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31.
Fabrication of high performance thin films from metal fluorocomplex aqueous solution by the liquid phase deposition 总被引:1,自引:0,他引:1
Hnin Yu Yu Ko Minoru Mizuhata Akihiko Kajinami Shigehito Deki 《Journal of fluorine chemistry》2003,120(2):157-163
The hetro-structured oxide thin films from metal fluorocomplex solution have been prepared by the liquid phase deposition (LPD) method. The Pt/Nb2O5 and Au/Nb2O5 composite films can be prepared from a mixed solution of niobium source, H3BO3, Pt(NH3)4Cl2 and HAuCl4 aqueous solutions under the ambient temperature and atmosphere. In the case of Au/SiO2 composite film, (NH4)2SiF6 solution is used as a mother solution. The Pt and Au ionic species are deposited in Nb2O5 and SiO2 matrices. They are reduced to their metallic state after treatment above 200 °C. The size of dispersed particles can be controlled by heat treatment temperature. It is also clear that, gold nanoparticles are also found to interact with SiO2, although the interaction is smaller than that with Nb2O5 showing the size of Au nanoparticles remain smaller in Nb2O5 that in SiO2. 相似文献
32.
First asymmetric total synthesis of tetrodotoxin 总被引:3,自引:0,他引:3
Tetrodotoxin, a toxic principle of puffer fish poisoning, is one of the most famous marine natural products because of the complex structure having many functional groups and its potent biological activity leading to death. Since the structure elucidation in 1964, this toxin has been recognized as a formidable target molecule for total synthesis. We have recently achieved the first asymmetric total synthesis from 2-acetoxy-tri-O-acetyl-d-glucal as a chiral starting material. The highly hydroxylated cyclohexane ring was constructed by Claisen rearrangement and regioselective hydroxylations of an acetone moiety and an intramolecular directed aldol condensation of the precursor having methyl ketone with dihydroxyacetone, which was synthesized through Sonogashira coupling. Installation of nitrogen functionality was unsuccessful through an attempted Overman rearrangement. We, therefore, employed a new intramolecular conjugate addition strategy between the carbamate and unsaturated ester groups. The alpha-hydroxyl lactone moiety was synthesized through an intramolecular epoxide opening by the Z-enolate of aldehyde, which was followed by oxidation-reduction of the resulting cyclic vinyl ether. The lactone was then converted to a protected ortho ester, and then gunanidinylation was followed by cleavage of the 1,2-glycol to give the fully protected tetrodotoxin. Selection of the protective groups has finally led us to accomplish the total synthesis of tetrodotoxin in an enantiomerically pure form. All the stereogenic centers were controlled with high selectivity, and the hydroxyl groups were differently protected to discriminate for the future analogue synthesis of a bioorganic program. The synthetic tetrodotoxin was purified by ion exchange chromatography and characterized to be identical with the natural compound. 相似文献
33.
Masuda Y Itoh T Itoh M Koumoto K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(13):5588-5592
We developed a novel self-assembly process to fabricate an orderly array of particle wires constructed from a close-packed colloidal crystal without preparation of patterned templates. A substrate was immersed vertically into a SiO2 colloidal solution, and the liquid surface moved downward upon evaporation of solution. Particles formed a mono-/multiparticle layer, which was cut by the periodic drop-off of solution. The orderly array of particle wires was successfully fabricated, showing the suitability of the self-assembly process for the fabrication of nano-/microstructures constructed from nano-/microparticles or blocks. The mechanism of the assembly process and control of thickness, width, and interval of particle wires were further discussed. Moreover, an array of particle wires constructed not from close-packed face-centered cubic (or hexagonal close packed) structure but from two kinds of particles was realized to fabricate an array of particle wires with NaCl structure by this self-assembly process. 相似文献
34.
Yoshiyasu Ichikawa Yohei Matsukawa Mari Tamura Fumiyo Ohara Minoru Isobe Hiyoshizo Kotsuki 《化学:亚洲杂志》2006,1(5):717-723
A new method for the synthesis of urea‐linked disaccharides in aqueous media has been developed. The key feature of our approach is two strained Steyermark‐type gluco‐ and galactopyranosyl oxazolidinones. Each oxazolidinone is attached to a pyranose ring in a di‐equatorial trans‐annulation framework. Reaction of these oxazolidinones with 4‐aminohexopyranose in water proceeded smoothly to afford the urea‐tethered cellobiose and lactose analogues. The galactose‐type oxazolidinone proved to be more reactive than the glucose‐type, which is explained by the presence of an axial hydroxy group at C4 in the former. 相似文献
35.
Changes in binding affinity to catalytic antibody 6D9 of chloramphenicol phosphonate derivatives (CPDs) containing H or F were investigated by performing free energy calculations based on molecular dynamics simulations. We calculated the binding free energy, enthalpy, and entropy changes (DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS) attributable to H-->F substitution by comparing results for CPDs containing a trifluoroacetylamino group (CPD-F) or an acetylamino group (CPD-H). The calculated DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS values were -2.9, -6.3, and 3.5 kcal mol(-1) and close to experimental values observed for a series of similar ligands, chloramphenicol phosphonates with F and H (-1.4, -3.5, and 2.1 kcal mol(-1)). Therefore, CPD-F binds more strongly to 6D9 than does CPD-H. To clarify the origin of the large difference in DeltaDeltaG, we apportioned the calculated values of DeltaDeltaG and DeltaG for the associated and dissociated states into contributions from various atomic interactions. We found that the H-->F substitution increased the binding affinity mainly by decreasing the hydration free energy and not by increasing favorable interactions with the antibody. The decreased hydration free energy of the ligand was mainly due to unfavorable coulombic interactions between the trifluoroacetylamino group and solvent waters, which increased the free energy of the dissociated state (by about 3.7 kcal mol(-1)). Also, the trifluoroacetylamino group slightly increased the free energy level of the associated state (about 0.8 kcal mol(-1)) because favorable van der Waals interactions compensated for unfavorable coulombic interactions with antibody atoms. In addition, the enthalpy and entropy changes, DeltaDeltaH and -TDeltaDeltaS (computationally -6.3 and 3.5 kcal mol(-1)), originated mainly from a decrease in hydration free energy in the dissociated state. The CPD-F and CPD-H ligands had substantially different structures in the dissociated and complexed states. 相似文献
36.
A series of parallel reactions were carried out for the tandem Ugi/Diels-Alder reaction on our MPEG-O-CH2- platform. Ninety-six out of a 100 entries were successful to give complex heterotricycles. The stereoselectivity was found not to be influenced by the building blocks used for amine and carboxylic acid components. An unexpected side pathway was found but was suppressed by employing appropriate reaction conditions. The reaction was also performed on solid phase, by which a larger library is potentially realized by employing the split-pool method. 相似文献
37.
Kazuhiro Watanabe Noboru Akino Tetsuo Aoyagi Noboru Ebisawa Yukio Fujiwara Atsusi Honda Takashi Inoue Takao Itoh Mikito Kawai Minoru Kazawa Junichi Koizumi Masaaki Kuriyama Kenji Miyamoto Naoki Miyamoto Kazuhiko Mogaki Yoshihiro Ohara Tokumichi Ohga Yoshikazu Okumura Hiroshi Oohara Katsumi Ohshima Fujio Satoh Kazuhiko Shimizu Syunji Takahashi Hirotsugu Usami Katsutomi Usui Masahiro Yamamoto Takeshi Yamazaki 《Radiation Physics and Chemistry》1997,49(6):631-639
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D− ion beam. In the preliminary experiment using one ion source, a D− ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D− beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID− < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H− ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator. 相似文献
38.
Kai Yang Xuan Zhang Enqin Fu Jingui Qin Minoru Kinoshita 《Journal of solid state chemistry》2004,177(11):4300-4304
Two new intercalation compounds were prepared by the reactions of Ni(II) cyclopolyamine complex cations with a preintercalate Mn1−xPS3K2x(H2O)y, respectively, through “ion exchange” process. Their structures were characterized by elemental analysis, X-ray powder diffraction and infrared spectroscopy. The lattice spacing increased 0.567 and 1.093 nm with respect to the pristine MnPS3. Ferrimagnetism of the intercalates was confirmed by SQUID experiment with Tc at 40 and 33 K, respectively. 相似文献
39.
Three newly prepared [Ni(mnt)2] complexes, (HMTTF)[Ni(mnt)2], (ChSTF)[Ni(mnt)2], and (DBTTF)2[Ni(mnt)2], are reported (DBTTF = dibenzotetrathiafulvalene, ChSTF = 2,3-cyclohexylenedithio-1,4-dithia-5,8-diselanafulvalene, HMTTF = bis(trimethylene)-tetrathiafulvalene, and mnt = maleonitrile dithiolate). The former two compounds have usual DA-type (D = donor, A = acceptor) mixed stacks, whereas the DBTTF complex has DDDDAA-type 6-fold columns. These compounds are electrical insulators, but the HMTTF and ChSTF complexes exhibit chiT minima at 16 and 55 K, respectively, followed by chiT peaks at 8 and 16 K. Below these temperatures the ESR signal disappears, indicating antiferromagnetic transitions. The origin of the ferromagnetic interaction is explained either from the difference of the g values between the donor and the anion or from the intrinsic ferromagnetic interaction of the [Ni(mnt)2] anions. 相似文献
40.
Chisuzu Tokoh Keiji Takabe Junji Sugiyama Minoru Fujita 《Cellulose (London, England)》2002,9(3-4):351-360
Acetobacter
xylinum was cultured in Schramm–Hestrin medium containing pectin (pectin medium), xylan (xylan medium), or glucomannan (mannan medium). X-ray diffractometry revealed that xylan and glucomannan affected the size of the cellulose crystals and their d-spacing values. Solid-state cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy indicated that the ratio of cellulose I was reduced by the addition of polysaccharides. These effects were more remarkable on the cellulose in the mannan medium than that in the xylan medium, and were scarcely observed in the pectin medium. Electron diffraction analysis revealed that these effects on hemicelluloses along cellulose microfibrils are continuous in the mannan medium and discontinuous in the xylan medium. These findings suggest that the uronic acid in the polysaccharides prevents interactions with cellulose leading to alterations of the structure of the cellulose crystal. 相似文献