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131.
Philippe Hennig Eric Raimbaud Christophe Thurieau Jean-Paul Volland André Michel Jean-Luc Fauchère 《Journal of computer-aided molecular design》1996,10(1):83-86
Summary The conformation in dimethylsulfoxide of the somatostatin derivative angiopeptin and of three disulfide-free analogs was estimated by two-dimensional nuclear magnetic resonance spectroscopy at room temperature. The resulting 3D molecular graphics were compared and shown to reflect the observed differences in the inhibition of restenosis after rat aorta balloon injury by these octapeptide inhibitors. Angiopeptin and its active analog 2 displayed a relatively rigid conformation of the cyclic hexapeptide backbone due to the presence of two well-defined hydrogen bonds, further stabilized by a third hydrogen bond outside the ring. No such constraints were detected for the two biologically inactive analogs, which, compared to 2, had a two-atom longer or shorter hexapeptide ring. The well-defined structure of compound 2 may serve as an improved pharmacophore for this new class of drugs. 相似文献
132.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
133.
Y Masuo H Wang D Pélaprat Z Q Chi W Rostène 《Chemical & pharmaceutical bulletin》1992,40(9):2520-2524
We have recently demonstrated that [3H]ohmefentanyl, a non-peptidergic opioid ligand which was suggested to cross the blood brain barrier in contrast to other peptidergic opioid ligands, bound not only to mu opioid receptor sites but also to sigma sites. In order to examine whether [3H]ohmefentanyl can be used as a marker for mu sites, we investigated the effects of brain lesions on [3H]ohmefentanyl binding site densities, as compared with [3H][D-Ala2, MePhe4, Gly-ol5]enkephalin ([3H]DAGO), a selective mu ligand. These binding site densities were measured by quantitative autoradiography in the rat striatum and substantia nigra, two brain structures known to contain a high density of mu receptors, following lesions of the nigro-striatal dopaminergic pathway and striatal intrinsic neurons. Following unilateral nigral lesion with 6-hydroxydopamine, [3H]ohmefentanyl binding site densities were decreased in the patches (-35%) and matrix (-20%) of the ipsilateral striatum and in the lesioned substantia nigra pars compacta (-49%). Unilateral striatal lesion with quinolinic acid induced 72%, 61% and 50% decreases in [3H]ohmefentanyl binding in the patches and matrix of the lesioned striatum and in the ipsilateral substantia nigra pars reticulata, respectively. Similar results were obtained in the binding of [3H]DAGO. Indeed, a significant linear correlation was observed between [3H]ohmefentanyl and [3H]DAGO binding site densities. Therefore, mu opioid receptors may be mainly located on intrinsic neurons in the striatum, dopaminergic cell bodies in the substantia nigra pars compacta and nerve terminals of striatal efferents in the substantia nigra pars reticulata.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
134.
Cremer GA Bureaud N Lelièvre D Piller V Piller F Delmas A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6353-6360
Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein. 相似文献
135.
Zusammenfassung Die Mikromethode zur Jodbestimmung in organischen Substanzen durch Verbrennen nachSchöniger und nachfolgende Titration mit 0,005-n Quecksilberperchlorat wird dahingehend vereinfacht, daß die Jodabsorption nach der Verbrennung anstatt mit Natronlauge direkt mit Quecksilberperchlorat erfolgt.
Summary The micro method for determining iodine in organic materials through combustion afterSchöniger and subsequent titration with 0.005N mercuric perchlorate is modified to the extent that after the combustion the iodine is absorbed directly in mercuric perchlorate rather than in sodium hydroxide.
Résumé On a simplifié la microméthode pour le dosage de l'iode dans les substances organiques avec combustion suivantSchöniger et titrage consécutif par le perchlorate de mercure 0,005N. L'absorption de l'iode après la combustion s'effectue directement par le perchlorate de mercure à la place de la lessive de soude.
Riassunto La microdeterminazione dello iodio nelle sostanze organiche per combustione secondoSchöniger e successiva titolazione con perclorato di mercurio 0,005-n, è stata semplificata riprendendo direttamente il prodotto di combustione in una soluzione di perclorato di mercurio invece di una soluzione di idrato sodico.相似文献
136.
Thérèse Dupuis 《Mikrochimica acta》1967,55(3):452-460
Résumé Par chauffage à 1000° de mélanges d'oxyde stannique et d'oxyde de cadmium en proportions diverses, comme par déshydratation de précipités mixtes des hydroxydes correspondants, il se forme une série de solutions solides de l'oxyde de cadmium dans l'oxyde d'étain. Elles sont solubles dans l'acide chlorhydrique et présentent un spectre d'absorption infrarouge caractéristique que l'on a comparé avec celui des 2 métastannates de cadmium CdSnO3, l'un de type ilménite, l'autre de type perovskite.
Summary By heating various mixture of stannic oxide and cadmium oxide to 1000° C, a series of solid solutions of cadmium oxide in stannic oxide results as is the case when mixed precipitates of the corresponding hydroxides are dehydrated. They are soluble in hydrochloric acid and yield a characteristic infrared absorption spectrum that was compared with that of the two cadmium métastannates CdSnO3, one of the ilmenite type, the other of the perovskite type.
Zusammenfassung Erhitzt man verschieden zusammengesetzte Gemische von Zinnoxid und Cadmiumoxid auf 1000° C oder werden Mischfällungen der entsprechenden Hydroxide dehydratisiert, so entsteht eine Reihe fester Lösungen von Cadmiumoxid in Zinnoxid. Sie sind in Salzsäure löslich und zeigen ein charakteristisches Absorptionsspektrum im IR. Dieses wurde mit dem Spektrum zweier Cadmium-Metastannate (CdSnO3) vom Typus des Ilmenits bzw. Perovskits verglichen.相似文献
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