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1.
Hiroyuki Suga Satoshi Higuchi Daisuke Ishimoto Yuta Hashimoto Teruko Tsuchida Toshihide Baba 《Tetrahedron》2010,66(16):3070-6287
High enantioselectivities (94-96% ee) were obtained for the inverse electron-demand 1,3-dipolar cycloadditions between cyclohexyl vinyl ether and 2-benzopyrylium-4-olate generated via Rh2(OAc)4-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone. The reactions were effectively catalyzed by Eu(OTf)3, Ho(OTf)3, or Gd(OTf)3 complexes (10 mol %) of chiral 2,6-bis[(4S,5S)-4,5-diphenyl-2-oxazolinyl]pyridine. The reactions with the other electron-rich dipolarophiles such as allyl alcohol, 2,3-dihydrofuran, and butyl-tert-butyldimethylsilylketene acetal showed moderate enanantioselectivities (60-73% ee). Good to high enantioselectivities (73-97% ee) were also obtained for the cycloadditions between 3-acyl-2-benzopyrylium-4-olates, generated from methyl 2-(2-diazo-1,3-dioxoalkyl)benzoates and butyl or cyclohexyl vinyl ethers, in the presence of binaphthyldiimine (BINIM)-Ni(II) complexes (10 mol %). Under similar conditions, the reaction between methyl 2-(2-diazo-1,3-dioxohexyl)benzoate and 2,3-dihydrofuran was highly endo-selective, and moderately enantioselective (70% ee). For the BINIM-Ni(II)-catalyzed reactions of cyclohexyl vinyl ether, the use of an epoxyindanone as the 3-acyl-2-benzopyrylium-4-olate precursor revealed that the chiral Lewis acid can function as a catalyst for asymmetric induction. The scope of the cyclic carbonyl ylides was extended to those generated from 1-diazo-2,5-pentanedione derivatives, which were reacted with butyl or TBS vinyl ether and catalyzed using the (4S,5S)-Pybox-4,5-Ph2-Lu(OTf)3 complex to give good levels of asymmetric inductions (75-84% ee). 相似文献
2.
Masakuni Tako Takeshi Teruya Yukihiro Tamaki Teruko Konishi 《Colloid and polymer science》2009,287(12):1445-1454
The 1H-nuclear magnetic resonance spectrum showed that the l-rhamnosyl residues of native gellan gum were coinvolved in both a small number of 4C1-pyranose conformations and a large number of 1C4-pyranose conformations, whereas for deacylated polymer, almost of the residues were involved in 4C1-pyranose conformation. The flow curves of native gellan gum showed plastic behavior above 0.2%. The elastic modulus stayed
at a constant value with increase in temperature up to 40 °C, then decreased rapidly. The elastic modulus increased with addition
of CaCl2 (6.8 mM) and stayed constant value with increase in temperature up to 65 °C, then decreased rapidly. The stronger elastic
modulus was observed in deacylated gellan gum with addition of CaCl2. The elastic modulus of native gellan gum showed larger value than that in aqueous solution in the presence of urea (4.0 M).
Intra- and intermolecular associations of native gellan gum molecules in the presence of Ca+2 were proposed. 相似文献
3.
Hiroshi Kamioka Yoshihito Ishihara Hans Ris Sakhr A Murshid Yasuyo Sugawara Teruko Takano-Yamamoto Soo-Siang Lim 《Microscopy and microanalysis》2007,13(2):108-117
The inaccessibility of osteocytes due to their embedment in the calcified bone matrix in vivo has precluded direct demonstration that osteocytes use gap junctions as a means of intercellular communication. In this article, we report successfully isolating primary cultures of osteocytes from chick calvaria, and, using anti-connexin 43 immunocytochemistry, demonstrate gap junction distribution to be comparable to that found in vivo. Next, we demonstrate the functionality of the gap junctions by (1) dye coupling studies that showed the spread of microinjected Lucifer Yellow from osteoblast to osteocyte and between adjacent osteocytes and (2) analysis of fluorescence replacement after photobleaching (FRAP), in which photobleaching of cells loaded with a membrane-permeable dye resulted in rapid recovery of fluorescence into the photobleached osteocyte, within 5 min postbleaching. This FRAP effect did not occur when cells were treated with a gap junction blocker (18alpha-glycyrrhetinic acid), but replacement of fluorescence into the photobleached cell resumed when it was removed. These studies demonstrate that gap junctions are responsible for intercellular communication between adjacent osteocytes and between osteoblasts and osteocytes. This role is consistent with the ability of osteocytes to respond to and transmit signals over long distances while embedded in a calcified matrix. 相似文献
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Teruko Imai Tetsumi Irie Masaki Otagiri Kaneto Uekama Masaki Yamasaki 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):597-604
Abstruct Some physicochemical properties of methylated -cyclodextrins, i.e., heptakis(2,6-di-O-methyl)--cyclodextrin (DM--CyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CyD) were compared with those of natural -cyclodextrin (-CyD). Inclusion behaviors of -CyD and methylated -CyDs in water and in solid state were studied by solubility analysis, spectroscopies (UV, CD,13C-NMR and IR), X-ray diffractometry and thermal analysis, using an antiinflammatory drug flurbiprofen (FP) as a guest molecule. The spectral data suggest that the inclusion mode of FP-TM--CyD is somewhat different from those of FP--CyD and FP-DM--CyD. The solid complexes of FP with - and methylated -CyDs were obtained in molar ratio of 11, and their dissolution behavior and release from suppository base were examined. The data are presented suggesting that DM--CyD is particularly useful for improving the pharmaceutical properties of FP in various dosage forms. 相似文献
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Kazuaki Harata Kaneto Uekama Teruko Imai Fumitoshi Hirayama Masaki Otagiri 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(5):443-460
Hepatakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CDx) forms crystalline complexes with (R)-Flubiprofen (R-FP), C63H112O35C15H13O2F·H2O, and (S)-Flurbiprofen (S-FP), C63H112O35C15H13O2F. The crystal structures were determined by X-ray analysis. Crystals of both compounds are orthorhombic and the space group isP212121 with cell dimensions:a=15.092(2),b=21.714(3), andc=28.269(4) Å for theR-FP complex, anda=15.271(2),b=21.451(3) andc=27.895(3) Å for theS-FP complex. The macrocyclic ring of TM--CDx is markedly distorted because of the inability to form intramolecular hydrogen bonds and the steric hindrance involving methyl groups. In both complexes, the phenyl group is inserted into the host cavity from the O(2), O(3) side, which is wider than the O(6) side. The biphenyl moiety ofR-FP is fixed in theR-configuration within the host cavity. The phenyl group ofS-FP is disordered, andR-andS-configurations are statistically distributed with equal probability. TM--CDx molecules are stacked along theb axis to form a column structure. The TM--CDx molecule is laterally shifted with respect to the column axis, and a half of the guest molecule protrudes outside from the crevis of the column. The carboxyl group ofR-FP forms a hydrogen bond with water located outside the host cavity, while the carboxyl group ofS-FP is hydrogen-bonded to an oxygen atom of an adjacent TM--CDx.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82064 (24 pages). 相似文献
8.
Mikio Fujii Taiki Kuramochi Yuhi Nakakuki Rina Hatazawa Kiju Konno Tatsuo Munakata Yasuaki Hirai 《Tetrahedron letters》2019,60(10):721-725
Gentianine is a metabolite of gentiopicroside and swertiamarin. Several biological activities have been reported for gentianine, such as antiinflammatory and antidiabetic activity, and hypotensive effect. Gentiopicroside is found in 0.9–9.8% content in Gentian root or Gentian scabra root, and Swertiamarin is contained in Swertia herb in 2–10%. These natural products can be potential starting materials for the synthesis of gentianine. This study describes the β-glucosidase-catalyzed hydrolysis of gentiopicroside and swertiamarin in the presence of hydroxylamine to afford gentianine N-oxide, which can be a synthetic precursor of gentianine derivatives. Enzymatic hydrolysis of swertiamarin selectively afforded gentianine N-oxide in 81% yield, whereas gentiopicroside afforded gentianine N-oxide and gentianol N-oxide. Plausible reaction pathways leading to gentianine, gentianol, and their N-oxides were also investigated. 相似文献
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Hisaki Kojima Minoru Inagaki Tsuyoshi Tomita Teruko Watanabe 《Rapid communications in mass spectrometry : RCM》2010,24(1):43-48
The lipopolysaccharide (LPS) of enterobacteria frequently contains various numbers of charged non‐stoichiometric substituents such as phosphate (P) and ethanolamine (EtN) groups and a third residue of 3‐deoxy‐D ‐manno‐2‐octulosonic acid (KDO) on the R‐core polysaccharide backbone. These substituents can modify the biological activities of LPS including varying the stability of the outer membrane, tolerance to cationic antibiotics, pathogenicity, and sensitivity to enterobacteria bacteriophages. These diverse substituents can be clearly detected in degraded samples of LPS from E. coli C using electrospray ionization single quadrupole mass spectrometry (ESI‐Q‐MS) from a 0.1 mg/mL solution in a 50:50 mixture of methanol and 10 mM ammonium acetate (pH 6.8). The O‐deacylated derivative showed multiple peaks of [M–3H]3? ions which corresponded to species having up to eight phosphates, two ethanolamines, and an additional KDO on the backbone of Hex5 Hep3 KDO2 GlcN2 C14:0(3‐OH)2. The major components of the O,N‐deacylated derivative were the species associated with four and five phosphates on Hex5 Hep3 KDO2 GlcN2. The polysaccharide portion of LPS also revealed species which corresponded to Hex5 Hep3 KDO associated with two to four phosphates and an ethanolamine. The present method was proved to be useful to investigate the structural diversity of enterobacterial LPS. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献