Organoclay formulations of acetochlor: effect of high salt concentration

This study aimed to evaluate new methodology for designing ecologically acceptable formulations of acetochlor. Modification of montmorillonite with phenyltrimethylammonium chloride (PTMA) or benzyltrimethylammonium chloride (BTMA) and organoclay formulations of acetochlor were prepared in the presence of high concentrations of sodium chloride (150 g/L). Acetochlor concentration in the equilibrium solutions was determined by HPLC. Release of acetochlor in a water system was performed by a funnel experiment. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA or BTMA were increased as NaCl concentration increased in the equilibrium solution. Leaching of acetochlor from organoclay formulations was significantly inhibited to the top soil layer (0-5 cm) when the formulations were prepared at extreme NaCl concentration (100-150 g/L). These results are in accord with a funnel experiment that showed a reduction in acetochlor release from the montmorillonite-based formulations. The application of this method for herbicide formulation would produce ecologically acceptable herbicide formulations that can significantly minimize the risk to groundwater pollution.     

Carbon flux and growth in mature deciduous forest trees exposed to elevated CO2

Whether rising atmospheric carbon dioxide (CO2) concentrations will cause forests to grow faster and store more carbon is an open question. Using free air CO2 release in combination with a canopy crane, we found an immediate and sustained enhancement of carbon flux through 35-meter-tall temperate forest trees when exposed to elevated CO2. However, there was no overall stimulation in stem growth and leaf litter production after 4 years. Photosynthetic capacity was not reduced, leaf chemistry changes were minor, and tree species differed in their responses. Although growing vigorously, these trees did not accrete more biomass carbon in stems in response to elevated CO2, thus challenging projections of growth responses derived from tests with smaller trees.     

A zinc clasp structure tethers Lck to T cell coreceptors CD4 and CD8

The T cell coreceptors CD4 and CD8 both associate via their cytoplasmic tails with the N-terminus of the Src-family tyrosine kinase Lck. These interactions require zinc and are critical for T cell development and activation. We examined the folding and solution structures of ternary CD4-Lck-Zn2+ and CD8alpha-Lck-Zn2+ complexes. The coreceptor tails and the Lck N-terminus are unstructured in isolation but assemble in the presence of zinc to form compactly folded heterodimeric domains. The cofolded complexes have similar "zinc clasp" cores that are augmented by distinct structural elements. A dileucine motif required for clathrin-mediated endocytosis of CD4 is masked by Lck.     

Activation of apoptosis in vivo by a hydrocarbon-stapled BH3 helix

BCL-2 family proteins constitute a critical control point for the regulation of apoptosis. Protein interaction between BCL-2 members is a prominent mechanism of control and is mediated through the amphipathic alpha-helical BH3 segment, an essential death domain. We used a chemical strategy, termed hydrocarbon stapling, to generate BH3 peptides with improved pharmacologic properties. The stapled peptides, called "stabilized alpha-helix of BCL-2 domains" (SAHBs), proved to be helical, protease-resistant, and cell-permeable molecules that bound with increased affinity to multidomain BCL-2 member pockets. A SAHB of the BH3 domain from the BID protein specifically activated the apoptotic pathway to kill leukemia cells. In addition, SAHB effectively inhibited the growth of human leukemia xenografts in vivo. Hydrocarbon stapling of native peptides may provide a useful strategy for experimental and therapeutic modulation of protein-protein interactions in many signaling pathways.     

Aroma compound analysis of Eruca sativa (Brassicaceae) SPME headspace leaf samples using GC,GC-MS,and olfactometry

The aroma compounds of rocket salad (Eruca sativa) SPME headspace samples of fresh leaves were analyzed using GC, GC-MS, and olfactometry. More than 50 constituents of the Eruca headspace could be identified to be essential volatiles, responsible for the characteristic intense green; herbal; nutty and almond-like; Brassicaceae-like (direction of cabbage, broccoli, and mustard); and horseradish-like aroma of these salad leaves. As aroma impact compounds, especially isothiocyanates, and derivatives of butane, hexane, octane, and nonane were identified. 4-Methylthiobutyl isothiocyanate (14.2%), cis-3-hexen-1-ol (11.0%), cis-3-hexenyl butanoate (10.8%), 5-methylthiopentyl isothiocyanate (9.3%), cis-3-hexenyl 2-methylbutanoate (5.4%), and 5-methylthiopentanenitrile (5.0%) were found in concentrations higher than 5.0% (calculated as % peak area of GC analysis using a nonpolar column).     

Aroma quality differentiation of pyrazine derivatives using self-organizing molecular field analysis and artificial neural network

The encoding of various aroma impressions and the distinction between different aroma qualities are unsolved problems, as differences between aroma impressions can be described only in a qualitative but not in a quantitative manner. As a consequence, classifications of various aroma qualities cannot easily be performed by standard QSAR methods. To find a proper way to encode aroma impressions for SAR studies, a total of 50 pyrazine-based aroma compounds showing the aroma quality of earthy, green-earthy, or green are analyzed. Special attention is thereby turned on the mixed aroma impression green-earthy. Classifications on the whole data set as well as on smaller subsets are calculated using self-organizing molecular field analysis (SOMFA) and artificial neural networks (ANNs). SOMFA classifies between two or three aroma impressions, leading to models satisfying in predictive power. ANN analysis using multilayer perceptron network architecture with one hidden layer and nominal output as well as genetic regression neural network) with two hidden layers and numerical output both lead to a rather good performance rate of 94%.     

Natürlicher gehalt und anthropogene anreicherung von Schwermetallen in den Sedimenten von Elbe, Eider, Trave und Schwentine

The sediments of four rivers in Northern Germany were analysed for heavy metals. 371 sediment samples were taken from 24 investigation sites of the rivers Elbe, Eider, Trave and Schwentine and from North Sea tidal flat areas. Within each investigation site strong positive relationships exist between the heavy metal contents and the contents of the fine size fractions < 2 μm and < 20 μm of the sediments. To compare the metal contents in the sediments from different areas, differences in grain size were eliminated by computing the metal contents for a clay content of 25% by means of regression equations.The fluvial sediments at a few inland investigation sites, as well as the tidal flat sediments are not detectably polluted with heavy metals. Their metal contents could be used as background values for computing enrichment factors of polluted fluvial deposits.Sediments from the river Elbe in and upstream of the port of Hamburg, and from some parts of the rivers Eider and Trave near industrial and densely populated districts, are highly enriched with heavy metals. The highest enrichment factors are for Hg 85, Cd 56, Pb 37, Cu 34, Zn 29, As 19, Cr 6, Ni 4 and Co 3 times the background values.The ecological importance of the heavy metal contents in the sediments is discussed.     

Spatial distribution of earthworms [Lumbricidae] in recultivated soils of the Rhenish lignite‐mining area,Germany

The spatial distribution of earthworms was studied by means of combined formalin expulsion and hand sorting in three arable fields of the Rhenish lignite‐mining area that differed in their recultivation age (6, 12, 24 yr). In addition, pH and the spatial distribution of penetration resistances were measured to see if they are corresponding with the distribution of earthworms. Already the 6 yr old field had a rich population of endogeic, anecic, and epigeic earthworms (119 ind. m^–2, 48 g m^–2, 6 species). This quantity was similar to the 24 yr old site. The 12 yr old field was only sparsely populated by earthworms (5 ind. m^–2, 5 g m^–2, 3 species). In the 6 yr old field, the spatial distribution pattern showed a center of maximal earthworm abundances, corresponding to the distributional pattern of penetration resistances. In the old field (24 yr), the species varied in their spatial distribution, and there was no correspondence with the distribution of penetration resistance. In general, the penetration resistance at the youngest site was clearly lower than at the two older sites. The earthworm population in the 6 yr old field can be explained by cocoons contained in the dumped material. A calculation using literature data on earthworm‐population dynamics shows that a founding population of 400–600 reproductive individuals per hectare and a continuity of favorable growth conditions during the time of soil management is necessary for the development of the situation found at the 6 yr old site in this study.     

Dosis- Wirkungs-Beziehungen zur Erfassung von Chemikalienwirkungen auf die mikrobielle Aktivität von Böden: I. Kurvenverläufe und Auswertungsmöglichkeiten

Dose response curves: their use in soil microbiological research and possibilities of evaluation The relation between different concentrations of a toxicant in soils and the resulting effects on biological parameters can be described with dose response curves. Dose response curves make it possible to determine the concentrations of a chemical that create definite effects (?Effective Doses”?, e.g. ED₁₀ and ED₅₀ for 10- and 50% inhibitory effects) or to evaluate the rate of increase of inhibition with increasing concentrations. Some of the mostly used ways to extract these parameters from dose response curves are presented and examined with regard to their suitability in soil microbiological research. Besides graphical procedures for the evaluation of dose response curves a mathematical model for fitting quantitative dose response curves is introduced. With this model the confidence intervals of effective doses can be computed. By showing eight frequently appearing shapes of dose response curves the advantages and limitations of different ways to calculate effective doses are discussed.     

Analysis of volatile compounds and triglycerides of seed oils extracted from different poppy varieties (Papaver somniferum L.)

Poppy seed oil (Oleum Papaveris Seminis) is used for culinary and pharmaceutical purposes, as well as for making soaps, paints, and varnishes. Astonishingly, hardly anything was yet known about the volatile compounds of this promising comestible. Likewise, there are no current published data about the triglyceride (TAG) composition of poppy seed oils available. In this investigation solid-phase microextraction (SPME) with DVB/Carboxen/PDMS Stable-Flex fiber was applied to the study of volatile compounds of several seed oil samples from Papaver somniferum L. (Papaveraceae). 1-Pentanol (3.3-4.9%), 1-hexanal (10.9-30.9%), 1-hexanol (5.3-33.7%), 2-pentylfuran (7.2-10.0%), and caproic acid (2.9-11.5%) could be identified as the main volatile compounds in all examined poppy seed oil samples. Furthermore, the TAG composition of these oils was analyzed by MALDI-ReTOF- and ESI-IT-MS/MS. The predominant TAG components were found to be composed of linoleic, oleic, and palmitic acid, comprising approximately 70% of the oils. TAG patterns of the different poppy varieties were found to be very homogeneous, showing also no significant differences in terms of the applied pressing method of the plant seeds.