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Plasticizers in toys are a recurring source of criticism and concern, as consumers feel they may endanger the health of their children. Most of the information available in literature concerns the presence or absence of certain phthalic acid ester plasticizers. Very little information can be found in the public domain with respect to the actually used plasticizers at a given time and place. In this paper, we present the plasticizer composition of 118 samples from 88 polyvinyl chloride toys found on the Swiss market in autumn 2015. Bis(2-ethylhexyl) terephthalate (DEHT) was by far the most frequent main plasticizer in the analyzed samples, which is a change when compared to the plasticizers found in toys and child care articles in 2007. Furthermore, the data show that the banned phthalates in toys are only a minor concern. The occurrence, however, is not evenly distributed between importers. If a toy is not designed to be sold on the European market by the manufacturer, it seems to be more likely to contain a banned phthalic acid ester. [ABSTRACT FROM PUBLISHER]

Plasticizers migrate from polyvinylchloride (PVC) infusion systems into lipid emulsions. The aim of this study was to investigate the leaching of different plasticizers from PVC perfusion lines by a selection of lipid emulsions under clinical conditions. Seven PVC perfusion lines with an equal length of 150 cm and three internal diameters were perfused with three lipid emulsions: Intralipid ® 20%, ClinOleic ® 20% and SMOFlipid ® 20%, mimicking clinical conditions. The concentrations of the plasticizers were measured directly in the emulsions by gas chromatography – mass spectrometry. Of the four plasticizers examined in this study, di (2-ethylhexyl) phthalate (DEHP) leached the most and was found, on average, at 46.5 μg/ml in the emulsions – around one order of magnitude higher than the other plasticizers. This study demonstrates that the leaching of DEHP by lipid emulsions in conditions of total parenteral nutrition is many times higher than should be accepted and higher when compared to the other plasticizers. There was no significant difference in leaching of plasticizers in relation to the type of lipid emulsion. The influence of tube diameter on the leaching rate of plasticizers should be taken into account especially in particular exposed patients. [ABSTRACT FROM AUTHOR]

Rösti, a fried potato product, is a large contributor to acrylamide exposure locally in Switzerland. A survey of 55 dishes prepared by 51 restaurants in the city of Zurich showed that the average rösti contained 702 µg/kg acrylamide. By analysing the content of reducing sugars in the potatoes used for frying, it is shown that with simple measures, the exposure to acrylamide could easily be reduced by factor 2 or more, while even improving the culinary experience. Though rösti is a typical dish in the German-speaking areas in Switzerland, the result may be of general interest for fried potato products which are popular in large areas of Central Europe. [ABSTRACT FROM PUBLISHER]

Passing from local converters backwards through the supply chain, nine major producers of polyolefin granulates were asked to supply the declaration of compliance (DoC) and supporting documentation (SD) underpinning the safety of the substances potentially migrating into foods, as legally required in Europe. Within half a year from the request, DoCs were delivered by the converters and the granulate producers, but no SD. Only two producers provided very limited information in addition to their DoC. Some producers refused responsibility in their DoC (general disclaimer), which implies that the customers should have done the complete compliance work – but none of them did. Virtually no data was obtained on substances used other than the specifically regulated monomers and additives, and none about reaction products (including oligomeric material) and impurities. Comprehensive two-dimensional gas chromatography (GC×GC) was used to generate semiquantitative pictures of the low molecular constituents in the granulates, visualizing the extent of compliance work expected. In conclusion, there is a broad gap between the legal requirements and reality that ought to be eliminated. It does not seem technically impossible. [ABSTRACT FROM AUTHOR]

The first joint European enforcement campaign on the migration of plasticizers from the gaskets of lids into oily foods in 2011 revealed exceeded legal limits in 24% of the samples. As a follow-up, a campaign was performed with the focus on systematic compliance work that ensures the abidance by the legal limits for the plasticizers. Chemical analysis was merely considered as a verification of the compliance work. This approach was new and a new procedure was proposed. Authorities of 12 European countries participated with 48 samples. They all used the same letters and explanatory texts. At best for 6 of the 48 products the submitted documents revealed receivable compliance work, whereby chemical analysis showed that for one of these in reality a different lid had been used. For 14 products compliance was supported by data from long term migration into test foods, but the legal limit was nevertheless exceeded for one of these and for 6 others the migrations was only slightly below it, clearly higher than in the tests reported in the supporting documentation. For 23 products compliance was only derived from conventional simulation, mostly at 10 d/40 °C, even though it was well known that such simulation may severely underestimate real migration. In fact, 9 of these products exceeded the legal limits. Most lid producers abdicated from their responsibility by delegating migration testing to the food packer, even though it is unrealistic that a packer performs tests lasting years before he uses the lids (in fact none of them did). Chemical analysis revealed wrongly declared plasticizers for 7 products. Legal limits were exceeded in 10 packed foods, which corresponded to 29% of those with free oil in contact with the gasket. Such disastrous results are seldom encountered by authorities and imperatively call for more effective enforcement. [ABSTRACT FROM AUTHOR]

The results of a joint European enforcement campaign are described. The two governmental food control laboratories in Stuttgart/Germany and Zürich/Switzerland analyzed the migration of the plasticizers from the gaskets of lids into food in glass jars for 411 products collected by the authorities of 21 European countries. Of these products, 308 contained free edible oil in contact with the gasket and were considered relevant for further evaluation. In 74 of the relevant products (24 %), either non-authorized plasticizers had been used or the migration exceeded the legal limits, in some cases for several parameters and by up to more than a factor of 10. Most of the products were 1-4 years from the end of their shelf life. Taking into account that migration proceeds throughout storage, sometimes even accelerates, limits are likely to be exceeded for many more products by the end of the shelf life. Polyadipate showed the lowest migration. Promising gaskets are either plasticized exclusively with a polyadipate or with combinations of substances. Joint enforcement is cost-effective, particularly when chemical analysis is demanding; accumulation of experience facilitates the evaluation of results, and joint measures are promising to be more effective. [ABSTRACT FROM AUTHOR]

Abstract: In recent years, lipidomics or lipid profiling, an extension of metabolomics where the lipid complement of a cell, tissue or organism is measured, has been the recipient of increasing attention as a research tool in a range of diverse disciplines including physiology, lipid biochemistry, clinical biomarker discovery and pathology. The advancement of the field has been driven by the development of analytical technologies, and in particular advances in liquid chromatography mass spectrometry and chemometric methods. In this review, we give an overview of the current methods with which lipid profiling is being performed. The benefits and shortcomings of mass spectrometry both in the presence and absence of chromatographic separation techniques such as liquid-, gas- and thin layer chromatography are explored. Alone these techniques have their limitations but through a combination many of the disadvantages may be overcome providing a valuable analytical tool for a variety of disease processes. [Copyright &y& Elsevier]

Electrosprayed spots of varying thickness were evaluated for use as reproducible, homogenous, high efficiency MALDI samples. Thin samples on stainless steel plates were found to give exceptionally strong signals, as did the last layers of thick samples, when ablated down to the steel substrate. A small enhancement was also observed for thin samples on a gold substrate, and with a few-nanometer gold coating on top of a thick sample. Ion yields and intensity ratios can be understood in the context of the previously described quantitative MALDI model including the matrix-metal interfacial ionization potential reduction effect (Knochenmuss, R.; Anal. Chem. 2004, 76, 3179–3184). The absolute and relative stabilities of ion signals were found to be at least a factor of two better for the thin electrosprayed spots, compared to spots prepared by dried droplet methods. [Copyright &y& Elsevier]

Matrix-assisted laser desorption/ionization mass spectrometly imaging is a technique for direct analysis of tissue sections without the use of molecular tags or contrast agents. The combination of spatial and mass resolution results in large and complex data sets that require powerful and efficient analysis and interpretation tools. Conventional images, derived from a specific analyte mass, do not identify the spatially localized correlations between analytes that are latent in the data. A new approach to find and visualize these correlations is presented. Clustering methods are used to classify pixels by spectral similarity, facilitating definition of distinct spatial regions. Principal component and discriminant analyses are combined to comprehensively identify changes in the mass spectra between regions. Images are generated by projecting the spectra of each pixel on the discriminant spectra; contrast is then a function of multiple correlated peaks. [ABSTRACT FROM AUTHOR]

The high mass accuracy and resolution of Fourier transform (FT)-ion cyclotron resonance (ICR) mass spectrometry are making it an increasingly useful tool in drug discovery and development. The basics of FT-ICR are described here, including modern ion sources and fragmentation methods. Although FT-ICR is not a high-throughput method in the traditional sense, previously difficult and complex problems are being efficiently approached using steadily improving instruments and magnets. Applications are surveyed in fields such as proteomics, metabonomics, natural product analysis and non-covalent complexes. [Copyright &y& Elsevier]

The central nervous system myelin components oligodendrocyte-myelin glycoprotein, myelin-associated glycoprotein and the Nogo-66 domain of Nogo-A inhibit neurite outgrowth by binding the neuronal glycosyl-phosphatidylinositol-anchored Nogo-66 receptor (NgR) that transduces the inhibitory signal to the cell interior via a transmembrane co-receptor, p75NTR. Here, we demonstrate that human NgR expressed in human neuroblastoma cells is constitutively cleaved in a post-ER compartment to generate a lipid-raft associated C-terminal fragment that is present on the cell surface and a soluble N-terminal fragment that is released into the medium. Mass spectrometric analysis demonstrated that the N-terminal fragment terminated just after the C-terminus of the iigand-binding domain of NgR. In common with other shedding mechanisms, the release of this fragment was blocked by a hydroxamate-based inhibitor of zinc metalloproteinases, but not by inhibitors of other protease classes and up-regulated by treatment with the cellular cholesterol depleting agent methyl-β-cyclodextrin. The N-terminal fragment bound Nogo-66 and blocked Nogo-66 binding to cell surface NgR but failed to associate with p75NTR, indicative of a role as a Nogo-66 antagonist. Furthermore, the N- and C-terminal fragments of NgR were detectable in human brain cortex and the N-terminal fragment was also present in human cerebrospinal fluid, demonstrating that NgR proteolysis occurs within the human nervous system. Our findings thus identify a potential cellular mechanism for the regulation of NgR function at the level of the receptor. [ABSTRACT FROM AUTHOR]

The matrix suppression effect (MSE) can lead to high-quality MALDI mass spectra: strong analyte signals and weak or negligible matrix background peaks. Experiment and theory suggest that MSE should be widespread and, therefore, generally applicable to measurement of low molecular weight (LMW) substances. These are otherwise impractical with MALDI due to interference from matrix. Appropriate conditions for MSE were investigated and tested on a variety of LMW substances. Straightforward and semiautomated interpretation was possible for 87.7% of these. Another 3.5% gave poor MSE due to sodium cationization rather than protonation of the analyte, but interpretation was possible. MALDI imaging shows that MSE varies significantly across a typical sample. Selective data accumulation could further increase the utility of the method. Samples containing more than one analyte were also studied. Analyte-analyte suppression was not found to be excessive, and moderately abundant minority species can be adequately detected. [ABSTRACT FROM AUTHOR]

Electrospray time-of-flight mass spectrometry was used to quantitatively determine the dissociation constant of chorismate mutase and a transition state analogue inhibitor. This system presents a fairly complex stoichiometry because the native protein is a homotrimer with three equal and independent substrate binding sites. We can detect the chorismate mutase trimer as well as chorismate mutase-inhibitor complexes by choosing appropriate conditions in the ESI source. To verify that the protein-inhibitor complexes are specific, titration experiments with different enzyme variants and different inhibitors were performed. A plot of the number of bound inhibitors versus added inhibitor concentration revealed saturation behavior with 3:1 (inhibitor:functional trimer) stoichiometry for the TSA. The soft ESI conditions, the relatively high protein mass of 43.5 kDa, and the low charge state (high m/z) result in broad peaks, a typical problem in analyzing noncovalent protein complexes. Due to the low molecular weight of the TSA (226 Da) the peaks of the free protein and the protein with one, two or three inhibitors bound cannot be clearly resolved. For data analysis, relative peak areas of the deconvoluted spectra of chorismate mutase-inhibitor complexes were obtained by fitting appropriate peak shapes to the signals corresponding to the free enzyme and its complexes with one, two, or three inhibitor molecules. From the relative peak areas we were able to calculate a dissociation constant that agreed well with known solution-phase data. This method may be generally useful for interpreting mass spectra of noncovalent complexes that exhibit broad peaks in the high m/z range. [Copyright &y& Elsevier]

Noncovalent complexes between chicken muscle adenylate kinase and two inhibitors, P1,P4-di(adenosine-5′)tetraphosphate (Ap4A) and P1,P5-di(adenosine-5′) pentaphosphate (Ap5A), were investigated with electrospray ionization mass spectrometry under non-denaturing conditions. The nonconvalent nature and the specificity of the complexes are demonstrated with a number of control experiments. Titration experiments allowed the association constants for inhibitor binding to be determined. Problems with concentration dependent ion yields are circumvented by a data evaluation method that is insensitive to the overall ionization efficiency. The Ka values found were 9.0 × 104 M−1 (Ap4A) and 4.0 × 107 M−1 (Ap5A), respectively, in very good agreement with available literature data. [Copyright &y& Elsevier]

Nickel is the most common cause of contact allergy affecting 8%-19% of the adult general population and 8%-10% of adolescents and children, whereas girls and women are affected disproportionally more often.[[1], [3]] Even though nickel release from articles in prolonged contact with skin has been regulated in Europe for more than 20 years, the prevalence of nickel allergy has not decreased enough and seems to have stabilized on a high level.[[1], [5]] Market studies have repeatedly demonstrated excessive nickel release from regulated articles.[[6], [8]] This indicates that there is not enough compliance testing by companies and authorities in relation to the number of articles on the market. Experimental evaluation of nickel and cobalt release from tools and self-reported prevalence of nickel and cobalt allergy in the German hairdressing trade. [Extracted from the article]

Swiss control authorities checked the safety assessment of nine major producers of polyolefin granulates for making food contact materials. It was a pilot project to gain experience on the procedure of collecting and evaluating compliance documentation, but also to obtain insight into the quality of compliance work performed by the main plastic producers. It revealed that there are fundamental problems in performing such control. These are reported with proposals for improvement. For most products, the safety assessment made available did not correspond to the requirements, as confirmed by a group of internationally recognised experts, who were asked for their opinion on whether the safety of the migrates was assessed in accordance to 'internationally accepted scientific methods on risk assessment', as required by Art. 19 of Regulation (EU) 10/2011 and specified by EFSA. [ABSTRACT FROM AUTHOR]

Contact allergy to Nickel is the most prevalent contact allergy in western societies. This has led to regulation for metallic items that come into prolonged and direct contact with the skin, such as buttons on clothing, belt buckles, jewelry and watches. In Europe, the legal provision is based on a test in which there is a limit to the amount of nickel that may be released from the item to an artificial sweat solution (EN 1811). This test is costly and has reproducibility issues. The resulting undertesting of items placed on the market, leads to many nickel releasing non-compliant articles being available in spite of the regulations that are in place. In this study, the performance of the standard release test is compared to the performance of a rapid nickel spot test based on dimethylglyoxime (DMG-test). The data suggest that using the rapid DMG-test for compliance testing is sufficiently equivalent to the current gold standard of EN 1811. Previously published comparisons between the DMG-test and EN 1811 did not consider the effect of accelerated wear and corrosion testing according to EN 12472. This study shows that by applying EN 12472, the number of deviating results between the DMG-test and EN 1811 decreases significantly. Regarding consumer protection, it is necessary for wear and corrosion resistance to be considered. [ABSTRACT FROM AUTHOR]

Di(2-ethylhexyl) maleate (DEHM) is a non-evaluated substance newly detected in the majority of the printed cardboard boxes used for food packaging. Concentrations in the board are often sufficient for a migration into food of around 1 mg/kg. This level was reached after storage over several months and in the absence of a functional barrier (such as a layer of aluminum). The maximum concentration determined in food was 1,500 μg/kg, even though the end of the shelf life of the product was not reached. DEHM is probably the non-reacted starting material in di(2-ethylhexyl) sulfosuccinate, which is used at concentrations of several percent as an emulsifier for water-based varnishes. A minor contribution is from recycled fibers, presumably contaminated through the same route. DEHM was absent in printing inks and almost all adhesives tested. No toxicological facts are available for DEHM. Through comparison with similar substances, the German BfR Committee for Consumer Products recommended a temporary migration limit of 50 μg/kg, whereas the Swiss Federal Office of Public Health concluded on a lower toxicity. The case shows that impurities in components used for printing cardboard may migrate at concentrations demanding substantial compliance work. [ABSTRACT FROM AUTHOR]

There is a significant lack of data on acrylamide in food which is prepared domestically, as obtaining samples of food cooked in people's homes is more complex than taking samples from shops. Rösti is a fried potato dish, which can be a significant contributor to acrylamide exposure, particularly in the German speaking areas of Switzerland. A set of 71 samples was collected from people who cooked the dish at home. The average acrylamide content was 709 µg/kg. Based on a food frequency questionnaire and on a Swiss national food survey the results enabled the determination of the exposure of the population to acrylamide through home-made rösti. The values for an exposure estimate to acrylamide from rösti are 7.8 µg/day for the whole population (including rösti eaters and non-eaters) and 27.2 µg/day for predominantly rösti consumers participating in this study. [ABSTRACT FROM AUTHOR]

Elastomers are not a uniform class of materials but comprise a broad spectrum of chemically different polymers. Sealing gaskets, gloves, teats, conveyor belts and tubing are examples of elastomers being used as food contact materials (FCMs). Ten elastomer samples were evaluated with respect to the content of extractable compounds, migration of substances into ethanolic food simulants, swelling in food simulants and release of elements in different food simulants. The number of extractable substances <1000 Da was determined by comprehensive two-dimensional gas chromatography coupled with flame ionisation detection (GC × GC–FID) analysis of tetrahydrofuran (THF) extracts. The number of signals ranged from 61 (a thermoplastic elastomer (TPE)) to 690 (a natural rubber/styrene-butadiene-rubber blend (NR/SBR)). As for risk assessment, the decisive factor is which substances reach the food. The extent of substances that migrate into ethanolic food simulants was investigated. Elastomer FCMs can be the source of food contamination with heavy metals. Notably, contamination with lead was detected in some samples investigated in this study. It was shown that food simulants harbour the potential to morphologically alter or even disintegrate elastomeric materials. The results presented here highlight the importance to carefully choose the elastomer type for the intended use as FCMs as not every application may prove safe for consumers. [ABSTRACT FROM AUTHOR]