The selectivity of the six platinum group metals has been studied in the bydrogenation of cycloolefins, cyclic enol ethers, and aromatic compounds. In the hydrogenation and deuteration of 1, 2- and 1, 6-dimethylcyclohexenes, the stereoselectivity for formation of the cis isomer and the average deuterium number in deuterated product, respectively, increased with decreasing olefin isomerization activity of the metal. In the catalytic hydrogenation of the enol ethers derived from cyclohexanones over palladium, the reverse trend in stereochemistry has been observed by comparison with that of the corresponding cycloolefins. The stereochemistry has been explained by assuming the half-hydrogenated states in which the carbon carrying the alkoxyl group is adSorbed. The observed trend in the hydrogenolysis of enol ethers in ethanol have been explained by the following two factors: a) the activity of the adsorbed ionized hydrogen as estimated by the acetal formation in ethanol and b) the olefin isomerization activity of the metal as obtained in the hydrogenation of 1-octene. The selectivities of the platinum metals in hydrogenation of aromatic compounds have been studied for the formation of intermediates'. Palladium has been shown to be highly selective for formation of the ketone, enol ether, and imine intermediates in the hydrogenation of phenols, aryl ethers and methoxyanilines, respectively. The selectivities of the platinum metals in the hydrogenolysis of these aromatic compounds have been discussed on the basis of the formation of the corresponding intermediates in relation to the hydrogenation and hydrogenolysis pathways.

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To maintain good fuel cell performance during long-term operation, a stabilized porous anode needs to be developed. The morphology and thickness of anode must not change substantially.
Various nickel anodes were prepared by impregnation of nitrate solutions of secondary elements, i. e., Li+Al (equiMolar ratio), Mg, La, Zr, Cr, Co and Ag, into sintere d porous nickel plaques, and subsequent calcination of the plaques for 4 h at 450°C in air and for 0.5 h at 700°C in a 70% H₂-30% N₂ atmosphere.
The results of out-of-cell sin tering test of these anodes showed that the addition of Lid-Al (equimolar ratio), Mg, La or Zr to the porous nickel plaque is effective in providing resistance to the shrinkage of the anode due to the sintering process.
The standard free energies of oxide formation of these secondary elements are lower than 1100kJ/g-mol O₂. In particular, it was found that the morphological conditions of the Ni-Mg anode do not change significantly and that the change of thickness is less than one fifth of that of the non-additive nickel anode.
On the basis of the characterization o f the surface of the Ni-Mg anode by EPMA, SIMS and XRD, it is concluded that the solid sOution, Mg_xNi_1-xO, is formed in the surface region of the Ni-Mg anode. This would explain the effectiveness of magnesium for reducing the progress of sintering and creep of the anode.

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The effect of P/V composition on the catalytic properties of V-P mixed oxides for butane oxidation was investigated in a P/V atomic ratio range of 0.75-4.30. Catalysts were prepared from aqueous solutions of dissolved V205, H3PO4 and NH2OHHC1, through a formation of solid precursors containing a crystalline phase of VOHPO4.0.5 H2O (Fig.1). Calcination of the precursors under N2 flow at 500°C gave (VO)2P207 as a principal phase, while calcination in air at 500°C gave P/V-dependent phases among which (VO)2P207 was formed at P/V >1.1(Fig.2). These results were consistent with the trend of average oxidation number of vanadium determined by chemical analysis (Fig.3). Thus the presence of excess phosphorus could stabilize the V4+ oxidation state against oxidation during the calcination in air. Such stabilization effects were also noted when the catalysts were used for the oxidation of butane: (VU)21-'207 in the phosphorus-poor catalysts tended to change into 9-vopo4 in the reaction atmosphere, whereas p-VOPO, in the phosphorus-rich catalysts tended to chang e into (VO)2P20(7F ig.7 ). It walka lso foundt hat the specificsu rfacea rea of the catalystsw as strongly dependent on the P/V ratio, with rather sharp maxima appearing at P/V=0.94 and 1.19 for the catalysts calcined in N2 and air, respectively (Fig.4). The conversions of butane and/or the selectivities to maleic anhydride (MA) were strongly influenced by the P/V ratio for both series of catalysts calcined under N2 (Fig.6) and in air (Fig.8). The changes in conversion with the P/V ratio were roughly ascribable to the changes in specific surface area, while the MA selectivities corresponded well with the contents of (VO)2P207 phase in the catalysts. It was noted that the catalysts with the P/V ratio of about 1.1 contained considerable amounts of (VO)2P2O7 even when calcined in air and exhibited good catalytic performance. Thus a role of excess phosphorus could be to stabilize the MA selective phase of (VO)2P207.

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Methylpolysilazanes were synthesized from several methylcyclosilazanes through ringopening reaction.
MeSiCl₃was used as an initiator.
The initiator plays two ro les: one being the opening of the silazane ring and the other is introducing chlorine into a ring-opened linear intermediates (chlorosilazane: C_z ).
Subsequently, the intermediates are ammonolyzed into aminosilazane ollgomer s (A_z), which have self-condensation character.
Aminosilazanes as pre pared are translucent and viscous liquid. They increase gradually viscosity and molecular weight due to their self-condensation character and transform into gel polymers even on standing at room temperature. Aminosilazanes are hence feasible to shape as gel forms by casting, dipping and spinning and to convert into ceramics by heating.
Thermal weight loss of the gel polymers was about 20 to 30%. It is reavealed that the products are available as precursors to ceramics.

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This research determined 'whether the calcium component in calcium aluminate sulfate (hauyne), used for expansive cement admixture ingredient, can be replaced with stro ntium or barium in homologous series. Properties and hydrating behavior of composed material were also examined. The material' with strontium as substitute showed a structure similar to that of the hauyne. Substitution with barium was actually done to 7.6 mol the hauyne composition of Ca₈Al₁₂O₂₄(SO₄)2(SO₄)2. These results were confirmed by measuring speci6c gravities by the metho4 of heavy liquid separation., The lattice constants of composed and substituted materia ls showed linear relationships to average ion radii of alkaline earth metals, i. e. Y=7.920+1.130 X where Y(Å) and X(Å) represented lattice constant and average ion radius (Shannon's value). The same structures were observed up to a maximum ion radius of 1.48Å. In the hydrating process, the material composed with strontium as the substitute was used to create tri(sulfate) hydrates and monosulfate hydrates. The time for conversion of the tri(sulfate)hydrates was retarded in proportion to solid solul?ility and remained stable for a long time. The composed material with barium as substitute, did not contain aluminate sulfate hydrates with barium, while creating BaSO₄. The composed materials which showed a similar structure to that of the hauyne had different setting times and compressive strengths. However, they all showed hydraulic properties. The strontium solid solution had slow expansibility, while the barium solid; solution did not expand.

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The quantitative estimation of mixing ratio of the mixture c omposed of aluminium hydroxide and aluminium oxide by flamelessa tomic a bsorption s pectrometry was att e mpted by utilizing the different effects of carbon black addition to the solid sample in the dire ctdetermination of metal oxides such as beryllium oxide w hich need high atomization Temperature. The relation between the increased sensitivity and the added amount of carbon black to aluminium oxide differed from that of aluminium h ydroxide. The. calibrationc urve was, miade, . for, each compound, and mixing ratio of the aluminium oxide a nd aluminium hydroxide i n the sample wasetermined by using the differenceso f carbon black e ffect. Analytical resu lt. of Al₂O₃⋅43H₂O was obtained for the anodicaluminium oxide film, b y applying t he'pro p osed method. The coefficient of variation of this method was 2.9% for a mixed salt sample containing 1 ppm aluminium (5 times determinations).

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The effect of pressure was examined for the reaction of aromatic ald ehydes with N, Ndimethylaniline under high pressure which gives triarylmethane derivatives [1]The conventional method requires the addition of more than equimolar amount of a strong acid, whereas, the reaction mixture under pressure of 200 to 400 MPa afforded [1] in good yields even though only 5 molar percent amount of the acid was added to the reaction mixture. The effect of pressure was remarkable especially in the reaction of hindered aldehydes and those having electron-donating substituents such as the case of the formation of leucocrystal violet [1 b]. Weak acids, such as benzoic or 2-chlorobenzoic acids hardly catalyzed the reaction under ordinary pressure, but under compression at 800 MPa they promoted effectively the reaction to give [1] in almost quantitative yield. The apparent activation volume of these reactions was measured to be -33 to 19 ml⋅mol^-1.

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Dehydration and substitution reactions of 2, 3-dihydro-1 linaphtho[2, 1-b]thiopyran-1-ol [2 a ] and its methyl derivatives under acid'bonditions have b een investigated.
While the reaction of [2 a ] in the presence of sulfuric acid in dry ether produced a mixture of 3 H-naphtho[2, 1-b]thiopyran [3 a] and 2, 3-dihydro-1 H-naphtho[2, 1-b]thiopyran[4 a], virtually a single product [3 a] was formed in quantitative yield when the reaction was carried out in chloroform in the presence of hydrochloric acid. Heating of [2 a] in polyphosphoric acid afforded [4 a] in a 70% yield. Heating a solution of [2 a ] a nd its methyl derivatives with alcohols, thiols, and thiocarboxylic acids in the presence of sulfuric acid at 30°C resulted in the' occurrence of substitution reactions to afford the corresponding ethers, thioethers, and thioesters in almost quantitative yield.
The substitution reaction with hydrogen sulfide and N, N-dimethylthioformamide also proceeded cleanly in dry ether.
Compound [2 a] and its analog [7 a ] react with acetyl bromide to give bromminated compounds, but in the presence of triethylamine, C2 a] afforded an acetoxy compound in good yield.

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As a basic study in order to develop industrial catalyst of phthalocyanine (PC) type compounds with a structure similar to porphyrin, Co-PC catalyst was applied to hydrocracking of Khafji asphaltene.
The reac tion was conducted in an autoclave at 380°C.
The product was separated into gaseous produc t, the liquid product of boiling range of 80-280°C and the residual solid product.
The solid product was further separated into benzene-solubleheptane-soluble (BS-HS)fraction, benzene-solubleheptane-insoluble (BS-HI) fraction, benzene-insolubletetrahydrofuran(THF)-soluble (BI-TS) fraction and benzene-insolubleTHF-insoluble (BI-TI) fraction (Fig.2 & Table 3).
The average st ructure of reaction products was analyzed by NMR in accordance with the Speight method.
In case of initial hydrogen pressure of 10 k g/cm', liquid fraction was obtained in 15%. yield when catalyst was used, while liquid fraction was produced in 4% without catalyst (Tabl'e 3).
The formation of BS-HS, BS-HI and BI-TS fractions was hardly affected by the use of catalyst. However, the amount of BI-TI fraction without catalyst(Table 3). was twice as much as that with catalyst (Fig.4).1
In the case of BS-HS fraction, the molecular weight and aromatic ity index f a. were r6latively low and the number and length of aliphatic side chains were decreased when the caalyst was used. In the case of BS-HI fraction the amount of naphthenic hydrogen and the number and length of aliphatic side chains were increased when the catalyst was 'used. These results suggest that the BI-TS fraction was decomposed to change into the BS-HI fraction. The difference of the average structure of reaction products, which is attributable to the use or non-use of Co-PC catalyst, is related to the production of liquid fraction (Figs.5 & 6).
It was recognized that Co-PC catalyst works as hydrogen catalyst (Fig.7). Co-PC c atalyst temporarily holds a large amount of hydrogen through the reduction of the PC itself and promotes the decomposition of ', asphaltene by donating hydrogen to the radical which was produced during hydrocracking.

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The reactions of diazoamino compounds [1] with several electrophiles have been investigated by using phase-transfer catalyst. It was found that 1, -(4-toly1)-3-methyltriazene [1a] easily reacted with such alkyl(aryl) halides as propyi and ally' bromides, and 2, 4-dinitrochlorobenzene to afford the corresponding N-alkylated(arylated) products. Michael-type addition of [1a ]to α, β-unsaturated ester, ethyl crotonate, was also observed, to occur. Furthermore, the reaction with isothiocyanate afforded thioxo derivative[3], while the reaction with thiocyanate afforded imine derivative [4] which arose from the addition of [1 a] to cyano moiety of thiocyanate, followed by further addition of another molecule of [1 a].
Diphenyltriazene [1b] was also alkylated effectively with alkyl halide s, whereas treatment of [1b] with benzoyl chloride afforded benzanilide. Possible pathways on the formation of benzanilide are briefly discussed.

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Poly[oxy-1, 4-phenylenecarbonylimino(chloro-1, 4-pheny lene)iminocarbony1-1, 4-phenylene]was prepared by a low-temperg. ture solution polycondensation of chloro-p-phenylenediamine with bis(4-chloroformylphenyl) ether in the presence of lithium carbonate as the acid accepter in N-methyl-2-pyrrolidone (NMP).
It was difficult to enhance the mec hanical properties of the polymer films by cold and heat drawings at a constant temperature. Therefore, the films were drawn in NMP/H20 mixture (60: 40, v/v) at 50°C and then were heat-treated under a tension of 95 MPa (the temperature was raised from the room temperature to a fixed temperature at the heating rate of 12-13°C/min).
The values of the tensile modulus, the strength at break and the breaking e nergy of 2.5-fold drawn and heat-treated films (sample (3 ) )were 19.8 GPa, 677 and 12.4 MPa, respectively. These values are about 8.3, 5.7 and 0.4 times as large as those of the undrawn films (sample ( 1)). The values of t he tensile modulus, the strength at break and the breaking energy of the sample 3 were changed into 21.6 GPa, 593 and 9.26 MPa after 2 h of heat aging at 300°C in air. These results showed the high-temperature durability of the drawn and heat-treated materials.

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Polymers containing the pendant benzophenone residue and the chloromethyl group were prepared by radical copolymerization of 4-vinylbenzophenone and p-(chloromethyl)styrene. Various multifunctional polymeric photosensitizers containing the pendant benzophenone moiety as a photosensitizer and some quaternary salt moiety as substrate-attracting groups were synthesized by the addition reaction of the obtained copolymers with various tertiary phosphines or amines.
The effects o f the concentration of photosensitizer, the photosensitizer content in the polymer chain, and the length of alkyl chain of the quaternary salts in the pctlymer were evaluated by the photoisomerization of potassium sorbate usingthese polymeric photosensitizers in water or methanol. This result showed that the polymer containing 11.0 mol% of benzophenone moiety and 80.0 mol% of benzyltriethylphosphonium salt moiety as a substrateattracting group had the highest photosensitization efficiency when the photoisomerization was carried out in the presence of 30 mol% of the photosensitizers. Furthermore, these multifunctional polymeric photosensitizers also showed higher activity than that of the corresponding low-molecular-weight photosensitizer.

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The Cu(II)-complexing capacity(CuCC) of the influent and the effluent waters of sewage treatment works was studied, using the newly established back extraction method.
According to our previous results, amino acids and/or proteins were proved to be important in evaluating the CuCC of environmental waters.
In the present works, the changes in pro tein and amino acid concentration in the influent and the effluent waters of the sewage treatment works were examined. The ratios of protein- and amino acid-derived carbon to the dissolved organic carbon in the influent water of the sewage treatment works amounted to almost 50%, and a good relationship between CuCC and the amino acid and protein concentrations was observed.
By using the ultrafiltration technique, it was found tha t the dissolved organic materials having high CuCC was distributed in less than 10000 molecular weight range. The same tendency was also observed in the previous results on seasonal and vertical changes of CuCC in lake waters and on the CuCC of the metabolic products of. algae.

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According to our previous reports, amino acids a nd prote ins were proved to be important in evaluating the CuCC of environmental waters.
In tills report, algal products of c hlorella sp. and vertical and seasonal changes of copper(II)-complexing capacity(CuCC) in Lake Haruna were examined in relation to th e concentration of amino acids and proteins. There were good relationships between CuCC and amino acids and proteins in algal products of chlorella sp. but not in Lake Haruna waters. Ain equation was proposed for the relation of the CuCC to amino acids and proteins i n Lake Haruna waters:
CuCC =k₁[protein]+k₂[amino acid]
This equation could explain the relations between CuCC and amino acids and proteins not only in Lake Haruna waters but also algal products of chlorella sp. Furthermore, this equation could also explain the relations of CuCC to amino acids and proteins in urban drainage and intermediate products of aerobic digestion of phenol and glucose studied in our previous reports,

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The adsorption of cationic surfactants of quaternary ammonium salt on five montmorillonite clays was examined for treatment of wastewater containig cationic surfactant. The adsorption capacities of montmorillonite clays were high as activated carbon and much higher than some other minerals. The adsorption isotherms of the clays of Na type and the other types showed different patterns, and this could be explained by their different behaviors in aqueous solution. Among the clays which have same exchangeable cation, the clay which had higher cationexchange capacity showed larger adsorption ability. The influence of pH on adsorption was small. Coexisting inorganic salts showed a positive effect on adsorption amount due to the increase of micellar aggregation number of the surfactant, and a negative effect due to the interference of cation exchange with the coexisting cation. The positive effect of coexisting anions followed the Hofmeister series: NO₃->Cl->SO₄^2-. The negative effect of coexisting'cations was inverse to the series of cation-exchange selectivity: Fe>Al³⁺>Ca²⁺>NH₄+>Na⁺. Increase of the basal spacings of the clays with the adsorption indicated that cationic surfactant intercalated in the interlayer space. After adsorption of cationic surfactant on clays, the clay suspension was easily filtrated. t Studies on the Adsorption Abilities of Montmorillonites and Their Application to Water Treatment. tr.

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Aqueous solutions containing N-phenylglycine (PhG) a nd, Aldrich humic acid (HA) were irradiated with a 100-W high-pressure mercury lamp at 25±1°C through a NaBr-Pb(NO₃)2filter solution which cut off light of wavelengths shorter than 330 nm. The decomposition of PhG was induced primarily by photoexcited HA and about 70% of pliG, decomposed was converted into aniline (Fig.1). A mechanism proposed to account for the aniline formation involves electron transfer from PhG to the excited HA and, in addition, inhibition by oxygen suggested the participation of the excited triplet state of HA. The decomposition-rate increased with decreasing pH (Fig.2). An increase in the decomposition rate by addition of an inorganic salt, NaClO₄ (Table 2) supported the idea that the low rate in neutral and basic solutions is attributable, at least in part, to electrostatic repulsion between the anionic form of PhG and anionic groups of HA. Further, the photodecomposition was accelerated by addition of diamagnetic metal ions such as Cdand Zn²⁺, while it was retarded by paramagnetic metal ions such as Ni²⁺, Co²⁺, and Mn²⁺, except Cu²⁺ (Table 3). The PhG photode-composition was also observed in pond and river water samples; the rate in the pond water having 6.6 mg. dm^-3 of dissolved organic carbon was comparable to that in an aqueous solution containing 2.4 mgCdm^-3 HA (Table 1).

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MezSi(NCO)4-x(x=0-3) have been prepared by the reaction of the corresponding chlorosilane with sodium cyanate in the presence of several additives in benzene. Lewis bases (MeNO₂, DMF, amines, MeCN, and THF) and alkylammonium salts (R_4-nNH_n⁺X^-, n=1-3; R=Me, Et, Buⁿ, Bu^t, PhCH₂, and octyl; X=HSO^₄, MeSO₃, RCOO, Cl, and H₂PO₃) wer e examined as an additive. The effects of Lewis bases and alkylammonium salts as additives are discussed.

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The optical resolution of (RS)-phenylsuccinic aci d ((RS)-PSA) was achieved via selective salt formation of (R)-PSA with equimolar amount of (R)-4--thiazolidinecarboxylic acid ((R)-THC). After evaporating the aqueous solution of (RS)-PSA and (R)-THC to dryness, the residue was treated with diethyl ether to be separated into free (S)-PSA and the insoluble salt of (R)-PSA and (R)-THC. Recrystallization of the (S)-PSA and the (R)PSA from the salt from water gave (S)- and (R)-PSA with 99% optical purity in over 80% yield, respectively.

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Kolbe-Schmitt type carboxylations of 1- and 2-na phthol by carbon dioxide in the homogeneous solution in aprotic solvents were found to proceed under ordinary pressure and ordinary temperature giving 1-hydroxy-2-naphthoic acid and 27hydroxy-1-naphthoic acid, respectively, in extremely high selectivities and yields, . The best yield (ca.80%) for the carboxylation of 1-naphthol was obtained by the reaction of its potassium salt in nitrobenzene at 80°C under 3.9 x 1O⁵ Pa of carbon dioxide within 30 min.

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The thermal decomposition of isolongifolene oxide (1) and j9-caryophyllene oxide (2) in the presence of, synthetic zeolites was investigated. With 3A, 4A or 13X zeolite, isolon gifolan-4-one (3) was obtained from (1) as a main product at high conversion and selectivity. With TSZ-320 HOA zeolite, d ihydrocaryophyllen-5-one (5) and isodihydrocaryophyllen-5one 7 were obtained from (2) as a main products, amounting to more thin 80% of the thermolytic products. t Studies o n the Decomposition of Terpenes in the Presence of Synthetic Zeolites.

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A highly sensitive staining method for protein detection was developed. In this method colloidal platinum adsorbed on the protein serves as a catalyst for copper plating. By using this method proteins were detected with a sensitivity 25--2500 times higher than that of the Auro Dye method.

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Polymerization of methyl methacrylate (MMA) initiated by trans-PtHX(PEt₃)₂, (X=Cl, Br, I, NO₃, NO₂, and CN) carbon tetrachloride, was studied at 50°C. Ligand effect of hydridoplatinum(n) complex on polymerization activity was found to decrease in the following order NO₃>Cl>Br>I>NO₂>CN These results agree with the direction, forward, decrease, of the value of Pt-H stretching vibration in the IR spectra of hydridoplatinum(II) complex. Thus it has been found that polymerization activity is closely related to the Pt-H bonding strength.

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The comprcespion molding of fumarate-incorporated diacetylene oligomer(FED) was investigated.
The title compound was prepared by an oxidative coupling reaction of dipropargyl fumarate. The obtained moldings have various excellent properties, such as modulus, Vickers hardness, and thermal conductivity. The maximum values of moduli and Vickers hardness reached 22.7 GPa and 222, respectively.
The relationships between the moduli and Vickers hardness in various materials containing the moldings of FED is also discussed.

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The uptake curves and concentration profiles for C. I. Direct Yellow 12 (25°C) and C. I. Direct Blue 15 (55°C) in a cellulose membrane have been determined by a single membrane method. and a multi-membrane method, respectively. The adsorption rate was found to be approximately controlled by surface diffusion. The theoretical uptake curve and concentration profile could be calculated from a simplified analytical solution for surface diffusion control without complicated numerical analysis as presented in our previous paper. The experimental data agreed reasonably well with the analytical solution.

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