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ACRILAMIDA

INTRODUCCIÓN

Acrylamide is a chemical compound that occurs as a solid crystal or in liquid solution. Its primary
use is to make polyacrylamide and acrylamide copolymers. Trace amounts of the original
(unreacted) acrylamide generally remain in these products. Polyacrylamide and acrylamide
copolymers are used in many industrial processes, including production of paper, dyes, and
plastics, and the treatment of drinking +water, sewage and waste. They are also present in
consumer products such as caulking, food packaging and some adhesives.

Historically, exposure to high levels of acrylamide in the workplace has been shown to cause
neurological damage. Acrylamide has not been shown to cause cancer in humans. However, the
relationship between acrylamide and cancer has not been studied extensively in humans. Because
it has been shown to cause cancer in laboratory rats when given in the animals' drinking water,
both the Environmental Protection Agency (EPA) and the International Agency for Research on
Cancer (IARC) in Lyon, France, consider acrylamide to be a probable human carcinogen. The
National Toxicology Program's Ninth Report on Carcinogens states that acrylamide can be
"reasonably anticipated to be a human carcinogen."

Recent studies by research groups in Sweden, Switzerland, Norway, Britain and the United States
have found acrylamide in certain foods. It has been determined that heating some foods to a
temperature of 120 ºC can produce acrylamide. Potato chips and french fries have been found to
contain relatively high levels of acrylamide compared to other foods, with lower levels also present
in bread and cereals. In September 2002, researchers discovered that the amino acid asparagine,
which is present in many vegetables, with higher amounts in some varieties of potatoes, can form
acrylamide when heated to high temperatures in the presence of certain sugars. High-heat cooking
methods, such as frying, baking or broiling, are most likely to result in acrylamide formation. Boiling
and microwaving appear less likely to form acrylamide. Longer cooking times increase the amount
of acrylamide produced when the temperature is high enough. However, there are other ways
humans are exposed to acrylamide, but exposure through food is one of the largest sources.
Cigarette smoke may be a major source for some people. Exposure to acrylamide from other
sources is likely to be significantly less than that from food or smoking, although scientists do not
yet have a complete understanding of all the sources. There are some industrial and agricultural
uses of acrylamide and polyacrylamide. However, regulations are in place to limit exposure in
those settings.

MECANISMOS DE REACCIÓN Y SISTEMAS MODELO

Glucose, fructose, sucrose, free asparagine, and free glutamine were analyzed in 74 potato
samples from 17 potato cultivars grown in 2002 at various locations in Switzerland and different
farming systems. The potential of these potatoes for acrylamide formation was measured with a
standardized heat treatment. These potentials correlated well with the product of the
concentrations of reducing sugars and asparagine. Glucose and fructose were found to determine
acrylamide formation. The cultivars showed large differences in their potential of acrylamide
formation which was primarily related to their sugar contents. Agricultural practice neither
influenced sugars and free asparagine nor the potential of acrylamide formation. It is concluded
that acrylamide contents in potato products can be substantially reduced primarily by selecting
cultivars with low concentrations of reducing sugars.

Structural considerations dictate that asparagine alone may be converted thermally into
acrylamide through decarboxylation and deamination reactions. However, the main product of
the thermal decomposition of asparagine was maleimide, mainly due to the fast intramolecular
cyclization reaction that prevents the formation of acrylamide. On the other hand, asparagine, in
the presence of reducing sugars, was able to generate acrylamide in addition to maleimide. Model
reactions were performed using FTIR analysis, and labeling studies were carried out using
pyrolysis-GC/MS as an integrated reaction, separation, and identification system to investigate the
role of reducing sugars. The data have indicated that a decarboxylated Amadori product of
asparagine with reducing sugars is the key precursor of acrylamide. Furthermore, the
decarboxylated Amadori product can be formed under mild conditions through the
intramolecular cyclization of the initial Schiff base and formation of oxazolidin-5-one. The
low-energy decarboxylation of this intermediate makes it possible to bypass the cyclization
reaction, which is in competition with thermally induced decarboxylation, and hence
promote the formation of acrylamide in carbohydrate/asparagine mixtures. Although the
decarboxylated Amadori compound can be formed under mild conditions, it requires
elevated temperatures to cleave the carbon-nitrogen covalent bond and produce
acrylamide.

A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-
posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different
temperatures (120-200 ºC) at pH 6.8. Besides the reactants, acrylamide, fructose, and
melanoidins were quantified after predetermined heating times (0-45 min). The proposed model
resulted in a reasonable estimation for the formation of acrylamide in an aqueous model system,
although the behavior of glucose, fructose, and asparagine was slightly underestimated. The
formation of acrylamide reached its maximum when the concentration of sugars was reduced to
about 0. This supported previous research, showing that a carbonyl source is needed for
the formation of acrylamide from asparagine. Furthermore, it is observed that acrylamide is an
intermediate of the Maillard reaction rather than an end product, which implies that it is also subject
to a degradation reaction.

The presentation by Mottram (Mottram and Wedzicha) and Stadler provide excellent summaries of
acrylamide formation pathways from asparagine. The pathway suggests that acrylamide arises
from reaction of asparagine with an Amadori dicarbonyl through a Strecker aldehyde
intermediate. Stadler provided clear evidence of acrylamide formation from pyrolytic
products of N-glucosides of asparagine and, to a much lesser extent, with methionine and
glutamine. Becalski showed in a sealed model system at 175°C that monocarbonyls (octanal and
2- octanone) also produced measurable acrylamide from asparagine hydrate. Zyzak independently
confirmed the ability of monocarbonyls to mediate acrylamide formation. Since monocarbonyls are
pyrolytic and/or oxidative decomposition products of fats, proteins and carbohydrate, their varied
origin suggests that a variety of minor pathways may feed acrylamide formation. Panel members
felt generally confident that free asparagine and carbohydrates (especially free reducing sugars)
accounted for the majority of acrylamide in fried potato products. Mottram presented data which
indicated a high level of free asparagine content in potatoes (40% of total free amino acids), wheat
(14% of TFAA) and high protein rye (18% of TFAA); suggesting a connection between free
asparagine and acrylamide formation in foods with moderate-to-high reported values for
acrylamide.

The formation of acrylamide from amino acids other than asparagine was not clear-cut. Some
acrylamide has been reported from glutamine, methionine, cysteine and aspartic acid. However,
Becalski reported finding 0.3% asparagine impurity in aspartic acid and 0.8% cysteine in
glutamine. Impurities in stock amino acids almost certainly account for some reported acrylamide.
The production of acrylamide from methionine appears genuine. While this mechanism probably
represents a minor pathway in foods of plant origin, its significance in forming acrylamides in
meats is yet to be tested. The group agreed that fats in general and acrolein in particular were not
major precursors to acrylamide. However, oxidized fats could compete with other carbonyl
compounds for a trivial role in acrylamide formation through the asparagine/carbonyl pathway
discussed above. Most published acrylamide studies are the product of research using model
systems of pure amino acids and not actual foods. However, attendees reported several
experiments performed in real food systems. Asparaginase (converts asparagine to aspartic acid)
reduced acrylamide to low levels in fried pureed potato foods. Disruption of cell membranes was
necessary to liberate asparagine and allow it to contact asparaginase. Other work examined the
effectiveness of reducing agents such as sodium bisulfite, cysteine and glutathione on acrylamide
reduction in bakery products. Reducing agents did not appear to significantly effect acrylamide
production. At best, levels were reduced by no more than 10%. Similarly, antioxidant
supplementation in wheat dough did not significantly decrease acrylamide formation in bakery
products.

There was an early temptation among group members to think that virtually all foodborne
acrylamide originated with free asparagine perhaps with minor contributions by other free amino
acids. This may yet prove to be the case. However, participants acknowledged that little work had
examined whole proteins, or other nitrogen sources such as nucleic acids and glycoproteins, and
virtually no mechanism work has been published on acrylamide mechanisms in whole foods. One
opinion expressed the possibility that free radicals may participate. There was a strong feeling that
kinetic data would be essential in developing reduction strategies for acrylamide.

The formation of acrylamide in crystalline model systems based on asparagine and reducing
sugars was investigated under low-moisture reaction conditions. The acrylamide amounts were
correlated with physical changes occurring during the reaction. Molecular mobility of the precursors
turned out to be a critical parameter in solid systems, which is linked to the melting behavior and
the release of crystallization water of the reaction sample. Heating binary mixtures of asparagine
monohydrate and anhydrous reducing sugars led to higher acrylamide amounts in the presence of
fructose compared to glucose. Glucose was the most reactive and fructose the least efficient sugar
in anhydrous liquid systems, indicating that at given molecular mobility the chemical reactivity of
the sugar was the major driver in acrylamide formation. Furthermore, reaction time and
temperature were found to be covariant parameters: acrylamide was preferably formed by reacting
glucose and asparagine at 120 ºC for 60 min, whereas 160 ºC was required at shorter reaction
time (5 min). These results suggest that, in addition to the chemical reactivity of ingredients, their
physical state as well as reaction temperature and time would influence the formation of
acrylamide during food processing.

Effect of added asparagine and glycine on acrylamide content in yeastleavened bread was studied
in a designed experiment. Added asparagines strongly increased acrylamide content in the breads,
while added glycine decreased the content. The more asparagine in the dough, the stronger was
the reducing effect of glycine. When glycine was applied on the surface of the fermented dough,
there was also a significant reduction of acrylamide content in the bread. Addition of glycine but not
asparagines caused an increased browning reaction during baking. The formation of suspected
carcinogenic acrylamide in heated starch-rich foods as a product of the Maillard reaction has been
widely reported (Tareke et al 2002; Taeymans et al 2004). The side chain of asparagine delivers
the backbone of the acrylamide molecule (Stadler et al 2002). Reducing sugars are not
incorporated into the molecule but they are needed for formation of the Schiff base of asparagine.
This Schiff base is transformed into a decarboxylated Amadori product known to be an
intermediate product on the reported pathway to acrylamide. Free asparagines has been shown to
be a limiting precursor for acrylamide formation in yeast-leavened bread (Surdyk et al 2004). White
wheat flour has a very low content of free asparagine (Fredriksson et al 2004), while certain
ingredients used in baking like germ, bran, and certain carrot products contain significant amounts.
A large addition of amino acids other than asparagine, such as glycine, leads to a reduction in the
formation
of acrylamide in bread and potato products (Rydberg et al 2003; Amrein et al 2004; Bråthen et al
2005). This reducing effect may be due to a competitive consumption of reactive carbonyls
between asparagine and glycine. Another reason for this effect might be an elimination of
acrylamide formed by a reaction with glycine because acrylamide reacts with the NH2 group of
glycine (Friedman 2003). Yeast-leavened bread represents a very important part of the human diet
(Svensson et al 2003). Due to the high intake of this type of bread, efforts must be made to reduce
the acrylamide contents of this food group.
Central crumb temperature, volume, weight, and crumb porosity of the yeast-leavened breads did
not significantly change when different amounts of amino acids were added to the dough. These
results are in agreement with previous findings because glycine readily reacted with α-dicarbonyls
(Piloty et al 1979) and strongly enhanced browning (Ashoor et al 1984), while in a previous study
the addition of asparagine to dough did not enhance browning of the bread crust with yeast-
leavened wheat bread (Surdyk et al 2004). Added asparagine strongly increased the content of
acrylamide of the breads and added glycine decreased the content. The higher the amount of
asparagines added, the higher the reducing effect of added glycine on the content of acrylamide in
the breads. This is due to the strong effect of added asparagine on the acrylamide content in bread
as shown by Surdyk et al (2004), while the reducing effect of added glycine seems to be more
moderate. In a very recent study, however, a stronger reducing effect of added glycine on
acrylamide content in bread crust of yeast-leavened bread was reported (Brathen et al 2005).
Other levels of amino acids in the dough and experimental conditions may be the reason for the
difference in effect. Because there were no significant differences between the two blocks in any of
the parameters measured in the breads, amino acids and reducing sugars in the doughs were only
measuered in one of the blocks. This result shows that the fermentation capacity of asparagine in
the dough was limited and could highly reduce the content (original and added) only when the
addition level was low. A similar relationship was found between added and analyzed glycine
content in the fermented dough, showing that the effect of yeast fermentation on free glycine was
very limited. Fredriksson et al (2004) found a strong and significant decrease in asparagine content
during yeast fermentation, but in that case, the level of asparagine in the dough was lower.
Addition of asparagine to the dough did not significantly influence the amount of reducing sugars in
the fermented doughs, but addition of glycine to the dough significantly increased the amount of
reducing sugars. One possible explanation could be that a high addition of glycine could lead to
reduced yeast fermentation, consuming less reducing sugars. Surdyk et al (2004) suggested in a
recent study, using the same basic recipe for the breads as in this experiment, that the molar
concentration of reducing sugars in the dough, mostly formed during fermentation, strongly
exceeds that of free asparagine. Thus, asparagine was considered to be the limiting factor for the
formation of acrylamide. In this model study, however, reducing sugars were not always in excess,
and the molar ratio between free amino acids (asparagine and glycine) and reducing sugars in the
doughs varied greatly from sample to sample. Reducing sugars can also be formed in the
crust from oligosaccharides and polysaccharides during heat treatment in the oven (Theander and
Westerlund 1988). This reduction in acrylamide content could be explained by both a competition
between the amino acids for the reducing sugars in the Maillard reaction or a further reaction of
formed acrylamide with the added glycine as previously suggested (Rydberg et al 2003; Bråthen et
al 2005). However, further studies are necessary to reveal the actual mechanisms. Glycine
Spraying A previous publication showed that all acrylamide was formed in the crust (Surdyk et al
2004). It may thus be possible to reduce the application rate by applying glycine only to the surface
of the fermented dough, thereby reducing the acrylamide content in the bread. Thus, an application
of glycine on the surface of the dough could be a method for lowering the content of acrylamide in
commercial breads. An addition of glycine during dough making or spraying of glycine on the
surface of fermented dough can lead to a significant reduction of acrylamide content in yeast-
leavened breads. The more asparagine present in the dough, the stronger the reducing effect of
added glycine.
Conclusion: The list of four urgent needs for acrylamide mechanisms research were:
1. Need data on the quantity of free asparagine on a dried weight basis for various foods
(database-variety, crop conditions, storage) and data on the quantity of glucose, fructose (and
other sugars) and amino acids other than asparagine for various foods to answer whether
asparagine is the only significant pathway to acrylamide production in foods. 2.
Time/Temperature/pH/Moisture/Surface area-mass mapping and kinetics of asparagine/carbonyls
reaction in various matrices. May include mathematical modelling. Process investigations and
study the kinetics/pathways of acrylamide formation versus the browning and flavor forming
reactions. (comment: This information addresses the question of formation kinetics and spatial
placement of acrylamide in fried and baked foods. Some mitigation strategies depend of whether
acrylamide forms on the surface, immediately below the surface or progresses as cooking
advances at some mobile interfacial point of optimal temperature and moisture). 3. Define the
direct correlation of asparagine to acrylamide production in foods. (Experimentally confirms
literature effort reported in objective 1 by analysing foods for free asparagine and examining
correlation with acrylamide formation) 4. What are the kinetics of acrylamide
inhibition/destruction/scavenging under various reaction/process conditions: a. Mixed amino acids
competitive reactions or scavenging. b. Ammonium ion as a possible competitive agent. c.
Glutathione/cysteine to promote sulfhydryls-disulfide interchange to provide scavengers. d.
Irradiation e. Pressure processing f. Fermentation. g. Hydrolyzed nucleic acids h. Asparaginase
conversion of asparagine to aspartic acid.