The thermal degradation over temperature and time of selected amino acids (Asp, Gln, and Glu) in the presence of reducing sugars was investigated in low moisture model systems. Copyrolysis of glucose-Asp mixtures led to the release of acrylic acid, attaining >5 mmol/mol Asp at 230 degrees C after 5 min. Spurious amounts of 3-butenamide were detected upon heating Gln together with a carbonyl source. Apparently, intramolecular cyclization is favored to procure 2-pyrrolidinone, reaching levels >3 mmol/mol above 230 degrees C. 2-Pyrrolidinone was also formed in comparable amounts in pyrolyzed sugar-Glu mixtures, indicating that the Maillard reaction may be an important contributor to the formation of 2-pyrrolidinone in certain cooked foods. The chemical route to acrylic acid and 3-butenamide is probably analogous to that described for acrylamide recently. Evidence is also presented that acrylic acid may be an intermediate in the formation of acrylamide, and yields could be augmented by coincubation of fructose-Asp with certain amino acids such as Gln, reaching approximately 5% of the yield obtained by the Asn route. A computational study to determine the reactivity of the vinylogous products indicated a reduced ability of 3-butenamide as compared to acrylamide to form stable intermediates by Michael nucleophilic addition. Acrylamide and acrylic acid exhibited a similar theoretical reactivity potential toward nucleophiles. No information is as yet available on the occurrence of acrylic acid in cooked foods. Extensive toxicological evaluation indicates that acrylic acid is of no concern at the amounts to be expected in foods.
Remote site deprotonation of a coordinated imidazole ligand switches the reduction potential of coordinated iron over a narrow pH range from +0.920 to 20.460 V.
Recently, reports have been published on the occurrence of chlorate mainly in fruits and vegetables. Chlorate is a by-product of chlorinating agents used to disinfect water, and can be expected to be found in varying concentrations in drinking water. Data on potable water taken at 39 sampling points across Europe showed chlorate to range from < 0.003 to 0.803 mg l(-1) with a mean of 0.145 mg l(-1). Chlorate, however, can also be used as a pesticide, but authorisation was withdrawn in the European Union (EU), resulting in a default maximum residue limit (MRL) for foods of 0.01 mg kg(-1). This default MRL has now led to significant problems in the EU, where routinely disinfected water, used in the preparation of food products such as vegetables or fruits, leaves chlorate residues in excess of the default MRL, and in strict legal terms renders the food unmarketable. Due to the paucity of data on the chlorate content of prepared foods in general, we collated chlorate data on more than 3400 samples of mainly prepared foods, including dairy products, meats, fruits, vegetables and different food ingredients/additives. In total, 50.5% of the food samples contained chlorate above 0.01 mg kg(-1), albeit not due to the use of chlorate as a pesticide but mainly due to the occurrence of chlorate as an unavoidable disinfectant by-product. A further entry point of chlorate into foods may be via additives/ingredients that may contain chlorate as a by-product of the manufacturing process (e.g. electrolysis). Of the positive samples in this study, 22.4% revealed chlorate above 0.1 mg kg(-1). In the absence of EU levels for chlorate in water, any future EU regulations must consider the already available WHO guideline value of 0.7 mg l(-1) in potable water, and the continued importance of the usage of oxyhalides for disinfection purposes.
A sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed to detect trace amounts of the antibiotic chloramphenicol (CAP) in honey. The methodology entailed a solid-phase extraction of aqueous honey solutions followed by liquid-liquid partitioning, filtration and direct injection onto the LC-MS/MS system. Honey extracts were spiked with an isotopically labelled internal standard (d(5)-CAP) to compensate for analyte loss and potential ion suppression during the MS stage. Detection of the analyte was achieved by negative ionization electrospray in the selected reaction monitoring (SAM) mode. For confirmation, four characteristic mass transitions were monitored each for the analyte and the surrogate standard. The method was validated according to the latest European Union criteria for the analyses of veterinary drug residues in food. At all three fortification levels studied (0.1, 0.2, 0.5 microg kg(-1)) the method was accurate to within 15%. The repeatability and within-laboratory reproducibilities were <12 and 18%, respectively. The decision limit (CC alpha) and detection capability (CC beta) were both <0.1 microg kg(-1). The procedure provides a sensitive and reliable method for the determination of residues of chloramphenicol in honey. Numerous raw honeys of various geographical origins were analysed, showing extensive contamination particularly those of Chinese origin.
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