Small-volume releases of gasoline in the vadose zone: impact of the additives MTBE and ethanol on groundwater quality

A controlled gasoline spill experiment was performed under outdoor conditions typical for winter in temperate regions to study the fate of methyl tert-butyl ether (MTBE), ethanol, benzene, and selected other petroleum hydrocarbons. Artificial gasoline containing MTBE and ethanol (5% w/w of each) was placed at a defined depth into a 2.3 m thick unsaturated zone of alluvial sand overlying a gravel aquifer in a lysimeter. During an initial period of 41 days without recharge, MTBE and hydrocarbon vapors migrated by vapor-phase diffusion to groundwater, while ethanol vapors were naturally attenuated. In a subsequent period of 30 days with 5-mm daily recharge, all soluble compounds including ethanol were transported to the groundwater. Ethanol disappeared concomitantly with benzene and all other petroleum hydrocarbons except isooctane from the aerobic groundwater due to biodegradation. MTBE persisted for longer than 6 months at concentrations larger than 125000 microg L(-1). No evidence for MTBE biodegradation was found, whereas > 99.6% of ethanol removal from the lysimeter was due to biodegradation. It is concluded that MTBE-free gasoline would be less harmful for groundwater resources and that ethanol is an acceptable substitute.     

Untersuchungen zur134+137Cäsium-Kontamination bei in Hessen erlegtem Schalenwild

European Food Research and Technology - Die Belastung mit134+137 Caesium von in Hessen erlegtem Schalenwild (556 Stück 1986/87) nach dem Reaktorunfall von Tschernobyl wurde untersucht. Es...     

Animal models are reliably mimicking human diseases? A morphological study that compares animal with human NAFLD

Non‐alcoholic fatty liver disease (NAFLD) is a clinical‐pathological syndrome that includes a wide spectrum of morphological alterations. In research, animal models are crucial in evaluating not only the pathogenesis of NAFLD and its progression, but also the therapeutic effects of various agents. Investigations on the ultrastructural features of NAFLD in humans are not copious, due to the difficulty to obtain human samples and to the long time of NAFLD to evolve. Translational comparative studies on the reliability of animal models in representing the histopathologic picture as seen in humans are missing. To overcome this lack of investigations, we compared the ultrastructural NAFLD features of an animal model versus human. Sprague‐Dawley rats were fed with a high fat diet (HFD) for 1–4 weeks, while control rats were fed with a standard diet. Human specimens were collected from patients with diagnosed fatty liver disease, undergoing liver biopsies or surgery. Rat and human samples were examined by light microscopy and by transmission and high resolution scanning electron microscopy. The present work demonstrated that NAFLD in animal model and in human, share overlapping ultrastructural features. In conclusion, animal HFD represent an appropriate tool in studying the pathogenesis of NAFLD. Microsc. Res. Tech. 77:790–796, 2014. © 2014 Wiley Periodicals, Inc.     

Kinetics of 3-deoxy-D-erythro-hexos-2-ulose in unifloral honeys

In this study, for the first time, the amount of 3-deoxy-D-erythro-hexos-2-ulose (3-DG) in fresh citrus and chestnut honeys was determined. 3-DG was measured as the corresponding quinoxalines after derivatization with orthophenylenediamine using reverse-phase high-performance liquid chromatography (RP-HPLC). Notwithstanding the freshness of the samples, high levels of 3-DG were detected in both honeys. The comparison of 3-DG and 5-hydroxymethylfurfural (HMF) concentrations, which was also quantified by RP-HPLC, showed that citrus honeys had the lowest amount of 3-DG (107 mg/kg) and the highest of HMF (16.7 mg/kg), while chestnut honeys had the opposite (398 and 1.2 mg/kg, respectively). During thermal treatment, different 3-DG and HMF trends were highlighted between the citrus and chestnut honeys; at the end, 3-DG formation was more favored with respect to HMF formation. Moreover, in citrus honeys, a good correlation between 3-DG and HMF levels was observed, which was not found in chestnut honeys, suggesting a role of the high pH values of these honeys on the degradation routes. The kinetic analysis showed the highest k value for 3-DG and HMF formation in chestnut and citrus honeys, respectively. The lowest Ea values related to 3-DG formation and the highest to HMF formation, indicating that the key intermediate 3-DG is easily formed at low temperatures, whilst the formation of HMF requires higher temperatures. For this reason, 3-DG seems to be an aging index rather than a thermal index and its use, at least for honeys at high pH values, together with HMF, could improve their quality assessment.     

Variation in the content of glucosinolates,hydroxycinnamic acids,carotenoids, total antioxidant capacity and low‐molecular‐weight carbohydrates in Brassica vegetables

Bioactive compounds were investigated in genotypes (cauliflower 10, white cabbage 10, curly kale 1) and plant parts of the three crops. The content of most of the major glucosinolates glucobrassicin, sinigrin and glucoiberin differed significantly between cultivars. Samples harvested in 2000 had higher amounts of several glucosinolates than samples from 1999. Within cauliflower the buds of the floret had 1.5 to 2.5‐fold higher concentration of glucobrassicin and 4‐methoxyglucobrassicin than the stalk. In white cabbage several glucosinolates had their highest content in the outer leaves (up to 2‐fold higher). Upper leaves of curly kale contained 5‐fold more of total glucosinolates than lower leaves. Chlorogenic acid was the dominating hydroxycinnamate in curly kale, which also contained at least ten times more of carotenoids (mainly lutein) than white cabbage. Total antioxidant capacity (TAC) assayed with the FRAP method was 0.76 (0.06) µmol/g fw (mean (SD)) in water‐soluble and 0.32 (0.04) in water‐insoluble extracts of cauliflower which was 62–68% higher than in white cabbage. Curly kale contained 6.4 and 6.1 µmol/g fw TAC in water‐soluble and water‐insoluble extracts. TAC did not differ between plant parts. Progoitrin and 4‐hydroxyglucobrassicin were correlated to water‐soluble TAC in white cabbage, probably reflecting a variation in other compounds. Cauliflower contained less glucose, fructose and sorbitol but more sucrose than white cabbage. Curly kale had lower contents of glucose (～2 times), fructose (～4–5 times) and sucrose (20 and 36 times, respectively) than cauliflower and white cabbage, while inositol was only found in curly kale. Storage of white cabbage reduced the amount of sorbitol and sucrose. The study shows that cultivar, plant part and storage affect the content of bioactive compounds in Brassica vegetables. The variation between years, as in cauliflower, is due to environmental factors. Since the cultivar ranking order was rather stable for several components the data could provide a basis for the selection of cultivars optimised for valuable health components for fresh market consumption. Copyright © 2005 Society of Chemical Industry     

Consumption of Hibiscus sabdariffa L. aqueous extract and its impact on systemic antioxidant potential in healthy subjects

BACKGROUND: To evaluate health benefits attributed to Hibiscus sabdariffa L. a randomized, open‐label, two‐way crossover study was undertaken to compare the impact of an aqueous H. sabdariffa L. extract (HSE) on the systemic antioxidant potential (AOP; assayed by ferric reducing antioxidant power (FRAP)) with a reference treatment (water) in eight healthy volunteers. The biokinetic variables were the areas under the curve (AUC) of plasma FRAP, ascorbic acid and urate that are above the pre‐dose concentration, and the amounts excreted into urine within 24 h (Ae_0–24) of antioxidants as assayed by FRAP, ascorbic acid, uric acid, malondialdehyde (biomarker for oxidative stress), and hippuric acid (metabolite and potential biomarker for total polyphenol intake). RESULTS: HSE caused significantly higher plasma AUC of FRAP, an increase in Ae_0–24 of FRAP, ascorbic acid and hippuric acid, whereas malondialdehyde excretion was reduced. Furthermore, the main hibiscus anthocyanins as well as one glucuronide conjugate could be quantified in the volunteers' urine (0.02% of the administered dose). CONCLUSION: The aqueous HSE investigated in this study enhanced the systemic AOP and reduced the oxidative stress in humans. Furthermore, the increased urinary hippuric acid excretion after HSE consumption indicates a high biotransformation of the ingested HSE polyphenols, most likely caused by the colonic microbiota. Copyright © 2012 Society of Chemical Industry     

Printing of Highly Integrated Crossbar Junctions

A new process is presented that combines nanoimprint lithography and soft lithography to assemble metal–bridge–metal crossbar junctions at ambient conditions. High density top and bottom metal electrodes with half‐pitches down to 50 nm are fabricated in a parallel process by means of ultraviolet nanoimprint lithography. The top electrodes are realized on top of a sacrificial layer and are embedded in a polymer matrix. The lifting of the top electrodes by dissolving the sacrificial layer in an aqueous solution results in printable electrode stamps. Crossbar arrays are noninvasively assembled with high yield by printing the top electrode stamps onto bare or modified bottom electrodes. A semiconducting and a quasi metal like conducting type of polymer are incorporated in the cross points to form metal‐polymer‐metal junctions. The electrical characterization of the printed junctions revealed that the functional integrity of the electrically addressed conductive polymers is conserved during the assembling process. These findings suggest that printing of electrodes represents an easy and cost effective route to highly integrated nanoscale metal‐bridge‐metal junctions if imprint lithography is used for electrode fabrication.     

Interactions Between Amino Acid‐Tagged Naphthalenediimide and Single Walled Carbon Nanotubes for the Design and Construction of New Bioimaging Probes

A new synthetic route to functionalized single walled carbon nanotubes (SWNTs) via supramolecular interactions using a specifically designed naphthalenediimide (NDI) nanoreceptor is demonstrated. The tendency of the NDI to spontaneously form composites with carbon nanomaterials leads to fluorescent amino acid tagged SWNTs, which are dispersible in widely accessible organic solvents (CHCl₃, DMSO) as well as in biocompatible cell medium (EMEM, Eagle's modified essential medium). The X‐ray crystal structure of the first iodine‐tagged and amino acid‐functionalized NDI molecule, designed especially to facilitate the high resolution transmission electron microscopy (HR TEM) imaging whilst retaining its ability to self‐assemble into a nanodimensional receptor in weakly polar solvents, is also described. A new hybrid material, NDI@SWNT, was prepared and characterized as dispersed in organic solvents and aqueous media and in the solid state by HR TEM, tapping mode atomic force microscopy (TM AFM), scanning electron microscopy (SEM), circular dichroism, Raman and fluorescence spectroscopies (steady‐state single and two‐photon techniques). Combined microscopy techniques, density functional theory (DFT) calculations using the Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) program and spectroscopic measurements in solution indicate that amino acid‐functionalized NDI interacts strongly with SWNTs and forms a donor‐acceptor complex. Density functional theory (DFT) calculations predicted the geometry and the binding energies of an NDI molecule loaded onto a SWNT strand and the possibility of charge transfer interactions within the hybrid. The NDI@SWNT composite translocates into cells (e.g. FEK‐4, HeLa, MCF‐7) as an intact object and localizes in the cells' cytoplasm and partially in the nucleus. The NDI coating enhances the biocompatibility of SWNTs and mediates its intracellular localization as shown by confocal fluorescence imaging and fluorescence lifetime imaging (FLIM) techniques. The excited state fluorescence lifetime of the probes in cells versus solution phase indicates that the probes remain unaffected by the change in their chemical environment within the experimental timescale (2 h).