Formation of amines and aldehydes from parent amino acids during thermal processing of cocoa and model systems: new insights into pathways of the strecker reaction

A method based on a derivatization with dansyl chloride and LC-MS-MS determination was developed for the quantitation of 2-methylbutyl-, 3-methylbutyl-, 2-phenylethyl-, 3-(methylthio)propyl-, and 2-methylpropylamine. Its application on unfermented, fermented, and roasted cocoas from Ghana and Sulawesi revealed an increase of all amines, except the 3-(methylthio)propylamine, during cocoa fermentation, suggesting an enzymic formation from the parent amino acids isoleucine, leucine, phenylalanine, and valine. However, a much more pronounced formation of most of the amines was measured after roasting of the cocoa, leading to concentrations in the milligrams per kilogram range. This result suggested a new "thermogenic" formation pathway of "biogenic amines". A comparison of the amounts of the amines and the aldehydes in roasted cocoa revealed similar concentrations, for example, for 2- and 3-methylbutanal and the respective amines, whereas the amounts of 2-phenylethylamine were much higher as compared to the amounts of phenylacetaldehyde. Strecker-type model systems, in which each parent amino acid was reacted with 2-oxopropanal, revealed the formation of both the amine and the aldehyde; however, in contrast to cocoa, the concentrations of the aldehydes were always much higher as compared to the amines. The results showed for the first time the thermally induced generation of "biogenic amines" from amino acids. Possible reasons for the different ratios of amines versus aldehydes formed during the roasting of cocoa or the model systems, respectively, are discussed.     

Oxalate content of cereals and cereal products

Detailed knowledge of food oxalate content is of essential importance for dietary treatment of recurrent calcium oxalate urolithiasis. Dietary oxalate can contribute considerably to the amount of urinary oxalate excretion. Because cereal foods play an important role in daily nutrition, the soluble and total oxalate contents of various types of cereal grains, milling products, bread, pastries, and pasta were analyzed using an HPLC-enzyme-reactor method. A high total oxalate content (>50 mg/100 g) was found in whole grain wheat species Triticum durum (76.6 mg/100 g), Triticum sativum (71.2 mg/100 g), and Triticum aestivum (53.3 mg/100 g). Total oxalate content was comparably high in whole grain products of T. aestivum, that is, wheat flakes and flour, as well as in whole grain products of T. durum, that is, couscous, bulgur, and pasta. The highest oxalate content was demonstrated for wheat bran (457.4 mg/100 g). The higher oxalate content in whole grain than in refined grain cereals suggests that oxalic acid is primarily located in the outer layers of cereal grains. Cereals and cereal products contribute to the daily oxalate intake to a considerable extent. Vegetarian diets may contain high amounts of oxalate when whole grain wheat and wheat products are ingested. Recommendations for prevention of recurrence of calcium oxalate stone disease have to take into account the oxalate content of these foodstuffs.     

Induction of cell death in Caco-2 human colon carcinoma cells by ellagic acid rich fractions from muscadine grapes (Vitis rotundifolia)

Possible anticancer mechanisms exerted by polyphenolic compounds contained in fruits and vegetables include antioxidant activity, the inhibition of proliferation, and the induction of apoptosis in cancer cells. This study examined the effects of four isolated polyphenolic extracts from red muscadine grapes (Vitis rotundifolia) on vital cell parameters and the induction of apoptosis in Caco-2 colon carcinoma cells. The magnitude of effects in cell culture was then correlated to polyphenolic composition and antioxidant capacity. Whereas anticancer effects of individual polyphenolic compounds have been demonstrated multiple times, information relating to anticancer effects of polyphenolic extracts is not available in abundance. All four extracts induced apoptosis, decreased cell number, and caused alterations in cell cycle kinetics in a concentration-dependent manner. The efficacy of the polyphenolics on vital cell parameters correlated well to the presence of ellagic acid glycosides and flavonoids and also to the antioxidant capacity. This study demonstrated the anticancer properties of ellagic acid rich extracts from red muscadine juice.     

Soil water storage appears to compensate for climatic aridity at the xeric margin of European tree species distribution

Based on macroecological data, we test the hypothesis whether European tree species of temperate and boreal distribution maintain their water and nutrient supply in the more arid southern margin of their distribution range by shifting to more fertile soils with higher water storage than in their humid core distribution range (cf. soil compensatory effects). To answer this question, we gathered a large dataset with more than 200,000 plots that we related to summer aridity (SA), derived from WorldClim data, as well as soil available water capacity (AWC) and soil nutrient status, derived from the European soil database. The soil compensatory effects on tree species distribution were tested through generalized additive models. The hypothesis of soil compensatory effects on tree species distribution under limiting aridity was supported in terms of statistical significance and plausibility. Compared to a bioclimatic baseline model, inclusion of soil variables systematically improved the models’ goodness of fit. However, the relevance measured as the gain in predictive performance was small, with largest improvements for P. sylvestris, Q. petraea and A. alba. All studied species, except P. sylvestris, preferred high AWC under high SA. For F. sylvatica, P. abies and Q. petraea, the compensatory effect of soil AWC under high SA was even more pronounced on acidic soils. Soil compensatory effects might have decisive implications for tree species redistribution and forest management strategies under anthropogenic climate change. Therefore, soil compensatory effects deserve more intensive investigation, ideally, in studies combining different spatial scales to reduce the uncertainty associated with the precision of soil information.     

Tentative Avenanthramide‐Modifying Enzyme in Oats

A decrease of the concentration of the synthetic avenanthramide N‐(4′‐hydroxy‐(E)‐cinnamoyl)‐5‐hydroxyanthranilic acid in a buffered slurry of milled oat groats (Avena sativa L.) was temperature and pH‐dependent, with a maximum rate at 30°C and pH 9. The reaction was inhibited in the presence of 2‐mercaptoethanol, acetic acid and at high temperature; suggestive of enzymatically catalyzed nature. Among eight different synthetic avenanthramides tested, the tentative enzyme had highest affinity for avenanthramides comprising caffeic and p‐coumaric acids and lowest for those comprising sinapic and ferulic acids. The activity was found in samples from several oat cultivars and was equally pronounced in both bran and endosperm flour of oats. Steeping of oat grains did not influence the reaction.