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     

An enhanced,acoustic emission-based,single-fiber-composite test

In the single-fiber-composite (SFC) test, a fiber imbedded in a matrix is loaded in tension, resulting in a fragmentation of the fiber. In the conventional version of this test, the final fiber fragmentation length distribution is used with a micro-mechanical model to determine the average fiber/matrix interfacial shear stress. In the enhanced version of this test, one also determines the applied stress at each fiber fracture, and from this, one can evaluate the strength of the fiber at short gage lengths. In our measurement system, we utilize an acoustic emission (AE) technique to detect the fiber fractures and to locate the fiber breaks and so determine both the fiber failure stresses as well as the fiber fragmentation lengths while the test is in progress. Critical to the success of this test is a broadband AE system that utilizes point-like AE sensors, procedures for evaluatingin situ, the wavespeed of the first wave arrival and signal processing techniques for determining the arrival time of this signal as precisely as possible for a broad range of wave shapes. Here we describe the application of such an enhanced SFC test procedure to investigate the failure of a Nicalon fiber in an epoxy matrix.     

Analysis of grain boundary movement analogous to dislocation movement – both with a matrix having precipitates

In the present investigation it has been shown exemplarily for an austenite microstructure containing carbonitrides that the specific restraining force of a grain boundary due to the distribution of precipitates can be described by a modified Orowan's law, so that the grain boundary movement is considered to be analogous to the dislocation movement. This is achieved by using a modified restraining force F_r (corresponding to the cubic geometry of the particles), a detailed thermodynamic analysis of the precipitates (in this case, carbonitrides) and selected relation for the interparticle spacing L_a. The specific restraining force and the interparticle spacing depend on temperature within the austenite range. Each temperature is attached to a couple (F_r/L_a). The plot F_r against shows straight lines for each steel and from their average slope, a shear module G' of grain boundaries, which is about 64300 N·cm^?2, is obtained. Hence, it is possible to describe the specific restraining force of a grain boundary with the help of Orowan's law or as it is conventionally done by using Zener's modell. At a critical temperature T*, which is different for each steel, the specific restraining force is equal to the driving force of the grain boundary. The corresponding values of L_a are also different for each steel and the steel which is the most resistant to grain coarsening is allowed to have the greatest value of L_a which still retains the capacity of impeding grain coarsening.     

X-ray Fluorescence Uptake Measurement of Functionalized Gold Nanoparticles in Tumor Cell Microsamples

Quantitative cellular in vitro nanoparticle uptake measurements are possible with a large number of different techniques, however, all have their respective restrictions. Here, we demonstrate the application of synchrotron-based X-ray fluorescence imaging (XFI) on prostate tumor cells, which have internalized differently functionalized gold nanoparticles. Total nanoparticle uptake on the order of a few hundred picograms could be conveniently observed with microsamples consisting of only a few hundreds of cells. A comparison with mass spectroscopy quantification is provided, experimental results are both supported and sensitivity limits of this XFI approach extrapolated by Monte-Carlo simulations, yielding a minimum detectable nanoparticle mass of just 5 pg. This study demonstrates the high sensitivity level of XFI, allowing non-destructive uptake measurements with very small microsamples within just seconds of irradiation time.     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002