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The macrocyclic ring interconversion of four maleonitrile mixed oxadithia crown ethers of variable ring size, mn-12-S2O2, mn-15-S2O3, mn-18-S2O4 and fn-12-S2O2, were studied by 1H and 13C NMR spectroscopy and by molecular modelling. The barriers to ring interconversion were estimated using variable temperature NMR spectroscopy and from the calculated activation energies, together with the spin-lattice relaxation times of the CH2 carbon atoms, conclusions were drawn regarding the intramolecular flexibility of the crown ethers in both the free state as well as the complexed state incorporating either AgI, BiIII, SbIII, PdII or PtII metal cations. Furthermore, both the stoichiometry of the complexes and the coordination sites of the crown ethers to the various cations were also clearly implicated. Molecular modelling was also utilised to ascertain the preferred conformers of the four compounds and their corresponding complexes, the results of which corroborated the experimental NMR results to a high degree.
Breton and Irish, two Celtic and strongly endangered European minority languages, enjoy (or suffer) different fates of official recognition. While France does not officially recognise Breton as an independent language and has no even signed the European Charter of Minority Languages as most other EU countries did, Irish is by its constitution the first national language of the Republic of Ireland and therefore enjoys a very high official prestige. It is an obligatory subject in the schools and all EU documents need to be translated both into Irish and English. In spite of this difference of status and prestige, both languages have suffered, during the past 50 years, from a dramatic loss of speakers, as the young generation sees no need to preserve a regionalised minority heritage in a world of globalised communication and exchange. While both inherited languages were, traditionally and sociologically speaking, the medium of communication of the rural population, albeit with a long and venerable written tradition reaching back to the middle ages, the language of the future is that of the urban middle classes learnt as a second language (L2) und for all intents and purposes not used as a community language in the home. Middle class Breton and Irish are token languages, serving its users as identity markers in order to set themselves off from the English and French, most of whom only speak English and French and have no additional regional language. The linguistic gap between the inherited rural and the new urban varieties is great, so that older native rural speakers do not understand school Breton and school Irish. It is predictable that only the urban varieties will survive for still quite a while, whereas the rural varietes are unlikely to escape language death due to the ongoing change of living conditions in the rural areas and the absence of localised language engineering.
Krimi und Gesellschaft
(2001)