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A microstructured ionic crystal, K(3)[Cr(3)O(OOCH)(6)(H(2)O)(3)][alpha-SiW(12)O(40)].16 H(2)O (1) was synthesized by the complexation of the Keggin-type polyoxometalate of [alpha-SiW(12)O(40)](4-) with a macrocation of [Cr(3)O(OOCH)(6)(H(2)O)(3)](+). Compound 1 possessed a straight channel, with an opening of approximately 0.5x0.8 nm, which contained the water of crystallization. The use of the macrocation with large size (0.7 nm) and small charge (+1) reduced the anion-cation interaction and was essential for the channel formation. The molecular structures of the polyoxometalate and the macrocation in 1 were retained under vacuum at 473 K. Analogues of 1 were synthesized with [alpha-PVW(11)O(40)](4-) or [Fe(3)O(OOCH)(6)(H(2)O)(3)](+). The water of crystallization in 1 was removed under vacuum at room temperature to form the closely packed guest-free phase 2. Compound 2 reversibly and repeatedly included water and polar organic molecules with two carbon atoms or less. Guest inclusion was highly selective and a difference of even one methylene group in the organic guest molecule was discriminated by the host. Polar organic molecules with longer methylene chains and nonpolar molecules such as dinitrogen and methane were completely excluded. The guest-inclusion properties could be explained by the ion-dipole interaction between the host and the guest, which is proportional to the dipole moment of the guest molecule and inversely proportional to the ion-dipole (host-guest) distance. Thus, small polar molecules were selectively absorbed. These distinctive guest-inclusion properties were successfully applied to the oxidation of methanol from a mixture of C(1) and C(2) alcohols. These results show unique guest inclusion and catalysis by rationally designed ionic crystals. 相似文献
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Usui T Kazami S Dohmae N Mashimo Y Kondo H Tsuda M Terasaki AG Ohashi K Kobayashi J Osada H 《Chemistry & biology》2004,11(9):1269-1277
The actin-targeting toxins have not only proven to be invaluable tools in studies of actin cytoskeleton structure and function but they also served as a foundation for a new class of anticancer drugs. Here, we describe that amphidinolide H (AmpH) targets actin cytoskeleton. AmpH induced multinucleated cells by disrupting actin organization in the cells, and the hyperpolymerization of purified actin into filaments of apparently normal morphology in vitro. AmpH covalently binds on actin, and the AmpH binding site is determined as Tyr200 of actin subdomain 4 by mass spectrometry and halo assay using the yeast harboring site-directed mutagenized actins. Time-lapse analyses showed that AmpH stimulated the formation of small actin-patches, followed by F-actin rearrangement into aggregates via the retraction of actin fibers. These results indicate that AmpH is a novel actin inhibitor that covalently binds on actin. 相似文献
156.
Electrochemical synthesis of layered manganese oxides intercalated with tetraalkylammonium ions 总被引:2,自引:0,他引:2
Nakayama M Konishi S Tagashira H Ogura K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):354-359
Thin films of birnessite-type layered manganese oxides with various interlayer spacings have been prepared on a platinum electrode by a one-step electrochemical procedure. The process involves a potentiostatic oxidation of aqueous Mn(2+) ions at around +1.0 V (Ag/AgCl) in the presence of tetraalkylammonium cations with different alkyl chain lengths. X-ray diffraction indicates that the films deposited with tetrabutylammonium (TBA), tetrapropylammonium (TPA), and tetraethylammonium (TEA) ions are composed of a single phase where unhydrated tetraalkylammonium ions are accommodated as a monolayer between manganese oxide layers. The interlayer spacing of the products increases in an order of TEA < TPA < TBA. The film deposited with tetramethylammonium (TMA) is a mixture of two phases relating to hydrated and unhydrated guest cations, the former being predominant probably as a result of less hydrophobic property of TMA compared to that of other tetraalkylammonium ions. The TBA(+)-intercalated Mn oxide film-coated electrode exhibits a good charge/discharge property in a KCl solution between 0 and +0.8 V. In this case, TBA(+) ions between the Mn oxide layers are rapidly replaced with K(+) in solution by ion exchange, accompanying a shrinkage of the interlayer. The incorporated K(+) ions as well as protons play an important role in the electrochemical conversion between Mn(4+) and Mn(3+) in the oxide layer. In the TBACl solution, the interlayer TBA(+) ions can be excluded electrochemically during the positive-going scan, concomitant with the oxidation of Mn(3+) sites. This causes an anodic current and the accompanying shrinkage of the interlayer. On the reverse scan, however, the compressed interlayer does not allow the incorporation of bulky TBA(+) ions from the electrolyte, with virtually no cathodic current observed. Such an obvious difference in electrochemical behavior between the two electrolytes can be recognized by considering that most of the Mn oxide surface is present inside the layered structure, not on the external surface. This indicates that the layered structure is formed over the entire film. 相似文献
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Kinoshita S Kinoshita H Iwamura T Watanabe S Kataoka T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(7):1496-1502
Reactions of but-3-yn-2-one (2) with aldehydes 1 in the presence of a Lewis acid and dimethyl sulfide (3 a) predominantly gave (E)-alpha-(halomethylene)aldols 4-5 in high yields, while reactions of methyl propiolate (6 a) mainly afforded (Z)-3-halogeno-2-(hydroxymethyl)acrylates 7-8 in low to moderate yields. A reaction of dimethyl acetylenedicarboxylate (10) with 1 a in the presence of TiCl(4) and 1,1,3,3-tetramethylthiourea (3 c) produced maleate (E)-11 (40 %) and butenolide 12 (40 %). When a reaction of 6 a with 1 a was carried out in the presence of TiBr(4) and 3 a (0.2 equiv) at -20 degrees C for 60 h, 3-(methylthio)-2-(hydroxyalkyl)acrylate 9 a was obtained in an 8 % yield. Experiments were conducted in order to elucidate the formation mechanism of 9 a, and it was made clear that 9 a was formed via the processes of the Michael addition of sulfide 3 a to alkynoate 6 a and an aldol reaction with 1 a and demethylation. 相似文献
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Yamana K Fukunaga Y Ohtani Y Sato S Nakamura M Kim WJ Akaike T Maruyama A 《Chemical communications (Cambridge, England)》2005,(19):2509-2511
A pyrene-excimer-forming probe allowed the easy and sensitive detection of a single base mismatch in target DNA. This was due to the faster strand exchange rate compared to a fully-matched target. 相似文献
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Mitsunori Oda Kazutaka Ogura Sayaka Kishi Kunihide Fujimori Noritaka Abe 《Tetrahedron letters》2007,48(26):4471-4475
The title azaazulene 3 was synthesized either by reaction of tropone with N-{(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S1 state but from the S2 state like azulene does, the protonated species of 3 exhibited emission from the S1 state. Cationic metal-dependent absorption and emission relating to complexation were also studied. 相似文献
160.
Matsushita S Yanai Y Fusyuku A Ikeda T Ono M Nohara T 《Chemical & pharmaceutical bulletin》2007,55(7):1079-1081
It has been revealed that the absolute configurations at C-22 of 23-hydroxyspirostane and 23-hydroxyspirosolane could be unambiguouly judged by the (1)H- and (13)C-NMR spectroscopies. 相似文献