Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in ¹H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between ¹H spins is strong. ²⁹Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the ²⁹Si relaxation of relatively pure samples under static and slow-spinning conditions. ²⁷Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between ²⁷Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.     

In Situ Immobilization of Ultrafine Particles Synthesized in a Water/Oil Microemulsion

We investigated the in situ immobilization of ultrafine particles synthesized in a water/oil (w/o) microemulsion to silica for its possible application to supported metal catalysts. ZnS particles immobilized to silica by the ME method were consistent with those synthesized in a w/o microemulsion. Therefore, ZnS particles in a w/o microemulsion could be immobilized to silica without aggregation by this method. The relationship between the method of synthesizing Rh ultrafine particles in a w/o microemulsion and the diameter and diameter distribution of Rh particles immobilized to silica was studied. Rh-SiO(2) catalysts with a sharp diameter distribution could be prepared by immobilizing Rh-hydrazine complex particles because these complex particles would be very stable in a w/o microemulsion. The Rh particle diameters of Rh-SiO(2) catalysts prepared by changing the amount of silica produced were almost identical. Accordingly, the Rh particle diameter of Rh-SiO(2) catalysts could be controlled independently of Rh content by the ME method. Copyright 2001 Academic Press.     

Fragmentation in doubly charged ion mass spectra of anhydropisatin and related compounds

The doubly charged ion mass spectra of anhydropisatin, 4-methoxyanhydropisatin, 3, 8, 9-trimethoxypterocarpen and 3, 4, 8, 9-tetramethoxypterocarpen were determined, and the fragmentation was explained by assuming that the paired electrons were partially localized in the fragmentations and by comparing the spectra with that of 3-(CD₃)-anhydropisatin. Conventional mass spectra of these compounds were very simple, but the doubly charged ion spectra were sufficiently characteristic for the reliable identification.     

Reaction of indium ate complexes with allylic compounds. Controlling SN2/SN2′ selectivity by solvents

Vinyl and methylindium ate complexes (indates) were prepared and both the tendency of immigration and regioselectivity toward cinnamyl bromide were investigated. The vinyl group was more preferably transferred than the Me group, giving a regioisomeric mixture of S_N2 and S_N2′ products. The ratio of S_N2/S_N2′ selectivity can be controlled by solvents; in the presence of polar solvents, such as N-butylpyrrolidone (NBP) and THF, the S_N2′ product was mainly obtained, whereas the S_N2 product was selectively prepared in solutions containing hexane. The vinylindium compound, generated by the reaction of allylic-type diindium reagents with imine, was also converted to the corresponding vinyl indate, which was allowed to react with allyl chloride to give a three-component coupling product.