The study of electron beam flue gas treatment for coal-fired thermal plant in Japan

The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NO_x and SO_x were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NO_x removal. The target SO_x and NO_x removals (94% and 80%, respectively) with low NH₃ leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH₃ stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm³/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992.     

Evaluation of the disintegration time of rapidly disintegrating tablets via a novel method utilizing a CCD camera

Many kinds of rapidly disintegrating or oral disintegrating tablets (RDT) have been developed to improve the ease of tablet administration, especially for elderly and pediatric patients. In these cases, knowledge regarding disintegration behavior appears important with respect to the development of such a novel tablet. Ordinary disintegration testing, such as the Japanese Pharmacopoeia (JP) method, faces limitations with respect to the evaluation of rapid disintegration due to strong agitation. Therefore, we have developed a novel apparatus and method to determine the dissolution of the RDT. The novel device consists of a disintegrating bath and CCD camera interfaced with a personal computer equipped with motion capture and image analysis software. A newly developed RDT containing various types of binder was evaluated with this protocol. In this method, disintegration occurs in a mildly agitated medium, which allows differentiation of minor distinctions among RDTs of different formulations. Simultaneously, we were also able to detect qualitative information, i.e., morphological changes in the tablet during disintegration. This method is useful for the evaluation of the disintegration of RDT during pharmaceutical development, and also for quality control during production.     

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields.     

New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.     

Cloning and sequence analysis of the poly(3-hydroxyalkanoic acid)-synthesis genes ofPseudomonas acidophila

Pseudomonas acidophila can grow with CO₂ as a sole carbon source by the possession of a recombinant plasmid that clones genes that confer chemolithoautotrophic growth ability derived from the H₂-oxidizing bacteriumAlcaligenes hydrogenophilus. H₂-oxidizing bacteria produce poly(3-hydroxybutyric acid) (PHB) from CO₂, but recombinant P.acidophila can produce the more useful biopolymer poly(3-hydroxyalkanoic acid) (PHA). In this study, thepha genes ofP. acidophila were cloned and a sequence analysis was carried out. A gene library was constructed using the cosmid vector pVK102. A recombinant cosmid carrying thepha genes was selected by the complementation of a PHB-negative mutant ofAlcaligenes eutrophus H16. The resulting recombinant cosmid pIK7 contained a 14.8-kb DNA insert. Subcloning was done, and the recombinant plasmid pEH74 was selected by hybridization with theA. eutrophus H16pha genes.Escherichia coli possessing pEH74 produced PHB, indicating that pEH74 contained thepha genes ofP. acidophila. The nucleotide sequences of the PHA-synthesis genesphaA (3-ketothiolase),phaB (acetoacetyl-CoA reductase), andphaC (PHA synthase) in pEH74 were determined. The homologies ofphaA, phaB, andphaC betweenP. acidophila andA. eutrophus H16 were 64.7, 76.1, and 56.6%, respectively.

     

The counterion releasing effect and the partition coefficient of branched alkanols in ionic micellar solution

In the micellar solution of SDS, the partition coefficient (K_x) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-C_mH_2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dX_am and dC_sf/dC_af in addition to K_x. The following results have been obtained. (1) The dependence of K_x on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: X_am) and the acceleration rate, d!/dX_am (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: C_af) depresses the concentration of free monomer surfactant (C_sf), and the depressing rate, dC_sf/dC_af, in micellar solution is identical with the corresponding quantity, ((CMC/(C_a)_o at CMC.     

Mössbauer study of semiconducting and ferrimagnetic fly ash-recycled glass

Summary Room temperature M?ssbauer spectrum of fly ash-recycled glass (FARG), prepared with more than 86 mass% of fly ash and less than 14 mass% of Fe₂O₃, comprises two types of doublets due to Fe(II) and Fe(III) of magnetite nanoparticles. Isothermal annealing of fly ash-recycled glass at 1100 °C for 60 minutes results in a precipitation of ferrimagnetic magnetite phase having an internal magnetic field of 46.4-48.2 T. When the Fe₂O₃ content is equal to or more than 14%, room temperature M?ssbauer spectrum of FARG shows a magnetic hyperfine structure due to a magnetite phase, in addition to two doublets due to Fe(II) and Fe(III). An increase in the electric conductivity is observed from the order of 10^-8 to 10^-6 S ^. cm^-1 after heat treatment at around the crystallization temperature. This can be ascribed to an improved step-by-step electron hopping from Fe(II) to Fe(III) of distorted FeO₄ tetrahedra in the three-dimensional glass network.     

Synthesis of Six-Membered Compounds by Environmentally Friendly Cyclization Using Indirect Electrolysis

[Ni(cyclam)](ClO(4))(2)-catalyzed indirect electroreduction of olefinic bromides produced six-membered compounds in low to high yields. The synthetic intermediate 49 of Ipecac and Corynanthe alkaloids was obtained in 88% yield in a highly stereoselective manner. Lactam 66, the synthetic precursor of tacamonine, was prepared in 49% yield as a mixture of two diastereoisomers. The electrolysis of the bromoacetates gave the debrominated compounds in good yields.