Copper phthalocyanine (CuPc) was sublimed in plasma of various gases (argon, nitrogen oxygen) and vapors (benzene, acetone, methanol and water), and the structures of the CuPc film were studied by means of infrared spectroscopy, mass spectroscopy and surface energy analysis. Infrared spectra of CuPc sublimed in various gas plasmas showed a weak absorption band at 1380 cm^-1 which was assigned to the NO₂ group. The strong peaks of H2O+ and CO2+appeared in mass spectrum when the CuPc film was irradiated with argon, oxygen, methanol and water plasmas. A strong peak of CO+ was observed in mass spectrum of the product obtained from CuPc irradiated with acetone plasma. C₃H₃⁺, C₆H₃⁺ nd many other fragments were observed with benzene plasma. The electron micrograph of the CuPc film irradiated with benzene plasma showed that it was covered with a thin film of plasma-polymerized benzene. The contact angles of water, glycerol, formamide and diiodomethane were 0° when the CuPc films were irradiated with argon, nitrogen and, oxygen plasma. The dipole force component in the surface energy of the CuPc films was increased by irradiation with vapor plasma in order of benzene, acetone, methanol and water. This finding suggested that the CuPc film adsorbed the hydroxyl and carbonyl groups produced by the plasma irradiation.

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Fine magnetite particles were prepared in the presence of iron (iron wire or iron powder)and iron010 hydroxide sol which had been produced by addition of aqueous iron(III) chloride solution into boiling water. Iron wire was used in order to elucidate the mechanism of the reaction and iron powder was used in order to find the conditions of the reaction, respect ively. The amount of iron powder, the amount of aqueous iron (III) chloride solution or the reflux time were changed to find the optimal conditions for the reaction.
The weight of iron wire consumed, pH of the media after the reaction and the weight oi products were approximately independent of the amount of iron wire. On the other hand, the formation time of black dispersion decreased and the principal products varied from T-Fe20, to Fe₃O₄ with an increase of the amount of iron wire. It was assumed from this result thai the overall reaction was composed of the reactions of formula ( 1 ) to ( 6 ).
pH of the media and the weight of products were independent of the amount of iron powder, similarly to the case of iron wire. On the other hand, the formation time decreasec markedly with the increase of the amount of iron powder. All the products were changec into Fe_aO₄ and the degree of crystallinity observed by X-ray diffraction patterns was constani over 24 m/ of the amount of 1.1 mol/l aqueous iron (III) chloride solution (the initial concent ration of iron(III) chloride in boiling water was over 0.236 mol/l). The amount of products and pH were nearly constant and the products were all Fe₃O₄ with a change in the refluy time. The degree of crystallinity was also independent of the reflux time.
It was found that monodispersed fine particles of magnetite with highly developed crystallinity were prepared under a certain condition for the reaction.

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Photopolymers on aluminum plates were studied by the reflection absorption spectrometry using Fourier transform infrared spectrometer. Samples were prepared by coating photopolymers, viz, diazo resin type polymer (mixture of a copolymer of 2-hydroxyethyl methscrylate, methacrylic acid, etc. and a copolymer of 4-diazoniodiphenylamine chloride and formaldehyde) or poly(vinyl cinnamate) on the electrochemically roughened and anodized aluminum (Al) plates (roughness value; R_z =4.8 μm, R_max. = 5.6μm, R₌0.7μm, R_s = 0.9μm, the quantity of Al oxide; 0.15 mg/cm²). These samples are widely used as presensitized o ffset printing plates (PS plates) in printing industry. Spectra of the samples before and aft er light exposure were measured, and these spectral ratios were calculated and spectral changes with exposure were detected for the both photopolymers (Fig.1, 3). The relationships between the exposed energy and the amount of photochemically reacted polymers was obtained using some key bands, which were 1730, 1710and 1630 cm^-1 for poly (vinyl cinnamate), and 1580 and 1110 cm^-1 for diazo resin (Fig.5, 6). All the amount of diazo resin on the Al plate reacted completely after standard exposure, but on the other hand, only 25% of poly(vinyl cinnamate) reacted. Relations between the quantity of diazo resin type poly mers and the intensity of both bands at 1720 cm^-1 and at 1480 cm^-1 which were independent of photochemical changes, were examined and the linear relationships were found so far as the quantity was less than 100μgl cm^-1(1720 cm^-1), and less than 200μg/cm² (1480cm^-1). Using this relationship, a characte ristic curve of the diazo resin type PS plate was established (Fig.7). Very small amount of the diazo resin type polymer (ca.3 pgicm²) on non-image area remaining after exposure and development was detected for the first time, and the effect of this residue on scumming which occurs during long-run printing was discussed.

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The poly(tetrafluoroethylene) (PTFE)-bonded carbon electrodes with catalysts (Fig.1) were investigated to develop a high performance cathode for the oxygen depolarized alkali chloride electrolytic cell (Table 1). The addition of noble metal catalysts to the carbon electrodes increased the activity for oxygen reduction in the following order: ikg>t't t-'cli-vii. I ne order agrees with that of the catalytic activity for the H202 decomposition. In the case of the electrodes with silver catalysts, the electrode performance greatly depended on the silver-loading process to carbon (Fig.3). The "ion exchange method" (Fig.2) gave the most effective electrode, i. e., the current density as high as 300 mA/cm2 was obtained at 0.12 V (vs. Hg/HgO) for oxygen reduction in 9 mol/dm3 NaOH at 80°C (Figs.3 and 4). The high perf ormance of this electrode was found to come in part from the high dispersion of silver particles (Tables 2 and 3 as well as Fig.9) and in part from the HNO3-treatment on the carbon surface (Figs.4 and 6). The electrode activity was stable in a short term operation for 10 h at the current density as high as 500 mA/cm2 (Fig.10). t Studies on Oxygen Cathode for Brine Electro lysis. III.

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Kinetics of the Landolt reaction (reduction of IO₃^- by HSO₃^-) was studied by use of a glass electrode under conditions of the ionic strength 0.1 mol dm^-3 (NaClO₄), the pH range 2.2 3.5, and the temperature range 15-30°C. A computer simulation method was applied to analyze the kinetics of the reaction., It was confirmed that the reaction proceeded by th e following mechanism:
were V₁, V₂, and V₃ show reaction rate. The rates are expressed as V₁=k₁[I^O₃^-][HSO₃^-][H⁺]( 4 ), V₂= k₂[IO₃-] [I^-₂[H⁺]²( 5 ), V₃ = k₃[_I2] HSO₃^-] ( 6 ), where k₁= ( 7.7 ±0.2) X 10²M ^-2S-¹ (ΔH=18±5 kJ mol^-1, ΔS=-128±17JK^-1mol^-), k2= (4.0±0.1) x 10³M^-4S^-1(ΔH=54±16 kJ mol^-1, ΔS =101±58 JK^-1mol^-1), k3>3 x 10³M^-1s^-1 at 25.0 °C. Characte ristics of the Landolt reaction were also examined by the computer simulation (Fig.3 ).

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The reactions between TiP₂O₇ and CuO have been studied for the sample mixtures containing 10 to 90 mol% CuO. All the mixtures were heated at 900°C for 200 h and some of them up to several temperatures of 600, 1100°C(Ch eating rate: 10°Cmin-1) in air. After reactions the quenched samples were subjected to X-ray powder diffractometry.
The reaction products were CuTi4(PO4) 6, Cu₂P₂0 7, 5 T i02-2 P₂O₅, Ti0₂(Rutile), Cus ( POO 2, 4 Cu0.13205 and 5 CuO. P₂0₅. The double phosphate CuTi₄ (PO₄) was formed when the mixtures contained 10 to 54.5 mol% CuO. This double phosphate was isomorphous with MiTi2(PO₄) 3Na, K or Rb) and its latti6e parameter (Hexagonal: a = 8.5 00±0.009 Å, c=21.43±: 0.06Å) was calculated. The X-ray diffraction patterns of 4 Cu0.13, 05 and 5 CuO⋅P₂O₅ corresponded to those of the products obtained from the mixtures of theoretical composition. In a diffusion couple of CuO and TiP207 pellets, the reaction layer of CuO pellet was produced as the mixture of CuO and 5 Cu0.1)205 at 900°C and that of Ti13207 pellet as the mixture of Ti0₂, 5 Ti02.2 P₂0₅ and CuTi4 ( PO₄)₆.

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The mechanism for the absorption of NOz(NO+NO₂) gas mixtures in ammonium hydrogensulfite solutions was investigated to produce hydroxylamine using a packed-absor ber with continuous gas-liquid flow. _ The reaction gas containing 10 vol% of NO and NO₂/NO, m olar ratios with 0.2 3 to 0.4 8 m olA na was introduced for the absorption in the solutions o f pHs with 0.0 to 4.4 at the iteinperattre ranges from 5 to 25°C. The color and pH of the solutions were controled by the feed rate of the hydrogensulfite ' solution and aqueous ammoni a. HON(S0₈)₂2- was efficiently produced in the solutions of light purple or light brown color at 5°C and pH 4. N₂O, NO₃, N(SO₃)₈³-, FIN(SO3)₂
^2- and N₂ were also byproduced. Th e purple or brown color may be given by the following reactions;

Different from the hydroxylamine production process by the absorption of SO ₂ gas in nitrite solutions, a considerable amount of N₂O was produced by the described method. The re action between N₂03 and ON(SO₃)₂2- may occur at the gas-liquid interfaca to form N₂O. N ₂O was the main product at 5°CCa nd pH 0.

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ZrSiO4 single crystals were grown from the Na20.3 V205 fluxed melt at constant soaking temperatures of 900°C and 1000°C for periods up to 1710 h, using the natural zircon s eeds. Temperature difference between the seed and nutrient was 0.5, --#5°C. A solubility curve o f the natural zircon in Na20.3 V205 was determined. It was found that about 5.7 g of th e natural crystal dissolved in Na²0.3 V20, in 48 h at 1000°Cand about 7.5 g at 1200°C. T h e maximum growth weight was about O.3 52g under conditions of the temperature differenc e of 2°C and the soaking for 1205 h at 1000°C. The grown crystal was initially bounded with the-c-, p-, a-planes and very small planes consisting of the u- and x-, and finally b o undedwith the m- and p-planes. The observed linear growth rates of planes of ZrSiO₄ s ingle crystals were in the following order: a (100) > c (001)>p (111)> m (110). The growth rates of a- and m-planes were about 5'-'7x 10_-4m m/h and 0.9 -1. 0x 1 0^-4m m/h, respectively. The growth hillocks of rounded triangular shape and elliptic shape extended to the direction of c-axis, were observed on the p- and m-planes, respectively. The observe d step distance of the spiral and the step height were about O.9 75p m and 0.1 72p m, respe c tively. The observed linear rate of advance of the step on the m-plane was about 0.4 ₀-4.2 x 10-8c m/s. A linear growth rate of the m-plane was then calculated to be 0.2 _⁵, ..., 07_^., X 1 0^-4m m/h by the B CF theory, which agreed in order of magnitude with the observed growth rate of the m-plan e. t Study on Synthesis of Large Single Crystal for Industrial Use. XIII.

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Correlation of catalytic activity for the oxidation of CO an d sensor response to CO was investigated for a variety of perovskite oxides prepared by partial substitution of Fe of LaFeO₃ with _other 3d transition metal M to give LaFe_1-xM_xO₃. The catalytic activity of LaFei_zCox0₃(x=0 to 0.2) increased with an increase in x, but the highest sensor response was achieved at x=0.1. It was found that the sensor respons eincreased in proportion to the catalytic activity, provided that the apparent activation energy for electrical conduction was unaffected by the substitution.

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The distribution and the change in content of 23 elements dissolved in a ground water in the Musashino area was studied using neutron activation method. The results are as follows.
( 1 ) 29 out of 30 ground water samples were (Ca²⁺HCO₃^-) types as shown in Fig.8. ( 2 )The average contents of major elements such as Cl, Na, Ca and Mg dissolved in the ground water collected from 30 survey wells were found to be 9.0, 10.1, 15.3 and 3.5 ppm, respectively. The average contents of minor elements such as Al, Sr, Fe, Zn, Mn and Ba were found to be 190, 110, 14, 9.7, 8.2 and 6.2 ppb, respectively. Furthermore, the average contents of trace elements such as V, Rb, As, Cr, Se, W, Sb, Co, . La, Cs, Sm, Sc and Eu were found to be respectively 1.1, 0.82, 0.51, 0.24, O.081, 0.037, 0.035, 0.027, 0.027, 0.007, O.0 06, O.0 02 and O.0 007 ppb. ( 3 ) The coefficients of variation of the elements such as Na, Ca, Mg, Al, Sr, Sb, etc. among 30 survey wells were low values, but it was recognized that the elements such as Fe, Zn, Mn, As, W, Co, etc. showed high values of the coefficient amcng the wells as shown in Fig.9. ( 4 ) The content of each element dissolved in the ground water changed respectively with several characteristic patterns as shown in Fig.11-43.

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An improved standard addition method in which neither electrode potential nor response slope of an ion-selective electrode is required for linear plots is proposed.
A sample solution, of volume V, is titrated with a solution con taining a known amount (cs)of the same ion to be determined and subsequently with a diluent at a constant ionic strength. If the volumes which correspond to the identical electrode potential on the titration curves are. read off and denoted by vs and v respectively, the concentration, cx, of the analyte is determined from a slope of a linear plot of y vs. x:
_??_
where x=vvs, y=vs(V-I-v), p is a constant.
Concentrations of fluoride solutio ns ranging from 10-2 to 10-5mo1dm-3 were determined with an error of less than O.3% and a coefficient of variation of less than 0.4%.

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A new type of flow-coulometry with potential scanning, coulopotentiography (CP), was used in the study of electrolytic behavior of various metal ions in alkaline solution. Since the working electrode used consists of glassy carbon grains, accessible potential range is rather wide. All ions studied were electrolyzed quantitatively by selecting appropriate potentials. But the reduction-oxidation processes of some metal ions were irreversible. Reduction behaviors of those metal ions, except for copper (II) ion in sodium hydroxide solution, were in accordancew ith those in voltammetry with a rotating glassy carbon disk electrode. C opper0 0ion in sodium hydroxide solution showed two reduction waves in coulopotentiogram and each reduction proceeded by one electron process per molecule. From the results with double-cell, CP, it was suggested that soluble copper (I) species was produced by a column electrolysis. With respect to the quantitative analysis, metal ions of concentrations higher than 10^-6mol dm^-3 were directly determined without preparing any standards, and trace metal ions d own to 10^-7mold m^-3 were also determined by an anodic stripping coulopotentiographyw ith th e, double-cell. As an example, the determination of cadmium in ammoniacal solution was examined.

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Dithiooxalate (Ethanebis(thioate), abbr. L^2-) reacts with nickel(II) ion to form water-soluble 1: 2 chelate, [NiL2]2-, which can be readily extracted into chloroform as 1: 2 ion-pairs, Q2[NiL2], with bulky organic cations (Q+). The extraction constants of ion-pairs, Ke. (=[Q₂(NiL₂)] (o)[ Q+]^-2[NiL, ^2-]^-1, subscript (o) represents the species in the chloroform p hase), were determined and the values of log KX were 8.97 for dodecyltrimethylammonium ion, 9.38for tetrabutylammonium ion 11.37 for N-dodecylpyridinium ion, 12.88 for hexadecyltrimethylammonium ion, 14.75 for benzyldimethyldodecylammonium ion, 14.82 for N-hexadecylpyridinium ion, 16.46 for benzyldimethyltetradecylammonium ion, and 18.05 for tetrahexylammonium ion, respectively, at 1=0.3 ((Na+, IC+), (SO₄^2-, OAc, C10₄^-, I^-) and 25°C, for waterchloroform system. Linear cor relation was obtained between log Kex and the number of carbon atoms constituting Q+ ions (Fig.4). In the plots of log Kox vs. van der Waals volume of Q+ ions, however, the data of ones having an aromatic group and the others fall on two independent lines, respectively (Fig.5). From these results, empirical parameters for estimating extraction constants were deduced. The values of the parameters, 4 log Kex (the contribution, of the functional group to log Kex), were O.47 for methylene group, O.82 for methyl group, 3.18 for phenyl group, O.95 for ammonium ion, 4.52 for pyridinium ion and 9.79 for [Ni1212- ion, respectively. The utility of the parameters was verified for [N11212-ion, as well as perchlorate, iodide, picrate and 2-naphtalenesulfonate with various kinds of bulky organic cations.

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A rimmed steel coated with zinc-iron phosphate, in which phosphophyllite [FeZn2(PO4)2.4 H20] was contained as a main constituent, was heat-treated in air (oxidizing atmosphere), 92% nitrogen+8% hydrogen (reducing atmosphere) and nitrogen (inert atmosphere), and the chemical states of iron present in the pyrolysis products were characterized by iron-57. conversion electron MOssbauer spectrometry. The coated surface was also analyzed by means of electron probe X-ray microanalysis, fluorescent X-ray spectrometry and thermal analyses (TG and DTA). In air, there appeared cracks in the coating, due to the dehydration of iron(n) zinc phosphate under 330°C, and the coating was easily stripped off as a result of the oxidation of the interfacial surface of the substrate at a higher temperature than 330°C. In reducing atmosphere, cracks also appeared in the coating due to the dehydration of phosphate compounds, and the chemical constitution of the coating material was changed from phosphophyllite to T-form of anhydrous iron( II) zinc orthophosphate through di- and monohydrate of iron(ff) zinc phosphate. Both zinc and phosphorus in the coating disappeared at a higher temperature than 570°C, and almost none of these elements could be detected on the coated sample heated at 850°C. In inert atmosphere, similar behavior was recognized at a lower temperature than 570°C, but only zinc evaporated gradually from the coating above 570°C, and graftonite [Fee (PO4)2] was produced on the steel. The substrate iron was found to contribute to the reduction of zinc(1j) and phosphorus(V) in phosphate coating.

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The reaction of cis- and trans-1, 2-dichloroethylene with sodium alkanethiolates in HMPT was found to proceed sterospecifically at room temperature to give the corresponding cis- and trans-1, 2-bis(alkylthio)ethylenes, respectively, in good yields. When DMF or DMSO w as used as a solvent, stereoselective substitution of cis-1, 2-dichloroethylene took place also readily, but trans-isomer gave a mixture of cis- and trans-1, 2-disubstituted ethylenes in low yield. cis-1, 2-Dichloroethylene reacted with sodium benzenethiolates to give cis-1, 2-bis(arylthio)ethylenes in good yields, but the trans-isomer did not react under similar reaction conditions.

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Bis(2-aminoethyl) disulfide was obtained by the reaction of 2-aminoethyl hydrogensulfate with sodium hydrogensulfide or disodium sulfide added sulfur in more than 90% yield. The disulfide was considered to be produced through the bond-formation between 2-aminoethylium ion and disulfide anion, which is the major component in the reagent prepared from sulfur and sodium hydrogensulfide or disodium sulfide.

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The esterification of potassium acetate with butyl bromide in a solid-liquid two-phase system was carried out in ethyl methyl ketone at 60°C using various tertiary amines as catalyst. It was found that the catalytic species were the quaternary salts of amines and the apparent catalytic effect was dependent on the reactivity of these amines for quaternization and the catalytic activity of the resulting quaternary salts.
The catalytic efficiency of monoamines dec reased in the order: TPB>TEA>T0A (Fig.1), while that of the corresponding quaternary salts was found to be as follows; TBPB rzETOAB---ITBAB>BTEAB (Fig.4). N, N, N', 11P-Tetramethyl-α, ω-alkanediamines were more efficient than the coresponding bis(quaternary salt)s (Fig.4) and the primary active species was considered to be the mono(quaternary salt)s. However the bis(quaternary salt)s of the polyamines were still considered to be active. Both the catalytic activity of the polyamines and their reactivity for quaternization decreased similarly in the order: diame>triamine >tetramine (Fig.2 and Fig.6). Added potassium iodide, known as an effective cocatalyst, resulted in a decrease of efficacy of amines (Fig.8).

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The effect of the ammonium salt on the carboxylation of indene, fluorene and acetophenone with carbon dioxide was examined in the presence of carbonates, phosphates or acetates as a base.
The carboxylation of these active methylene compounds was remarkably promoted by the addition of benzyltributyl- and benzyltriethylammonium chlorides in the presence of IC, CO, at room temperature under the CO, pressure of 5kg/cm2.1, 3-Indenedicarboxylic acid, 9-fluorenecarboxylic acid and benzoylacetic acid were obtained in good yields. The yield of the carboxylated products varied with the counter anion of the ammonium ion in the order: Cl->Br->I- > ClO₄^-.
Although indene was effectively carboxylated by using CH₃CO₂K, fluorene and acetophenone were scarcely carboxylated under the similar conditions. Potassium phosphate caused the carboxylation of these active methylene compounds in considerable yields. Sodium carbonate and acetate proved to be poorer base than the corresponding potassium salts.

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The dimerization of styrene (St) by the action of Ni[P(OPh)₃₄-CF₃CO₂H catalysts was investigated. The two component system showed a high catalytic activity at CF₃CO₂H/Ni (molar ratio) 4 in o-dichlorobenzene (Table 1 and Fig.1), yielding only linear dimers, trans-1, 3-diphenyl-l-butene and a small amount of the cis isomer, as dimeric styrenes. The selectivities of the dimers were significantly affected by the reaction temperature (Table 2) and the St/Ni ratio (Fig.2); with a St/Ni ratio of 14, the total selectivity for isomeric dimers decre ased from 90% (translcis=5.4) at 5°C to 54% (translcis=3.7) at 50°C, while at 20°C, from 72%with St/Ni =14 to 43% with St/Ni= 52. The decrease may be due to the loss of styrene by polymerization.
The overall initial rate of dimerization can be represented by the form: R= 2 d[Dimer]idt =k[St][Ni]₀, k=101^0.8 exp ( -19300/R T ) lmol^-1-1 where [St] and [Ni], are the concentrations of styrene and Ni[P(OPh), ], used, respectively. The activation parameters are 41P =18.7kcal and %IS*= 11.1 cal der' mol-1. A reaction mechanism involving a z-benzylnickel intermediate (a n-allyl type) formed from styrene and a nickel hydride species is proposed for the dimerization to account for the experimental results. The polymerization of styrene, being a side reaction, is also discussed.

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A series of 2-(2-hydroxyalkylamino)ethanesulfonic acids and their sodium salts were prepared by the reaction of 1, 2-epoxyalkanes with sodium 2-aminoethanesulfonate in methanol at 120°C for 5 h. The amino sulfonic acids showed good surface-active properties (lowering of surface tension, emulsification of liquid paraffin in water, solubilization of a pigment (Orange OT), and foaming power) and pH buffering capacities. The compounds were also tested for the antimicrobial activity against a gram-positive bacterium, Staphylococcus aureus, a gramnegative bacterium, Escherichia coli, and a fungus, Asper gillus oryzae.

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The reaction of acetophenones with dichlorocarbene formed in the presence of phase-transfer catalysts was investigated. A mixture of acetophenone, chloroform and catalytic amounts of tetrabutylammonium chloride was treated with a 50%aq. NaOH solution at 20°C for 20 h to give 2-hydroxy-2-phenylpropionic acid hemihydrate [3 a] and 2-phenylacrylic acid [4 a] in the combined yield of ca.74%. The yield of main product [3 a] increased with increasing concentration of the catalyst and aqueous sodium hydroxid6, and with increase in the volume ratio of aqueous phase to organic phase in the reaction system. Product [4 a] was considered to be formed the dehydration of [3 a] under alkaline conditions. The yields of both products were influenced to decrease by high temperature. Tetrabutylammonium and tetrapentylammonium chlorides were most effective as catalysts among the quaternary ammonium salts examined.
In addition, the reaction with other p-alkyl-substituted acetophenones afforded the corresponding products of both types anhydrous [3 b], --[3 f] and [4 b] -[4 f] under similar conditions, but no reaction was observed with p-nitro-, p-cyano-, and p-carboxyacetophenones. By treatment with boiling water, [4 b] -[4 f] were easily dimerized to 1, 3-bis- (p-alkylphenyl)1, 3-cyclobutanedicarboxylic acid.

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Bis(acetylacetonato)cobalt(II) was found to initiate the polym erization of methyl methacrylate(MMA) in aqueous solution containing a surfactant under nitrogen atmosphere. The polymerization of MMA by this initiator proceeded via a radical mechanism. trans-Bis(acetylacetonato)diaquacobalt(II), formed readily by the hydration of bis(acetylacetonato)cobalt(II) in aqueous solution containing a surfactant, was found to be an electron donor. The results suggest that trans-bis(acetylacetonato)diaquacobalt(II) is an initiation species for the polymerization of MMA. All of the Tween series, Brij 35 and sodium dodecylbezenesulfonate were the effective surfactants for the polymerization of MMA.

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As degree of dissociation and molecular comformation of polyelectrolytes a re dependent on hydrogen ion concentration, polyelectrolyte complexes (PEC) have been prepared by mixing a mixture of (carboxymethyl)dextran (CMD) and poly(styrenesulfonate) (NaSS) with [2-(diethy1amito)ethyl]dextran hydrochloride (EA) at different hydrogen ion concentrations, especially in concentrated alkaline and acidic solutions in different order of mixing. IR spectroscopy, elemential, analyses, and solubilities of PEC, have revealed that the structure an d properties of PEC prepared in concentrated alkaline and acidic solutions are enormously different from those of PEC prepared in dilute alkaline and acidic solutions and also from those prepared from E A, CMD, and DS or EA, NaSSa nd etc. reportedin the previoups aper. The d ifference would be due to different properties of component materials.

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A novel chemical reaction of [2-(diethylamino)ethyl]dextran hydrochloride (EA) with poly(sodium L--glutamate) (PSLG) has been studied at different hydrogen ion concentration. The properties and the structure of the polyelectrolyte complex (PEC) produced were also e xamined. IR spectra, elemental analyses, blood clotting test, swelling with water and solubi l ity revealed that the properties and structure of PEC formed at pH 5.0 were different fro m those formed at pH 6.0, 8.0 and 11. O. The degree of dissociation and the conformation of EA. and PSLG seemed to change with the hydrogen ion concentration to effect a different neut r alization reaction with respect to different order of mixing. In addition, blood tests we r e performed for PEC by the Imai's method to evaluate its antithrombogenicity. The amount of the clot on the PEC sample having carboxyl group was largest irrespective of the PSLG co n tent (suppression of coagulation) in PEC.

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The removal-deodorization of sulfur compounds with the catalytic oxidation methods was investigated. The sulfur compounds studied were (CH3)2S, (CH3)2S2, C2H5SH and H2S. The experiment was carried out by using a packed bed flow reactor under atmospheric pressure at 150-4009C. The catalysts studied were Ti02-supported V205 ( 5%), Pt (0.3 %), CuSO4 (10% )and FeA(SQ4)11(10%)-. The inlet gas was a mixture of sulfur compound (10-'230 ppm), 02 (2, 10rOsC)H, O (0; 191 0%)a ndN 2. Thet otalf lowr ate was5 00N c m3/mfionr 0.5-2.0m/o f the catalyst with, average diameter of 0.7mm. The space velocity was 1.5 x 104-4 X 104h-1. The following results were obtained:
1)V₂O₅-TiO₂v eth e highesatc tivityfo r the removaolf ( CH23S). Theo rdero f the apparent activity was17₂O₅CuSO₄ Fe₂(SO₄>Pt. For example, (CF-102S was completely oxdized to CO, CO, , SO₂ and H₂O over V205--Ti02 at 300°C and 1.5x 10⁴h^-1. The order of ap arwt activity of V₂O₂-TiO₂ for the oxidation of sulfur compounds was H₂S> (CI-13) ₂S >C21-15Sn> (CH)₂S₂. Especially, H₂S was completely oxidized to SO₂ over V₂O₅-TiO₂ at 200°C and 6 X 10⁴h^-1.
2) From the consideration on the distribution of oxidative products of (CH₃)₂S, the four kinds of catalysts were classified into two groups, a group of V₂O₅-TiO₂ and Pt-TiO₂ and that of CuSO_4-TiO₂ and Fe₂(SO₄)₃-TiO₂. The former group gave unknown compounds, besides HCHO, CO, CO₂ and SO_x low temperature, and the latter group gave mainly HCHO and SO₂.
3) From the view-point of the formation of HCHO and unknown compounds as intermediate products the oxidations of (CF-13)₂S, (CH₃) ₂S₂ and C₂H5SH over V₂O₂-TiO₂ were considered to proceed in a similar manner.

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A method for the in situ determination of fluorescent brightening agents (FBA's) in natural waters by fluorometry was established. The fluorescence characteristics of surfactant, detergent builder, tannic acid, pectin and humic acid, and their interaction with FBA's were studied. The above substances except humic acid did not interfere with the determination. Humic acid has a weak fluorescence and behaved as a quencher to FBA. An equation (Eq.3) was proposed to calculate the concentration of FBA from fluorescence intensity and the humic acid content determined on 'a separate portion of the sample.
Suspended solids in water did not interfere with the deter mination, and the water samples were stable at least for two weeks at 10-30°C. From comparison of the fluorescence spectra of several river water samples (Table 5), it was found that relative concentration of two classes of FBA's could be estimated by checking the following items. ( 1 ) The fluorescence intensity must be more than 1 mV ( equivalent to 4.8 ppb quinine sulfate in O.1 N H2SO4) under selected experimental conditions. ( 2 ) The maximum wavelength for emission should lie between 430 nm and 435 nm. ( 3 ) The ratio of the fluorescence intensities at 432 nm and 452 nm (F₄₃₂/F₄₅₂) should be more than 1.1. ( 4 ) The maximum wavelength for excitation should lie between 340 nm and 355 nm. ( 5 ) The ratio of the fluorescence intensities for excitation at 350 nm and 300 nm (F350IF800) should be more than 1.0.
For obtaining reliable results, above ( 1 ), ( 2 ), ( 4 ) and more than one out of two requirements [( 3 ) or ( 5 )] should be fulfilled. The fluorescence substance in river water was identified as two typical FBA's (FBA-1 and FBA-2) commonly used in detergent and the ratio of the two FBA's was found to be 2 to 1by fluorometric determination after thin-layer chromatographic separation (Fig.12). The error caused by humic acid was estimated to be 4.6 to +10% in several river waters if no correction is made (Table 7). Thus, the minimum detectable concentration of FBA in river waters should be 0.5μ gel, assuming the ratio of FBA's as 2 to 1.

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The spin-Hamiltonian parameters of hexakis(hexahydro-2 H-azepin-2-one)copper On perchlorate, magnetically diluted with the corresponding Cd(II) complex, have been determined by the ESR measurements at 77 K using single crystals. The molecular orbital parameters of the copper-ligand bonds were calculated. The parameters are as follows: g11= 2.463, gi=2.090, A= 00.1156 c m^-1, B= 0.00132c m^-1, α2=0.85, α =0.21, β, ²=0.98 and β²=0.91. It was found that the ligands coordinate to the copper atom through the carbonyl oxygen atoms having tetragonal symmetry and the coordination bonds are highly ionic.

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The behaviors of a direct dye, C. I. Direct Red 81, in a queous polyethylene glycols (PEG)solutions have been studied by the measurements of the solubility and absorption sp ectra. The dye is highly soluble both in water and PEGs, but is less soluble in the mixed s olvents. The solubility, c urves of the dye have the minima at about 50 wt% of PEG conce ntration. The absorption spectrum of the dye shows that the degree of aggregation of th e dye reduces with PEG concentration up to about 50 w t%, and then remains constant for any further addition of PEG. The results suggest that the hydration of PEG affects the solubili ty and aggregation of the dye.

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The effects of CdSO₄, Cd(NO₃)₂, (CH₃COO)₂Cd, ZnSO₄, Zn(NO₃)₂, (CH₃COO)₂Zn, K₂SO₄, KNO₃ and CH₃COOK on the anodic oxidation of ethanol were studied at a platinum el ectrode in aqueous acidic solution by means of linear sweep voltammetry. The anodic current due to ethanol oxidation increased by the addition of cadmium or zinc salts. The active species responsible for ethanol oxidation was suggested to be univalent Cd⁺ and Zn⁺, which may oxidize the reaction intermediates of ethanol. The order of the catalytic activity is as follows: CdSO, >Cd (NO₃) ₂>(CH₃COO) ₂Cd ZnSO₄ (NO₃) ₂. Potassium salts and (CH₃COO)₂Zn are either ineffective or inhibitory.

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Both 3-methyl-1-acenaphthenone [1b] and 5-methyl-1-acenaphthenone [1c] gave anomalous Leuckart reaction products, pyrimidine and pyridine derivatives, similar to that of 1-acenaphthenone [1 a].1-Formylamino-3-methylacenaphthene [5b] or 1-f ormylamino-5-methylacenaphthene [5c] were also produced. The aldol type condensation product was obtained in the reaction of [1c] as in [1a], but [1b] gave no such a product. The products [2c], [3b], [3c], [4b] and [4c] were identified by comparison with the corresponding authentic specimen. t Anomalous Leuckart Reaction of Acenaphthenones. II.

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It is well known that isomerization of s-butylbenzene induced by AlC13 and HC1 gives a equilibrium Mixture of both s-butyl- and isobutylbenzene. To separate isobutylbenzene from the mixture, selective transalkylation of s-butylbenzene was performed by using a m-xylene complex with AlC18 and HCI. When the reaction of the m-xylene complex with the butylbenzene mixture was carried out at 20-30° for 30 min, all of the s-butylbenzene reacted with m-xylene to give 4-s-butyl-2, 6-dimetyl-benzenium heptachlorodialuminate and isobutylbenzene unaltered. After hydrolysis of the reaction mixture, isobutylbenzene could be separated in a sufficiently high purity by usual distillation. The complex solution obtained as bottom layer after the transalkylation was measured directyl by¹³3C-NMR and the reaction path was discussed.

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Steroids, triterpenoids, and flavonoids were isolated from the leaves of Rabdosia japonica (BURMANf. ) HARA and their structures were elucidated β-sitosterol, stigmasterol, campesterol, friedelin, β-amyrin, ursolic acid, and quercetin 3-glucoside by comparison of their spectroscopic data with those of the authentic samples.

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