The following novel processes have been commerciallized first in the world by using the new catalytic systems together with new methods of the product separation.1) The new process of preparing 1, 4-butanediol is described in which allyl alcohol is hydroformylated using a rhodium catalyst in the presence of an equimolar amount of 1, 4-bis (diphenylphosphino)butane to rhodium: The separation of products is carried out by means of the water extraction.2) The new process of obtaining 3-methyl-1, 5-pentanediol is mentioned in which 3methyl-3-buten-l-ol is hydroformylated employing tris(2, 4-di-t-butylphenyl)phosphite modified rhodium catalyst: The separation of products is conducted dy bistillation.3) The new process of producing 1-octanol is described i n which butadiene is hydrodimerized using a palladium catalyst in the presence of large excess of the hydrophilic phosphonium salt and triethylammonium hydrogencarbonate: The separation of products is achieved by means of the hexane extraction.

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Cholic acid and its derivatives form molecular assemblies consisted of stacked bilayers. On the basis of behaviors of the assemblies similar to proteins, we can say that cholic acid and its derivatives express their molecular information through the flexible bilayered assemblies. The assemblies have the following characteristics. They have common bilayered structures, while they have variable hydrogen bonding networks, molecular arrangements, and stacking modes. The characteristic flexibility is that the side groups can change their conformations and neighbors for hydrogen bonding, when guest molecules are included. This led to the first proof of the intercalation phenomena in organic layered crystals and guest-dependent inclusion spaces. Another important proof of the expression comes from one-dimensional polymerization using a pair of hosts, which enable us to observe space effects on the polymerization.

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Solution properties of sodium chondroitin-6-sulfate (Na2Chs) mixed with sodium oxalate (Na2Ox) was studied, taking Donnan equilibrium and intrinsic viscosity of Na2Ch s into consideration. Volume excluding oxalate anion (0x2-) from the polymer domain of chondroitin6-sulfate (Chs2-) was estimated by means of a two-phase model (Fig.1) on the basis of Donnan Effect. Oxalate ion penetrated into the polymer coil but was rejected from neighborhood of the polymer chain when the polymer coil of Chs2- throughly expanded and/or the concentration of 0x2- was low. At a medium concentration of Na2Ox, the polymer coil shrinked and the exclusion volume against Ox2- was as much as that of the polymer coil itself. The excluded volume became larger than that of the polymer coil when a concentration of added Na2Ox was high enuogh. It was concluded that the exclusion effect of polyanion works beyond hydrated layer of Chs2- at any experimental conditions. The mechanism of competitive adsorption of Ox2- with Chs2- on the solid surface (e. g., calcium oxalate) is explained in terms of the exclusion due to electrostatic repulsion, hydrated volume, and steric hindrance of these adsorbates.

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Acid and base amounts of four titanium dioxide pigments (Ti02-A, -B, -C, and -D) were estimated by a back titration method using bases and acids with various strengths. The dispersibility in acidic, neutral and basic acrylic resins was correlated to the acid and the base amounts of the pigments. For each pigment, acid amount was small, when it was analyzed by use of weak base. For two pigments (Ti02-C and -D), smaller base amount was detected by use of weak acids. On the other hand, base amount of two pimgments (Ti02-A and -B) was almost the same even though the acids of different strength was used. The gloss values of the dispersed pastes for the acidic an d the basic acrylic resins, which are regarded as indexes of dispersion, were higher than that for the neutral one if they were compared at the same dispersion time. The difference between the gloss valu es in the acidic and the neutral resins showed good correlation with the base amount of the pigments measured using acids having almost the same strength as the acid of resin. The same result was obtained for the gloss values in the basic and the neutral resins, and for the acid amounts of the pigmnets.

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Ammonia synthesis reaction over Ru/Si02, Ru/Al203, RufTi02, Ru/Nb205, and Nb205promoted Ru/Si02 catalysts has been studied under 20 atm. pressure in order to elucidate the effect of strong metal-support interaction (SMSI) on the activation of dinitrogen. High temperaure reduction (HTR) of Ru catalysts supported on TiO2 or N13205 (SMSI oxide) at 500°C caused a suppression in the activity by ca. one or two orders of magnitude, compared with low temperature reduction (LTR) at 200°C (Fig.1). Ammonia synthesis is, like hydrocarbon hydrogenolysis, a structure sensive reaction in which large ensemble sites are required for a high activity. However, the extent of the suppression is not so drastic as the case of the hydrogenolysis reactions, for which the activity is depressed by ca.6 orders of magnitude. The turnover frequency (TOF) value of Ru/Nb205, based on hydrogen chemisorption (Fig.2 and Table 3), was increased after HTR (i. e., in the SMSI state), as shown in Fig.3. On the other hand, no change in the activities of Ru catalysts supported on Al203 and Si02 (non-SMSI oxides) was observed between LTR and HTR (Fig.1). The addition of Nb205 onto the Ru/Si02 catalyst (atomic ratio of Nb/Ru=1) resulted in an enhancement of the activity even after LTR, and the Nb205--Ru/Si02 (Nb/Ru=3) catalyst exhibited a more suppression in the activity after HTR (Fig.4). The higher TOF values after HTR were also observed in the Nb205-Ru/Si02 catalysts (Fig.5). Moreover, the decrease in the activation energies was observed by HTR of the Ru/Nb205 and Nb205-promted Ru/SiO, catalysts (Tables 3 and 4). These results suggest that both geometric and electronic effects should be taken into account for the activation of dinitrogen: a suppression of the activity due to the decoration of Ru surface with NbO, and a promotion of the activity by an electronic (or ligand) effect.

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The behavior of the vapor phase hydrogen-transfer reaction between methacrylaldehyde and ethanol to form 2-methyl-2-propen-1-ol selectively has been studied in a flow reaction system using Mg0-Zr02 catalyst under various reaction conditions. The methacrylaldehyde conversion increased and the se lectivity to 2-methyl-2-propen-l-ol decreased with elevating temperature and decreasing space velocity. In a lower conversion region (below ca.60%), the selectivity to 2-methyl-2-propen-1-ol was higher and almost constant, and the formation of 2-methyl-1-propanol which was formed by parallel hydrogenation of methacrylaldehyde was observed. However, in a higher conversion region (above ca.60%), the selectivity decreased remarkably due to formation of 2-methyl-1-propa nol which was produced by the consecutive hydrogenation of 2-methyl-2-propen-1-ol initially formed. This suggests that the present hydrogen-transfer reaction is a type of parallelconsecutive reaction. Furthermore, the adsorption and desorption behavior of ethanol and methacylaldehyde over the catalyst has been studied by the pulse reaction method in order to investigate the reaction mechanism. It was observed that the desorption rate of ethanol from the catalyst was slower than that of methacrylaldehyde. This suggests that ethnol is very strongly adsorbed on the catalyst than methacrylaldehyde. When methacrylaldehyde was pulsed over the catalyst on which a large amount of ethanol had been adsorbed, 2-methyl-2-propen-1-ol was formed instantaneously. It is concluded that methacrylaldehyde reacts with ethanol, which is dissociatively adsorbed and activated on the catalyst, to form 2-methyl-2-propen-1-ol.

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The complex dihydrido(1, 3-diphenyltriazenido)bis(triphenylphosphine)rhodium(1) (dihydridorhodium complex) has been shown to be an effective catalysts for the homogeneous hydrogenation of cinnamic acid under a 1 atm pressure of hydrogen at 30°C. For cinnamic acid in dimethyl sulfoxide solution the rate law has been found to be: R Kk[Rh]o[H, ][Cinnamic acid]ate= 1+K[Cinnamic acid]Where [Rh]o, [H2], and [Cinnamic acid] are the concentration of catalyst, hydrogen, and cinnamic acid, respectively. K is the formation constant for a cinnamic acid intermediate complex and k is the rate constant for the rate-determining hydrogen activation step.

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Catalytic activity and reaction selectivity of platinum- and nickel-doped magnesium oxide (Pt/MgO, Ni/MgO) prepared by a wet method have been investigated for steam reforming of ethanol (EtOH) in connection with fuel cell systems. A fixed-bed flow type tubular reactor was used for the catalytic reaction at the temperature range of 250-500 °C (523-773 K). The steam reforming of ethanol on Pt/Mg0 yielded CH4, CO, and CH8CHO as well as main products, H2 and CO. The effect of Pt loading on the catalytic activity became samll for the catalysts with higher Pt contents (ca.2 wt%), especially at lower reaction temperature (350 °C). A maximum H2 evolution rate was observed when the 1120/Et0H molar ratio in the feed was unity. The reaction on Ni/MgO gave higher selectivity for H2 and CO formation, but the total catalytic activity of Ni/MgO was lower than that of Pt/MgO. The activity loss was caused by deposition of carbon on Ni/MgO during the initial period of the reaction. The formation of CH4 was slightly suppressed by using a mixture of Pt/MgO and Ni/MgO.

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On the synthesis of aluminium hydroxide from aluminium salt solution by homogeneous precipitation method, effect of sulfate ion on the initial precipitation behavior of aluminium hydroxide and coalescence of the particles were investigated. Sulfate ion promoted remarkably the precipitation of aluminium hydroxide at the lower [SO42-]/[Al8+] ratio, but suppressed weakly the precipitation at the higher ratio. On the precipitation process of aluminium hydroxide particles from aluminium salt solution in the presence of sulfate ion, number of aluminium hydroxide particles decreased in the first stage of precipitation and then increased gradually. Decrease in the number of particles in the first stage shows that particle growth occurs by coagulation of small particles (0.2 pm). SEM photographs showed that particles grown into the larger size coagulated again in the progress of precipitation of aluminium hydroxide. This second coalescence of particles was remarkably promoted by stirring of reaction solution. When aluminium hydroxide particles were synthesized without strirring, the second coalescence of particles decreased with decreases in synthesis temperature and urea concentration, and population of discrete spherical particles showed a maximum for aluminium sulfate and sulfate ion concentrations.

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A highly sensitive, selective and rapid method for the determination of trace amounts of vanadium(V), cobalt(II), nickel(II) and iron(M) has been developed. The method wa s based on the preliminary chelation of the metal ions with 2-(5-bromo-2-pyridylazo)-5(diethylamino)phenol (5-Br-PADAP) and the subsequent separation by reversed-phase highperformance liquid chromatography (RP-HPLC). Tetrabutylammonium bromide (TBA) was added into the mobile phase of aqueous acetonitrile (Fig.2). The recommended procedure was carried out as follows: to a sample solution, definite amounts of 5-Br-PADAP solution (in 10 %w/v PONPE-10 solution), pH 4.5 acetate buffer solution and water were added. After heating for 30 min on a boiling water bath and then coiling, the whole mixture (about 20 cm') was diluted to 25 cm' with water. A 100 mrns portion of the whole solution thus prepared was injected onto a Cosmosil 5 TMS column (4.6 mm x 250 mm). The mobile phase was 46%wiw aqueous acetonitrile containing TBA (2 x 10-3 mol kg-'), sodium acetate (5 x 10-3 mol kg-') and EDTA (10-4 mol kg-1). Chromatograms were obtained by measuring absorbances at 595 nm. The calibration curves were linear over upto several hundreds pg of the respective metal ions in 100 mm3 injected. The relative standard deviations at three determinations were 1-5%. The detection limit, defined as three times standard deviation of a blank signal, was respectively 2.2 pg of vanadium, 0.72 pg of cobalt, 16.5 pg of nickel and 98.8 pg of iron in 100 mmLinjection. The method was successfully applied to the simultaneous determination of the metal ions in high-purity silicon, coal fly ash, mussel, and several environmental water samples (Figs.4-6 and Tables 1-4).

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In order to obtain a new magnetic resonance imaging (MRI) agent which adsorbs selectively to atheroma, eight kinds of manganese(111)-tetrakis(sulfoaryl)porphyrin derivatives were synthesized (Fig.1). Among these, manganese(M) a, /3, r, 5-tetrakis(4-sulfobiphenylyl)porphyrin(Mn-TSBP) which have four sulfobiphenylyl groups, has the following merits: ( )High solubility in water (solubility: 5 x 10-3 mol. dm-3 at 25 °C and pH =7.0, Table 3), (ii)stable (it did not dissociate the manganese at pH range from 1.5 to 13.5), and (iii) it adsorbed well to deoxycolic acid as an atheroma model (Table 4). The Mn-TSBP, injected to male New Zedland white rabits with experimental atheroma, was selectively adsorbed to atheroma more than 2-6 fold of that of normal aortic wall (Table 5).

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Phenol derivatives are known as uncouplers that penetrate into the lipid matrix and transfer protons across the mitochondria interior membrane. Adsorption behavior (partition coefficients) of phenol derivatives into the syntheric lipid matrix were measured by using a lipid membrane-coated quartz crystal microbalance (QCM) in aquenous buffer solution (45 °C, pH 7.0). QCMs are known to detect a mass change on an electrode from the resonance frequency change in a nanogram level. A good linear correlation was observed between partition coefficients of various phenol derivatives into the lipid matrix and uncoupling activities of the same compounds for mitochondria membranes. One of advantages of the QCM method is to measure separately partition coefficients of the neutral phenol type derivatives (UH) and the phenolate anion type (U-) into the lipid matrix. The neutral UH derivatives were found to absorb 5--500times more than the anionic U- derivatives, however, both types of phenol derivatives had similar uncoupling activities. Thus, the partition of anionic U- into the lipid matrix is small, but the ability of proton transfer is large; on the contrary, the neutral UH can penetrate into the lipid matrix in a large amount, but can permeate very slowly protons through the lipid membrane.

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The asymmetric poly(amide-imide) hollow fiber membranes were prepared by the dry-jetwet spinning method 'from N, N-dimethylacetamid solution of Torlon commercialized by Amoco Performance Product, Inc.. The heat treament at 265 °C gives a high separation factor of water to ethanol. The module having a membrane surface of 1 m2 was prepared by binding the hollow fibers of 3000pieces and potting in potting resin. This module has a good pervaporation performance of a separation factor of 600 and a permeation rate of 30 girn2h for 95 wt% EtOH at 60 °C, and a separatiOn factor of 300--400 and a permeation rate of 15-20 g/m2.11 for 99 wt%EtOH at 75°C. By using this module a 95 wt% ethanol aqueous solution is able to concentr ate to a 99.8 wt% solution.

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The activated carbon loaded with aromatic nitro compounds was regenerated by supercritical carbon dioxide from a viewpoint of the effect of the substituent of adsorba te on the regeneration. o-Nitrophenol (ONP) did not suffered from any chemical change by supercritical extraction with carbon dioxide. Above a pressute of 200 kg/cm', the fractional regeneration of ONP loaded activated carbon increased as temperature increased, but below 100 kg/cm', the fractio nal regeneration decreased reversely as temperature increased. It was considered t hat this phenomenon was caused by the reversal of the effect of temperature on the solubility of ONP in supercritical carbon dioxide. The order of the fractional regeneration at 200 kg/cm 2and 35 °C was as follows: o-nitrotoluene#nitrobenzene>o-nitrochlorobenzene1-7-0NP>2, 4-dinitrophenol>o-nitroaniline. Weak correlations between the fractional regeneragions and solubilities of aromatic nitro compounds to hexane or melting points of compounds w e re observed. The fractional regeneration seemed to be low when Hammett number was too large or too small. t Separation of Chemicals by Supercritical Fluid. II.

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In aqueous soltions, chlorophyllin was found to exist in a polymeric form, because it does not show a fluorescence spectrum. Because chlorophyllin in ethanol solutions showed double peaks in its electronic spectrum and gave a fluorescence spectrum having a maximum at 700nm, it exists as an equilibrium mixture between monomer and dimer. Addition of poly (N-vinylpyrrolidone) to the chlorophyllin aqueous solutions did not convert the polymeric to the monomer form. The elctronic spectrum of chlorphyllin dispersed in poly(N-vinylpyrrolidone) did not change with irradiation of light, but addition of 30% glycerol to the system caused a reversible spectrum change. It is clarified that chlorophyllin exists in the polymer form in the solid state matrix and is dimerized by irradiation of light.

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Photochromic N-benzylimide derivative of fulgide; N-benzyl-(E)-2-[1-(2, 5-dimethy1-3-furyl)ethylidene]-3-isopropylidene succinimide was synthesized and the photochromic performance was investigated. The fulgide showed poor photochmical fatigue resistance in comparison with succinic anhydride derivative of fulgide and, however, thermal storage stability of the colored form in protic solvent was significantly improved.

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[in Japanese]

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