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21.
Erich Metzger Roland Aeschimann Martin Egli Gaby Suter Ren Dohner Daniel Ammann Max Dobler Wilhelm Simon 《Helvetica chimica acta》1986,69(8):1821-1828
Lipophilic neutral carriers were synthesized which show Li+/Na+ selectivities of up to ca. 80 in highly lipophilic liquid membranes. The sensor membranes exhibit improved response times and increased lifetimes as compared to systems described earlier. They allow reliable measurements of Li+ in blood serum within the clinical concentration range. A 1:1 Li+/ionophore complex of one representative (N,N,N′,N′-tetracyclohexyl-5,5-dimethyl-3,7-dioxaazelaamide) has been prepared, and its structure was elucidated by X-ray analysis. 相似文献
22.
Erich Novak 《Numerische Mathematik》1986,50(2):245-252
Summary The definition of the average error of numerical methods (by example of a quadrature formula
to approximateS(f)= f d on a function classF) is difficult, because on many important setsF there is no natural probability measure in the sense of an equidistribution. We define the average a posteriori error of an approximation
by an averaging process over the set of possible information, which is used by
(in the example of a quadrature formula,N(F)={(f(a
1), ...,f/fF} is the set of posible information). This approach has the practical advantage that the averaging process is related only to finite dimensional sets and uses only the usual Lebesgue measure. As an application of the theory I consider the numerical integration of functions of the classF={f:[0,1]/f(x)–f(y)||x–y|}. For arbitrary (fixed) knotsa
i
we determine the optimal coefficientsc
i
for the approximation
and compute the resulting average error. The latter is minimal for the knots
. (It is well known that the maximal error is minimal for the knotsa
i
.) Then the adaptive methods for the same problem and methods for seeking the maximum of a Lipschitz function are considered. While adaptive methods are not better when considering the maximal error (this is valid for our examples as well as for many others) this is in general not the case with the average error. 相似文献
23.
Germer A Mügge C Peter MG Rottmann A Kleinpeter E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(9):1964-1973
The solution-state conformations of N,N',N"-triacetyl chitotriose (1) and other potential chitinase inhibitors 2-4 were studied using a combination of NMR spectroscopy (NOESY) and molecular mechanics calculations. Determination solely of the global energy minimum conformation was found to be insufficient for an agreement with the NMR results. An appropriate consistency between the NMR experimental data and theoretical calculations was only reached by assessing the structures as population-weighted average conformers based on Boltzmann distributions derived from the calculated relative energies. Analogies, but also particular differences, between the synthetic compounds 2-4 and the naturally-occurring N,N',N"-triacetyl chitotriose were found. Furthermore, the conformation of compounds 1 and 2 when bound to hevamine was also studied using transferred NOESY experiments and the binding process was found to impart a level of conformational restriction on the ligands. The preferred conformation as determined for 1 in the bound state to hevamine belonged to one of the conformational families found for the compound when free in solution, although full characterisation of the bound-state conformations was impeded due to severe signal overlap. Saturation transfer difference NMR experiments were also employed to analyse the binding epitopes of the bound compounds. We thus determined that it is mainly the acetyl amido groups of the trisaccharide and the heterocyclic moiety which are in close contact with hevamine. 相似文献
24.
Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN3 affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2. 相似文献
25.
Intermolecular rhodium-catalyzed [m + n + o] reactions of 1,6-enynes and various pi-components (carbon monoxide, alkynes, 1,3-butadienes, etc.) provide an expeditious approach for the construction of polycyclic fragments that represent important synthons for target-directed synthesis. We present computational and experimental evidence for the existence of a previously undescribed reaction pathway for the rhodium-catalyzed [4 + 2 + 2] reaction involving a 1,6-enyne. This model clearly demonstrates the origin of the excellent diastereoselectivity in this type of reaction and the remarkable tolerance of both (E)- and (Z)-isomers within the 1,6-enyne, which is generally prone to competitive ene-cycloisomerization. 相似文献
26.
Wolfgang Reischl Harald Bernhard Christoph Kratky Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1985,116(6-7):831-839
Epoxidation of vitamin D3 with benzonitrile ¦H2O2¦ KHCO3 (Payne's reagent) yields exclusively the 5,6-mono-oxirane2. Further epoxidation with the same reagent gives the 5,6-7,8-bisepoxide3 a. Its stereochemistry and therefore the stereochemistry of2 was established by single crystal X-ray analysis of thep-Brbenzoate3b. Thereby for the first time a directive effect of a homoallylic hydroxyl group during thePayne-epoxidation was established.
Herrn Prof.Mihailovic (Universität Belgrad) mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
27.
Zellner M Winkler W Hayden H Diestinger M Eliasen M Gesslbauer B Miller I Chang M Kungl A Roth E Oehler R 《Electrophoresis》2005,26(12):2481-2489
For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment. 相似文献
28.
The zero-field transitions in the photoexcited triplet state of benzo[α]pyrene bound to DNA have been observed by optical detection of magnetic resonance of 2 K. The transition frequencies individual spin sublevel intersystem crossing rates were measured by monitoring the microwave-induced intensity changes of the triplettriplet absorption at 465.8 nm. The triplet state zero-field splitting and dynamics for the benzo[α]pyrene DNA complex are compared with these properties measured for benzo(α)pyrene in other solvent systems. 相似文献
29.
The azido tetrazolo valence isomerism of twenty 9-methyl-s-triazolo[4,3-c]tetrazolo[1,5-a]pyrimidines with different substituents at position 5 has been studied by means of 1H NMR spectroscopy. All the compounds have been found to be tetrazoles in the solid state and in (CD3)2SO solution; in CF3COOH azido and tetrazolo isomers are in equilibrium. From equilibrium constants K and thermodynamic data determined it is concluded that in this series K depends on both electronic effects and steric requirements of the 5-substituents. A linear relation between K and σ was found for 5-arylderivatives because ΔS° keeps approximately constant and the substituent mainly operates on ΔH°. 相似文献
30.
3-O-Acetyl-1,2-O-isopropylidene--D-allofuranose (2 b) was prepared from 1,2:5,6-di-O-isopropylidene--D-allofuranose (1 b). Treatment of2 b with triphenylphosphine-diethyl azodicarboxylate afforded regio- and stereospecifically the 5,6-epoxy--D-allo derivative (3). The other diastereomeric compound, 5,6-epoxy-1,2-O-isopropylidene--L-talofuranose (6) was also prepared stereoselectively from2 b
via the intermediates5 a and5 b. The epoxy sugars3 and6 were converted with lithium aluminum hydride to the corresponding 6-deoxy-1,2-O-isopropylidene--D-allofuranose (4 a) and --L-talofuranose (7 a) derivatives. Hydrolysis of4 a and7 a afforded 6-deoxy-D-allose and 6-deoxy-L-talose, respectively. The corresponding 3,5-di-O-acetyl- (4 b and7 b) and the 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) derivatives (4 c and7 c) are also described. Selective removal of the isopropylidene group and subsequent acetylation offers a convenient route to prepare sugar derivatives containing furanose ring, like8 b, as a suitable precursor for nucleoside analogs.Herrn Prof. Dr.K. Komarek mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献