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21.
Matsuda R Kitaura R Kitagawa S Kubota Y Kobayashi TC Horike S Takata M 《Journal of the American Chemical Society》2004,126(43):14063-14070
In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds. 相似文献
22.
1,1-Difluoroethysilanes (R3SiCF2CH3, R = Me or Et) were synthesized from 1,1-difluoroethyl phenyl sulfone and chlorosilanes using magnesium metal via reductive 1,1-difluoroethylation. It was confirmed that 1,1-difluoroethylsilanes were effective 1,1-difluoroethylating reagents for carbonyl compounds. 相似文献
23.
Sphingomyelinase (SMPLC) from Bacillus cereus was modified with a polyethylene glycol (PEG) derivative, methoxypolyethylene glycol-succinimidyl succinate (ss-PEG). The molecular weight of the ss-PEG-modified SMPLC was calculated to be approx. 150 kDa by gel-filtration whereas that of the native enzyme, was 25 kDa. By this modification, the enzyme increased its thermostability and retained its hydrolytic activity toward 2-(N-hexadecanoylamino)-4-nitrophenylphosphocholine (HNP) and sphingomyelin (SM) in the mixed micelles with the surfactants such as Triton X-100 and sodium deoxycholate (SDC). However, the activity toward liposomal SM was significantly decreased, and all the enzyme activities toward bovine erythrocytes, including membraneous SM-hydrolyzing and hemolytic activities as well as the enzyme adsorption onto the erythrocyte membranes, were completely lost. 相似文献
24.
The intercalation of 4-phenylazoaniline (PAA) in supercritical carbon dioxide (SC-CO(2)) into montmorillonite (TMA-Mnt) pillared with tetramethylammonium ions at 313 K and 15 MPa was investigated. The adsorption rate and equilibrium PAA uptake were compared with those in n-hexane, CCl(4) and benzene solutions at 313 K. The XRD and N(2) adsorption/desorption analyses showed that TMA-Mnt after adsorption of PAA in SC-CO(2) had the same pore structure as after adsorption of PAA in normal solvents. SC-CO(2) was found to be a good medium for PAA adsorption owing to its having a relatively high adsorption rate and the highest adsorptivity at the same PAA concentration. The properties of PAA adsorption on TMA-Mnt could be well elucidated by the difference in solubility parameters between liquid and solid phases. 相似文献
25.
The reversible transportation of droplets was realized by spatiotemporal control of the wetting gradient. The surface wetting was reversibly regulated by using electrochemical reactions of the ferrocenyl (Fc) alkanethiol monolayer, and the wetting gradient was generated by the application of the in-plane bias voltage to the substrate. The back-and-forth motion of the wetting boundary, where the surface changed from wetting to repulsive, sequentially caused a droplet unidirectional spreading and shrinking on the surface. These unidirectional deformations resulted in the net transport of the droplet in an inchwormlike manner. The droplet moved backward when the direction of the in-plane bias voltage was reversed. 相似文献
26.
Toshiyuki Chikuma Yoko ShimabukuroTakeya Iguchi Akira TanakaKyoji Taguchi Takeshi KatoMitsune Yamaguchi Hiroshi Hojo 《Analytica chimica acta》2002,457(2):157-164
A rapid and sensitive assay for the determination of Dns-His-Lys-Arg-His-Lys cleaving enzyme activity is reported. This assay is based on fluorimetric detection of a dansylated dipeptide, 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys, enzymatically formed from the substrate 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys-Arg-His-d-Lys, after separation by high-performance liquid chromatography (HPLC) using a C-18 reversed-phase column by isocratic elution. This assay is sensitive enough to measure 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys at concentrations as low as 7 pmol, and yields highly reproducible results and requires less than 9.0 min per sample for separation and quantitation. The optimum pH for Dns-His-Lys-Arg-His-Lys cleaving enzyme activity was 7.5-8.0. The Michaelis constant (Km) and the maximum velocity (Vmax) values were 33.3 μM and 47.07 pmol/(μg h), respectively with the use of enzyme extract obtained from bovine pituitary. By using this assay, axonal transport of this enzyme activity was observed 48 h after double ligations of rat sciatic nerves. The high sensitivity and selectivity of this assay would be useful for clarification of the physiological role of this enzyme. 相似文献
27.
Fumiyo Saito Ryo Takeuchi Tomoyuki Kamino Kouji Kuramochi Kengo Sakaguchi Susumu Kobayashi Masashi Tsuda 《Tetrahedron letters》2004,45(43):8069-8071
A total synthesis of the proposed structure of plakevulin A was accomplished. However, the NMR spectral data of the synthetic plakevulin A were not identical of those of the reported compound. We next converted the synthetic plakevulin A into 1-dihydrountenone A. The 1H and 13C NMR spectral data of 1-dihydrountenone A were identical with those of reported plakevulin A except for the peaks derived from levulinic acid. Thus, we repurified sample of the natural product and confirmed that the natural sample contained 1-dihydrountenone A and levulinic acid in the ratio of one to one. We also found that not plakevulin A but 1-dihydountenone A possessed the inhibitory activity against mammalian DNA polymerases α and β. 相似文献
28.
Hashizaki K Taguchi H Itoh C Sakai H Abe M Saito Y Ogawa N 《Chemical & pharmaceutical bulletin》2005,53(1):27-31
Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states. 相似文献
29.
On treatment with metallic lithium in the presence of dimethylaminonaphthalene, trialkylsilyl enol ethers of α-phenylseleno ketones were converted into the corresponding α-trialkylsilyl ketones in good yields. 相似文献
30.
Kawai H Katoono R Fujiwara K Tsuji T Suzuki T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(3):815-824
The molecular recognition of catecholamines by hydrindacene-based receptors 1 and 2, as well as the durene-based receptor 3, and the guest-induced conformational changes are reported. These receptors selectively bind adrenaline and dopamine salts through the guests' ammonium group and 3-hydroxyl group on the aromatic ring. In the case of adrenaline, an additional hydrogen bond with a benzylic hydroxyl group is formed. In 2 % CD3CN/CDCl3, the association constants are of the order of 10(4) M(-1), which is much larger than with guests without the 3-hydroxyl groups (10(3) M(-1)). The two amide groups of receptor 1 can rotate freely around the C(aromatic)--C(amide) bond, whereas the tert-amide in 2 changes between two stable conformations at a slow enough rate to allow detection by (1)H NMR spectroscopy. In the absence of a guest molecule, the syn-conformer is less stable than the anti-conformer. On complex formation with adrenaline, the syn-conformer becomes dominant due to an intramolecular dipole-reversal effect in addition to multipoint hydrogen bonding. 相似文献