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21.
Ogawa T Araki M Miyamae T Okayama T Hagiwara M Sakurada S Morikawa T 《Chemical & pharmaceutical bulletin》2003,51(7):759-771
To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l). 相似文献
22.
Toshiaki Sunazuka Masaki Handa Tatsuya Shirahata Kazuhiko Otoguro Satoshi ōmura 《Tetrahedron》2004,60(36):7845-7859
In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins. 相似文献
23.
Fluorine has come to be recognized as a key element in materials science: in heat‐transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine‐containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets. 相似文献
24.
Fluorine has come to be recognized as a key element in materials science: in heat-transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine-containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets. 相似文献
25.
Katsuyoshi Shibata Isamu Katsuyama Hideaki Izoe Masaki Matsui Hiroshige Muramatsu 《Journal of heterocyclic chemistry》1993,30(1):277-281
A new one-pot synthesis of title compounds by the reactions of α,β-unsaturated carbonyl compounds with β-aminocrotononitrile in the presence of sodium hydroxide is described. 相似文献
26.
A synthesis of the thromboxane A2 analog, -(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A2 is described. 相似文献
27.
Toshiyuki Yamashita Takeo Fujino Norio Masaki Hiroaki Tagawa 《Journal of solid state chemistry》1981,37(2):133-139
The structural parameters of α- and β-CdUO4 crystals are determined by X-ray powder diffraction technique. α-CdUO4 is rhombohedral and cell parameters are a = 6.233(3) Å and α = 36.12(5)°. β-CdUO4 crystallizes in a C-centered orthorhombic cell with a = 7.023(4), b = 6.849(3), c = 3.514 (2) Å. The space groups are for α-CdUO4 and Cmmm for β-CdUO4. α-CdUO4: 1U in (000), 1Cd in (), 2O(1) in ±(uuu), 2O(2) in ±(vvv); u = 0.113, v = 0.350, Z = 1. β-CdUO4: 2U in (), 2Cd in (), 4O(1) in (), 4O(2) in (); x = 0.159, y = 0.278, Z = 2. β-CdUO4 contains collinear uranyl UO2+2 groups with a UO(1) distance of 1.91 Å, located either along or parallel to the c axis whereas the UO(1) bond length in α-CdUO4 is 1.98 Å which is longer than the usual uranyl bond length. 相似文献
28.
Vortex shedding from a bluff ring in a linear shear flow has been investigated experimentally. The shedding frequency, measured using a hot wire in various positions within the near wake of the ring, was found to be remarkably insensitive to a mean flow shear parameter, , defined by (d/U
o).U/y, where d is the mean ring diameter and U
o is the undisturbed upstream velocity on the ring axis; even for = 0.41, corresponding to a velocity variation of about ±24% across the outer ring diameter, the Strouhal number was only about 5% lower than in uniform flow. However, the strong axisymmetric shedding which dominates the flow for = 0 is significantly affected by shear. Indeed, spatial correlation measurements demonstrated that the shedding actually becomes anti-symmetric at the highest values of . The implication of these results is that vortex flowmeters constructed using a ring as the shedding body would be relatively unaffected by changes in the upstream mean flow profile. 相似文献
29.
Fujita M Nakao Y Matsunaga S Seiki M Itoh Y Yamashita J Van Soest RW Fusetani N 《Journal of the American Chemical Society》2003,125(51):15700-15701
A novel MMP inhibitor, ageladine A (1) with antiangiogenic activity was isolated from a marine sponge Agelas nakamurai. Structure 1 was determined by a combination of spectroscopic and chemical methods to be an unprecedented structure of 4-(4,5-dibromo-1H-pyrrol-2-yl)]-1H-imidazo[4,5-c]pyridin-2-amine. 相似文献
30.
Masaki Takeguchi Kazutaka Mitsuishi Miyoko Tanaka Kazuo Furuya 《Microscopy and microanalysis》2004,10(1):134-138
About 1 monolayer of palladium was deposited onto a silicon (111) 7 x 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 x 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 x 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 x 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 x 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 x 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described. 相似文献