Development of Oxidation Sources in Preparation of High-Tc Oxide Superconductor Thin Films Using the Molecular Beam Epitaxy Method

Film preparation of oxide superconductors, mainly of the 1-2-3 (RBa₂Cu₃O_x) and Bi-containing (Bi-Sr-Ca-Cu-O) systems, by evaporation of either metals or metal compounds by low pressure is summarized, with a particular focus on the development of oxidation sources essential to the technique. Oxidizing reagents that enable the oxidation of metal evaporates to take place in high (0·1 to 10_?3 Pa) or even ultra-high (<10_?5 Pa) vacuum are summarized using the experiments of those who tried to apply the molecular beam epitaxy method to atomically controlled fabrication of thin films of the material, especially for device processing. The evaporation in various kinds of oxidizing atmosphere, including the simple method of in situ annealing of the metal layers in oxygen to the more advanced in situ preparation of the films with strong oxidizing reagents such as atomic oxygen, ozone, nitric oxide, etc. along with the thermochemistry of the oxidation of metals by low pressure with these reagents is reviewed.     

A semiclassical approximation for massive transfer

A semiclassical approximation for the transition matrix for transfer reactions between heavy ions is developed from the distorted-wave Born approximation by means of the three-dimensional WKB approximation. It is designed to be applicable to massive transfer without adopting various assumptions and approximations of previous semiclassical approaches which are reasonable only for few-nucleon transfer. The final expression obtained is of a simple closed form similar to that of the Brink model. It gives a way of seeing the validity of the idea of Brink in massive transfer. Numerical study of illustrative examples indicates promising applicability of the present method to massive transfer.     

Nano‐imaging through tip‐enhanced Raman spectroscopy: Stepping beyond the classical limits

The spatial resolution in optical imaging is restricted by so‐called diffraction limit, which prevents it to be better than about half of the wavelength of the probing light. Tip‐enhanced Raman spectroscopy (TERS), which is based on the SPP‐induced plasmonic enhancement and confinement of light near a metallic nanostructure, can however, overcome this barrier and produce optical images far beyond the diffraction limit. Here in this article, the basic phenomenon involved in TERS is reviewed, and the high spatial resolution achieved in optical imaging through this technique is discussed. Further, it is shown that when TERS is combined with some other physical phenomena, the spatial resolution can be dramatically improved. Particularly, by including tip‐applied extremely localized pressure in TERS process, it has been demonstrated that a spatial resolution as high as 4 nm could be achieved.     

Chiral charge-density waves

We discovered the chirality of charge-density waves (CDW) in 1T-TiSe? by using STM and time-domain optical polarimetry. We found that the CDW intensity becomes Ia?∶Ia?∶Ia? = 1∶0.7 ± 0.1∶0.5 ± 0.1, where Ia(i) (i=1,2,3) is the amplitude of the tunneling current contributed by the CDWs. There were two states, in which the three intensity peaks of the CDW decrease clockwise and anticlockwise. The chirality in CDW results in the threefold symmetry breaking. Macroscopically, twofold symmetry was indeed observed in optical measurement. We propose the new generalized CDW chirality H(CDW) ≡ q?·(q?×q?), where q(i) are the CDW q vectors, which is independent of the symmetry of components. The nonzero H(CDW)-the triple-q vectors do not exist in an identical plane in the reciprocal space-should induce a real-space chirality in CDW system.     

Hydrogen Intercalation in Potassium-C60

Abstract

Solid state ¹H NMR of (KH)₃C₆₀ was measured in the temperature range between ?80 and 60 °C. A doublet spectrum composed of main peak at ?7.0 ppm and shoulder peak at ～0 ppm was observed at room temperature. The negative chemical shift of the main peak indicates that hydrogen in (KH)₃C₆₀ exists as a hydride-like ion. The 60 °C spectrum became singlet at ?5.8 ppm due to motional narrowing.     

Stereo-dynamical ion-pair formation in collisions of highly-charged ions with argon dimers

Multiple ionization process of a rare gas dimer BC collided with a slow highly charged ion A^q+ is investigated with the three-center Coulombic over-barrier model previously developed by the present authors. To reveal stereodynamical effects, we calculate asymmetric ion-pair formation cross sections σ(Q_B,Q_C) as a function of the orientation angle. We introduce a pair of atomic impact parameters b_B and b_C with which we distinguish the near and far sites. Furthermore, we distinguish the forward and backward emitted ions produced as a result of Coulomb explosion. Partial screening effects are also considered.     

Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radical ipso-Cyclization

We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses.     

Reaction dynamics of excited 2-(3-benzoylphenyl)propionic acid (ketoprofen) with histidine

Photoreaction dynamics of 2-(3-benzoylphenyl)propionic acid (ketoprofen, KP), one of nonsteroidal anti-inflammatory drugs, with histidine in a phosphate buffer solution (pH 7.4) was investigated with the laser flash photolysis. The deprotonated form of KP (KP(-)) was decarboxylated via UV laser excitation to form a carbanion. It was found that histidine accelerates the protonation reaction of the carbanion to 3-ethylbenzophenone ketyl biradical (3-EBPH) for the first time. The experimental results of the photoreaction of KP with alanine as well as the photoreaction of KP with 4-methylimidazole (a part of the side chain of histidine) in methanol, clearly showed that the protonated form of histidine is a key species for the protonation reaction of the carbanion. These series of the initial reactions should result in the occurrence of photosensitization in vivo. The reaction mechanism was discussed in detail.