Mössbauer spectroscopic study of photo-sensitive organic–inorganic hybrid system, (SP)[Fe(II)Fe(III)(dto)3](dto = C2O2S2, SP = spiropyran)

A photo-sensitive organic–inorganic hybrid system (SP)[Fe^IIFe^III(dto)₃] (SP = spiropyran, dto = C₂O₂S₂), has recently been developed, where the photo-isomerization of the intercalated spiropyran in solid state triggers the change of the magnetic properties, including the ferromagnetic transition temperature from 5 to 22 K. We performed ⁵⁷Fe Mössbauer measurement in order to probe the microscopic states of iron ions in (SP)[Fe^IIFe^III(dto)₃] and have investigated the photo-induced effect on them. The sample without UV-irradiation shows the charge transfer phase transition between 200 and 70 K and the higher and lower temperature phases coexist below 70 K, whereas the UV-irradiated sample does not undergo the charge transfer phase transition and the higher temperature phase is stable between 200 and 6 K.     

Nanoparticle preparation of quinacridone and β-carotene using near-infrared laser ablation of their crystals

Quinacridone nanoparticles with a mean size of about 200 nm are successfully prepared using nanosecond near-infrared (NIR) laser ablation of its microcrystalline powders in heavy water. The absorption spectra of the formed colloidal solutions depend on the excitation wavelengths, which is eventually ascribed to number and energy of absorbed photons. β-carotene has low photostability and is easily decomposed upon UV/VIS laser ablation of its solid, while its nanoparticles are prepared utilizing this NIR laser ablation technique. The advantage of nanoparticle preparation by NIR laser ablation is discussed.     

Synthesis of calix[4]arene library substituted with peptides at the upper rim

A fluorescence-labeled calix[4]arene library substituted with peptides at the upper rim was synthesized. Screening of the library for binding a dye-labeled oligopeptide indicated that some peptidocalix[4]arenes selectively bind the oligopeptide. The chemosensitivity of the library members for a target peptide was also investigated.     

Precise nuclear moments of extremely proton-rich nuclus 23 Al

Electric quadrupole coupling constant eqQ/h of the extremely proton-rich ²³Al (I ^π ?=?5/2^?+?, T _1/2?=?0.47 s) nucleus implanted into an Al₂O₃ single crystal has been measured for the first time, using the β-ray detecting nuclear quadrupole resonance method (β-NQR) in a high magnetic field. As a preliminary result, the quadrupole coupling constant was determined as |eqQ/h(²³Al) |?=?2.66±0.77 MHz. Using the quadrupole coupling constant of ²⁷Al in Al₂O₃ as a reference, the Q moment of the ground state of ²³Al was extracted as |Q(²³Al)|?~?160 mb, which is well explained by the shell model calculation in the sd-shell model space with the USD interaction.     

Multinuclear cobalt–salen complexes with phenylene linker for epoxide polymerizations

Di‐ and trinuclear cobalt (Co)–salen complexes with a benzene ring as a rigid linker were explored for epoxide polymerizations. The dinuclear Co–salen complex with a 1,2‐phenylene linker showed higher catalytic activity than the dinuclear Co–salen complex with a 1,3‐phenylene linker and the trinuclear Co–salen complex with a 1,3,5‐benzenetriyl linker for the copolymerization of propylene oxide (PO) with carbon dioxide. A combination of the absolute configuration of the two Co–salen moieties was found to affect its catalytic activity. The optimized dinuclear Co–salen complex with a heterochiral combination demonstrated highest activity and maintained its catalytic activity under a low catalyst concentration. The heterochiral dinuclear Co–salen complex also showed high activity for the copolymerization of PO with cyclic anhydride. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2150–2159     

Time-dependent quadrupole interactions for <Superscript>140</Superscript>Ce ions implanted in highly oriented pyrolytic graphite

The time-differential perturbed angular correlation (TDPAC) method was applied to a study on the behavior of ¹⁴⁰Ce atoms implanted in highly oriented pyrolytic graphite (HOPG). Exponential-type gradual attenuation of the directional anisotropy of the relevant γ-ray cascade was observed in the perturbation patterns. From temperature dependence of the relaxation rate, a thermally activated dynamic motion of the probe atoms was suggested.     

Development of ion transportation, extraction and neutralization systems for atomic beam resonance method

A device that produces a low-energy and largely spin polarized RI beam based on the atomic beam resonance method (RIABR) has been developed. We have performed measurements of stopping and drifting an incoming RI ion beam in a gas chamber, extraction of the ions into a vacuum region, and neutralization of the extracted low-energy ion beam. The drift efficiency of RI ions in a gas and the extraction efficiency at a Laval-type glass nozzle were found to be 0.72±0.04 and 0.033, respectively. The result of the experiment for the neutralization is also discussed.     

Asymmetric Total Synthesis of ent‐Pyripyropene A

An asymmetric total synthesis of ent‐pyripyropene A was achieved by a convergent synthetic route. We used our originally developed Ti^III‐catalyzed radical cyclization to construct an AB‐ring portion that consisted of a trans‐decalin skeleton with five contiguous stereogenic centers. The coupling between the AB‐ring and the DE‐ring portions, and a subsequent C‐ring cyclization, led to the total synthesis of ent‐pyripyropene A. An evaluation of the insecticidal activity of ent‐pyripyropene A against two aphid species revealed that ent‐pyripyropene A was 35–175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A.