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41.
5(4H)-Thiazolone derivative 4 , obtained from N-dithiocarbobenzoxyglycine ( 1 ) and N,N-dimethyl-N′-heteroarylformamidines 3 in acetic anhydride, was rearranged with sodium methoxide in methanol followed by acidification with acetic acid into imidazole-4-carboxylic acid derivatives 5, 6 and 7 . These were further converted with methyl iodide into methylthio derivatives 8 , with hydrogen peroxide into the corresponding disulphide 9 , with hydrazine and amines into hydrazide 10 and amides 11 . In the reactions of 4a and 6a with amines in the presence of dichloromethane symetrically disubstituted methanes 14–18 were formed. 相似文献
42.
Herforth C Wiesner J Franke S Golisade A Jomaa H Link A 《Journal of combinatorial chemistry》2002,4(4):302-314
We have investigated the in vitro antimalarial activity of a new series of adenosine derivatives. The results show that N(6)-(1-naphthylmethyl)-5'-deoxy-5'-(amido)adenosines as well as N(6)-(4-phenylbenzyl)-5'-deoxy-5'-(amido)adenosines display significant activity against the malaria-causing parasites, with the sterically demanding bisubstituted species reported being active in most cases in the low-micromolar range. The novel compounds with unusual substitution pattern were obtained applying an efficient convergent polymer-assisted solution-phase (cPASP) synthesis protocol. Thus, we were able to prepare a series of substituted derivatives in parallel that would have been difficult to synthesize by standard techniques. The scope and limitations of the synthetic methodology are discussed. 相似文献
43.
Bhattarai KM Davis AP Perry JJ Walter CJ Menzer S Williams DJ 《The Journal of organic chemistry》1997,62(24):8463-8473
The macrocyclic "cholaphanes" 3a-c were synthesized from the inexpensive steroid cholic acid. Like earlier relatives they feature substantial cavities with inward-directed hydroxyl groups, suitable for binding polar molecules such as carbohydrates in nonpolar media. New features are the externally directed alkyl chains, promoting solubility in organic solvents, and (in the case of 3b/c) reduced conformational freedom resulting from truncation of the steroidal side-chain. In particular, modeling shows that the smallest macrocycle 3c possesses very little flexibility, preferring an open conformation which is also revealed in the X-ray crystal structure of its pentahydrate. NMR studies indicated that all three cholaphanes form 1:1 complexes with octyl beta-D-glucoside in CDCl(3), with K(a) = 600-1560 M(-)(1). Cholaphanes 3b/c proved able to extract methyl beta-D-glucoside from aqueous solutions into CHCl(3). The transport of methyl beta-D-glucoside across a chloroform barrier was also demonstrated for 3c. 相似文献
44.
Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.
Stephan G Zech Wei-Chuan Sun Vincent Jacques Peter Caravan Andrei V Astashkin Arnold M Raitsimring 《Chemphyschem》2005,6(12):2570-2577
A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins. 相似文献
45.
Vitamin-B12-Catalyzed C, C-Bond Formation: Synthesis of Jasmonates via Sequential Radical Reaction The Cbl-catalyzed electroreduction of 3-(2′-bromo-1′-ethoxyethoxy)cyclopenten ( 1a ) in presence of 1-cyanovinyl-acetate ( 8 ) gave, in a sequential radical reaction (5-exo-trig-cyclization of 1a followed by addition to 8 ), 1-cyano-2-(2′-ethoxy-hexahydro-2′H-cyclopenta[b] furan-4′-yl)ethyl acetate ( 10a ). This intermediate was transformed to methyl jasmonate ( 7 ; four steps) and epituberolide ( 9 ; three steps) in 20 and 31% yield, respectively, from cyclopent-2-en-l-ol. 相似文献
46.
Liu J Pan D Tseng Y Hopfinger AJ 《Journal of chemical information and computer sciences》2003,43(6):2170-2179
A training set of 55 antifungal p450 analogue inhibitors was used to construct receptor-independent four-dimensional quantitative structure-activity relationship (RI 4D-QSAR) models. Ten different alignments were used to build the models, and one alignment yields a significantly better model than the other alignments. Two different methodologies were used to measure the similarity of the best 4D-QSAR models of each alignment. One method compares the residual of fit between pairs of models using the cross-correlation coefficient of their residuals of fit as a similarity measure. The other method compares the spatial distributions of the IPE types (3D-pharmacophores) of pairs of 4D-QSAR models from different alignments. Optimum models from several different alignments have nearly the same correlation coefficients, r(2), and cross-validation correlation coefficients, xv-r(2), yet the 3D-pharmacophores of these models are very different from one another. The highest 3D-pharmacophore similarity correlation coefficient between any pair of 4D-QSAR models from the 10 alignments considered is only 0.216. However, the best 4D-QSAR models of each alignment do contain some proximate common pharmacorphore sites. A test set of 10 compounds was used to validate the predictivity of the best 4D-QSAR models of each alignment. The "best" model from the 10 alignments has the highest predictivity. The inferred active sites mapped out by the 4D-QSAR models suggest that hydrogen bond interactions are not prevalent when this class of P450 analogue inhibitors binds to the receptor active site. This feature of the 4D-QSAR models is in agreement with the crystal structure results that indicate no ligand-receptor hydrogen bonds are formed. 相似文献
47.
Lytchak Alexander Petrunin Anton 《Journal of Optimization Theory and Applications》2022,194(2):636-642
Journal of Optimization Theory and Applications - We show that cyclic products of projections onto convex subsets of Hadamard spaces can behave in a more complicated way than in Hilbert spaces,... 相似文献
48.
Stephan Wehner 《Archive for Mathematical Logic》1995,34(3):183-196
To date the problem of finding a general characterization of injective enumerability of recursively enumerable (r.e) classes of r.e. sets has proved intractable. This paper investigates the problem for r.e. classes of cofinite sets. We state a suitable criterion for r.e. classesC such that there is a boundn with |-A|n for allAC. On the other hand an example is constructed which shows that Lachlan's condition (F) does not imply injective enumerability for r.e. classes of cofinite sets. We also look at a certain embeddability property and show that it is equivalent with injective enumerability for certain classes of cofinite sets. At the end we present a reformulation of property (F).Thank you for technical support, Wolfgang Eppler, for intellectual support, Alistair Lachlan, and for proof-reading, Martin Kummer. Thanks also to the anonymous referee 相似文献
49.
We consider the Hopfield model withM(N)=N patterns, whereN is the number of neurons. We show that if is sufficiently small and the temperature sufficiently low, then there exist disjoint Gibbs states for each of the stored patterns, almost surely with respect to the distribution of the random patterns. This solves a provlem left open in previous work. The key new ingredient is a self-averaging result on the free energy functional. This result has considerable additional interest and some consequences are discussed. A similar result for the free energy of the Sherrington-Kirkpatrick model is also given. 相似文献
50.
We study the Hopfield model of an autoassociative memory on a random graph onN vertices where the probability of two vertices being joined by a link isp(N). Assuming thatp(N) goes to zero more slowly thanO(1/N), we prove the following results: (1) If the number of stored patternsm(N) is small enough such thatm(N)/Np(N) 0, asN, then the free energy of this model converges, upon proper rescaling, to that of the standard Curie-Weiss model, for almost all choices of the random graph and the random patterns. (2) If in additionm(N) < ln N/ln 2, we prove that there exists, forT< 1, a Gibbs measure associated to each original pattern, whereas for higher temperatures the Gibbs measure is unique. The basic technical result in the proofs is a uniform bound on the difference between the Hamiltonian on a random graph and its mean value. 相似文献