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  • Author: R. Wünsch x
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Several homologous series of biaromatic liquid crystals with structure type CnH2n+1O • C6H4 • M•C6H4-CN are investigated. By studying the phase transition temperatures in binary mixed systems a "re-entrant" nematic phase N(re) is established for all compounds exhibiting smectic A phases. The virtual transition temperatures N(re) - SA are found to decrease with increasing chain length of the alkyloxy group. The influence of the middle group M on the re-entrant behaviour can be attributed mainly to its dipole moment. The temperature range of the smectic A phase decreases when the middle group dipole moment is additive to that of the nitrile group. To summarize it can be said that the "re-entrant" behaviour of biaromatic liquid crystals is found to be very similar to that of triaromatic systems reported recently

Recent reports [1] have shown that compounds of the homologous series of the 4(4-n-alkyloxy- benzoyloxy)-4′-cyanoazobenzenes (Cn; n = 1 - 12), all have a low temperature smectic A phase (SA″). The homologues with alkyl chain length n≧9 exhibit in addition a high temperature smectic A phase (SA′), separated from the first one by a re-entrant nematic phase (N(re)). Homol­ogues of this series were used for miscibility studies with some compounds of the biaromatic liquid crystal series of the 4-cyano-4′-n-alkyloxybiphenyls (n̄ CBP) and of the 4-cyanobenzylidene- 4′-n-alkyloxyanilines (CN · n̄). The phase diagrams studied show that the smectic A phases of biaromatic liquid crystalline nitrile compounds correspond to the high temperature smectic SA′ type and are not miscible with the low temperature SA″ phase. Moreover, the shapes of the transition temperature curves to the SA″ phase indicate a low temperature smectic A phase (SA″) for the biaromatic compounds. This suggests that for biaromatic compounds with re-entrant behaviour, the dependence of liquid crystalline phase sequences on the alkyl chain length is very similar to that of triaromatic compounds.

in Ileus

A new total synthesis of the tetratriacontapeptide amide corresponding to the proposed primary structure of human big gastrin I is described. The synthetic route was based on the preparation of six suitably protected fragments, related to sequence 28 - 34, 23 - 27, 21 - 22, 15-20, 9 - 14, and 1 - 8, to be used as building blocks for the total synthesis. The protecting groups were selected according to the Schwyzer-Wünsch strategy of maximum side chain protection based on tertiary alcohols, also for the imidazol function of histidine. Subsequent assembly of the six fragments by three different pathways using the highly efficient Wünsch-Weygand condensation procedure to ensure minimum racemization, followed by deprotection of the synthetic products via exposure to trifluoroacetic acid and final purification by ion-exchange chromatography on DEAE-Sephadex A-25 and partition chromatography on Sephadex G-25, led to human big gastrin I, homogeneous within the limits of the analytical methods used. The biological activity of the synthetic product proved to be 50 percent higher than that of human little gastrin I. The 32-leucine analogue of human big gastrin I was prepared in the same way.