Ultrafast Photoinduced Electric-Polarization Switching in a Hydrogen-Bonded Ferroelectric Crystal.

Croconic acid crystals show proton displacive-type ferroelectricity with a large spontaneous polarization reaching 20 µC/cm^{2}, which originates from the strong coupling of proton and π-electron degrees of freedom. Such a coupling makes us expect a large polarization change by photoirradiations. Optical-pump second-harmonic-generation-probe experiments reveal that a photoexcited croconic-acid crystal loses the ferroelectricity substantially with a maximum quantum efficiency of more than 30 molecules per one absorbed photon. Based on density functional calculations, we theoretically discuss possible pathways toward the formation of a one-dimensional domain with polarization inversion and its recovery process to the ground state by referring to the dynamics of experimentally obtained polarization changes.

Revealing the photorelaxation mechanism in a molecular solid using density-functional theory.

Photorelaxation in a molecular crystal is investigated by a density-functional theory for the first time. A quasi-one-dimensional molecular compound, (EDO-TTF)(2)PF(6), is known to exhibit a photoinduced phase transition, which is characterized as a transition from a (0110)-type charge-ordering insulator phase to a high-temperature metallic phase. First, we apply the method of embedding a cluster in a self-consistent environment and succeed in constructing a stable tetramer structure of EDO-TTF molecules. The reliance of this cluster is ensured by a vibrational analysis that well reproduces the IR and Raman frequencies particularly for C=C stretching modes including a relatively large degree of electron-'molecular vibration' coupling. Second, relaxations in the photoexcited states of this cluster are investigated by adiabatic potential-surface analyses and full structural optimization. A reaction coordinate is found to be quite unique for a relatively high-energy excitation, namely, the so-called CT2 excitation, which is interpreted as leading to the photoinduced phase transition.

Novel electronic ferroelectricity in an organic charge-order insulator investigated with terahertz-pump optical-probe spectroscopy.

In electronic-type ferroelectrics, where dipole moments produced by the variations of electron configurations are aligned, the polarization is expected to be rapidly controlled by electric fields. Such a feature can be used for high-speed electric-switching and memory devices. Electronic-type ferroelectrics include charge degrees of freedom, so that they are sometimes conductive, complicating dielectric measurements. This makes difficult the exploration of electronic-type ferroelectrics and the understanding of their ferroelectric nature. Here, we show unambiguous evidence for electronic ferroelectricity in the charge-order (CO) phase of a prototypical ET-based molecular compound, α-(ET)2I3 (ET:bis(ethylenedithio)tetrathiafulvalene), using a terahertz pulse as an external electric field. Terahertz-pump second-harmonic-generation(SHG)-probe and optical-reflectivity-probe spectroscopy reveal that the ferroelectric polarization originates from intermolecular charge transfers and is inclined 27° from the horizontal CO stripe. These features are qualitatively reproduced by the density-functional-theory calculation. After sub-picosecond polarization modulation by terahertz fields, prominent oscillations appear in the reflectivity but not in the SHG-probe results, suggesting that the CO is coupled with molecular displacements, while the ferroelectricity is electronic in nature. The results presented here demonstrate that terahertz-pump optical-probe spectroscopy is a powerful tool not only for rapidly controlling polarizations, but also for clarifying the mechanisms of ferroelectricity.

Application of high-performance liquid chromatography to the study of esterified 7-dehydrocholesterol in rat skin.

A novel and precise method for determining free and esterified 7-dehydrocholesterol in rat skin was developed by using a two-step high-performance liquid chromatography system. This method involves initial lipid extraction, separation of the free and esterified 7-dehydrocholesterol by, firstly, preparative high-performance liquid chromatography, saponification, and determination by, secondly, analytical high-performance liquid chromatography. This method was applied to the study of the 7-dehydrocholesterol in rat skin. Almost all of the 7-dehydrocholesterol in rat skin was present in an esterified form (78-93%). Ultraviolet exposure of the skin increased total 7-dehydrocholesterol content, however, the percentage of esterified 7-dehydrocholesterol was not altered appreciably. Application of this method to the study of the photo-metabolism of 7-dehydrocholesterol in rat skin revealed that almost all of the vitamin D3 produced by ultraviolet rays was in the esterified form.

A 5 kDa protein (SCS23) from the 30 S subunit of the spinach chloroplast ribosome.

The proteins of the 30 S ribosomal subunits from spinach chloroplasts were investigated using a radical-free and highly reducing (RFHR) method of two-dimensional polyacrylamide gel electrophoresis (PAGE). Twenty-three proteins were resolved on the gel down to the smallest protein of 5 kDa. The N-terminal amino acid sequence of the 5 kDa protein showed no homology with that of any other protein stored in databases, and the copy numbers were estimated to be 0.88 +/- 0.16 and 0.72 +/- 0.04 in the 30 S subunits and the 70 S ribosomes, respectively. The results suggest that the 5 kDa protein, which we have called SCS23, may be an essential ribosomal protein specific to spinach chloroplasts.