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441.
442.
443.
K Tsuzuki T Sunazuka S Marui H Toyoda S Omura N Inatomi Z Itoh 《Chemical & pharmaceutical bulletin》1989,37(10):2687-2700
Chemical modifications of 8,9-anhydroerythromycin A 6,9-hemiacetal (1), which showed gastrointestinal motor stimulating (GMS) activity 10 times more potent than that of erythromycin A (EM-A), were undertaken to search for derivatives having stronger GMS activity and no antimicrobial activity; details are described in this and a subsequent paper. Displacement of a methyl group of the dimethylamino group of 1 with an ethyl group and an isopropyl group provided de(N-methyl-N-ethyl-8,9-anhydroerythromycin A 6,9-hemiacetal (55) and de(N-methyl)-N-isopropyl-8,9-anhydroerythromycin A 6,9-hemiacetal (58), respectively. They showed significant GMS activity and no antibacterial activity. In particular, the GMS activity of 58 was increased to 248 times that of EM-A. EM-A and the derivatives obtained in this study mimic exogenous motilin in the dog. The name "motilide", meaning a motilin-like macrolide, is proposed for this new family of macrolide compounds. 相似文献
444.
Kazushige Hori Mina Tamura Keita Tani Nagatoshi Nishiwaki Masahiro Ariga Yasuo Tohda 《Tetrahedron letters》2006,47(18):3115-3118
Asymmetric epoxidation of (E)-chalcone with alkaline hydrogen peroxide by novel chiral phase-transfer catalysts (chiral PTCs) with quaternary ammonium salts of azacrown ether proceeded in high yield and good enantioselectivity. Remarkably, this reaction depended on the length of the carbon chain on the nitrogen atom with the chiral PTCs and on the bulk of the base. 相似文献
445.
Omura Y Okazaki N 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(8):1895-1904
In monitoring the time course of conformational disorder by Fourier transform infrared spectroscopy for intact Acholeplasma laidlawii cells grown at 37 degrees C on binary fatty acid mixtures containing oleic acid and for cells grown on pure palmitic acid, an absorption band at 2343 cm(-1) was observed. The band intensity was found to increase with time. This band was not observed in the spectra for isolated membranes. It is suggested that the 2343 cm(-1) band is due to CO(2) dissolved in water, most likely produced at the final point of fermentation of amino acid by this microorganism. 相似文献
446.
Akai S Naka T Omura S Tanimoto K Imanishi M Takebe Y Matsugi M Kita Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4255-4264
The first lipase-catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (+/-)-3 with a 1-ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels-Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one-pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7-oxabicyclo[2.2.1]heptene derivatives 5, which has five chiral, non-racemic carbon centers, from achiral 1 and racemic 3. The overall efficiency of this process was dependent on the substituent at the C-3 position of 3, and the use of the 3-methylfurfuryl derivatives, (+/-)-3 b and (+/-)-3 f, exclusively produced diastereoselectivity with excellent enantioselectivity to give (2R)-syn-5 (91->/=99 % ee) and (S)-3 (96->/=99 % ee). Similar procedures starting from the 3-bromofurfuryl alcohols (+/-)-3 h-j provided the cycloadducts (2R)-syn-5 j-q (93->/=99 % ee), in which the bromo group was utilized for the installation of bulky substituents to the 7-oxabicycloheptene core. 相似文献
447.
The effect of pixel size on image quality was investigated. The image quality was examined by abnormality detection and image preference for clinical images displayed with different pixel sizes. Smaller pixel size was found to be superior to large one in image quality using large field of gamma camera (FWHM 6.42 mm), 1.6mm pixel size (a 256 x 256 matrix) was found to be the best in image quality. Examined image minification effect, 3.2 mm pixel size (image size: 5 cm phi) was found to be superior to 1.6 mm pixel size (image size: 10 cm phi) in image preference and to be almost equal to 1.6 pixel size in abnormality detection. 相似文献
448.
Heat-set gel-like networks of lipophilic Co(II) triazole complexes in organic media and their thermochromic structural transitions 总被引:1,自引:0,他引:1
Kuroiwa K Shibata T Takada A Nemoto N Kimizuka N 《Journal of the American Chemical Society》2004,126(7):2016-2021
A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T(d)) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T(d) coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 degrees C. A pale pink solution is obtained at 0 degrees C, indicating the formation of octahedral (O(h)) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 degrees C, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 degrees C) and in the solution phase (temperature below 25 degrees C). These observations indicate that T(d) complexes are present as low-molecular weight species around at 25-27 degrees C. They are self-assembled to polymeric T(d) complexes by heating and form gel-like networks. Upon cooling the solution below 25 degrees C, T(d) complexes are converted to O(h) complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution --> blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires. 相似文献
449.
Lambert F Policar C Durot S Cesario M Yuwei L Korri-Youssoufi H Keita B Nadjo L 《Inorganic chemistry》2004,43(14):4178-4188
X-ray structures for six Fe(II) and Fe(III) complexes from two closely heptadentate N-tripodal ligands, L1H(3) = tris[(imidazol-4-yl)-3-aza-3-butenyl]amine and L2H(3) = tris[(imidazol-2-yl)-3-aza-3-butenyl]amine, are described: three complexes in the L1 series (namely, [Fe(II)(L1H(3))](2+) and [Fe(III)(L1H(3))](3+) at low pH and [Fe(III)(L1)](0) at high pH) and three complexes in the L2 series (namely, [Fe(II)(L2H(3))](2+) at low pH and [Fe(II)(L2H)](0) and [Fe(III)(L2)](0) at high pH). Most of these complexes are stable in both Fe(II) and Fe(III) redox states and with the ligand in various protonation states. In the solid state, hydrogen bonds networks were obtained. Structural differences induced by 2- or 4-imidazole substitution are described and discussed. In solution, interconversions between different forms, with regard to oxidation and protonation states, were investigated by UV-visible spectroscopy, cyclic voltammetry, and potentiometry. The deprotonation pattern of these polyimidazole iron(II) and iron(III) complexes is described in detail. pK(a)s of the imidazolate/imidazole moieties in MeOH/H(2)O are reported. Two new species, namely, [Fe(II)(L1)](-) and [Fe(II)(L2)](-), were shown to be obtained in DMSO upon strong base addition and characterized by UV-vis spectroscopy and cyclic voltammetry. Half-wave potentials of Fe(III)/Fe(II) complexes with ligand moieties in several protonation states are reported, both in DMSO and in MeOH/H(2)O. Because of the presence of free imidazole groups coordinated to the iron, the potential of the iron(III)/iron(II) couples can be tuned by pH. A shift of DeltaE = E(deprot) - E(prot) ranging from -270 to -320 mV per exchanged proton in DMSO was measured. This study shows moreover that interconversions (with regard to both redox and protonation states) can be reversed several times. As the complexes have been isolated in order to be tested as superoxide dismutase mimics, preliminary reactions with dioxygen and with superoxide, considered as oxidant and reducer of biological importance, are reported. In these two series, O(2)(-) behaves either as a base or as a reducer and no adducts have been observed. 相似文献
450.
Mbomekalle IM Keita B Nadjo L Berthet P Hardcastle KI Hill CL Anderson TM 《Inorganic chemistry》2003,42(4):1163-1169
Reaction of the trivacant lacunary complex, alpha-Na(12)[As(2)W(15)O(56)], with an aqueous solution of Fe(NO(3))(3).9H(2)O yields the sandwich-type polyoxometalate, alphabetabetaalpha-Na(12)(Fe(III)OH(2))(2)Fe(III)(2)(As(2)W(15)O(56))(2) (Na1). The structure of this complex, determined by single-crystal X-ray crystallography (a = 13.434(1) A, b = 13.763(1) A, c = 22.999(2) A, alpha = 90.246(2) degrees, beta = 102.887(2) degrees, gamma = 116.972(1) degrees, triclinic, Ponemacr;, R1 = 5.5%, based on 25342 independent reflections), consists of an Fe(III)(4) unit sandwiched between two trivacant alpha-As(2)W(15)O(56)(12)(-) moieties. UV-vis, infrared, cyclic voltammetry, and elemental analysis data are all consistent with the structure determined from X-ray analysis. Magnetization studies confirm that the four Fe(III) centers are antiferromagnetically coupled. A cyclic voltammogram of Na1 reveals that a three-wave W(VI) system replaces the two-wave W(VI) system found in the precursor alpha-As(2)W(15)O(56)(12)(-) complex. The observed modifications in the CV patterns of Na1 and alpha-As(2)W(15)O(56)(12)(-) are most likely due to subsequent changes in the acid-base properties of two reduced POMs that occur as a result of Fe(III) incorporation. Na1 is shown to be more efficient than the monosubstituted complex alpha(2)-As(2)(Fe(III)OH(2))W(17)O(61)(7)(-) in the electrocatalytic reduction of dioxygen. This is attributed to cooperativity effects among the adjacent Fe(III) centers in Na1. 相似文献