Kinetic modelling of acrylamide formation during the finish-frying of french fries with variable maltose content.

In light of a recent update in EU regulations governing levels of acrylamide in foodstuffs, further understanding of the role of different precursors is fundamental to extending mitigation strategies into a wider product range. Kinetic modelling was used to investigate the role of maltose in the formation of acrylamide during the finish-frying of french fries. The maltose concentration of raw white potato strips was systematically increased from 0 to 1.4% to observe the effect of this reducing disaccharide on acrylamide formation. A mathematical model, incorporating glucose, fructose and maltose and based on known Maillard reaction pathways, was developed which showed that acrylamide formation from maltose only contributed <10% to the total acrylamide. An additional kinetic model allowed for the formation of acrylamide directly from sugar-asparagine glycoconjugates. This model suggested that under these conditions, it is unlikely that acrylamide is formed directly from the maltose-asparagine conjugate.

Factors affecting migration kinetics from a generic epoxy-phenolic food can coating system.

This study investigated how the properties of a polymeric can coating film, such as thickness and crosslink density as well as the type of migrant, influence the migration kinetics of model migrants in an attempt to better understand, model and control the migration process. Four model migrants were used BADGE (bisphenol A diglycidyl ether), BADGE·H2O, cyclo-diBADGE and Uvitex OB, that differ in size and polarity. Fatty and aqueous food simulants were used at high temperatures (70-130°C). The apparent diffusion coefficients were found to decrease with increasing crosslink density, while they increased with increasing film thickness. The apparent activation energy of BADGE and BADGE-related compounds was calculated from the diffusion data and were high, in the range of 250-264kJmol-1. The polarity of the simulant and the polarity of the migrant were found to influence migration. The results can be used to improve existing migration models, and thereby help to reduce migration from packaging into food by using safety-by-design approaches in new product development.

Kinetic model for the formation of acrylamide during the finish-frying of commercial french fries.

Acrylamide is formed from reducing sugars and asparagine during the preparation of French fries. The commercial preparation of French fries is a multistage process involving the preparation of frozen, par-fried potato strips for distribution to catering outlets, where they are finish-fried. The initial blanching, treatment in glucose solution, and par-frying steps are crucial because they determine the levels of precursors present at the beginning of the finish-frying process. To minimize the quantities of acrylamide in cooked fries, it is important to understand the impact of each stage on the formation of acrylamide. Acrylamide, amino acids, sugars, moisture, fat, and color were monitored at time intervals during the frying of potato strips that had been dipped in various concentrations of glucose and fructose during a typical pretreatment. A mathematical model based on the fundamental chemical reaction pathways of the finish-frying was developed, incorporating moisture and temperature gradients in the fries. This showed the contribution of both glucose and fructose to the generation of acrylamide and accurately predicted the acrylamide content of the final fries.

Kinetic modeling of the generation of 2- and 3-methylbutanal in a heated extract of beef liver.

Quantitative control of aroma generation during the Maillard reaction presents great scientific and industrial interest. Although there have been many studies conducted in simplified model systems, the results are difficult to apply to complex food systems, where the presence of other components can have a significant impact. In this work, an aqueous extract of defatted beef liver was chosen as a simplified food matrix for studying the kinetics of the Maillard reaction. Aliquots of the extract were heated under different time and temperature conditions and analyzed for sugars, amino acids, and methylbutanals, which are important Maillard-derived aroma compounds formed in cooked meat. Multiresponse kinetic modeling, based on a simplified mechanistic pathway, gave a good fit with the experimental data, but only when additional steps were introduced to take into account the interactions of glucose and glucose-derived intermediates with protein and other amino compounds. This emphasizes the significant role of the food matrix in controlling the Maillard reaction.

Investigations on the effect of amino acids on acrylamide, pyrazines, and Michael addition products in model systems.

Acrylamide and pyrazine formation, as influenced by the incorporation of different amino acids, was investigated in sealed low-moisture asparagine-glucose model systems. Added amino acids, with the exception of glycine and cysteine and at an equimolar concentration to asparagine, increased the rate of acrylamide formation. The strong correlation between the unsubstituted pyrazine and acrylamide suggests the promotion of the formation of Maillard reaction intermediates, and in particular glyoxal, as the determining mode of action. At increased amino acid concentrations, diverse effects were observed. The initial rates of acrylamide formation remained high for valine, alanine, phenylalanine, tryptophan, glutamine, and leucine, while a significant mitigating effect, as evident from the acrylamide yields after 60 min of heating at 160 degrees C, was observed for proline, tryptophan, glycine, and cysteine. The secondary amine containing amino acids, proline and tryptophan, had the most profound mitigating effect on acrylamide after 60 min of heating. The relative importance of the competing effect of added amino acids for alpha-dicarbonyls and acrylamide-amino acid alkylation reactions is discussed and accompanied by data on the relative formation rates of selected amino acid-AA adducts.

Acrylamide and pyrazine formation in model systems containing asparagine.

The effect of different sugars and glyoxal on the formation of acrylamide in low-moisture starch-based model systems was studied, and kinetic data were obtained. Glucose was more effective than fructose, tagatose, or maltose in acrylamide formation, whereas the importance of glyoxal as a key sugar fragmentation intermediate was confirmed. Glyoxal formation was greater in model systems containing asparagine and glucose rather than fructose. A solid phase microextraction GC-MS method was employed to determine quantitatively the formation of pyrazines in model reaction systems. Substituted pyrazine formation was more evident in model systems containing fructose; however, the unsubstituted homologue, which was the only pyrazine identified in the headspace of glyoxal-asparagine systems, was formed at higher yields when aldoses were used as the reducing sugar. Highly significant correlations were obtained for the relationship between pyrazine and acrylamide formation. The importance of the tautomerization of the asparagine-carbonyl decarboxylated Schiff base in the relative yields of pyrazines and acrylamide is discussed.

Role of glucose in the maillard browning of maltose and glycine: a radiochemical approach.

We followed the contribution of released glucose to the formation of melanoidins in the maltose-glycine reaction by adding (14)C glucose to the maltose-glycine mixture, after it already had undergone some reaction. This approach allowed us to confirm the turnover of glucose in this reaction and hence the role of glucose in forming melanoidins. A comparison of the total amount of glucose converted into the melanoidins with the total concentration of melanoidins formed from maltose and glycine showed that the concentration of melanoidins originating from the released glucose was relatively small in comparison to the total melanoidins concentration. Hence, the parallel glucose-glycine reaction is considered to be only a minor pathway in the formation of maltose-glycine melanoidins. The incorporation of glucose into the nondialyzable melanoidins in the maltose-glycine reaction was in excellent agreement with the amount estimated from a kinetic model for the reaction of maltose with glycine. The rate constants were estimated by nonlinear regression, via multiresponse modeling.

Kinetic models as a route to control acrylamide formation in food.

A kinetic model for the formation of acrylamide in potato, rye and wheat products has been derived, and kinetic parameters calculated for potato by multi-response modeling of reducing sugar (glucose and fructose), amino acid, asparagine and acrylamide concentrations with time. The kinetic mechanism shares, with Maillard browning, a rate limiting (probably dicarbonylic) intermediate, and includes reaction steps of this intermediate which are competitive with respect to acrylamide formation. A pathway representing physical and/or chemical losses of acrylamide accounts for the measured reduction of acrylamide yield at long reaction times. A mechanistic hypothesis regarding the competing reactions of Strecker aldehyde formation and tautomerization followed by beta-elimination to give acrylamide, features in the kinetic model and can be used to determine the factors which steer the reaction towards acrylamide. A predictive application of this model is for 'what-if' experiments to explore the conditions which lead to reduced acrylamide yields.

The effect of cooking on acrylamide and its precursors in potato, wheat and rye.

The relationship between acrylamide and its precursors, namely free asparagine and reducing sugars, was studied in simple cakes made from potato flake, wholemeal wheat and wholemeal rye, cooked at 180 degrees C, from 5 to 60 min. Between 5 and 20 min, large losses of asparagine, water and total reducing sugars were accompanied by large increases in acrylamide, which maximized in all three products between 25 and 30 min, followed by a slow linear reduction. Acrylamide formation did not occur to any extent until the moisture contents of the cakes fell below 5%. A comparison of each type of cake with a commercial product, made from the same food material, showed that acrylamide levels in all three commercial products were well below the maximum levels in the cooked cakes.

Comparative study of the composition of melanoidins from glucose and maltose.

The composition of melanoidins formed in the reactions of either glucose or maltose with glycine (70 degrees C, pH 5.5, [glucose] = [maltose] = [glycine] = 0.25 M) (MW > 3500) was investigated by microanalysis and the use of (14)C-labeled sugars and amino acid. The most reliable parameter obtained from microanalysis data is the C/N value, as it was calculated with no model assumption. The C/N value (7.6 +/- 0.2 for glucose and 10.5 +/- 0.2 for maltose) does not change with molecular weight (MW > 3500) as the polymers grow in size. A comparison between the radiochemically determined composition and that obtained from microanalysis suggests that the amino ketone, which is one of the products of Strecker degradation reaction, forms part of the of the melanoidin structure, together with the sugar-derived moiety and the Strecker aldehyde. Evidence is presented that glucose is formed at intermediate stages of the maltose-glycine reaction. The melanoidins are the result of the polymerization of glucose and intact, or substantially intact, maltose residues with glycine.

A kinetic model for the glucose-fructose-glycine browning reaction.

The browning of glucose-fructose-glycine mixtures involves parallel glucose-glycine and fructose-glycine reactions, which share a common intermediate, the immediate precursor of melanoidins in the kinetic model. At pH 5.5, 55 degrees C glucose is converted into this intermediate in a two step process where k(1) = (7.8 +/- 1.1) x 10(-)(4) mol L(-)(1) h(-)(1) and k(2) = (1.84 +/- 0.31) x 10(-)(3) h(-)(1) according to established kinetics, whereas fructose is converted into this intermediate in a single step where k(4) = 5.32 x 10(-)(5)()()mol L(-)(1) h(-)(1). The intermediate is converted to melanoidins in a single rate limiting process where k(mix) = 0.0177 h(-)(1) and the molar extinction coefficient (based on the concentration of sugar converted) of the melanoidins so formed is 1073 +/- 4 mol(-)(1) L cm(-)(1). Whereas the value of k(mix) is the same when the individual sugars undergo browning, the value of the molar extinction coefficient is similar to that for melanoidins from the glucose-glycine reaction (955 +/- 45 mol(-)(1) L cm(-)(1)) but it is approximately double the value for melanoidins from the fructose-glycine reaction (478 +/- 18 mol(-)(1) L cm(-)(1)). This is the reason that the effects of glucose and fructose on the rate of browning are synergistic.

Acrylamide is formed in the Maillard reaction.

Reports of the presence of acrylamide in a range of fried and oven-cooked foods have caused worldwide concern because this compound has been classified as probably carcinogenic in humans. Here we show how acrylamide can be generated from food components during heat treatment as a result of the Maillard reaction between amino acids and reducing sugars. We find that asparagine, a major amino acid in potatoes and cereals, is a crucial participant in the production of acrylamide by this pathway.