Free energy changes by mixing aqueous solutions of D-glucose with aqueous solutions of calcium chloride or guanidinium bromide were measured at 25°C by the isopiestic comparison method. As shown in Figs.5 and 6, excess free energy changes of mixing (°G_m^ex) were positive for the D-glucose-calcium chloride-water systems. The signs of °G_m^ex of both solutes were positive at the total molality (M) of 1 mol·kg^-1 (Fig.5), but the sign of °G_m^ex of CaCl2 turned to be negative in the high mole fraction region of CaCl₂ at the total molality of 2 ·kg^-1 (Fig.6). These results were interpreted in terms of structural incompatibility of the hydration cospheres around these two kinds of the solutes and the ion-dipole intractions. As shown in Figs.8 and 9, °G_m^ex Gex for the D-glucose-guanidinium bromide-water system was in negative values, indicating mutual salting-in. This result is attributed to the structure breaking effect of the guanidinium ion.

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1-Bromo-3-chloropropane (BCP) was methoxylated with methanol over activated alumina into 1-halo-3-methoxypropanes and 1, 3-dimethoxypropane, and the catalytic reaction was accompanied by the disproportionation of BCP into 1, 3-dibromopropane (DBP) and 1, 3-dichloropropane (DCP) at the temperature range from 160 to 280°C. Furthermore, no dehydrohalogenation of BCP into allyl halides was observed in the catalytic reaction over the activated alumina with methanol.
Since halogen atoms were converted into methyl halides, methoxylation of BCP was always more favorable than disproportionation of BCP into DBP and DCP. The degree of methoxylation was found to be almost constant with the increase in the molar ratio of methanol to BCP. The yields of products due to methoxylation increased with the increase of the reaction temperature as well as with the increase in the contact time for the reaction (W/F). The bromine atom in 1, 3-dihalopropanes was more preferentially replaced by the methoxyl group than the chlorine atom. The kinetic results obtained also indicated the lower reactivity of 1, 3-dihalopropanes in the following order: DBP>BCP>>DCP.
It is considered that the methoxide ion generated on the basic sites of activated alumina attacks the terminal carbon of 1, 3-dihalopropane through a 5, 2 reaction mechanism.

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Photographic properties of poly(vinyl p-azidobenzoate) sensitized with 4-(4-butoxypheny1)2, 6-diphenylthiopyrylium perchlorate were studied under laser scanning exposure. The 488 nm line of argon ion laser was used and the laser beam was focused by optics on rotating sensitive layer. Characteristic curves were obtained by plotting the line width of cured polymer on the plate against exposure energy. The reciprocity law failure appeared when the intensity of exposure was higher than 10⁴J/cm²·s: the photographic sensitivity of the polymer decreased with increasing the intensity of laser. A deviation from the reciprocity law was estimated by Schwarzschild's p-value. From the measurements of electronic and phosphorescence spectra, it was found that the spectral sensitization of this polymer system was due to the triplettriplet energy transfer. The conversion among different multiplicities was a time-consuming process. Consequently, under the laser scanning exposure with high intensity and short exposure time, the number of sensitizer molecules in ground state in the photosensitive layer was reduced. Main reason of the reciprocity law failure observed in spectrally sensitized azido polymer was due to the energy transfer process from the sensitizer in triplet state to the photopolymer.

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Poly(o-hydroxystyrene) (PStOH) was obtained by radical polymerization o-hydroxystyrene monomer which was synthesized by decarboxylation of o-cumaric acid. A film prepared from PStOH and aromatic azide compounds resulted in photosensitivity for ultraviolet and visible light. The film was colored and insolubilized in alkaline water by irradiation with active light. The color change was versatile according to the molecular structure of aromatic azide compound used. For example, the film of PStOH with p-dimethylaminophenylazide became a deep blue color image by imagewise exposure. The mechanisms of photo-coloration and photocuring of PStOH film by aromatic azide compounds were investigated by using o-cresol as a monomeric model compound for PStOH. It was found that the photoinduced color development was attributable to the formation of dye having quinone-imine structure through the reaction of nitrene, formed by the photolysis of aromatic azide compounds, with the phenol group of the PStOH. The decrease in the solubility of the exposed PStOH/azide film in alkaline water could be explained by the change in solubility parameter of PStOH owing to the reduced hydroxyl group by the formation of quinone-imine structure.

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Fine powders of ZnO with the size from 21 to 36 nm were prepared by the vapor phase reaction using zinc acetylacetonate. complex and water at 100-800°C. However, ZnO powders were not produced by the reaction using zinc acetylacetonate complex and dry 02 gas at 400°C or below. The formation of ZnO powders was confirmed by X-ray powder diffraction patterns and IR spectra. The particle size of powders was mainly measured by means of an electron microscope with high resolving power. The particle size increased with the elevation of reaction temperature above 200°C. At 800°C, the particle size grew big gradually with increasing vapor pressure of the chelate, and became smaller with increasing flow rate of gas into the reactor.

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In the preparation of β, β″-alumina sintered body from its powders with the composition of O.87Na₂O·O, 6MgO·5Al₂O₃ which were produced by a spray pyrolysis technique, the effects of forming and sintering conditions on the microstructure (duplex structure and grain orientation)and anisotropy of electrical conductivity of the sintered body were investigated. The density of green compact was dependent on the forming method and increased in the order uniaxial press(A) <uniaxial pressing after granulation(B)<isolatic pressing after granulation (C). On firing at 1560-1620°C for 5-90 min, the microstructure of sintered body tended to become a duplex structure due to abnormal grain growth as the density of green compact decreased. In green compact formed by method(B), the c-planes of β, β″-alumina particles oriented preferentially perpendicular to the press direction; the degree of orientation was increased markedly by firing. Forming method C gave green compact and sintered body with low degree of orientation, indicating that the dense compaction is essential to suppress the 1727preferential orientation of β, β″-alumina particles. The fraction of β″ phase in sintered body was higher as the grains grew into larger ones. The specific resistivity of sintered body in the press direction (pr) was generally larger than that in the perpendicular direction (pR). With increasing in the degree of particle orientation, pp increased markedly, whereas pa remained nearly constant.

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A single crystal of the system MgTiO3-CaTiO3 was grown by the floating zone method (Figs.1 and 2) and the dis tribution of constituents was analyzed by powdered X-ray differaction, SEM and EPMA (Figs.3 and 4, and Table 1). The experimental results showed that CaTiO3 did not form solid solutions effectively with MgTiO3 and was present independently as an island. A sintered specimen which had the same composition as the single crystal was also analyzed by SEM; the distribution of CaTiO3 in both materials was qualitatively identical. A proposed equivalent electric circuit (Fig.5) is consistent with the geometric distribution of CaTiO3 in MgTiO3 and explains fairly well the composition-dependence of dielectric constants (Fig.6). In the present system, addition of a small amount of CaTiO3 improved the temperature coefficient (77, ) of resonant frequency of MgTiO3. This improvement does not result from the formation of soild solutions with 77, -0, but is ascribed to the fact that 72, s for both materials have mutually opposite signs, 77ffor the mixed system becoming comple? mentarily zero. The ratio where 72, became zero was r(CaTiO3/MgTiO3)-4 ?6%, while the calculation from the equivalent electric circuit gave the ratio of CaTiO3/MgTiO3-9%. The agreement between both ratios is acceptable, supporting that the equivalent electric circuit adequately approximates the dielectric properties of the present system.

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The bis type cobalt(III) complex containing terdentate ligand which forms two sixmembered rings, bis ibis(3-aminopropyl)aminel cobalt(11) complex [Co(dpt)₂]³⁺, and the unis type complex [Co(dpt)₂]³⁺ were prepared by the various methods in organic solvents. For the complex [Co(dpt)₂]³⁺, three possible geometric isomers exist (Fig.1). The structure of the [Co(dpt)₂]³⁺ prepared in this work was indentified on the basis of the spectroscopical data as the mer type. Then the optical isomers, trans-2-NH- and trans-o-NHmer-[Co(dpt)₂]³⁺ were resolved by column chromatography. The complexes were characterized by elemental analysis, electronic spectra (Fig.5), IR spectrum and circular dichroism spectra (Fig.6).

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The relative-efficiency curves were presented previously for various sizes of Ge(Li) detectors to determine X-ray intensity for many nuclides. In the present work, the curves have been revised and applied to the estimation of the intensity of X-rays appeared in r-ray spectrograms (in literature) which had never been analyzed. The X-ray intensities thus obtained are shown below together with the names of the corresponding radioactive nuclides. These measured intensities are useful for X-ray spectrometry combined with activation analysis.

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he optical resolution by preferential crystallization procedure of (±)-a-methylbenzylamine salt of (±)-malic acid was attempted. It is possible to consider, by the mixing of (-4-)-malic acid ((±)-[1]) and (±)-α-methylbenzylamine (±)-[ 2], four kinds of combinations (-)-1. (-)-2, (+)-1. (+)-2, (-)-1. (+)-2, and (+)-1. (-)-2. However, it was concluded, , from the comparison with the infrared spectra, melting points and solubilities of these salts, that the salt crystallized out of the racemic solution was the equivalent mixture of (-)-1. (+)-2 and (+)-1. (-)-2 and the racemic structure was a conglomerate. This result was in agreement with that found on the binary phase diagram of melting point. It was able to resolve the (±)-1. (±)-2 by preferential crystallization procedure in methanol at 10 and 20°C. The (-)-1. (+)-2 having an optical purity of 88.2% was obtained in a degree of resolution of 82.3%, from the supersaturated racemic solution of 106% at 10°C.

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Electrooxdation of 5-hydroxymethylf urf ral [1a] and its derivatives in methanol has been studied. (Z)-Methyl 5-acetoxy-4, 4-dimethoxy-2-pentenoate [5a] was obtained from 5-acetoxymethylfurfral [1b] and 5-acetoxymethylf urf uryl alcohol [2] in 91-92% yields (see Table 5). (Z)-Methyl 5-acetoxy-5-alkyl-4, 4-dimethoxy-2-pentenoate [5b-f] was obtained from 2-(1-acetoxyalkyl)-5-(ethoxymethyl)furan (4 a-e) in 79---93% yields (see Table 5). However, (1a) and 2-(1-hydroxyethyl)-5-(ethoxymethyl)furan (3a) were oxidized further, giving methly maleate ( 8) and methyl succinate [9].

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The electrochemical behavior of 2, 3-dipenyl-1-indenone (DPI) in N, N-dimethylformamide containing O.1 mol·dm^-3 supporting electrolyte was studied by DC-polarography, cyclic voltammetry, controlled-potential electrolysis and uv ? vis spectroscopy. The electrochemical reduction of DPI occurred in two one-electron steps. The reversible first electron transfer step give a relatively stable anion radical. In the presence of electrophilic reagents such as proton donor and acetic anhydride, the anion radical was reduced via the ECE mechanism. The second electron transfer to the dianion was followed by the rapid chemical reaction with proton donor. The protonation of the anion radical yielded trans-form as a main reduction product. On the other hand, the protonation of the dianion yielded the trans- and cis-2, 3dipheny1-1-indanone. On the basis of the experimental results, the possible mechanisms for the electrochemical reduction were proposed.

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Methylol compounds were prepared by the reaction of 2-imidazolidinone [1 a] and 2-imidazolidinethione[ b] with formaldehyde. In all these reactions, bis(hydroxymethyl) cornpounds were stable and can easily be isolated. Pyrolysis of [1 a], [1b], 1, 3-bis(hydroxymethyl)2-imidazolidinone [2 a] and 1, 3-bis(hydroxymethyl)-2-imidazolidinethione [2b] were investigated by the thermal analysis. The cleavage mechanism by electron impact for [2 a]and [2b] was investigated by mass spectra. The pyrolysis reaction of bis(hydroxymethyl)compounds was found to be thermal decomposition via the polycondensation reaction stage after the molten state (Fig.2). The polycondensation stage obeyed the first order kinetics which characterizes the ordinary thermal polymerization in the solid state (Fig.5). The kinetic data of the polycondensation reaction were evaluated by analysis of the dependences of the area of isothermal DSC curves upon the reaction time (Table 2, 3, 4). The DTA and DSC curves for [1 a] revealed a single reversible endothermic peak resulting from polymorphism at a temperature lower than its melting point (Fig.1). In the decomposition by electron impact of [2 a] and [2b], the cleavage of the fivemembered ring which corresponded to the molecular ion peaks for [1 a] and [1 b] was considered to take place after a successive cleavage of the two side chains. The main fragmentation mechanism for [1a]and C.. /1: 1 was found to consist of three cleavage modes (Scheme 2, 3, 4). Deuterium labeling has enabled mechanistic interpretations for the principal ion (m/e 30)being formed in the mass spectric fragmentation of [1 a]. High resolution mass spectrometry established the composition of many peaks in the low-resolution spectra of the compounds studied (Table 5).

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A variety of α-chloro-r-butyrolactones were prepared by the dichlorotris(triphenylphosphine)ruthenium(II)-catalyzed reaction of various olefins with a-polychloro carboxylic acids. Reactions of monoalkylethylenes with a-polychloro carboxylic acids such as trichloroacetic acid, dichloroacetic acid and 2, 2-dichloropropionic acid gave a-chloro-r-alkyl-r-butyrolactones in 50-84% yields (Table 2). In the reaction of cyclopentene, cyclohexene and cycloheptene with trichloroacetic acid, cis-fused r-butyrolactones were obtained in yields of 35, 22 and 32%, respectively (Table 3). Reactions of 1, 1-dialkylethylenes with a-polychloro carboxylic acids afforded isomeric mixtures of a pair of the expected and rearranged r-butyrolactones in combined yields of 42-67% (Table 3). The reaction of olefins such as 5-hexen-2-one and 3-butenoic acid gave the corresponding r-butyrolactones in somewhat low isolated yields (24 and 24%, respectively) (Table 5). No r-butyrolactones were obtained from the reaction of styrene and isoprene because of the prevailing cationic polymerization.

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Various α-chloro-r-butyrolactones were prepared by the dichlorotris(triphenylphosphine)ruthenium(II)-catalyzed reaction of a variety of olefins with trimethylsilyl a-polychloro car-. boxylates such as trimethylsilyl trichloroacetate, trimethylsilyl dichloroacetate, and trimethylsilyl 2, 2-dichloropropionate. In the reaction of 1-octene with trimethylsilyl trichloroacetate, α, α-dichloro-r-hexyl-r-butyrolactone was obtained in 94% yield (GLC). The reaction of cyclopentene, cyclohexene and cycloheptene with the trichloroacetate afforded the respective cis-fused a, α-dichloro-γ-butyrolactone in 52 (GLC), 61 and 57% yield. Even the reactions of polymerizable olefins such as styrene, α-methylstyrene, methyl acrylate, and methyl metacrylate with trimethylsilyl α-polychloro carboxylates gave the corresponding α-chloro-γ-butyrolactones in 53-87% yields. Also, the similar reaction of isoprene, 2, 3-dimethyl-1, 3-butadiene, and 1, 3-cyclooctadiene gave the corresponding α-chloro-1-butyrolactones in 25-65% yields.

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New compounds, 1-(2-aminoethylamino)-2-alkanols, have been prepared by the reaction of long-chain 1, 2-epoxyalkanes and ethylenediamine. The 2-aminoethylamino alcohols were readily converted to new 2-alkylpiperazines when heated in xylene in the presence of Raney Ni W-4.
A new class of surfactants, 3-(3-alkyl-1-piperaziny1)-1-propanesulfonic. acids (R=n-C_mH_2m+1; m=8, 10, 12, 14, 16; abbreviated as C_mPHS-H in the text) and their sodium salts [1] (abbreviated as C_mPPS-Na) have been prepared by the reaction of the 2-alkylpiperazines with 1, 3-propanesultone. For comparison, 3-(4-tetradecy1-1-piperaziny1)-1-propanesulfonic acid and its sodium salt [2] (abbreviated as N-C₁₄PPS-H and N-C₁₄PPS-Na, respectively), and 2-(3-tetradecy1-1-piperazinyl) ethanesulfonic acid and its sodium salt [3] (abbreviated as C₁₄PES-H and C14PES-Na, respectively) have also been prepared. Compounds [1]-[3] showed good surface-active properties: i. e., these compounds lowered the surface tention of their aqueous solutions to 36-47 dyn/cm; Ci, PPS-Na, CiaPPS-Na, and N-C14PPS-Na had larger solubilizing power for Orange OT than that of sodium dodecylbenzenesulfonate (DBS). Compounds [1] (except C6PPS-Na) and[2] were also as good as or even superior to DBS in emulsification of liquid paraffin and in foaming ability and stability. CBPPS-H was an ampholytic weak acid (pK_a′=9.10) and showed a pH buffering property in the pH range of 8.5 to 10.1; its pH buffer capacity [9] was a little less than that of Good's buffer, HEPES. Compounds[1] had little or no activity against Escherichia coli and Staphylococcus aureus, whereas C₁₄PPS-Na showed remarkable antifungal activity against Aspergillus oryzae.

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Salt-dye ratio (p) and substantivity ratio ( q ) in the system of dyeing for cellulose-direct dye in the presence of polylectorlyte were defined on the assumption that the polyelectrolyte presents only in the bulk phase because of its molecular size. Thus, both of pq equation described by Standing and relative equation of substantivity described by Vickerstaff were able to apply to the system under the conditions of the presence of polylectrolyte, indicating the adaptability with our proposed adsorption model in which the dye ions are accumualted inside of cellulose by a Donnan membrane-equilibrium effect due to the presence of polyelectrolyte in the bulk solution.

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In order to investigate the effect of water on the esterification and the transesterification by lipase, the reaction of glycerol (containing O.6, 7.0, 15.0% H₂O) with oleic acid, methyl, ethyl and butyl oleate was carried out using lipase from Chromobacterium viscosum at 40°C.
Water showed different effect on the reactions as follows. For the esterification, water disturbed the reaction. The presence of water made the initial reaction rate fast, but the final conversion decreasing. For the transesterification, water accelerated the reaction rate. Especialy, it was distinct on the reaction of glycerol with ethyl oleate. By increasing water content in glycerol from O.6 to 7.0%, the conversion increased from 14 to 73% after 24 h.

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New isopropenyl-1, 3, 5-triazines, e. g., 2-anilino-4-dimethylamino-[1], diethylamino-[2], (1-pyrrolidinyl)-[3] and piperidino-C 4 J 6-isopropenyl-1, 3, 5-triziries, were prepared by the reaction of the correspo nding biguanides with methacryloyl chloride. The homopolymerization of these monomers and their copolymerizations with styrene and methyl methacrylate (M₁) were carried out in dimethyl sulf oxide at 60°C using azobisisobutyronitrile as an 1813initiator. The copolymerization parameters (r₁, r₂, Q₂ and e₂). were determined for these monomers. Thermal polymerzation of these monomers was studied by DSC measurement. The ceiling temperature and the heat of polymerization of these monomers were obtained from the DSC data. These values were in good agreement with that measured by the equibrium monomer concentration determined by isothermal DSC measurement.

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The flowers of Liliiflorae plants (Lycoris radiata Herb., Lilium longiflorum Thunb. and Crinuin asiaticum L.) were divided into leaf, peduncle, bract, perianth, filament, anther, ovary, style, stigma etc. and the distribution of elements in each part was determined. The analytical results revealed that (1) almost all elements were distributed with different concentration according to a part of the flowers, (2) abnormal distribution of cobalt and nickel to genital organ was noticed in Lilium longiflorum Thunb., and (3) high content of cadmium to genital organ and low content of calcium in each part were observed on Crinum asiaticum L.

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The hydration of 1-p-menthene [1], 3-p-menthene [2], 1, 8-p-menthadiene [3], isoprene [4] mycrene [5], dihydromycrene [6], longifolene C7J and p-caryophyllene C8D with mono-, di- and trichloroacetic acids in the presence of synthetic zeolites (A-3, A-4, A-5, F-9 and TSZ-301) was investigated. The hydration of[1], [2] and [3]gave cis-1-p-menthanol [1 0 ], trans-4-p-menthanol [13] and a-terpineol [ 14 ], respectively as a main product with high conversion (89-400%, at best) and high selectivity. Hydration of C 4 J gave geraniol [15] as a major product. Linalool C. /8 J and myrcenol [19] were obtained as major two products from C 5 J. Under particular conditions, the [18]/[19] ratio was 57: 28 or 46: 42. Dihydromyrcenol [20]was obtained from [6] as a main product, amounting to 80% of the hydration products under the best conditions. Longicamphene hydrate [21]was obtained in high selectivity (86% and 92%) from [7]. β-Caryophyllene alcohol [24] was obtained from [8] as a main product, amounting to 84% of the hydration products under the best conditions.

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