Copper- or phosphine-catalyzed reaction of alkynes with isocyanides. Regioselective synthesis of substituted pyrroles controlled by the catalyst

The copper-catalyzed reaction of isocyanides (CNCH2EWG1) 1 with electron-deficient alkynes (RC[triple bond]CEWG2) 2 gave the 2,4-di-EWG-substituted pyrroles 3 selectively, whereas the phosphine-catalyzed reaction of 1 with 2 afforded the 2,3-di-EWG-subsituted pyrroles 4. Accordingly, regioselective synthesis of substituted pyrroles has been achieved by merely choosing the catalyst.     

Determination of alpha-tocopherol and alpha-tocopherylquinone in rat tissues and plasma by high-performance liquid chromatography with electrochemical detection

Alpha-tocopherol and alpha-tocopherylquinone in rat tissues and plasma were determined simultaneously by using high-performance liquid chromatography-electrochemical detection (HPLC-ED) with dual electrodes in the series mode. Biological samples were saponified in the presence of a mixture of butylated hydroxytoluene, ascorbic acid, and pyrogallol and then extracted with hexane. The compounds were separated on a C18 column using a mobile phase containing 95% methanol and 0.05 M sodium perchlorate as the supporting electrolyte. After HPLC separation, alpha-tocopherylquinone was first reduced at an upstream electrode at -500 mV Both alpha-tocopherol and the reduction product of alpha-tocopherylquinone were then oxidized downstream at +600 mV. Only the downstream electrode current was monitored for the determination. Linearity of the standard curves was obtained over the range 5-30 pmol for alpha-tocopherol and alpha-tocopherylquinone. Minimum detectable quantities (S/N of 3) were 0.25 pmol for alpha-tocopherol and 0.31 pmol for alpha-tocopherylquinone. The method was applied to analysis of the contents of alpha-tocopherol and alpha-tocopherylquinone in rat tissues and plasma. By hyperoxia, the content of alpha-tocopherol was decreased remarkably in lung, and in contrast, the contents of alpha-tocopherylquinone were increased in all tissues studied with the exception of plasma, though the content of alpha-tocopherylquinone in normal rats is quite small. The technique is particularly useful in the quantitation of the oxidation of alpha-tocopherol in biological samples.     

A locally most powerful invariant test for the equality of means associated with covariate discriminant analysis

In this paper, the authors propose a locally most powerful invariant test for the equality of means in the presence of covariate variables. Also the null and nonnull distributions associated with the above test are developed. This problem arises in covariate discriminant analysis and has been treated by various authors, notably Cochran and Bliss 1948, Ann. Math. Statist.19, 151–176 and Rao 1949, Sankhyã9 343–366; 1966. The test derived here locally dominates in power the tests proposed so far. It is also shown that the Cochran-Bliss test is uniformly most powerful in the class of conditional invariant tests.     

Supramolecular polar thin films built by surfactant liquid crystals: polarization-tunable multilayer self-assemblies with in-plane ferroelectric ordering of ion-based dipoles.

Polar order in the phosphonium liquid crystal thin films, which are composed of two-dimensional ion-pair-based domains separated by the insulating hydrocarbon layers, was probed by second harmonic generation (SHG) analysis. Despite the ordinary amphiphilic self-assemblies containing no pi-electron moieties, the solid-state thin films retaining a smectic layer structure showed clearly an SHG activity, while the disordered films without the layer structure were not active at all for the SHG. It was found that the multilayer structure plays a crucial role for the SHG from the phosphonium thin films and the ionic layers act as an SHG-active site. The most significant characteristic of this system is to possess an ability to control SHG intensity electrically. The efficiency of the SHG process in the thin-film assemblies was enhanced by applying an external electric field parallel to the layer plane. Furthermore, through evaluation of thermal stability of the sample films, it was revealed that the SHG signals were detected only in the solid-state temperature range and the disappearance of the SHG occurs earlier than the solid-to-liquid crystalline phase transition. These results demonstrated that the origin of polar order in the phosphonium thin films is due to in-plane noncentrosymmetric arrangement (ferroelectric ordering) of ion pairs as an electric dipole, that is, dipole symmetry in an ionic layer.     

Beta and gamma decays of J π = 1+, 24mAl state

A β-γ spectroscopy of the J ^π , 426 keV isomeric state of ²⁴Al (^24m Al) has been carried out by using a ²⁴Al secondary beam with high purity and high isomeric ratio. From the absolute γ-ray and β-particle intensities observed in the decay of the isomeric state, the branching ratio R _B of the isomeric γ decay from ^24m Al to the J ^π = 4⁺, ground state of ²⁴Al have been derived. The obtained R _B value of 69.6(7)% is much smaller than the previously accepted value of 82.5(30)%. The precise half-life for the isomer decay, T _1/2 ^m = 130.9(13) ms, has been also determined in this experiment. Accordingly, the M3 γ-decay strength B(M3) of the ^24m Al decay becomes smaller and the total β-decay branching ratio becomes larger. In particular, the β-decay branching ratio to the ground state of ²⁴Mg becomes 24.3(9)%, which is 2.4 times larger than the previous value of 10.1(28)%. By combining the branching ratio and the half-life, the Gamow-Teller (GT) transition strength B(GT) of 0.0194(7) is deduced for the GT transition from ^24m Al to the J ^π = 0⁺, ground state of ²⁴Mg. This value is in good agreement with the values derived from charge-exchange reactions.     

A first sub-stage in stage III in quenched pure aluminium studied by positron annihilation

It has been found for the first time by positron annihilation that the line-shape parameter h increases and subsequently decreases in the initial region of stage III annealing, below ≈-60°C, in quenched pure aluminium. It is deduced that the change in h parameter in this temperature region seems to correspond to the formation and sebsequent collapse of small vacancy clusters.     

Observation of two-hole states at high excitation energy in (p,t) reactions

Bumps of two-hole states at high excitation energies were observed systematically in the triton spectra from (p, t) reactions with 52 MeV protons on nuclei in a broad range of masses. The cross sections of the bumps are almost equal for various targets with the same deep major shells. These cross sections vary discontinuously with variation of the corresponding deep major shell. About 20 to 50 % of the total expected strength is observed experimentally, if the bumps are assumed to arise from two-neutron pickup from the deep major shells. The centres of gravity of the bumps are located at excitation energies of about 7 to 9 MeV in all cases. On the other hand, the widths of the bumps change from about 3 MeV for ⁶⁶Zn to about 9 MeV for ²³⁰Th.     

Kinetics of oxygen transfer at a solid-oxide electrolyteMo,MoO2 electrode interface

Galvanostatic overvoltage measurements were performed with the symmetrical cell;Mo + MoO₂/ZrO₂(CaO)/Mo + MoO₂. The magnitude of the overvoltage was consistent with the oxygen transfer rate being limited by the diffusion of oxygen through the metal component of the two-phase electrode. The overvoltages were found to be reduced by increasing the fraction of metal component in the electrode. The solubility-diffusivity product for oxygen in metals is a good guideline for the selection of reference electrode to obtain accurate EMF of electrochemical cells.     

Characteristics of the H(+)-translocating adenosine triphosphatase of Vibrio parahaemolyticus

We have characterized H(+)-translocating adenosine triphosphatase (ATPase) in membrane vesicles of Vibrio parahaemolyticus. The ATPase required high concentrations (about 0.5 M) of Na2SO4 (or other salts) for its maximum activity. Magnesium ion stimulated the ATPase activity, but Ca2+ did not. The activity of ATPase was inhibited by tetrachlorosalicylanilide, an H+ conductor, but not by another H+ conductor, carbonylcyanide-m-chlorophenylhydrazone. The activity was strongly inhibited by dicyclohexylcarbodiimide or Zn2+, and partially inhibited by azide, but not at all by vanadate.