Low-energy D scattering from Cs and CsCl adsorbed on the Si(100)2 × 1 surface

On the basis of neutralization and inelastic scattering of low-energy D⁺ ions, the bond nature of Cs and CsCl adsorbed on the Si(100)2 × 1 surface has been investigated. In a low-coverage regime ( < 0.2 ML), Cs is adsorbed ionically on Si(100) and subsequent oxygen adsorption readily causes the ionic Cs---O bond. CsCl is dissociatively adsorbed on the surface in a low-coverage regime due to the preferential reaction of Cl with the Si dangling bond and the resultant Cs is ionically bonded to Si.     

Regioselective oxidative polymerization of 1,5-dihydroxynaphthalene catalyzed by bilirubin oxidase in a water–organic solvent mixed solution

Bilirubin oxidase (EC1.11.1.7) was used to catalyze the oxidative polymerization of 1,5-dihydroxynaphthalene to its polymer in a mixed solvent composed of dioxane, ethyl acetate, and acetate buffer. In an aqueous solution, the enzymatic oxidative polymerization hardly occurred and resulted in negligible yield mainly due to the poor solubility of 1,5-dihydroxynaphthalene. In the mixed solvent the conversion proceeded with a yield of ca. 70%. The polymer yield was studied with respect to reaction time and solvent components. Elemental analysis, UV-visible, fluorescent, and FT-IR spectroscopic analyses, proton NMR and electrochemical studies, and solubility in various organic solvents revealed that 1,5-dihydroxynaphthalene is polymerized by the C? C coupling. The molecular weight of the polymeric products solubilized with DMF varied from low molecular weight product to high molecular weight polymer. From the chromatographic studies, the organic solvent–insoluble residue was suggested to be highly polymerized material. Based on these findings a possible mechanism for enzymatic polymerization of 1,5-dihydroxynaphthalene is presented: less stable intermediates produced enzymatically from 1,5-dihydroxynaphthalene undergo coupling and polymerization to ortho-1,5-dihydroxynaphthalene polymer, thereby resulting in a regioselective polymerization of 1,5-dihydroxynaphthalene. © 1993 John Wiley & Sons, Inc.     

Isotope separation by laser-enhanced chemical reaction

Reactivity enhancement was studied using a reaction between a laser excited atomic beam and a molecular beam. This method was applied to lithium isotope separation, in which the excited Li isotopic atom reacts with CHCIF₂. It is found that the specified lithium isotope is enriched in the reaction product LiF, whereas LiCl has no selectivity.     

Recent developments in magnetism and magnetic materials

In the last decade we have obtained a deeper understanding of basic magnetism in alloys and a variety of new magnetic materials have been developed. In this review article two kinds of recent topics in these fields will be discussed. The first one is the magnetic properties of rare earth-3d transition intermetallics. After describing the magnetic properties of RMn₂ very briefly, we discuss the magnetic properties of YMn₂ in detail, particularly its magnetovolume effect which is closely related with the magnetic moment of Mn atoms below and above the magnetic transition temperature. Then, as an example of recent developments in soft magnetic materials, Fe-Ni-Cr alloys with very high permeability and low coercive force will be discussed including impurity effects on their magnetic properties.     

A statistical theory of excitable membranes. Nonlinear force-flux relation and fluctuation

A statistical theory of an excitable membrane is proposed under the assumptions that the membrane is composed of an ensemble of a number of active patches, and that the flip-flop transition of an active patch is governed by the dissipative interaction caused by an electric eddy current. By the method of expanding the master equation in the system size together with the Gaussian approximation, the time course of an excitation and the steady N-shaped relation between current and voltage are derived from the ensemble theory of open systems. The fluctuation of electric current under a fixed voltage becomes anomalously large in the marginal state at the threshold potential. The fluctuation associated with an action potential increases sharply at the jump-up transition, but it is not so large at the flip-back catastrophe. The fluctuation-dissipation relation at the steady state of the membrane system is discussed on the basis of a variational principle.This study was supported partly by a grant from the Ministry of Education, Japan.     

Stereoselective preparation, structures, and reactivities of phosphine-bridged mixed-metal trinuclear and pentanuclear complexes with tris[2-(diphenylphosphino)ethyl]phosphine

The phosphine-bridged linear trinuclear and pentanuclear complexes with Pd(II)-Pt(II)-Pd(II), Ni(II)-Pt(II)-Ni(II), and Rh(III)-Pd(II)-Pt(II)-Pd(II)-Rh(III) metal-ion sequences were almost quantitatively formed by the stepwise phosphine-bridging reaction of the terminal phosphino groups of tris[2-(diphenylphosphino)ethyl]phosphine (pp3), which is the tetradentate bound ligand of the starting Pd(II) and Ni(II) complexes. The solid-state structures of the trinuclear complexes were determined by X-ray structural analyses, and the structures of the polynuclear complexes in solution were characterized by NMR spectroscopy. The trans and cis isomers of the trinuclear and pentanuclear complexes, which arise from the geometry around the Pt(II) center, were selectively obtained simply by changing the counteranion of the starting complexes: the tetrafluoroborate salts, [MX(pp3)](BF4) [M = Pd(II) or Ni(II), X = Cl- or 4-chlorothiophenolate (4-Cltp-)], gave only the trans isomers, and the chloride salt, [PdCl(pp3)]Cl, gave only the cis isomers. The formation of the trinuclear complex with the 4-Cltp- and chloro ligands, trans-[Pt(4-Cltp)2{PdCl(pp3)}2](BF4)2, proceeded with exchange between the thiolato ligand in the starting Pd(II) complex, [Pd(4-Cltp)(pp(3))](BF4), and the chloro ligands in the starting Pt(II) complex, trans-[PtCl2(NCC6H5)2], retaining the trans geometry around the Pt(II) center. In contrast, the formation reaction between [PdCl(pp3)]Cl and trans-[PtCl2(NCC6H5)2] was accompanied by the trans-to-cis geometrical change on the Pt(II) center to give the trinuclear complex, cis-[PtCl2{PdCl(pp3)}2]Cl2. The mechanisms of these structural conversions during the formation reactions were elucidated by the 31P NMR and absorption spectral changes. The differences in the catalytic activity for the Heck reaction were discussed in connection with the bridging structures of the polynuclear complexes in the catalytic cycle.     

Unprecedented CO2-promoted aminochlorination of olefins with Chloramine-T

[STRUCTURE: SEE TEXT] A new synthetic procedure for the aminochlorination of olefins for the synthesis of vicinal chloroamine derivatives using a combination of Chloramine-T and carbon dioxide is described. The method can be applied to a variety of olefins, including an electron-sufficient olefin and a conjugated diene.     

Unprecedented 1,4-stannatropy: effective generation of azomethine ylides as nitrile ylide equivalents from N-(stannylmethyl)thioamides

Generation and cycloaddition of less- or non-stabilized azomethine ylides, or nitrile ylide equivalents, via unprecedented 1,4-stannatropy of N-(tributylstannylmethyl)thioamides were achieved. The reactions with dipolarophiles, such as electron-deficient alkenes and alkynes, afforded corresponding pyrrolidine and pyrrole derivatives effectively.     

The search for a hair-growth stimulant: new radicicol analogues as WNT-5A expression inhibitors from Pochonia chlamydosporia var. chlamydosporia

WNT-5A, a secretory glycoprotein, is related to the proliferation of dermal papilla cells. While searching for an inhibitor of WNT-5A expression, we identified an active compound, radicicol (1), and isolated four unique analogues, pochonins G-J (2-5), from a culture broth of the fungus Pochonia chlamydosporia TF-0480. Structural elucidation of 2-5 and their biological activities against WNT-5A are described.