Determination of furazolidone residues in eggs by HPLC followed by confirmation with a diode-array UV/Vis detector

A sensitive HPLC method for the determination of furazolidone residues in eggs (10-1,000 micrograms/kg) is described. Recovery is about 86%. With the aid of a UV/Vis Diode-Array detector confirmation up to the 15-ppb level was possible. In order to test this method with "real" samples, three laying hens received 30 mg each of furazolidone in feed (single dose). The eggs were collected for five days. After five days traces of furazolidone (5 micrograms/kg) could still be detected.     

GCase and LIMP2 Abnormalities in the Liver of Niemann Pick Type C Mice

The lysosomal storage disease Niemann–Pick type C (NPC) is caused by impaired cholesterol efflux from lysosomes, which is accompanied by secondary lysosomal accumulation of sphingomyelin and glucosylceramide (GlcCer). Similar to Gaucher disease (GD), patients deficient in glucocerebrosidase (GCase) degrading GlcCer, NPC patients show an elevated glucosylsphingosine and glucosylated cholesterol. In livers of mice lacking the lysosomal cholesterol efflux transporter NPC1, we investigated the expression of established biomarkers of lipid-laden macrophages of GD patients, their GCase status, and content on the cytosol facing glucosylceramidase GBA2 and lysosomal integral membrane protein type B (LIMP2), a transporter of newly formed GCase to lysosomes. Livers of 80-week-old Npc1^−/− mice showed a partially reduced GCase protein and enzymatic activity. In contrast, GBA2 levels tended to be reciprocally increased with the GCase deficiency. In Npc1^−/− liver, increased expression of lysosomal enzymes (cathepsin D, acid ceramidase) was observed as well as increased markers of lipid-stressed macrophages (GPNMB and galectin-3). Immunohistochemistry showed that the latter markers are expressed by lipid laden Kupffer cells. Earlier reported increase of LIMP2 in Npc1^−/− liver was confirmed. Unexpectedly, immunohistochemistry showed that LIMP2 is particularly overexpressed in the hepatocytes of the Npc1^−/− liver. LIMP2 in these hepatocytes seems not to only localize to (endo)lysosomes. The recent recognition that LIMP2 harbors a cholesterol channel prompts the speculation that LIMP2 in Npc1^−/− hepatocytes might mediate export of cholesterol into the bile and thus protects the hepatocytes.     

Asymmetric synthesis and conformational analysis by NMR spectroscopy and MD of Aba- and α-MeAba-containing dermorphin analogues

Dermorphin analogues, containing a (S)‐ and (R)‐4‐amino‐1,2,4,5‐tetrahydro‐2‐benzazepin‐3‐one scaffold (Aba) and the α‐methylated analogues as conformationally constrained phenylalanines, were prepared. Asymmetric phase‐transfer catalysis was unable to provide the (S)‐α‐Me‐o‐cyanophenylalanine precursor for (S)‐α‐MeAba in acceptable enantiomeric purity. However, by using a Schöllkopf chiral auxiliary, this intermediate was obtained in 88 % ee. [(S)‐Aba 3‐Gly 4]dermorphin retained μ‐opioid affinity but displayed an increased δ‐affinity. The corresponding R epimer was considerably less potent. In contrast, the [(R)‐α‐MeAba 3‐Gly 4]dermorphin isomer was more potent than its S epimer. Tar‐MD simulations of both non‐methylated [Aba 3‐Gly 4]dermorphin analogues showed a degree of folding at the C‐terminal residues toward the N terminus of the peptide, without however, adopting a stabilized β‐turn conformation. The α‐methylated analogues, on the other hand, exhibited a type I/I′ β‐turn conformation over the α‐MeAba 3 and Gly 4 residues, which was stabilized by a hydrogen bond involving Tyr 5‐H_N and D ‐Ala 2‐CO.     

Investigation of the Equivalence of National Dew-Point Temperature Realizations in the ?50?°C to +?20?°C Range

In the field of humidity quantities, the first CIPM key comparison, CCT-K6 is at its end. The corresponding European regional key comparison, EUROMET.T-K6, was completed in early 2008, about 4?years after the starting initial measurements in the project. In total, 24 NMIs from different countries took part in the comparison. This number includes 22 EURAMET countries, and Russia and South Africa. The comparison covered the dew-point temperature range from ?50?°C to +20?°C. It was carried out in three parallel loops, each with two chilled mirror hygrometers as transfer standards in each loop. The comparison scheme was designed to ensure high quality results with evenly spread workload for the participants. It is shown that the standard uncertainty due to the long-term instability was smaller than 0.008?°C in all loops. The standard uncertainties due to links between the loops were found to be smaller than 0.025?°C at ?50?°C and 0.010?°C elsewhere. Conclusions on the equivalence of the dew-point temperature standards are drawn on the basis of calculated bilateral degrees of equivalence and deviations from the EURAMET comparison reference values (ERV). Taking into account 16 different primary dew-point realizations and 8 secondary realizations, the results demonstrate the equivalence of a large number of laboratories at an uncertainty level that is better than achieved in other multilateral comparisons so far in the humidity field.     

Multi-level Modeling of Silica–Template Interactions During Initial Stages of Zeolite Synthesis

Zeolite synthesis is driven by structure-directing agents, such as tetrapropyl ammonium ions (TPA⁺) for Silicalite-1 and ZSM-5. However, the guiding role of these organic templates in the complex assembly to highly ordered frameworks remains unclear, limiting the prospects for advanced material synthesis. In this work, both static ab initio and dynamic classical modeling techniques are employed to provide insight into the interactions between TPA⁺ and Silicalite-1 precursors. We find that as soon as the typical straight 10-ring channel of Silicalite-1 or ZSM-5 is formed from smaller oligomers, the TPA⁺ template is partially squeezed out of the resulting cavity. Partial retention of the template in the cavity is, however, indispensable to prevent collapse of the channel and subsequent hydrolysis.

Uncertainties in the fate of nitrogen I: An overview of sources of uncertainty illustrated with a Dutch case study

This study focuses on the uncertainties in the fate of nitrogen (N) in the Netherlands. Nitrogen inputs into the Netherlands in products, by rivers, and by atmospheric deposition, and microbial and industrial fixation of atmospheric N₂ amount to about 4450 Gg N y^–1. About 60% of this N is transported out of the Netherlands in products. The fate of the remaining 40%, however, is less clear. We discuss uncertainties in losses to the atmosphere (as ammonia or through denitrification), by leaching and runoff, and in N accumulation in biomass and soils. These processes may account for the fate of about 40% of the N in the Netherlands, and for the fate of about 60% of the N in Dutch agricultural soils. Reducing uncertainties in the estimates of these fluxes is necessary for reducing the impact of excess N in the environment. In particular, monitoring the environmental effects of ammonia emissions and nitrate leaching to groundwater and aquatic systems requires an increased understanding of the fate of N. Uncertainties arise because (1) some N fluxes cannot be measured directly and are usually quantified indirectly as the balance in N budgets, (2) direct measurements of N fluxes have inevitable inaccuracies, (3) lack of experimental data and other information (e.g. statistics) needed for upscaling, (4) large spatial and temporal variability of fluxes, and (5) poor understanding of the processes involved. These uncertainties can be reduced by additional experimental studies and by further development of process-based models and N budget studies. We prioritize these future research needs according to a range of different criteria.     

Aquatic suction feeding dynamics: insights from computational modelling

Aquatic suction feeding in vertebrates involves extremely unsteady flow, externally as well as internally of the expanding mouth cavity. Consequently, studying the hydrodynamics involved in this process is a challenging research area, where experimental studies and mathematical models gradually aid our understanding of how suction feeding works mechanically. Especially for flow patterns inside the mouth cavity, our current knowledge is almost entirely based on modelling studies. In the present paper, we critically discuss some of the assumptions and limitations of previous analytical models of suction feeding using computational fluid dynamics.     

Enhanced Quantitative Extraction and HPLC Determination of Hop and Beer Bitter Acids

A pleasant and consistent bitterness is an essential flavour attribute of beer. Hop‐derived iso‐α‐acids are largely responsible for beer bitterness and accurate determination of these primary flavour compounds is very important in relation to quality control. The most widely used way to determine beer bitterness is based on spectrophotometry, measuring the absorbance of an iso‐octane extract of acidified beer. However, this approach is far from specific as it measures all of the extracted compounds, including non‐bittering principles. For that particular reason, High Performance Liquid Chromatography (HPLC) is increasingly applied for the quantitative determination of hop‐derived iso‐α‐acids and, if present, reduced iso‐α‐acids. However, to obtain accurate data on beer bitterness profiles, both quantitative sample preparation and state‐of‐the‐art HPLC are essential. In this paper, several extraction procedures based on solid phase extraction (SPE) and liquid‐liquid extraction (LLE), respectively, were evaluated and an optimised extraction methodology using H₃PO₄ for sample acidification prior to extraction is presented. The proposed extraction/HPLC methodology allows for the quantitative recovery and analysis of hop‐derived beer bitterness.