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51.
A series of molecularly imprinted polymer (MIP) synthetic receptors selective for the sedative thalidomide (5) have been designed and synthesized based upon the functional monomer 9-(2'-methacryloyloxyethyl)adenine (2). (1)H-NMR studies were used to establish the existence of DNA-like binding interactions between 2 and the template (5). A series of ethylene glycol dimethacrylate cross-linked copolymers was synthesized using either 2 or methacrylic acid, or a combination of these functional monomers. Zonal HPLC studies demonstrated enantioselectivity (alpha = 2.11) and ligand selectivity which could be attributed to the interaction of 2 with the imide moiety of 5. Compound 2 provided a more significant contribution to the binding of 5 than methacrylic acid, though a combination of these two functional monomers resulted in improved enantioselectivity. Frontal chromatographic and batch binding studies confirmed the observed differences in affinity of the imprinted and reference polymers for the template. 相似文献
52.
We generalize the concept of a 2-coloring of a graph to what we call a semi-balanced coloring by relaxing a certain discrepancy condition on the shortest-paths hypergraph of the graph. Let G be an undirected, unweighted, connected graph with n vertices and m edges. We prove that the number of different semi-balanced colorings of G is: (1) at most n+1 if G is bipartite; (2) at most m if G is non-bipartite and triangle-free; and (3) at most m+1 if G is non-bipartite. Based on the above combinatorial investigation, we design an algorithm to enumerate all semi-balanced colorings of G in O(nm2) time.Acknowledgments The authors thank Tetsuo Asano, Naoki Katoh, Kunihiko Sadakane, and Hisao Tamaki for helpful discussions and comments.Supported in part by Sweden-Japan FoundationFinal version received: November 17, 2003 相似文献
53.
Bromine-lithium exchange using tert-butyllithium at -78 degrees C initiates a cascade process whereby either xanthone derivatives or pentacyclic 13-azadibenzo[a,de]anthracenes are produced in high yields. The reaction proceeds via a sequential intramolecular trapping of organolithium intermediates. 相似文献
54.
55.
De novo design and total chemical synthesis of proteins provide powerful approaches to critically test our understanding of protein folding, structure, and stability. The 4-alpha-helix bundle is a frequently studied structure in which four amphiphilic alpha-helical peptide strands form a hydrophobic core. Assembly of protein models on a template has been suggested as a way to reduce the entropy of folding. We have previously developed the concept of carbohydrates as templates in the de novo design of protein models termed 'carboproteins'. Here we present the chemical synthesis of three 8.1 kDa 4-alpha-helix bundles by oxime ligation of tetra-aminooxyacetyl functionalized D-galacto-, D-gluco-, and D-altropyranoside templates with an amphiphilic C-terminal hexadecapeptide aldehyde sequence. CD spectroscopy indicated that the choice of template has an effect on the overall structure of the carboprotein, as the altro-based carboprotein was found to be more alpha-helical than the corresponding galacto- and gluco-carboproteins. However, an influence on stability could not be detected in the present experiments, as the three carboproteins gave similar free energy of foldings (deltaG(F)H2O) and melting points in chemical and thermal denaturation experiments. 相似文献
56.
Tsang WC Jernelius JA Cortez GA Weatherhead GS Schrock RR Hoveyda AH 《Journal of the American Chemical Society》2003,125(9):2591-2596
An enantiomerically pure Mo-based complex that bears an alkylimido ligand is prepared and characterized through NMR spectroscopy and X-ray analysis. Mo complex 4 is the only reported chiral alkylimido catalyst; all previous chiral complexes are arylimido systems. These studies show that the chiral Mo catalyst exists exclusively as the syn isomer and that it offers unique reactivity and selectivity profiles in asymmetric olefin metathesis. 相似文献
57.
Sorensen JL Auclair K Kennedy J Hutchinson CR Vederas JC 《Organic & biomolecular chemistry》2003,1(1):50-59
Two mutants of Aspergillus terreus with either the lovC or lovA genes disrupted were examined for their ability to transform nonaketides into lovastatin 1, a cholesterol-lowering drug. The lovC disruptant was able to efficiently convert dihydromonacolin L 5 or monacolin J 9 into 1, and could also transform desmethylmonacolin J 15 into compactin 3. In contrast, the lovA mutant has an unexpectedly active beta-oxidation system and gives only small amounts of 1 upon addition of the immediate precursor 9, with most of the added nonaketide being degraded to heptaketide 22. Similarly, the lovA mutant does not accumulate the polyketide synthase product 5 and rapidly degrades any 5 added as a precursor via two cycles of beta-oxidation and hydroxylation at C-6 to give 20. The possible involvement of epoxides 21a and 21b in the biosynthesis of 1 was also examined, but their instability in fermentation media and fungal cells will require purified enzymes to establish their role. 相似文献
58.
59.
The aim of this paper is to formulate a conjecture for an arbitrary simple Lie
algebra g in terms of the geometry of principal nilpotent pairs. When g is specialized to sln,
this conjecture readily implies the n! result and it is very likely that, in fact, it is equivalent
to the n! result in this case. In addition, this conjecture can be thought of as generalizing an
old result of Kostant. In another direction, we show that to prove the validity of the n! result
for an arbitrary n and an arbitrary partition of n, it suffices to show its validity only for the
staircase partitions. 相似文献
60.
We study the chromatic polynomials for m×n square-lattice strips, of width 9m13 (with periodic boundary conditions) and arbitrary length n (with free boundary conditions). We have used a transfer matrix approach that allowed us also to extract the limiting curves when n. In this limit we have also obtained the isolated limiting points for these square-lattice strips and checked some conjectures related to the Beraha numbers. 相似文献