Acrylamide in roasted almonds and hazelnuts

The influences of composition and roasting conditions on acrylamide formation in almonds and hazelnuts were investigated. Eighteen samples of almonds originating from the U.S. and Europe were analyzed for sugars and free amino acids, and acrylamide formed during roasting was determined. Asparagine was the main free amino acid in raw almonds and correlated with the acrylamide content of dark roasted almonds. Roasting temperature was another key factor and had a very strong influence on acrylamide formation. Almonds of European origin contained significantly less free asparagine and formed significantly less acrylamide during roasting as compared to the almonds from the U.S. Roasted hazelnuts contained very little acrylamide because of the low content of free asparagine in the raw nut. Reducing sugars, although being consumed much faster than free amino acids in both types of nuts, were not decisive for the extent of acrylamide formation during roasting.     

Determination of advanced glycation endproducts by LC-MS/MS in raw and roasted almonds (Prunus dulcis)

A sensitive and reliable LC-(ESI)MS/MS method was developed and validated for the simultaneous analysis of five common advanced glycation endproducts (AGEs) after enzymatic digestion in raw and roasted almonds. AGEs included carboxymethyl-lysine (CML), carboxyethyl-lysine (CEL), pyralline (Pyr), argpyrimidine (Arg-p), and pentosidine (Pento-s). This method allows accurate quantitation of free and AGE-protein adducts of target AGEs. Results indicate that CML and CEL are found in both raw and roasted almonds. Pyr was identified for the first time in roasted almonds and accounted for 64.4% of free plus bound measured AGEs. Arg-p and Pento-s were below the limit of detection in all almond samples tested. Free AGEs accounted for 1.3-26.8% of free plus bound measured AGEs, indicating that protein-bound forms predominate. The roasting process significantly increased CML, CEL, and Pyr formation, but no significant correlation was observed between these AGEs and roasting temperature.     

Determination of acrylamide during roasting of coffee

In this study different Arabica and Robusta coffee beans from different regions of the world were analyzed for acrylamide after roasting in a laboratory roaster. Due to the complex matrix and the comparably low selectivity of the LC-MS at m/ z 72, acrylamide was analyzed after derivatization with 2-mercaptobenzoic acid at m/ z 226. Additionally, the potential precursors of acrylamide (3-aminopropionamide, carbohydrates, and amino acids) were studied. The highest amounts of acrylamide formed in coffee were found during the first minutes of the roasting process [3800 ng/g in Robusta ( Coffea canephora robusta) and 500 ng/g in Arabica ( Coffea arabica)]. When the roasting time was increased, the concentration of acrylamide decreased. It was shown that especially the roasting time and temperature, species of coffee, and amount of precursors in raw material had an influence on acrylamide formation. Robusta coffee contained significantly larger amounts of acrylamide (mean = 708 ng/g) than Arabica coffee (mean = 374 ng/g). Asparagine is the limiting factor for acrylamide formation in coffee. 3-Aminopropionamide formation was observed in a dry model system with mixtures of asparagine with sugars (sucrose, glucose). Thermal decarboxylation and elimination of the alpha-amino group of asparagine at high temperatures (>220 degrees C) led to a measurable but low formation of acrylamide.     

Analysis of acrylamide in green tea by gas chromatography-mass spectrometry

Optimization of the solid-phase extraction cleanup procedure enabled the GC-MS analysis of acrylamide in tea samples without the interference of bromination by tea catechins. Although polyvinylpolypyrrolidone (PVPP) is available for removing tea catechins from tea extract, the peaks derived from PVPP had the same retention time as brominated acrylamide in mass chromatograms obtained by GC-MS. A considerable amount of acrylamide was formed at roasting temperatures of > or =120 degrees C; the highest acrylamide level was observed when tea samples were roasted at 180 degrees C for 10 min. Higher temperatures and longer processing times caused a decrease in the acrylamide content. Furthermore, an analysis of 82 tea samples showed that rather than the reducing sugar content, the asparagine content in tea leaves was a significant factor related to acrylamide formation in roasted products. The acrylamide level in roasted tea products was controlled by asparagine in the presence of reducing sugars.     

Changes in the concentrations of acrylamide, selected odorants, and catechins caused by roasting of green tea

This research aims to optimize roasted green tea (Houjicha) processing by using roasting treatments to achieve acrylamide mitigation without compromising the quality. 2-Ethyl-3,5-dimethylpyrazine and 2-ethyl-3,6-dimethylpyrazine were identified as potent odorants by aroma extract dilution analysis. In preliminary sensory experiments, the desirable Houjicha flavor was produced in products roasted at 160 degrees C for 30 min and at 180 degrees C for 15 min. Under these conditions, potent odorants were formed at levels adequate for contributing to the Houjicha flavor. Acrylamide amounts in tea infusions were 2.0 and 4.0 microg/L by roasting at 160 degrees C for 30 min and at 180 degrees C for 15 min, respectively. Compared to roasting at 180 degrees C, the degradation of tea catechins was suppressed by roasting at 160 degrees C. Hence, roasting at 160 degrees C for is recommended for Houjicha processing for acrylamide mitigation, formation of potent odorants, and suppression of degradation of tea catechins.     

Effects of asparagine, fructose, and baking conditions on acrylamide content in yeast-leavened wheat bread

A repeatable procedure for studying the effects of internal and external factors on acrylamide content in yeast-leavened wheat bread has been developed. The dough contained wheat endosperm flour with a low content of precursors for acrylamide formation (asparagine and reducing sugars), dry yeast, salt, and water. The effects of asparagine and fructose, added to the dough, were studied in an experiment with a full factorial design. More than 99% of the acrylamide was found in the crust. Added asparagine dramatically increased the content of acrylamide in crusts dry matter (from about 80 microg/kg to between 600 and 6000 microg/kg) while added fructose did not influence the content. The effects of temperature and time of baking were studied in another experiment using a circumscribed central composite design. Mainly temperature (above 200 degrees C) but also time increased the acrylamide content in crust dry matter (from below 10 to 1900 microg/kg), and a significant interaction was found between these two factors. When baked at different conditions with the same ingredients, a highly significant relationship (P < 0.001) between color and acrylamide content in crust was found. Added asparagine, however, did not increase color, showing that mainly other amino compounds are involved in the browning reactions.     

Acrylamide in French fries: influence of free amino acids and sugars

The free amino acid profile and sugar (fructose, glucose, and sucrose) composition were determined in potato samples selected to give a large range of variation (a total of 66 samples). From these samples French fries were produced in a laboratory-scale simulation of an industrial process followed by a finish fry at 180 degrees C for 3.5 min using a restaurant fryer. The final product was blast frozen and analyzed for acrylamide. Acrylamide was detected in all samples, but its concentration varied significantly from 50 to 1800 ng/g. For isotope dilution (13C3) acrylamide analysis, samples were extracted with water, cleaned up on HLB Oasis polymeric and Accucat mixed mode anion and cation exchange SPE columns, and analyzed by LC-MS/MS. Statistical analysis of the data indicates that the effect of sugars and asparagine on the concentration of acrylamide in French fries is positive and significant (p < 0.001). It appears that one of the ways acrylamide formation in French fries can be effectively controlled is by the use of raw products with low sugar (and to a lesser degree, asparagine) content.     

Correlation of acrylamide generation in thermally processed model systems of asparagine and glucose with color formation, amounts of pyrazines formed, and antioxidative properties of extracts

The relations between the formation of acrylamide and color, pyrazines, or antioxidants in an asparagine/d-glucose browning model system under various conditions were investigated. The highest level of acrylamide was produced in the asparagine/glucose (1:3) system heated at 170 degrees C for 30 min (2629 microg/g asparagine). Color intensity increased with temperature and heating time. The formation of pyrazines increased steadily with an increase of temperature (140-170 degrees C) and heating time (15-60 min). Antioxidant formation varied among the samples heated under different conditions. A clear correlation between formation of acrylamide and browning color was obtained. The formation of acrylamide was linearly correlated with the formation of total pyrazines during the initial stages of the Maillard reaction. No obvious correlation between formation of acrylamide and antioxidants was observed. However, excess amounts of asparagine increased the formation of antioxidants, whereas excess amounts of glucose reduced its formation.     

Gas chromatographic investigation of acrylamide formation in browning model systems

Acrylamide formed in browning model systems was analyzed using a gas chromatograph with a nitrogen-phosphorus detector. Asparagine alone produced acrylamide via thermal degradation at the level of 0.99 microgram/g of asparagine. When asparagine was heated with triolein-which produced acrolein at the level of 1.82 +/- 0.31 (n = 5) mg/L of headspace by heat treatment-acrylamide was formed at the level of 88.6 microgram/g of asparagine. When acrolein gas was sprayed onto asparagine heated at 180 degrees C, a significant amount of acrylamide was formed (114 microgram/g of asparagine). On the other hand, when acrolein gas was sprayed onto glutamine under the same conditions, only a trace amount of acrylamide was formed (0.18 microgram/g of glutamine). Relatively high levels of acrylamide (753 microgram/g of ammonia) were formed from ammonia and acrolein heated at 180 degrees C in the vapor phase. The reaction of acrylic acid, which is an oxidation product of acrolein and ammonia, produced a high level of acrylamide (190 000 microgram/g of ammonia), suggesting that ammonia and acrolein play an important role in acrylamide formation in lipid-rich foods. Acrylamide can be formed from asparagine alone via thermal degradation, but carbonyl compounds, such as acrolein, promote its formation via a browning reaction.     

Formation of lipid oxidation and isomerization products during processing of nuts and sesame seeds

The aim of the present study was to quantify some nutritional and safety quality parameter changes that take place in nuts (roasting) and sesame seeds (dehulling, roasting, milling, and sterilization) during processing. Such evaluation was based on chemical analysis of various indicators of lipid alteration in raw and processed pistachios, almonds, peanuts, and tahina. Lipid oxidation was assessed by the evolution of lipid oxidation products including hydroperoxides, p-anisidine, and thiobarbituric acid reactive substances, as well as carboxymethyllysine (CML) and trans fatty acids (tFAs). All these parameters were significantly affected by the different processing stages, especially by roasting and sterilization (tahina). Nut roasting and sesame heat treatment increased the primary (hydroperoxides) and secondary (aldehydic compounds) lipid oxidation products, with the p-anisidine value reaching 6-11.5 and thiobarbituric acid reactive substances 3-5 mg/kg (equiv of malondialdehyde) in the different end products. In addition, roasting led to the formation of CML (between 12.7 and 17.7 ng/mg) and tFAs (between 0.6 and 0.9 g/100 g) in nuts and tahina, which were absent in the raw material. Roasting parameters appear as the critical factor to control to limit the CML and tFA formation in the final product.