Gas chromatographic enantiomer separation of agrochemicals and polychlorinated biphenyls (PCBs) using modified cyclodextrins

The enantiomers of the polychlorinated polycyclic xenobiotics heptachlor, cis- and trans-chlordane, cis- and trans-heptachlorepoxide, oxychlordane, and bromocyclen have been resolved by gas chromatography with selectively substituted cyclodextrins. The order of elution of these compounds and of α-hexachlorocyclohexane (α-HCH) was determined by comparison with enantiomerically enriched reference compounds obtained by preparative enantioselective gas chromatography. A separation of the eight stereoisomers of the pyrethroid insecticide allethrin into seven peaks was achieved. Both trans-diastereomers were separated into their enantiomers and the order of elution could be determined by comparison with commercially available (S)-bioallethrin and trans-bioallethrin. Also one cis-diastereomer was separated, wheras the other cis-isomer could not be resolved. In addition 15 out of 19 stable atropisomeric polychlorinated biphenyls with 5, 6 and 7 chlorine substituents, some chiral organophosphorus pesticides, including acephate and malaoxon and the herbicide bromoacil were separated.     

Unusual and Novel C11H16 Hydrocarbons from the Southern Australian Brown Alga Dictyopteris acrostichoides (Phaeophyceae)

Unusual and novel C₁₁H₁₆ olefins with (E)- or (E,E)-configuration instead of the previously known (Z)- or (E,Z)-configuration at the double bond(s) within the longer side chain are the main products of the Australian phaeophyte Dictyopteris acrostichoides. This configuration anomaly refers to all four series of alicyclic C₁₁H₁₆ hydrocarbons, namely the disubstituted cyclopentenes and cyclopropanes, as well as the monosubstituted cycloheptadienes and cyclopentenes. Chiral compounds within the above series have the same absolute configuration. The two (cyclopent-3-enyl)hexa-1, 3-dienes 11 and 13 are found for the first time. The absolute configuration and optical purity of the hydrocarbons are determined by gas chromatography on modified cyclodextrins as chiral stationary phases. The synthesis of chiral references via lipase-catalyzed resolutions is described.     

Gasdurchlässigkeit von gummielastischen Werkstoffen für Stickstoff

Zusammenfassung Es wird über Messungen der Gasdurchlässigkeit von gummielastischen Werkstoffen für Stickstoff berichtet. Der Gasdurchtritt von Stickstoff durch gummielastische Materialien ist ein Permeations- oder Lösungsdiffusionsvorgang. Die Theorie der Permeation wird dargelegt, und zwei Methoden zur Auswertung von Permeationsmessungen werden angegeben. Nach Beschreibung der Meßanordnung wird an Hand von einigen grundsätzlichen Messungen der Gasdurchlässigkeit von gummielastischen Werkstoffen für Stickstoff gezeigt, daß es sich hier tatsächlich um einen Lösungsdiffusionsvorgang handelt; d. h. dasFicksche Diffusionsgesetz und dasHenrysche Löslichkeitsgesetz sind erfüllt, und die Diffusion ist der geschwindigkeitsbestimmende Vorgang. Die Betrachtung der Temperaturabhängigkeit der Permeation zeigt, daß man für Diffusionskoeffizient, Löslichkeitskoeffizient und Permeationskoeffizient jeweils eine Aktivierungsenergie angeben kann. Meßergebnisse, die an einer Vielzahl von gummielastischen Werkstoffen erhalten wurden, werden mitgeteilt.Mit 11 Abbildungen und 2 Tabellen     

Lifetime simulation of thermo-mechanically loaded components

The estimation of the lifetime of thermo-mechanically loaded components by testing is very costly and time-consuming, since the high temperature cycle time in practical application dominates the test duration. Common frequencies for TMF (thermo-mechanical fatigue) tests are at about 0.01 Hz compared to 10–100 Hz at HCF (high cycle fatigue) and about 0.1–1 Hz at isothermal LCF (low cycle fatigue) tests. Therefore, the simulation of fatigue life is an important design step in the fast moving and competitive automotive industry, where the steady rise of engine power and the demand for lightweight construction concurrent with enhanced reliability require an optimised dimensioning process. Methods and models are usually derived from results made on tests with specimens, since it is possible to systematically and exactly define loading parameters and measurement categories. After an extensive test programme (tensile tests, creep tests, low cycle fatigue tests and thermo-mechanical fatigue tests with different influences on specimens) it was possible to develop material models for the simulation of the time- and temperature dependent stress–strain hystereses and damage models for the simulation of the TMF lifetime. Based on this knowledge the whole simulation chain to determine the TMF life of a component is introduced: thermal calculation, mechanical calculation and lifetime calculation. Furthermore the transferability of specimen based simulation models to real components (an alternative test piece and a cylinder head) is investigated.     

Assessment of asymmetric crack initiation in open-hole plates using a coupled stress and energy criterion

An application of the finite fracture mechanics concept to open-hole plates subject to combined tensile and bending loading is presented. In finite fracture mechanics, the simultaneous satisfaction of both, a stress and an energy criterion, is enforced as a condition for crack initiation. Efficient modeling and closed-form expressions for the dependence of the stress and energy quantities on governing structural and material parameters allow for a comprehensive numerical analysis of the onset of asymmetric crack patterns. The obtained failure load predictions are found to agree well with a cohesive zone model and experimental data from literature. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of aryl substituents on the thermal and solubility behavior of poly(p-phenylene terephthalate) and poly(p-phenylene terephthalamide)

The substitution of poly(p-phenylene terephthalate) and poly(p-phenylene terephthalamide) with phenyl and biphenylyl substituents (4-biphenylyl and 2-biphenylyl) in the terephthalic acid unit lowers the melting temperatures and crystallization tendency and increases the solubility. The melting temperatures of the polyesters are in the range of 285–350°C. Melting of the polyamides occurs between 440–490°C. The polyamides begin to decompose in the same temperature range. In polyesters as well as in polyamides the 2-biphenylyl substituent was found to be more effective in decreasing the crystallinity, lowering the melt transition temperatures and increasing the solubility.