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Purpose To introduce a study design and statistical analysis framework to assess the repeatability, reproducibility, and minimal detectable changes (MDCs) of metabolite concentrations determined by in vivo MRS. Methods An unbalanced nested study design was chosen to acquire in vivo MRS data within different repeatability and reproducibility scenarios. A spin-echo, full-intensity acquired localized (SPECIAL) sequence was employed at 7 T utlizing three different inversion pulses: a hyperbolic secant (HS), a gradient offset independent adiabaticity (GOIA), and a wideband, uniform rate, smooth truncation (WURST) pulse. Metabolite concentrations, Cramer-Rao lower bounds (CRLBs) and coefficients of variation (CVs) were calculated. Both Bland-Altman analysis and a restricted maximum-likelihood estimation (REML) analysis were performed to estimate the different variance contributions of the repeatability and reproducibility of the measured concentration. A Bland-Altmann analysis of the spectral shape was performed to assess the variance of the spectral shape, independent of quantification model influences. Results For the used setup, minimal detectable changes of brain metabolite concentrations were found to be between 0.40 µmol/g and 2.23 µmol/g. CRLBs account for only 16 % to 74 % of the total variance of the metabolite concentrations. The application of gradient-modulated inversion pulses in SPECIAL led to slightly improved repeatability, but overall reproducibility appeared to be limited by differences in positioning, calibration, and other day-to-day variations throughout different sessions. Conclusion A framework is introduced to estimate the precision of metabolite concentrations obtained by MRS in vivo, and the minimal detectable changes for 13 metabolite concentrations measured at 7 T using SPECIAL are obtained.

Biodiversity is under pressure worldwide, with amphibians being particularly threatened. Stressors related to human activity, such as chemicals, are contributing to this decline. It remains, however, unclear whether chemicals exhibiting a fungicidal activity could indirectly affect tadpoles that depend on microbially conditioned leaf litter as food source. The indirect effect of fungicides (sum concentration of a fungicide mixture composed of azoxystrobin, carbendazim, cyprodinil, quinoxyfen, and tebuconazole: 100 µg/L) on tadpoles was assessed relative to leaf litter colonized by microbes in absence of fungicides (control) and a worst‐case scenario, that is leached leaf litter without microbial colonization. The quality of leaf litter as food for tadpoles of the European common frog (Rana temporaria) was characterized through neutral lipid fatty acid profiles and microbial sum parameters and verified by sublethal responses in tadpoles (i.e., feeding rate, feces production, growth, and fatty acid composition). Fungicides changed the nutritious quality of leaf litter likely through alterations in leaves’ neutral lipid fatty acid profiles (i.e., changes in some physiologically important highly unsaturated fatty acids reached more than 200%) in combination with a potential adsorption onto leaves during conditioning. These changes were reflected by differences in the development of tadpoles ultimately resulting in an earlier start of metamorphosis. Our data provide a first indication that fungicides potentially affect tadpole development indirectly through bottom‐up effects. This pathway is so far not addressed in fungicide environmental risk assessment and merits further attention., Tadpoles consuming leaf litter of different quality show changes in their energy reserves, more specifically the composition of fatty acids, and growth dynamics. Low‐quality food ultimately leads to a higher number of individuals entering metamorphosis.

TiN coatings are widely used in different applications for extending the lifetime of components due to their high hardness and good wear resistance. However, it is not convenient to deposit them on soft stainless steels. In this work, the wear and corrosion behavior of commercial TiN coatings deposited by Arc-PVD on nitrided and non-nitrided martensitic stainless steel was studied. Two different nitriding conditions were used, one at high temperature (HTN) and the other at low temperature (LTN). Nanohardness and microhardness were measured. The microstructure was characterized by OM, SEM, XRD and XPS. Pin on disk and erosion tests were carried out in order to evaluate their wear resistance. The corrosion behavior was analyzed in salt spray fog and electrochemical tests in NaCl solution and the adhesion was measured in Scratch and Rockwell C Indentation tests.The coating thickness was about 1.5 µm and its hardness of 34 GPa. The nitrided layers were 13 µm and 17 µm thick for LTN and HTN, the hardness was approximately 12 GPa for both nitrided samples. The nitrided layer improved TiN coating adhesion in the Scratch tests. The wear loss volume was similar for both duplex and only coated samples in pin on disk tests. Nevertheless, wear resistance was not good for the LTN or HTN + TiN coating system in the erosion tests. Regarding corrosion behavior, the coatings showed poor corrosion resistance and this could be related to the presence of porous defects, which allow the solution to reach and attack the substrate, thus producing coating detachment around the pits.

Large magnitude tropical volcanic eruptions emit sulphur dioxide and other gases directly into the stratosphere, creating a long-lived volcanic aerosol cloud which scatter incoming solar radiation, absorbs outgoing terrestrial radiation, and can strongly affect the composition of the stratosphere.Such major volcanic enhancements of the stratospheric aerosol layer have strong “direct effects” on climate via these influences on radiative transfer, primarily surface cooling via the reduced insolation, but also have a range of indirect effects, due to the volcanic aerosol cloud’s effects on stratospheric circulation, dynamics and chemistry.In this study, we investigate the 3 largest volcanic enhancements to the stratospheric aerosol layer in the last 100 years (Mt Agung 1963; Mt El Chichón 1982; Mt Pinatubo 1991), comparing co-ordinated simulations within the so-called HErSEA experiments (Historical Eruptions SO2 Emission Assessment) several national climate modelling centres carried out for the model intercomparison project ISA-MIP.The HErSEA experiment saw participating models performing interactive stratospheric aerosol simulations of each of the volcanic aerosol clouds with common upper-, mid- and lower-estimate amounts and injection heights of sulfur dioxide, in order to better understand known differences among modelling studies for which initial emission gives best agreement with observations. First, we compare results of several models HErSEA simulations with a range of observations, with the aim to find where there is agreement between the models and where there are differences, at the different initial sulfur injection amount and altitude distribution.In this way, we could understand the differences and limitations in the mechanisms that controls the dynamical, microphysical and chemical processes of stratospheric aerosol layer.

Pesticides are one of the main drivers of the worldwide amphibian decline. Their actual toxicity depends on a number of factors, like the species in focus or the developmental stage of exposed individuals. As ectothermic species, the metabolism of amphibians is influenced by ambient temperature. Therefore, temperature also affects metabolic rates and thus processes that might enhance or reduce toxic effects. Studies about the interactive effect of temperature and toxicity on amphibians are rare and deliver contrasting results. To investigate the temperature-dependent pesticide sensitivity of larvae of two European species we conducted acute toxicity tests for the viticultural fungicide Folpan® 500 SC with the active ingredient folpet at different temperatures (6°C, 11°C, 16°C, 21°C, 26°C). Sensitivity of Rana temporaria and Bufotes viridis was highly affected by temperature: early larvae (Gosner stage 20) were about twice more sensitive to Folpan® 500 SC at 6°C compared to 21°C. Next to temperature, species and developmental stage of larvae had an effect on sensitivity. The most sensitive individuals (early stages of R. temporaria at 6°C) were 14.5 times more sensitive than the least sensitive ones (early stages of B. viridis at 26°C). Our results raise concerns about typical ecotoxicological studies with amphibians that are often conducted at temperatures between 15°C and 20°C. We suggest that future test designs should be performed at temperatures that reflect the temperature range amphibians are exposed to in their natural habitats. Variations in the sensitivity due to temperature should also be considered as an uncertainty factor in upcoming environmental risk assessments for amphibians.

Aim: Bipolar disorder is a multifactorial disorder being linked with dysregulation of several genes. Among the recently acknowledged factors in the pathophysiology of bipolar disorder are non-coding RNAs (ncRNAs). Methods: We searched PubMed and Google Scholar databases to find studies that assessed the expression profile of miRNAs, lncRNAs and circRNAs in bipolar disorder. Results: Dysregulated ncRNAs in bipolar patients have been enriched in several neuron-related pathways such as GABAergic and glutamatergic synapses, morphine addiction pathway and redox modulation. Conclusion: Altered expression of these transcripts in bipolar disorder provides clues for identification of the pathogenesis of this disorder and design of targeted therapies for the treatment of patients.

Human PEX14 plays a dual role as docking protein in peroxisomal protein import and as peroxisomal anchor for microtubules (MT), which relates to peroxisome motility. For docking, the conserved N-terminal domain of PEX14 (PEX14-NTD) binds amphipathic alpha-helical ligands, typically comprising one or two aromatic residues, of which human PEX5 possesses eight. Here, we show that the PEX14-NTD also binds to microtubular filaments in vitro with a dissociation constant in nanomolar range. PEX14 interacts with two motifs in the C-terminal region of human ß-tubulin. At least one of the binding motifs is in spatial proximity to the binding site of microtubules (MT) for kinesin. Both PEX14 and kinesin can bind to MT simultaneously. Notably, binding of PEX14 to tubulin can be prevented by its association with PEX5. The data suggest that PEX5 competes peroxisome anchoring to MT by occupying the ß-tubulin-binding site of PEX14. The competitive correlation of matrix protein import and motility may facilitate the homogeneous dispersion of peroxisomes in mammalian cells.

PEX14 functions as peroxisomal docking protein for the import receptor PEX5. For docking, the conserved N-terminal domain of PEX14 (PEX14-NTD) binds amphipathic alpha-helical ligands, typically comprising one or two aromatic residues, of which human PEX5 possesses eight. Here, we show that the PEX14-NTD also binds to microtubular filaments in vitro with a dissociation constant in nanomolar range. PEX14 interacts with two motifs in the C-terminal region of human ß-tubulin. At least one of the binding motifs is in spatial proximity to the binding site of microtubules (MT) for kinesin. Both PEX14 and kinesin can bind to MT simultaneously. Notably, binding of PEX14 to tubulin can be prevented by its association with PEX5. The data suggest that PEX5 competes peroxisome anchoring to MT by occupying the ß-tubulin-binding site of PEX14. The competitive correlation of matrix protein import and motility may facilitate the homogeneous dispersion of peroxisomes in mammalian cells.

While pesticides are generally recognized as contributing to amphibian declines, there is a lack of knowledge about effects of co-formulants that are present in pesticide formulations and adjuvants which are mixed with these formulations. Since aquatic and terrestrial stages of amphibians can be exposed to these substances, adverse effects cannot be excluded. We investigated acute aquatic and terrestrial effects of the herbicide formulation Focus® Ultra, its active substance cycloxydim, its co-formulants solvent naphtha and docusate as well as the stabilizing adjuvant Dash® E.C. on larval and juvenile Rana temporaria. Aquatic toxicity was determined as 96-h LC50 values. Cycloxydim was the least toxic and solvent naphtha the most toxic substance of the formulation. The addition of Dash® E.C. increased the formulation toxicity substantially. Terrestrial toxicity was determined as lethal effects after a 48-h exposure to contaminated soil with 100% of the recommended field rate (FR) and as sublethal effects after the exposure to 10% of the recommended FR. The exposure to solvent naphtha and docusate at 100% FR led to mortalities of 42–100% probably due to their inhalation toxicity and dermal as well as eye irritation, respectively. Cycloxydim, Focus® Ultra and Dash® E.C. did not lead to any mortality. Sublethal effects on juvenile locomotor activity (i.e. moved distance) were observed for cycloxydim and the combined exposure of Focus® Ultra and Dash® E.C. Juvenile body masses declined significantly for all substances except for cycloxydim. The present results show that aquatic sensitivity does not predict terrestrial sensitivity. It was shown that pesticide toxicity for amphibians can highly depend on the presence and amount of co-formulants and added adjuvants. Therefore, substances included in pesticide formulations which are known to be toxic by inhalation or harmful to eyes or skin should be specifically considered in the environmental risk assessment for amphibians.

Micro-organisms populate on rapeseed after harvest during storage depending on the growing conditions. The composition of the bacterial colonization is unknown, although its contribution to the profile of volatile aroma-active compounds determines the sensory quality of virgin cold-pressed rapeseed oil.; Results: From four rapeseed samples, 46 bacterial strains were isolated. By DNA-sequencing, the identification of four bacteria species and 17 bacteria genera was possible. In total, 22 strains were selected, based on their typical off-flavors resembling those of virgin sensory bad cold-pressed rapeseed oils. The cultivation of these strains on rapeseed meal agar and examination of volatile compounds by solid phase microextraction-gas chromatography-mass spectrometry allowed the identification of 29 different compounds, mainly degradation products of fatty acids such as alkanes, alkenes, aldehydes, ketones and alcohols and, in addition, sulfur-containing compounds, including one terpene and three pyrazines. From these compounds, 19 are described as aroma-active in the literature.; Conclusion: Micro-organisms populating on rapeseed during storage may strongly influence the sensory quality of virgin rapeseed oil as a result of the development of volatile aroma-active metabolic products. It can be assumed that occurrence of off-flavor of virgin rapeseed oils on the market are the result of metabolic degradation products produced by micro-organisms populating on rapeseed during storage. © 2017 Society of Chemical Industry.; © 2017 Society of Chemical Industry.

For many years now the use of aluminum as a light weight construction material in the aviation and automotive industry is on the rise. Without the innovative aluminum materials the strategies of constructing in light-weight design cannot be implemented. Last but not least this trend is driven by official requirements directing the reduction of greenhouse gas emissions. Aluminum is used both for structural components as well as for external body parts. Aluminum products for these industries have to undergo a production process which includes homogenizing of the ingots, hot rolling and cold rolling. Subsequent to the cold rolling process, the aluminum sheets have to undergo a heat treatment process to regain formability as well as the required material strength. The material properties required by the aviation and automotive industry are achieved in the annealing furnace and downstream cooling equipment. Equal and well-aimed heating and cooling along the length and across the width provide the strips with the metallurgical properties with regard to hardness and grain size. Hence the annealing furnace and the downstream cooling equipment are the decisive process components and critical for the high quality of the end material. First the material is heated up to a temperature above 500 °C for the solution heat treatment process. The following process step foresees cooling down the material to ambient temperature. Especially 6xxx automotive-alloys as well as 2xxx and 7xxx aerospace-alloys require high cooling rates. Eventually, the material gets heated up again for a certain time to apply an artificial aging process. In floatation heat treatment furnaces the strip is guided sinusoidal and contactless by floatation nozzles through the furnace. The strip is heated up and kept at the required strip temperatures in time, so the aluminum-alloy obtains their structure. The cooling process with high cooling rates is executed as a combination of water and air cooling. A mathematical model calculates the necessary settings for the annealing and cooling process under consideration of the mechanical properties. Paper and presentation will introduce the furnace technology for aluminum strips. Especially, the heat treatment facilities for heat and chemical treatment lines will be presented. It will especially emphasize on heat treatment cycles, the materials and the applications.

In this work the influence of pre-treatment cleaning processes in the adhesion of TiN films deposited by the plasma based ion implantation and deposition (PBII&D) process over plasma nitrided AISI 316L stainless steel was investigated, varying the gas composition, the duration of the sputtering process and the temperature in the same deposition chamber. The TiN film morphology was scrutinized with scanning electron microscopy on the surface complemented with focus ion beam for the cross section. The film microstructure was characterized with X ray diffraction. The adhesion of the coatings was studied using the Scratch Test with constant load at different values and the Rockwell C indentation method as well. It was found that only with the sputtering carried out in a H2 - Ar gas mixing at 300 ºC temperature used as pre-treatment was successful to prepare the nitrided surface for the subsequent TiN deposition by the PBII&D process. Fil: Vaca, Laura Silvia. Universidad Tecnológica Nacional. Facultad Regional Concepción del Uruguay; Argentina Fil: Quintana, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física del Plasma. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física del Plasma; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina Fil: Guitar, María Agustina. Universitat Saarland; Alemania Fil: Vega, Daniel. Comisión Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones No Nucleares. Gerencia Física (CAC). Departamento de Física de la Materia Condensada; Argentina Fil: Brühl, Sonia Patricia. Universidad Tecnológica Nacional. Facultad Regional Concepción del Uruguay; Argentina Fil: Marquez, Adriana Beatriz. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física del Plasma. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física del Plasma; Argentina

Spatially selective excitation in two dimensions (2D-SSE) utilizing parallel transmission was applied as a means to acquire signal from voxels adapted to the anatomy of interest for in vivo (1) H MR spectroscopy. A novel method to select spectroscopy voxels with arbitrary shapes in two dimensions was investigated. An on-off scheme with an adiabatic slice selective inversion pulse preceding a 2D-SSE pulse together with a segmented inward spiral excitation k-space trajectory enabled rapid free induction decay acquisitions. Performance of the sequence was evaluated in simulations, phantom experiments, and in vivo measurements at 3 T. High spatial fidelity of the excitation profile was achieved for different target shapes and with little off-resonance deterioration. Metabolite concentrations in human brain determined with the new sequence were quantified with Cramer-Rao lower bounds less than 20%. They were in the physiological range and did not deviate systematically from results acquired with a conventional SPECIAL sequence. In conclusion, a new approach for shaped voxel MRS in the human brain is presented, which complements existing sequences. Simulations show that 2D-SSE pulses yield reduced chemical shift artifact when compared with conventional localization methods. Copyright © 2016 John Wiley & Sons, Ltd.

Most agricultural soils are expected to be contaminated with agricultural chemicals. As the exposure to pesticides can have adverse effects on non-target organisms, avoiding contaminated areas would be advantageous on an individual level, but could lead to a chemical landscape fragmentation with disadvantages on the metapopulation level. We investigated the avoidance behavior of juvenile common toads (Bufo bufo) in response to seven pesticide formulations commonly used in German vineyards. We used test arenas filled with silica sand and oversprayed half of each with different pesticide formulations. We placed a toad in the middle of an arena, filmed its behavior over 24 hours, calculated the proportion of time a toad spent on the contaminated side and compared it to a random side choice. We found evidence for the avoidance of the folpet formulation Folpan® 500 SC, the metrafenone formulation Vivando® and the glyphosate formulation Taifun® forte at maximum recommended field rates for vine and a trend for avoidance of Wettable Sulphur Stulln (sulphur). No avoidance was observed when testing Folpan® 80 WDG (folpet), Funguran® progress (copper hydroxide), SpinTorTM (spinosad), or 10% of the maximum field rate of any formulation tested. In the choice-tests in which we observed an avoidance, toads also showed higher activity on the contaminated side of the arena. As video analysis with tracking software is not always feasible, we further tested the effect of reducing the sampling interval for manual data analyses. We showed that one data point every 15 or 60 minutes results in a risk of overlooking a weak avoidance behavior, but still allows to verify the absence/presence of an avoidance for six out of seven formulations. Our findings are important for an upcoming pesticide risk assessment for amphibians and could be a template for future standardized tests.

The ceramic and carbon coatings such as titanium nitride (TiN) and diamond-like carbon (DLC) coatings are characterised by good mechanical properties and chemical inertia. The objective of this work is to compare the wear, friction, adhesion and corrosion behaviour of commercial TiN and DLC coatings deposited on AISI 420 stainless steel, by plasma-assisted techniques. The microstructure of the coatings was characterised by optical and electronic microscopy and X-ray diffraction. The hardness and Young’s modulus were measured by nanoindentation. Pin-on-disk, fretting and abrasive wear tests were performed. Adhesion was evaluated by means of Scratch Test and Rockwell C Indentation. The corrosion behaviour was evaluated by Salt Spray Fog and electrochemical tests in chloride solutions. The thickness of both coatings was between 1 and 1.5 µm. The hardness was 26 GPa and 34 GPa for DLC and TiN coating, respectively. The results showed that the TiN coatings presented better abrasive wear resistance than the DLC coatings; however, the latter was more resistant to the pin-on-disk test, fretting and it had a lower friction coefficient. Both coatings showed far better wear resistance than the untreated steel. Finally, TiN coatings had better adhesion to the substrate than DLC coatings, proved in both tests. Regarding the corrosion behaviour, both coatings exhibited acceptable corrosion resistance in the Salt Spray Fog Test, but only the DLC coatings had both nobler corrosion potential and higher breakdown potential than the TiN coatings in electrochemical tests.

Formation of toxic alkylbenzenes, total polar compounds (%TPC) and degradation of tocochromanol are monitored. Analyses of the oil extracted from fried potatoes confirm the trend observed in the frying oil. The fresh oil has a TPC content of 3%, which increases with the frying time, exceeding the acceptable value (25%) after about 25 h for deep‐frying and 1.5 h for pan‐frying. During deep‐frying, total tocochromanol decreases to about half (25 mg per 100 g) of the initial value, pan‐frying shows faster, degradation (complete after 1.5 h). Toluene concentration increases with the frying time reaching a maximum, and afterwards gradually decreases. Except for butylbenzene during pan‐frying, pentylbenzene and butylbenzene concentration, increase with the frying time, but remain much lower than toluene. Practical Applications: This is the first systematic work comparing alkylbenzenes evolution under different frying conditions. Different from previous works, frying experiments are carried out following the indication of many European countries that recommend using temperature lower than 180 °C. The amount of alkylbenzenes assumed through a standard portion of fried potatoes (200 g) is assessed, which is relevant for evaluating dietary exposure to these contaminants.

The Stratospheric Sulfur and its Role in Climate (SSiRC) Interactive Stratospheric Aerosol Model Intercomparison Project (ISA-MIP) explores uncertainties in the processes that connect volcanic emission of sulfur gas species and the radiative forcing associated with the resulting enhancement of the stratospheric aerosol layer. The central aim of ISA-MIP is to constrain and improve interactive stratospheric aerosol models and reduce uncertainties in the stratospheric aerosol forcing by comparing results of standardized model experiments with a range of observations. In this paper we present four co-ordinated inter-model experiments designed to investigate key processes which influence the formation and temporal development of stratospheric aerosol in different time periods of the observational record. The Background (BG) experiment will focus on microphysics and transport processes under volcanically quiescent conditions, when the stratospheric aerosol is controlled by the transport of aerosols and their precursors from the troposphere to the stratosphere. The Transient Aerosol Record (TAR) experiment will explore the role of small- to moderate-magnitude volcanic eruptions, anthropogenic sulfur emissions, and transport processes over the period 1998–2012 and their role in the warming hiatus. Two further experiments will investigate the stratospheric sulfate aerosol evolution after major volcanic eruptions. The Historical Eruptions SO2 Emission Assessment (HErSEA) experiment will focus on the uncertainty in the initial emission of recent large-magnitude volcanic eruptions, while the Pinatubo Emulation in Multiple models (PoEMS) experiment will provide a comprehensive uncertainty analysis of the radiative forcing from the 1991 Mt Pinatubo eruption.

The chemical composition, antiradical and antimicrobial activity of cold-pressed edible oils from nutty fruits (almond and walnut) and oils from poppy seed and wheat germ from Macedonia were studied. Regarding the fatty acid composition, the highest level of oleic acid was determined in almond oil (67.6±0.02%) whereas poppy seed oil was the richest sources of linoleic acid with abundance of 72.3±0.06%. The highest level of α-tocopherol (23.8±0.01 mg/100 g of oil) was quantified in almond oil while γ-tocopherol was the most abundant in walnut and wheat germ oil. Wheat germ oil was the richest source of phytosterols (3894±155.0 mg/kg) with domination of β-sitosterol and campesterol. Although DPPH radical is less sensitive against phenolic compounds in comparison to ABTS radical, its relationship with tocopherols and tocotrienols was indicative. Poppy seed oil had the lowest level of tocopherols, but it indicated the highest antibacterial activity against Listeria monocytogenes and antifungal activity against Candida albicans. Keywords: Bioactive compounds, extracts, cold-pressed oils, nutty fruits, antiradical activity, antimicrobial activity

BackgroundAbnormalities in reward circuit function are considered a core feature of addiction. Yet, it is still largely unknown whether these abnormalities stem from chronic drug use, a genetic predisposition, or both.MethodsIn the present study, we investigated this issue using a large sample of adolescent children by applying structural equation modeling to examine the effects of several dopaminergic polymorphisms of the D1 and D2 receptor type on the reward function of the ventral striatum (VS) and orbital frontal cortex (OFC), and whether this relationship predicted the propensity to engage in early alcohol misuse behaviors at 14 years of age and again at 16 years of age.ResultsThe results demonstrated a regional specificity with which the functional polymorphism rs686 of the D1 dopamine receptor (DRD1) gene and Taq1A of the ANKK1 gene influenced medial and lateral OFC activation during reward anticipation, respectively. Importantly, our path model revealed a significant indirect relationship between the rs686 of the DRD1 gene and early onset of alcohol misuse through a medial OFC × VS interaction.ConclusionsThese findings highlight the role of D1 and D2 in adjusting reward-related activations within the mesocorticolimbic circuitry, as well as in the susceptibility to early onset of alcohol misuse.

The bioactive compounds and ‘‘in vitro’’ antioxidant activity measured by three antioxidant assays of some traditional and non-traditional cold-pressed edible oils from Macedonia were object of this study. The fatty acid composition showed dominance of monounsaturated oleic acid in ‘‘sweet’’ and ‘‘bitter’’ apricot kernel oils with percentages of 66.7 ± 0.5 and 57.8 ± 0.3%, respectively. The most dominant fatty acid in paprika seed oil was polyunsaturated linoleic acid with abundance of 69.6 ± 2.3%. The most abundant tocopherol was c-tocopherol with the highest quantity in sesame seed oil (57.6 ± 0.1 mg/100 g oil). Paprika seed oil, sesame seed oil and sweet apricot oil were the richest source of phytosterols. DPPH assay was the most appropriate for the determination of the antioxidant activity of cold-pressed sunflower oil due to high abundance of a-tocopherol with a level of 22.8 ± 1.1 mg/100 g of oil. TEAC assay is the best for the determination of the antioxidant activity of sesame seed oil and paprika seed oils as the richest sources of phenolic compounds. b-carotene assay was the most suitable assay for oils obtained from high pigmented plant material. Triacylglycerols and phytosterol profiles can be used as useful markers for the origin, variety and purity of the oils.

Mineral oil hydrocarbon contaminations can often be found in oilseeds, oils, and fats as these matrices are good keepers to accumulate them from all kind of sources along the production chain. In addition, seeds and vegetable oils contain naturally occurring hydrocarbons in various compositions. These naturally hydrocarbons can serve for a proof of authentication and they have to be taken into account for the analysis of mineral oil hydrocarbons as contaminants. In this review, the many sources of contamination like environmental effects, production machinery, and packaging materials are referred to and reported data for contaminated vegetable oils like sunflower, olive, and palm oil and in addition raw materials and feed are focused on. This is of special importance for the food survey and for the production as it is a challenging task to survey the many routes of contamination along the production chain and during storage in order to improve the food quality. There is still discussion where to fix a reasonable limit for such contaminants in oils and fats, where levels are often very high compared to levels found for migration from packaging materials into low fat products. For the later ones draft limits have been discussed, but it will be a challenge to reduce mineral oil hydrocarbon contamination in oils and fats to a similar extend. In addition, the determination of low levels of hydrocarbon contamination is demanding and validation of sophisticated coupled LC–GC methods in collaborative trials is still in development. Practical applications: An overview about the analysis of mineral oil hydrocarbon contaminations of oilseeds, oils, and fats is given. For seeds and vegetable oils also contain naturally occurring hydrocarbons in various compositions, reference data on these naturally hydrocarbons are provided. The many sources of contamination like environmental effects, production machinery, and packaging materials are referred to and vegetable oils like sunflower, olive, and palm oil and in addition raw materials and feed are focused on. The arguments for a reasonable limit for such contaminants in oils and fats are discussed. Analysis of mineral oil hydrocarbon contamination of oilseeds, oils, and fats is reviewed. Reference data on naturally hydrocarbons are provided, which occur in various compositions. The many sources of contamination like environmental effects, production machinery, and packaging materials are referred to and vegetable oils like sunflower, olive, palm oil, raw materials, and feed are focused on. The arguments for a reasonable limit for such contaminants in oils and fats are discussed.

Thick and soft a-C:H:Si coatings containing more than 45% hydrogen (thickness: 25–27 μm, hardness: 6 GPa, Young's Modulus 38 GPa and low ratio of sp3 bonds) were deposited by PACVD with a DC pulsed discharge on nitrided (duplex sample) and non-nitrided austenitic stainless steel (coated sample). After deposition, the chemical, microstructural and tribological properties were studied. Finally, the adhesion and the atmospheric corrosion resistance of a-C:H:Si coatings were also investigated. In pin-on-disk tests, the friction coefficient using an alumina pin of 6 mm in diameter as counterpart, under 0.59 GPa Hertzian pressure was 0.05 for the coated samples and 0.076 for the duplex samples. These values were more than one order of magnitude smaller than the friction coefficient of the nitrided sample without coating, which was around 0.65. In the coated samples, the wear loss could not be measured. In ball-on-disk tests under dry sliding conditions, the coatings were tested under different Hertzian pressures (1.29, 1.44 and 1.57 GPa) using a steel ball with a diameter of 1.5 mm as counterpart. Using a normal load of 9 N, the a-C:H:Si coating of the coated samples was broken and detached thus leading to a coefficient of friction of around 0.429. However, in contrast to that, the friction coefficient of the duplex samples remained stable and reached as maximum a value of 0.208. In abrasive tests, mass loss was undetectable in both duplex and coated samples. Furthermore it could be seen that the a-C:H:Si film showed only some smaller grooves and no severe damage or deformation. On the contrary, severe damage was observed in the only nitrided sample. With respect to adhesion, the critical load to break the coating was higher in the duplex sample (27 N) than in the only coated sample (16.3 N). By chemical analysis using the salt spray fog test, the duplex sample remained clean, but the coated sample failed and presented film delamination as well as general corrosion.

The occurrence of monoepoxy fatty acids in used frying oils and in other common foods has been determined. Monoepoxy fatty acids with trans-9,10- and cis-9,10-epoxystearate and trans-12,13-, trans-9,10-, cis-12,13- and cis- 9,10-epoxyoctadecenoate were found at average levels of 3.7 g/kg in used frying fats and oils, but also at about 2 g/kg in the fat fraction of chocolate. They were also detected in pumpkin seed, sweet almond, groundnut, sunflower, and olive oils at average levels of 3.4, 1.7, 1.4, 1.0, and 0.2 g/kg, respectively. Their formation during heating at 175°C was observed for sunflower, rapeseed, soybean, and linseed oil and compared with the increase of polar compounds and polymerized triacylglycerols as other important quality indicators for frying oils. During heating for 16 h, the level of monoepoxy fatty acids increased to about 30, 18, 8, and 4 g/kg for olive, sunflower, linseed, and rapeseed oils, respectively. The influence of the heating temperature was surveyed for refined soybean oil at 160, 170, 180, and 200°C. Heating of two sets of five different refined and virgin rapeseed oils revealed a significant lower formation of monoepoxy fatty acids for refined oils at a median level of 4.6 g/kg compared to7.7 g/kg for virgin oils. Practical applications: Determination of fatty acid methyl esters is one of the most common analyses for the evaluation of oils and fats. The assessment of the monoepoxy fatty acids as part of these analyses can provide a first indication about used frying fats and oils, which reached the end of their applicability. The formation of monoepoxy fatty acids is affected by the fatty acid composition of the oil, the heating temperature, and the production of the oil. Therefore, frying oils may contain varying amounts of monoepoxy fatty acids at the maximum limit for polar compounds and polymerized triacylglycerols as used in the official food control. However, all used frying oils investigated by the official food control showing more than 7 g/kg of monoepoxy fatty acids had to be rejected due to the limits exceeded for polar compounds and polymerized triacylglycerols. Therefore, this limit of 7 g/kg monoepoxy fatty acids level is proposed as a level for screening the usability of used frying fats and oils. Epoxy fatty acids are formed in oils and fats during frying and heating. In addition, they are also detectable in unheated foods like chocolate and pumpkin seed oil. Frying fats and oils heated too much show contents of monoepoxy fatty acids above 7 g/kg.

The chemical composition and quality of eight pure cold-pressed oils and two blend oils from Macedonia were examined in this work. The highest level of oleic acid was determined in apricot kernel oil and rapeseed oil with abundance of 70.9 and 59.2 %, respectively. The highest level of polyunsaturated fatty acids had flaxseed and hemp seed oil with abundance of α-linolenic acid of 55.1% for flaxseed oil and linoleic acid of 57.4% for hemp seed oil. Apricot kernel oil and roasted sesame seed oil had the highest oxidative stability with induction times of 7.6 and 10.9 h. Apricot oil, hemp seed oil and flaxseed oil had the highest level of total vitamin-E-active compounds with 58.8 mg, 58.1 mg and 69.7 mg per 100 g of oil with predomination of γ-tocopherol. The highest peroxide number was detected in blend oils (oil 2 and oil 8) with values over 10 meq O2/kg of oil. The highest FFA was detected in rapeseed oil (1.57 %). Roasted and unroasted sesame seed oils had relatively high specific extinction (K232 values 3.55 and 3.33 respectively). However, the highest UV extinction had a blend of pumpkin seed oil and sunflower oil with a value of 3.84. Practical applications: The results of this study can be applied for determination of the most important major and minor components responsible for quality evaluation of cold-pressed oils. Statistical results indicated strong relationship between the level of monounsaturated fatty acids in the oil and their oxidative stability. The level of tocopherols and other vitamin-E-related compounds was in strong relationship with the antioxidant activity of the oils measured by DPPH method. Phytosterols, as minor compounds present in the oils, did not contribute significantly to the total antioxidant potential of the oils but, their levels in particular oils, together with fatty acids, can be useful and reliable markers for the purity of the oils and determination of the composition of blends.

Since its introduction in 1974, the use of glyphosate in agriculture has been continuously increasing; however, the application modes of this herbicide have been changing. Therefore, glyphosate-based herbicides can be used as an appropriate indicator for assessing how changes in pesticide application modes affect wild-living organisms in agricultural landscapes over time. Amphibians that migrate through arable fields may be exposed to the chemicals applied to field crops. Using data on the tem-poral coincidence of four amphibian populations with glyphosate applications from a three-year in-vestigation in northeast Germany as well as data on the application of glyphosate to field crops in German agriculture over 20 years, we estimated the species-specific increasing rates of coincidence likelihoods during this period. The overall consumption of glyphosate used in German agriculture between 1992 and 2012 increased by a factor of 5.7, while the species-specific coincidence likelihood increased from 2.2 to 6.1, respectively. Our results reveal the highest increases in coincidence for both adult and juvenile great crested newt (Triturus cristatus) and fire-bellied toad (Bombina bombina). Adults and juveniles of moor frog (Rana arvalis) and adults of spadefoot toad (Pelobates fuscus) were subjected to moderate increases, with rates ranging from 3.2 to 3.6; in contrast, juvenile individuals of P. fuscus showed small increases. We suggest that the risk assessments of pesticide application (in this case, glyphosate) should not only consider the present use at the time of authorization but also consider changes in application modes over time that may lead to increases in potential exposure of non-target organisms, such as amphibians.

Hydrogenated carbon-based films, such as DLC (“Diamond Like Carbon”), have interesting properties such as excellent tribological behavior, low friction coefficient, high superficial hardness and good wear resistance; they are chemically inert and highly corrosion resistant. They are deposited by means of PACVD (plasma-assisted chemical vapor deposition) with variable film thickness. The load carrying capacity grows with the thickness, so it is possible to deposit thick films on “soft” steels (e.g. low alloyed steels). When increasing coating thickness, surface defects are generated during the deposition process compromising their excellent properties. In this work, different metal substrates have been used to compare adhesion and quantify superficial defects: AISI 316L, DIN 42CrMo4 (AISI 4140) and Böhler K110 (AISI D2). The films were deposited at different temperatures, changing the silicon content and the coating thickness. The samples were placed in the furnace on different positions (standing, lying or up-side down). The films were analyzed with optical and electron microscopy, 3D topography profilometer, and they were tested under sliding wear conditions. Friction coefficient and wear volume were measured, with an average friction coefficient which resulted below 0.05. A higher amount of surface defects was obtained on lying samples compared to the ones up-side down. The quantity of defects increased with the thickness of the coating and decreased with the temperature. The geometry and the growth mechanism of the defects were analyzed.

The quality of the adaptive immune response depends on the differentiation of distinct CD4(+) helper T cell subsets, and the magnitude of an immune response is controlled by CD4(+)Foxp3(+) regulatory T cells (Treg cells). However, how a tissue- and cell type-specific suppressor program of Treg cells is mechanistically orchestrated has remained largely unexplored. Through the use of Treg cell-specific gene targeting, we found that the suppression of allergic immune responses in the lungs mediated by T helper type 2 (TH2) cells was dependent on the activity of the protein kinase CK2. Genetic ablation of the β-subunit of CK2 specifically in Treg cells resulted in the proliferation of a hitherto-unexplored ILT3(+) Treg cell subpopulation that was unable to control the maturation of IRF4(+)PD-L2(+) dendritic cells required for the development of TH2 responses in vivo.

Plasma nitriding of austenitic stainless steel is of high technological importance due to its ability to improve the surface hardness, wear and corrosion resistance. Therefore, such process presents a significant potential as a treatment of materials for biomedical applications. The resulting properties obtained on the nitrided layer depend on the nitriding parameters used, such as temperature, gases partial pressures, process time, among others. In this work, austenitic stainless steel AISI 316L was nitrided in a DC plasma using two different N2-H2 atmospheres: 25% N2 and 20% N2. A detailed analysis of surface microstructure has been carried out and related to corrosion behaviour in two saline solutions. The results were compared with the 316L unnitrided (UN). The chemical composition of the nitrided layer was determined by GDOES. The phases present in the nitrided layer were analysed by X-ray diffraction (XRD) and the phases in the surface of nitrided layer were analysed by grazing incidence X-ray diffraction mode (GIXRD). The corrosion behaviour of the samples was studied by an electrochemical corrosion test in 3 wt% NaCl and Ringer's solutions. The GDOES (Glow Discharge Optical Emission Spectroscopy) analysis shows a higher N concentration of in the surface of 25% N2 samples, named HN. The phases observed, by GIXRD, in HN samples were expanded austenite γN, CrN, Fe3N and Fe4N and, in the 20% N2 samples, named LN, only peaks of expanded austenite and Fe4N were observed. The corrosion results showed that LN present better corrosion resistance than HN, this could be due to the absence of chromium nitrides in the surface of LN as a consequence of lower N percentage in the nitriding atmosphere. Fil: de Las Heras, Maria Evangelina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina Fil: Ybarra, Gabriel Omar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Instituto Nacional de Tecnología Industrial; Argentina Fil: Lamas, Diego Germán. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Cabo, Amado. IONAR S.A.; Argentina Fil: Dalibon, Eugenia Laura. Universidad Tecnológica Nacional; Argentina Fil: Brühl, Sonia Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Tecnológica Nacional; Argentina

Seventeen argan oils from Swiss and German markets were evaluated regarding the sensory quality, identity, oxidative state as well as contaminants in order to give an overview about the characteristics of this high-value product on the market. At least one sensory defect was detected in each argan oil by a trained sensory panel showing that the sensory quality in most oils should be improved. Adulterations of expensive argan oil with cheaper oils are detectable by the dominant occurrence of γ-tocopherol and α-spinasterol and 7-stigmastenol (Schottenol) as characteristic Tocopherol and Phytosterols, respectively. Only one oil exceeded the limit of the total oxidation value (TOTOX) of 20; the shelf-life calculated from the induction period (Rancimat method at 120 °C) was 196–435 days. Some oils contained higher amounts of mineral oils while the content of Benzo[a]pyrene in all oils was remarkably below the limit of 2 µg/kg.

The modelling of aerosol radiative forcing is a major cause of uncertainty in the assessment of global and regional atmospheric energy budgets and climate change. One reason is the strong dependence of the aerosol optical properties on the mixing state of aerosol components, such as absorbing black carbon and, predominantly scattering sulfates. Using a new column version of the aerosol optical properties and radiative-transfer code of the ECHAM/MESSy atmospheric-chemistry–climate model (EMAC), we study the radiative transfer applying various mixing states. The aerosol optics code builds on the AEROPT (AERosol OPTical properties) submodel, which assumes homogeneous internal mixing utilising the volume average refractive index mixing rule. We have extended the submodel to additionally account for external mixing, partial external mixing and multilayered particles. Furthermore, we have implemented the volume average dielectric constant and Maxwell Garnett mixing rule. We performed regional case studies considering columns over China, India and Africa, corroborating much stronger absorption by internal than external mixtures. Well-mixed aerosol is a good approximation for particles with a black-carbon core, whereas particles with black carbon at the surface absorb significantly less. Based on a model simulation for the year 2005, we calculate that the global aerosol direct radiative forcing for homogeneous internal mixing differs from that for external mixing by about 0.5 W m−2.

Herbicides are widely used pesticides that affect plants by changing their chemistry. In doing so, herbicides might also influence the quality of plants as food for herbivores. To study the effects of herbicides on host plant quality, 3 plant species (Plantago lanceolata L., P. major L., and Ranunculus acris L.) were treated with sublethal rates of either a sulfonylurea (Atlantis WG, Bayer CropScience) or a glyphosate (Roundup LB Plus, Monsanto) herbicide, and the development of caterpillars of the cabbage moth Mamestra brassicae L. that fed on these plants was observed. Of the 6 tested plant–herbicide combinations, 1 combination (R. acris + sulfonylurea herbicide) resulted in significantly lower caterpillar weight, increased time to pupation, and increased overall development time compared with larvae that were fed unsprayed plants. These results might be caused by a lower nutritional value of these host plants or increased concentrations of secondary metabolites that are involved in plant defense. The results of the present and other studies suggest potential risks to herbivores that feed on host plants treated with sublethal rates of herbicides. However, as the effects of herbicides on host plant quality appear to be species-specific and as there are numerous plant–herbicide–herbivore relationships in agricultural landscapes, a general reduction in herbicide contamination of nontarget habitats (e.g., field margins) might mitigate the negative effects of herbicides on host plant quality. Environ Toxicol Chem 2014;33:2633–2638. © 2014 SETAC

Oils and fats degrade during the frying process and many reactions with numerous fatty acid alteration products have been examined. The geometrical isomerisation of double bonds leads to the formation of trans fatty acids. At frying temperatures also conjugated double bond systems are detected. The reaction of oxygen with unsaturated fatty acids results in hydroperoxides, which immediately degrade in further radical reactions at frying temperature. A set of oxygenated fatty acids has been detected including epoxy-, keto- and hydroxyl fatty acids. Another route leads to β-scission at the carbonyl- or the alkyl side of the oxygen bearing carbon atom in the fatty acid chain. In this case short chain fatty acids, aldehydic, keto, and hydroxyl acids appear together with volatile compounds. Also the formation of cyclic and furan fatty acids was detected. As a reaction between fatty acids also dimeric and polymerised fatty acids can be observed. Taking into account the different amounts of these fatty acid degradation products the physiological relevance has to be discussed. Due to high concentrations of dimeric and polymerised molecules these substances can lower significantly the digestibility of fried foods, while oxidised fatty acid monomers are readily absorbed and raise concern about their effect on lipid metabolism. These two different effects of altered TAGs and fatty acids have to be considered separately.

Bees provide essential ecosystem services and help maintain floral biodiversity. However, there is an ongoing decline of wild and domesticated bee species. Since agricultural pesticide use is a key driver of this process, there is a need for a protective risk assessment. To achieve a more protective registration process, two bee species, Osmia bicornis/Osmia cornuta and Bombus terrestris, were proposed by the European Food Safety Authority as additional test surrogates to the honey bee Apis mellifera. We investigated the acute toxicity (median lethal dose, LD50) of multiple commercial insecticide formulations towards the red mason bee (O. bicornis) and compared these values to honey bee regulatory endpoints. In two thirds of all cases, O. bicornis was less sensitive than the honey bee. By applying an assessment factor of 10 on the honey bee endpoint, a protective level was achieved for 87% (13 out 15) of all evaluated products. Our results show that O. bicornis is rarely an adequate additional surrogate species for lower tier risk assessment since it is less sensitive than the honey bee for the majority of investigated products. Given the currently limited database on bee species sensitivity, the honey bee seems sufficiently protective in acute scenarios as long as a reasonable assessment factor is applied. However, additional surrogate species can still be relevant for ecologically meaningful higher tier studies.

Trans-fatty acids (TFA) should be avoided in the nutrition due to health concerns. Despite that there are several frying fats available on the market with reduced content of TFA this has to be implemented for the production of doughnuts in many bakeries. In this frying experiment the commonly used fat consisting of partially hydrogenated peanut oil (PHPO) and fats with a reduced content of TFA below 2 g/100 g were assessed at the same time for their oxidative stability, technological and sensorial performance for the production of doughnuts. Some of the TFA free products provided even better heat stability compared to PHPO and in addition also technological requirements were covered. However, the sensory assessment of the fats in the frying trial showed significant differences between the products. While a TFA free fat showed best assessment results during the whole course of the frying test others produced significant off-flavours. Surprisingly, for the reduction of TFA these fatty acids were not exchanged by saturated fatty acids. The best product showed a moderate content of 37 g/100 g saturated fatty acids and 55 g/100 g mono unsaturated fatty acids and a low content of about 8 g/100 g poly unsaturated fatty acids (linoleic acid).

Austenitic stainless steels are the preferred materials for mechanical components in the food, oil and chemical industries due to their good corrosion resistance but they often suffer severe wear due to their poor tribological properties. Plasma surface engineering has been extended to stainless steel hardening, through the modification of the surface with ion nitriding or the application of hard coatings. In this work, AISI 316L samples were coated with titanium nitride by means of a cathodic arc (CA) and this technique was combined with plasma immersion ion implantation, in a process called plasma based ion implantation and deposition (PBII&D). The effect on corrosion resistance was analyzed, also considering ion nitriding as a pre-treatment. Microstructure and composition were analyzed by means of glancing angle XRD, SIMS, SEM, SEM-FIB and EDS. Localized corrosion resistance was analyzed in a cyclic potentiodynamic polarization experiment in 3.5% NaCl solution, and the corroded surface was analyzed with AFM, SEM and EDS as well. It was found that nitriding at 400 °C produces a thin nitrided layer with good corrosion resistance. A duplex TiN coating resulted in a further improvement of the corrosion resistance. Comparing cathodic arc and PBII&D coating techniques, the last one gives the thickest film and also the best corrosion behavior with good adhesion. Fil: Escalada, Lisandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación En Ciencia y Tecnología de Materiales (i); Argentina. Universidad Nacional de Mar del Plata. Facultad de Ingeniería; Argentina Fil: Lutz, J.. Leibniz Institute of Surface Modification; Alemania Fil: Brühl, S.P.. Universidad Tecnologica Nacional. Facultad Regional Concepcion del Uruguay; Argentina Fil: Fazio, Mariana Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Instituto de Física del Plasma; Argentina Fil: Marquez, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Instituto de Física del Plasma; Argentina Fil: Mändl, S.. Leibniz Institute of Surface Modification; Alemania Fil: Manova, D.. Leibniz Institute of Surface Modification; Alemania Fil: Simison, Silvia Noemi. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación En Ciencia y Tecnología de Materiales (i); Argentina. Universidad Nacional de Mar del Plata. Facultad de Ingeniería; Argentina

Virgin rapeseed (Brassica napus) oil is a valuable niche product, if delivered with a high quality. In this study, the effects of moist storage of B. napus seeds for 1 to 4 days on the seed metabolome and the chemo-sensory properties of the produced oils were determined. The concentrations of several primary metabolites, including monosaccharides and amino acids, rapidly increased in the seeds, probably indicating the breakdown of storage compounds to support seed germination. Seed concentrations of indole glucosinolates increased with a slight time offset suggesting that amino acids may be used to modify secondary metabolism. The volatile profiles of the oils were pronouncedly influenced by moist seed storage, with the sensory quality of the oils decreasing. This study provides a direct time-resolved link between seed metabolism under moist conditions and the quality of the resulting oils, thereby emphasizing the crucial role of dry seed storage in ensuring high oil quality.

Increasing pesticide use is suggested to contribute to amphibian population declines. Most European species have terrestrial life-stages after aquatic development. Many species that occur in the cultivated landscape have a high risk of coming into contact with pesticides, either by exposure to residues on food (oral uptake) or by dermal uptake (owing to direct over-spraying or contact with contaminated plant material or soil). Although species-specific differences in sensitivity are well known in amphibian toxicology, only 8% of European amphibian species have ever been used as test organisms in toxicological studies and urodele species are especially underrepresented. Birds and mammals, which are currently serving as surrogate species for pesticide toxicity to terrestrial life-stages of amphibians, dramatically differ in their biology and ecology. In particular, the fast dermal uptake of xenobiotics by amphibians questions the unique use of data obtained by oral administration of pesticides to surrogate species in pesticide approval. Furthermore, indirect effects (mainly strong reduction of food resources owing to pesticide applications) are not considered in current risk assessments and, finally, added substances in the formulations (adjuvants), which are often more toxic than the active ingredient, are not adequately assessed.

BackgroundGlyphosate-based herbicides are the most widely used pesticides in agriculture, horticulture, municipalities and private gardens that can potentially contaminate nearby water bodies inhabited by amphibians and algae. Moreover, the development and diversity of these aquatic organisms could also be affected by human-induced climate change that might lead to more periods with extreme temperatures. However, to what extent non-target effects of these herbicides on amphibians or algae are altered by varying temperature is not well known.MethodsWe studied effects of five concentrations of the glyphosate-based herbicide formulation Roundup PowerFlex (0, 1.5, 3, 4 mg acid equivalent glyphosate L−1as a one time addition and a pulse treatment of totally 4 mg a.e. glyphosate L−1) on larval development of Common toads (Bufo bufo, L.; Amphibia: Anura) and associated algae communities under two temperature regimes (15 vs. 20 °C).ResultsHerbicide contamination reduced tail growth (−8%), induced the occurrence of tail deformations (i.e. lacerated or crooked tails) and reduced algae diversity (−6%). Higher water temperature increased tadpole growth (tail and body length (tl/bl) +66%, length-to-width ratio +4%) and decreased algae diversity (−21%). No clear relation between herbicide concentrations and tadpole growth or algae density or diversity was observed. Interactive effects of herbicides and temperature affected growth parameters, tail deformation and tadpole mortality indicating that the herbicide effects are temperature-dependent. Remarkably, herbicide-temperature interactions resulted in deformed tails in 34% of all herbicide treated tadpoles at 15 °C whereas no tail deformations were observed for the herbicide-free control at 15 °C or any tadpole at 20 °C; herbicide-induced mortality was higher at 15 °C but lower at 20 °C.DiscussionThese herbicide- and temperature-induced changes may have decided effects on ecological interactions in freshwater ecosystems. Although no clear dose-response effect was seen, the presence of glyphosate was decisive for an effect, suggesting that the lowest observed effect concentration (LOEC) in our study was 1.5 mg a.e. glyphosate L−1water. Overall, our findings also question the relevance of pesticide risk assessments conducted at standard temperatures.

Corynebacterium glutamicum metabolizes sialic acid (Neu5Ac) to fructose-6-phosphate (fructose-6P) via the consecutive activity of the sialic acid importer SiaEFGI, N -acetylneuraminic acid lyase (NanA), N -acetylmannosamine kinase (NanK), N -acetylmannosamine-6P epimerase (NanE), N -acetylglucosamine-6P deacetylase (NagA), and glucosamine-6P deaminase (NagB). Within the cluster of the three operons nagAB , nanAKE , and siaEFGI for Neu5Ac utilization a fourth operon is present, which comprises cg2936 , encoding a GntR-type transcriptional regulator, here named NanR. Microarray studies and reporter gene assays showed that nagAB , nanAKE , siaEFGI , and nanR are repressed in wild-type (WT) C. glutamicum but highly induced in a Δ nanR C. glutamicum mutant. Purified NanR was found to specifically bind to the nucleotide motifs A[AC]G[CT][AC]TGATGTC[AT][TG]ATGT[AC]TA located within the nagA-nanA and nanR-sialA intergenic regions. Binding of NanR to promoter regions was abolished in the presence of the Neu5Ac metabolism intermediates GlcNAc-6P and N -acetylmannosamine-6-phosphate (ManNAc-6P). We observed consecutive utilization of glucose and Neu5Ac as well as fructose and Neu5Ac by WT C. glutamicum , whereas the deletion mutant C. glutamicum Δ nanR simultaneously consumed these sugars. Increased reporter gene activities for nagAB , nanAKE , and nanR were observed in cultivations of WT C. glutamicum with Neu5Ac as the sole substrate compared to cultivations when fructose was present. Taken together, our findings show that Neu5Ac metabolism in C. glutamicum is subject to catabolite repression, which involves control by the repressor NanR. IMPORTANCE Neu5Ac utilization is currently regarded as a common trait of both pathogenic and commensal bacteria. Interestingly, the nonpathogenic soil bacterium C. glutamicum efficiently utilizes Neu5Ac as a substrate for growth. Expression of genes for Neu5Ac utilization in C. glutamicum is here shown to depend on the transcriptional regulator NanR, which is the first GntR-type regulator of Neu5Ac metabolism not to use Neu5Ac as effector but relies instead on the inducers GlcNAc-6P and ManNAc-6P. The identification of conserved NanR-binding sites in intergenic regions within the operons for Neu5Ac utilization in pathogenic Corynebacterium species indicates that the mechanism for the control of Neu5Ac catabolism in C. glutamicum by NanR as described in this work is probably conserved within this genus.

The current terrestrial risk assessment of insecticides regarding nontarget arthropods considers exclusively beneficial organisms, whereas herbivorous insects, such as grasshoppers, are ignored. However, grasshoppers living in field margins or meadows adjacent to crops may potentially be exposed to insecticides due to contact with or ingestion of contaminated food. Therefore, the present study assessed effects of five active ingredients of insecticides (dimethoate, pirimicarb, imidacloprid, lambda-cyhalothrin, and deltamethrin) on the survival of Chorthippus sp. grasshopper nymphs by considering two routes of exposure (contact and oral). The experiments were accompanied by monitoring field margins that neighbored cereals, vineyards, and orchards. Grasslands were used as reference sites. The laboratory toxicity tests revealed a sensitivity of grasshoppers with regard to the insecticides tested in the present study similar to that of the standard test species used in arthropod risk assessments. In the field monitoring program, increasing grasshopper densities were detected with increasing field margin width next to cereals and vineyards, but densities remained low over the whole range of field margins from 0.5 to 20 m next to orchards. Grasshopper densities equivalent to those of grassland sites were only observed in field margins exceeding 9 m in width, except for field margins next to orchards. These results may indicate that current insecticide risk assessments are insufficiently protective for grasshoppers in field margins. Environ. Toxicol. Chem. 2012;31:1874-1879. # 2012 SETAC

Ferrites are iron containing, non-conducting ceramics, which exhibit magnetic properties. One of the most common is (Ni,Zn)1Fe2O4. Bulk ferrites are typically made by conventional ceramic sintering. However, manufacture of thick coatings is of growing interest, and deposition by thermal spraying is potentially attractive. The present paper reports work on the development of (Ni0·549Zn0·333Co0·028Mn0·049)O0·958Fe2O3 based powder feedstock by self-propagating high temperature synthesis and coating deposition by both air plasma and high velocity oxy-fuel spraying. The results obtained show that some decomposition of the ferrite material occurred with the loss of zinc and oxygen. The Zn loss is dependent to a large extent on the surface/volume ratio of the powder used in spray deposition. The influence of the spraying technique on the electromagnetic properties was also measured and compared to bulk ferrite materials. The air plasma sprayed coatings showed similar absorption coefficient compared to th...

Plasma nitriding is a well established technology to improve wear and corrosion properties of austenitic stainless steels. Nevertheless, in the case of martensitic stainless steels, it continues being a problem mainly from the corrosion resistance viewpoint.In this work, three high chromium stainless steels (M340, N695 and Corrax) were hardened by ion nitriding at low temperature, intending to preserve their corrosion resistance.Corrosion behavior was evaluated by CuSO4 spot, salt spray fog and potentiodynamic polarization in NaCl solution. Microstructure was analyzed by optical microscopy, SEM (EDS) and glancing angle X-ray diffraction. All the samples showed an acceptable corrosion resistance in experiments with CuSO4, but in salt spray fog and electrochemical tests, only Corrax showed good behavior. The poor corrosion performance could be explained by chromium carbides formed in thermal treatment stage in martensitic steels and chromium nitrides formed during nitriding, even though the process was carried out at low temperature. Fil: Brühl, Sonia Patricia. Universidad Tecnológica Nacional. Facultad Regional Concepción del Uruguay; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Charadia, R.. Universidad Tecnológica Nacional. Facultad Regional Concepción del Uruguay; Argentina Fil: Simison, Silvia Noemi. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina Fil: Lamas, Diego Germán. Instituto de Investigaciones Científicas y Técnicas de las Fuerzas Armadas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Cabo, A.. IONAR; Argentina

Decreased levels of N-acetylaspartate (NAA) and brain-derived neurotrophic factor (BDNF) in the anterior cingulate cortex (ACC) have been linked to neuronal loss and psychiatric disorders like schizophrenia and bipolar disorder. We previously found that BDNF serum concentration was predicted by the concentration of NAA in the ACC, indicating that neuronal integrity and vitality of a cortical region like the ACC, as reflected by a high concentration of NAA, might be related to high concentrations of BDNF in serum. Moreover, our recent finding that Val66Met genotype appears to predict the BDNF serum level in healthy human volunteers suggests the Met allele to be connected to higher concentrations of BDNF in serum. We examined absolute NAA concentrations in the ACC and hippocampus of 40 male and 42 female healthy volunteers (age: 33.3+/-9 years). We found NAA in the ACC to be significantly increased in Met carriers (F=5.2, df=1, p=0.025). On the other hand, the concentration of creatine+phosphocreatine in the hippocampus was significantly decreased in Met carriers. We hypothesize that higher NAA levels in the ACC might contribute to the protection of Met allele carriers against major psychiatric disorders as schizophrenia and bipolar disorder.

We investigated the photon-emission spectrum of Xe atoms upon photoionization of the Xe 3d-subshell. The 5p-4d spectrum is emitted in the process of the cascading decay of the 3d-vacancy and has a complex multi-component structure reflecting a great number of transitions from various ionic configurations produced during the cascade development. The spectrum is assigned by the direct construction of the cascade de-excitation tree. 21 different transitions between configurations of multiply charged Xe ions (+2 to +6) are found to be contributing to the spectrum. The 5p-4d partial fluorescence yield is found to be six times greater for the 3d-ionization than for the 4d-ionization. The effect of the multiplet splitting in the initial and final states of the emitting transitions is studied.

MCrAlY materials are widely used as bond coats for thermal barrier coatings on turbine blades. The aim of this work is to improve mechanical properties and wear resistance of thermal sprayed NiCoCrAlY-coatings by strengthening the coating with hard phase particles. In order to retain the effect of the dispersion reinforcement at high temperatures, the use of temperature-stable oxide hard phases such as ZrO2 is necessary. To realise this new material structure, the high energy ball milling process is applied and analysed. With this process it is possible to achieve a homogeneous distribution of the oxide hard phases in the NiCoCrAlY matrix. The mixture ratio between NiCoCrAlY and ZrO2 was varied between 5 wt-% and 10 wt-% ZrO2. The influences of the milling time of the high energy ball milling process on the distribution of the hard phases in the metal matrix were analysed. After spraying with a HVOF system the mechanical properties of the coatings are measured and compared with conventional NiCoCrAlY coatings.

Freshly pressed linseed oil shows a delicate nutty flavor. However, after only 1 day of storage, a bitter off-taste develops. It is caused mainly by the formation of a cyclic octa-peptide named cyclolinopeptide E (CLE) containing the oxidized amino acid methionine. A simple and fast determination by solid-phase extraction and high-performance liquid chromatography with UV detection has been developed in order to measure the formation of this cyclic peptide during storage in correlation with the increasing bitter off-taste of the oil, which was determined by a sensory panel. The development of this bitter off-taste was analyzed in several oils prepared from linseed of a single variety from seeds obtained during a growing test. Highest bitterness was perceived in oil from the variety Eurodor, corresponding to CLE contents of 925 mg/kg, and lowest bitterness was perceived in oil from the variety Baladin, corresponding to a CLE content of 485 mg/kg. In some varieties, additional bitter compounds might be present in significant amounts.

Virgin hemp seed oil is not widespread on the market, although it is characterised by an interesting fatty acid composition with a high content of polyunsaturated fatty acids. Linoleic acid is the predominant fatty acid, which comes, together with α-linolenic acid (18:3n-3), to approximately 80% of the total fatty acids. From a nutritional point of view, up to 7% γ-linolenic acid (18:3n-6) and 2.5% stearidonic acid (18:4n-3) are very interesting. The total amount of tocopherols is high between 80 and 110 mg/100 g, with γ-tocopherol as the main tocopherol (85%). Due to the high amount of unsaturated fatty acids, hemp seed oil is very susceptible to oxidative deterioration, which results in a fast impairment of the oil during storage. In addition, the high amounts of chlorophyll in the oil due to harvesting of high amounts of immature seeds require light protection, which is often neglected because of merchandising purposes. The virgin oil is characterised by a nutty taste with a slightly bitter aftertaste. The use of virgin hemp seed oil is recommended during mild processing of food without heat.

The determination of fatty acid composition by gas chromatography as a routine task is established in most laboratories dealing with oils and fats. The scope of this method can be enlarged for a preliminary quality control of used frying fats and oils, which is commonly characterized by the determination of polar compounds and polymerized triacylglycerols. However, for screening purposes the determination of the short-chain fatty acids C7:0 and C8:0 can give an early indication about the quality of used frying fats and oils.

The chemistry climate model ECHAM5/MESSy1 (E5/M1) in a setup extending from the surface to 80 km with a vertical resolution of about 600 m near the tropopause with nudged tropospheric meteorology allows a direct comparison with satellite data of chemical species at the same time and location. Here we present results out of a transient 10~years simulation for the period of the Antarctic vortex split in September 2002, where data of MIPAS on the ENVISAT-satellite are available. For the first time this satellite instrument opens the opportunity, to evaluate all stratospheric nitrogen containing species simultaneously with a good global coverage, including the source gas N2O and ozone which allows an estimate for NOx-production in the stratosphere. We show correlations between simulated and observed species in the altitude region between 10 and 50 hpa for different latitude belts, together with the Probability Density Functions (PDFs) of model results and observations. This is supplemented by global maps on pressure levels showing the comparison between the satellite and the simulated data sampled at the same time and location. We demonstrate that the model in most cases captures the partitioning in the nitrogen family, the diurnal cycles and the spatial distribution within experimental uncertainty. This includes even variations due to tropospheric clouds. There appears to be, however, a problem to reproduce the observed nighttime partitioning between N2O5 and NO2 in the middle stratosphere using the recommended set of reaction coefficients and photolysis data.

A series of low-dimensional quantum-spin systems, including isolated Cu II dimers, various coupled Cu II -dimer systems and a 1-D uniform S = 1/2 Heisenberg antiferromagnet has been synthesized. All materials are based on hydroquinone-derived linkers connecting Cu II ions carrying a spin of S = 1/2. Magnetic measurements covering wide ranges of temperature 0.06 K ≤ T ≤ 300 K and magnetic fields B ≤ 50 T reveal an antiferromagnetic coupling constant J of moderate strength for all systems. Electron-spin resonance measurements over wide frequency ranges have been used to determine the local coordination environment of the Cu II centers. The distinct magnetic properties of these materials along with their flexibility against chemical modifications make them excellent model systems for exploring fundamental aspects of quantum magnetism.