Molecular and synthetic design of o-sulfonamidophe nol dye-releasers for instant color photography is described. These dye-releasers are oxidized to the corresponding o-quinone monosulfonamides, which are in turn hydrolyzed to release diffusible dyes. The efficiency of the dye-releasing process is influenced by substituents on the phenyl group of the osulfonamidophenyl moiety. Side reactions of the intermediate o-quinone monosulfonamides are reduced by steric hindrance of t-alkyl substituents. The effects of substitutents on the heat-fastness of released dyes are discussed. Several unit reactions are developed: e. g. benzoxazole synthesis, convenient methods of preparing sulfonyl chlorides, a procedure of nuclepophilic substitution of aromatic ring, and a new reducing agent of quinones.

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In order to reveal the origin of acid sites generated on TiO₂-SnO₂ binary oxide, the influences of Ti-O-Sn bonds formed in the binary oxide and of the particle size of the component metal oxides on acid properties were studied.
The binary oxides were prepared by two differen t methods one is simultaneous hydrolysis of Ti and Sn mixed alkoxide solution and the other is physical mixing of two oxides which were separately prepared by hydrolysis of Ti and Sn alkoxides. These powdered samples were calcined at 420°C in air. The formation of solid solution between TiO₂ and SnO₂, suggesting the presence of Ti-O-Sn bonds, was observed by x-ray diffraction and Raman spectroscopy on the co-precipitated oxide, but was never observed in the physically mixed oxide. Strong acid sites (H₀=-3.0) were observed on both the binary oxides. This suggests that the presence of Ti?O?Sn bonds will not affect upon the acid properties of the binary oxide system.
On the other hand, titration tests and NH₃-TPD measurements showed that the acid strength increased with a decrease in the particle size of TiO₂ and SnO₂ single oxides themselves. We concluded that the formation of small sized particles in TiO₂, SnO₂ and the binary oxide makes an important contribution to the generation of strong acid sites.

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Reductive amination of hindered alicyclic ketones has been stu died using menthone 1 and isomenthone 2 with 5% platinum metlas on carbon and Raney Ni and Co in ethanolic ammonia solution at 60°C and 70 kg/cm² H₂ pressure.
Although the reaction of 1 gave three isomeric primary amines, i. e., neomenthylamine 4, menthylamine 5 and isomenthylamine 6, no secondary amines were detected. The total yields of the primary amine isomers ranged between 24-84%, and increased in the order of Raney Ni <Raney Co<5%Pt-C<5%Rh-C≤5%Ru-C<5%Pd-C. Selectivities for the formation of the primary amine isomers also depended on catalysts used. On reaction of 1 over 5%Pd-C, 4, 5 and 6 were obtained in 45%, 16% and 23% yields, respectively. Whereas on 5%Ru-C, isomer 6 was most dominant (41%). The reaction of 2 afforded primary amine isomers in lower yields than that of 1. It is very likely that the product amines are produced via the corresponding imines as intermediates, which are in tautomeric equilibrium with the enamic forms. The observed stereochemical selectivity as well as the difference in reactivities of 1 and 2 can be accounted for by considering this tautomerism. t Reductive Alkylation. iT.

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Crystals of SrCe0₃ and SrCe_0.95Yb_0.05O_3-a_were grown by Xe arc-image FZ m ethod. The crystal structures of SrCeO₃ and SrCe_0.95Yb_0.05O_3-a were determined by the powder X-ray diffraction profile refinement (Rietveld method). The trial model for the refinement was determined with the technique suggested by Glazer for distorted perovskite-type structures. The crystal data for SrCeO₃ are orthorhombic. Pnma (No.62) and a=6.1473(2), b=8.5803(5), c=6.0066(2) Å with a^-b⁺a^- anion octahedra tilt system. SrCe_0.95Yb_0.05O_3-a_haa s the same symmetry with SrCeO₃ and a=6.1409(2), b=8.5783(7), c=5.9997(4)Å. The refined structure parameters were approximately the same between SrCeO₃ and SrCe_0.95Yb_0.05O_3-a within a standard deviations. The protonic conduction of SrCeO₃, which is ca used by the partial substitution of Ce with Yb, is not accompanied by obvious structural changes. The refined structual parameters also showed that the anion octahedra tilt 13.2° about [100]and [001] and 10.7° about [010], which are extremely large among perovskite-type compounds with similar a^-b⁺a^- tilt systems. Precession photographs and polarization micrographs showed that the grown crystals had complex twin structures which were seemed to be formed by successive transformations accompanying the tilt of the anio octahedra.

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Sodium fluorine micas having variable layer charges [Na_χMg_3-χ Li_χ(Si₄O₁₀)F₂; χ=1.0, O.8, 0.6] and their cation-exchanged forms (Ba-, Ni-type) were heated at high temperatures (-1000°C) under various conditions such as i) in air, ii) in fluoride-containing m ixture, and iii) in a sealed platinum vessel, and swelling characteristics and cation exchangeability of fluorine micas were investigated by XRD, IR and AAA methods to clarify the effects of heat treatment on swelling tendencies. The content of exchangeable Na⁺, the ratio of nonswelling to swelling phase and/or low-hydration phase to high-hydration phase increased with increasing temperature and heat-treating time for Na-micas having high charges (χ= 1.0, 0.8), showing reduction in swelling tendencies by heating. However, thermal decomposition of micas occurred above 700°C in air and above 800°C in fluoride-containing mixture, respectively, while it was prevented in the sealed vessel at 700-1000°C. When Na-micas (χ=1.0, O.8) and their Ni-exchanged forms were heated in the sealed vessel at 1000°C for prolonged time and above 800°C, respectively, the infrared absorption band (ca.980 cm^-1)ascribable to Si-O_b (basal oxygen) vibration shifted to lower frequencies for the former and to higher frequencies for the latter, respectively. This shows that the interlayer structure of mica was rearranged through the migration of interlayer cations into hexagonal holes of tetrahedral sheets; the migration is easier for smaller cation than for larger cation and the buried cations in hexagonal cavities lose their hydration properties. The changes in b-dimension of the mica lattice were also observed with increasing temperature, supporting above-mentioned concepts in the mechanism of loosing swelling properties for heated micas. Heat treatment was also effective for making Ba-exchanged mica nonswelling, however, the mechanism is different from the one described above because the largest Ba²⁺ cation can establish a similar stable coordination interlayer polyhedron to that of the typical nonswelling K-mica. On the contrary, heat treatment for Na-micas having low charge (χ=0.6) was less effective because susbstantial unstableness results from the weaker interlayer bonding.

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Absorption behavior of copper(II) with poly[N-(8-hydroxy-5-quinolylmethyl)-4 -sulfamoyl styrene] resin (PQS resin), which was prepa red by the reaction of poly(chlorosulfonylstyrene)resin (styrene-2% divinylbenzene copolymer, 100-300 mesh) with 5-aminomethy1-8-quinolinol, was investigated by batch method. The functional 8-quinolinol moiety in PQS resin was found to be 0.97 mmol/g-resin by the elemental analysis. The water regain of PQS resin was to be 1.36 gig-resin, which was almost the same as that of iminodiacetic acid chelate resin, suggesting that PQS resin was characterized by a less hydrophobicity. The PQS resin is very stable even in 2mol⋅dm^-3 hydrochloric acid solution, but gradually decomposes to release 8-quinolinol group in 1mol⋅dm^-3 sodium hydroxide solution. The maximum loading capacity for copper(II) was determined to be 0.13 mol/g-resin at pH 5.5in the presence of 1.0 mol⋅dm^-3 sodium chloride. From a 20 cm³' solution of 1.0 x 10^-4' moldm^-3' copper(II), copper(II) was quantitatively adsorbed onto 50 mg of PQS resin at pH 3.5in the presence of 1.0 mol. dm-3 Sodium chloride. The equal amount of nickel(II), zinc(II)and cobalt(II) to copper(II) does not affect the adsorption efficiency of copper(II) at pH 2.7. However, in a case of [Ni(II)]/[Cu(II)] =50, the adsorption efficiency of copper(II)decreased by ca.10%. On the other hand, the adsorption efficiency of copper(II) does not lower even in the presence of fifty-times excess of zinc(II) at pH 2.7-3.3.

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The reaction of aromatic amines with a calculated amount of benzyltrimethylammonium tetrachloroiodate in acetic acid at room temperature or at 70°C gave chloro-substituted aromatic amines in good yields. Futhermore, th e reaction of the chloro-substituted aromatic amines with sodium nitrite and phosphinic acid in 18 N-sulfuric acid at 0-5°C gave the deamination products, chloro-substituted aromatic compounds, in fairly good yields.

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The synthesis of substituted benzochromones via a ring closure reaction of alkyl-substituted naphthodioxaborins with a Vilsmeier reagent have been investigated.2-Naphthol 1 and 1-naphthol 2 were allowed to react with acetic aicd 3 a or substituted acetic acids such as propionic acid 3 b, phenylacetic acid 3 c and 3-phenylpropionic acid 3 d in the presence of boron trifluoride-diethyl ether (BF₃.⋅Et₂O) at 100°C for 3h to produce methyl-(4 a and 5 a), ethyl-(4 b and 5 b, benzyl-4 c and 5 c and (2-phenylethyl-substituted naphtho[1, 3, 2]dioxaborins 4 d and 5 d in good yields, respectively. Each of dioxaborins, 4 b, 4 c, 4 d, 5 b, and 5 d, react ed with an equimolar amount of the Vilsmeier reagent at 60°C for 1 h to give the corresponding 3-methy-(6 b and 7 b), 3-phenyl(6 c), and 3-benzyl-substituted chromone derivatives (6 d and 7 d) via 2-(dimethylamino)vinyl-substituted naphthodioxaborins in high yields. A similar reaction of 4 a, 5 a, and 5 c, however, afforded 2-(dimethylamino) vinyl-substituted naphthodioxaborins 8 a, 9 a, and 9 c), which were treated with an acid such as HCl or polyphosphoric acid to produce 1 Hnaphtho[2, 1-b]pyran-1-one 6 a, 4 H-naphtho[1, 2-b]pyran-4-one 7 a, and 2-phenyl-1 H-naphtho [2, 1-b]pyran-4-one 7 c, in yields of 85%, 78%, and 86%, respectively. It is considered that the formation of 3-substituted benzoc hromones from alky-substituted naphthodioxaborins takes place through the ring closure of 2-(dimethylamino)vinyl compounds, which are produced by the Vilsmeier reaction of alkyl-substituted naphthodioxabori ns. In the reaction of 4 a and 5 a with two equivalent of the Vilsmeier reagent, formyl-substituted benzochromones (6 f and 7 f) were formed as main products without producing 6 a or 7 a. In bromination reactions 8 a and 9 a gave bromo-substituted benzochromones (6 e and 7 e).

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In order to study a mechanism of photopolymerization of pyrrole, pyrrole in water was irradiated by mercury lamp and the polymerization rate of pyrrole was followed by GC and UV-visible absorption spectrum. Effects of pH by adding HC1 and oxygen in the solution on the rate of polymerization of pyrrole were investigated. Without the evacuation of solution, although the rate of the decrease of pyrrole did not depend on in the concentration of pyrrole and proton, the concentration of proton affected the formation of product which had a visible absorption at 460 nm. Since the formation rate of the product increased in proportion as pH decreased, it was found that the polymerization reaction depended on pH. When 2, 5-di(2-pyrrolyl)pyrrolidine which was produced by protonation of pyrrole was irradiated in the presence of HC1, the spectra were same as those of the products in pyrrole solution irradiated in the presence of HC1. Consequently, in acidic aqueous solution, pyrrole polymerized mainly by the protonation and dehydrogenation; an absorption of terpyrrole (320 nm) appeared under the irradiation of pyrrole or 2, 5-di(2pyrroly1) pyrrolidine, and H₂ was detected by GC. In neutral aqueous solution with oxygen, an absorption of bipyrrole (270 nm) was detected. From these results, a mechanism of ph o topolymerization of pyrrole was proposed.

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Formation and properties of calcium oxalate monohydrate, dihydrate and trihydrate were studied as compared with the calcium oxalate crystals isolated from plants. Calcium oxalate monohydrate precipitates at temperatures higher than those for the formation of calcium oxalate dihydrate and trihydrate. Calcium oxalate dihydrate and trihydrate were produced in the presence of sodium citrate or malate depending on the concentration of citrate or malate. The solubility at room temperature of calcium oxalate dihydrate or trihydrate was little greater than that of monohydrate as shown in Table 3. The solubility of calcium oxalate monohydrate slightly increased at 100°C. The shapes of single crystals of calcium oxalate monohydrate, dihydrate and trihydrate were hexagonal plates, octahedron, and parallelogram plates respectively. Calcium oxalate dihydrate and trihydrate changed to monohydrate by boiling in water for 10 min. The nucleus of calcium oxalate monohydrate was assumed to be Ca₃(C₂O₄)₃n⋅H₂O from the measurement of the induction period of the precipitation. Calcium oxalate monohydrate and dihydrate were found to be present in plant leaves and trunks. Those formed in plants were very stable and they changed into monohydrate after boiling one or for several hours in water.

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Radical copolymerizations of styrene and methyl m ethacrylate (MMA) were carried out in the presence of poor solvents (50 vol%) at 60°C. When copolymerizations were carried out in methanol, turbidity was found at 20 mol% of feed MMA, and at 30 mol% or above gelatinous copolymer precipitated without turbidity. However, rate of copolymerization (R_cp), copolymer composition, monomer reactivity ratios(γ1, γ2), and degree o f polymerization (P_n) in methanol were similar to those in good solvents. When copolymerizations were carried out in hexane turbidity and precipitate were found at 40 mol% of feed MMA or above, but no turbidity was found at 20 mol%. Although the values of R_cp between 20-80mol% of feed MMA in hexane were smaller than those in methanol, copolymer composition and Pi, except respective values at 80 mol% were similar to those in good solvents. The values of γ1 and γ2 determined by neglecting the value at 80 mol% of feed MMA were also similar to those in good solvents. It is considered that the propagating radical at 80 mol% of feed MMA in hexane precipitated by itself and the radical was trapped to increase the MMA composition of copolymer.

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Thermal behaviors of ozone-oxidized polypropylene and methyl methacr ylate grafted poly propylene were investigated by using differential scanning calorimeter (DSC), and the results obtained were compared with that by X-ray diffraction. The peak temperatures in the processes of melting and crystallization for ozone -oxidized polypropylene decreased with ozone-oxidation time. Two appreciable peaks appeared in the process of remelting after crystallization, and the lower temperature peak dropped more markedly than the higher one with ozone-oxidation time. The peak temperature at melting of methyl methacrylat e grafted polypropylene lowered with degree of grafting, and at the same time the width of the peak broadened. Two peaks appeared in the process of remelting after crystallization; the lower temperature peak shifted to lower side with degree of grafting, while the higher temperature peak was constant virAtually. Crystallinity measured by means of DSC coincided with that of X-ray diffraction. vrami's plots obtained from the isothermal crystallization curves of DSC showed that the methyl methacrylate grafted polypropylene had two different crystal forms; the ungrafted polypropylene crystallized first, and then the grafted polypropylene or polypropylene prevented from crystallization by graft polypropylene crystallized later.

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The fibrous-structured cheese, called "string cheese", is p r epared by kneading and stretching Mozzarella cheese curds. The fibrous-structured cheese can be easily torn with fingers, l eaving a stringy texture along the torn part. The amount of stringy material determines the quality of fibrous-structured cheese, and the area of stringy material was able to regard as "stringiness". Until now, this quality evaluation of fibrous-structured cheese has been done subjectively by sensory evaluation technique. For evaluating the stringiness of fibrous-structur ed cheese, an objective method based on di gital image analysis technique was proposed. A sample of milk-white cheese was put on black paper for contrast and then torn at a constant speed. This process was videotaped (Figs.1, 2). Stringy material image enclosed in a window was digitized, then extracted f rom the background and the area was calculated. Stringiness tended to be higher at a sample tempe rature of about 25°C (Fig.7). Measurement conditions determined here were as follows: thickness of sample 1 cm, tearing speed 1 cm/s, and the area of the stringy material was calculated when the length of the samples torn

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The pressure dependence of the substrate affinity of the subsite-1 of an immobilized glucoamylase was studied, using the hydrolysis of maltose as a test reaction and gluconolatone as an inhibitor. The pressure dependences of the substrate affinities of the subsite-2, and subsite-3 were also studied, using hydrolyses of maltose and maltotriose as test reactions. The pressure range used was 0.1-98 MPa and the temperature was 25±0.1°C. The inhibition effect of gluconolactone upon the maltose hydrolysis was enhanced by pressure (Table 1), giving a volume change of -14±4cm³⋅mol^-1 for the subsite-1-inhibitor interaction. A hydrogen-bond formation between the subsite and a gluconolactone molecule would be responsible for the volume change observed. The affinity (A₂) of the subsite-2 and the affinity (A₃) of the subsite-3 were 21.9 and 5.6 kJ⋅mol^-1, respectively. These values were almost unchanged by the increase in the applied pressure (Table 2).

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The regeneration of nicotinamide-adenine dinucleotide (reduced form, NADH) by the reduction of NAD⁺ with hydrogen gas was carried out in the p resence of the hydrogenase f rom Alcaligenes eutrophus. The syntheses of formic acid and isocitric acid were performed by combinations of the above system with formate dehydrogenase and isocitrat e dehydrogenase, respectively. The conversion of CO₂ to formic acid was 0.2% after 12 h, and the conversion of 2-oxoglutaric acid to isocitric acid was 11.4% after 24 h.

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Eggshell was treated by hydrogen chloride drop method, an d the adsorptions of water vapor and carbon dioxide were studied at the temperature of 20°C. The amounts of adsorption of both water and carbon dioxide increased with increase in calcium chloride content, and also increased with decrease in particle diameter. The amount of water adsorption was about 7-8 times that of carbon dioxide adsorption. SEM micrographs showed that spherical particles were obtained in samples containing 40 mol% of calcium chloride. It is concluded that eggshell treated by the hydrogen chloride drop method could be used for economical adsorption of water and carbon dioxide.

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