Imre Blank

Acrylamide from Maillard reaction products

The discovery of the adventitious formation of the potential cancer-causing agent acrylamide in a variety of foods during cooking has raised much concern, but the chemical mechanism(s) governing its production are unclear. Here we show that acrylamide can be released by the thermal treatment of certain amino acids (asparagine, for example), particularly in combination with reducing sugars, and of early Maillard reaction products (N-glycosides). Our findings indicate that the Maillard-driven generation of flavour and colour in thermally processed foods can — under particular conditions — be linked to the formation of acrylamide.

Food chemistry: Acrylamide from Maillard reaction products

The discovery of the adventitious formation of the potential cancer-causing agent acrylamide in a variety of foods during cooking has raised much concern, but the chemical mechanism(s) governing its production are unclear. Here we show that acrylamide can be released by the thermal treatment of certain amino acids (asparagine, for example), particularly in combination with reducing sugars, and of early Maillard reaction products (N-glycosides). Our findings indicate that the Maillard-driven generation of flavour and colour in thermally processed foods can — under particular conditions — be linked to the formation of acrylamide.

A Review of Acrylamide: An Industry Perspective on Research, Analysis, Formation, and Control

Acrylamide is a synthetic monomer with a wide scope of industrial applications, mainly as a precursor in the production of several polymers, such as polyacrylamide. The main uses of polyacrylamides are in water and wastewater treatment processes, pulp and paper processing, and mining and mineral processing. The announcement by the Swedish National Food Administration in April 2002 of the presence of acrylamide predominantly in heat-treated carbohydrate-rich foods sparked intensive investigations into acrylamide, encompassing the occurrence, chemistry, agricultural practices, and toxicology, in order to establish if there is a potential risk to human health from the presence of this contaminant in the human diet. The link of acrylamide in foods to the Maillard reaction and, in particular, to the amino acid asparagine has been a major step forward in elucidating the first feasible chemical route of formation during the preparation and processing of food. Other probably minor pathways have also been proposed, including acrolein and acrylic acid. This review addresses the analytical and mechanistic aspects of the acrylamide issue and summarizes the progress made to date by the European food industries in these key areas. Essentially, it presents experimental results generated under laboratory model conditions, as well as under actual food processing conditions covering different food categories, such as potatoes, biscuits, cereals, and coffee. Since acrylamide formation is closely linked to food composition, factors such as the presence of sugars and availability of free amino acids are also considered. Many new findings that contribute towards a better understanding of the formation and presence of acrylamide in foods are presented. Many national authorities across the world are assessing the dietary exposure of consumers to acrylamide, and scientific projects have commenced to gather new information about the toxicology of acrylamide. These are expected to provide new scientific knowledge that will help to clarify whether or not there is a risk to human health from the consumption of foods containing low amounts of acrylamide.

Potent odorants of the roasted powder and brew of Arabica coffee

ZusammenfassungDie Aromaextrakt-Verdünnungsanalyse (AEVA) von Röstkaffee ergab 13 wichtige Geruchsstoffe: 2-Methyl-3-furanthiol (I), 2-Furfurylthiol (II), Methional (III), 3-Mercapto-3-methylbutylformiat (IV), 3-Isopropyl-2-methoxypyrazin (V), 2-Ethyl-3,5-dimethylpyrazin (VI), 2,3-Diethyl-5-methylpyrazin (VII), 3-Isobutyl-2-methoxypyrazin (VIII), 3-Hydroxy-4,5-dimethyl-2(5H)-furanon (Sotolon, IX), 4-Vinylguajacol (XII) und (E)-β-Damascenon (XIII). Die vergleichende AEVA von Röstkaffee und daraus hergestelltem Aufguß zeigte im Aufguß eine Zunahme von III, IX, Vanillin und 4-Hydroxy-2,5-dimethyl-3(2H)-furanon und eine Abnahme von I, II, IV, V, VII und VIII.SummaryAroma extract dilution analysis (AEDA) revealed 13 compounds as important contributors to the aroma of roasted coffee (powder): 2-methyl-3-furanthiol (I), 2-furfurylthiol (II), methional (III), 3-mercapto-3-methylbutylformate (IV), 3-isopropyl-2-methoxypyrazine (V), 2-ethyl-3,5-dimethylpyrazine (VI), 2,3-diethyl-5-methylpyrazine (VII), 3-isobutyl-2-methoxy-pyrazine (VIII), 3-hydroxy-4,5-dimethyl-2(5H)-furanone (sotolon, IX), 4-ethylguaiacol (X), 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone (XI), 4-vinylguaiacol (XII), and (E)-β-damascenone (XIII). A comparative AEDA of the coffee powder and brew showed in the brew an increase of III, IX, vanillin and 4-hydroxy-2,5-dimethyl-3(2H)-furanone and a decrease of I, II, IV, V, VII, and VIII.

Formation of Furan and Methylfuran by Maillard-Type Reactions in Model Systems and Food

The formation of furan and 2-methylfuran was studied in model systems based on sugars and selected amino acids. Both compounds were preferably formed under roasting conditions in closed systems yielding up to 330 micromol of furan and 260 micromol of 2-methylfuran per mol of precursor. The amounts obtained under pressure cooking conditions were much lower, usually below 20 micromol/mol, except for 2-furaldehyde, which yielded 70-100 micromol/mol of furan. Labeling studies indicated two major formation pathways for both furans: (i) from the intact sugar skeleton and (ii) by recombination of reactive C(2) and/or C(3) fragments. Under roasting conditions in the absence of amino acids, furan was mainly formed from the intact sugar skeleton. Formic and acetic acid were identified as byproducts of sugar degradation, indicating the split off of C(1) and/or C(2) units from hexoses. The presence of alanine, threonine, or serine promoted furan formation by the recombination of C(2) fragments, such as acetaldehyde and glycolaldehyde, which may originate from both sugars and amino acids. In aqueous solution, about half of furan was generated by the recombination of sugar fragments. 2-Methylfuran was preferably formed in the presence of amino acids by aldol-type reactions of C(2) and C(3) fragments with lactaldehyde as a key intermediate, the Strecker aldehyde of threonine. The total furan levels in cooked vegetables were increased by spiking with hexoses. However, in pumpkin puree, only about 20% of furan was formed from sugars, preferably from the intact carbon skeleton.

Formation of furan and methylfuran from ascorbic acid in model systems and food

Previous model studies have suggested ascorbic acid as one of the major sources of furan, a possibly hazardous compound found in thermally processed foods (e.g. canned products, jars). The study showed that about 2 mmol mol−1 furan was obtained when dry-heating ascorbic acid, while much lower amounts were formed upon pressure cooking, i.e. 58 µmol mol−1 at pH 4 and 3.7 µmol mol−1 at pH 7. Model reactions also generated 2-methylfuran (MF). However, the MF levels were generally very low with the exception of the binary mixture ascorbic acid/phenylalanine (1 mmol mol−1). Studies with 13C-labelled ascorbic acid indicated that furan comprises an intact C4 unit, mainly C-3 to C-6, generated by splitting off two C1 units, i.e. CO2 and formic acid. Possible intermediates are 2-deoxyaldoteroses, 2-furoic acid and 2-furaldehyde, which are known as ascorbic acid degradation products. The mechanism of furan formation from ascorbic acid was validated based on the labelling pattern of furan and the identification of 13CO2 and H13COOH. Furan formation is significantly slowed down in binary mixtures, e.g. the presence of erythrose led to 80% less furan under roasting conditions. This is most likely due to competing reactions in complex systems, thus disfavouring furan formation. The mitigation effect is because furan, contrary to MF, is formed without recombination of ascorbic acid fragments. Therefore, furan levels are definitely much lower in foods than expected from trials with pure ascorbic acid. Consequently, conclusions should be drawn with much caution from model reactions, avoiding extrapolation from oversimplified model systems to food products.

Intensive neutral odourants of linden honey Differences from honeys of other botanical origin

ZusammenfassungDie Aromaextrakt-Verdünnungs-analyse der flüchtigen Verbindungen aus Lindenhonig ergab 21 Geruchsstoffe mit hohen FD-Faktoren; 18 davon wurden identifiziert: l-Hexen-3-on, 2-Acetyl-1 -pyrrolin, Dimethyltrisulfid, Methional, Phenylacetaldehyd, 2-Phenylethanol, Linalool, p-Kresol, 3,9-Epoxy-1 p-menthen, 4-Methylacetophenon, 3,9-Epoxy-1,4(8)p-menthadien (Lindenether), 1,3 -p-Menthadi-en-7-al,p-Anisaldehyd, 4-Vinylguajacol, (E)-β-Da-mascenon, Eugenol, Vanillin undcis-Rosenoxid. Lindenether undcis-Rosenoxid, die auch in einem Extrakt von Lindenblüten (Tilla cordata) vorkamen, fehlten in Honigen anderer botanischer Herkunft. Diese beiden Aromastoffe und das geruchlosetrans-Limonen-1,2-diol werden als Indikatoren für Linden honig vorgeschlagen. Die Geruchsschwellen (in Luft) der 18 Aromastoffe wurden bestimmt.SummaryAroma extract dilution analysis of linden honey volatiles resulted in 21 odour compounds having high factors of dilution (FD); 18 of these compounds were identified as 1-hexen-3-one, 2-acetyl-1 -pyrroline, dimethyl trisulphide, methional, phenylacetaldehyde, 2-phenylethanol, linalool, p-cresol, 3,9-epoxy-lpmenthene, 4-methylacetophenone, 3,9-epoxy-1,4(8)-p-menthadiene (linden ether), 1,3 p-menthadien-7-al, p-anisaldehyde, 4vinylguaiacol, (E)-p-damascenone, eugenol, vanillin andcis-rose oxide. Linden ether andcis-rose oxide, which were also found in an extract obtained from the blossoms of the lime tree (Tifa cordata), were absent in honeys of other botanical origin. These two odourants and the odourlesstrans-limonene-1,2-diol are proposed as indicators for linden honey. The odour thresholds (in air) of the 18 aroma compounds are reported.

When machine tastes coffee: instrumental approach to predict the sensory profile of espresso coffee.

A robust and reproducible model was developed to predict the sensory profile of espresso coffee from instrumental headspace data. The model is derived from 11 different espresso coffees and validated using 8 additional espressos. The input of the model consists of (i) sensory profiles from a trained panel and (ii) on-line proton-transfer reaction mass spectrometry (PTR-MS) data. The experimental PTR-MS conditions were designed to simulate those for the sensory evaluation. Sixteen characteristic ion traces in the headspace were quantified by PTR-MS, requiring only 2 min of headspace measurement per espresso. The correlation is based on a knowledge-based standardization and normalization of both datasets that selectively extracts differences in the quality of samples, while reducing the impact of variations on the overall intensity of coffees. This work represents a significant progress in terms of correlation of sensory with instrumental results exemplified on coffee.

Synthesis of Deuterated Volatile Lipid Degradation Products To Be Used as Internal Standards in Isotope Dilution Assays. 2. Vinyl Ketones

The isotopically labeled compounds [5,6-(2)H(2)]-(Z)-1, 5-octadien-3-one (d-I) and [1-(2)H(1;2),2-(2)H(1;1)]-1-octen-3-one (d-II), as well as the unlabeled reference compound (Z)-1, 5-octadien-3-one (I) were prepared by improved synthesis procedures. Labeling position, chemical purity, and isotopic distribution of the compounds were characterized by various MS and NMR techniques. These molecules are used as internal standards in quantification experiments based on isotope dilution assay. The newly prepared compound d-II was synthesized in a simple two-step procedure, and formation of the main isotopomers was studied in model systems.

Current Status of Acrylamide Research in Food: Measurement, Safety Assessment, and Formation

Abstract: Relatively high amounts of acrylamide have recently been reported in carbohydrate‐rich foods under low moisture conditions. This sparked intensive investigations into acrylamide, encompassing its occurrence, chemistry, and toxicology/potential health risk in the human diet. Robust and efficient analytical methods have been developed to obtain reliable quantitative data. Recent epidemiological studies failed to evidence an association of cancer incidence and dietary acrylamide exposure. The link of acrylamide in foods to Maillard‐type reactions and, in particular, to asparagine has been a major step in elucidating feasible chemical formation routes. Decarboxylation of the Schiff base derived from asparagine and a carbonyl reactant plays a key role in acrylamide formation leading to azomethine ylide intermediates, which offer an attractive mechanistic explanation of the acrylamide amounts found experimentally, including the fact that acrylamide is preferentially formed in the presence of fructose, as compared to glucose or α‐dicarbonyls. However, the physical state of the reaction system may also affect acrylamide formation by influencing molecular mobility, particularly under low moisture conditions. Current research deals mainly with mitigation studies to reduce acrylamide during food processing and the role of water.