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Structural information about the bis(benzo crown ether)s I-VI and their complexes with alkali metal cations was deduced from the 13C NMR chemical shifts, the salt-induced 1H and 13C chemical shifts and the vicinal 1H,1H coupling constants. Especially the isomerism with respect to the amide O=C - NH bonds and imine fragments were assigned by various useful NMR parameters ( C=O, 1JN,H, 1JC,H) and proved to be E,E-anti,anti. Furthermore, stereochemical information about preferred conformations about flexible bonds was obtained from 2D ROESY NMR experiments. The complex formation (2:1 complexes and sandwich-like 1:1 complexes, respectively) were determined also by 23Na NMR spectroscopy. The conformational study of the crown ethers was accompanied and corroborated by molecular dynamics and quantum chemical calculations.
A simple way to prepare cucurbit[5]uril is described. The macrocycles of the cucurbituril type are nearly insoluble in water. The solubilities of cucurbit[5]uril, decamethylcucurbit[5]uril and cucurbit[6]uril in hydrochloric acid, formic acid and acetic acid of different concentrations have been investigated. Due to the formation of complexes between cucurbit[n]urils and protons the solubility increases in aqueous acids. The macrocyclic ligands are able to form complexes with several organic compounds. Thus, the complex formation of the cucurbituril macrocycles with different amines has beenstudied by means of calorimetric titrations. The reaction enthalpy gives noevidence of the formation of inclusion or exclusion complexes. 1H-NMR measurements show that in the case of cucurbit[5]uril and cucurbit[6]uril the organic guest compound is included within the hydrophobic cavity. Decamethylcucurbit[5]uril forms only exclusion complexes with organicamines. This was confirmed by the crystal structure of the decamethylcucurbit[5]uril-1,6- diaminohexane complex. complex formation - cucurbit[5]uril - cucurbit[6]uril - decamethylcucurbit[5]uril - solubility - synthesis
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.
Social Organization
(2001)
Nachkaufverhalten
(2001)
Umweltzeichen
(2001)
Ökologisches Marketing
(2001)
Öko-Controlling
(2001)
Aporien der Moderne am Ausgang des Jahrtausends: Gesellschaft, Kultur und Politik in der Krise?
(2001)
Paulus
(2001)
Jüdische Aufklärung
(2001)
Aufklärung und "Judenfrage"
(2001)
Herzen, Aleksandr
(2001)
In soils of the Rustenbug Minig Area microorganism concentration and activity of several enzymes (dehydrogenase, phosphatase, protease, amylase, cellulase, xylanase) were determined. First results indicate an increase of heavy metal resistant Microorganisms and a possible inhibition of carbohydrate degrading enzymes.
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.
Der Beitrag stellt Teilergebnisse zu Prozessen der Selbstregulation von Schülern mit geistiger Behinderung in den Mittelpunkt. Die Einzelfallanlyse erfolgt unter Kenntnis physiologischer Parameter der Selbstregulation im pädagogischen Kontext. Aspekte der chronopsychobiologischen Regulationsdiagnostik finden Einbindung in den Beitrag.
Krimi und Gesellschaft
(2001)
The factors that determine the efficiency of energy transfer in aquatic food webs have been investigated for many decades. The plant-animal interface is the most variable and least predictable of all levels in the food web. In order to study determinants of food quality in a large lake and to test the recently proposed central importance of the long-chained eicosapentaenoic acid (EPA) at the pelagic producer-grazer interface, we tested the importance of polyunsaturated fatty acids (PUFAs) at the pelagic producer-consumer interface by correlating sestonic food parameters with somatic growth rates of a clone of Daphnia galeata. Daphnia growth rates were obtained from standardized laboratory experiments spanning one season with Daphnia feeding on natural seston from Lake Constance, a large pre-alpine lake. Somatic growth rates were fitted to sestonic parameters by using a saturation function. A moderate amount of variation was explained when the model included the elemental parameters carbon (r2 = 0.6) and nitrogen (r2 = 0.71). A tighter fit was obtained when sestonic phosphorus was incorporated (r2 = 0.86). The nonlinear regression with EPA was relatively weak (r2 = 0.77), whereas the highest degree of variance was explained by three C18-PUFAs. The best (r2 = 0.95), and only significant, correlation of Daphnia's growth was found with the C18-PUFA a-linolenic acid (a-LA; C18:3n-3). This correlation was weakest in late August when C:P values increased to 300, suggesting that mineral and PUFA- limitation of Daphnia's growth changed seasonally. Sestonic phosphorus and some PUFAs showed not only tight correlations with growth, but also with sestonic alpha-LA content. We computed Monte Carlo simulations to test whether the observed effects of alpha-LA on growth could be accounted for by EPA, phosphorus, or one of the two C18-PUFAs, stearidonic acid (C18:4n-3) and linoleic acid (C18:2n-6). With >99% probability, the correlation of growth with alpha-LA could not be explained by any of these parameters. In order to test for EPA limitation of Daphnia's growth, in parallel with experiments on pure seston, growth was determined on seston supplemented with chemostat-grown, Plimited Stephanodiscus hantzschii, which is rich in EPA. Although supplementation increased the EPA content 80-800x, no significant changes in the nonlinear regression of the growth rates with alpha-LA were found, indicating that growth of Daphnia on pure seston was not EPA limited. This indicates that the two fatty acids, EPA and alpha-LA, were not mutually substitutable biochemical resources and points to different physiological functions of these two PUFAs. These results support the PUFA-limitation hypothesis for sestonic C:P < 300 but are contrary to the hypothesis of a general importance of EPA, since no evidence for EPA limitation was found. It is suggested that the resource ratios of EPA and alpha-LA rather than the absolute concentrations determine which of the two resources is limiting growth.
Bildung und Medien
(2001)
Deutsche reden Deutsch
(2001)