Optically active, cage-functionalized crown ether (R)-3 which contains a 1,1′-bi-2-naphthol moiety has been prepared. Subsequently, the ability of (R)-3 to selectively recognize the enantiomers of guest ammonium salts, i.e., 4 and 5 in transport experiments was studied. Host (R)-3 displays significantly enhanced enantiomeric selectivity toward complex formation with 4 vis-à-vis complex formation with 5. The relative energetics of various relevant host–guest complexes have been investigated computationally. 相似文献
Specifically we investigate the polyhedral structure of the knapsack problem with a single continuous variable, called the
mixed 0-1 knapsack problem. First different classes of facet-defining inequalities are derived based on restriction and lifting. The order of
lifting, particularly of the continuous variable, plays an important role. Secondly we show that the flow cover inequalities
derived for the single node flow set, consisting of arc flows into and out of a single node with binary variable lower and
upper bounds on each arc, can be obtained from valid inequalities for the mixed 0-1 knapsack problem. Thus the separation
heuristic we derive for mixed knapsack sets can also be used to derive cuts for more general mixed 0-1 constraints. Initial
computational results on a variety of problems are presented.
Received May 22, 1997 / Revised version received December 22, 1997 Published online November 24, 1998 相似文献
Systems of strongly coupled chaotic maps generically exhibit collective behavior emerging out of extensive chaos. We show how the well-known renormalization group (RG) of unimodal maps can be extended to the coupled systems, and in particular to coupled map lattices (CMLs) with local diffusive coupling. The RG relation derived for CMLs is nonperturbative, i.e., not restricted to a particular class of configurations nor to some vanishingly small region of parameter space. After defining the strong-coupling limit in which the RG applies to almost all asymptotic solutions, we first present the simple case of coupled tent maps. We then turn to the general case of unimodal maps coupled by diffusive coupling operators satisfying basic properties, extending the formal approach developed by Collet and Eckmann for single maps. We finally discuss and illustrate the general consequences of the RG: CMLs are shown to share universal properties in the space-continuous limit which emerges naturally as the group is iterated. We prove that the scaling properly ties of the local map carry to the coupled systems, with an additional scaling factor of length scales implied by the synchronous updating of these dynamical systems. This explains various scaling laws and self-similar features previously observed numerically. 相似文献
Pim kinases (proviral integration site for Moloney murine leukemia virus kinases) are overexpressed in various types of hematological malignancies and solid carcinomas, and promote cell proliferation and survival. Thus, Pim kinases are validated as targets for antitumor therapy. In this context, our combined efforts in natural product-inspired library generation and screening furnished very promising dibenzo[b,d]furan derivatives derived from cercosporamide. Among them, lead compound 44 was highlighted as a potent Pim-1/2 kinases inhibitor with an additional nanomolar IC50 value against CLK1 (cdc2-like kinases 1) and displayed a low micromolar anticancer potency towards the MV4-11 (AML) cell line, expressing high endogenous levels of Pim-1/2 kinases. The design, synthesis, structure–activity relationship, and docking studies are reported herein and supported by enzyme, cellular assays, and Galleria mellonella larvae testing for acute toxicity. 相似文献
The missing link : Ferrocene and porphyrin monolayers are tethered on silicon surfaces with short (see picture, left) or long (right) linkers. Electron transfer to the silicon substrate is faster for monolayers with a short linker.
A conceptually novel macrolactonization protocol has been developed. It is a domino process involving a sequence of: 1) protonation of 5-aminooxazole leading to the electrophilic iminium salt; 2) trapping of the iminium species by the neighboring C-terminal carboxylic acid leading to a putative spirolactone; and 3) intramolecular nucleophilic addition of the tethered alcohol to the spirolactone followed by fragmentation. The strategically incorporated 5-aminooxazole serves as an internal traceless activator of the neighboring C-terminal carboxylic acid, since it became an integral part of the peptide backbone after cyclization. No coupling reagent is required and the entire sequence is triggered by just a few equivalents of trifluoroacetic acid under very mild conditions (MeCN as the solvent at room temperature). The spirolactone as an activated form of the carboxylic acid has been evidenced by a sulfur-migration experiment. By combining with a three-component synthesis of 5-aminooxazole, a two-step synthesis of structurally complex cyclodepsipeptides from readily accessible starting materials was developed. 相似文献
In this work, the simultaneous determination of four organometallic species (monomethylmercury, monobutyltin, dibutyltin and tributyltin) in environmental samples by using a GC-MS system with electron ionisation has been established. The measurement of isotope ratios in each species was accomplished by selecting the most adequate molecular cluster, and simple mathematical equations were applied to correct the contributions of 13C from the organic groups attached to the tin and mercury atoms. The influence of different parameters such as dwell time on the precision and accuracy of the measured isotope ratios in each target species has also been studied. The determination and the sample preparation procedures presented in this work were first individually validated by analysing several certified reference materials for butyltin compounds (mussel tissue CRM-477 and marine sediment SOPH-1) and for monomethylmercury (tuna fish CRM-464) using an innovative focused microwave technology for the extraction of the species from the solid samples. Additionally, the simultaneous determination of the four species was successfully validated by obtaining quantitative recoveries in spiked natural waters and by analysing the certified reference material BCR-710 (certified in tributyltin and monomethylmercury). The values obtained in such certified tissue were fully in agreement not only with the certified mass fractions but also with the proposed indicative values for mono- and dibutyltin. 相似文献
We report the synthesis and first characterization of N-alkyldiaminoresorcinols (or 4,6-bis-dialkylaminobenzene-1,3-diols C6H2(NHR)2(OH)2) (10a, R = CH2-2-Py; 10b, R = CH2-3-Py; 10c, R = CH2-4-Py) which result from one-pot stepwise reactions: (i) air-oxidation of diaminoresorcinol 3, (ii) transamination reaction leading to the corresponding functional 6π+6π quinonemonoimine zwitterions C6H2(NHR)2(O)2 (9a, R = CH2-2-Py; 9b, R = CH2-3-Py; 9c, R = CH2-4-Py), (iii) reduction and re-aromatization in the presence of the corresponding primary amine bearing a pyridine moiety. 相似文献