Food Chemistry xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Role of plant polyphenols in acrylamide formation and elimination

Yanbing Liu a, Pengpu Wang a, Fang Chen a,, Yuan Yuan b,, Yuchen Zhu a, Haiyang Yan b, Xiaosong Hu a
a
College of Food Science and Nutritional Engineering, National Engineering Research Centre for Fruits and Vegetables Processing, Key Laboratory of Fruits and Vegetables
Processing, Ministry of Agriculture, Engineering Research Centre for Fruits and Vegetables Processing, Ministry of Education, China Agricultural University, Beijing 100083, China
b
College of Quartermaster Technology, Jilin University, Changchun 130062, China

a r t i c l e

i n f o

Article history:
Received 15 January 2015
Received in revised form 29 March 2015
Accepted 30 March 2015
Available online xxxx
Chemical compounds studied in this article:
Acrylamide (PubChem CID: 6579)
Asparagine (PubChem CID: 6267)
3-Aminopropionamide (PubChem CID:
192802)
Methylglyoxal (PubChem CID: 880)
Acrolein (PubChem CID: 7847)
Glucose (PubChem CID: 53782692)
Epicatechin (PubChem CID: 72276)
Naringenin (PubChem CID: 932)
Phloretin (PubChem CID: 4788)

a b s t r a c t
Acrylamide found in thermal-treated foods has led to an intensive and persistent research effort, since it
is a neurotoxic, genotoxic and probable carcinogenic compound to humans. Plant polyphenols are the
most abundant antioxidants in human diet. Several researches indicated that the polyphenols affected
the acrylamide formation during heating. However, the controversial effects of the polyphenols on acrylamide formation were related to their structure, concentrations, and antioxidant capacity, as well as
reaction condition. Polyphenols can inhibit acrylamide formation through trapping of carbonyl compounds and preventing against lipid oxidation, while some special polyphenols can enhance the acrylamide content by providing carbonyl groups, accelerating the conversion from 3-aminopropionamide
(3-APA) to acrylamide and inhibiting acrylamide elimination. This review concludes the effects of
polyphenols in the Maillard reaction and food systems conducted so far, aimed to give an overview on
the role of plant polyphenols in acrylamide formation and elimination.
2015 Published by Elsevier Ltd.

Keywords:
Acrylamide formation
Plant polyphenol
Mechanism
Elimination

1. Introduction
Acrylamide can be formed in thermal-treated foods, especially
in the carbohydrate-rich foods, such as French fries, potato chips
and bakery products. Nowadays, acrylamide has arose a worldwide
attention since acrylamide has been known as a neurotoxic, genotoxic and probable carcinogenic compound.

Abbreviations: ANN, articial neural network; AOB, antioxidant of bamboo;

3-APA, 3-aminopropionamide; BHA, butylated hydroxyanisole; BHT, butylated
hydroxytoluene; EGT, extracts of green tea; ESI-MS, electrospray ionization-mass
spectrometry; GCE, green coffee aqueous extract; GTE, green tea aqueous extract;
LC/MS, liquid chromatography coupled with tandem mass spectrometry; MLR,
multiple linear regression; NMR, nuclear magnetic resonance; TP, tea polyphenols;
VOO, virgin olive oil.
Corresponding authors. Tel./fax: +86 10 6273 7645 18 (F. Chen). Tel./fax: +86
431 87836376 (Y. Yuan).
E-mail addresses: chenfangch@sina.com (F. Chen), yuanyuan1024@gmail.com
(Y. Yuan).

Soon after the discovery of acrylamide in food, the Maillard

reaction between reducing sugar and asparagine was considered
to be mainly responsible for acrylamide formation (Stadler et al.,
2002). Some possible inhibition or mitigation strategies for
acrylamide formation both in the model systems and actual food
systems were explored, including decreasing the heating temperature and time, choosing raw materials with fewer precursors and
adding the exogenous additives. In the exogenous additives,
polyphenols are widely used in acrylamide migration.
Polyphenols are naturally occurring compounds found largely
in the fruits, vegetables, herbs, spices, grains and beverages with
different kinds of species. So far, more than 8000 phenolic structures have been found. Plant polyphenols are characterized by
the presence of an aromatic ring bearing one or more hydroxyl
substituent. Based on the structure, they could be divided into several groups, for example, avonoids, phenolic acids, hydroxycinnamic acids as well as avolans.
Some polyphenol-rich foods, such as green tea, coffee, red wine
and chocolate, are consumed by a large population in many

http://dx.doi.org/10.1016/j.foodchem.2015.03.122
0308-8146/ 2015 Published by Elsevier Ltd.

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10.1016/j.foodchem.2015.03.122

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countries. Recently, some plant extracts containing a large amount

of polyphenols, were classied into food additives in many countries, for example, rosemary extract and antioxidant of bamboo
leaves. Compared with the synthetic antioxidants of butylated
hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), plant
polyphenols are safer and more acceptable by the consumers,
which is the reason why plant polyphenols represent an important
component of humans daily diets.
Recently, Vinci, Mestdagh, and Meulenaer (2012) summarized
the effects of antioxidants used in fried potato products on
acrylamide formation. Jin, Wu, and Zhang (2013) reviewed the
relationship between antioxidants and acrylamide formation and
proposed that reactive carbonyl groups were the major key sites
on which antioxidants inuenced the acrylamide formation
mainly. Plant polyphenols are crucial parts of phytochemicals,
whose effects on acrylamide formation and elimination and the
mechanisms about the exact inuences of polyphenols on
acrylamide have not been reviewed specially yet. This paper
focuses on the present understanding of the inuence and mechanisms plant polyphenols involved on acrylamide formation and
elimination in the model system or food during heating.

2. Chemical mechanisms for acrylamide formation

Recently, researchers have proposed some hypotheses to
explain the mechanisms for acrylamide formation, of which
Maillard reaction and acrolein pathway are two main pathways
accepted (Fig. 1). In the Maillard reaction, the Schiff base, a condensate of reducing sugar and asparagine, facilitated the decarboxylation step and formed decarboxylated Schiff base via the
formation of oxazolidin-5-one by intramolecular cyclization
(Yaylayan, Wnorowski, & Locas, 2003). The decarboxylated products could decompose to acrylamide via direct elimination of an
imine or after hydrolyzed to form 3-APA or 3-oxopropanamide.
The 3-APA was a transient but main precursor for acrylamide
formation during heating (Zyzak et al., 2003). Zamora, Delgado,
and Hidalgo (2009) indicated that there were diverse competitive
pathways by which 3-APA was converted into acrylamide, depending on the water activity and temperature. The excess sugar could
also enhance the conversion from 3-APA to acrylamide. The 3-oxopropananmide is similar to 3-APA structurally with the only distinction in the group attached to C-3. Amino group in 3-APA is
replaced by aldehyde group (Perez & Yaylayan, 2008). In this

Fig. 1. Formation mechanisms of acrylamide via Maillard reaction and acrolein way.

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Y. Liu et al. / Food Chemistry xxx (2015) xxxxxx

pathway, asparagine is a crucial reactant that provides an amide

group attached to a chain of three carbon atoms for acrylamide,
while glutamine and aspartic acid can only generate trace quantities of acrylamide. However, maleimide instead of acrylamide
occurred when asparagine was heated alone. The roles of reducing
sugar in this mechanism were enabling the conversion of asparagine into acrylamide and preventing intramolecular cyclization of
asparagine (Yaylayan et al., 2003). With the continuous research,
the reducing sugar was found not essential for the formation of
acrylamide. The carbonyl compounds, such as 2-deoxyglucose,
2,3-butanedione, octanal, decanal could produce the same results
as reducing sugar. These carbonyl compounds were formed by
the Maillard reaction, by degradation of sugars or by lipid peroxidation (Arribas-Lorenzo & Morales, 2010; Zyzak et al., 2003). Free
radicals formed during the Maillard reaction were thought to be
responsible for the oxidation of lipids. Then oxidized lipids converted asparagine either into their corresponding Strecker aldehydes or into vinylogous derivatives depending on the amount of
oxygen present in the reaction system (Zamora & Hidalgo, 2008).
The dicarbonyl intermediates in the Maillard reaction, such as
methylglyoxal, could also take part in this pathway and enhance
the formation of acrylamide (Yuan et al., 2008).
Acrolein is considered as another main precursor for acrylamide
formation. It can be produced by the degradation of glycerol in oil
heated at temperatures above the smoke point and further be oxidized to acrylic acid, which induced the formation of acrylamide in
the presence of asparagine (Yasuhara, Tanaka, Hengel, &
Shibamoto, 2003). In the acrolein pathway, the carbon source
comes from the acrylic acid and asparagine provides the amino
group. Moreover, peroxy radicals could initiate the polymerization
of acrylamide in the presence of oxygen (Hedegaard, Granby,
Frandsen, Thygesen, & Skibsted, 2007).
3. Factors inuencing the effect of plant polyphenols on
acrylamide formation
The addition of a avonoid-rich spice mix was rstly reported
by Fernndez, Kurppa, and Hyvnen (2003) to reduce the amount
of acrylamide in potato chips by up to 50%. The studies on the
effects of plant polyphenols on the formation of acrylamide conducted from 2003 up to now are listed in Table 1 as a summary
to reect the inuences of various factors on the content of
acrylamide.
3.1. Structure of plant polyphenols
Plant polyphenols are a considerably large family including
many compounds with different structures, which have signicant
impacts on the formation of acrylamide during heating. Recent
studies showed that the green tea extracts, cinnamon and oregano
led to a reducing effort on acrylamide in fried potatoes, whereas
two plant extracts from thyme and bougainvillea had no signicant
inuence on acrylamide formation in the same condition (Morales,
Jimenez, Garcia, Mendoza, & Beristain, 2014). Cheng, Chen, Zhao,
and Zhang (2015) tested the effect of six fruit extracts on acrylamide formation in glucose/asparagine model system. The results
showed that only apple extract inhibited the acrylamide formation,
while the dragon fruits with white esh and red esh enhanced
acrylamide formation, but other three fruit extracts had no signicant impacts on acrylamide formation. Similarly, the opposite
effects on acrylamide formation in the same condition were
observed between both main phenolic compounds in extracts, hesperetin and p-coumaric acid. Heated at 180 C for 15 min, p-coumaric acid caused a 53% reduction, whereas hesperetin increased
acrylamide content by up to 9% (Oral, Dogan, & Sarioglu, 2014).

In addition, VOO phenolic extract and the pure polyphenols

from VOO showed inconsistent effect on acrylamide formation
(Kotsiou, Tasioula-Margari, Kukurov, & Ciesarov, 2010).
Addition of VOO phenolic extract into glucose/asparagine model
system resulted in an inhibition on acrylamide formation at the
concentration of 2.2 mg/kg, while the acrylamide content
increased with the addition of phenolic extract at the higher
concentration of 216.9 mg/kg. On the contrary, both commonlyoccurring phenols from VOO, oleuropein and p-hydroxyphenylacetic acid, signicantly lowered the acrylamide content. The
results could be explained by complex constituents in the plant
extracts. Moreover, it was found that during VOO extraction
oleuropein was hydrolyzed to form dialdehydic or aldehydic
derivatives which may enhance the acrylamide formation.

3.2. Matrix
Reaction model system is commonly used in many researches
on the acrylamide formation, since the simple constituents in the
model system are in favor of understanding reaction mechanism.
However, the results obtained in the model system were often
totally different from the real food system. Because foods, like
potato chips and bakery cookies, contain complex ingredients,
including oil, starch, sucrose, etc, which mean more reactions
and complicated products are resulted (Aar & Gkmen, 2009).
Seven polyphenols and three solid phase extracts of plants were
added into both the asparagine/fructose model system and biscuits
(Oral et al., 2014). The acrylamide inhibition ratios were in the
range of 30.8% to 85.0% in glycine/glucose model system under a
quarter-hour heated at 180 C. However, the inhibition ratios in
biscuits were ranged between 10.3% and 19.2%, which were lower
than that in the model system. It could be explained that the large
amount of amino acids and reducing sugars existing in biscuits led
to more acrylamide be generated. The amount of acrylamide in the
model system and biscuits were 2.9 0.1 mg/kg and 206.01 3.31
mg/kg, respectively. Similarly, addition of curcumin promoted the
acrylamide formation in the asparagine/fructose model system,
whereas curcumin lowered the acrylamide content when heating
from 0 to 20 min in the crust model (Hamzalioglu, Mogol,
Lumaga, Fogliano, & Gkmen, 2013).

3.3. Concentration
A great number of researches proved that the correlation
between acrylamide formation and concentration of polyphenols
was non-linear. Zhang, Ying, and Zhang (2008) evaluated the inhibitive effect of AOB and EGT on acrylamide in asparagine/glucose
model systems during microwave heating at 180 C, when the concentrations of AOB and EGT were set at concentration sequences of
101, 102, 103, 104, 105, 106, 107 and 108 mg/mL. The
results showed that there was a negative correlation between
acrylamide content and concentration levels of polyphenols which
ranged from 101 to 106 mg/mL, but a positive correlation was
observed at the concentration levels of polyphenols from 106 to
108 mg/mL.
GTE and GCE, of which the main ingredients were avonoids
and phenolic acids, were added into yeast donuts at the concentra_ zelewicz,
_
tions of 0.25, 0.5, and 1 g/100 g (Budryn, Zy
Nebesny,
Oracz, & Krysiak, 2013). Results showed that the minimum additions of GTE and the maximum addition of GCE caused an increase
of acrylamide and other concentrations reduced the acrylamide
formation. The various polyphenolic contents and compounds
were responsible for the different results led to GTE and GCE.
The different consequences at series of concentrations reected

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Table 1
Summary of studies and ndings on mitigating acrylamide formation by plant polyphenols.
Effects

Kind of polyphenols

Matrix

Concentration
of addition

Heating time

Condition

Results

References

Decreasing
effects

Antioxidant from bamboo

leaves (AOB)
AOB and extract of green tea
(EGT)

Chicken
wings
Phosphate
buffer

0.01%, 0.1%,
0.5%, 1%
108101
mg/mL

4 min

170 C

Up to 59% ;a

3 stages,
15 min
totally

Maximum ; on the level

of 106 mg/mL

AOB and tea polyphenols (TP)

Cookies

AOB (0.2 g/kg)

and TP (0.1 g/
kg)

7 min

Microwave
heating
180 C, pH
6.8
190 C

Zhang, Xu, Wu, Zhang,

and Zhang (2007)
Zhang et al. (2008)

63.9%, 43.0% ;
respectively

Li et al. (2012)

Extracts from green tea,

cinnamon and oregano.
Crude aqueous extracts from
cinnamon, clove, coriander,
cumin and turmeric
Crude aqueous extracts from
cinnamon, clove, coriander,
cumin and turmeric
Rosemary extract

Fried
potatoes
Cookies

3 min

150 C

Morales et al. (2014)

0.25%, 0.5%,
1.0%, 2.0%, 4.0%

15 min

210 C

62%, 39% and 17% ;

respectively
Up to 50.9% ;

0%, 0.05%, 0.1%,

0.25%, 0.5%,
1.0%, 2.0%
50 mg/kg

20 min

190 C

Up to 62.2% ;

Zhu et al. (2011)

Deep-fat
frying, 180 C

38% ;

Aqueous rosemary extract,

rosemary oil and dried
rosemary leaves
Naringenin

Wheat buns

1% and 10%

10 days, 2
cycle/day,
5 min/cycle
20 min

225 C

62%, 67%, 57% ;

respectively

Urbancic, Kolar,
Dimitrijevic, Demar,
and Vidrih (2014)
Hedegaard et al.
(2007)

Phosphate
buffer
solution
Model potato
matrix
Phosphate
buffer

5, 10, 25 mM

60180 min

128 C, pH
7.0

Up to 50% ;

Cheng et al. (2009)

20 min

180 C

Up to 75% ;

15 min

180 C

20 min

180 C

Up to 75% ; by extracts
up to 59% ; by phenolic
compounds
Up to 49% ;

Ciesarov, Suhaj, and

Horvthov (2008)
Zhu, Cai, Ke, and Corke
(2009)
Kotsiou et al. (2010)

30 min

160 C

; Signicantly

Cheng et al. (2010)

10 min,
20 min

180 C

Hamzalioglu and
Gkmen (2012)

5, 10, 20, 30,

60 min

180 C

Curcumin and silymarin

can convert asparagine
into acrylamide.
"b Under long-term
heating conditions

Hamzaloglu et al.
(2013)

20 min

180 C

Up to 48% "

Kotsiou et al. (2010)

1060 min

105 C 115 C
125 C

" Signicantly

30 min

160 C

" Signicantly

Kotsiou, TasioulaMargari, Capuano, and

Fogliano (2011)
Cheng et al. (2010)

15 min

180 C, pH
6.8

30.885.0% ;

Oral et al. (2014)

15 min

185 C

10.319.2% ;

Oral et al. (2014)

5, 10, 15,
20 min

160 C, pH
6.8

Cai et al. (2014)

1060 min

105 C 115 C
125 C
200 C, pH
5.8

" With chlorogenic acid, "

with its quinone
derivative
Up to 70% ;

Kotsiou et al. (2011)

Up to 17% "

Bassama et al. (2010)

; With 1.0 mM additions,

no effect with 0.1 mM
additions
; With 0.05% and 0.1%
addition, no effect with
0.01%Addition
" With 0.25% of GTE and
1.0% of GCE, ; with other
levels

Hedegaard et al.
(2007)

Extracts from pimento, black

pepper, marjoram, oregano
35 crude aqueous extracts
from dietary plants and 11
phenolic compounds
Oregano
Apple extract
Increasing
effect

Curcumin and silymarin

Curcumin

Virgin olive oil (VOO)

VOO

Discordant
effect

Dry potato
starch
Distilled
water

10 mg/mL

15, 20, 25
mg/mL

Aqueous
solutions
with silica gel
Aqueous
solutions
with silica gel
Dry potato
starch
Sunower oil

Distilled
water

Caffeic acid, chlorogenic acid,

ellagic acid, epicatechin

Asparagine
fructose
model system
Biscuit

15, 20, 25
mg/mL

Phosphate
buffer
solution
Sunower oil

0.5, 5, 50 mM

Citrate buffer

2.5, 5, 7.5,
10 mM

Cacodylate
buffer

0.1 mM and
1.0 mM

30 min

160 C, pH
7.0

Proanthocyanidins

Fried potato
crisps

0.01%, 0.05%,
0.1%

30 min

95 C

Green tea extract (GTE) and

green coffee extract (CTE)

Fried donuts

0.25%, 0.5%,
1.0%

90 s

180 C

Trolox, ferulic, gallic,

protocatechuic and caffeic acid
Gallic, ferulic, coumaric, caffeic
acids, catechin, and
epicatechin
Epicatechin and
epigallocatechin gallate

Fried
potatoes

Frugon fruit extract

Caffeic acid, chlorogenic acid,

ellagic acid, epicatechin,
oleuropein
Chlorogenic acid and its
quinone derivative

Starch-based
model

Zhu, Cai, Ke, and Corke

(2011)

Cheng et al. (2010)

Budryn et al. (2013)

; Refers to acrylamide decrease.

" Refers to acrylamide increase.

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that there was more than one reaction between polyphenols and
reactant.
Compared to plant extracts, pure compounds may lead to a
more complex trend depending on the concentration. The study
conducted by Bassama, Brat, Bohuon, Boulanger, and Gnata
(2010) demonstrated that the addition of caffeic acid in the asparagine/glucose model system at the concentrations from 2.5 mM to
10 mM led to the uctuations of acrylamide content. The addition
of caffeic acid at 5 mM and 10 mM did no inhibit the acrylamide
formation, while 14% and 17% acrylamide increase were found
when the addition levels increased to 2.5 mM and 7.5 mM resulted,
respectively. Likewise, apple proanthocyanidins were efcient to
reduce the acrylamide content in fried potato crisps at the concentration of 0.50% as well. However, the acrylamide content at the
concentration of 0.25% and 1.00% was higher than that at the
concentration of 0.50% (Cheng, Shi, Ou, Wang, & Jiang, 2010).

capacity was not the unique factor to inuence the acrylamide

formation.
4. Possible mechanisms of plant polyphenols on acrylamide
formation and mitigation
Plant polyphenols represent a large group sharing at least one
aromatic hydrocarbon ring with more than one hydroxyl group
attached, all of which can resist oxidation by scavenging of free
radicals. In addition to the common antioxidative feature, some
polyphenols with their own special structures, such as o-diphenols
group and diunsaturated carbonyl group, are involved into acrylamide formation and elimination, which leads to discordant
effects of polyphenols on the acrylamide formation (Visioli, 2012).
4.1. Trapping of carbonyl compounds

3.4. Antioxidant capacity

Plant polyphenols are antioxidant because they scavenge free
radicals. The antioxidant capacity of polyphenols depends on the
number and position of their hydroxyl substituent and structure
of aromatic nucleus. Indeed, the hydrogen atom of the polyphenolic OH can combine with free radicals and will terminate the
propagation of free radical chain reactions. The more hydroxyl
group polyphenols occupy, the stronger antioxidant capacity they
have (Bassama et al., 2010). However, the relevance between
antioxidant capacity and inhibitory effects is still unclear.
Cheng et al. (2015) indicated that there was a strong positive
correlation between antioxidant capacity and inhibition ratio of
acrylamide. Articial neural network (ANN) model and multiple
linear regression (MLR) model were established for predicting
the acrylamide reduction based on antioxidant capacity. Results
showed that the inhibition rate of acrylamide formation correlated
well with the change of trolox equivalent antioxidant capacity.
Both ANN model and MLR model could predict the reduction of
acrylamide inuenced by the addition of avonoids.
Some other researches demonstrated that the relationships
between reduction rate of acrylamide and antioxidant capacity of
plant extracts were a bit different from pure compounds. In previous research of Kotsiou et al. (2010), the antioxidant capacity
before heating treatment and inhibition rates of oregano and
VOO were evaluated in the model potato starch system. With the
addition of oregano extract, the increase of antioxidant capacity
and the decline of acrylamide content were observed. Whereas,
adding VOO extract led to the increase of both antioxidant capacity
and acrylamide content. This research conrmed that antioxidant

Flavonoids represent the most widely distributed group, which

can be divided into subclasses, including avonols, avanones,
chalcones and so on (Fig. 2). Some of avonoids were very efcient
trapping agents of reactive carbonyl and dicarbonyl species.
Epicatechin was reported to react directly with C2, C3 and C4
sugar fragments including glyoxal, methylglyoxal, acetol and erythrose in aqueous glycine/glucose Maillard reaction model system
(Totlani & Peterson, 2006). The mechanism they revealed was that
epicatechin could form covalent bonds with reactive carbonyls via
electrophilic aromatic substitution reactions at the C-6 and C-8
position of A-ring.
Naringenin could inhibit the formation of acrylamide signicantly by up to 50% in the asparagine/glucose model system heated
at 128 C from 60 to 180 min as well (Cheng et al., 2009). The possible mechanism was proposed that C-6 and C-8 of the A-ring in
naringenin were the active sites bonding with aldehyde groups
in 3-oxopropanamide. The depletion of 3-oxopropanamide
reduced the conversion from decarboxylated Schiff base to
3-APA, thus lowered the acrylamide formation rate.
Phloretin and phloridzin, extracted from apple, were also tested
to inhibit the yield of acrylamide under physiological conditions as
trapping agents of reactive dicarbonyl species, such as methylglyoxal and glyoxal (Shao et al., 2008). The liquid chromatography
coupled with tandem mass spectrometry (LC/MS) and nuclear
magnetic resonance (NMR) data showed that the key active sites
located the C-3 or C-5 of A-ring. According to the researches above,
it was proved that the type of o-diphenols might be effective to
reduce acrylamide formation. A-ring was considered more reactive
than B-ring, due to the orthopara activitation resulting from a
hydroxy group on benzene.

Fig. 2. (i) Structure of epicatechin belonging to avanols; (ii) structure of naringenin belonging to avanones; (iii) structure of phloretin belonging to chalcones.

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4.2. Preventing against lipid oxidation

Lipid oxidation is important to the formation of acrylamide in
lipid-rich food, such as the French fries. It is well-known that a
large amount of acrolein can be produced from deeply heating oils,
especially the linoleic acid and linolenic acid. Then acrolein can be
oxidized into acrylic acid and then reacts with ammonia to
produce acrylamide (Yasuhara et al., 2003b). In addition, methyl
linoleate, an un-oxidized lipid could be oxidized by the free radicals into the a, b, c, d-diunsaturated carbonyl compounds in the
presence of glucose, which also could involve in carbonyl-asparagine reactions in competition with carbohydrates (Zamora &
Hidalgo, 2008). It was proposed that polyphenols could react with
lipid radicals to form phenoxyl radicals, which were stabilized by
delocalization of unpaired electrons around the aromatic ring
(Tichonov, Roginsky, & Pliss, 2010). Thus, polyphenols could serve
as chain-breaking antioxidant and prevent against the lipid
oxidation.
It was found that 11 plant extracts could extend oxidative stability of sunower oil and soybean oil and retard the primary
and secondary oxidation products, while signicant differences
were observed under disparate condition and plants (Anwar,
Jamil, Iqbal, & Sheikh, 2006). VOO phenolic compounds were also
tested to prevent the lipid oxidant (Napolitano, Morales, Sacchi,
& Fogliano, 2008). The results showed that the concentration of
acrylamide formed in fried potato slices was related to the concentration of phenol compounds. Furthermore, the ortho-diphenolic
compounds were the most efcient inhibitors to acrylamide formation. Oleuropein, another main polyphenolic compound, proved
to scavenge free radicals by the structure of CH at C-3 position,
instead of the phenolic OH sites.
4.3. Providing carbonyl groups for acrylamide formation
Silymarin and curcumin, the plant polyphenols with carbonyl
groups were investigated in the binary and ternary model systems
of asparagine/polyphenol and asparagine/polyphenol/fructose
model system (Hamzalioglu & Gkmen, 2012; Hamzalioglu et al.,
2013). The results in the binary model system showed that both
silymarin and curcumin could convert asparagine into acrylamide
at conversion ratios of 0.57% and 0.59% respectively in 20 min.
Though the reaction rate was lower than that in asparagine and
fructose system, the acrylamide formation process was some
threefold longer. In the ternary model system, silymarin and curcumin presented a promotional effect on acrylamide formation,
which proved that carbonyl groups adducting asparagine, instead
of mitigating acrylamide formation, was the main reaction
silymarin and curcumin took part in. The mechanism of acrylamide
formation in curcumin-asparagine model system was that the
carbonyl group of curcumin reacted with a-amine group of asparagine, yielding the corresponding Schiff base, which was decarboxylated and then led to the formation of acrylamide. Further
studies demonstrated that the melting point of carbonyl compounds was related to conversion ratio under low moisture
conditions.
4.4. Inhibiting the acrylamide elimination
The content of acrylamide is a dynamic consequence of acrylamide formation and elimination. Signicant decline can be found
in many researches after a long-term thermal treatment, which
means the elimination rate is higher than the formation rate in
the nal stage. The polymerization of acrylamide induced by
oxidative radicals is a possible pathway to elimination. In previous
research (Hedegaard et al., 2007), high peroxide value emulsion
and low peroxide value emulsion model systems were established

respectively. After being heated at 180 C for 60 min, 38% of spiked

acrylamide was detected in high peroxide value oil, which was
lower than that in low peroxide value oil. It was proposed that a
reaction via peroxy radicals of acrylamide with double bonds of
rapeseed triglycerides was happening in the system. It was also
found that acrylamide decreased faster in aqueous system under
nitrogen than that in air condition by the study of Hidalgo,
Delgado, and Zamora (2010). The author thought that it was a consequence of radical reactions, for the amount of absent acrylamide
reduced after the addition of gallic acid, even in the presence of air.
Plant polyphenols are considered as a type of antioxidant conferred by the phenolic hydroxyl groups attached to ring structure.
Gallic acid was proved to inhibit the acrylamide elimination by
scavenging free radicals, which was a new explanation for some
polyphenols increasing the amount of acrylamide.
4.5. Accelerating the conversion from 3-APA to acrylamide
3-APA can be transformed to acrylamide directly after deamination. It was observed that 3-APA solution with chlorogenic acid
produced more acrylamide compared to that in the control group
without chlorogenic acid at 160 C and pH value of 6.8 (Cai et al.,
2014). By determining the reaction rate at different temperatures,
activation energy for acrylamide formation from 3-APA was gured out, which was lowered by chlorogenic acid from
173.2 kJ/mol to 136.6 kJ/mol. Moreover, some compounds with
odd numbers of molecular weight were detected by electrospray
ionization-mass spectrometry (ESI-MS), which might contain one
nitrogen atom. Though they have not been obtained due to their
low concentration, these compounds might be adducts of 3-APA
and chlorogenic acid and its fragments. It was thought that phenol
hydroxy group in chlorogenic acid played a signicant role in the
conversion from 3-APA to acrylamide.
5. Conclusion and outlook
Plant polyphenols, one part of phytochemicals, have attracted a
great deal of attention for its natural antioxidative feature. After
the nding of acrylamide in food, plant polyphenols were applied
to inhibit acrylamide formation. However, the results were confusing, which depended on the structure, concentrations, and antioxidant capacity of the polyphenols, as well as reaction conditions. In
other words, besides the antioxidant capacity, some other mechanisms were involved in.
Some mechanisms have been proved to take part in the reaction, including trapping carbonyl compounds, preventing against
lipid oxidation, providing carbonyl groups for acrylamide formation, inhibiting the acrylamide elimination and accelerating the
conversion from 3-APA to acrylamide. Whereas, some other
mechanisms are likely related to acrylamide formation. There have
not been enough evidences to support the hypothesis yet. For
example, melanoidins, the end products of Maillard reaction, have
strong antioxidant activities to scavenge free radicals. Whether
free radicals generated from the degradation of glucose served as
reactive intermediates in the Maillard reaction and what the role
plant polyphenols play are still needed to investigate.
Fig. 3 summarizes the possible pathways to affect the acrylamide formation and elimination mentioned above. Some
polyphenols can trap the carbonyl compounds [marked as (1)] or
3-oxopropanamide [marked as (2)] to mitigate acrylamide formation, while some other polyphenols may provide carbonyl groups
[marked as (3)] to participate in the Maillard reaction. Plant
polyphenols can prevent against lipid oxidation and limit the oxidized lipids [marked as (4)] or acrylic acid [marked as (5)] by their
antioxidant capacity. 3-APA is a major precursor during the

Please cite this article in press as: Liu, Y., et al. Role of plant polyphenols in acrylamide formation and elimination. Food Chemistry (2015), http://dx.doi.org/
10.1016/j.foodchem.2015.03.122

Y. Liu et al. / Food Chemistry xxx (2015) xxxxxx

Fig. 3. Possible reactions polyphenols might be involved in [marked as (1)(7)]. Arrows pointing to polyphenols mean the reactions steps increase acrylamide formation;
arrows pointing to intermediates mean the reaction steps reduce acrylamide formation.

reaction, and the activation energy of conversion from 3-APA to

acrylamide can be lowered by some polyphenols [marked as (6)].
After forming, acrylamide can be polymerized by free radicals. In
the presence of polyphenols, acrylamide elimination is blocked
[marked as (7)].
Further study should focus on the following points. Firstly,
building up the stable reaction systems in which the data is able
to be compared among different researches. Thus, it is more efcient to analyze the trend and change inuenced by plant polyphenols with big data. Secondly, the valid and economical plant
polyphenols should be applied into food industry to reduce the
acrylamide content in food. Thirdly, deeper investigating on
mechanisms concerning on plant polyphenols should be operated
continuously for many phenomena are still confusing. For example,
how the concentration of plant polyphenols and antioxidant capacity inuence the acrylamide formation and elimination is unclear
so far.
Conict of interest
The authors declare that there are no conicts of interest.
Acknowledgements
We gratefully acknowledge the nancial support from the
National Basic Research Program of China (973 Program, No.
2012CB720805), the National Natural Science Foundation of
China (No. 31222044, 31471666).
.
References
Aar, O. C., & Gkmen, V. (2009). Investigation of acrylamide formation on bakery
products using a crust-like model. Molecular Nutrition & Food Research, 53,
15211525.
Anwar, B. F., Jamil, A., Iqbal, S., & Sheikh, M. A. (2006). Antioxidant activity of various
plant extracts under ambient and accelerated storage of sunower oil. Grasas y
Aceites, 57, 189197.
Arribas-Lorenzo, G., & Morales, F. J. (2010). Analysis, distribution, and dietary
exposure of glyoxal and methylglyoxal in cookies and their relationship with
other heat-induced contaminants. Journal of Agricultural and Food Chemistry, 58,
29662972.

Bassama, J., Brat, P., Bohuon, P., Boulanger, R., & Gnata, Z. (2010). Study of
acrylamide mitigation in model system: Effect of pure phenolic compounds.
Food Chemistry, 123, 558562.
_ zelewicz,
_
Budryn, G., Zy
D., Nebesny, E., Oracz, J., & Krysiak, W. (2013). Inuence of
addition of green tea and green coffee extracts on the properties of ne yeast
pastry fried products. Food Research International, 50, 149160.
Cai, Y., Zhang, Z., Jiang, S., Yu, M., Huang, C., Qiu, R., et al. (2014). Chlorogenic acid
increased acrylamide formation through promotion of HMF formation and 3aminopropionamide deamination. Journal of Hazardous Materials, 268, 15.
Cheng, J., Chen, X., Zhao, S., & Zhang, Y. (2015). Antioxidant-capacity-based models
for the prediction of acrylamide reduction by avonoids. Food Chemistry, 168,
9099.
Cheng, K., Shi, J., Ou, S., Wang, M., & Jiang, Y. (2010). Effects of fruit extracts on the
formation of acrylamide in model reactions and fried potato crisps. Journal of
Agricultural and Food Chemistry, 58, 309312.
Cheng, K., Zeng, X., Tang, Y. S., Wu, J., Liu, Z., Sze, K., et al. (2009). Inhibitory
mechanism of naringenin against carcinogenic acrylamide formation and
nonenzymatic browning in Maillard model reactions. Chemical Research in
Toxicology, 22, 14831489.
Ciesarov, Z., Suhaj, M., & Horvthov, J. (2008). Correlation between acrylamide
contents and antioxidant capacities of spice extracts in a model potato matrix.
Journal of Food and Nutrition Research, 47, 15.
Fernndez, S., Kurppa, L., & Hyvnen, L. (2003). Content of acrylamide decreased in
potato chips with addition of a proprietary avonoid spice mix (Flavomare) in
frying. Innovations in Food Technology, 18, 2426.
Hamzaloglu, A., & Gkmen, V. (2012). Role of bioactive carbonyl compounds on the
conversion of asparagine into acrylamide during heating. European Food
Research and Technology, 235, 10931099.
Hamzaloglu, A., Mogol, B. a., Lumaga, R. B., Fogliano, V., & Gkmen, V. (2013). Role
of curcumin in the conversion of asparagine into acrylamide during heating.
Amino Acids, 44, 14191426.
Hedegaard, R. V., Granby, K., Frandsen, H., Thygesen, J., & Skibsted, L. H. (2007).
Acrylamide in bread. Effect of prooxidants and antioxidants. European Food
Research and Technology, 227, 519525.
Hidalgo, F. J., Delgado, R. M., & Zamora, R. (2010). Role of mercaptans on acrylamide
elimination. Food Chemistry, 122, 596601.
Jin, C., Wu, X., & Zhang, Y. (2013). Relationship between antioxidants and
acrylamide formation: A review. Food Research International, 51, 611620.
Kotsiou, K., Tasioula-Margari, M., Capuano, E., & Fogliano, V. (2011). Effect of
standard phenolic compounds and olive oil phenolic extracts on acrylamide
formation in an emulsion system. Food Chemistry, 124, 242247.
Kotsiou, K., Tasioula-Margari, M., Kukurov, K., & Ciesarov, Z. (2010). Impact of
oregano and virgin olive oil phenolic compounds on acrylamide content in a
model system and fresh potatoes. Food Chemistry, 123, 11491155.
Li, D., Chen, Y., Zhang, Y., Lu, B., Jin, C., Wu, X., et al. (2012). Study on mitigation of
acrylamide formation in cookies by 5 antioxidants. Journal of Food Science, 77,
C1144C1149.
Morales, G., Jimenez, M., Garcia, O., Mendoza, M. R., & Beristain, C. I. (2014). Effect of
natural extracts on the formation of acrylamide in fried potatoes. LWT Food
Science and Technology, 58, 587593.
Napolitano, A., Morales, F., Sacchi, R., & Fogliano, V. (2008). Relationship between
virgin olive oil phenolic compounds and acrylamide formation in fried crisps.
Journal of Agricultural and Food Chemistry, 56, 20342040.

Please cite this article in press as: Liu, Y., et al. Role of plant polyphenols in acrylamide formation and elimination. Food Chemistry (2015), http://dx.doi.org/
10.1016/j.foodchem.2015.03.122

Y. Liu et al. / Food Chemistry xxx (2015) xxxxxx

Oral, R. A., Dogan, M., & Sarioglu, K. (2014). Effects of certain polyphenols and
extracts on furans and acrylamide formation in model system, and total furans
during storage. Food Chemistry, 142, 423429.
Perez, L. C., & Yaylayan, V. A. (2008). Further insight into thermally and pH-induced
generation of acrylamide from glucose/asparagine model systems. Journal of
Agricultural and Food Chemistry, 56, 60696074.
Shao, X., Bai, N., He, K., Ho, C., Yang, C. S., & Sang, S. (2008). Apple polyphenols,
phloretin and phloridzin: New trapping agents of reactive dicarbonyl species.
Chemical Research in Toxicology, 21, 20422050.
Stadler, R. H., Blank, I., Varga, N., Robert, F., Hau, J., Guy, P. A., et al. (2002).
Acrylamide from Maillard reaction products. Nature, 419, 449450.
Tichonov, I., Roginsky, V., & Pliss, E. (2010). Natural polyphenols as chain-breaking
antioxidants during methyl linoleate peroxidation. European Journal of Lipid
Science and Technology, 112, 887893.
Totlani, V. M., & Peterson, D. G. (2006). Epicatechin carbonyl-trapping reactions in
aqueous Maillard systems: Identication and structural elucidation. Journal of
Agricultural and Food Chemistry, 54, 73117318.
Urbancic, S., Kolar, M. H., Dimitrijevic, D., Demar, L., & Vidrih, R. (2014).
Stabilisation of sunower oil and reduction of acrylamide formation of potato
with rosemary extract during deep-fat frying. Food Science and Technology, 57,
671678.
Vinci, R. M., Mestdagh, F., & Meulenaer, B. D. (2012). Acrylamide formation in fried
potato products Present and future, a critical review on mitigation strategies.
Food Chemistry, 133, 11381154.
Visioli, F. (2012). Olive oil phenolics: Where do we stand? Where should we go?
Journal of the Science of Food and Agriculture, 92, 20172019.
Yasuhara, A., Tanaka, Y., Hengel, M., & Shibamoto, T. (2003). Gas chromatographic
investigation of acrylamide formation in browning model systems. Journal of
Agricultural and Food Chemistry, 5, 39994003.

Yaylayan, V. A., Wnorowski, A., & Locas, C. P. (2003). Why asparagine needs
carbohydrates to generate acrylamide. Journal of Agricultural and Food
Chemistry, 51, 17531757.
Yuan, Y., Zhao, G., Chen, F., Liu, J., Wu, J., & Hu, X. (2008). Correlation of
methylglyoxal with acrylamide formation in fructose/asparagine Maillard
reaction model system. Food Chemistry, 108, 885990.
Zamora, R., Delgado, R. M., & Hidalgo, F. J. (2009). Conversion of 3aminopropionamide and 3-alkylaminopropionamides into acrylamide in
model systems. Molecular Nutrition & Food Research, 53, 15121520.
Zamora, R., & Hidalgo, F. J. (2008). Contribution of lipid oxidation products to
acrylamide formation in model systems. Journal of Agricultural and Food
Chemistry, 58, 60756080.
Zhang, Y., Xu, W., Wu, X., Zhang, X., & Zhang, Y. (2007). Addition of antioxidant from
bamboo leaves as an effective way to reduce the formation of acrylamide in
fried chicken wings. Food Additives & Contaminants, 24, 242251.
Zhang, Y., Ying, T., & Zhang, Y. (2008). Reduction of acrylamide and its kinetics by
addition of antioxidant of bamboo leaves (AOB) and extract of green tea (EGT)
in asparagine-glucose microwave heating system. Journal of Food Science, 73,
C60C66.
Zhu, F., Cai, Y.-Z., Ke, J., & Corke, H. (2009). Evaluation of the effect of plant extracts
and phenolic compounds on reduction of acrylamide in an asparagine/glucose
model system by RP-HPLC-DAD. Journal of the Science of Food and Agriculture, 89,
16741681.
Zhu, F., Cai, Y. Z., Ke, J., & Corke, H. (2011). Dietary plant materials reduce acrylamide
formation in cookie and starch-based model systems. Journal of the Science of
Food and Agriculture, 91, 24772483.
Zyzak, D. V., Sanders, R. A., Stojanovic, M., Tallmadge, D. H., Eberhart, B. L., Ewald, D.
K., et al. (2003). Acrylamide formation mechanism in heated foods. Journal of
Agricultural and Food Chemistry, 51, 47824787.

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