Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.

     

Depassivation-repassivation behavior of a pure iron surface investigated by micro-indentation

Depassivation-repassivation behavior on a pure iron surface in borate buffer solution was examined under potentiostatic control by a micro-indentation test. Current peaks emerge during both downward and upward drives of the indenter due to depassivation which is caused by plastic deformation of the substrate but not elastic deformation and repassivation. The total electric charge of the current peaks is proportional to the maximum load. The total electric charge also increases with increase in intermission time of the indentation, indicating that the passive film is ruptured even during stress relaxation. It is estimated from the electric charge balance that 82% and 18% of the film rupture occurs during the downward drive and intermission, respectively, and that no rupture occurs during the upward drive. Furthermore, the film-ruptured area is estimated to be 80% of the plastic deformed surface area. The partial retainment of the passive film on iron suggests that the ductility of the passive film is higher than that of the substrate.     

Functional analysis of genes encoding putative oxidoreductases in Aspergillus oryzae, which are similar to fungal fructosyl-amino acid oxidase

We found 11 genes (FAO1-11) encoding putative oxidoreductases in the Aspergillus oryzae genome, which are similar to fungal fructosyl-amino acid oxidases. The cDNAs corresponding to the genes were cloned and expressed in Escherichia coli. rFao2 had fructosyl-amino acid oxidase activity, whereas rFao1 did not show any enzyme activity, even though the deduced amino acid sequence of Fao1 is identical to that of one of the fructosyl-amino acid oxidase isozymes from Aspergillus oryzae. rFao7 and rFao8 showed oxidase activity toward sarcosine, L-pipecolate, and L-proline. rFao10 was active toward only sarcosine, of the substrates tested. The functions of the other proteins were also predicted from a phylogenetic analysis.     

Estimation of concentrations of antifungal agents allowed as food additives in foods and their daily intake based on official inspection results in Japan in fiscal year 1998

The mean concentrations and daily intake of four antifungal agents were estimated based on the results of an analysis of 7,005 samples of food obtained in official inspections by Japanese local governments in fiscal year 1998. The mean concentration of diphenyl was 0.0004% of the allowable limit, and those of imazalil, o-phenylphenol, and thiabendazole were 14.0%, 3.5%, and 5.7%, respectively. The daily intakes of these antifungal agents per person, estimated from their concentrations and the daily consumption of the foods, were 0.000326, 1.89, 11.5, and 23.3 micrograms, respectively, and assuming a body weight of 50 kg, the amounts of these antifungal agents consumed were 0.000013%, 0.15%, 0.12%, and 0.47% of the acceptable daily intake, respectively. These values are similar to the values obtained on the basis of the results of the official inspection in fiscal years 1994 and 1996, except that the amount of diphenyl is much lower (1/100).     

Pressure-sensitive molecular film for investigation of micro gas flows

For the development of micro- and nano-technology, it has been strongly desired to understand thermo-fluid phenomena inside or around micro- and nano-devices. An optical measurement technique based on the absorption and the emission of photons by molecules is useful for experimental analyses of thermo-fluid phenomena of micro and nanoflows. The pressure-sensitive paint (PSP) technique is a potential diagnostic tool for pressure measurements of micro/nano gas flows because it works as a so-called “molecular sensor”. However, the micro-scale measurement of PSP has been limited by the aggregation of the luminescent molecules and their thick film due to the use of a polymer binder. In our previous work, we adopted the Langmuir–Blodgett (LB) technique to fabricate pressure-sensitive molecular film (PSMF) with ordered molecular assemblies, and investigated properties of PSMF. In this study, a novel approach to enhance the luminescent intensity of PSMF is proposed, and the pressure distribution in a micro-nozzle is successfully measured by using PSMF. Moreover, we compared the pressure distribution measured by PSMF with that numerically analyzed by the direct simulation monte carlo (DSMC) method, showing good agreement with each other.     

Heat Source in Infinite Plane with Elliptic Rigid Inclusion and Hole

The plane thermoelastic problems of a stationary heat source in an infinite plane with an elliptic rigid inclusion and an elliptic hole are analyzed under thermally adiabatic and isothermal boundary conditions. The problems of an elliptic rigid inclusion are derived for the following cases: (1) the case that there are rigid-body displacement and rotation; and (2) the case that there is no rigid-body displacement or rotation. To analyze these problems, the following three fundamental solutions are derived: Problem A, in which a point heat source exists within an infinite domain; Problem B, in which the inclusion has a small amount of rotation; and Problem C, in which the inclusion is subjected to concentrated loads. Two cases can be obtained by superimposing these fundamental solutions. For the hole problem, the fundamental solution (Green's function) is also derived. In analysis, the complex stress functions, the mapping function, and the thermal dislocation method are used. The complex stress functions are obtained as a closed form. For analytic examples, the stress distributions are shown under thermally adiabatic and isothermal boundary conditions. For the crack problem, the stress intensity factors are shown for the location of the heat source.     

Preparation of π-conjugated polymers consisting of 1-aminopyrrole and 4-amino-1,2,4-triazole units

π-Conjugated polymers based on 1-aminopyrrole and 4-amino-1,2,4-triazole were prepared. Pd-catalyzed organometallic polycondensation gave poly(arylene-ethynylene) (PAE)-type π-conjugated polymers consisting of BOC-protected 4-amino-1,2,4-triazole (Taz(BOC)) units (BOC = t-butoxycarbonyl). The number average molecular weights (M_n) were determined to be 5200–19,200 using GPC. An alternating copolymer of Taz(BOC) and bithiophene (Th–Th) units, P(Taz(BOC)-Th-Th)_n-Pd, with an M_n of 10,800 was also prepared by Pd-catalyzed organometallic polycondensation. (Taz(BOC)-Th-Th)_n-Pd showed a UV–Vis absorption peak at λ_max = 425 nm, which is reasonable for a π-conjugated five-membered ring polymer with a coplanar structure. The deprotection of the BOC group of the polymers proceeded at 200 °C; this BOC-deprotection was investigated using a model compound. The optical and electrochemical properties of the π-conjugated polymers are reported.