The synthesis of azoniadithia[6]helicenes

A new short‐step synthesis of 8a‐azonia[6]helicene (1) and the novel dithieno derivatives ( 2 and 3 ) is described. Double photocyclization of 2,8‐distyrylquinolizinium salt (8) gave 1 in 35% yield. Similarly, 2,8‐bis[2‐(2‐thienyl)vinyl]‐ and 2,8‐bis[2‐(3‐thienyl)vinyl]‐quinolizinium salts ( 9 and 10 ) afforded new azonia[6]helicenes containing two thiophene rings at the ends of helix, that is 7a‐azonia‐3,12‐dithia[6]helicene (2) and 7a‐azonia‐1,14‐dithia[6]helicene (3) , in 43 and 35% yields, respectively. The total assignment of their ¹H‐ and ¹³C‐nmr spectra was performed by utilizing two‐dimensional and NOE nmr spectroscopic methods.     

Adsorption of dyes onto carbonaceous materials produced from coffee grounds by microwave treatment

Organic wastes have been burned for reclamation. However, they have to be recycled and reused for industrial sustainable development. Carbonaceous materials were produced from coffee grounds by microwave treatment. There are many phenolic hydroxyl and carboxyl groups on the surface of carbonaceous materials. The base consumption of the carbonaceous materials was larger than that of the commercially activated carbon. The carbonaceous materials produced from coffee grounds were applied to the adsorbates for the removal of basic dyes (methylene blue and gentian violet) in wastewater. This result indicated that the adsorption of dyes depended upon the surface polar groups on the carbonaceous materials. Moreover, the Freundlich constants of isotherms for the adsorption of methylene blue and gentian violet onto the carbonaceous materials produced from coffee grounds were greater than those for adsorption onto activated carbon or ceramic activated carbon. The interaction was greatest between the surface or porosity of the carbonaceous materials and methylene blue and gentian violet. The microwave treatment would be useful for the carbonization of organic wastes to save energy.     

Synthesis of Monoazacryptands and their Excellent Transport Ability Toward Alkali Metal Cations in Comparison with Monoazacrown Ethers

The effects of transport conditions and the structure of monoazacrownethers on their transport ability for alkali metal cations through a bulkliquid membrane are summarized and discussed based on transport dataobtained in our laboratories. To improve the transport ability,monoazacryptands have been prepared. A lipophilic derivative consisting oftwo 18-crown-6 rings and one 20-crown-6 ring can selectively transport K+from a mixture of Na+, K+, Mg2+, and Ca2+ under pH control.     

Theorie der diffusions-kontrollierten Reaktionen innerhalb von Polymerketten

Ohne Zusammenfassung     

Natural crystallization

Natural mineral crystals grow under a broad spectrum of conditions; from vapors, from hydrothermal solutions, from magmas (high temperature solutions), or through metasomatic or metamorphic reactions. In understanding kinetic problems involved in natural crystallization, there are two ways of approach; (1) experimentally stimulating textures of rocks, and (2) decoding the paragenetic information contained in natural crystals. The latter approach is especially important, since in situ observation is impossible. Key Key features which aid in deciphering natural growth processes and conditions include external forms, surface microtopographs of crystal faces, internal inhomogeneity (growth bands, growth sectors, inclusions, twin or exsolution textures), lattice defects (plane defects, dislocations) and impurities (precipitations). Mainly based on the observations of surface microtopographs of natural crystals, characteristics of crystallization in magma, in hydrothermal solution, in vapor phase, in hydrothermal metasomatism and in regional metamorphism are analysed and reviewed in this paper. The difference and similarity between natural and synthetic crystals are also discussed.     

Study on the cell wall skeleton derived from Mycobacterium bovis BCG Tokyo 172 (SMP-105): establishment of preparation and analytical methods

Mycobacterial cell walls have diverse adjuvant activities, and in particular, cell wall skeleton (CWS) of Mycobacterium bovis BCG has been expected as a drug for tumor immunotherapy. However, its molecular structure-biological activity relationship has not been fully elucidated despite more than 30 years of intensive research. Since it is important to secure purified CWS for such investigation, we established a preparation method of CWS from M. bovis BCG Tokyo 172 (SMP-105) and developed accurate, precise, and reliable analytical methods, based on previous reports. Furthermore, we confirmed that SMP-105 is composed of mycolic acids; arabinogalactan consisting of arabinose, galactose, and rhamnose; and peptidoglycan consisting of alanine, glutamic acid, diaminopimeric acid, muramic acid, glucosamine, and galactosamine. We also determined the levels of potential impurities that might be contaminated in the original bacterium or arise during the manufacturing process, such as glucose, mannose, non-constituted amino acids, as well as nucleic acid, trehaolse di-mycolate, and bacterial endotoxins. These results demonstrated that the prepared SMP-105 was of sufficient quality for research into the chemistry, bioactivity, and structure-activity relationship of CWS.     

Semilinear hyperbolic systems violating the null condition

We consider systems of semilinear wave equations in three space dimensions with quadratic nonlinear terms not satisfying the null condition. We prove small data global existence of the classical solution under a new structural condition related to the weak null condition. For two-component systems satisfying this condition, we also observe a new kind of asymptotic behavior: Only one component is dissipated and the other one behaves like a non-trivial free solution in the large time.