Biomedical subjects

Tadahiko Ishikawa

Publications and source records attributed to Tadahiko Ishikawa.

5 recordsLinked to original sources

PubMed2006

Static magnetic-field-induced phase lag in the magnetization response of tris(dipicolinato)lanthanides.

Alternating-current (ac) magnetic susceptibility measurements for tris(dipicolinato) complexes with a trivalent heavy lanthanide ion, [N(C2H5)4]3[Ln(dipic)(3)] x nH2O (dipic = pyridine-2,6-dicarboxylate; Ln = Tb, Dy, Ho, Er, Tm, or Yb) are reported. While none of the six complexes showed a magnetization lag from the ac magnetic field of 10-10(3) Hz above 1.8 K, the Dy, Er, and Yb complexes with odd numbers of 4f electrons exhibited the magnetization lag in a static magnetic field. This phenomenon is explained to be caused by the elimination of a fast relaxation path, which is only effective for the Kramers doublet ground states in near zero field. At higher static fields, the remaining paths such as Orbach and/or direct processes govern the dynamics of the two-level systems comprised of spin-up and spin-down states. The non-Kramers complexes were found to have a nondegenerate ground state with large energy gaps from higher states, which is consistent with their fast magnetization relaxation.

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PubMed2005

Intramolecular nitro-assisted proton transfer in photoirradiated 2-(2',4'-dinitrobenzyl)pyridine: polarized optical spectroscopic study and electronic structure calculations.

The nitro-assisted proton transfer (NAPT), responsible for the photoactivity of ortho-nitrobenzylpyridines and a model for the nitro-based caged compounds, is studied along with the parent compound 2-(2',4'-dinitrobenzyl)pyridine (DNBP) with polarized optical spectroscopy and theoretical calculations. The transition dipole moments of a DNBP single-crystal identified oriented molecules of the long-lived enamine tautomer (NH), rather than of the aci-nitro tautomer (OH), as carriers of the photoinduced blue coloration. It is clarified that the blue second singlet transition owes to intramolecular charge transfer from the allyl-pyridinium part to the dinitrophenyl fragment of NH. The theoretical modeling of the ground-state potential energy surface showed that while NH and OH can interconvert by means of direct proton transfer, such a process between the initial form CH and either OH and NH would require significant rotation of the aromatic rings. In the ground state, OH is less stable but the kinetically preferred product over NH. Once created, regardless of whether via ground-state or excited-state routes, the aci-nitro group of OH undergoes energetically inexpensive rotation to deliver the proton to the nitrogen acceptor. The "softening" of the energy surface around OH due to its structural flexibility, that is, mediation of the proton transfer by the nitro group, is crucial to overcome the high barrier for a direct proton jump from CH to NH, even in cases of unfavorable donor-acceptor geometry. The very small structural change experienced by the surrounding of a molecule undergoing NAPT is promising for the design of photoactive systems which retain their crystallinity during a prolonged operation.

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PubMed2005

Gigantic photoresponse in 1/4-filled-band organic salt (EDO-TTF)2PF6.

We report that the organic salt (EDO-TTF)2PF6 with 3/4-filled-band (1/4-filled in terms of holes), which forms an organic metal with strong electron and lattice correlation, shows a highly sensitive response to photoexcitation. An ultrafast, photoinduced phase transition from the insulator phase to the metal phase can be induced with very weak excitation intensity at near room temperature. This response makes the material attractive for applications in switching devices with room-temperature operation. The observed photo-induced spectroscopic change shows that this photoinduced phase transition process is caused by the cooperative melting of charge ordering assisted by coherent phonon generation.

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PubMed2004

Upward temperature shift of the intrinsic phase lag of the magnetization of Bis(phthalocyaninato)terbium by ligand oxidation creating an S = 1/2 spin.

An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons.

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PubMed2003

Lanthanide double-decker complexes functioning as magnets at the single-molecular level.

Double-decker phthalocyanine complexes with Tb3+ or Dy3+ showed slow magnetization relaxation as a single-molecular property. The temperature ranges in which the behavior was observed were far higher than that of the transition-metal-cluster single-molecule magnets (SMMs). The significant temperature rise results from a mechanism in the relaxation process different from that in the transition-metal-cluster SMMs. The effective energy barrier for reversal of the magnetic moment is determined by the ligand field around a lanthanide ion, which gives the lowest degenerate substate a large |Jz| value and large energy separations from the rest of the substates in the ground-state multiplets.

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