Reactivity of 3-alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines in protic solvents: 1,4-Addition reactions and dimroth rearrangement

3-Alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines 5a and 5b undergo facile 1,4-addition of methanol or ethanol to afford stable crystalline hydrazones, 6 and 8 which have been characterised by spectroscopic analysis. In particular, the nmr spectrum of 8 shows novel features due to the diastereotopic nature of the CH₂ protons in the two O-ethyl groups. Compound 5b shows a property unique to the compounds in this series; refluxing this arylazomethylenetriazine in ethanol affords a rearranged product, characterised as the 1-aryl-2-cinnolinylhydrazine ( 9 ). The formation of 9 is rationalised as a ring opening-ring closure process analogous to the Dimroth rearrangement. The cinnoline 9 displays some novel chemistry arising from the facility of the arylhydrazino substituent to react with acid to give a fragmentation product, 3-methylindazole ( 7 ).     

Many-neighbour interaction and non-locality in traffic models

The optimal-velocity model, as proposed by Bando et al. [1], shows unrealistic values of the acceleration for various optimal-velocity functions [2,3]. We discuss different approaches of how to correct this problem. Multiple look-ahead (many-neighbour interaction) models are the most promising candidates in reducing accelerations and decelerations to realistic values. We focus on two such models and, in particular, their linear stability and how these affect the vehicle dynamics and wave solutions. As found earlier [4], multiple look-ahead models reproduce many real flow features, and our results further support the necessity of this ansatz. However, the problem of non-locality arises when they are transformed into the corresponding continuum model. We discuss three methods of how to interpret many-neighbour interaction in macroscopic models.Received: 27 March 2004, Published online: 12 July 2004PACS: 45.70.Vn Granular models of complex systems; traffic flow - 89.90. + n Other topics in areas of applied and interdisciplinary physics - 47.50. + d Non-Newtonian fluid flows     

Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Speciation and biosynthetic variation in four dictyoceratid sponges and their cyanobacterial symbiont, Oscillatoria spongeliae

Four species of marine sponges (Phylum Porifera, Order Dictyoceratida), which contain the filamentous cyanobacterial symbiont Oscillatoria spongeliae, were collected from four locations in Palau. The halogenated natural products associated with the symbiont were characterized from each sample, revealing that each species contained either chlorinated peptides, brominated diphenyl ethers, or no halogenated compounds. Analysis of the host sponges and the symbionts indicated that each species of sponge contained a distinct strain of morphologically similar cyanobacteria. Although cospeciation may be present in this group, we have identified that at least one host switching event has occurred in this symbiosis. Only the strain of O. spongeliae in the sponge containing the chlorinated compounds possessed genes involved in the biosynthesis of chlorinated leucine precursors, indicating that the chemical variation observed in these animals has a genetic foundation.     

Analysis of ephedrine in ephedra callus by acetonitrile modified capillary zone electrophoresis

A simple method has been developed for the quantitative determination of ephedrine in ephedra callus. The dependence of effective mobility of ephedrine on pH was investigated, and a simulated equation was obtained. The separation was performed in an uncoated capillary and detected at 185 nm. A new Tris–NaOH–H₃PO₄ run buffer was used and the pH was adjusted to 3.20. To increase the solubility of hydrophobic analytes and improve the separation efficiency, 15% acetonitrile was used in the buffer as a modifier. The content of ephedrine in an ephedra callus sample and an ephedra herba sample were determined with this method, and the result was satisfactory.