Direct determination of benzamides in serum by column-switching high-performance liquid chromatography.

A column-switching high-performance liquid chromatographic method with fluorescence detection was developed for the simultaneous determination of four benzamide-type anti-psychotic drugs: sulpiride, tiapride, sultopride and metoclopramide in human serum. In this method, a TSKgel Super-ODS column was used as an analytical column, and a TSKgel G 2000SW was prepared as a pretreatment column. Under the optimized analytical conditions, four benzamide-type anti-psychotic drugs were eluted within 18 min. The detection limits (S/N = 3) for sulpiride, tiapride, sultopride and metoclopramide are 1 ng/ml, 4 ng/ml, 2 ng/ml and 0.5 ng/ml, respectively. Finally, the method was applied to the determination of sulpiride in human serum samples obtained after a single oral dose of sulpiride.     

Peak effect and dynamic melting of vortex matter in NbSe2 crystals

We present a mode locking (ML) phenomenon of vortex matter observed around the peak effect regime of 2H-NbSe2 pure single crystals. The ML features allow us not only to trace how the shear rigidity of driven vortices persists on approaching the second critical field, but also to demonstrate a dynamic melting transition of driven vortices at a given velocity. We observe the velocity dependent melting signatures in the peak effect regime, which reveal a crossover between the disorder-induced transition at small velocity and the thermally induced transition at large velocity. This uncovers the relationship between the peak effect and the thermal melting.     

Electronic structure of dysprosium silicide films grown on a Si(1 1 1) surface

The thickness-dependent electronic structures of Dy silicide films grown on a Si(1 1 1) surface have been investigated by angle-resolved photoelectron spectroscopy. Two (1×1) periodic bands, both of them cross the Fermi level, have been observed in the silicide films formed by Dy coverages of 1.0 monolayer and below, and more than five () periodic bands have been observed in thicker films. Taking the () periodic structure of Dy atoms in the submonolayer silicide film into account, the periodicity of the two metallic bands indicate that they mainly originate from the orbitals of Si atoms, which form a (1×1) structure. Of the () periodic bands observed in thick films, four of them are well explained by the folding of the (1×1) bands into a () periodicity. Regarding the other band, the three () periodic bands would originate from the electronic states related to the inner Si layers that form a () structure, and the one observed in the 3.0 ML film only might originate from the electron located at the interface between bulk Si and the Dy silicide film.     

The unstable behavior of cellular premixed flames induced by intrinsic instability

The unstable behavior of cellular premixed flames induced by intrinsic instability is studied by two-dimensional unsteady calculations of reactive flows. In the present numerical simulation, the compressible Navier–Stokes equation including a one-step irreversible chemical reaction is employed. We consider two basic types of phenomena to account for the intrinsic instability of premixed flames, i.e., hydrodynamic and diffusive-thermal effects. The hydrodynamic effect is caused by the thermal expansion through the flame front; the diffusive-thermal effect is caused by the preferential diffusion of mass versus heat. A disturbance with several wavelength components is superimposed on a planar flame, and the formation of a cellular flame induced by hydrodynamic and diffusive-thermal effects is numerically simulated. After the cellular-flame formation, the combination and division of cells are observed. The behavior of cellular-flame fronts becomes more unstable when the Lewis number is lower than unity, since the diffusive-thermal effect has a great influence on the unstable behavior. The cell size changes with time, and its average is greater than the critical wavelength and becomes smaller by decreasing the Lewis number. The flame velocity of cellular flames depends strongly on the length of computational domain in the direction tangential to the flame front. As the length of computational domain increases, the flame velocity becomes larger. This is because the long-wavelength components of disturbances play an important role in the shape of cellular flames, i.e., in the flame-surface area.     

Proper composition for superconductivity in Pb(Ba, Sr)2(Y, Ca)Cu3O7

Superconductivity and composition analysis of PbBaSr(Y, Ca)Cu₃O_y with fixed ratio of Sr/Ba = 1 were studied. Synthesis condition and superconductivity of Pb(Ba, Sr)₂(Y, Ca)Cu₃O_y with various ratio of Sr/Ba and Ca/Y were also studied. It was found that T_c increased with increasing Ca concentration, and that Sr-rich specimens allowed to contain more Ca. PbBa_0.8Sr_1.2Y_0.6Ca_0.4Cu₃O₇ showed superconductivity with zero-resistance temperature of 42 K, which was higher than PbBaSrY_0.7Ca_0.3Cu₃O₇ with maximum Ca content for Sr/Ba = 1. Decrease in averaged ionic radii of Ba and Sr in Sr-rich compositions would be favorable for the contraction of Cu-O bonds by hole-doping via Ca substitution for Y.     

Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes

A series of nitrogen‐tethered allenynes (‘5‐aza‐1,2‐dien‐7‐ynes’) 1 were transformed to the corresponding 3‐acyl‐4‐alkenylpyrrolidines 3 when treated with a catalytic amount of PtCl₂ in MeOH at 70°. Initial Pt‐promoted cyclization forms a nonclassical carbocationic intermediate. In contrast to the cycloisomerization in toluene, which produced the bicyclic cyclobutenes 2 , the intermediate is intercepted by addition of an oxygen nucleophile to achieve the formal hydrative cyclization.     

Beta-isocupreidine-catalyzed Baylis-Hillman reaction of chiral N-boc-alpha-amino aldehydes

[Structure: see text] Beta-isocupreidine (beta-ICD)-catalyzed Baylis-Hillman reaction of chiral N-Boc-alpha-amino aldehydes and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) takes place without racemization and exhibits the match-mismatch relationship between the substrate and the catalyst. In the case of acyclic amino aldehydes, L-substrates show excellent syn selectivity and high reactivity in contrast to D-substrates. On the other hand, in the case of cyclic amino aldehydes, D-substrates rather than L-substrates show excellent anti selectivity and high reactivity.     

Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes utilizing silyl group-substituted titanium carbene complexes as bimetallic synthetic reagents

Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes by the sequential reactions using silyl group-substituted titanium carbene complexes was studied. Dienylsilanes were obtained by the olefination of carbonyl compounds with γ-silylvinylcarbene complexes. Cyclopropanation of 1-alkenes with the vinylcarbene complexes produced (E)-(β-silylvinyl)cyclopropanes with high stereoselectivity. The reaction of β-(trialkylsilyl)carbene complexes with zinc alkoxides of homopropargyl alcohols produced 6-silyl-3,5-hexadien-1-ols with high regio- and stereoselectivity. The (E)-alkenylsilanes thus obtained were transformed into a range of unsaturated compounds by the palladium-catalyzed or copper(I)-promoted cross-coupling with organic halides with retention of configuration.