Magnetically driven ferroelectric order in Ni3V2O8

We show that long-range ferroelectric and incommensurate magnetic order appear simultaneously in a single phase transition in Ni3V2O8. The temperature and magnetic-field dependence of the spontaneous polarization show a strong coupling between magnetic and ferroelectric orders. We determine the magnetic symmetry using Landau theory for continuous phase transitions, which shows that the spin structure alone can break spatial inversion symmetry leading to ferroelectric order. This phenomenological theory explains our experimental observation that the spontaneous polarization is restricted to lie along the crystal b axis and predicts that the magnitude should be proportional to a magnetic order parameter.     

Fluorescence properties of 2-aminopurine-cytidine-7-deazaguanine (5'-ApCdzG-3') trimer in B- and Z-DNA

The electron transfer quenching of 2-aminopurine by guanine and 7-deazaguanine was investigated in B- and Z-DNA, and an increase in the fluorescence intensity of 2-aminopurine upon B- to Z-DNA transition was demonstrated.     

A novel procedure for the preparation of zinc reagents: a practical synthesis of (+)-biotin

The use of bromine for activation of zinc dust allowed smooth and reproducible reduction of iodide 1 to the corresponding zinc reagent 2. The zinc reagent 2 obtained by the present protocol was allowed to the Fukuyama coupling reaction with thiolactone 3 to provide a key intermediate 4 for (+)-biotin in high yield using a reasonably fair amount of 1 (1.4 equiv).     

In situ organogelation at room temperature: direct synthesis of gelators in organic solvents

Organogels are formed through a conventional organogelation involving a heating process and an in situ organogelation at room temperature. The conventional organogelation is carried out by dissolution of gelators by heating, while the in situ organogelation is performed by mixing of highly reactive methyl 2,6-diisocyanatohexanoate (LDI) or 2-isocyanatoethyl 2,6-diisocyanatohexanoate (LTI) and alkylamines. The in situ organogelation produced the organogels within several seconds after mixing. The organogels prepared by the in situ organogelation showed quite similar FT-IR spectra and SEM photographs to those formed by conventional organogelation. Moreover, the in situ organogelation using LTI and octylamine as well as dodecylamine produced organogels of acetone, ethyl acetate, and acetonitrile that gelators 5 and 6 cannot gel through conventional organogelation.     

Synthetic studies on the taxane skeleton: construction of eight-membered carbocyclic rings by the intramolecular B-alkyl Suzuki-Miyaura cross-coupling reaction

Construction of eight-membered carbocyclic rings via the intramolecular B-alkyl Suzuki-Miyaura cross-coupling reaction has been studied. This protocol proved its potency through the formation of the eight-membered ring possessing a quaternary carbon on its ring in high yield, affording promise of a new access to the eight-membered ring of Taxol. [reaction: see text]     

Highly enantioselective catalytic carbon dioxide incorporation reaction: nickel-catalyzed asymmetric carboxylative cyclization of bis-1,3-dienes

A method for nickel-catalyzed asymmetric carbon dioxide (CO2) incorporation via carbon-carbon bond formation was developed. In the presence of a catalytic amount of Ni(acac)2 and MeO-MOP, various bis-1,3-dienes reacted with CO2 (1 atm) and a diorganozinc reagent (Me2Zn or Ph2Zn) to afford cyclic carboxylic acids in good yields (71-100%) and with high enantioselectivities (90-96% ee).     

Novel in-gap spin state in Zn-doped La1.85Sr0.15CuO4

Low-energy spin excitations of La(1.85)Sr(0.15)Cu(1-y)Zn(y)O4 were studied by neutron scattering. In y=0.004, the incommensurate magnetic peaks show a well-defined "spin gap" below T(c). The magnetic signals at omega=3 meV decrease below T(c)=27 K for y=0.008, also suggesting the gap opening. At lower temperatures, however, the signal increases again, implying a novel in-gap spin state. In y=0.017, the spin gap vanishes and elastic magnetic peaks appear. These results clarify that doped Zn impurities induce the novel in-gap state, which becomes larger and more static with increasing Zn.     

Field-induced thermal metal-to-insulator transition in underdoped La(2-x)Sr(x)CuO(4+delta)

The transport of heat and charge in cuprates was measured in single crystals of La(2-x)Sr(x)CuO(4+delta) (LSCO) across the doping phase diagram at low temperatures. In underdoped LSCO, the thermal conductivity is found to decrease with increasing magnetic field in the T-->0 limit, in striking contrast to the increase observed in all superconductors, including cuprates at higher doping. In heavily underdoped LSCO, where superconductivity can be entirely suppressed with an applied magnetic field, we show that a novel thermal metal-to-insulator transition takes place upon going from the superconducting state to the field-induced normal state.