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21.
22.
The crystal habit of fcc metal particles formed on an amorphous carbon film electrode in solution at different electrode
potentials is discussed. The fcc metal particles have different crystallographic habits depending on applied electrode potential;
that is, icosahedral and/or decahedral particles are formed at lower potentials, and fcc single-crystalline or polycrystalline
particles at higher potentials. It was found that decahedra and icosahedra of Cu-Au alloy particles are formed in the potential
region of underpotential deposition (UPD) of Cu at which only fcc Au single-crystalline particles and Au polycrystalline particles
appear. This is attributed to the charge transfer from the UPD Cu ions to the Au overlayer of Cu-Au alloy particles. The formation
of decahedral and icosahedral Cu-Au alloy particles depends on the composition of the Cu-Au alloy. On the basis of these results
it was deduced that the contraction of the surface lattice of the growing particles is responsible for the formation of icosahedral
and decahedral particles.
Received: 25 February 1997 / Accepted: 21 April 1997 相似文献
23.
Munakata R Katakai H Ueki T Kurosaka J Takao K Tadano K 《Journal of the American Chemical Society》2003,125(48):14722-14723
The first total synthesis of (+)-macquarimicin A (1), a novel inhibitor of neutral sphingomyelinase (N-SMase) with antiinflammatory activity, has been accomplished. The present work determined the absolute configuration of (+)-1 and revised the C(2)-C(3) geometry to be Z. The synthesis features a transannular Diels-Alder reaction, which constructed the tetracyclic framework stereoselectively, and a convergent and efficient synthetic pathway, which afforded (+)-macquarimicin A (1) in 27 steps (longest linear sequence) with 9.9% overall yield. 相似文献
24.
Sensitive, reactive, and hydrophilic fluorogenic reagents for thiols with the benzofurazan skeleton, 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (AcABD-F) and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (TCAcABD-F) have been developed. These reagents reacted with thiols within 10 min at 60 degrees C. AcABD-F and TCAcABD-F themselves do not fluoresce but are strongly fluorescent after the reaction with thiol compounds. The generated derivatives were highly water-soluble, since they dissociated a proton and ionized in the neutral pH region. The derivatives with four biologically important thiol compounds were separated on a reversed-phase HPLC column and detected fluorometrically at 504 nm with excitation at 388 nm. The detection limit attained for homocysteine with AcABD-F was 25 fmol on column (11 nM) (signal-to-noise ratio = 3), and that for glutathione with TCAcABD-F was 45 fmol on column (20 nM). 相似文献
25.
Hiroki Kiyama Tsubasa Inokuma Yusuke Kuroda Yousuke Yamaoka Kiyosei Takasu Ken-ichi Yamada 《Tetrahedron letters》2019,60(2):175-177
A new catalytic method for separating enantiomers of racemic compounds is proposed. Catalytic asymmetric addition of racemic trans-2-substituted cyclohexanols to imines provided diastereomeric mixtures of aminals, and the subsequent separation of the enantiomers by silica-gel column chromatography and the hydrolysis of the aminals produced the alcohols in an optically active form. 相似文献
26.
Masahiko Ishikawa Ken-ichi Okamoto Jinsai Hidaka Hisahiko Einaga 《Helvetica chimica acta》1985,68(7):2015-2021
Substitution reaction with ethylenediamine of coordinated glycinate ligand in bis(ethylenediamine)-glycinatocobalt(III) complex has been studied in the presence of photo-excited tris(2,2′-bipyridine)ruthenium(II) complex in alkaline aqueous solution (buffered around pH 12) containing 1.0M chloride ion at 25°C. VIS absorption and CD spectra were used for the racemate and the optically active isomers of the Co(III) complexes, respectively. The reaction was catalyzed by the excited Ru(II) complex to give tris(ethylenediamine)cobalt(III) complex. Mechanism of the ligand-substitution reaction and role of the excited Ru(II) complex were discussed. 相似文献
27.
Phototriggered self-assembly of hydrogen-bonded rosette 总被引:2,自引:0,他引:2
Yagai S Nakajima T Karatsu T Saitow K Kitamura A 《Journal of the American Chemical Society》2004,126(37):11500-11508
Azobenzene-appended melamine M2 and barbiturate B2, both possessing bulky tridodecyloxyphenyl (TDP) wedge(s), were designed and synthesized to establish a photoresponsive hydrogen-bonded supramolecular assembly. The geometrical isomer EE-M2 bearing two E-azobenzene moieties easily complexed with B2, affording a remarkably stable cyclic hexamer EE-M2(3).B2(3) (rosette) in chloroform, toluene, and methylcyclohexane, as confirmed by size exclusion chromatography, dynamic light scattering, (1)H NMR, and UV-vis studies. The E --> Z photoisomerization of the azobenzene moieties upon irradiation with UV light was significantly suppressed in the rosette because of the steric crowding of the TDP wedges (total of nine TDP wedges in a rosette), whereas irradiation of the monomeric EE-M2 resulted in facile transformation into ZZ-M2 bearing two Z-azobenzene moieties. (1)H NMR studies of the complexation of the initially photogenerated ZZ-M2 with B2 revealed that it is hard for ZZ-M2 to form a rosette with B2 because of the intermolecular steric interaction between the TDP wedges. The photoregulatable complexation efficiency of M2 allowed us to accomplish the phototriggered formation of the rosette by irradiation of a monomeric mixture of ZZ-M2 and B2 using visible light. 相似文献
28.
Tomohisa Yasuhara Katsumi Nishimura Ken-ichi Yamada Kiyoshi Tomioka 《Tetrahedron letters》2004,45(15):3043-3045
(±)-γ-Lycorane 3 was synthesized in 52% overall yield via seven steps from 5 by employing the highly stereoselective nitro-Michael cyclization of 5 to 9 and diastereoselective conjugate addition of aryllithium to a nitroolefin 10 as two key steps. 相似文献
29.
Vibrational Raman spectra of C=C stretching modes of ethylene derivates (cis-C(2)H(2)Cl(2), cis-stilbene, and trans-stilbene) were measured in supercritical fluids along an isotherm as functions of their densities. The substitution effect of the Raman shift is so significant that a difference among three solutes can be 20 times and is observed similarly in dipolar (CHF(3)) and non-dipolar (CO(2)) fluids. In particular, the shifts of trans-stilbene were enormously large among all systems for studies of vibrational spectroscopies of supercritical fluids and were equivalent to those of typical hydrogen-bonded fluids. Such large shifts arising from the significant attractive energy between solute and solvent molecules were attributed to a site-selective solvation around a phenyl group, which was driven by a dispersion force in the absence of steric hindrance. We found that the absence of steric hindrance causes the significant local density augmentation. To the best of our knowledge, Raman experiments and their theoretical analysis are the first ones quantifying how the difference of steric hindrance produces solvation structures in solution as well as supercritical solutions. 相似文献
30.
A highly efficient and convenient CuCl/2-pyridonate catalytic system for oxidative homocoupling of azoles affording a biazole product has been developed. With this system, a variety of biazoles have been effectively synthesized in good to excellent yields in the presence of a very small amount of copper catalyst (1.0 mol%). It was feasible to employ air as a green oxidant. 相似文献