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1.
2.
Tohru OishiHiroshi Tsuchikawa Michio Murata Manabu YoshidaMasaaki Morisawa 《Tetrahedron letters》2003,44(34):6387-6389
A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity. 相似文献
3.
Time-resolved cavity ringdown (τ-CRD) spectroscopy has been applied to monitor the silyl (SiH3) radicals and nanoparticles in a pulsed very high frequency (VHF) silane-hydrogen plasma under microcrystalline silicon (μc-Si:H) deposition conditions. The measured cavity loss reveals four time intervals (I up to VI) in the first 4 s of the plasma pulse. By variation of the laser wavelength, it is demonstrated that the small cavity loss at 220 nm reflects the SiH3 absorption in interval I. In intervals II and III, an additional cavity loss appears. This additional cavity loss corresponds to Rayleigh and Mie scattering by growing nanoparticles. Interval IV reflects the loss of nanoparticles between the electrodes during the afterglow of the plasma pulse. The evolution of the nanoparticle generation determined from the τ-CRD measurements are further confirmed by additional scanning electron microscopy analyses on the nanoparticles created in the plasma pulse. 相似文献
4.
Shigeru Katayama Mika Horiike Kazuyuki Hirao Naoto Tsutsumi 《Journal of Polymer Science.Polymer Physics》2002,40(24):2800-2806
We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002 相似文献
5.
Six sulfonazo-III isomers were synthesized, and their color reactions with alkaline earth metals and lanthanum investigated. All six reagents had good sensitivities for lanthanum (? = 1.9–5.0·104), but the sensitivities for alkaline earth metals were fairly low except for the barium chelate of sulfonazo-III (? = 2.8 · 104). The position of the sulfo group on the phenyl ring and the symmetry of the reagent are important for the barium reactions, but of little significance for the lanthanum reactions. The effects of water-miscible solvents are also described. 相似文献
6.
We prepared novel zinc 8-ethyl-8-methyl-7-oxo- and 7-ethyl-7-methyl-8-oxo-bacteriochlorins 1 and 2 possessing substituents characteristic of chlorosomal chlorophylls, exclusively observed in extramembraneous light-harvesting antennas of photosynthetic green bacteria. The electronic absorption spectra of monomeric 1 and 2 in THF were obviously different: the Q(y) maximum of the former was 724 and that of the latter was 683 nm. This observed spectral difference was clearly explained by theoretical ZINDO/S calculation of their energetically minimized molecules. The optical properties of monomeric 1/2 were controlled by the electronic effect of the 7/8-oxo groups. Specific spectral changes in the electronic, CD, and FT-IR absorption spectra by dilution of the monomeric THF solutions of 1/2 with a 100/200-fold volume of cyclohexane showed the formation of chlorosomal self-aggregation species constructed by 13-C=O...H-O(3(1))...Zn and pi-pi stacking. Especially, the red-shift values in the Q(y) band of 1/2 by self-aggregation were 2450/1970 cm(-1), indicating that exciton interaction among the composite molecules in the self-aggregation of 1 was stronger than in those of 2. Molecular model calculations for dodecamers of 1/2 based on a parallel chain arrangement gave partially different supramolecular structures; the specific hydrogen-bonding distances in 2-dodecamer were larger than those of 1-dodecamer, while both coordinations gave the same Zn-O distance. These modeling results showed that 1 was more tightly packed in the self-aggregates to give a larger red-shift value in the Q(y) band by self-aggregation than 2. The difference in the supramolecular structures is mainly ascribable to the steric effect of 8/7-dialkyl groups in self-aggregates of 1/2. 相似文献
7.
Matsumori N Yamaji N Matsuoka S Oishi T Murata M 《Journal of the American Chemical Society》2002,124(16):4180-4181
Polyenemacrolides such as amphotericin B (AmB) were thought to assemble together and form an ion channel across plasma membranes. Their antimicrobial activity has been accounted for by this assemblage, whose stability and activity are dependent on sterol constituents of lipid bilayer membranes. The structure of this channel-like assemblage formed in biomembranes has been a target of extensive investigations for a long time. For the first step to this goal, we prepared several AmB dimers with various linkers and tested for their channel-forming activity. Among these, AmB dimers that bore an aminoalkyl-dicarboxylate tether covalently linked between amino groups of AmB showed potent hemolytic activity. Furthermore, K+ influx actions monitored by measuring the pH of the liposome lumen by 31P NMR revealed that the dimers formed the molecular assemblage similar to that of AmB in phospholipid membrane. Judging from changes in 31P NMR spectra, the dimers appeared to induce "all-or-none"-type ion flux across the liposome membrane in the presence of ergosterol, which suggested that the ion channel formed by ergosterol/dimer is similar to that of AmB. With these data in hand, we are now trying to elucidate the structure of the ion-channel complex by making the labeled conjugates of AmB for NMR measurements. 相似文献
8.
Amphotericin B (AmB 1) is known to assemble together and form an ion channel across biomembranes. The antibiotic consists of mycosamine and macrolactone moieties, whose relative geometry is speculated to be determinant for the drug's channel activity and sterol selectivity. To better understand the relationship between the amino-sugar orientation and drug's activity, we prepared conformation-restricted derivatives 2-4, in which the amino and carboxyl groups were bridged together with various lengths of alkyl chains. K+ influx assays across the lipid-bilayer membrane revealed that ergosterol selectivity was markedly different among derivatives; short-bridged derivative 2 almost lost the selectivity, while 3 showed higher ergosterol preference than AmB itself. Monte Carlo conformational analysis of 2-4 based on NOE-derived distances indicated that the amino-sugar moiety of 2 comes close to C41 because of the short bridge, whereas those of 3 and 4 are pointing outward. The mutual orientation of the amino-sugar moiety and macrolide ring is so rigid in derivatives 2 and 3 that these conformations should be unchanged upon complex formation in lipid membranes. These results strongly suggest that the large difference in sterol preference between derivatives 2 and 3 is ascribed to the different orientation of amino-sugar moieties. These findings allowed us to propose a simple model accounting for AmB-sterol interactions, in which hydrogen bonding between 2'-OH of AmB and 3beta-OH of ergosterol plays an important role. 相似文献
9.
Shigendo?Enomoto Ken-ichi?Kumagai Taro?Tamura Miki?Hasegawa Kyoko?Nakada Toshihiko?Hoshi Michio?KobayashiEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):471-481
Summary. Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The 1H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the 1H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of CS symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the 1H NMR spectral shifts mentioned above and the experimentally predicted CS structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure. 相似文献
10.
A NKT cell repertoire is characterized by the expression of the Valpha19-Jalpha26 invariant TCR alpha chain (Valpha19 NKT cell). This repertoire, as well as a well-established Valpha14-Jalpha281 invariant TCR alpha(+) NKT cell subset (Valpha14 NKT cell), has been suggested to have important roles in the regulation of the immune system and, thus, is a major therapeutic target. Here, we attempted to find specific antigens for Valpha19 NKT cells. Valpha19 as well as Valpha14 NKT cells exhibited reactivity to alpha-galactosyl ceramide (alpha-GalCer). Thus, a series of monoglycosyl ceramides with an axially oriented glycosidic linkage between the sugar and ceramide moiety were synthesized and their antigenicity to Valpha19 NKT cells was determined by measuring their immune responses in culture with glycolipids. Comprehensive examinations revealed substantial antigenic activity for Valpha19 NKT cells by alpha-mannosyl ceramide. 相似文献