Counter‐Anion‐Regulated Mixed‐Valency of Cobalt(II/III) Centers in a Metallosupramolecular Framework

A diamagnetic Au^I₄Co^III₂ hexanuclear complex, [Au₄Co₂(dppe)₂(l ‐nmc)₄]²⁺ ([ 1_{L ‐ nmc} ]²⁺; dppe=1,2‐bis(diphenylphosphino)ethane, l ‐H₂nmc=N‐methyl‐l ‐cysteine), was newly synthesized by the reaction of [Co(l ‐nmc)₂]^? with [Au₂Cl₂(dppe)] and crystallized with different inorganic anions (X=ClO₄^?, NO₃^?, Cl^?, SO₄^2?) to produce ionic solids ([ 1_{L ‐ nmc} ]X_n). Single‐crystal X‐ray analysis revealed that all the solids crystallize in the chiral space group F432 with a face‐centered‐cubic lattice structure consisting of supramolecular octahedra of complex cations. The paramagnetic nature of all the solids was evidenced by magnetic susceptibility measurements, showing the variation of the oxidation states of two cobalt centers in [ 1_{L ‐ nmc} ]ⁿ⁺ from Co^II_1.00Co^III_1.00 for X=ClO₄^? or NO₃^? to Co^II_0.67Co^III_1.33 for X=Cl^?, via Co^II_0.83Co^III_1.17 for X=SO₄^2?. The difference in the Co^II/III mixed‐valences was explained by the difference in sizes and charges of counter anions accommodated in lattice interstices with a fixed volume.     

The adsorption-induced thermal step-bunching on the hexagonal lattice system

We present restricted solid-on-solid model coupled with Ising system (RSOS-I model) on the hexagonal system. Without long-range interaction such as elastic interaction, the adsorption-induced thermal step-bunching is obtained by the Monte Carlo calculation on the hexagonal RSOS-I model.     

High‐Resolution Crystal Structure of a Silver(I)–RNA Hybrid Duplex Containing Watson–Crick‐like C?Silver(I)?C Metallo‐Base Pairs

Metallo‐base pairs have been extensively studied for applications in nucleic acid‐based nanodevices and genetic code expansion. Metallo‐base pairs composed of natural nucleobases are attractive because nanodevices containing natural metallo‐base pairs can be easily prepared from commercially available sources. Previously, we have reported a crystal structure of a DNA duplex containing T Hg^II T base pairs. Herein, we have determined a high‐resolution crystal structure of the second natural metallo‐base pair between pyrimidine bases C Ag^I C formed in an RNA duplex. One Ag^I occupies the center between two cytosines and forms a C Ag^I C base pair through N3 Ag^I N3 linear coordination. The C Ag^I C base pair formation does not disturb the standard A‐form conformation of RNA. Since the C Ag^I C base pair is structurally similar to the canonical Watson–Crick base pairs, it can be a useful building block for structure‐based design and fabrication of nucleic acid‐based nanodevices.     

Preparation and characterization of microcapsules containing particulate phosphorescent agent with suspension polymerization

Microcapsules containing particulate phosphorescent agent (strontium aluminate) were prepared by the suspension polymerization method and characterized about a few items such as the mean diameters, the content, the inner structure and the afterglow luminance property. Furthermore, the fundamental experiments were conducted to investigate how the dispersing feature of particulate phosphorescent agent affects the afterglow luminance property. In the experiment, the concentration of oil soluble surfactant, the crosslinking agent species, the added weight of the phosphorescent agent and the pre‐bulk polymerization time were mainly changed stepwise. Afterglow luminance of particulate phosphorescent agent gradually decreased with the afterglow time and considerably decreased because of soaking them in water. Decline of afterglow luminance because of soaking in water could be prevented by microencapsulation. Afterglow luminance of the multicore type microcapsules was found to be higher than that of the core–shell type microcapsules. The content of particulate phosphorescent agent could be increased by performing pre‐bulk polymerization and increasing the concentration of the oil soluble surfactant. Copyright © 2016 John Wiley & Sons, Ltd.     

Microencapsulation of phosphor particles with the drying‐in‐liquid method in parallel with the suspension polymerization method and effect on afterglow luminance property

Strontium aluminate particles as phosphor particles were microencapsulated with the drying‐in‐liquid method in parallel with the suspension polymerization method in order to increase the waterproof and to improve afterglow luminance property. In this study, ethylene glycol was used as the continuous phase instead of water to prevent phosphor particles from deteriorating at the microencapsulation process, and polystyrene was used as the more hydrophobic microcapsule shell. Styrene monomer was used as the solvent of polystyrene at the drying‐in‐liquid method and as the polymerizable monomer at the suspension polymerization method at the same time. The content and the waterproof could be considerably increased with the drying‐in‐liquid method in parallel with the suspension polymerization method as compared with only the drying‐in‐liquid method, because the denser microcapsule shell without any tiny holes and cracks could be formed. The decrease due to water in brightness of afterglow luminance of phosphor particles could be prevented by microencapsulating with the drying‐in‐liquid method in parallel with suspension polymerization method. Copyright © 2017 John Wiley & Sons, Ltd.     

A new definition of boundary point between early reflections and late reverberation in room impulse responses

The early reflections in the room impulse response are usually defined as those observed within the initial 80 ms after the arrival of the direct sound, after which time the sound field is called reverberant. This number was chosen from measurements of other functions in a limited number of halls. In order to give an objective foundation to this time separation and to establish a physical indicator for it, a new method is proposed that defines a "transition time t(L)," which is the time at which the energy correlation between the direct plus initial sound and the subsequent decaying sound first achieves a specified low value. For various halls this number is shown and its relevance as a new parameter is discussed.     

Asymmetric synthesis by the intramolecular haloetherification reaction of ene acetal: discrimination of prochiral dienes in cyclohexane systems

A novel asymmetric synthesis of the cyclohexane derivative functionalized by some substituents has been developed from the diene acetals (1), prepared from the corresponding diene aldehyde and (+)-hydrobenzoin. The treatment of 1 with NBS in the presence of MeOCH2CH2OH predominantly afforded 2 in a stereoselective manner. Subsequent alkylation of the methoxyethoxy group produced the optically active cyclohexene compounds (3) in good yields. The stereoselective chemical modification of the remaining olefin in 3 was made by OsO4-oxidation.