju-
gated configuration-contained products when they were heated
at 250 ◦ C (Christy, 2009b). Similar to the formation mechanism
of above-mentioned CFAMs, [1,5]-sigmatropic rearrangements of
formation of CLA in heated oil with different levels of linoleic
acid has been proposed and verified by the identified mono trans
CLA isomers, such as 9-cis,11-trans, 9-trans,11-cis, 10-trans,12-cis,
10-cis,12-trans, 8-trans,10-cis and 11-cis,13-trans octadecadienoic
acid (Destaillats and Angers, 2002). A mixture of 9-cis, 11-trans-
octadecadienoic acid and 10-trans, 12-cis-octadecadienoic acid
was also used to directly synthesize CLA under the similar per-
icyclic [1,5]-sigmatropic rearrangement mechanism (Destaillats
and Angers, 2003). Furthermore, when methyl linoleate was solely
heated at 200 and 220 ◦ C for a series of time period, the formation of
9-trans,11-trans and 10-trans,12-trans CLA isomers was explained
by both a free-radical chain reaction mechanism (1) and [1,3]-
sigmatropic rearrangement of intramolecular (2) under thermal
oxidation condition, which can be seen in Fig. 5 (Destaillats and
Angers, 2005b).
From the proposed mechanism, the formation of trans isomers
is unescapable. However, the yield of these isomers including cyclic
monomers is small under the condition of appropriate frying time
and temperature. Therefore, there is no misgiving in terms of view
of rational intake of fried food, but the understanding of the for-
mation of these trans products would be beneficial to control the
formation of undesirable products.
2.4. TAG polymerized products
TAG polymers, such as dimmers, trimers and oligomers (Steel
et al., 2006; Tasioula-Margari et al., 1996) are categories of thermal-
oxidized products whose molecule weight is higher than that of
the parent TAGs. Under the two main factors of oxygen and heat-
ing, oxidized polymerization and thermal polymerization occur
and lead to many complex polymers with the linkages of –C–C–,
–C–O–C– and –C–O–O–C– among the TAG molecules (Stevenson
et al., 1984; Christopoulou and Perkins, 1989a). Therefore, oxygen
is present or not would make different kinds of polymeric products,
namely non-polar polymers without extra oxygen and polar poly-
mers with extra oxygen. With the production and accumulation of
polymers, many undesirable phenomena such as the easily deteri-
oration, color deepening and viscosity increasing of the frying oil,
occur and usually indicate the abandonment of the frying oil (Tseng
et al., 1996).
Generally, the structure and content of polymeric products are
affected by frying condition and the nature of frying oil (mainly
the fatty acid composition) (Tompkins and Perkins, 2000; Takeoka
et al., 1997; Choe and Min, 2007), which lead to complex reaction
process. When oxygen is absent, dimerization or polymerization
is achieved by linkage of –C–C– to form dimers or polymers with-
out extra oxygen atom. Two kinds of reactions named free radical
chain reaction and Diels-Alder reaction are mainly used to inter-
pret the formation mechanism of polymers. By the way, acyclic and
cyclic polymers can be produced in the light of different positional
carbons reacting with radicals (mainly allyl radicals). According to
Fig. 6-1, on one hand, two allyl radicals bonded to form a dehy-
drodimer. On the other hand, an allyl radical was absorbed by an
unsaturated molecule to form a dimeric radical, consequently com-
bined with a hydrogenous radical to produce a malposed acyclic
dimer. As described in Fig. 6-2, TAGs with polyunsaturated fatty
chain lost a hydrogenous radical to form a radical with structure of
conjugated diene, which then combined with another unsaturated
molecule to form a dimeric radical intermediate, consequently
intramolecular addition took place and to form a cyclic dimer. The
rest high-molecular polymers can be formed in the same manner.
Diels-Alder reaction is an important combination reaction between
conjugated diolefinic and olefinic structures for formation of cyclo-
hexene or cyclohexenyl-contained compounds, which also can be
assigned to the cyclic polymers.
However, extra oxygen is involved in participating in the sophis-
ticated chemical reactions during deep-fat frying and forming the
above-mentioned oxidized TAG monomers which have one or sev-
eral oxygen-contained groups. Under the effect of radical catalysis,
these oxygen-contained TAG monomers would be polymerized
by linkage of not only –C–C–, but also –C–O–C– and –C–O–O–C–
(Christopoulou and Perkins, 1989b; Márquez-Ruiz et al., 1995), as
shown in Fig. 7. Furthermore, one, two, or more additional oxygen
atoms could be present as bridging oxygen in the formed dimmers,
trimers or oligomers when the sample was heated at 190 ◦ C for 6 h
(Byrdwell and Neff, 2004). This combination is consisted with the
termination step of lipid oxidation. Allyl radical easily produced
by oxidation could combine with an alkoxy radical formed by scis-
soring of hydroperoxides to produce oxydimers. Meanwhile, two
molecules of peroxy radicals bonded together and formed a peroxy
dimer (Choe and Min, 2007).
Polymers are an inevitable kind of products formed during
deep-fat frying and can involve both the original polyunsaturated
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681 671

OO OOH
1 RH
R 1 11 R2 R 1 11 R2 11-trans

9 R2
O2
R1 9 R 2 RH R1 9 R2 9-cis
R1
OO OOH
O2 OO RH OOH
R 1 11 R2 R1
11 R2 R1
11 R2 11-tran s

11 8
R1 R2
OO OOH
O2 RH
R1 R1 8 R2 8-cis
8 R2 R1
8 R2
O2 RH
R1 10 R2 R1 10 R2 R1 10 R2 10-trans
OO HO O
R1 8 R RH R 1 8 R2 8-trans
2
OO OOH

X R2
H
2 X + R1 R2 H R2 X +
R1 R1

R 1= C 7H 15, R 2= (CH 2 )6COO CH 3

RH= methyl oleate

Fig. 4. The formation mechanism of trans configuration induced by free radical chain reaction (1) and addition–elimination (2) of methyl oleate oxidation.

constituents of frying oil and the decomposed products of parent
TAGs in various polymerizations. Furthermore, the simultaneous
formation of non-polar and polar polymers and the formation ten-
dency of the two polymers are still needed to be investigated.
Therefore, rightly out of the structural complexity and lack of effec-
tive analysis methods of the polymers, there have been few studies
focused on the structure analysis and formation pathways of poly-
mers produced during deep-fat frying.
2.5. Sterol derivatives
As minor components existing in the oils and fats, sterols, mainly
the phytosterols, have many benefits to human health (Ostlund,
2002). The known kinds of sterols are cholesterol (animal sterol),
stigmasterol, stigmastenol, ␤-sitosterol, campesterol, brassicast-
erol, avenasterol, etc., which broadly exist in various kinds of
food. As a kind of triterpenoid, 28 or 29 carbons and one or two
C C (the first one in sterol nucleus and the second one in the
alkyl side chain) are present in the most phytosterols (Moreau
et al., 2002). Out of the special molecule structure, many reac-
tions could occur in sterols during the deep-fat frying course.
The most important one is oxidation which leads to many sterol
derivatives and the sterol oxidation products have been widely
investigated (Ryan et al., 2009; Soupas et al., 2007). In addition,
the side-effect of these oxidation products has also been studied
and some of these products have been considered to have cell

RH R
1 R1 R2 R1 R2
R , RO RH, ROH trans-10,tran-12 18:2
R2 R1 R2 R1
H H RH R
R1 R2 R1 R2
trans-9,trans-11 18:2

R1 R2
2
trans-10,tran-12 18:2
R2 R1 R1= (CH2)6COOH
R2= C4H9
H H
R1 R2
trans-9,trans-11 18:2

Fig. 5. The formation of conjugated linoleic oil resulted from free radical chain reaction (1) and intramolecular [1,3]-sigmatropic rearrangement (2) during linoleic oil heat
treatment. (Destaillats and Angers, 2005b).
672 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681

1 Acyclic polymers
R 1 -CH 2 -CH=CH-R 2
H + R 1 -CH-CH =CH-R 2 R 1 -CH-CH=CH-R 2
R 1 -CH-CH=CH-R 2
R 1 -CH-CH =CH-R 2
+ R 1 -CH 2 -CH=CH-R 2
dimers
R 1 -CH-CH=CH-R 2 +H R 1 -CH-CH=CH-R 2

R 1 -CH 2 -CH-CH-R 2 R 1 -CH 2 -CH-CH 2 -R 2

+ R 1 -CH 2 -CH=CH-R 2

R 1 -CH-CH=CH-R 2 R 1 -CH-CH =CH-R 2

R 1 -CH 2 -CH-CH-R 2 +H
R 1 -CH 2 -CH-CH-R 2 trimers
R 1 -CH 2 -CH-CH-R 2 R 1 -CH 2 -CH-CH 2 -R 2
+ R 1 -CH 2 -CH=CH-R 2
polymers
2 Cycli c polymers H
R 1 -CH=CH-CH 2 -CH=CH-R 2 R 1 -CH-CH=CH-CH=CH-R 2
+ R 1 -CH=CH-CH 2 -CH=CH-R 2
R 1 -CH-CH -CH-CH =CH-R 2 R 1 -CH-CH =CH-CH=CH-R 2

R 1 -CH-CH-CH 2 -CH=CH-R 2 R 1 -CH-CH-CH 2 -CH=CH-R 2

+H
+ R 1 -CH=CH-CH 2 -CH=CH-R 2
R 1 -CH-CH-CH-CH=CH-R 2 R 1 -CH-CH 2 -CH-CH =CH-R 2 R 1 -CH-CH-CH 2 -CH=CH-R 2

R 1 -CH-CH-CH 2 -CH-CH-R 2 R 1 -CH-CH-CH 2 -CH=CH-R 2 R 1 -CH-CH-CH-CH=CH-R 2

+H mon ocyclic diene dimers
R 1 -CH-CH-CH 2 -CH=CH-R 2
R 1 -CH-CH-CH-CH=CH-R 2
+H

R 1 -CH-CH-CH 2 -CH-CH 2 - R 2 R 1 -CH-CH 2 -CH 2 -CH=CH-R 2

bicyclic mon oene dimers
R 1 -CH-CH-CH-CH=CH-R 2
O
R 1 : R'-C R' : Glyce ridic bac kbo ne R 1 -CH-CH-CH 2 -CH=CH-R 2
R 2 : Ali phatic chain mon ocyclic tri ene tri mers
Fig. 6. The formation mechanism of acyclic and cyclic polymers via radical chain reaction on the condition of lacking of extra oxygen during deep-fat frying (Choe and Min,
2007).

cytotoxicity in vivo studies (Adcox et al., 2001; Koschutnig et al.,
2009).
Similar to the oxidation of TAGs, sterol hydroperoxide and
its decomposition products would be formed due to the free
radical chain reaction. The main identified oxidation products
are hydroxy, keto and epoxy group-contained compounds (Lampi
et al., 2002; Smith, 1996). Taking stigmasterols for an example
(Kemmo et al., 2005), 6-OOH-stigmasterol, 7-OOH-stigmasterol,
25-OOH-stigmasterol were initially formed and their amount
decreased with the proceeding of heating at 180 ◦ C. Free radical
chain reaction, rearrangement and epoxidation were proposed to
interpret the formation of 6␤-hydroxy-stigmasterol, 7␤-hydroxy-
stigmasterol, 7␣-hydroxy-stigmasterol, 25-hydroxy-stigmasterol,
6␣-hydroxy-3-ketostigmasterol, 6␤-hydroxy-3-ketostigmasterol,
7-ketostigmasterol, 5␣,6␣-epoxystigmasterol, 5␤,6␤-
epoxystigmasterol and stigmastanetriol. The oxidation products
of other sterols are similar to those of stigmasterol (García-
Llatas and Rodríguez-Estrada, 2011). Further studies showed
that the amount of oxidized sterols decreased along with the
increase of heating temperature, indicating that these oxidized
sterols could be used as precursors of some other products,
such as sterol dimmers, trimers, oligomers, etc. (Rudzińska
et al., 2009, 2010). Thermo-oxidation products of stigmasterol
have been identified as monomeric, dimeric and polymeric
products according to their polarity and proposed as a result
of the dehydration and condensation when the stigmasterol
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681 673

O R (CH2)6 CH CH CH R'
R (CH2)6 CH CH CH R' + R (CH2)6 CH CH CH R' O
R (CH2)6 CH CH CH R'

O R (CH2)6 CH CH CH R'
O
R (CH2)6 CH CH CH R' + R (CH2)6 CH CH CH R' O
O
O R (CH2)6 CH CH CH R'
O
R: R''-C R'' : Glyceridic backbone
R': (CH2)7-CH3 oleic
CH2-CH=CH-(CH2)5-CH3 linoleic
CH2-CH=CH-CH2-CH=CH-CH2-CH3 linolenic
O

Fig. 7. The formation mechanism of acyclic and cyclic polymers via radical chain reaction on presence of extra oxygen during deep-fat frying. Structural formula A shows a
possible extra oxygen-contained trimer (Choe and Min, 2007).

samples were heated at 180 ◦ C for different time (Lampi et al.,
2009).
The effect of concentration and structure of phytosterol on the
performance of frying oil has been studied by adding exogenous
phytosterol into frying oil whose indigenous tocopherols and phy-
tosterols were aforehand removed away. The added phytosterols
significantly impacted the thermal and oxidative stability of frying
oils at higher concentration (Winkler and Warner, 2008a). In addi-
tion, the number and location of double bonds in the ring structure
have been confirmed to be more related to the anti-polymerization
effect than the presence of an ethylidene group in the side chain of
phytosterol (Winkler and Warner, 2008b). These phenomena indi-
cated that phytosterols should be involved in interaction with the
components of frying oil or the intermediate products formed dur-
ing the thermal treatment, which should be confirmed in further
research.
Sterol derivatives in fried food also have been investigated. After
14th frying at 180 ◦ C for 24.5 min in total, the amount of total
phytosterols decreased and the amount of total oxyphytosterols
(mainly the epoxy- and 7-hydroxyphytosterols) increased in both
frying oil and French-fries (Rudzińska et al., 2005). According to
previous studies of different thermally treatments, the total phytos-
terol content decreased more rapidly in French-fries and fish fillets
than that of noodles, minced meats and readymade fish products
which may resulted from the initial high total phytosterol con-
tent of the former products (Derewiaka and Obiedziński, 2012).
However, the correlation between the phytosterol loss or formed
oxyphytosterols and the fatty acid profile of chosen frying oil was
not significant (Tabee et al., 2008; Winkler et al., 2007). Due to
complex chemical environment of deep-fat frying system, more
derivatives of sterol could be produced and shouldl be isolated and
identified in further research.
2.6. Antioxidant alterations
Due to the loss of natural antioxidants in frying oil during the
refining course, some natural and synthetic antioxidants such as
tocopherol, butylated hydroxytoluene (BHT), BHA, etc., are always
added into frying oil to prevent the oxidation of frying oil and
improve the performance of deep-fat frying course. Specifically,
the reduction of formation amount of total polar compounds
(Aladedunye and Przybylski, 2011), 4-hydroxynonenal (Gerde et al.,
2011), trans fatty acids (Filip et al., 2011), CLA (Ko et al., 2010), sterol
oxidation products (Kmiecik et al., 2011), acrylamide (Ou et al.,
2010), nonvolatile compounds which contribute to the negative
odor (Neff et al., 2003), and anti-polymerization effects (Lampi and
Kamal-Eldin, 1998) were observed under the presence of antiox-
idant during the deep-fat frying. On the other hand, under the
treatment of high temperature, the antioxidation activity of them
would be influenced, such as ␣- and ␦-tocopherol lost their effec-
tiveness when the temperature was higher than 150 ◦ C (Réblová,
2006). These alterations were found to be related to the degradation
of antioxidant or the interaction between antioxidant and other
components.
Free radical scavengers have been introduced to describe the
role of the antioxidant when it is added into the frying system
(Rossi et al., 2007; Yeo et al., 2011). 1,1-diphenyl-2-picrylhydrazyl
(DPPH) tests have been investigated and the results indicated that
the rosemary extract showed more antioxidative effect than that of
␣-, ␥-, ␦-tocopherols alone, their homologous mixture and BHT in
the TAGs isolated from rapeseed oil (Nogala-Kalucka et al., 2005).
In view of the free radical reaction easily occurred during deep-fat
course, a lot of free radicals are present in the frying system. The
antioxidative effect is related to their ability to inhibit the formation
of free radicals or quench the formed free radicals. From this point
of view, antioxidant works on the initial steps of the free radical
reaction in order to inhibit the formation of the above-mentioned
products.
Besides the description of antioxidant loss during frying, the
specific chemical alterations occurred in antioxidants have been
reported for these years (Barrera-Arellano et al., 1999; Bruscatto
et al., 2009). However, its loss during the high-temperature treat-
ment is possibly related with their degradation for the reason
of their volatility (Marmesat et al., 2010). The ␣-tocopherol
oxidation products, ␣-tocopherolquinone, 4a,5-epoxy-␣-
tocopherolquinone, and 7,8-epoxy-␣-tocopherolquinone, have
been identified when the triolein mixed with ␣-tocopherol and
heated at different temperatures for different times (Verleyen et al.,
2001a,b). It was proposed that peroxyl radicals were captured by
␣-tocopherol to form the polar oxidation products (Verleyen et al.,
2001a,b). Tocopherolquinones increased along with the increase
of frying time when the heating treatment of sunflower and soy-
bean oils mixed with ␣-tocopherol (Rennick and Warner, 2006).
Esterification and dimerization were proposed to interpret the
674 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
formation of 2,4 -di-tert-butyl-5 -hydroxy-2 ,4-dimethoxy-
diphenyl ether, 2,2 -dihydroxy-5,5 -dimethoxy-3,3 -di-tert-
butylbiphe, etc., when BHA are subjected to high temperature
treatment, which had been investigated with other three synthetic
antioxidants in heating of individual antioxidant at 185 ◦ C for
different heating time (Hamama and Nawar, 1991).
2.7. Products derived from interactions between frying oil and
food material constituents
Based on aforementioned detected products and their possi-
ble formation mechanisms, it can be observed that deep-fat frying
without food material is already a complex physicochemical pro-
cess. However, the practical deep-fat frying is a more intricate
process which involves not only the components of frying oil, but
also the components of food material, such as water, protein, lipid,
carbohydrate, inorganic salt in participating in the various alter-
ations (Dobarganes et al., 2000a,b). In other words, it is considerably
abstruse that a system refers to so many reaction substrates and
drastic reaction condition. The following content introduced is on
the basis of studies reported previously.
Strictly, the hydrolysis products come from the reaction
between TAGs and food material constituents in that the water
is present by food materials. However, they were discussed
in an indie unit due to their properties of degradation prod-
ucts. Even though except for water, the conventional fried food
material is still a sophisticated composition matrix and each
constituent of food material could participate in the complex
reactions during deep-fat frying (Karel et al., 1975). Broadly speak-
ing, heat and mass transfer dominate the whole frying process
involving interrelated physicochemical alterations among vari-
ous components of both frying oil and food material (Dana and
Saguy, 2006; Mellema, 2003). Consequently, the delicious taste
and attractive color and aroma are obtained by suitable frying
condition.
The typical and well-studied alterations come into contact with
the changes of both frying oil and food material components are
lipid oxidation and maillard reaction. Maillard reactions which are
also called as non-enzymatic browning reactions between carbonyl
and amino group are a series of important chemical alterations
contributing to both color and odor of food in processing (Hodge,
1953). On one hand, the formation of aldehydic compounds sup-
plies the presence of carbonyl group in the frying system as a result
of the thermal oxidation. On the other hand, the amino group was
supplied by frying materials.
These two kinds of chemical alterations run through the whole
frying course and both influence other reactions. But most impor-
tant of all, these two typical alterations had certain relation in
the mutual influence of intermediates and end-products. As a
kind of maillard reaction products, nonenzymatically browned pro-
teins had been confirmed to have good antioxidative effect and
well induce lipid oxidation (Mastrocola et al., 2000; Ahmad et al.,
1998; Alaiz et al., 1997). The interaction relationships between
the lipid oxidation and maillard reaction has been reviewed and
come to the conclusion that both reactions were so interrelated
that they should be considered simultaneously to understand the
products of the lipid oxidation in the presence of proteins and vice
versa (Zamora and Francisco, 2005; Zamora and Hidalgo, 2011).
Thus, even under the condition of absence of reducing sugar, the
maillard reaction would also occur during deep-fat frying and
the main volatile nitrogen-containing heterocyclic compounds,
such as pyrazines, pyridines, pyrroles, etc. could be produced.
Another worth concerned nitrogen-containing compound is acry-
lamide which has become a hot topic in the field of baking
food.
2.7.1. Nitrogen- and sulphur-containing heterocyclic compounds
With the exception of previously discussed volatile decom-
position compounds, nitrogen- or sulfur-containing heterocyclic
compounds are other typical volatile products which contribute to
the main odor of frying oil or fried material (Van Loon et al., 2005;
Hartman et al., 1983; Kiatsrichart et al., 2003). Obviously, the source
of nitrogen or sulfur is protein which extensively exist in common
fried material.
A total of 130 volatile compounds were isolated and identi-
fied from fried chicken at 185 ◦ C for 8 min (Tang et al., 1983).
Except for the little molecular compounds formed by degra-
dation of hydroperoxides, several heterocyclic compounds of
pyridines, thiazoles, thiazolines, oxazoles, oxazolines, thiophenes,
pyrroles, furans, and thialdine were also present in the volatile
part. Apart from lipid auto-oxidation and lipolysis, proteoly-
sis was also the reason for the formation of flavor compounds
(Jerković et al., 2007). 2,4-decadienal which is the well known
as a secondary lipid oxidation product was reacted with either
cysteine or glutathione and come to the following conclusions:
both the two mixtures had complex reactions occurred under
the simulated fried condition and the corresponding hetero-
cyclic compounds were formed. The possible reaction pathway
of 2-pentylpyridine production which involves electrocyclic and
aromatization reactions is shown in Fig. 8-1 (Henderson and Nawar,
1981; Zhang and Ho, 1989). Model systems with different two
kinds of amino acids under simulated deep-fat frying conditions
of 180–183 ◦ C in corn oil were investigated and the results of
producing of volatile pyrazines were obtained (Chun and Ho,
1997).
As a kind of minor byproduct of food processing, heterocyclic
aromatic amines (HAAs) have been recognized as an important kind
of potential mutagens and carcinogens for human health (Cheng
et al., 2006; Jägerstad and Skog, 2005). The main precursors of these
HAAs are creatinine, reducing sugars and amino acids which com-
monly exist in the deep-fat frying system. The maillard reaction
and strecker degradation were also proposed to be the formation
pathways of these HAAs, such as imidazo-quinolines and imidazo-
quinoxalines in the fried products (Jägerstad et al., 1998; Murkovic,
2004). Along with the increase of frying temperature and frying
time, the amount of HAAs increased. The influence of frying oil type
on the formation of HAAs has also been studied. The results indi-
cated that the amount of HAAs was significantly lower in sunflower
seed oil and margarine than that in butter, margarine fat phase, liq-
uid margarine and rapeseed oil when the beefburgers were fried at
165 and 200 ◦ C (Johansson et al., 1995) and extra virgin olive oil was
effective to inhibit the formation of HAAs in the fried beefsteak in
suitable adding amount (Lee et al., 2011). Fortunately, heating could
be used to decrease the amount of imidazo-quinoxalines and 2-
amino-1-methyl-6-phenylimidazo[4,5-b]pyridine and the content
of unsaturated fatty acids in frying and their primary or secondary
lipid oxidation products were related with the chemical degrada-
tion of HAAs (Randel et al., 2007).
Garlic slices were treated by frying, oil-cooking, microwave-
frying, baking, and microwave-baking and the produced volatile
compounds were studied and identified. The identifying analy-
sis indicated that the sulfur-containing volatile compounds were
possibly decomposed and/or rearranged products of alk(en)yl thio-
sulfinates (Yu et al., 1993). Cysteine and corn oil were mixed and
heated at 180 ◦ C for 4 h and fifty-four volatile compounds were
identified. Being produced in greatest amount, 2-alkylthiophenes
was proposed to be formed from reaction of ␣,␤-unsaturated
fatty aldehydes and hydrogen sulfide, as explained in Fig. 8-2
(Macku and Shibamoto, 1991b). As a nucleophile, hydrogen sulfide
attacked ␣,␤-unsaturated fatty aldehydes and made the oxygen
atom replaced by sulfur atom. Afterward, the resulting sulphur-
containing radical rearranged its electrons through carbon atoms
 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681 675

O
C H CH CH
CH CH
CH CH CH CH
(CH2)4 H 2O (CH2)4
1 CH3 + CH3 N CH
A
NH2
B HO CH
R R COOH
O
R
CH (CH2)4
COOH N
(CH2)4 CH3
CH3 N CH
R COOH
H O
N OH
R: N
(CH2)4 O H
CH3 N O
HS

O H 2O S
+R S
2 R-CH2-CH=CH-C + H 2S R-CH2-CH=CH-C R-CH-CH=CH-C
H H RH H

HC CH HC CH HC CH
HC C-R HC C-R C CH-R
S H S H H S
+ OH OH
HC CH
HC C-R R
S H H 2O S

Fig. 8. The possible reaction pathways for the formation of 2-pentylpyridine from 2,4-decadienal (A) and glutathione (B) (Zhang and Ho, 1989) and 2-alkylthiophenes from
cysteine and corn oil on the condition of heating (Macku and Shibamoto, 1991b).

and reacted with a hydroxyl radical to produce a thiophene ring by
dehydration.
2.7.2. Acrylamide
It is well known that acrylamide (AA) possesses neurotoxicity,
genetic toxicity and carcinogenicity (Friedman, 2003; Hagmar et al.,
2005; Keramat et al., 2011a,b) and it has been highly kept a watch-
ful eye on since it was observed in heated starch-rich foodstuffs
with high amount (Zhang et al., 2005; Tareke et al., 2002). Dur-
ing the food processing, AA is mainly produced by the reaction
between some amino acids and reducing sugar on high temper-
ature or during the course of maillard reaction (Keramat et al.,
2011a,b; Stadler et al., 2002). As shown in Fig. 9 (Mottram et al.,
2002), an amino acid combined with a dicarbonyl compound by
losing a water and then subjected to intramolecular rearrangement
of ion and strecker degradation to form an acrolein, a hydrogen
nitride and other compounds or strecker aldehyde. At last, AA was
formed from the combination of acrylic acid and hydrogen nitride
or ammonium originated from nitrogen containing compounds.
Except the reducing sugar source of carbonyl compound,
another possible source is the lipid oxidation which occurs during
deep-fat frying. In addition, the more susceptible to oxidation of
the frying oil, the more AA was formed in model systems (Capuano
et al., 2010). Obviously, some of the lipid oxidation products pro-
mote or participate in the formation of AA. Some typical lipid
oxidation products such as 2,4-decadienal, 2-octenal, methyl 13-
oxooctadeca-9,11-dienoate and 4,5-epoxy-2-decenal have been
mixed with asparagines to investigate the formation degree of
AA under certain frying conditions. The results indicated that
␣,␤,␥,␦-diunsaturated carbonyl compounds were the most reac-
tive compounds to participate in the synergism of AA (Zamora and
Hidalgo, 2008).
As it often happens, conventional fried material such as potato
and cereal food contains the reaction substrates of AA (Matthäus
et al., 2004). It is easy to form AA when these foods are subjected
to high temperature process. It also could be said that the for-
mation of AA is related to the type of the fried food. During the
process of potato chips, when the frying temperature and other
factors were controlled, the yield of AA directly related to the fry-
ing time (Romani et al., 2008). Secondly, the yield of AA increased
when the frying temperature was increased (Fiselier et al., 2006;
Sanny et al., 2012). Furthermore, the effect of frying oil types on
the formation of AA has been studied and no significant differ-
ences were observed among the vegetable oils (Mestdagh et al.,
2005). But the AA concentration was much higher when palm olein
was used as frying oil due to its high content of 6 to 8% of diglyc-
erides. This might be attributed to another formation pathway of
the AA precursor of acrolein which derived from electro rearrange-
ment during the hydrolysis of MAGs (Gertz and Klostermann, 2002)
or formed from glycerol when the frying temperature was higher
than the smoke point of frying oil (Claeys et al., 2005). There-
fore, control of the type of frying oil, frying temperature and time
are effective to control the producing of AA during French fries
process.
676 Q. Zhang et al. / Chemistry and Physics of Lipids 165 (2012) 662–681
Amino acid Dicarbonyl
compound R1
X-CH-NH2 H2N
O O Amino
C +
R1-C=C-R2 ketone
O OH R2
O C-CH2-CHO
- H2O +
H
Strecker
X N R1 X X C
aldehyde
H - CO2 C=N R1 O H2N
H ?
O OO R2
HO R2
H R1-CO-CO-R2
+NH3 + CH3S H
+ CH2=CH-CHO
Acrolein
Fig. 9. The proposed formation mechanism of acrylamide between asparagines or methionine and dicarbonyl compounds from maillard reaction. (It is asparagines when X
means –CH2 CONH2 and methionine when X means –CH2 CH2 SCH3 .) (Mottram et al., 2002).
3. Summary
The benefits of well understanding of the chemical alterations
occurred during deep-fat frying are mainly embodied in analyzing
the beneficial part (e.g. attractive favor, color and tasty crispness
resulted from maillard reaction and caramelization) and hazard
part (e.g. trans fatty acids and AA formed during frying) of the
products produced during the high-temperature process in order
to improve the mouthfeel and safety of fried food, choose suitable
frying conditions, determine the appropriate service life of the fry-
ing oil, etc. and reusing the used frying oil in the field of energy and
chemical industry. At last, it is useful for both healthy prospective
of consumers and the economic prospective of fried food industry
or the whole society.
Though the reaction products formed during deep-fat frying are
of multiformity and complexity, they could be identified and clas-
sified into several categories according to their similar nature. In
addition, the reaction substrates also have certain exploitable rules
such as the TAGs profile of frying oil and the presence of water
in conventional food frying. As previously mentioned, the applied
frying conditions which comprise frying temperature, time, con-
tinuous or incontinuous frying, fryer type, oil turnover rate or fresh
oil replenishment, etc. would impact the product types and for-
mation routes. Therefore comprehensively consideration of all of
these possible factors is achievable to expound the product forma-
tion mechanism and forecast the possible products during deep-fat
frying.
According to above-mentioned varieties of products, there are
several overlaps among the varieties and even more mutual influ-
ence among them. From their corresponding possible formation
mechanisms, homolytic reaction, also called as free radical reac-
tion, heterolytic reaction, also called as ionic reaction and concerted
reaction have been successfully used to interpret their forma-
tion pathways. These three reactions dominate the whole typical
reactions of organic chemistry, which also reflect the complex of
deep-fat frying course.
Free radicals are pervasive during the whole frying course in
spite of their instantaneous lifetime. The initiation step of ther-
mally oxidation is the main source for the presence of free radicals.
As a kind of reactive intermediate, free radicals easily attack other
chemicals and capture their electro to form a more stable sub-
stance. In the sight of this point of view, the interpreting to the
formation of some volatile products, short-chain compounds, oxi-
dized TAG monomers, CFAMs, trans isomers polymers, heterocyclic
compounds, etc. is reasonable and acceptable. Heterolytic reaction
seems not so obviously like homolytic reaction, but the presence of
H2N
O ?
C-CH=CH2 Acrylamide
O
NH3
CH2=CH-COOH CH2=CH-COO NH4+
water supplies a nucleophile and the hydrolysis is supposed to be an
ionic reaction. In addition, the proposed formation mechanism of
2-alkylthiophenes is another application of nucleophilic reaction.
Concerted reaction is an important reaction which just refers to
the transition state of chemical bond transformation or the forma-
tion and breakage of chemical bond in one step. The recommended
[1,j]-prototropic migrations and sigmatropic rearrangement well
explain the formation of some CMFAs and trans isomers. More-
over, the diene synthesis, i.e. Diels-Alder reaction also belongs to
concerted reaction. Therefore, the deep-fat frying products which
have been detected and identified so far are well interpreted by
these three reactions.
However, on the basis of the three main organic chemistry reac-
tions and the conditions of high temperature and various reaction
substrates, the possible reaction products are more complex than
those of known at present. Take polymers as example, the pos-
sible produced structure is so multifarious that it is difficult and
unnecessary to clearly understand their specific formation path-
ways. Furthermore, being accompanied with the development of
instrument and its raised detection precision, more and more trace
products would be detected and identified. As a result, to con-
clude and interpret the formation mechanism of reaction products
become more difficult. These obstacles should be paid more atten-
tion to and conquered in the future studies.
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