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21.
HUN-7293 (1), a naturally occurring cyclic heptadepsipeptide, is a potent inhibitor of cell adhesion molecule expression (VCAM-1, ICAM-1, E-selectin), the overexpression of which is characteristic of chronic inflammatory diseases. Representative of a general approach to defining structure-function relationships of such cyclic (depsi)peptides, the parallel synthesis and evaluation of a complete library of key HUN-7293 analogues are detailed enlisting solution-phase techniques and simple acid-base liquid-liquid extractions for isolation and purification of intermediates and final products. Significant to the design of the studies and unique to solution-phase techniques, the library was assembled superimposing a divergent synthetic strategy onto a convergent total synthesis. An alanine scan and N-methyl deletion of each residue of the cyclic heptadepsipeptide identified key sites responsible for or contributing to the biological properties. The simultaneous preparation of a complete set of individual residue analogues further simplifying the structure allowed an assessment of each structural feature of 1, providing a detailed account of the structure-function relationships in a single study. Within this pharmacophore library prepared by systematic chemical mutagenesis of the natural product structure, simplified analogues possessing comparable potency and, in some instances, improved selectivity were identified. One potent member of this library proved to be an additional natural product in its own right, which we have come to refer to as HUN-7293B (8), being isolated from the microbial strain F/94-499709. 相似文献
22.
The electron-transfer-catalyzed rearrangement of the housanes 1 affords regioselectively the two cyclopentenes 2 and 3 by 1,2-migration of a group at the methano bridge. Appropriate ring annelation in the intermediary cyclopentane-1,3-diyl radical cation 1(*+) changes the stereochemical course of the rearrangement from complete stereoselectivity (stereochemical memory) for the structurally simple housane 1b to partial loss of stereoselectivity through competing conformational interconversion for the tricyclic housane 1c. Additional cyclohexane annelation, as in the tetracyclic housane 1a, results in complete loss of stereocontrol through Curtin-Hammett behavior, as substantiated by the viscosity dependence on the product ratio of the rearrangement. Whereas in the radical cations 1b(*+) and 1c(*+) the 1,2-shifts (k(2) and k(3)) are faster than the conformational anti <==> syn change (k(1), k(-1)), the reverse applies for the radical cation 1a(*+). Such structural manipulation of conformational effects in radical cation rearrangements has hitherto not been documented. 相似文献
23.
Xiaojuan Hao Luca Albertin L. John R. Foster Thomas P. Davis Christopher Barner‐Kowollik 《Macromolecular bioscience》2003,3(11):675-683
A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.
24.
We calculate the chiral anomaly in 2 dimensions within a dispersion relation approach and we compare its features with then-dimensional regularization scheme.Supported by Fonds zur Förderung der wissenschaftlichen Forschung in Österreich, Projekt Nr. P8444-TEC 相似文献
25.
26.
J. Adam Jr. J. Mareš O. Richter M. Sotona S. Frullani 《Czechoslovak Journal of Physics》1992,42(11):1167-1196
Formalism for the electroproduction of strange particles based on the one photon exchange approximation and the Feynman diagrams representation of hadron current is reviewed. Different photoproduction models are compared with available photo and electroproduction data. New experiments are proposed that may resolve existing uncertainties and inconsistencies. The formation of hypernuclei via kaon electroproduction is investigated theoretically and compared with other reactions involving purely hadronic processes. 相似文献
27.
John A. Adam 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1982,33(4):473-486
Summary A derivation is given of the basic equation governing the behaviour of small disturbances in a stratified compressible atmosphere (with a locally unstable region bounded by semi-infinite stable regions) in which the time of radiative relaxation is constant.By means of a new independent variable that is a function of the equilibrium entropy stratification, various properties of such media can be established in a straightforward manner. A general expression for the wave energy flux is derived, and integral properties arising from this quantity are used to obtain in particular, results pertaining to the eigenfunctions and eigenvalues for strongly radiating systems. In addition, a model of an atmosphere with a strongly-radiating region embedded in a convective zone, and bounded by semi-infinite radiation-free layers is discussed in some detail. The paper is an approach towards providing some preliminary but unified results in the theory of stellar hydrodynamics.
Résumé Nous donnons une dérivation de l'équation de base qui détermine la propagation des petites perturbations dans une atmosphère compressible stratifiée (présentant une zone d'instabilité locale entre des zones de stabilité semi-infinies) dont le temps de relaxation radiative est constant.Au moyen d'une nouvelle variable indépendante, fonction de la stratification de l'entropie en équilibre, diverses propriétés de tels milieux sont déterminées simplement. On donne une formulation du flux de l'énergie ondulative et on emploie les propriétés intégrales qui en résultent pour obtenir en particulier des résultats concernant les eigenfonctions et les eigenvalues pour des systèmes à forte radiation énergétique. En outre, on étudie en détail le modèle d'une amtosphère caractérisée par une zone à forte radiation insérée dans une zone convective entre des couches semi-infinies sans radiation.Ce travail présente quelques conclusions préliminaires mais cohérentes dans le domaine de la théorie de l'hydrodynamique stellaire.相似文献
28.
Photocycloadditions of dimethyl 3-dehydrogibberellenate 1 to ethylene, 1,1-dichloroethylene and trich-loro-ethylene were investigated The results exhibited markedly the competition between photodimerization and photocycloaddition of 1, and showed that the yields of cycloaddition products increased with increasing polarity of the olefins. Strangely, photocycloaddition of 1 to olefins was found to proceed through the singlet excited state 相似文献
29.
Ravindra K. Pandeyi † William R. Potter Isabelle Meunier Adam B. Sumlin Kevin M. Smith 《Photochemistry and photobiology》1995,62(4):764-768
Abstract— A first report on the biological evaluation of a series of isomerically pure benzoporphyrin derivatives ( cis- and frarcs-isomers) as methyl esters is described. In preliminary in vivo studies, the n- bexyl ether analogues of both cis- and trans -isomers of benzoporphyrin derivatives were found to be more active than the industrially prepared benzoporphyrin derivative, a mixture of monocarboxylic acids (BPDMA, Quadralogic Technologies, Vancouver). Further studies with 4-de-vinyl-4-(I-hexyloxyethyl) benzoporphyrin derivative showed that, like BPDMA, it had reduced residual skin phototoxicity compared in mice with Photofrin®. The uptake and clearance characteristics of BPDMA were also compared with the 4-(1-hexyloxyethyl)-derivative by in vivo reflection spectroscopy. 相似文献
30.
Highly selective extraction of chromate from slightly acidic solutions (0.1-0.2M sulphuric acid) with a chloroform solution of trioctylamine (Alamine 336-S) or trioctylmethylammonium chloride Aliquat 336-S) is described. Many metals such as iron, nickel, cobalt, copper, alluminium, zinc, are not extracted, even if present in large concentrations. Coextraction of vanadium(V) and uranium(VI) is prevented by addition of sodium chloride. Traces of extracted molybdenum are scrubbed with ammonium oxalate. Final determination of chromium is based on measurement of the absorbance of the extract at 445-450 nm. 相似文献