Mesophase behaviour and thermal stability of octa-alkoxy substituted phthalocyaninatocobalt (II) complexes

Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C₄H₉O) and n-octadecyloxy (C₁₈H₃₇O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Col_h). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C₁₃H₂₇O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry.     

A reexamination of the pyrolysis of bis trifluoromethyl peroxide. Addendum: Concerning D(CF3O2-CF3) and D(CF3-O2)

Earlier arguments concerning D(CF₃O₂-CF₃) and D(CF₃-O₂) are shown to be probably wrong. New values of 86 and 49 kcal/mol, respectively, are derived. C–O bond strengths are compared between CF₃- and CH₃-containing compounds.     

Identification of secondary metabolites in medicinal and spice plants by NIR-FT-Raman microspectroscopic mapping

This paper demonstrates the special potential of vibrational NIR FT Raman microspectroscopy for the study of fennel fruits, chamomile inflorescence and curcuma roots to obtain detailed information about their microstructure and chemical composition. Microscopic Raman maps of fennel fruits demonstrate that anethole, which is the main essential oil component, is present in the whole mericarp with highest concentration at the top of the fruit. In situ measurements obtained of the essential oil cells are dominated by two bands observed at 1657 cm(-1) and 1609 cm(-1) which are characteristic for anethole. Raman images of chamomile inflorescence show that spiroethers, identified by significant bands between 2150 and 2250 cm(-1), are accumulated in the middle part of the flower head. Due to the intense curcumin bands in the Raman spectrum of curcuma root, the distribution of this dyeing substance can be clearly determined; highest concentration of curcumin was observed on the core of the root.     

A bending wave simulator for investigating directional vibration sensing in insects

Substrate vibrations are important in social and ecological interactions for many insects and other arthropods. Localization cues include time and amplitude differences among an array of vibration detectors. However, for small species these cues are greatly reduced, and localization mechanisms remain unclear. Here we describe a method of simulating the vibrational environment that facilitates investigation of localization mechanisms in small species. Our model species was the treehopper Umbonia crassicornis (Membracidae; length 1 cm), which communicates using bending waves that propagate along plant stems. We designed a simulator consisting of a length of dowel and two actuators. The actuators were driven with two time signals that created the relationship between slope and displacement characteristic of steady-state bending wave motion. Because the surface of the dowel does not bend, as would a natural stem, close approximation of bending wave motion was limited to a region in the center of the dowel. An example of measurements of the dynamic response of an insect on the simulator is provided to illustrate its utility in the study of directional vibration sensing in insects.     

Thermal and optical behaviour of octa-alkoxy substituted phthalocyaninatovanadyl complexes

This paper deals with the synthesis of vanadyl phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions. The alkoxy chain length was varied, and octa-octyloxy (C₈H₁₇O), octa-dodecyloxy (C₁₂H₂₅O) and octa-hexadecyloxy (C₁₆H₃₃O) substituted vanadyl phthalocyanine complexes were prepared. Studies by polarizing optical microscopy and small angle X-ray diffraction (XRD) revealed that all the complexes are liquid crystalline and that these metallomesogens exhibit a columnar phase. The symmetry of the 2D lattice is rectangular, with a ^c 2 ^mm space group, as determined by the indexation of the XRD reflections; hence a rectangular columnar phase (Col_r) was assigned. A double periodicity, although weak, along the axis of the columns was found, which indicates some degree of pairing or dimerization. A tentative explanation based on an antiferroelectric stacking is given. Transition enthalpies were determined by differential scanning calorimetry. The compounds start to decompose above 250°C before reaching the clearing temperatures. A significant bathochromic shift of the Q-band in the UV/Vis spectra of the vanadyl complexes compared with the metal-free ligands and other metallophthalocyanines (M=Co^II, Ni^II, Cu^II, Zn^II) was also observed.     

Mesophase behaviour and thermal stability of octa-alkoxy substituted phthalocyaninatocobalt (II) complexes

Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C₄H₉O) and n-octadecyloxy (C₁₈H₃₇O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Col_h). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C₁₃H₂₇O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry.     

ZUR REAKTION VON ORGANODICHLORPHOSPHINEN MIT 1,2-DIOLEN

Abstract

Die Reaktion von Organodichlorphosphinen mit aliphatischen 1,2-Diolen in Abhängigkeit von der Basenkonzentration und den Substituenten wird untersucht; das Produktspektrum umfaßt neben 1,3,2-Dioxaphospholanen auch 2-Oxo-1,3,2-dioxaphospholane und Oxiphosphorane. Letztere lassen sich zum Hauptprodukt machen.

The reaction of phosphorus dichlorides with aliphatic 1,2-diols is studied. The range of products varies strongly with the concentration of the base and the organic substituents. In addition to 1,3,2-dioxaphospholanes the corresponding 2-oxo-1,3,2-dioxaphospholanes and oxiphosphoranes are also formed. Using proper conditions the latter may become the dominant product.     

Numerical methods for fourth order nonlinear degenerate diffusion problems

Numerical schemes are presented for a class of fourth order diffusion problems. These problems arise in lubrication theory for thin films of viscous fluids on surfaces. The equations being in general fourth order degenerate parabolic, additional singular terms of second order may occur to model effects of gravity, molecular interactions or thermocapillarity. Furthermore, we incorporate nonlinear surface tension terms. Finally, in the case of a thin film flow driven by a surface active agent (surfactant), the coupling of the thin film equation with an evolution equation for the surfactant density has to be considered. Discretizing the arising nonlinearities in a subtle way enables us to establish discrete counterparts of the essential integral estimates found in the continuous setting. As a consequence, the resulting algorithms are efficient, and results on convergence and nonnegativity or even strict positivity of discrete solutions follow in a natural way. The paper presents a finite element and a finite volume scheme and compares both approaches. Furthermore, an overview over qualitative properties of solutions is given, and various applications show the potential of the proposed approach.     

ON IDEAL CLASS GROUPS AND UNITS IN TERMS OF THE QUADRATIC FORM x^2＋32y^2

§1. IntroductionIt is a classical topic to study, for quadratic number ?elds F = Q(√2p) with a prime p,the exact 2-power dividing the narrow class number h (F) and the norm of the fundamentalunit ε of F.The 2-primary subgroup of the narrow class group …