Efficient synthesis of optically active α-substituted glutamate analogs possessing α-hydroxymethyl and α-alkoxymethyl groups

Highly enantioselective synthesis of (2R)-α-(hydroxymethyl)glutamate (1), a selective agonist of mGluR2 and 3, was achieved in short steps using an asymmetric version of the Strecker synthesis. This was converted into its α-methoxymethyl- and α-benzyloxymethyl derivatives 2 and 3, possible ligands as tools to investigate glutamate receptors, via protection of the sterically hindered amino group by means of phase transfer catalyst.     

Study of Si(0 0 1)4 × 2-Ga structure by scanning tunneling microscopy and ab initio calculation

We have studied Si(0 0 1)-Ga surface structures formed at Ga coverages of slightly above 0.50 monolayer (ML) at 250 °C by scanning tunneling microscopy (STM). 4 × 2-, 5 × 2-, and 6 × 2-Ga structures were observed in a local area on the surface. The 4 × 2-Ga structure consists of three protrusions, as observed in filled- and empty-state STM images. The characters of these structures are clearly different from those of other Si(0 0 1)-Ga structures. We also performed an ab initio calculation of the energetics for several possible models for the 4 × 2-Ga structure, and clarified that the three-orthogonal-Ga-dimer model is the most stable. Also, the results of comparing the simulated STM images and observation images at various bias voltages indicate that this structural model is the most favorable.     

Assignment of surface IR absorption spectra observed in the oxidation reactions: 2H + H2O/Si(1 0 0) and H2O + H/Si(1 0 0)

Infrared reflection absorption spectroscopy that used buried metal layer substrates (BML-IRRAS) and density functional cluster calculations were employed to investigate the water related oxidation reactions of 2H + H₂O/Si(1 0 0)-(2 × 1), 2D + H₂O/Si(1 0 0)-(2 × 1), and H₂O + H/Si(1 0 0)-(2 × 1). In addition to the oxygen inserted coupled monohydrides, which were previously reported in the former reaction system, we report several other oxidized Si hydride species in our BML-IRRAS experiments. Three new pairs of vibrational bands are identified between 900 and 1000 cm⁻¹. These vibrational frequencies were calculated using Si9 and Si10 cluster models that included all possible structures from zero to five oxygen insertions into the top layer silicon atoms using a B3LYP gradient corrected density functional method with a polarized 6-31G** basis set for all atoms. The three pairs of vibrational modes are assigned to the scissoring modes of adjacent and isolated SiH₂ with zero, one, and two oxygen atoms inserted into the Si back bonds. All the other newly observed vibrational peaks related to Si oxidation are also assigned in this study. The Si-O stretching bands observed in the reaction 2D + H₂O/Si(1 0 0)-(2 × 1) show an isotope effect, which suggests that in the system 2H + H₂O/Si(1 0 0)-(2 × 1) also, hydrogen atom tunneling plays an important role for the insertion of oxygen atoms into Si back bonds that form oxidized adjacent dihydrides.     

Improvement of stability of phenacyloxycarbamidomethyl (Pocam) group,a cysteine protecting group removable with zinc reduction,under acidic conditions

In order to improve the stability of phenacyloxycarbamidomethyl (Pocam) group, a cysteine protecting group removable with zinc reduction, under acidic conditions, various alkyl substituents on the nitrogen atom of Pocam group were examined. As a result, attachment of an electron-withdrawing group improved the stability, and 2,2,2-trifluoroethyl (Tfe) group was most effective among four substituents tested. Tfe-Pocam group could be used in solid-phase peptide synthesis and peptide condensation reactions, and it was also useful for regioselective disulfide formation reactions.     

A novel anthracene-based fluorescent colorimetric sensor for the simple naked-eye diagnosis of methylmalonic aciduria

A novel molecular sensor using anthracene bearing two amidopyridines emits blue fluorescence in the presence of succinic acid and green fluorescence in the presence of malonic acid, and its fluorescence intensity increased upon binding. Using this molecular sensor, we succeeded in detecting the difference of one carbon atom between succinic acid and malonic acid with the naked-eye. Furthermore, when methylmalonic acid was dissolved in urine to provide a model system for methylmalonic aciduria, the fluorescence changed from blue to green, and methylmalonic acid was successfully detected with the naked-eye.     

Water-soluble supramolecular porphyrin dimer: self-organization of mono(imidazolyl)-substituted Zn porphyrin to a special-pair type dimer in water

Tris(4-carboxylphenyl)-mono(N-methylimidazolyl)-substituted Zn porphyrin was synthesized as a precursor for a water-soluble supramolecular porphyrin dimer. The dimer formation was performed in a NaHCO₃ aq solution (pH 8.4) and phosphate buffer solutions (pH 7.4-9.0). The split Soret bands of Zn porphyrin observed in the absorption spectra clearly showed self-organization to a special-pair type slipped cofacial dimer via metal coordination of imidazole even in water.     

Novel superconducting phases in copper oxides and iron-oxypnictides: NMR studies

We reexamine the novel phase diagrams of antiferromagnetism (AFM) and high-T_c superconductivity (HTSC) for a disorder-free CuO₂ plane based on an evaluation of local hole density (p) by site-selective Cu-NMR studies on multilayered copper oxides. Multilayered systems provide us with the opportunity to research the characteristics of the disorder-free CuO₂ plane. The site-selective NMR is the best and the only tool used to extract layer-dependent characteristics. Consequently, we have concluded that the uniform mixing of AFM and SC is a general property inherent to a single CuO₂ plane in an underdoped regime of HTSC. The T=0 phase diagram of AFM constructed here is in quantitative agreement with the theories in a strong correlation regime which is unchanged even with mobile holes. This Mott physics plays a vital role for mediating the Cooper pairs to make T_c of HTSC very high. By contrast, we address from extensive NMR studies on electron-doped iron-oxypnictides La1111 compounds that the increase in T_c is not due to the development of AFM spin fluctuations, but because the structural parameters, such as the bond angle α of the FeAs₄ tetrahedron and the a-axis length, approach each optimum value. Based on these results, we propose that a stronger correlation in HTSC than in FeAs-based superconductors may make T_c higher significantly.