Photodegradation of the carbamate insecticide propoxur

Summary In order to examine the photostability of the insecticide propoxur (2-isopropoxyphenyl-N-methylcarbamate) in the field model experiments with organic solvents were performed. Photodegradation (>280 nm) of propoxur was found to be more efficient in isopropanol solution than in the presence of cyclohexane or cyclohexene. Photolysis in isopropanol and cyclohexane mainly resulted in formation of isopropylphenyl ether. As a trace component 2-isopropoxyphenol was detected. In the presence of cyclohexene on the other hand photomineralisation was found to be the main degradation pathway.

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Photoabbau des Carbamat-Insecticides Propoxur

Zusammenfassung Zur Voruntersuchung der Photostabilität des Insecticides Propoxur (2-Isopropoxyphenyl-N-methylcarbamat) im Freiland wurden Modellexperimente in organischen Lösungsmitteln durchgeführt. Der Photoabbau (>280 nm) von Propoxur verlief in Isopropanol deutlich schneller als in Cyclohexan oder Cyclohexen. Bei Bestrahlung in Isopropanol und Cyclohexan entstand als Hauptprodukt Isopropylphenylether, daneben Spuren von 2-Isopropoxyphenol. Dagegen erfolgte in Cyclohexen der Abbau hauptsächlich über eine Photomineralisierung.

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Dedicated to Professor Dr. H. Niebergall on the occasion of his 65th birthday     

Compatibilization of polymer blends from poly(styrene‐co‐acrylonitrile) and polycarbonate by oxazoline modification of poly(styrene‐co‐acrylonitrile) in the melt

A good way of achieving compatibility in polymer blends of poly(styrene‐co‐acrylonitrile) (S/AN) and bisphenol A polycarbonate (PC) is the chemical modification of S/AN in the melt. A catalyzed reaction of the nitrile groups with a substituted 2‐amino alcohol or 2‐amino phenol resulted in a conversion of nitrile groups of 55–75% in 60 min. The introduced heterocyclic structures were ethyl hydroxymethyl oxazoline (EHMOXA) and benzoxazole (BenzOXA), respectively. The use of dibutyltin oxide as a catalyst led to the highest efficiency. The modified polymer was characterized by Fourier transform infrared and NMR spectroscopy, elemental analysis, and reactions with organic acids and anhydrides. The modified S/AN showed good technical compatibility (single glass‐transition temperature) with PC in blends made from solution and from the melt. All blends were characterized with oscillating rheometry and differential scanning calorimetry. Rheological measurements showed that EHMOXA–S/AN reacted with PC and had crosslinked structures, whereas BenzOXA–S/AN showed compatibilization without any (crosslinking) reaction. The melt blends of BenzOXA–S/AN and PC showed a downward shift in the complex viscosity due to the influence of the BenzOXA group. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2322–2332, 2003     

Hyperphagia modifies FA profiles of plasma phospholipids,plasma FFA,and adipose tissue TAG

Hyperphagia was achieved by continuous intracerebroventricular infusion of a melanocortin receptor antagonist (HS024; Neosystem, Strasbourg, France) in rats. The effects of hyperphagia on FA composition and concentration of plasma phospholipids (PL), plasma FFA, and adipose tissue TAG were studied in rats for 8 d [short-term hyperphagia (STH); n=8], or 28 d [longterm hyperphagia (LTH); n=9]. The control rats were treated with artificial cerebrospinal fluid for 8 d (n=8) or 28 d (n=10). The rats were fed the same regular diet. In STH rats the plasma PL and fasting plasma FFA contained higher concentrations of saturated FA (SFA) and monounsaturated FA (MUFA), and plasma FFA contained lower n−6 PUFA than in the control rats. In LTH rats the plasma PL contained higher concentrations of SFA, MUFA, and n−3 PUFA and higher proportions of 16∶1n−7 and 18∶1n−9 at the expense of 18∶2n−6 than in the control rats. In LTH rats the abundant dietary intake of 18∶2n−6 did not enrich 18∶2n−6 of the plasma PL or adipose tissue TAG. In LTH rats the fasting plasma FFA contained more than twofold higher concentrations of SFA and MUFA, and higher proportions of 16∶1n−7 and 18∶1n−9 at the expense of 18∶2n−6 than in the control rats. This animal obesity model shows that LTH affects the FA composition and concentration of plasma PL, plasma FFA, and adipose tissue TAG, a result consistent with changes associated with increased risk of various diseases in humans. These results also demonstrate that LTH alters the FA composition of plasma PL and adipose tissue TAG in a way that does not reflect the FA composition of dietary fat.     

A Synthetic Approach to Star‐Like Polymers of Styrene and Butyl Acrylate by Linking Reactions using Functionalized Methacrylates

Summary: Coupling reactions between terminal functionalized polymer chains were chosen for the synthesis of star‐like polymers consisting of polystyrene and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] arms. For the preparation of terminal functionalized polymer chains a side reaction of the 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) mediated free radical polymerization of methacrylates could be used successfully to convert TEMPO terminated polymers into end functionalized polymers. The number of functionalized monomer units attached to the polymer chain is directly related to the TEMPO concentration during this reaction. Different polystyrenes and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] block copolymers were functionalized with a variable number of epoxide and alcohol groups at the chain end. For the determination of the optimal reaction parameters for the coupling reactions between these polymer chains, epoxy functionalized polystyrenes were converted with hydroxy functionalized polystyrenes under basic and acidic conditions. By activation with sodium hydride or boron trifluoride star‐like polymers were synthesized under mild conditions. The transfer of the reaction conditions to coupling reactions between end functionalized polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] copolymers showed that star‐like polymers with more than 12 arms were formed using boron trifluoride as activating agent.

     

Local polarity analysis: a sensitive method that discriminates between native proteins and incorrectly folded models

The evaluation of calculated protein structures is an importantstep in the protein design cycle. Known criteria for this assessmentof proteins are the polar and apolar, accessible and buriedsurface area, electrostatic interactions and other interactionsbetween the protein atoms (e.g. HO, S-S),atomic packing, analysisof amino acid environment and surface charge distribution. Weshow that a powerful test of accuracy of protein structure canbe derived by analysing the water contact of atoms and additionallytaking into account their polarity. On the basis of estimatedreference values of the polar fraction of typical globular proteinswith known structure (mean, SD and distribution), the evaluationof misfolded structures can be improved significantly. The referencevalues are derived by moving windows of different length (3–99amino acid residues) over the amino acid sequence. Model proteins,which are included in the Brookhaven protein structure databank,deliberately misfolded proteins, hypothetical proteins and predictedprotein structures are diagnosed as at least partially incorrectlyfolded. The local fault, mostly observed, is that polar groupsare buried too frequently in the interior of the protein. Thedatabase-derived quantities are useful in screening the designedproteins prior to experimentation and may also be useful inthe assessment of errors in the experimentally determined proteinstructures.     

CTmod-a toolkit for Monte Carlo simulation of projections including scatter in computed tomography

The CTmod toolkit is a set of C++ class libraries based on the CERN's application development framework ROOT. It uses the Monte Carlo method to simulate energy imparted to a CT-scanner detector array. Photons with a given angle-energy distribution are emitted from the X-ray tube approximated by a point source, transported through a phantom, and their contribution to the energy imparted per unit surface area of each detector element is scored. Alternatively, the scored quantity may be the fluence, energy fluence, plane fluence, plane energy fluence, or kerma to air in the center of each detector element. Phantoms are constructed from homogenous solids or voxel arrays via overlapping. Implemented photon interactions (photoelectric effect, coherent scattering, and incoherent scattering) are restricted to the energy range from 10 to 200keV. Variance reduction techniques include the collision density estimator and survival biasing combined with the Russian roulette. The toolkit has been used to estimate the amount of scatter in cone beam computed tomography and planar radiography.     

Supporting casual interactions between board games on public tabletop displays and mobile devices

As more interactive surfaces enter public life, casual interactions from passersby are bound to increase. Most of these users can be expected to carry a mobile phone or PDA, which nowadays offers significant computing capabilities of its own. This offers new possibilities for interaction between these users’ private displays and large public ones. In this paper, we present a system that supports such casual interactions. We first explore a method to track mobile phones that are placed on a horizontal interactive surface by examining the shadows which are cast on the surface. This approach detects the presence of a mobile device, as opposed to any other opaque object, through the signal strength emitted by the built-in Bluetooth transceiver without requiring any modifications to the devices’ software or hardware. We then go on to investigate interaction between a Sudoku game running in parallel on the public display and on mobile devices carried by passing users. Mobile users can join a running game by placing their devices on a designated area. The only requirement is that the device is in discoverable Bluetooth mode. After a specific device has been recognized, a client software is sent to the device which then enables the user to interact with the running game. Finally, we explore the results of a study which we conducted to determine the effectiveness and intrusiveness of interactions between users on the tabletop and users with mobile devices.     

Toxicity of different wheat gliadins in coeliac disease

Summary To determine the toxic effect of different gliadins on coeliac patients, which has been variably assessed in the literature, wheat prolamines (gliadin) were separated into the main fractions-, -, -, and-gliadins by chromatography on Sulfopropyl Sephadex C-50. The chemical compositions of the gliands were characterized by polyacrylamide gel electrophoresis, amino-acid analysis, determination of amide nitrogen and peptide maps.The peptide fractions B2 and B3 were isolated from the gliadins by a peptic tryptic digestion, ultrafiltration and gel filtration on Sephadex G-50.The gliadins and the peptide fractions were examined for coeliac activity by immunological tests (LIF tests) and by organ-culture tests.The results show that the peptide fractions are generally more active than their respective gliadins. The peptide fractions of all gliadins have a coeliac-specific toxic effect; their activities correlate with the chemical composition of the gliadins.

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Untersuchungen von Gliadinfraktionen des Weizens auf Cöliakieaktivität

Zusammenfassung Zur Überprufung der teilweise widersprüchlichen Angaben in der Literatur über die cöliakieauslösende Wirkung einzelner Gliadinfraktionen wird Weizenprolamin (Gliadin) durch Ionenaustauschchromatographie an Sulfopropyl-Sephadex C-50 in die Hauptfraktionen-, -, - und-Gliadin aufgetrennt. Die Gliadine werden durch PAG-Elektrophorese, Aminosäureanalyse, Amid-N-Bestimmung und über die nach partieller enzymatischer Hydrolyse erhaltenen Peptidmuster in ihrer chemischen Zusammensetzung charakterisiert. Durch peptisch-tryptische Partialhydrolyse, Ultrafiltration und Gelchromatographie an Sephadex G-50 werden aus den einzelnen Gliadinen die Peptidfraktionen 132 und 133 gewonnen. Die Protein- und Peptidfraktionen werden in einem immunologischen Test (LIF-Test) bzw. in einem Organkultur-Test auf Cöliakieaktivität untersucht.Die Ergebnisse zeigen, daß die Peptidfraktionen durchweg größere Aktivität haben als die entsprechenden Proteine, und daß von den Peptidfraktionen aller Gliadine eine cöliakiespezifische Wirkung ausgeht, wobei die Aktivität mit der chemischen Zusammensetzung der Gliadine korreliert ist.

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Supported by a grant from Stiftung Volkswagenwerk     

SME tailor-designed patent portfolio analysis

The management of patents is acknowledged to be closely correlated to a company’s profits. Thus, evaluation of patent portfolios is an essential task for companies producing or depending on technology-related products. While global players and consultants already have considerable experience in this field, no tool has so far been available that meets SME requirements. The Innovation and Patent-Centre at the Chamber of Commerce in Hamburg, a German think tank for patent management, has now developed a tool specially suited for SMEs. The article describes the methodology of the tool and compares it to other state-of-the-art tools. The tool gives an easy-to-understand overview for personnel with different professional backgrounds and facilitates strategic cross-functional discussions. Field tests carried out with SMEs in different industry sectors and with varying patent portfolio sizes and structures have shown good results.     

Bolus ingestion of white and green tea increases the concentration of several flavan‐3‐ols in plasma,but does not affect markers of oxidative stress in healthy non‐smokers

White tea (WT) is rich in flavan‐3‐ols as green tea (GT) and might provide health protective effects due to the strong antioxidant properties of flavan‐3‐ols. Since intervention studies with WT are lacking, we evaluated the effects of WT consumption on antioxidant status, antioxidant capacity and biomarkers of oxidative stress compared to water and GT. After an overnight fast, 70 healthy non‐smokers were randomized to consume 600 mL of WT, GT or water (control). Plasma (epi‐)catechin and epi(gallo)catechingallate, antioxidant capacity (Folin assay, trolox equivalent antioxidant capacity test), 8‐iso‐prostaglandin F_2α, ascorbic acid and uric acid were determined before and several times within 8 h after consumption. DNA strand breaks were measured in vivo and ex vivo (H₂O₂ stimulation) in leukocytes. Plasma flavan‐3‐ols significantly increased after WT and GT ingestion. Trolox equivalent antioxidant capacity was lower after 5 h in controls versus WT (p=0.031) and GT (p=0.005). Folin‐Ciocalteu reducing capacity, ascorbic and uric acid as well as markers of oxidative stress (8‐iso‐prostaglandin‐F_2α, DNA strand breaks) were not affected by the beverages. A short‐term increase of catechins does not change plasma antioxidant capacity in healthy subjects. Conclusions with respect to health protective effects of WT and GT on the basis of these biomarkers can, thus, not be drawn.