Overview of coupled map lattices

Studies in coupled map lattices are briefly surveyed in connection with the papers in the present focus issue.     

A new nonpeptide tachykinin NK1 receptor antagonist isolated from the plants of Compositae

To find new tachykinin NK1 receptor antagonists from natural sources, we examined the tachykinin antagonist activity in the extracts of approximately 200 species of plants by the use of isolated guinea pig ileum. As a result, we discovered a novel and potent NK1 receptor antagonist in the extract of dried flowers of Matricaria chamomilla L. (chamomile). The structure of the antagonist was established as N1,N5,N10,N14-tetrakis[3-(4-hydroxyphenyl)-2-propenoyl]-1,5,10,14-tetraazatetradecane (tetracoumaroyl spermine, 1a). The Ki values of 1a, estimated from the inhibitory action on the substance P (SP)-induced contraction of the guinea pig ileum and the inhibition of the binding of [3H][Sar9, Met(O2)11]SP to human NK1 receptors, were 21.9 nM and 3.3 nM, respectively. 1a is the first potent NK1 receptor antagonist from natural sources and it has a unique structure of a polyacylated spermine. 1a was concentrated in pollen of Matricaria chamomilla L. and was also found in the extracts of flowers of other four species of Compositae. In addition, we found N1,N5,N10-tris[3-(4-hydroxyphenyl)-2-propenoyl]-1,5,10,14-tetraazatetradecane (2) as a new compound in the extract of flowers of Matricaria chamomilla L., which did not exhibit any tachykinin antagonist activity. A number of related compounds were synthesized, and the structure-activity relationship was studied.     

LOSS OF PHOTOREACTIVATION IN UV-IRRADIATED CULTURED FISH CELLS UNDER DIFFERENT CONDITIONS

Abstract— CAF-MM1 cells derived from a goldfish have photoreactivability for the damage induced by ultraviolet light (UV). When UV-irradiated cells were incubated in the dark at 26_AoC, the longest interval in which photoreactivation (PR) was observed (i.e. effective time for PR), measured by colony formation technique, was about 30 h after the UV irradiation. However, if the cells were incubated at 20_AoC, the effective time was prolonged. Since each time appeared to correspond to the doubling time of the cells at each temperature, the loss of photoreactivability is suggested to be closely related to cell growth or progression of cell cycle. The loss of PR was not observed in the cells held in confluence up to 48 h after UV irradiation, in support of the above suggestion. Photoreactivating enzyme in growing CAF-MM1 cells incubated in the dark for 24 h after UV irradiation was shown to be active, so that it is not possible that the cause of the loss of PR is change in the activity of photoreactivating enzyme.     

Asymmetric Michael reactions of α-substituted acetates with cyclic enones catalyzed by multifunctional chiral Ru amido complexes

Well-defined 16-electron chiral Ru amido complexes, Ru[(R,R)-diamine](η⁶-arene), efficiently catalyze asymmetric Michael additions of Michael donors to cyclic enones to give adducts in high yields and with excellent ee’s. β-Ketoesters or nitroacetate as Michael donors react with 2-cyclopentenone in toluene or t-butyl alcohol containing the Ru amido catalyst (S/C=50) to afford the Michael adduct in 99% yield and with up to 92% ee. The outcome of the reaction was delicately influenced by the structures of the diamine and arene ligands as well as reaction conditions.     

Novel Ti-O-Ti bonding species constructed in a metal-oxide cluster

The preparation and structural characterization of a novel Ti-O-Ti bonding complex constructed in the mono-lacunary alpha-Keggin polyoxometalate (POM), are described. The water-soluble, crystalline complex with a formula of K5H2[[{Ti(OH)(ox)}2(micro-O)](alpha-PW11O39)] x 13H2O 1 was prepared in 30.2% (0.60 g scale) yield in a 1 : 3 molar-ratio reaction of the tri-lacunary species of alpha-Keggin POM, Na9[A-PW9O34] x 19H2O, with the titanium(IV) source, K2TiO(ox)2 x 2H2O (H2ox = oxalic acid), in HCl-acidic solution (pH 0.08), and characterized by complete elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solution (31P, 183W, 1H and 13C) NMR spectroscopy and X-ray crystallography. The complex was also obtained in 47.6% (0.81 g scale) yield in a 1 : 2 molar-ratio reaction of the mono-lacunary Keggin POM, K7[PW11O39] x 10H2O, with the anionic titanium(IV) complex under acidic conditions. The molecular structure of [[{Ti(OH)(ox)}2(micro-O)](alpha-PW11O39)]7- 1a, was successfully determined. This POM in the solid state is composed of one host (mono-lacunary site) and two guests (two octahedral Ti groups), in contrast to most titanium (IV)-substituted POMs consisting of one host and one guest. On the other hand, the 31P NMR measurements revealed that in aqueous solution this POM was present under a dissociation equilibrium which depends upon both temperature and pH.     

Highly regioselective lipase-catalyzed acetylation and hydrolysis of acyclic α,ω-terpenediols and their diacetates

Highly regioselective transformations of the acyclic α,ω-terpenediols and their diacetates to the monoacetates using lipase were accomplished. The acetylation of the α,ω-terpenediols gave regioselectively the ω-monoacetates 3, whereas the α-monoacetates 2 were obtained by hydrolysis of the α,ω-diacetates.     

Effective UV photolytic decomposition of organic compounds with a low-pressure mercury lamp as pretreatment for voltammetric analysis of trace metals

The effectivity of UV irradiation with low and high pressure mercury (L-Hg and H-Hg) lamps on the decomposition of organic compounds in aqueous solutions, as pretreatment for the voltammetric determination of trace metals, is compared. The photolytic decomposition with the L-Hg lamp was much faster than with the H-Hg lamp. The higher efficiency of the L-Hg lamp is caused by its greater light intensity at short wavelengths. Interferences of organic compounds on the voltammetric determination of nickel and indium were eliminated successfully by 90 min irradiation with the L-Hg lamp. Humic acid and organic interference with the voltammetric determination of nickel in natural river water were successfully eliminated. The decomposition using the L-Hg lamp can be carried out without added oxidizing reagents and at room temperature, thus eliminating loss of water samples by evaporation at higher temperature.     

A general catalytic allylation using allyltrimethoxysilane

A general and mild catalytic allylation of carbonyl compounds, applicable to aldehydes, ketones, and imines is developed using allyltrimethoxysilane as the allylating reagent. The reaction proceeds smoothly with 1-10 mol % of CuCl and TBAT in THF at ambient temperature. Mechanism studies indicated that the copper alkoxide, allylfluorodimethoxysilane, and allyltrimethoxysilane are essential to promote the reaction efficiently. Preliminary extension of the reaction to the first catalytic enantioselective allylation of ketones using an allylsilane produced the product with 61% ee from acetophenone, using a CuCl-p-tol-BINAP-TBAT catalyst (15 mol %).     

A convenient preparation of N- (arenesulfonyl) sulfoximines by oxidation of N- (arenesulfonyl) sulfilimines with sodium hypochlorite in a two phase system

N-(Arenesulfonyl) sulfilimines can be oxidized to the corresponding sulfoximes in high yields with sodium hypochlorite in an AcOEt-H₂O two phase system in the presence of quaternary ammonium salts as catalysts.     

New design of a radio-frequency plasma torch

A numerical model has been developed for predicting the two-dimensional flow and temperature fields in a radio-frequency (rf) plasma torch. The method employed here is based on Boulos' model with the exception of the boundary conditions for the electric and magnetic field equations. Calculations have been made for the confirmation of a new sample injection method, which is capable of completely evaporating refractory materials at high feeding rates without interfering with the stability of the plasma. In the newly designed torch, the reagent is radially injected into the hottest part of the plasma through quartz capillary tubes set symmetrically between an inductor coil. Experimental investigations have also been performed for verifying the proper function of the design. These results provide evidence that our radial injection method developed here is more effective in practical processing than the conventional axial injection methods.