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ACRILAMIDA
INTRODUCCIÓNAcrylamide is a chemical compound that occurs as a solid crystal or in liquid solution. Its primaryuse is to make polyacrylamide and acrylamide copolymers. Trace amounts of the original(unreacted) acrylamide generally remain in these products. Polyacrylamide and acrylamidecopolymers are used in many industrial processes, including production of paper, dyes, andplastics, and the treatment of drinking +water, sewage and waste. They are also present inconsumer products such as caulking, food packaging and some adhesives.Historically, exposure to high levels of acrylamide in the workplace has been shown to causeneurological damage. Acrylamide has not been shown to cause cancer in humans. However, therelationship between acrylamide and cancer has not been studied extensively in humans. Becauseit 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 onCancer (IARC) in Lyon, France, consider acrylamide to be a probable human carcinogen. TheNational 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 Stateshave found acrylamide in certain foods. It has been determined that heating some foods to atemperature of 120 ºC can produce acrylamide. Potato chips and french fries have been found tocontain relatively high levels of acrylamide compared to other foods, with lower levels also presentin 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 formacrylamide when heated to high temperatures in the presence of certain sugars. High-heat cookingmethods, such as frying, baking or broiling, are most likely to result in acrylamide formation. Boilingand microwaving appear less likely to form acrylamide. Longer cooking times increase the amountof acrylamide produced when the temperature is high enough. However, there are other wayshumans 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 notyet have a complete understanding of all the sources. There are some industrial and agriculturaluses of acrylamide and polyacrylamide. However, regulations are in place to limit exposure inthose settings.MECANISMOS DE REACCIÓN Y SISTEMAS MODELO
Glucose, fructose, sucrose, free asparagine, and free glutamine
were analyzed in 74 potatosamples from 17 potato cultivars grown in 2002 at various locations in Switzerland and differentfarming systems. The potential of these potatoes for acrylamide formation was measured with astandardized heat treatment. These potentials correlated well with the product of theconcentrations of reducing sugars and asparagine. Glucose and fructose were found to determineacrylamide formation. The cultivars showed large differences in their potential of acrylamideformation which was primarily related to their sugar contents. Agricultural practice neither influenced sugars and free asparagine nor the potential of acrylamide formation. It is concludedthat acrylamide contents in potato products can be substantially reduced primarily by selectingcultivars with low concentrations of reducing sugars.
Structural considerations dictate that asparagine alone may be converted thermally intoacrylamide 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, inthe presence of reducing sugars, was able to generate acrylamide in addition to maleimide. Modelreactions were performed using FTIR analysis, and labeling studies were carried out usingpyrolysis-GC/MS as an integrated reaction, separation, and identification system to investigate therole of reducing sugars.
The data have indicated that a decarboxylated Amadori product of asparagine with reducing sugars is the key precursor of acrylamide. Furthermore, thedecarboxylated Amadori product can be formed under mild conditions through theintramolecular 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 cyclizationreaction, which is in competition with thermally induced decarboxylation, and hencepromote the formation of acrylamide in carbohydrate/asparagine mixtures. Although thedecarboxylated Amadori compound can be formed under mild conditions, it requireselevated temperatures to cleave the carbon-nitrogen covalent bond and produceacrylamide.
 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 modelresulted 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. Theformation of acrylamide reached its maximum when the concentration of sugars was reduced toabout 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 anintermediate of the Maillard reaction rather than an end product, which implies that it is also subjectto 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 arisesfrom reaction of asparagine with an Amadori dicarbonyl through a Strecker aldehydeintermediate. Stadler provided clear evidence of acrylamide formation from pyrolyticproducts of N-glucosides of asparagine and, to a much lesser extent, with methionine andglutamine.
Becalski showed in a sealed model system at 175°C that monocarbonyls (octanal and2- octanone) also produced measurable acrylamide from asparagine hydrate. Zyzak independentlyconfirmed the ability of monocarbonyls to mediate acrylamide formation. Since monocarbonyls arepyrolytic and/or oxidative decomposition products of fats, proteins and carbohydrate, their variedorigin suggests that a variety of minor pathways may feed acrylamide formation. Panel membersfelt generally confident that free asparagine and carbohydrates (especially free reducing sugars)accounted for the majority of acrylamide in fried potato products. Mottram presented data whichindicated 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 freeasparagine 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.
Someacrylamide 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 inglutamine. Impurities in stock amino acids almost certainly account for some reported acrylamide.The production of acrylamide from methionine appears genuine. While this mechanism probablyrepresents a minor pathway in foods of plant origin, its significance in forming acrylamides inmeats 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 carbonylcompounds for a trivial role in acrylamide formation through the asparagine/carbonyl pathwaydiscussed above. Most published acrylamide studies are the product of research using modelsystems of pure amino acids and not actual foods. However, attendees reported severalexperiments 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 wasnecessary to liberate asparagine and allow it to contact asparaginase. Other work examined theeffectiveness of reducing agents such as sodium bisulfite, cysteine and glutathione on acrylamidereduction in bakery products. Reducing agents did not appear to significantly effect acrylamideproduction. At best, levels were reduced by no more than 10%. Similarly, antioxidantsupplementation in wheat dough did not significantly decrease acrylamide formation in bakeryproducts.There was an early temptation among group members to think that virtually all foodborneacrylamide originated with free asparagine perhaps with minor contributions by other free aminoacids. This may yet prove to be the case. However, participants acknowledged that little work hadexamined whole proteins, or other nitrogen sources such as nucleic acids and glycoproteins, andvirtually no mechanism work has been published on acrylamide mechanisms in whole foods. Oneopinion expressed the possibility that free radicals may participate. There was a strong feeling thatkinetic data would be essential in developing reduction strategies for acrylamide.The formation of acrylamide in crystalline model systems based on asparagine and reducingsugars was investigated under low-moisture reaction conditions. The acrylamide amounts werecorrelated with physical changes occurring during the reaction. Molecular mobility of the precursorsturned out to be a critical parameter in solid systems, which is linked to the melting behavior andthe release of crystallization water of the reaction sample.
Heating binary mixtures of asparaginemonohydrate 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 andtemperature 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 reactiontime (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 studiedin 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 wasthe 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 notasparagines caused an increased browning reaction during baking. The formation of suspectedcarcinogenic acrylamide in heated starch-rich foods as a product of the Maillard reaction has beenwidely reported (Tareke et al 2002; Taeymans et al 2004). The side chain of asparagine deliversthe backbone of the acrylamide molecule (Stadler et al 2002). Reducing sugars are notincorporated 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 anintermediate product on the reported pathway to acrylamide. Free asparagines has been shown tobe a limiting precursor for acrylamide formation in yeast-leavened bread (Surdyk et al 2004). Whitewheat flour has a very low content of free asparagine (Fredriksson et al 2004), while certainingredients 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 theformationof acrylamide in bread and potato products (Rydberg et al 2003; Amrein et al 2004; Bråthen et al2005). This reducing effect may be due to a competitive consumption of reactive carbonylsbetween 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 NH
2
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 reducethe acrylamide contents of this food group.
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