The methodology to synthesize mesoscopic inorganic materials is of crucial importance not only in the development of novel functional materials but also for understanding their size-dependent properties. Construction of organic-inorganic superlattices by the use of highly ordered organic molecular assemblies provides one of the efficient methodologies to fabricate inorganic nanostructures. In this study, multibilayer cast films were employed as macroscopically oriented organic template, and synthesis and two-dimensional organization of lead halide clusters, cyano-bridged bimetallic complexes were studied. Lead halide clusters of [PbBr4]2- were formed by ion exchange of counter ions of ammonium cast film or by the co-casting method. Electrostatic interaction between ordered bilayer surfaces and inorganic clusters is crucial for the dimensional control and their organization at multibilayer-interfaces. Preorganization of [Ni (CN) 4]2- at the cationic interface and succeeding reaction with Cu ( II ) ion lead to the formation of macroscopically oriented (CN) 41-Cu ( ) networks. Mild synthetic processes at ordered bilayer surfaces are effective for the fabrication of metastable low-dimensional aggregates.

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Microcrystals of solid-state polymerizable diacetylene compounds have been successfully prepared by a reprecipitation from their acetone solution in water, and were converted into polydiacetylene microcrystals dispersed in water. Effect of size-determining factors such as concentration of solution and temperature of water were investigated. Based on the results, microcrystal formation mechanism, i. e. first reprecipitation of amorphous microparticles, followed by the competing processes of crystallization in particle and adhesion of particles, was suggested. Some characteristic features of the microcrystals, compared with those of large bulk crystals, have been revealed: for example, excitonic absorption of polydiacetylenes took place a blue shift with decreasing size, in almost one order of magnitude larger size range than those of metals and semiconductors. It has also been demonstrated that polydiacetylene microcrystal dispersion gives good enough optical quality to conduct optical Kerr-shutter experiment, and the large X value of ca.10^-9 esuM^-1 at a nonresonant wavelength was clarified.

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Realtime and nonlabelled sensing based on antigen-antibody reaction has been investigated by a surface plasmon resonance (SPR) -based optical biosensor. The sensor detects the change in the refractive index of the metal film surface upon injection of antigen/antibody. In this paper the characteristics of the sensor in immobilized format of antigen (antibody) on gold surface are described; immobilization of antigen/antibody on gold surface was performed either by physical adsorption or by covalent immobilization to an organic film in the monolayer and polyer film. Although the former method was simpler, however, constant response was not obtained in repetitive antigen/antibody bindings.
For the detection of antigen/antibody by the SPR sensor with a sensitivity that cannot be easily attained in other methods, it is desired to immobilize antigen/antibody as much as possible in a polymer matrix having low refractive index. Covalent binding of oxidized hydroxyethylstarch polymer was performed onto thin gold film surface via self-assembled monolayer of aminoethanethiol. The immobilized starch layer was reduced by sodium borohydride after antigen/antibody immobilization, because Schiff's base is not necessarily stable through the repeated association-dissociation by an acidic buffer, glycine-HC1 (pH 2.5). By the NaBH₄ treatment of sensing layer the repeated detection of the determinant was carried out at least 20 times.

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The composition of complexes formed in aqueous solution consisting of a binary mixture of sodium 1octanesulfonate (NaOS) and lanthanum (III) chloride (LaCl₃) was studied by measuring surface tension, electric conductivity and proton spin-lattice relaxation time. In the molar ratio of octanesulfonic anion and lanthanum (III) cation below 0.1, a 3:1-complex was formed. The area per the 3: 1-complex adsorbed at air-water interface was 208 Ųon the assumption of a monomolecular layer. The formations of 2:1- and 1:1-complex were found in the vicinity of 0.5 and above 1.2 of LaCl₃/NaOS, respectively. Whereas, when LaCl₃ was added to 15 mol m^-3 NaOS, the bactericidal activity of the mixed solution against Escherichia coli ATCC 25922 markedly increased with increasing the molar ratio (LaCl₃/NaOS) up to 1.0 and finally remained constant. The contribution of complexes on the bactericidal activity was estimated at 1.5: 1: 1 from the combination of data of complex distributions and bactericidal activity.

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Dichloro or chloro ruthenium (III) complexes with polyaminopolycarboxylato ligands were synthesized (ligands: ethylenediaminetetraacetate (edta), N, N'-dimethylethylenediamine-NX-diacetate (N, N'-Me₂edda), and nitrilotriacetate (nta)). Magneti c moments of these ruthenium (III) complexes are about 2. So they are low spin complexes. The oxidation of olefines (cyclohexene, styrene or 1-hexene) catalyzed by these ruthenium (III) complexes in the presence of hydrogen peroxide has been studied: catalyst, polyaminopolycarboxylatoruthenium (III) complex (1.0×10^-3 mol dm^-3); substrate, olefin (0.2 mol dm^-3); co-oxidizing reagent, hydrogen peroxide (0.75 mol dm^-3); solvent, 1, 4-dioxanewater (1:1 (v/v) ). The chloro Hedta ruthenium complex ([RuCl (Hedta)] -) was the most effective catalyst for the oxidation under these conditions. The main product of this reaction was diol (yield: 48%, 1, 2-cyclohexanediol; 68%, 1-phenyl-1, 2-ethanediol; 6.5%, 1, 2-hexanediol). Since UV/visible spectrum of the edta complex in the presence of hydrogen peroxide shows the formation of the oxoruthenium (V) complex, the oxoruthenium (V) species is supposed to be the active species.

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The oxidation of alcohols with a layered double hydroxide (LDH), Mg²⁺-Al³⁺-MnO₄^-, was investigated. The interlayer MnO₄^- anions show the activity of oxidizing alcohols at room temperature in a nonpolar solvent such as benzene. The reaction proceeds selectively to afford the corresponding aldehyde or carboxylic acid depending on a starting alcohol. For instance, when the alcohol was benzyl alcohol, benzaldehyde was obtained predominantly even when a small quantity of the alcohol still remained in the reaction system. On the contrary, the oxidation of 1-octanol proceeds consecutively to give a carboxylic acid, while the alcohol remained sufficiently, with a reduced yield of 1-octanal.
Adsorption of these alcohols and the corresponding aldehydes on the LDH w as examined using benzene as a solvent. Adsorption amount of benzaldehyde was far smaller than that of benzyl alcohol, whereas there was little difference in the adsorption amounts of 1-octanol and 1-octanal. This low ability of benzaldehyde to adsorb on the LDH explains the selective oxidation of benzyl alcohol to yield benzaldehyde.

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In the NaOH hydrothermal synthesis of zeolite using Hadong Kaolin of Korea, the structure of Hadong Kaolin changes variously depending on treatment conditions.
The conventional research has been investigated for low te mperature, because the synthesis of low silica zeolite was performed at temperatures less than 100°C.
When Hadong Kaolin is used as raw material of high silic a zeolite, the synthesis needs higher temperatures than 100°C. However, the study has been investigated rarely.
The hydrothermal synthesis of high silica zeolite was tried at 175°Cby adding amorphous silica to Hadong Kaolin. Water content was changed as an experimental parameter. Special attention was given to the structural change of Kaolin.
The results were summar ized as follows.
1) In the case of water content 9 8%, sodalite, zeolite A, zeolite Pi, unknown T and mixture of those compounds were formed. Zeolite A was formed in extremely narrow range of formation. In the case of water content, 95%, the mixture of them was obtained.
2) In former case, Kaolin changed with the lapse of time as Kaolin→amorphous phase→sodalite→zeolite A→sodalite. In latter case, Kaolin changed without forming amorphous phase as Kaolin→mixture of Kaolin and sodalite→sodalite.
3) The dissoluti on of SiO₂ and Al₂O₃ from Kaolin to NaOH aqueous solution increased with the increase of NaOH concentration. The concentration of Al₂O₃ in solution increased with the lapse of time. But the quantity of SiO₂was lower than that of Al₂O₃, and became constant after a certain reaction time.
4) The dissolution rate of Hadong Kaolindepends on concentration of NaOH solution. The dissolution rate coefficient, R₁, was 0.0590 min^-1 in 1.5 M (1 M =1 mol dm^-3), which was about 30 times as fast as that in 0.2 M (R₁ =0.0018 minR^-1).

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The hydrothermal synthesis of zeolite from Hadong Kaolin (SiO₂/Al₂O₃ mole ratio = 2.54) with addition of amorphous silica has been studied. The experiment was carried out inconditions, by using stainless steel autoclaves of 24 mL with stirred system at 175°C . Reaction time, SiO₂/Al₂O₃ mole ratio, and water content were changed.
For the convention al synthesis of ZSM-5 zeolite, the particular organic reagent such as TPAOH (tetrapropylammonium hydroxide) has been added as soil humic substances. The conditions of zeolite synthesis and effectiveness of Hadong K aolin without addition to any organic reagent as template were investigated, because Hadong Kaolin is supposed to contain such organic compound. The results were summarized as follows.
1) When Hadong Kaolin was use d as a raw materials for the synthesis of ZSM-5, no organic reagent was necessary.
2) The obtained zeolites were ZSM-5, mordenite, and analcite respectively.
3) For the transformation to ZSM-5 and mordenite from amorph ous material, the formation of zeolite in 98% water content was more rapid than those of 95%. But in the formation of analcite the result was opposite.
4) For the dissolution of solids by N aOH, the quantity of SiO₂ and Al₂O₃ in liquid varied until ZSM-5was synthesized. But, SiO₂ was almost constant and Al₂O₃ increased in the formation range of ZSM-5.

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The electronic absorption spectra of N, N'-disalicylidene-o-phenylenediamine (abbreviated to H₂(saloph)) were measured in cyclohexane and ethanol. H₂(saloph) shows absorption bands at 37 2, 339.6, 269.8, 262, 231.2 and 209.8 nm in cyclohexane. The corresponding bands appear at 384, 331, 272, 251, 220 and 210 nm in the stretched PVA film at 14 K. The 384, 272 and 210 nm bands are polarized along the longer-molecular-axis and assigned to S₀→S₁S₇ and S₁₅transitions and the 331 and 251 nm bands along the shorter-molecular-axis and to the S₀→S₂ and S₈, respectively. It is considered that out of plane polarized transition components are included in the observed 384, 272 and 220 nm bands. H₂ (saloph) exists as an enol-imine type in nonpolar media such as cyclohexane. On the other hand, in polar media such as ethanol a trace amount of keto-amine type exists as an equilibrium mixture of keto-amine and enol-imine. According to the X-ray diffraction analysis, H₂ (saloph) forms a van der Waals dimer in the crystalline states. This dimer formation is also shown as newly appeared bands at_??_ 490 and 403 nm in the crystalline spectrum. The electronic absorption spectrum of the crystal als o shows the dimer formation.

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Reaction of 3- (2-substituted ethenyl) guaiazulenes having nitro group or trifluoroacetyl group as the substituent with alkenes were investigated. Treatment of either of t he compounds with cyanoalkenes in the presence of sodium methylate brought, besides dimerization and intramolecular cyclization of ethenylguaiazulene, addition of a dimeric product to t he alkene. On the other hand, addition of 3-buten 2-one or of methyl acrylate at the side chain of 3- (2-nitroethenyl) guaiazulene afforded butenylazulene and benz[a]azulene derivatives. Moreover, reaction of 3-buten-2-one with 3-(2-trifluoroacetylethenyl)guaiazulene was accompanied by solvolysis at the side chain to give 3-trifluoroacetylguaiazulene, followed by two addition pathways yielding dihydrocyclopenta [ef] lheptalene derivatives. Com. petition of the double bonds of alkene and ethenylguaiazulene to form dihydrocyclopenta[ef] heptalene skeleton was hardly observed in t hese reactions. Hence the double bond concerned in t he ring f ormation was v irtually restricted to that of ethenylguaiazulene which would be activated by the contrib ution of a tropylium cation structure.

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This paper discusses the hydration and hydration products of calcium silicate compound containing chlorine (called alinite) compared with the case of alite with or without CaCl₂. Alinite is a main cOrnpound for the production of the cement with chlorine and alite is a main compound of ordinary Portland cement.
Heat of early hydration was measured by conduction calorimeter. The rate of heat liberation of alite with or without CaCl₂ at early stage of hydration has an induction period. But the induction period of alinite was not observed. Reaction ratio of alinite and alite was measured by XRD at late stage of hydration. The hydration ratio of alinite are larger than that of alite cured for 1 or 3 days. The hydration ratios of alite and alinite cured for 28 days were respectively about 80%. The production amounts of Ca (OH) 2for alite were larger than that of alinite. The CaO/SiO₂ ratio of calcium silicate hydrates in hardened alinite was greater than that of in hardened alite. In the case of alinite, calcium silicate hydrates included chlorine, and the ratio of Cl/SiO₂ for hydrated products was 0.3.

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Dehalogenation of chlorofluoro carbons (CFC) has been achieved using metal alkoxide co-polymerization method. Considering that chlorine atoms of p-dichlorobenzene react with tetrabutyl orthotitanate Ti (OBu) 4 forming a [ (Ti = O ) -O-C₆H₄-O]type copolymer, it is naturally anticipated tha t CFCs polymerize with Ti(OBu)4 to form a copolymer of CFC (less halogen atoms) and -Ti (= O)-O-. Experimentally, to a tetrahydrofuran solution of Ti (OBu)₄, one of the two model compounds of CFCs, namely CFC (112) or CFC (110), was added and dissolved. By illuminating with the visible light of a fluorescent lamp, the mixture polymerized to form a copolymeric substance of CFC and Ti (OBu)₄. The results of elementary analyses indicated that halogen atoms are not left in the copolymeric substance but carbon content was some 10 times as large as that of a neat polymer of Ti (OBu)₄. This fact indicates that only carbon atoms originated from the model CFC compound are incorporated into the copolymeric substance produced, but halogen atoms of the CFC compounds are excluded. Infrared spectra have also indicated that C-Cl bonds or C-F bonds are not found in the copolymer obtained. Reflectance spectra and ESR spectra have indicated that the copolymer thus obtained has photophysical properties which are essentially similar to those of a neat polymer of Ti (OBu)₄. Thus two conclusions have been obtained: (1)CFCs are dehalogenated by tetrabutyl orthotitanate. (2) The copolymeric substance obtained from a CFC and tetrabutyl orthotitanate can be useful as an element of a visible light energy conversion system.

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A laboratory study on heterogeneous reaction of solid benzo[a]pyrene (BaP) and chrysene (CH)supported on seven kinds of inorganic particles, were conducted under photoirradiation in the air containing 10 ppm of NO₂ to understand the effects of support particles on the reactivity of those polycyclic aromatic hydrocarbons. The degradation of BaP was greatly dependent on the kind of support-particles while that of CH was almost independent of it. The product distributions for BaP and CH showed similar support-dependence. More than 80% of degraded BaP and CH were transformed to 6-nitro derivatives on basic CaO and MgO and the maximum yields of them were 36.9% on MgO and 21.6% on CaO, respectively. The major reaction pathway on photoconductive TiO₂ and ZnO was oxidation for both of BaP and CH.

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Polymer solution are fallen into three region as function of concentration C: dilute, semidilute and concentrated (0 < C_dil < C* < C _semidil < C** < C _conc ).T he concentration of tri- or multi-critical point in PStransdecalin solution has been determined in ultrasonic method as a function of cross over line C* and C. Chain crossover concentration C*' from neutron scattering method differs from C* that's viscos ity and ultrasonic method by an order of magnitude. New suggestion was made in this work that the polymer solutions in dilute zone were appeared new additional tri- or multi-critical phenomena under anisotropic stress of polymer expansion in end-end direction. The new multi- critical phenomena have been shown by ultrasonic method.

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