Oligomers in polyethylene furanoate - identification and quantification approach via LC-UV LC-MS response ratio.

Polyethylene furanoate polymer is intended to be used as a food contact material. A PEF polymer sample was investigated for its oligomer composition by solvent extraction and using HRLC-MS. The 20 oligomers found were divided into four groups: group I contains cyclic oligomers consisting of furandicarboxylic acid and monoethylene glycol units, group II comprises cyclic oligomers consisting of furandicarboxylic acid, monoethylene glycol units and one diethylene glycol unit, group III are cyclic oligomers were two monoethylene glycol units are substituted by diethylene glycol units and group IV are linear oligomers consisting of furandicarboxylic acid and monoethylene glycol units. Oligomers of group I account for around 87% of the total oligomer content, group II oligomers 12% and group III oligomers 1%. The contribution of group IV oligomers is very small: less than 0.05%. MS-MS experiments showed similar fragmentation patterns for all oligomers. The results of this study demonstrate that oligomers are abundant in the PEF material and are potential migrants to foods that are in contact with the polymer. Oligomers of group I and group II have the same absorption maxima in UV detection which was used to develop a quantification approach for these oligomers using dimethyl 2,5-furandicarboxylate as external standard.

Migration of oligomers from PET: determination of diffusion coefficients and comparison of experimental versus modelled migration.

Polyethylene terephthalate (PET) is increasingly used as food-contact material in, for example, containers for beverage such as bottles for soft drinks, mineral water, juices and beer. Mass transport of substances present in packaging materials into the packed food and beverages is monitored to verify the food law compliance of the materials. PET is known to contain or give rise to migrants that are oligomers derived from the polymeric material. Until now their actual migration potential has been investigated only poorly. A convenient way to determine their migration would be by using models. To verify existing models with experimental data, a migration kinetic study of PET oligomers was conducted. PET bottle material was submerged in 50% ethanol at 80°C for 15 h. The oligomer content in the migration solutions was determined every hour using LC-MS with the first-series cyclic PET trimer as standard. Diffusion coefficients of five PET oligomers (first-series dimer and trimer, second-series dimer and trimer, and third-series dimer) were calculated from the obtained data and compared with the calculated diffusion coefficients using the models of Welle and Piringer. This is the first study to provide diffusion characteristics of oligomers in PET other than the first-series cyclic trimer.

Identification of 34 N-glycan isomers in human serum by capillary electrophoresis coupled with laser-induced fluorescence allows improving glycan biomarker discovery.

Alterations in glycosylation have been observed in many human diseases and specific changes in glycosylation have been proposed as relevant diagnostic information. Capillary electrophoresis coupled with laser-induced fluorescence (CE-LIF) is a robust method to quantify desialylated N-glycans that are labeled with 8-aminopyrene-1,3,6-trisulfonic acid prior to analysis. To date, only a maximum of 12 glycan structures, the most abundant ones, have been identified by CE-LIF to characterize glycome modulations of total serum in the course of the diseases. In most forms of cancer, findings using CE-LIF were limited to the increase of triantennary structures carrying a Lewis(x) epitope. In this work, we identified 32 linkage and positional glycan isomers in healthy human serum using exoglycosidase digestions as well as standard glycoproteins, for which we report the assignment of novel structures. It was possible to identify and quantify 34 glycan isomers in the serum of primary epithelial ovarian cancer patients (EOC). Reduced levels of diantennary structures and of high-mannose 5 were statistically significant in the EOC samples, and also, elevated branching as well as increased antennary fucosylation were observed. For the first time, we could demonstrate that not only antennary fucosylation was of relevance in tetraantennary structures but also core-fucosylated tetraantennary N-glycans were statistically increased in EOC patients. The results of the current study provide an improved dataset to be used in glycan biomarker discovery.

Presence and sources of anthropogenic perfluoroalkyl acids in high-consumption tap-water based beverages.

This study investigates the presence and sources of perfluorinated alkyl acids (PFAAs) in tap water and corresponding tap-water based beverages such as coffee and cola collected in the city of Amsterdam, The Netherlands. Exposure pathways studies have shown that low concentrations of PFAA in tap water already may pose a high contribution to daily human exposure. Tap water samples (n=4) had higher concentrations of PFAAs than the corresponding post-mixed cola (n=4). The lower PFAA levels in the cola were attributed to the pre-treatment of tap water in the mixing machines and dilution with cola syrup. In coffee samples from a coffee machine perfluorooctanoic acid (PFOA) at 4 ng L(-1) was the dominating analyte (n=12). The concentrations of PFHpA, PFOA and non branched PFOS were found to be significantly higher in manually (self) brewed coffee than in the corresponding tap water (n=4). The contribution from short-chain PFAA analogs could not be quantified due to low recoveries. Leaching experiments at different temperatures were performed with fluoropolymers-containing tubes to investigate the potential of leaching from tubes used in beverage preparation (n=16). Fluoropolymer tubes showed leaching of PFAAs at high (80°C) temperature but its relevance for contamination of beverages in practice is small. The specific contribution from perfluoropolymer tubing inside the beverage preparation machines could not be assessed since no information was available from the manufacturers. The present study shows that although different beverage preparation processes possibly affect the concentrations of PFAAs encountered in the final consumed product, the water used for preparation remains the most important source of PFAAs. This in turn has implications for areas where drinking water is contaminated. Tap-water based beverages will possibly be an additional source of human exposure to PFAAs and need to be considered in exposure modeling.