Isoxazolidine derivatives 7 and 8 were synthesized from N-benzyl-C-(2-benzyloxyethyl)nitrones by 1,3-dipolar cycloaddition with ethyl crotonate. The isoxazolidine derivatives were converted to β-amino acid esters 9a and 9b by reduction with zinc in acetic acid. The β-amino acid esters were reacted with methylmagnesium bromide to give the 2-azetidinones (13a, 13b). The benzyl group of 2-azetidinones were removed by Birch reduction. The products were oxidized with PDC to give 3-[1-(t-butyldimethylsilyloxy)ethyl]-4-carboxymethyl-2-azetidinone derivatives (2a, 2c).

Sr1+xSm1-xFeO4-y solid solutions with a composition range 0.00 ≤x≤1.00 have been prepared at 1200 ℃ in air under normal atmospheric pressure. All the solutions exhibit the K2NiF4-type structure of tetragonal system. Mohr salt analysis shows that the mole ratio of Fe4+ ion to Fe3+ ion or the τ value increases with the x value. Nonstoichiometric chemical formulas have been formulated from the x, τ, and y values. Electrical conductivity was measured in the temperature range of 173-373 K under atmospheric air pressure. The conductivities of each sample are varied within the semiconductivity range. The conductivity at constant temperature increases steadily with x value and activation energies are varied from 0.14 to 0.32 eV. The conduction mechanism of the ferrite system may be proposed as a hopping model of conduction electrons between the mixed valence states. The Mossbauer spectrum for the composition of x=0.00 shows a six line pattern by which the existence of Fe3+(I.S.=0.32 mm/sec) can only be identified. The spectra for the compositions of x=0.50 and 1.00 presents broad single line patterns showing a mixed valence state.

We examined the formal oxidation states of Pb and Cu in the Pb2CuO4 slab of Pb2Sr2ACu3O8(A=Y1-xCaxor Nd1-xSrx) and their possible changes by oxygen incorporation in the Cu layer of the slab by performing tight-binding band electronic structure calculations on the Pb2CuO4+δ slab. Our results show that the most likely oxidation state of Pb is +2 and that of Cu is +1 for the Pb2CuO4 slab prior to oxidation. With small δ values, the oxygen incorporation occurs by the formation of such chain fragments as in YBa2Cu3O7-y along the a+b axis. The four-coordinate Cu atoms in the chain fragments are in the +3 oxidation states. For values of δ larger than 0.5, however, an additional oxygen (Oad) goes to the site along the b axis to form short Pb-Oad distances oxidizing Pb2+ to Pb4+. This change in the Pb oxidation state leads to the suppression of superconductivity due to the decrease of holes in the CuO2 layer.

New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.

Tetra-chlorodibenzo-p-dioxins (tetra-CDDs) were prepared by microscale pyrolysis of trichlorophenates. During the pyrolysis reaction, tri-, di-, and mono-CDDs were also formed by the thermolysis of tetra-CDDs. The dechlorination pathways of tetra-CDDs were suggested for this reaction. The identification of these products was performed with capillary column gas chromatography-mass spectrometry.

A sensitive method for the determination of trace cadmium after the preconcentration by extracting its 8-hydroxyquinoline complex into a molten benzophenone was developed. Several experimental conditions such as the pH of solution, the amounts of 8-hydroxyquinoline and benzophenone, stirring time, and standing time were optimized. Trace cadmium in 100 mL water sample was chelated with 2.5 mL of 0.001 M 8-hydroxyquinoline at pH 8.0. After 0.07 g benzophenone was added, the solution was heated to about 70 ℃ and stirred vigorously for 1 minute to dissolve the complex quantitatively in a molten benzophenone, and stood for 30 minutes to reproduce the microcrystalline benzophenone. The benzophenone containing Cd-8-hydroxyquinoline complex was filtered and dissolved in acetone. Cadmium was determined by a flame atomic absorption spectrophotometry. The interfering effects of diverse concomitant ions were investigated and eliminated. This method could be applied to natural water samples and the recovery of more than 90% was obtained in the real samples.

Voltammetric determination of phenol derivatives, such as phenol, o-, m-, and p-cresols was studied with a β-Cyclodextrin (β-CD) modified-carbon paste electrode composing of the graphite powder and Nujol oil. Phenol derivatives were chemically deposited via the complex formation with β-CD by immersing the CME into a sample solution. The resulting surfaces were characterized with cyclic and differential pulse voltammetry. Treating the CME with 1 M nitric acid for five sec after a measurement could regenerate the electrode surface. Linear sweep and differential pulse voltammograms were recorded for the above system to optimize the experimental parameters for analysing the phenol derivatives. In this case, the detection limit for phenols was 5.0×10-7M for 25 min of the deposition time with differential pulse voltammetry. The relative standard deviation was ±5.2% of 3.0×10-6M (four repetitions). The interference effect of the following organic compounds was also investigated; Bezoic acid, hippuric acid, o-, m-, and p-methylhippuric acid. Adding the organic compounds into the sample solution reduces the peak current of the phenols to about 25%.

A set of substituent constants, σc+, has been widely used comparing the stability of carbocation in super acid condition. Plotting of 13C chemical shifts of cationic carbon (Δδc+) against σc+ constants yields an excellent correlation with a good correlation coefficient (r=0.999) for a cyclopentyl cation system. But these σc+ constants show poor linearity in norbornenyl cations that well known to show homoallylic stabilization in a cationic condition. We calculated the new substituent constant, σc+π, and found that the new substituent constants give an excellent correlation in π- and πσ-participating cation systems.

Electrical capacitance at the interface between electrolyte solution and conducting polypyrrole film electrode was measured by a simple electrochemical method. The polymer films were electropolymerized in the presence of perchlorate (PPy-ClO4) or Nafion (PPy-Nafion) anions as the dopant ions. Both polymers exhibited large double layer capacitances which were slightly potential dependent within the potential range where the polymers are conductive. The capacitance increased in proportion to the polymer thickness. The specific capacitance were about 10 Fg-1and 44 F g-1 for PPy-Nafion and PPy-ClO4, respectively.

Second-order rate constants have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with Z-substituted phenoxides in absolute ethanol at 25.0±0.1 ℃. The nucleophilic substitution reaction gives both S-O bond and C-O bond cleavage products. The extent of S-O bond cleavage increases significantly with increasing electron withdrawing ability of the sulfonyl substitutent X, while that of the C-O bond cleavage is independent on the electronic effect of the substituent. On the contratry, the effect of the substituent Z in the nucleophilic phenoxide is more significant for the C-O bond cleavage than for the S-O bond cleavage. Aminolyses of 2,4-dinitrophenyl benzenesulfonate (1) with various 1°, 2° and 3°amines have revealed that steric effect is little important. The extent of S-O bond cleavage increases with increasing the basicity of the amines, but decreases with increasing the basicity of the nucleophilic aryloxides, indicating that the HSAB principle is not always operative. Besides, reactant and solvent polarizability effect has also been found to be an important factor in some cases but not always to influence the reaction site.

The ionic strength dependent binding mode of 9-aminoacridine (9AA), a well-known DNA intercalator, to DNA is studied by flow linear dichroism, circular dichroism, fluorescence techniques and equilibrium dialysis. The DNA-bound 9AA exhibits spectral properties corresponding to the intercalative binding mode disregarding the salt concentrations; the angle between the long-axis transition moment of the 9AA molecule and DNA helix axis is calculated to be about 65°, indicating a significant deviation from the classical intercalation. At low salt concentrations, however, upwards bending curve in Stern-Volmer plot is observed (where 9AA is a fluorophore and DNA a quencher), indicating the coexistence of both static and dynamic quenching mechanisms or the existence of an additional binding site.

Carbonyl compounds 1, alkyl- and arylaldehydes and alkyl, aryl, benzylic, and cyclic ketones were converted to the corresponding 1,3-dioxolanes 2 and 1,3-dioxanes 4 with ethylene glycol and 2,2-dimethyl-1,3-propanediol in the presence of 1-3 mol% of 1-(p-substituted)benzyl-1,1-dimethyl-2-(p-substituted)-benzoyl hydrazinium hexafluoroantimonates 3 in high yields.

Time profile of the transient grating signal induced by a nanosecond pulsed laser excitation of methyl red is investigated in alcohols and toluene at several solvent temperatures. The signal decays biexponentially with well-separated time constants; the faster decay is identified as due to thermal diffusion of the solvents and the slower one as mainly due to translational diffusion of the solute. The measured translational diffusion constants of methyl red in toluene are close to a hydrodynamic prediction with a slip boundary condition while those in alcohols are larger by 30% and increase slightly with the size of alcohols. We compare the results with modified hydrodynamic models.

The bulk thermal and photopolymerization of methyl methacrylate(MMA) with phenylsilane were performed to produce poly(MMA)s containing phenylsilyl moiety presumably as an end group. It was found for both thermal and photopolymerization that while the polymerization yields and polymer molecular weights decreased as the relative phenylsilane concentration increases, the TGA residue yields and the relative intensities of SiH IR stretching bands increased with increasing molar ratio of phenylsilane over MMA. The polymerization yield, molecular weight, and TGA residue yield for the thermal polymerization were higher than those for the photopolymerization. Thus, the phenylsilane seemed to significantly influence on the polymerization as both chain initiation and chain transfer agents. However, an appreciable silane effect was not observed on the thermal and photopolymerization of 4-vinylpyridine, acrylonitrile, styrene, and vinyltrimethoxysilane.

The bulk photopolymerization of methacrylic acid (MA) with phenylsilane was performed to produce poly(MA)s containing phenylsilyl moiety presumably as an end group. It was found that while the polymerization yields and intrinsic viscosities decreased, the TGA residue yields and the relative intensities of SiH IR stretching bands increased with increasing molar ratio of phenylsilane over MA. The phenylsilane seemed to significantly influence on the photopolymerization as both chain initiation and chain transfer agents.

Lithium trimethylalkynylaluminates, prepared conveniently by reacting trimethylaluminum with lithium alkynide, readily react with aldehydes and ketones to give the corresponding propargyl alcohols in 70-95% yields. The reaction is highly chemoselective; thus many other functional groups such as amides, nitriles, epoxides and halogen compounds are inert under the reaction conditions. The reagents also show an excellent 1,2-regiospecificity in the reactions with cyclic or acyclic α,β-unsaturated carbonyl compounds.

It has been well known that the Grad thirteen-moment equations have solutions only when the Mach number is less than a limiting value for the stationary plane shock-waves. The limit of Mach number has been re-examined by including successive terms in the series expansion of distribution function. The method employed is the linear analysis of moment equations near up-streaming and down-streaming flows. For the thirteen moment case, it has been confirmed that equations have solutions only when the Mach number is less than 1.6503, which is consistent with the literature value. For the case of twenty moments, the limit of Mach number is decreased to 1.3416.