The preparation of 1,4-dicarbonyl compounds by photoreaction of ketones in the presence of oxidants

Phenyl alkyl ketones were photo-irradiated in the presence of Cr(VI) or Mn(VII) oxidants to yield 1,4-dicarbonyl compounds regiospecifically while 2-octanone gave a regioisomeric mixture of 2,5-, 2,6-, and 2,7-octadiones.     

Charmed hadron production in \pi p and Kp collisions and leading particle effect by constituent quark-diquark cascade model

We investigate the meson, baryon and anti-baryon productions in and collisions in terms of a constituent cascade model which includes charm flavour. The constituent diquark in an incident baryon has a tendency to get a large momentum fraction, resulting in considerable difference of subenergies for particle productions from quark-diquark and quark-antiquark chains in a meson-baryon collision. As a consequence, the leading particle effects on meson productions are expected to be quite different in and beams at present accelerator energies. Received: 5 November 1996 / Revised version: 30 June 1997 / Published online: 20 February 1998     

Transition from periodic to non-periodic oscillation observed in a mathematical model of bioconvection by motile micro-organisms

Bioconvection observed in a culture of motile micro-organisms was analyzed numerically. The governing equations are the Navier-Stokes equations with the Boussinesq approximation and a diffusion equation for the motile micro-organism. A transition from a static condition to periodic oscillation was observed according to the increase of the Rayleigh number. It was found that the system of bioconvection could be led into chaotic conditions via a single-frequency oscillatory behavior to a sequence of period-doubling bifurcations by increasing the Rayleigh number, which is analogous to Bénard convection.     

Reformatsky type additions of haloacetonitriles to aldehydes mediated by metallic nickel

Nickel in the metallic state was found to carry out the Reformatsky type addition of haloacetonitriles to aldehydes via cyanomethylnickel halides to give β-hydroxynitriles in good yields.     

Identification problems for the damped Klein-Gordon equations

In this paper we study the identification problems for the damped Klein-Gordon equation (KG). In particular, when the diffusion parameter of KG is unknown, we prove the existence of the optimal parameter and deduce the necessary conditions on the optimal parameter by using the transposition method.     

A novel method to introduce durable hydrophilicity onto hydrophobic polymer surface by plasma treatment

We have examined a novel method to fabricate a durable hydrophilic surface of hydrophobic polymeric materials modified by plasma treatment. The method involves a trapping of maleic anhydride-containing polymer onto poly(ethylene naphthalate) (PEN) by a plasma-induced crosslinking reaction of PEN followed by hydrolysis of maleic anhydride moiety to generate hydrophilic carboxyl groups on the PEN surface. In fact, the PEN film surface thus treated has shown an effective stability of wettability based on the water contact angle measurement.     

Complete thermal-unfolding profiles of oxidized and reduced cytochromes C

The complete thermal-unfolding profiles of both oxidized and reduced forms of cytochrome c551 (PA) from mesophilic Pseudomonas aeruginosa and cytochrome c552 (HT) from thermophilic Hydrogenobacter thermophilus were obtained by the newly developed pressure-proof cell compartment installed in a circular dichroic spectrometer, which facilitates protein thermal-unfolding experiments up to 180 degrees C. The thermodynamic cycle, which relates protein stability and redox function, indicated that the redox potentials of PA and HT in the native state are regulated by the stability of the oxidized proteins rather than by that of the reduced ones.     

Carbonylation of lithium enolates with carbon monoxide mediated by selenium

[reaction: see text] Lithium enolates of ketones and aldehydes undergo carbonylation with carbon monoxide with the aid of selenium under mild conditions to yield beta-keto and beta-formyl selenol esters after trapping with alkyl iodides. This reaction proceeds via a unique carbonylation mechanism comprised of O-carbonylation and subsequent migration of the SeCO moiety to the alpha-carbon.     

Novel photo-induced oxidative cyclization of 1,3-dimethyl-5-(1-arylmethylidene)pyrimidine-2,4,6(1,3,5H)-triones: synthesis and properties of areno[5,6]pyrano[2,3-d]pyrimidine-2,4(1,3H)-dionylium ions and their photo-induced autorecycling oxidizing reaction toward some amines

Novel photo-induced oxidative cyclization was accomplished to synthesize areno[b]pyrimido[5,4-e]pyran-2,4(1,3H)-dionylium ions 13a-c⁺·ClO₄⁻. Furthermore, 13a-c⁺·BF₄⁻ and their phenyl-substituted derivatives 19a,b⁺·BF₄⁻ were alternatively synthesized by the reaction of salicylaldehyde and its naphthyl derivatives with barbituric acids and subsequent treatment with aq. HBF₄. Structural characteristics of 13a-c⁺ and 19a,b⁺ were clarified on inspection of the UV-vis and NMR spectral data as well as X-ray crystal analyses. The electrochemical properties were studied by the CV measurement. In a search for reactivity, reactions of 13a-c⁺·BF₄⁻ with some nucleophiles, hydride, benzylamine, and H₂O, were also carried out. The photo-induced autorecycling oxidation reactions of 13a-c⁺·BF₄⁻ toward some amines under aerobic conditions were carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) in 643-3600% yield (recycling number of 13a-c⁺·BF₄⁻: 6.4-36.0).     

Binary and ternary complexes involving manganese(II), 2,2’-bipyridine and halide or thiocyanate ions inN,N-dimethylformamide

Ternary complexation involving the manganese(II) ion, 2,2’-bipyridine (bipy), and halide (chloride, bromide) or pseudohalide (thiocyanate) ions has been studied by precise titration calorimetry inN,N -dimethylformamide (DMF) at 298K. All the titration curves are explained well in terms of formation of mononuclear complexes of the type [MnX_m(bipy)_n](^2-m) + (X = CI, Br or SCN), and the formation of [MnCl(bipy)]⁺, [MnCl₂(bipy)], [MnCl(bipy)₂]⁺ and [MnCl₂(bipy)₂] has been established in the chloride system, [MnBr(bipy)]⁺, [MnBr₂(bipy)], [MnBr(bipy)₂]⁺ in the bromide system, and [Mn(NCS)(bipy)]⁺, [Mn(NCS)₂(bipy)], [Mn(NCS)₃(bipy)]^-, [Mn(NCS)(bipy)₂]⁺, and [Mn(NCS)₂(bipy)₂] in the thiocyanate system. The data were analyzed on the basis of the thermodynamic parameters for the binary Mn^lIbipy and Mn^II-X (X = Cl, Br and SCN) systems, the latter being determined in previous work. The formation constants, reaction enthalpies, and entropies of the ternary complexes were extracted. The thermodynamic parameters thus obtained are discussed in comparison with those of the corresponding systems of other transition metal(II) ions.