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951.
952.
Eiji Tanahashi Kyoko Fukunaga Yuko Ozawa Tsuyoshi Toyoda Hidcharu Ishida Makoto Kiso 《Journal of carbohydrate chemistry》2013,32(6):747-768
ABSTRACT A series of sialyl-α-(2→3)-neolactotetraose derivatives containing N-acetyl-(NeuAc), N-glycolyl- (NeuGc) and N-butanoylneuraminic acid, and 3-deoxy-D-glycero-D-galacto-2-nonulosonic acid (KDN) have systematically been synthesized as molecular probes for elucidation of substrate specificity of human α1,3-fucosyltransferases (Fuc-TVII and Fuc-TVI). 2-Methyl-(3,4,6-tri-O-acetyl-1,2-dideoxy-α-D-glucopyrano)-[2',1':4,5]-2-oxazoline (1) was coupled with 2-(trimethylsilyl)ethyl (2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1 → 4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (2) to give a trisaccharide 3 which, upon successive O-deacetylation, benzylidenation and reductive opening of the benzylidene group, afforded a common glycosyl acceptor 5. Glycosylation of 5 with sialyl-α-(2→3)-galactose donors 6-8, 19 and 21 gave the corresponding pentasaccharides 22-25, which were converted to a series of sialyl-α-(2→3)-neolactotetraose derivatives 30-33. In the competitive enzyme assay, the NeuGc derivative 32 showed the most potent activity for Fuc-TVII, while the KDN derivative 31 was less active than the standard NeuAc derivative 30. In contrast, the N-butanoylation of neuraminic acid enhanced the activity for Fuc-TVI. 相似文献
953.
Takaoka Y Tsutsumi H Kasagi N Nakata E Hamachi I 《Journal of the American Chemical Society》2006,128(10):3273-3280
A new and simple method to tether a functional molecule at the proximity of the active site of an enzyme has been successfully developed without any activity loss. The one-pot sequential reaction was conducted on a surface of human carbonic anhydrase II (hCAII) based on the affinity labeling and the subsequent hydrazone/oxime exchange reaction. The reaction proceeds in a greater than 90% yield in the overall steps under mild conditions. The enzymatic activity assay demonstrated that the release of the affinity ligand from the active site of hCAII concurrently occurred with the replacement by the aminooxy derivatives, so that it restored the enzymatic activity from the completely suppressed state of the labeled hCAII. Such restoring of the activity upon the sequential modification is quite unique compared to conventional affinity labeling methods. The peptide mapping experiment revealed that the labeling reaction was selectively directed to His-3 or His-4, located on a protein surface proximal to the active site. When the fluorescent probe was tethered using the present sequential chemistry, the engineered hCAII can act as a fluorescent biosensor toward the hCAII inhibitors. This clearly indicates the two advantages of this method, that is (i) the modification is directed to the proximity of the active site and (ii) the sequential reaction re-opens the active site cavity of the target enzyme. 相似文献
954.
Maeda K Mochizuki H Watanabe M Yashima E 《Journal of the American Chemical Society》2006,128(23):7639-7650
A series of novel phenylacetylenes bearing optically active cyclodextrin (CyD) residues such as alpha-, beta-, and gamma-CyD and permethylated beta-CyD residues as the pendant groups was synthesized and polymerized with a rhodium catalyst to give highly cis-transoidal poly(phenylacetylene)s, poly-1alpha, poly-2beta, poly-3gamma, and poly-2beta-Me, respectively. The polymers exhibited an induced circular dichroism (CD) in the UV-visible region of the polymer backbones, resulting from the prevailing one-handed helical conformations. The Cotton effect signs were inverted in response to external chiral and achiral stimuli, such as temperature, solvent, and interactions with chiral or achiral guest molecules. The inversion of the Cotton effect signs was accompanied by a color change due to a conformational change, such as inversion of the helicity of the polymer backbones with a different twist angle of the conjugated double bonds, that was readily visible with the naked eye and could be quantified by absorption and CD spectroscopies. The dynamic helical conformations of poly-2beta showing opposite Cotton effect signs in different solvents could be further fixed by intramolecular cross-linking between the hydroxy groups of the neighboring beta-CyD units in each solvent. The cross-link between the pendant CyD units suppressed the inversion of the helicity; therefore, the cross-linked poly-2betas showed no Cotton effect inversion, although the polymer backbones were still flexible enough to alter their helical pitch with the same handedness, resulting in a color change depending on the degree of intramolecular cross-linking. 相似文献
955.
Poly[1,2,(4)-phenylenevinyleneanisylaminium] 1 was synthesized by one-pot palladium-catalyzed polycondensation of N-(3-bromo-4-vinylphenyl)-N-(4-methoxyphenyl)-N-(4-vinylphenyl)amine 3 and subsequent oxidation with the thianthrene cation radical tetrafluoroborate: compound 1 three-directionally satisfies a non-Kekulé-type pi-conjugation and the ferromagnetic connectivity of the unpaired electrons of the triarylaminium cationic radical. The average molecular weight of the polymer was 4700-5900 (degree of polymerization = 11-14), which gave a single molecular-based and globular-shaped image of ca. 15 nm diameter by atomic and magnetic force microscopies under ambient conditions. The aminium polyradical 1 with a spin concentration (determined by iodometry) of 0.65 spin/unit displayed an average S (spin quantum number) value of 7/2 even at 70 degrees C according to NMR and magnetization measurements. 相似文献
956.
Magnetic and specific heat measurements were performed in a single-phased powder BiMnO3 sample prepared at 6 GPa and 1383 K. The imaginary part of the ac susceptibilities showed strong frequency dependence below the ferromagnetic Curie temperature of 98 K. The relaxation measurements revealed time-dependent magnetic properties below 98 K. These data indicate the appearance of a "spin-glass-like" state in BiMnO3. Specific heat measurements showed the existence of ferromagnetic spin waves. However, no simple term Cm [directly proportional] T3/2 was found indicating an unconventional behavior of the magnetic specific heat. The Debye temperature was estimated to be 410 K using isostructural compounds BiScO3 and BiCrO3. 相似文献
957.
Sakata Y Shiraishi S Takayama K Otsuka M 《Colloids and surfaces. B, Biointerfaces》2006,53(2):149-156
The effects of heat conduction and pulverization on dehydration kinetics and tablet hardness were studied by a variety of kinetic equations and physical models. The dehydration behavior of unpulverized calcium lactate pentahydrate (UCLP) and pulverized calcium lactate pentahydrate (PCLP) tablets was investigated by using differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). The hardness of both UCLP and PCLP tablets was significantly decreased after dehydration. The relationship between the extent of dehydration and the tablet hardness of both UCLP and PCLP tablets was linear. The results suggest that the reduction in tablet hardness is dependent on the dehydration of crystal water, and the values of the slopes indicate that the bonding energy of the UCLP was stronger than that of the PCLP. The dehydration of both UCLP and PCLP tablets at 55 °C followed a one-dimensional diffusion mechanism, whereas dehydration at storage temperatures of 60–80 °C followed a three-dimensional diffusion mechanism. UCLP and PCLP tablets contracted in thickness and diameter during dehydration, but final contraction ratios showed that PCLP tablets were more affected than UCLP tablets. In contrast, the micropore radius of both UCLP and PCLP tablets increased after dehydration. Thus, the pharmaceutical properties of calcium lactate pentahydrate (CLP) tablets are affected both by pulverization and by the extent of dehydration of the bulk powder in the tablet formulation. 相似文献
958.
Hideki Abe Akira Satoh Kenji Nishida Eiji Abe Takashi Naka Motoharu Imai Hideaki Kitazawa 《Journal of solid state chemistry》2006,179(5):1521-1524
The development of a disposal technique for the radiotoxic 137Cs in nuclear wastes is one of the most urgent issues in nuclear fuel technology. An effective disposal method of 137Cs is to immobilize it in a synthetic rock (SYNROC) material: cesium titanate hollandite, 137CsxTi8O16 (I4/m, , ). Practical applications of 137CsxTi8O16 have been restricted so far because the conventional synthetic method requires strong chemical reducers and reaction temperatures higher than 1250 °C. In this report, we present a milder preparation method of CsxTi8O16 by electrolysis of a mixture of Cs2MoO4 and TiO2 in ambient atmosphere at 900 °C. The Cs content in the resultant single-crystalline Cs1.35Ti8O16 is competitive with the highest value in polycrystalline Cs1.36±0.03Ti8O16 prepared by the conventional synthetic method. The electrochemical preparation of Cs1.35Ti8O16 is a promising way to immobilize a high quantity of 137Cs ions in a stable form of single-crystalline SYNROC. 相似文献
959.
We describe novel optically active double helices consisting of complementary strands stabilized by amidinium-carboxylate salt bridges. The m-terphenyl groups of each strand are joined by trans-Pt(II) acetylide complexes with pendant PPh(3) ligands as the surrogate linker, which converts to cis counterparts by a ligand exchange reaction with cis-1,2-bis(diphenylphosphino)ethylene, resulting in the formation of double helices with different structures. Subsequent iodine-promoted reductive elimination on the Pt(II) atoms generates the fully organic, enantiomerically pure double helices. [structure: see text] 相似文献
960.
[reaction: see text] A new triradical molecule, 2,6,10-tris(dianisylaminium)-3,7,11-tris(hexyloxy)triphenylene 1(3+), was synthesized by oxidative trimerization, palladium-catalyzed amination, and subsequent oxidation. It was chemically stable with a half-life > 1 month and displayed the magnetic parameter of S = 3/2 even at room temperature. 相似文献