Abnormal Li diffusion in β-LiGa by the formation of defect complex

The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of ⁸Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects.     

Design of sugar–oligonucleotide conjugates installed gold nanoparticle for effective delivery to hepatic parenchymal cells

A novel oligonucleotide delivery system that is based on oligonucleotide–nanoparticle conjugates has been described. Installed oligonucleotides were modified with the carbohydrate at the 3′ terminus, accordingly, constructed nanoparticles display clustered carbohydrates on their outer layer for the targeted delivery of oligonucleotides. The method for the construction of ligand-functionalized nanoparticle was simple and reproducible. The stability of the nanoparticles displaying clustered carbohydrates greatly increased in serum compared to nanoparticles without carbohydrates. In order to investigate the targetability of oligonucleotide–nanoparticle conjugates into primary hepatic parenchymal cells, freshly isolated rat hepatocytes were incubated with nanoparticles and the amount of internalized gold nanoparticles was evaluated by an inductively coupled plasma mass spectroscopy analysis. Nanoparticles displaying clustered carbohydrates internalized more efficiently than nanoparticles without carbohydrate modifications. In particular, the cellular uptakes of oligonucleotide-conjugated gold nanoparticle increased 1.7 ～2.0-fold by galactose modification. Competition assay revealed that clustered galactose enhanced the internalization of the nanoparticle into primary hepatic parenchymal cells by a receptor-mediated process.

Asymmetric α‐Hydroxylation of Tetralone‐Derived β‐Ketoesters by Using a Guanidine–Urea Bifunctional Organocatalyst in the Presence of Cumene Hydroperoxide

Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ).     

NMR studies on the ligand exchange reactions between diaryl tellurides and phenyllithium: Detection of hypervalent triaryl tellurium ate complexes

Diaryl tellurides undergo rapid ligand exchange and disproportionation reactions on treatment with phenyllithium at −78°C. Triarylteliuranes [10-Te-3(C₃)]⁻ Li⁺ were identified as discrete intermediates during the reactions by ¹²⁵Te, ¹H, ¹³C, and CH-COSY NMR studies.     

Poly(2,5-dimethoxyaniline) film coating for corrosion protection of iron

A poly(2,5-dimethoxyaniline) (PDMA) film was coated on the iron surface by the electropolymerization of 2,5-dimethoxyaniline in neutral buffer solution (pH?6.86). The PDMA film strongly adhered to the surface because of the polar methoxy groups of the PDMA molecules. The fact that no electrochemical response of the PDMA film-coated iron electrode to dissolved Fe²⁺ exhibited that the PDMA film was less permeable to dissolved species, acting as a diffusion barrier against agents causing corrosion such as H₂O and O₂. The PDMA film coating greatly lowered the anodic current peak ascribed to the anodic dissolution of iron and the corrosion current in strongly acidic medium, 0.5?M H₂SO₄ aqueous solution (1?M?????mol?dm^??) as well as neutral medium (pH?6.86). The high anti-corrosion ability was due to a hybrid effect of the PDMA film not only as the diffusion barrier, but also as an in situ oxidant in spite of the slight redox activity of PDMA. In addition, the PDMA film is much more durable and adhesive than polyaniline film against over-oxidation.     

Epitaxial strain effects on the metal-insulator transition in V2O3 thin films

Effects of epitaxial stress on the metal-insulator transition of V₂O₃ have been studied for in the form of epitaxial thin films grown on α-Al₂O₃ (0001) and LiTaO₃ (0001) substrates. A metallic phase is stabilized down to 2 K in the V₂O₃ thin film on α-Al₂O₃ (0001), where the a-axis is compressed by 4% owing to large epitaxial stress. On the other hand, the transition temperature T_MI is raised by 20 K from the value of 170 K in bulk samples in the film on LiTaO₃ (0001), where the a-axis is expanded. These results suggest an intimate relationship between the a-axis length and T_MI in V₂O₃. The conductivity of the metallic ultrathin films shows logarithmic temperature dependence below 20 K, probably due to the Anderson localization in two-dimensional systems.     

One-loop Kähler potential in 5D gauged supergravity with generic prepotential

We calculate one-loop contributions to the Kähler potential in 4D effective theory of 5D gauged supergravity (SUGRA) on S¹/_Z2$S^1/Z_2$ with a generic form of the prepotential   and arbitrary boundary terms. Our result is applicable to a wide class of 5D SUGRA models. The derivation is systematically performed by means of an N=1$N=1$ superfield formalism based on the superconformal formulation of 5D SUGRA. As an illustrative example, we provide an explicit expression of the Kähler potential in the case of 5D flat spacetime.     

Conformation of solvent N,N-dimethylpropionamide in the coordination sphere of the zinc(II) ion studied by Raman spectroscopy and DFT calculations

Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion.     

A Unified Strategy for Exceptionally High Diastereoselectivity in the Photochemical Ring Closure of Chiral Diarylethenes

Into my arms : Photochemical cyclization of diarylethenes that have two chiral side arms showed up to 100 % de (see scheme). Introduction of these chiral side arms onto the carbon atoms where ring closure occurs is a general strategy for the highly diastereoselective cyclization of diarylethenes.