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Yoshifumi Tanimoto

Publications and source records attributed to Yoshifumi Tanimoto.

4 recordsLinked to original sources

Three-dimensional morphological chirality induction using high magnetic fields in membrane tubes prepared by a silicate garden reaction.

Using a vertical superconducting magnet (max. 15 T), we studied magnetic field effects on membrane tube morphology prepared by a silicate garden reaction. At zero field, semipermeable membrane tubes grew upward when metal salts were added to a sodium silicate aqueous solution. In the presence of a magnetic field (15 T, downward) right-handed helical membrane tubes grew along a glass vessel's inner surface when magnesium chloride and copper sulfate were added. Referring to membrane tubes by the names of metal cations used in their preparation, in the case of Mg(II) and Zn(II) membrane tubes, the left-handed helical tubes grew when the field direction was reversed upward. The left-handed helical Mg(II) membrane tubes grew in the magnetic field when a glass rod was placed in a vessel. Mg(II) and Zn(II) tubes, separate from a vessel wall, grew in a twisted shape in the magnetic field. In situ observation of the solution's motion during the reaction revealed that the Lorentz force on the outflow from the opened top of the hollow membrane tube induced convection of the solution near the tube exit, engendering chiral growth of the membrane tubes. Relative orientation of the outflow and a boundary (a vessel wall or glass rod surface) helped to determine the convection's direction.

Journal Article↗

Evidence for a transition state model compound of in-plane vinylic SN2 reaction.

[reaction: see text] To isolate a transition state model compound of an in-plane vinylic S(N)2 reaction, vinyl bromide 6 bearing a newly synthesized tridentate ligand derived from 1,8-dimethoxythioxanthen-9-one (5) was prepared as a precursor. Although irradiation of 6 gave demethylated benzofuran 12, a transient broad peak which indicates formation of the desired transition state model compound was observed in the laser flash photolytic study.

Journal Article↗

Photoinduced intramolecular electron transfer and triplet energy transfer in a steroid-linked norbornadiene-carbazole dyad.

Bichromophoric compound 3 beta-((2-(methoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-3-yl)carboxy)androst-5-en-17 beta-yl-[2-(N-carbazolyl)acetate] (NBD-S-CZ) was synthesized and its photochemistry was examined by fluorescence quenching, flash photolysis, and chemically induced dynamic nuclear polarization (CIDNP) methods. Fluorescence quenching measurements show that intramolecular electron transfer from the singlet excited state of the carbazole to the norbornadiene group in NBD-S-CZ occurs with an efficiency (Phi SET) of about 14 % and rate constant (kSET) of about 1.6 x 10(7) s-1. Phosphorescence and flash photolysis studies reveal that intramolecular triplet energy transfer and electron transfer from the triplet carbazole to the norbornadiene group proceed with an efficiency (TET + TT) of about 52 % and rate constant (kTET + kTT) of about 3.3 x 10(5) s-1. Upon selective excitation of the carbazole chromophore, nuclear polarization is detected for protons of the norbornadiene group (emission) and its quadricyclane isomer (enhanced absorption); this suggests that the isomerization of the norbornadiene group to the quadricyclane proceeds by a radical-ion pair recombination mechanism in addition to intramolecular triplet sensitization. The long-distance intramolecular triplet energy transfer and electron transfers starting both from the singlet and triplet excited states are proposed to proceed by a through-bond mechanism.

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