The reaction of 1,2-dichloroethane with copper

The decomposition of 1,2-dichloroethane on polycrystalline copper has been studied using a microreactor. The reaction is found to have an activation energy of 81±5 kJ mol^–1 generating gaseous ethene and chemisorbed chlorine. The reaction terminates on completion of a monolayer of chemisorbed chlorine and is followed by a much slower reaction. The rate limiting step is thought to be C₂H₄Cl_2(phys)C2H₄Cl(_ads)+Cl_ads The reaction is compared with a UHV study of the same molecule on Cu(l 11) and the possibility of a negative ion transition state is discussed.     

An ionene with spirane structure (spiroionene)

The secondary diamine 1,3,5,7-tetrahydro[1,2c:4,5c'] benzodipyrrole (3) and 1,2,4,5-tetrabromomethylbenzene (1) form a polymeric ionene with spirane structure through a repetitive alkylation reaction. The structure of the product could be proven by¹³C-NMR spectroscopy by comparison with suitable reference compounds. Solutions in aqueous methanol exhibit a typical polyelectrolyte effect. Variation of the counterions produces sufficient solubility in organic solvents. From the crystal structure of a similar model compound one can conclude that the synthesized polymer has a rod-like shape.     

Physiological and behavioral effects of coniferyl benzoate on avian reproduction

Various plant secondary metabolites related to cinnamic acid are of interest because of their repellency to birds and their occurrence in ecologically important food items. Coniferyl benzoate (CB), a phenylpropanoid ester that occurs in quaking aspen (Populus tremuloides) is of particular ecological interest because of its effect on ruffed grouse (Bonasa umbellus) feeding behavior and its possible influence on the population dynamics of this bird. During detoxification processes, CB and other analogous compounds are metabolized into by-products, such as ferulic acid (FA), that can cause anti-reproductive effects. We tested whether consumption of CB produces antire-productive effects similar to FA using male and female Japanese quail (Coturnix coturnix) as avian models for ruffed grouse. The parameters we investigated included: the production, morphology, and development of eggs; reproductive characteristics influenced by estrogen; serum prolactin levels; and male reproductive behavior. Dietary CB did not produce antireproductive effects similar to FA at intake levels that Japanese quail and ruffed grouse would freely consume. Consumption of CB by Japanese quail significantly reduced egg production and body mass but did not affect male reproductive performance. Coniferyl benzoate's effect on egg production may be explained by lower energy acquisition and retention rather than endocrine changes per se. Contrary to previous reports, it is unlikely that FA, or similar compounds act directly as estrogen mimics or antagonists. Although, CB did reduce egg production in quail, it is unlikely that it would affect egg production in wild ruffed grouse. Detoxification costs and the effects of CB on nutrient utilization may explain why ruffed grouse avoid high dietary levels of CB.     

PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006     

On Modulus and Fracture Toughness of Rigid Particulate Filled High Density Polyethylene

A Kaolin-filled, high-density polyethylene (HDPE) system was used to illustrate the influence of particulates on modulus and toughness of the bulk material. A variation of filler content, particulate size and coupling quality for two HDPE-matrix systems with different viscosity led to a strong dependency of elastic modulus and fracture toughness under various testing conditions, e.g. static loading, fatigue and impact.

A stiffness improvement with increasing filler content was achieved by all coupling qualities. The developed Kaolin reinforcement of HDPE with optimised coupling offers an improvement of the stiffness and toughness under all investigated loading conditions. The degree of improvement depends on the particulate size and matrix viscosity. The energy dissipation mechanisms were investigated by fractographic analysis.     

Einsatz von Enzymen und Antikörpern in organischen Lösungsmitteln

Application of Enzymes and Antibodies in Organic Solvents . This review outlines the influence of organic solvents on antibodies, enzymes and their reactions, the different kinds of enzyme-solvent systems, the various advantages of organic solvents compared with water and how they can be used for synthetic and analytical purposes. Main applications are the enzymatic synthesis of optically pure organic chemicals used as drugs, research chemicals, dyes or fragrants, as well as the analysis of hydrophobic compounds. Examples can be given of bioconversions in organic media by microbial cells and of syntheses with catalytic antibodies. Moreover, the full biotechnological potential of chemically or genetically engineered enzymes can only be exploited if the diversity of possible media is taken into account.     

On the incremental growth and shrinkage of LR goto-graphs

The LR(0) goto-graph is the basis for the construction of parsers for several interesting grammar classes such as LALR and GLR. Early work has shown that even when a grammar is an extension to another, the goto-graph of the first is not necessarily a subgraph of the second. Some authors presented algorithms to grow and shrink these graphs incrementally, but the formal proof of the existence of a particular relation between a given goto-graph and a grown or shrunk counterpart seems to be still missing in literature as of today. In this paper we use the recursive projection of paths of limited length to prove the existence of one such relation, when the sets of productions are in a subset relation. We also use this relation to present two algorithms (Grow and Shrink) that transform the goto-graph of a given grammar into the goto-graph of an extension or a restriction to that grammar. We implemented these algorithms in a dynamically updatable LALR parser generator called DEXTER (the Dynamically EXTEnsible Recognizer) that we are now shipping with our current implementation of the Neverlang framework for programming language development.     

Fat-simulating and accelerating solvents for polyolefins and MWD of solvent extracts of polyethylenes

Migration kinetics of straight-chain oligomers and antioxidants from several polyolefins at different temperatures into various solvents have been studied by radioactive tracer techniques. Anhydrous ethanol appears to be a well suited food-oil or liquid-fat simulant for extracting different types of migrants from polyolefins. Pure and mixed triglycerides are also good oil or fat simulants, but the triglycerides offer no simpler analytical procedures than the use of oil or fat themselves. n-Octanol may also be considered as a reasonable oil or fat simulant; however, its action depends somewhat on the choice of migrants. The accelerating action of n-heptane over that of oil or simulants is quantitatively demonstrated. The accelerating effects are greater for migration systems with lower diffusion coefficients. The diffusion coefficients for migration into n-heptane are about 20 times greater than the diffusion coefficients into ethanol or oil for otherwise identical migration systems yielding diffusion coefficients of about 10^?7 cm²s^?1 into oil or ethanol. For systems yielding diffusion coefficients into oil or ethanol of about 10^?12 cm²s^?1, the corresponding diffusion coefficients into n-heptane are about 1000 times greater. The molecular weight distributions (MWDs) of the n-heptane and ethanol extracts of polyolefins have been analysed. n-Heptane can not only accelerate the migration of the individual migrant but also remove oligomer species that are slightly soluble or present at low levels in the oil or simulant extracts.     

2-Layer Right Angle Crossing Drawings

A 2-layer drawing represents a bipartite graph where each vertex is a point on one of two parallel lines, no two vertices on the same line are adjacent, and the edges are straight-line segments. In this paper we study 2-layer drawings where any two crossing edges meet at right angle. We characterize the graphs that admit this type of drawing, provide linear-time testing and embedding algorithms, and present a polynomial-time crossing minimization technique. Also, for a given graph G and a constant k, we prove that it is $\mathcal{NP}$ -complete to decide whether G contains a subgraph of at least k edges having a 2-layer drawing with right angle crossings.