Iron oxide pillared graphite

We show that alpha-Fe2O3- and Fe3O4-pillared graphites can be prepared by pillaring graphite oxide with trinuclear iron acetato complex ion and calcining it in air and in vacuo, respectively. A pillared graphite structure is confirmed by transmission electron microscopy observations. The adsorption isotherms of water indicate that the mesopores of Fe3O4-pillared graphite constitute a hydrophobic nanospace.     

Synthesis of γ-Cyclodextrin Pyrene-Labeled at the Hetero Rim and Its Use in Fluorescent Molecular Sensing

Fluorogenic active host labeled at the upper and lower rims of -cyclodextrin, namely, mono-3^A-deoxy-3^A-pyrenebutylamido-6^X-O-mono-pyrenebutylate-mono-altro--cyclodetrin (mixture -1,X = A, B, C, D, E, F, G, or H), has been synthesized in order to investigate their host-guest complexation with steroidal compoundsusing fluorescence spectra. Monomer and excimer fluorescence was observed for mixture host. Inclusion of a guest molecule in the cyclodextrin cavity resultedin increased monomer fluorescence and decreased excimer fluorescence. The extent of monomerand excimer fluorescence variations ofmixture -1 with the guestwas used as an indication for the sensing ability. The guest inducedfluorescence changes were measured for 10^-7 M solutions of mixture -1.The values I/I ⁰ , where I ⁰ and I are fluorescence intensities in the absence and presence of a guest, respectively, and I is I ⁰ - I, were then used to describe the sensing ability.     

NMR study of local hole distribution, spin fluctuation and superconductivity in Tl2Ba2Ca2Cu3O10

⁶³Cu, ¹⁷O and ²⁰⁵Tl NMR have been performed in the high-T_c superconductor Tl₂Ba₂Ca₂Cu₃O₁₀ whose T_c(max) is 127 K. The hole densities at Cu and oxygen sites in the CuO₂ plane have been extracted from the nuclear quadrupole frequency ν_Q. The striking feature is that the Cu holes are significantly transferred to oxygen site due to strong hybridization between Cu and oxygen. From an analysis of T₁ and T_2G, it has been found that the spectral weight of the spin fluctuation is transferred to higher energy compared to YBa₂Cu₃O₇, while the magnetic correlation length ξ does not differ much. Thus, it is suggested that the higher T_c is due to higher characteristic energy of spin fluctuations, i.e. the superconductivity is spin fluctuation mediated. The superconducting properties are consistently explained by a d-wave superconductivity model with a finite density of states (DOS) at the Fermi level. We show that the disorder of the Ca/TlO layer caused by the partial inter-substitution of Tl and Ca is responsible for the potential scattering to produce such a DOS. It is found that if such a potential scattering were absent, T_c would go up to 132 K which is quite close to the record T_c realized in the Hg based compound.     

Differential pulse Polarographic study of simple and mixed ligand complexes of cadmium(II) with some dicarboxylate anions and imidazole

Transition Metal Chemistry - The composition and stability of binary and ternary complexes of Cd(II) with phthalate and adipate anions as primary ligands and imidazole as a secondary ligand have...     

P-Chirogenic diaminophosphine oxide: a new class of chiral phosphorus ligands for asymmetric catalysis

We successfully synthesized a novel P-chirogenic diaminophosphine oxide 4, which was applied to catalytic enantioselective construction of quaternary carbon centers using Pd-catalyzed asymmetric allylic substitution with various beta-keto esters (up to 99% yield, 94% ee). Preliminary mechanistic studies indicated that two molecules of 8 coordinate to the Pd metal in a monodentate fashion, resulting in the formation of Pd complex 9 (Pd:8 = 1:2), which functions as the active species.     

Parametric optimization of a narrow-band 13.5-nm emission from a Li-based liquid-jet target using dual nano-second laser pulses

We demonstrate the applicability of a Li-based liquid jet as a regenerative source of narrow-band extreme-ultraviolet (EUV) emission at 13.5 nm. It was found that a conventionally used single laser pulse did not produce optimum plasma conditions for a low-Z target, like Li. It was shown that deployment of dual nano-second laser pulses enhanced the in-band EUV conversion efficiency (CE) at 13.5 nm in 2 sr by three times its value using a single laser pulse. Dependence of the emission spectra and EUV CE on the delay time between dual laser pulses revealed that the emission at 13.5 nm from Li ions was preferably enhanced at a lower plasma temperature compared to that at 13.0 nm from oxygen ions.     

Self-running droplet: emergence of regular motion from nonequilibrium noise

Spontaneous motion of an oil droplet driven by nonequilibrium chemical conditions is reported. It is shown that the droplet undergoes regular rhythmic motion under appropriately designed boundary conditions, whereas it exhibits random motion in an isotropic environment. This study is a novel manifestation on the direct energy transformation of chemical energy into regular spatial motion under isothermal conditions. A simple mathematical equation including noise reproduces the essential feature of the transition from irregularity into periodic regular motion. Our results will inspire the theoretical study on the mechanism of molecular motors in living matter, working under significant influence of thermal fluctuation.     

Direct observation of charge transfer in double-perovskite-like RbMn[Fe(CN)6

The charge density distribution has been determined for a transition metal cyanide, RbMn[Fe(CN)(6)], by means of the maximum entropy-Rietveld method combined with the highly angularly resolved synchrotron radiation x-ray powder diffraction at SPring-8 BL02B2. We directly observed a charge transfer from the Mn site to the Fe site in the low-temperature phase. On the basis of a local density approximation calculation, we discuss the origin for the anisotropic bonding electron distribution around the Mn3+ ion in the low-temperature phase.     

Asymmetric epoxidation with a photoactivated [Ru(salen)] complex

(Nitrosyl)(salen)ruthenium(II) complex 1 was found to serve as an efficient catalyst for the epoxidation of conjugated olefins under photoirradiation, with 2,6-dichloropyridine N-oxide (2) or tetramethylpyrazine N,N'-dioxide as a stoichiometric oxidant. High enantioselectivity was achieved irrespective of the substitution pattern of olefins. The choice of solvent depends on stability of the resulting epoxides: high enantioselectivity is generally observed in the reaction with ethereal solvents, but use of benzene is recommended when the resulting epoxides are acid-sensitive.