X-ray gated Mössbauer spectroscopic studies on57Co-labelled cobalt/II/ fluoride

KX-ray-gated emission Mössbauer spectra of⁵⁷Co-labelled CoF₂ and CoF₂.2H₂O were measured at room temperature, using the coincidence technique. A difference was found in the relative intensity of⁵⁷Fe(II)/⁵⁷Fe(III) between the X-ray-gated and non-gated emission spectra. The results are explained in terms of local radiolytic effects of water of crystallization and the chemical effects associated with the de-excitation processes caused by EC-decay.     

Noncatalytic kinetic study on site-selective H/D exchange reaction of phenol in sub- and supercritical water

The site-selective H/D exchange reaction of phenol in sub- and supercritical water is studied without added catalysts. In subcritical water in equilibrium with steam at 210-240 degrees C, the H/D exchange proceeds both at the ortho and para sites in the phenyl ring, with no exchange observed at the meta site. The pseudo-first-order rate constants are of the order of 10(-4) s(-1); 50% larger for the ortho than for the para site. In supercritical water, the exchange is observed also at the meta site with the rate constant in the range of 10(-6)-10(-4) s(-1). As the bulk density decreases, the exchange slows down and the site selectivity toward the ortho is enhanced. The enhancement is due to the phenol-water interaction preference at the atomic resolution. The site selectivity toward the ortho is further enhanced when the reaction is carried out in benzene/water solution. Using such selectivity control and the reversible nature of the hydrothermal deuteration/protonation process, it is feasible to synthesize phenyl compounds that are deuterated at any topological combination of ortho, meta, and para sites.     

Recent progress in the solid-phase synthesis of glycopeptide

The recent understanding of the biological role of glycoproteins has brought about a demand for the highly homogeneous glycopeptides as the functional model for glycoproteins. Thus, much efforts have been made to establish easy and efficient method for glycopeptide synthesis. In this paper, we briefly review the recent advances in the synthesis of O- and N-linked glycopeptide based on the solid-phase method. In O-glycopeptide section, the preparation of glycosylated amino acid units with mucin type and other O-linked carbohydrate chains and their use for solid-phase synthesis are summarized. Other approaches, such as the glycosylation of resin bound peptide are also overviewed. In N-glycopeptide section, the synthesis using glycosylated amino acid units as well as other methods are described.     

Polymer‐Assisted Solution‐Phase Synthesis and Neurite‐Outgrowth‐Promoting Activity of 15‐Deoxy‐Δ12,14‐PGJ2 Derivatives

An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ^12,14‐PGJ₂ (15dPGJ₂) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ₂ derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ₂ derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ₂ derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ₂ derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ₂.     

A dynamic free-entry oligopoly with sluggish entry and exit adjustments

We study a dynamic free-entry oligopoly with sluggish entry and exit of firms under general demand and cost functions. We show that the number of firms in a steady-state open-loop solution for a dynamic free-entry oligopoly is smaller than that at static equilibrium and that the number of firms in a steady-state memoryless closed-loop solution is larger than that in an open-loop solution.     

Potassium-ion-selective sensing based on selective reflection of cholesteric liquid crystal membranes

It is well-known that cholesteric liquid crystals have an optical property, selective reflection, due to changes in the pitch of their helical structure. This unique property of cholesteric liquid crystals can be used to attain a visual sensing system showing color changes as the detection signal. In this paper, we report a visual sensing membrane comprising cholesteric liquid crystals, in which a 15-crown-5 derivative was incorporated as ion recognizing sites, for K⁺ in aqueous solution. The resulting CLC membrane showed a shift of the reflection peak sensitive to K⁺ in water. We have also designed polymer-dispersed liquid crystal membranes that showed ion-selective reflection peak shifts with improved response time.     

Non-destructive elemental analysis of large meteorite samples by prompt gamma-ray neutron activation analysis with the internal mono-standard method

Prompt gamma-ray neutron activation analysis (PGNAA) using the internal mono-standard method was tested for its applicability to analyzing large solid samples including irregularly shaped meteorite samples. For evaluating the accuracy and precision of the method, large quantities of the Geological Survey of Japan standardized rock powders (JB-1a, JG-1a, and JP-1) were analyzed and 12 elements (B, Na, Mg, Al, Cl, K, Ca, Ti, Mn, Fe, Sm, and Gd) were determined by using Si as an internal standard element. Analytical results were mostly in agreement with literature values within 10 %. The precision of the method was also shown to be within 10 % (1σ) for most of these elements. The analytical procedure was then applied to four stony meteorites (Allende, Kimble County, Leedey, Lake Labyrinth) and four iron meteorites (Canyon Diablo, Toluca (Mexico), Toluca (Xiquipilco), Squaw Creek) consisting of large chunks or single slabs. For stony meteorites, major elements (Mg, Al, Si, S, Ca, and Ni), minor elements (Na and Mn) and trace element (B, Cl, K, Ti, Co, and Sm) were determined with adequate accuracy. For iron meteorites, results for the Co and Ni mass fractions determined are all consistent with corresponding literature values. After the analysis, it was confirmed that the residual radioactivity remaining in the sample after PGNAA was very low and decreased down to the background level. This study shows that PGNAA with the internal mono-standard method is highly practical for determining the elemental composition of large, irregularly shaped solid samples including meteorites.     

Synthesis of 2,3-dihydro-1H-isoindole-1-thiones via the bromine–lithium exchange between 1-bromo-2-(1-isothiocyanatoalkyl)benzenes and butyllithium

The reaction of 1-bromo-2-(1-isothiocyanatoalkyl)benzenes, which are easily derived from 2-bromophenyl ketones or (2-bromophenyl)methanamine, with butyllithium generates 1-(1-isothiocyanatoalkyl)-2-lithiobenzenes, which immediately underwent intramolecular cyclization to give rise to the corresponding 3-substituted and 3,3-disubstituted 2,3-dihydro-1H-isoindole-1-thiones in good yields.