Eur Food Res Technol (2008) 227:519–525
DOI 10.1007/s00217-007-0750-5
ORIGINAL PAPER
Acrylamide in bread. EVect of prooxidants and antioxidants
Rikke Vingborg Hedegaard · Kit Granby ·
Henrik Frandsen · Jonas Thygesen · Leif H. Skibsted
Received: 23 April 2007 / Revised: 22 August 2007 / Accepted: 30 August 2007 / Published online: 26 September 2007
© Springer-Verlag 2007
Abstract Addition of 1% aqueous rosemary extract with
approximately 40 mg of gallic acid equivalents or compara-
ble addition of rosemary oil or of dried rosemary leaves to
wheat dough reduced the content of acrylamide in wheat
buns by 62, 67 and 57%, respectively, compared to wheat
buns without rosemary. Increasing the addition of aqueous
rosemary extract to 10% did not decrease the acrylamide
content further compared to the addition of a 1% extract.
The spice dittany showed less eVect in wheat buns com-
pared to rosemary and even increased acrylamide formation
slightly. The eVect of antioxidants on acrylamide formation
was conWrmed by addition of 1.0 mM (but not 0.1 mM) of
the green tea Xavonoids epicatechin or epigallocatechin
gallate to an aqueous food model. Free radicals were
detected by ESR using the spin trap
-(4-Pyridyl 1-oxide)-
N-tert-butylnitrone (POBN) in an aqueous model system of
0.060 M glucose and 0.060 M asparagine heated under con-
ditions generating acrylamide, further conWrming the
impact of free radical intermediates in formation of acryl-
amide. A modest eVect of the peroxides in oxidized oil on
acrylamide elimination was observed pointing towards an
oxidative induced polymerization of acrylamide. The
impact of oxidative processes on acrylamide elimination
should not be neglected, since oxidized vegetable oil seems
to promote degradation of acrylamide.
R. V. Hedegaard · J. Thygesen · L. H. Skibsted (&)
Food Chemistry, Department of Food Science,
Faculty of Life Science, University of Copenhagen,
Rolighedsvej 30, 1958 Frederiksberg C, Denmark
e-mail: ls@life.ku.dk
K. Granby · H. Frandsen
National Food Institute, Technical University of Denmark,
Mørkhøj Bygade 19, 2860 Søborg, Denmark
Keywords Acrylamide · Wheat bread · Rosemary ·
Green tea Xavonoids · Degradation
Introduction
The neurotoxic and carcinogenic compound acrylamide
found in heat-processed food is mainly formed from aspar-
agine and a reducing sugar through Maillard reactions,
which also generate compounds responsible for the brown
color and important Xavor components of heated food [1–
3]. Several factors, such as the initial concentration of the
precursors, their ratio, heating temperature, time of process-
ing, pH and water activity of product, have been found to
inXuence the content of acrylamide in heat-processed foods
[4].
The eVect of various additives on the content of acrylam-
ide in food has been examined in order to develop strategies
for minimizing the amount of acrylamide in food. A possi-
ble coupling with oxidative processes in food has led to
investigation of eVects of antioxidants on acrylamide for-
mation in foods [5–8]. Antioxidants such as the lipophilic
ascorbyl palmitate and the hydrophilic sodium ascorbate
were found to have no eVect or even a slightly promoting
eVect on formation of acrylamide in a potato model [6] and
butylated hydroxytoluene (BHT), sesamol and vitamin E
led to an increase in the content of acrylamide in lean meat,
with BHT having the largest eVect [7]. Vattem and Shetty
[8] used antioxidants from cranberry and oregano in fried
potato slices and found no eVect of these phenolic antioxi-
dants except for cranberry, which lowered the content of
acrylamide in deep-fried potato slices, and concluded that
formation of acrylamide in this product was the result of
non-oxidative processes. However, rosemary was found to
lower the formation of acrylamide up to 25% [5] in
123
520
commercial potato chips processed with olive oil and rose-
mary herb. Furthermore, green tea Xavonoids were recently
found to hamper Maillard reactions in UHT milk [9]. In
concentrations of 0.1 and 1.0 mM both epicatechin and epi-
gallocatechin gallate reduced formation of Xuorescent
Maillard reaction product following UHT treatment. Epi-
catechin and epigallocatechin gallate are known to be anti-
oxidants, but epicatechin has recently been also been
proposed to add to carbonyl compounds formed in Maillard
reactions [10]. The reactants to yield acrylamide in food
may be reducing sugars or be fragments of glucose and
fructose generated as intermediates in the Maillard reac-
tions [11, 12]. However, an alternative to the proposed
mechanism involving addition of reactive sugar fragments
to the conjugate system of polyphenols is a mechanism in
which the polyphenols scavenge free radical fragments of
sugars otherwise being intermediates in a reaction sequence
leading to acrylamide.
The aim of the present study was to evaluate the eVect of
antioxidants on the content of acrylamide in wheat bread as
a heated food product often spiced with herbs. Aqueous
extracts of the two spices rosemary (Rosmarinus oYcinalis
L.) and dittany (Origanus dictamnus L.) with known anti-
oxidative properties were used to determine the eVect of
antioxidants on the formation of acrylamide [13–15]. In
addition, the eVects of the green tea Xavonoids epicatechin
and epigallocatechin gallate on the formation of acrylamide
in an aqueous model system of asparagine and glucose
were also investigated as examples of well-deWned poly-
phenols for which radical scavenging kinetics and rate con-
stants are known [16, 17]. As an example of a prooxidant,
rapeseed oil with a high peroxide value was also investi-
gated in order to explore a possible role of prooxidants in
acrylamide formation and elimination. Moreover, we have
included ESR spectroscopy in order to clarify whether free
radicals are formed in aqueous glucose/asparagine systems
during heating under conditions where acrylamide is
known to be generated.
Materials and methods
Rosemary leaves from the rosemary plants produced by
Christen Olsen (Thorslunde, Denmark) obtained through
COOP (Albertslund, Denmark) were separated from the
plants and dried at 40 °C for 65 h and ground in a mortar.
Dried dittany leaves were bought locally at the farmers
market in Chania (Crete, Greece), kept frozen until used,
and ground in a mortar. Bakers yeast from De Danske
Spritfabrikker A/S, (Copenhagen, Denmark) and wheat
Xour from Amo (Vejle, Denmark) and rapeseed oil from
COOP (Albertslund, Denmark) were of standard food grade.
Water puriWed on a MilliQ puriWcation train (Millipore,
123
Eur Food Res Technol (2008) 227:519–525
Waters, France) was used throughout. Neat rosemary oil of
0.9064 density and sodium chloride, D-glucose, L-aspara-
gine, Tween 20, 2-morpholinoethanesulfonic acid monohy-
drate (MES), sodium cacodylate trihydrate, epicatechin,
epigallocatechin gallate,
-(4-pyridyl-1-oxide)-N-tert-
butylnitrone (POBN) and acrylamide all of analytical grade
were from Sigma-Aldrich (Steinheim, Germany).
Aqueous extracts of rosemary and dittany
Rosemary and dittany were extracted with water. Water
(10 mL) and the coarsely crushed leaves (0.50 g) were
homogenized in an Ultra Turrax mixer (T25, Jahnke &
Kunkel, Staufen, Germany) (13,500 rpm, 1 min). After
rinsing the knives of the homogenizer with 3 mL liquid and
centrifugation (2,300g, 10 min), the supernatant was
removed and the residue resuspended in 7 mL liquid. The
suspension was placed in darkness under stirring for
10 min. After repeated centrifugation (2,300g, 10 min) and
combination of supernatants (corresponding to a Wnal
amount of 25 mg spice/mL solvent), the extract was Wltered
to yield a clear extract. The extracts were Xushed with
nitrogen and stored at ¡18 °C until used.
Wheat buns
Buns of wheat Xour were prepared from a traditional recipe
containing 89.4 g wheat Xour, 3.1 g yeast, 62.5 g water and
1.0 g sodium chloride. Aqueous dittany extract (25 mg
spice/mL solvent), aqueous rosemary extract (25 mg spice/
mL solvent), rosemary leaves or rosemary oil were added
to the dough, for rosemary leaves according to a standard
recipe (2 tablespoons dried spice/kg Xour), and for the spice
extract at two levels (1 and 10% of the dough partly replac-
ing the water). The ingredients were mixed and kneaded,
and left to rise for 40 min. The dough was kneaded again
and buns formed, which were left to rise for another
20 min. The buns were baked in an oven for 20 min at
225 °C.
Food model system with epicatechin
and epigallocatechin gallate
A food model system was prepared by mixing glucose and
asparagine to yield a concentration of 0.060 M for each
reactant in aqueous cacodylate buVer (0.040 M) with ionic
strength (0.16) and pH 7.0 together with epicatechin or epi-
gallocatechin gallate in a concentration of 0.10 or 1.0 mM.
Three millilitre samples of the solution were heated in
sealed preparation Duran glass from VWR (Rødovre, Den-
mark) at 160 °C for 30 min in a thermostated oven and
immediately cooled in ice and stored in a freezer until
analysis.
Eur Food Res Technol (2008) 227:519–525
Model system with acrylamide
A model system was prepared with 3,500 ppb acrylamide
in aqueous phosphate buVer (0.040 M) with pH 7.0 and
heated in sealed Duran preparation glass at 180 °C for up to
60 min in a thermostated oven and immediately cooled in
ice and stored in freezer until analysis.
Emulsions with acrylamide
Acrylamide to yield a concentration of 500 mg/L was dis-
solved in an aqueous cacodylate buVer (0.040 M) with pH
7.0 from which an o/w emulsion with rapeseed oil stripped
of chlorophyll and antioxidants were prepared by the
method described by Fuster et al. [18]. The emulsions were
prepared by mixing 15.0 g oil, 8.0 g Tween 20 and aqueous
500 mg/L acrylamide solution to yield 100 mL and homog-
enized by an Ultra Turax mixer followed by homogeniza-
tion by a EmulsiFlex-05 Homogenizer from Avestin
(Ottawa, Canada). Control emulsions without acrylamide
were also prepared in a similar way. Both newly stripped
oil and oxidized oil were used for the emulsion, and the
oxidized oil was prepared by heating stripped oil in an oven
for 20 h at 50 °C. The degree of oxidation was determined
as the peroxide value [19]. The newly stripped rapeseed oil
had a peroxide value of 1.1 § 0.3 meq/kg oil and the heated
oil a peroxide value of 14.1 § 0.8 meq/kg oil. Samples
were made in triplicates and were heated in sealed Duran
preparation glass in a thermostated oven at 180°°C for
30 min, and immediately cooled in ice before analysis for
acrylamide content by LC-MS/MS.
Detection of free radicals by ESR
A model system was prepared by dissolving glucose and
asparagine to yield 0.060 M glucose or 0.060 M asparagine
or a mixture of 0.060 M glucose and 0.060 M asparagine in
Mes buVer (0.040 M) with pH 7.0. To each solution was
added
-(4-pyridyl 1-oxide)-N-tert-butylnitrone (POBN) to
yield a concentration of 0.0050 M, and 3 mL sample of
each solution were heated in sealed headspace vials at
120°°C for 120 min and cooled in ice before analysis. The
samples were transferred to an ESR Xow cell for measure-
ment of aqueous solutions from Wilmad (Buena, USA). A
JES-FR30 ESR-spectrometer from JEOL Ltd. (Tokyo,
Japan) was used operating in X-band mode. The following
parameters were used in all ESR experiments: microwave
power, 4 mW; sweep width 7.5 mT; sweep time 4 min;
modulation width 0.1 mT; time constant 0.3 s. The relative
signal intensity was calculated using an internal manganese
standard by measuring the peak-to-peak amplitude of the
Wrst line of the middle tops in the spectrum. Each measure-
ment was made in duplicate on two separate samples.
521
Analysis of acrylamide by LC-MS/MS
The samples were prepared for the LC-MS/MS analysis
according to the procedure previously described [4]. The
content of the acrylamide was measured in the puriWed
extracts by LC-MS/MS according to the procedure
described by Granby and Fagt [20] and the acrylamide con-
tent was quantiWed relative to the internal D3-acrylamide
standard as the [M + H]+ = 73 peak in the positive mode
mass spectrum. The identity of acrylamide was conWrmed
by the daughter ion of m/z 55 [M ¡ H–NH3]+. The methods
were optimized to detect low concentrations (e.g. by
increasing the HPLC injection volume and by optimizing
the MS performance before analysing the bread samples),
so the method was able to quantify down to 5
g kg¡1. The
laboratory where the analysis were done has participated in
proWciency tests for acrylamide in food and all results
obtained have been with satisfactory test scores, including
the results obtained in recently held EU validation study on
acrylamide analyses in food with 22 samples (11 matrices
including bread and toasted bread: assigned value
38
g kg¡1, obtained results 41 and 44
g kg¡1) [21].
Results and discussion
The inXuence of antioxidants on the formation of acrylam-
ide during heat processing of food was examined in wheat
buns by addition of the spices rosemary and dittany to the
dough prior to baking. Both rosemary and dittany are
known to have antioxidative properties and are used in
many types of food [13]. The content of acrylamide was
reduced in the wheat buns by addition of rosemary either
when rosemary was added as an aqueous extract, as rose-
mary oil or dried leaves. The addition of 1% rosemary
extract (leaves extracted with water and containing approx-
imately 40 mg of gallic acid equivalents [13]), of the corre-
sponding amounts of rosemary oil or rosemary leaves
reduced acrylamide content by 62, 67 and 57 %, respec-
tively, in the wheat buns, compared to wheat buns prepared
without rosemary. Increasing the addition of aqueous rose-
mary extract to 10% did not decrease the acrylamide con-
tent further (Fig. 1), and for the rosemary oil and leaves a
similar increase in addition was likewise not found to
decrease the content of acrylamide signiWcantly compared
to the addition of a 1% extract (results not shown). It may
accordingly be concluded that even a small amount of rose-
mary reduces the content of acrylamide in wheat buns sig-
niWcantly. The water extract of dittany showed less eVect
on formation of acrylamide in wheat buns than rosemary
(Fig. 2) and even increased acrylamide formation slightly
(35%). The wheat buns without spices showed some day-
to-day variation in the acrylamide content probably due to
123
522 Eur Food Res Technol (2008) 227:519–525

25 frying process. The antioxidants used in the present study

were incorporated into the food matrix and accordingly
more readily available for reaction with the Maillard reac-
20
tions products formed in the product. In conclusion, diVer-
ent spices with documented antioxidative eVect in
Acrylamide (ppb)

15 processed foods and speciWc antioxidants may have diVer-

ent eVect on acrylamide formation and the way of applying
10 the antioxidant in the product seems also important for the
eVect of antioxidants on the content of acrylamide. The
large reduction in the content of acrylamide seen even for
5
the lowest addition of rosemary to wheat buns is, however,
promising, since the protection may be obtained with low
0 concentrations, which do not aVect the sensory quality of
0% extract 1% extract 10% extract the bread negatively.
Amount rosemary extract in the dough Flavoniods are known to have antioxidative properties
Fig. 1 The content of acrylamide in wheat buns (n = 2) following [16, 17] and the green tea Xavonoids epicatechin and epi-
addition of 0, 1 and 10% water extract of rosemary to the dough gallocatechin gallate were recently found to hamper the
Maillard reactions in UHT milk [9]. Both 1.0 mM epicate-
chin and 1.0 mM epigallocatechin gallate were also found
20
to decrease the content of acrylamide in aqueous cacodylate
buVer (0.040 M and pH 7.0) solutions of glucose and aspar-
agine, whereas the lower concentration of 0.1 mM did not
15 reduce the content of acrylamide (Fig. 3). The eVect of epi-
Acrylamide (ppb)

catechin and epigallocatechin gallate on the Maillard reac-

tions has previously been suggested to be due to a carbonyl
10 trapping capacity of the compounds. Epicatechin under
aqueous conditions was reported to form adduct reaction
products with C2, C3, and C4 sugar fragments [22] in a glu-
5
cose–glycine model system. Furthermore, under low mois-
ture conditions corresponding to roasting, epicatechin was
0 found to form adducts primarily with C6 sugar moieties, i.e.
0% extract 1% extract 10% extract 3-deoxyglucosone [23]. Notably, the eVect observed for
Amount of dittany to the dough rosemary on formation of acrylamide may be explained by
Fig. 2 The content of acrylamide in wheat buns (n = 2) following the same type of mechanism, since rosemary contains
addition of 0, 1 and 10% water extract of dittany to the dough compounds, which also may trap carbonyl compounds by a

5000

small Xuctuations in the heating proWle of the oven. This

explains the rather large standard deviation on the acrylam- 4000
Acrylamide (ppb)

ide content of the reference, which was prepared on diVer-

ent days. Dittany belongs to the Labiatae family like
3000
rosemary and its water extract has total phenol content
comparable to rosemary, but does not contain the phenolic
acids with catechol structure typical for rosemary and could 2000

be prooxidant under some conditions as most spices. Vat-

tem and Shetty [8] have investigated the eVect of phenolic
antioxidants in fried and deep fried potato slides but found
no eVect of oregano (Origanum vulgare) on the content of
acrylamide, whereas cranberry decreased the content of
acrylamide, but only in the deep-fried potatoes. However,
the antioxidants were applied by dipping the potato slides
in aqueous solution and the antioxidants may have been
consumed by oxidation reactions in the canola oil during
1000
0
Reference Epicatechin 0.1 Epicatechin 1.0 Epigallo 0.1 Epigallo1.0
Fig. 3 The content of acrylamide in aqueous solution of 0.060 M glu-
cose and 0.060 M asparagine with epicatechin or epigallocatechin gal-
late in concentrations of 0.1 or 1.0 mM in cacodulate buVer (0.040 M)
with pH 7.0 heated at 160 °C for 30 min

123
Eur Food Res Technol (2008) 227:519–525 523

similar mechanism in eVect inhibiting the Maillard reac- 1600

tions and acrylamide formation.
1400
Formation of radicals as intermediates in Maillard reac-
1200
tions was demonstrated using the spin trap
-(4-pyridyl 1-

Relative intensity
oxide)-N-tert-butylnitrone (POBN) in aqueous solutions of 1000
glucose and asparagine buVered either with Mes (0.040 M) 800
or with phosphate (0.040 M) at pH 7.0 and heated at 120 °C 600
for up to 120 min. Radicals were detected in the solutions 400
with aqueous Mes buVer in the samples containing both 200
glucose and asparagine after 90 min of heating, and the
0
concentration of radicals increased up to 120 min (Fig. 4). 40
-200
Radicals were also detected in the solutions with phosphate
buVer containing glucose alone and containing both glu- 0 20 60 80 100 120
cose and asparagine already after 15 min of heating at Time (min)
120 °C (Fig. 5). Phosphate buVer has been found to pro-
350
mote the Maillard reactions [24], in agreement with the
observation of a higher content of radicals in the samples 300
prepared with phosphate buVer. Furthermore, radicals were 250

Relative intensity
formed upon heating of glucose alone in phosphate buVer
as intermediates in the thermal degradation of glucose. 200
Hydroxyethanal, glyceraldehyde and dicarbonyl com- 150
pounds like glyoxyl have been found to be formed from
100
fragmentation of glucose and to generate much higher
amounts of acrylamide in reaction with asparagine as com- 50
pared to glucose [11]. Schieberle et al. [12] has investigated
0
the formation of acrylamide from diVerent oxo-compounds
and found that in the presence of 2-oxopropionic acid, -50
0 20 40 60 80 100 120
asparagine was very eVectively converted into acrylamide.
Time (min)
They furthermore suggested that tautomerization of the
SchiV base formed from asparagine and an
-hydroxycar- Fig. 5 The relative concentration of free radicals in aqueous phos-
phate buVer with pH 7.0 as blank (Wlled square), with 0.060 M glucose
bonyl compound e.g. a carbohydrate or a degradation prod-
(Wlled circle), with 0.060 M asparagine (Wlled triangle) or with
uct such as hydroxyacetone, would yield a enaminol, which 0.060 M glucose and 0.060 M asparagine (inverted Wlled triangle)
has been shown to be very susceptible to oxidation [25]. heated at 120 °C for up to 120 min (upper panel), or in Mes buVer
The vinylogous -keto acid formed by an oxidation step (0.040 M) with pH 7.0 of a blank (Wlled square), with 0.060 M glucose
(Wlled diamond), with 0.060 M asparagine (Wlled triangle) or with
0.060 M glucose and 0.060 M asparagine (inverted Wlled triangle)
2000 heated at 120 °C for up to 120 min (lower panel), as measured by ESR
with the use of the spin trap
-(4-pyridyl-1-oxide)-N-tert-butylnitrone
1500 (POBN) in a concentration of 0.0050 M
Relative intensity

1000
could easily decarboxylate and yield an
-oxo-imine, which
500 were suggested to be hydrolysed into 3-aminopropiona-
mide and an osone. 3-aminopropionamide has been shown
0
to be an eVective precursor of acrylamide [26]. Whether the
-500 free radicals trapped are involved in degradation of glucose
to such reactive intermediates or are intermediates in the
-1000
Maillard reactions needs to be further investigated, since it
-1500 was not possible to identify the radicals detected in the
328 330 332 334 336 338 340 342 344 present study. In a previous experiment, it was found that
mT the formation of acrylamide in aqueous mixtures of glucose
and asparagine was initiated after 100 min of heating at
Fig. 4 ESR-spectrum of 0.060 M glucose and 0.060 M asparagine in
120 °C [4]. Radicals were now detected right before the
aqueous Mes buVer (0.040 M) at pH 7.0, heated at 120 °C for 120 min
and using 0.0050 M
-(4-pyridyl-1-oxide)-N-tert-butylnitrone expected formation of acrylamide in the Mes buVer, which
(POBN) as spin trap provide circumstantial evidence for involvement of radicals

123
524 Eur Food Res Technol (2008) 227:519–525

4000 Acrylamide was found to be degraded during heat treat-

ment in an oven with the temperature of 180 °C (Fig. 6) in
3500 an air-saturated aqueous phosphate buVer in a closed con-
tainer. DiVerent elimination reactions are possible, but in
Acrylamide (ppb)

3000
the absence of proteins polymerization of acrylamide seems
2500 likely. Polymerization can be initiated by heat or prooxi-
dants such as peroxides (Fig. 7). As an example of a proox-
2000 idant, rapeseed oil with a high peroxide value
(PV = 14.1 § 0.8 meq/kg oil) was compared with a rape-
1500 seed oil with a low peroxide value (1.1 § 0.3 meq/kg oil)
for their eVect on acrylamide elimination in an o/w emul-
1000
sion as a food model. A lower content of acrylamide were
0 10 20 30 40 50 60 found in the emulsions containing oxidized rapeseed oil
Heating time (min) (38% of the spiked acrylamide was detected after heating at
Fig. 6 Degradation of acrylamide (3,500 ppb) in phosphate buVer at
180 °C for 60 min) compared to the emulsions with the
pH 7.6 heated at 180 °C for up to 60 min non-oxidized oil, where 46% of the spiked acrylamide was
detected. No acrylamide were formed in the control emul-
sions without added acrylamide. Although the eVect of the
H
H
peroxides in the oxidized oil on acrylamide elimination was
H2C C
RO O
+ RO O CH2 C only modest, the eVect points towards an oxidative induced
Peroxyl radical C O C O polymerization of acrylamide or a reaction via peroxy radi-
cal of acrylamide with double bonds of the rapeseed trig-
NH2 NH2 ycerides and subsequent degradation. Potato products
Acrylamide
contain high amounts of acrylamide and are often fried in
oil with diVerent oxidative status, and the elimination of
H H acrylamide may accordingly be inXuenced by the oxidative
RO O CH2 C H2C C
status of the oil.
C O
+ n
C O In conclusion, we have found that rosemary decreases
NH2
the acrylamide formation when added to dough prior to
NH2
baking. A free radical mechanism for acrylamide forma-
tion is further conWrmed by the eVect of the green tea
Xavonoids epicatechin and epigallocatechin gallate in a
model system of glucose and asparagine, in which the
Xavonoids decrease the formation of acrylamide, and by
H H
RO O CH2 C CH2 C
the detection of free radicals by ESR spectroscopy under
conditions, which lead to acrylamide in a simple aqueous
C O C O
glucose/asparagine solution. The impact of oxidative pro-
NH2 NH2 cesses on acrylamide elimination should not be neglected,
n
since oxidized vegetable oil seems to promote degrada-
Fig. 7 Proposed scheme of polymerization of acrylamide initiated by tion of acrylamide.
peroxides radicals generated from lipid hydroperoxides in the oxidized
rapeseed oil. Other radical like alkoxylradicals may also be involved Acknowledgments We thank Lone Hertz for her skilful and excel-
lent technical assistance with the chemical analyses. This research was
supported by The Directorate for Food, Fisheries and Agricultural
Business as a part of the project “Reduction of the formation and the
in the formation of acrylamide. Whether the radicals are occurrence of acrylamide in food”.
formed as intermediates in the Maillard reaction pathway
leading to acrylamide or are involved in formation of dicar-
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