S��������� B., N������ O., D������� V., R������ Z., D������ M., V������ J. (2004): Esters of 3-chloropropane-1,2-diol in foodstuffs. Czech J. Food Sci., We provide here for the first time the evidence that 3-chloropropane-1,2-diol (3-MCPD) occurs in foodstuffs in its free form and also in the form of esters with higher fatty acids. These esters represent a new class of food contaminants as 3-MCPD may be released in vivo by a lipase-catalysed hydrolysis reaction. We analysed 20 samples of selected retail food products for their free and bound 3-MCPD content. All samples contained free 3-MCPD at approximately 9.6-82.7 µg/kg food (3 replications, RSD = 0.4-7.0%). The levels of bound 3-MCPD (monoesters and diesters of 3-MCPD with higher fatty acids) found in the foodstuffs analysed varied between the LOD (1.1 mg per kg of fat) and 36.8 mg/kg fat with RSD = 0.3-3.3%. Five foodstuffs of plant origin processed at high temperatures contained elevated levels of bound 3-MCPD (0.14-6.10 mg/kg). A high level of bound 3-MCPD (0.28 mg/kg) was also found in a sample of pickled fish. Some variables potentially influencing the levels of either free or bound 3-MCPD in foodstuffs were determined (pH, water, chlorides, glycerol, fat and its components) and their significance was discussed.

No abstract

The formation of α-hydroxycarbonyl and α-dicarbonyl compounds from monosaccharides (glucose, fructose, arabinose, glyceraldehyde, and 1,3-dihydroxyacetone) was studied in three different model systems comprising an aqueous and alkaline solution of potassium peroxodisulfate (K₂S₂O₈), and a solution of sodium hydroxide, respectively. In total, six α-hydroxycarbonyl (in the form of O-ethyloximes) and six α-dicarbonyl compounds (as quinoxaline derivatives) were identified by GC/MS and quantified. Acetol, glycolaldehyde, 1,3-dihydroxyacetone, methylglyoxal, and glyoxal were the most abundant low molecular weight carbonyls. Within the model systems studied, the yield of α-hydroxycarbonyl and α-dicarbonyl compounds was 0.32−4.90% (n/n) and 0.35−9.81% (n/n), respectively. The yield of α-dicarbonyls was higher than that of α-hydroxycarbonyls only in aqueous solution of K₂S₂O₈ and in the other two model systems an inverse ratio of these two carbonyl types was found. For the first time, ethylglyoxal was identified as a sugar degradation product and several mechanisms explaining its formation were proposed. The achieved data indicated that low molecular weight α-hydroxycarbonyl and α-dicarbonyl compounds are predominantly formed by a direct retro-aldol reaction and α- and β-dicarbonyl cleavage. It was evident that some compounds were produced from the sugar fragmentation products. Thus, isomerisation, reduction of dicarbonyls by formaldehyde (cross-Cannizzaro reaction), and mutual disproportionation are possible reaction pathways participating in the formation of α-hydroxycarbonyl compounds. Oxidation and disproportionation of α-hydroxycarbonyl precursors as well as the aldol condensation of low molecular weight carbonyl species (followed by subsequent reactions) play an important role in the formation of several α-dicarbonyl compounds.

Phosphatidic acid (PA), important signalling and metabolic phospholipid, is predominantly localized in the subapical plasma membrane (PM) of growing pollen tubes. PA can be produced from structural phospholipids by phospholipase D (PLD) but the isoforms responsible for production of plasma membrane PA were not identified yet and their functional roles remain unknown. Following genome-wide bioinformatic analysis of PLD family in tobacco, we focused on the pollen-overrepresented PLDδ class. Combining live-cell imaging, gene overexpression or knock-down, lipid-binding and structural bioinformatics, we characterized 5 NtPLDδ isoforms. Distinct PLDδ isoforms preferentially localize to the cytoplasm or subapical PM. Using fluorescence recovery after photobleaching, domain deletion and swapping analyses we show that membrane-bound PLDδs are tightly bound to PM, primarily via the central catalytic domain. Knock-down, overexpression and in vivo PA level analyses revealed isofom PLDδ3 as the most important member of the PLDδ subfamily active in pollen tubes. PA promotes binding of PLDδ3 to the PM, thus creating a positive feedback loop, where PA accumulation leads to the formation of massive PM invaginations. Tightly controlled production of PA generated by PLDδ3 at the PM is important for maintaining the balance between various membrane trafficking processes, that are crucial for plant cell tip growth.

Cheeses are a group of fermented dairy products that are produced all over the world in various forms and flavours. Milk, especially sheep or goat milk, is still regarded as an expensive raw material in the world, which makes milk and milk products highly attractive as a fraud target. Most often, such fraud includes partial or complete substitution with cheaper sorts of milk (e.g. bovine milk). The aim of this work was to verify the authenticity of 27 cheeses commonly emerging on the Czech food market. The cheeses were distinguished on the basis of milk animal species origin. For this purpose, two mass spectrometry techniques were used: matrix‐assisted laser desorption/ionization with time of flight mass spectrometry together with principal component analysis method and liquid chromatography coupled with electrospray ionization and quadrupole time‐of‐flight mass spectrometry. The results were a partial success, because the cheeses could only be partially distinguished with the first mass spectrometry technique probably because of the influence of some protein additive materials in cheeses. The second technique allowed for collecting higher quality results and thus appears to be highly suitable for the research task.

The formation pathways of the N-containing roast-smelling compounds 2-acetyl-1-pyrroline, 2-acetyl-1(or 3),4,5,6-tetrahydropyridine, and their structural analogues 2-propionyl-1-pyrroline and 2-propionyl-1(or 3),4,5,6-tetrahydropyridine were studied upon extrusion cooking using the CAMOLA approach. The samples were produced under moderate extrusion conditions (135 °C, 20% moisture, 400 rpm) employing a rice-based model recipe enriched with flavor precursors ([U-(13)C6]-D-glucose, D-glucose, glycine, L-proline, and L-ornithine). The obtained data indicate that the formation of these compounds upon extrusion follows pathways similar to those reported for nonsheared model systems containing D-glucose and L-proline. 2-Acetyl-1-pyrroline is formed (i) by acylation of 1-pyrroline via C2 sugar fragments (major pathway) and (ii) via ring-opening of 1-pyrroline incorporating C3 sugar fragments (minor pathway), whereas 2-propionyl-1-pyrroline incorporates exclusively C3 sugar fragments. 2-Acetyl-1(or 3),4,5,6-tetrahydropyridine and the corresponding propionyl analogue incorporate C3 and C4 sugar fragments, respectively. In addition, it has been shown that the formation of 2-acetyl-1-pyrroline in low-moisture systems depends on the pH value of the reaction mixture.

Abstract

A survey of the levels of 3-chloropropane-1,2-diol (3-MCPD) and its precursors in a range of selected retail food products in the Czech Republic is reported. The foods were selected according to their content of water, chlorides and lipids and included foods processed at high temperatures and/or stored for a long time. The content of 3-MCPD was determined by the GC/MS method using deuterium-labeled 3-MCPD. Water content and pH value of the analysed foods were determined together with the recognised precursors of 3-MCPD, fat, glycerol and chlorides. An insight into the level of 3-MCPD influenced by these variables has been done by principal components analysis.