Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

Shedding light on hidden reaction pathways in radical polymerization by a porous coordination network

A coordination network comprising 2-vinyltriphenylene was treated with AIBN at a high temperature, but the radical polymerization of the vinyl monomer was completely suppressed by spatial separation and otherwise hidden aerobic oxidation pathways are enhanced.     

Alkaliphiles

The term alkaliphile is used for microorganisms that grow optimally or very well at pH values above 9, but cannot grow or grow only slowly at the near neutral pH value of 6.5. Alkaliphiles include prokaryotes, eukaryotes, and archaea. Alkaliphiles can be isolated from normal environments such as garden soil, although viable counts of alkaliphiles are higher in samples from alkaline environments. The cell surface plays a key role in keeping the intracellular pH value in the range between 7 and 8.5, allowing alkaliphiles to thrive in alkaline environments. Alkaliphiles have made a great impact in industrial applications. Biological detergents contain alkaline enzymes, such as alkaline cellulases and/or alkaline proteases that have been produced from alkaliphiles. Another important application is the industrial production of cyclodextrin with alkaline cyclomaltodextrin glucanotransferase. This enzyme reduced the production cost and paved the way for cyclodextrin use in large quantities in foodstuffs, chemicals and pharmaceuticals. It has also been reported that alkali-treated wood pulp could be biologically bleached by xylanases produced by alkaliphiles.     

The annealing behavior of hydrogen implanted into Al-1.5 at.% Si alloy

We have studied effects of added elements as well as defects on trap-sites of hydrogen in metals. For the purpose, we observed depth profiles and thermal behaviors of hydrogen implanted into Al-1.5 at.% Si alloy samples in an implantation-temperature range of liquid nitrogen temperature (LNT) to 373 K at different doses. The results were compared with those for pure aluminum samples. It was found that hydrogen is trapped as molecules in grain boundaries of Al/Si.     

Field-induced functions of porous Si as a confined system

Electroluminescent porous Si (PS) diodes exhibit various useful functions under a high-electric field. The experimental PS diodes are composed of thin semitransparent metal films, PS layers (about 500 nm thick in minimum), p- or n-type Si substrates and ohmic back contacts. Definite nonlinear electrical behavior (negative resistance and nonvolatile bistable memory effects) and cold electron emission phenomena appear in these PS diodes associated with the EL emission. Both the negative resistance and memory effects are related to the charging of Si nanocrystallites by field-induced carrier injection. The electron emission observed in the PS diodes formed on n+–Si substrates is caused by hot electrons tunnelling through the top contact. By an appropriate structural control of PS, the effective drift length under a high-field conduction is significantly increased, and then electrons are emitted ballistically. These functions reflect the activity of PS as a nanocrystalline confined system.     

Effects of localized triplet exciton on reactivity of photoinduced omega-bond dissociation in naphthyl phenyl ketones having pi,pi* lowest triplet (T1) states studied by laser flash photolysis

Photochemical properties of photoinduced omega-bond dissociation in naphthyl phenyl ketones having a phenylthiyl moiety as a leaving group, p-(alpha-naphthoyl)benzyl phenyl sulfide (NBPS) and 4-benzoyl-1-naphthylmethyl phenyl sulfide (BNMPS), in solution were investigated by laser flash photolysis techniques. Both ketones were shown to undergo photoinduced omega-bond cleavage of the C-S bond to release the phenyl thiyl radical (PTR) at room temperature. Irrespective of excitation wavelengths of NBPS, a quantum yield (Phi(rad)) of the PTR formation was obtained to be 0.1, whereas that for BNMPS was found to depend on the excitation wavelength, i.e., absorption bands from the ground state (S0) to the excited singlet states, S3, S2, and S1 of BNMPS; Phi(rad)(S3) = 0.77 and Phi(rad)(S2) = Phi(rad)(S1) = 1.0. By using triplet sensitization of p-phenylbenzophenone (PBP), efficiencies (alpha(rad)) of the radical formation in the lowest triplet state (T1(pi,pi*)) of NBPS and BNMPS were determined to be 0 and 1.0, respectively. The agreement between Phi(rad)(S1) and alpha(rad) values for BNMPS indicates that the C-S bond dissociation occurs in the T1 state via the S1 state via a fast intersystem crossing from the S1 to the T1 state. The wavelength dependence of the radical yields upon direct excitation of BNMPS was interpreted in terms of the C-S bond cleavage in the S3 state competing with internal conversion from the S3 to the S2 state. The smaller value of Phi(rad)(S3) than those of Phi(rad)(S1) and Phi(rad)(S2) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S3 state. Photoinduced omega-cleavage of NBPS was concluded to take place only in the S1(n,pi*) state. Difference in reactivity of omega-cleavage between the triplet states of NBPS and BNMPS was interpreted in terms of localized triplet exciton in the naphthoyl moieties.     

3-Band theory of Fe pnictide superconductors

For the Fe pnictide superconductors, band features important for superconductivity (SC) in the neighborhood of ε_F are mimicked by tight-binding bands with bases of Fe d_xz, d_yz and d_xy orbitals. In terms of this 3-band model, effective pair transfer processes originating from Coulombic integrals are shown to be largely enhanced due to the nesting between electron and hole pockets by explicitly summing up ladder diagrams. Obtained coupled gap equations lead to s^±-type SC. This framework are argued to provide a scheme for discussing important elements working for the high T_c SC, although its validity is restricted to the case where Dirac cones are away from ε_F. Experimental results on Fe pnictides are discussed in terms of the present results. The pair transfer process explicitly due to the exchange-like integral is suggested to be considerably important for the high T_c in MFeAsO_1−xF_x to occur.     

Microscopic Studies of 2H-NbSe2 Probed by Positive Muon

Abstract

The microscopic state of the positively charged light particle in the transition metal dichalcogenide 2H-NbSe₂ was studied using the muon spin relaxation method (μ⁺SR) and muon level crossing resonance method (μ-LCR). Muons are expected to stay at interlayer position and behaves as a hydrogen like intercalant. We discuss the relation between conduction electron properties and the muon's behavior.