A new paraffin salt bridge was developed for the concentration cell in high pressure system. The emf values of the concentration cells were measured to calculate the activity coefficients of the electrolytic ions depending upon the pressure of the system. The activity coefficients of sodium, chloride and bromide ions increase with the temperature of the cell and decreased, nearly half at 2500 bars, $20^{\circ}C$, with the pressure. These results can be explained to be attributed to the volume change of the hydrated ion due to the electrostriction. The volume change decreased with pressure due to an increase in the degree of the hydration.

In order to synthesize conformationally rigid etorphine analogues having potentially interesting pharmacological activities, synthesis of compound 3 by the reaction of compound 4 and compound 5 via intramolecular Diels-Alder reaction has been attempted. However, the reaction did not go well and the compound 3 would not be isolated. Therefore, intermolecular Diels-Alder reaction using dimethyl acetylene dicarboxylate was attempted. As shown in scheme 2, Diels-Alder adduct 9 was converted into the target molecule 14 containing the new [2.2.2] bicyclo octane ring in good yields.

The NMR chemical shift arising from 4d electron angular momentum and 4d electron angular momentum and 4d electron spin dipolar-nuclear spin angular momentum interactions for a $4d^1$ system in a strong crystal field environment of trigonal symmetry, when the threefold axis is chosen to be the axis of quantization axis, has been examined. A general expression using the nonmultipole expansion method (exact method) is derived for the NMR chemical shift. From this expression all the multipolar terms are determined. We observe that along the (100), (010), (110), and (111) axes the NMR chemical shifts are positive while along the (001) axis, it is negative. We observe that the dipolar term (1/R3) is the dominant contribution to the NMR chemical shift except for along the (111) axis. A comparison of the multipolar terms with the exact values shows also that the multipolar results are exactly in agreement with the exact values around $R{\geqslant}0.2$ nm. The temperature dependence analysis on the NMR chemical shifts may imply that along the (111) axis the contribution to the NMR chemical shift is dominantly pseudo contact interaction. Separation of the contributions of the Fermi and the pseudo contact interactions would correctly imply that the dipolar interaction is the dominant contribution to the NMR chemical shifts along the (100), (010), (001), and (110) axes, but along the (111) axis the Fermi contact interaction is incorrectly the dominant contribution to the NMR chemical shift.

A major polyacetylene compound from Panax ginseng roots, heptadeca-1-en-4,6-diyn-3,9,10-triol, was irradiated with 300 nm UV light to obtain a photooxidized acetylenic compound having the conjugated en-on-diyne chromophore, heptadeca-1-en-4,6-diyn-9,10-diol-3-one. The same oxidation product was obtained exclusively by 4-(dimethylamino) pyridinium chlorochromate at room temperature.

Self-atom polarizability were calculated for 17 polycyclic aromatic hydrocarbons and their metabolites by LCAO-MO method and examined the relation with the carcinogenicity. It has been found that ${\pi}_{1.2.4}$, the sum of self-atom polarizability of 1, 2 and 4 positions forming trans-butadiene frame in a compound, agree quite well with the observed carcinogenic activity, and also, ${\pi}_{1.2.4}$ value increase with the metabolic activiting in agreement with the experimental facts that parent carcinogens activated with metabolism. Accordingly, we suggest that the 1, 2 and 4 positions in the carcinogenic compounds play the most important role in the process of chemical carcinogenesis, and also self-atom polarizability, as one of theoretical reactivity indices, is to be used as a measure of carcinogenic activity.

Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

The structure of partially $Ag^+$-exchanged zeolite 4A, $Ag_{7.6}Na_{4.4}-A$, vacuum dehydrated at $370^{\circ}C$, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.311(1)${\AA}$) at $24(1)^{\circ}}C$. The structure was refined to the final error indices $R_1$ = $R_2$ (weighted) = 0.064 using 266 independent reflections for which $I_0$>$3{\sigma}(I_0)$. Three $Na^+$ ions occupy the 3 8-ring sites, and the remaining ions, 1.4 $Na^+$ and 6.6 $Ag^+$, fill the 8 6-ring sites; each $Ag^+$ ion is nearly in the [111] plane of its 3 O(3) ligands, and each $Na^+$ ion is 0.9${\AA}$ from its corresponding plane, on the large-cavity side. One reduced silver atom per unit cell was found inside the sodalite unit. It was presumably formed from the reduction of a $Ag^+$ ion by an oxide ion of a residual water molecule or of the zeolite framework. It may be present as a hexasilver cluster in 1/6 of the sodalite units, or, most attractively among several alternatives, as an isolated Ag atom coordinated to 4 Ag ions in each sodalite unit to give $(Ag_5)^{4+}$, symmetry 4mm.

The effect of the non-Coulombic long-range forces and the next nearest neighbor interactions on the lattice properties of alkali halide crystals is calculated using the Electron Gas model and Electron Gas Drude model. It is found that these often neglected interactions make changes in the lattice properties that are indeed small, but by no means negligible.

The solvent change and salt do not affect the fluorescence quantum yield of 1,3-dimethylnaphtho[1,2-e]uracil indicating the considerable energy gap between the lowest singlet $({\pi},\;{\pi}^{\ast})\;and\;(n,\;{\pi}^{\ast})$ states in the compound. The results are consistent with the strong quenching of fluorescence by ethyl iodide. Fluorescence quantum yield is nearly independent of temperature, probably due to the relatively inefficient internal conversion. Unusual spectral difference is observed in isopentane and ethanol at 77K. The temperature dependence of emission in isopentane and in ethanol suggests that the increase of charge transfer character by the conformational change in isopentane leads to the structureless and red-shifted fluorescence, while in ethanol the decrease of the charge transfer character by the hydrogen bonding interaction results in the structured and blue-shifted fluorescence along with phosphorescence at the low temperature. Temperature dependence of emission in poly(methylmethacrylate) matrix indicates that $T_1{\to}S_0$ radiationless decay is an important process responsible for the strong temperature dependence of phosphorescence.

Reduction of N-arylpyridinium compounds by $NaBH_4$ gave mixtures of the corresponding 1,2-dihydropyridine(major) and 1,4-dihydropyridine(minor), whereas similar reduction by $Na_2S_2O_4$ produced 1,4-dihydropyridines regioselectively. The proportion of 1,4-isomer in the product by $NaBH_4$ reduction appeared to increase with the electron-donating ability of N-aryl groups. When the N-aryl group is p-methylphenyl, p-ethylphenyl or p-methoxyphenyl, the 1,2-dihydropyridines in ethanol-water (4:1) solutions isomerized to the corresponding 1,4-dihydropyridines. N-(p-methylphenyl)-1,2-dihydropyridine and N-(p-ethylphenyl)-1,2-dihydropyridine in solid state also isomerized to the corresponding 1,4-dihydropyridines. The different behaviors of reduction among N-arylpyridiniums and isomerization of the reduction products depending on the substituent in N-aryl group were explained in terms of difference in the electronic effects of the substituents.

It is shown that the linear stability coincides with the thermodynamic stability in the case of stress tensor evolution for simple dense fluids even if the constitutive (evolution) equation for the stress tensor is nolinear. The domain of coincidence can be defined in the space of parameters appearing in the constitutive equation and we find the domain is confined in an elliptical cone in a three-dimensional parameter space. The corresponding state theory in rheology of simple dense fluids is also further examined. The validity of the idea is strengthened by the examination.

1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

A series of copolypeptides of glutamic acid and leucine have been synthesized by N-carboxy-${\alpha}$-amino acid anhydride procedure and cast to form injectable microparticulate monolithic devices in which indomethacin was physically dispersed. With these devices, various release properties and possible clinical application were studied. The release rate of the drug had a close relationship with the monomer composition of the copolymer matrix as well as the environmental pH condition. The monolithic device of glutamic acid/leucine = 50/50 was found to be the most promising one as a ploymeric delivery system of indomethacin. The intrinsic viscosity of this copolymer was 4.35 dl/g and the release rate was 18.5${\mu}g/g/day$.

The electronic structures of silane and chlorosilanes are studied by the SCF calculations using effective core potentials (ECP's). The results obtained with ECP's are in good agreement with corresponding all electron calculations demonstrating the reliability of ECP employed. The importance of polarization functions for the second row atoms is also evident in this study. The SCF calculations of silane and chlorosilanes are useful in qualitative understanding of many chemical properties since many trends are correctly obtained with the polarization functions included in basis sets of reasonable size.

A nonlinear theory is presented for the fluctuations of intermediates in the Brusselator near the critical point caused by diffusion. The method used is the two time scaling method different from the conventional method in the sense that a slight nonlinear effect is included in the initial time region where the linear approximation is conventionally valid. The result obtained by the nonlinear theory shows that fluctuations close to the critical point approach the value of a stable steady state or deviate infinitely from an unstable steady state, as time goes to infinity, while the linear theory gives approximately time-independent fluctuations. A brief discussion is given for the correlation at a time between fluctuating intermediates when the system approaches a stable steady state.

Diacetylene compound, 1,4-diphenyl-1,3-butadiyne, was photolyzed with 5-fluorouracil as a model reaction of the phototoxic conjugated poly-ynes with DNA or RNA and obtained a [2 + 2] photocycloadduct. The structure of the photoadduct was determined by spectral methods and compared with the [2 + 2] photoadducts of 1,4-diphenyl-1,3-butadiyne with tetramethylethylene and dimethyl fumarate.

MNDO and ab initio calculations for gas phase reactions of alkoxide-exchange at silicon and carbon centers have been performed. Results show that MNDO values of ${\Delta}$E's of these reactions closely parallel those of the STO-3G method. The alkoxide-exchange at silicon is shown to be facile due to the formation of stable five-coordinate intermediate while the reaction at carbon is predicted to proceed with high barrier; the difference in this substitution behavior between carbon and silicon is shown to be due to an easy valence shell expansion of silicon in accommodating an extra bond in the formation of stable five-coordinate intermediates.

Reaction of $(E)-{\beta}-chloro-{\gamma}$-hydroxyvinylmercurials, prepared by mercuration of propargyl alcohol and 2-methyl-3-butyne-2-ol, with olefins in the presence of a catalytic amount of $Li_2PdCl_4$ and 2 equiv of cupric chloride in methanol at $50^{\circ}C$ gave the corresponding (E,E)-2,4-dienols in moderate yields. However, addition of 1 equiv of inorganic bases such as magnesium oxide to the reaction mixture brings a rapid and clean vinylation and gave high yields of the dienols at room temperature. In the case of hindered (E)-2-chloro-3-chloromercuri-2-buten-1,4-diol prepared from 2-butyne-1,4-diol, reaction with olefins gave the dienols only in low yields even in the presence of 2 equiv of magnesium oxide.

Complex formations between syndiotactic poly(methacrylic acid) (st-PMAA) and poly(N-vinyl pyrrolidone) (PVP), and that between st-PMAA and polyethyleneoxide (PEO) through hydrogen bonding were studied by viscometry and potentiometry. Reduced viscosity (${\eta}_{red}$) was measured at various mole fraction of PVP or PEO with respect to a constant amount of st-PMAA. Observation shows a sharp minimum at the 1:1 mole ratio of st-PMAA:PVP or st-PMAA:PEO, which shows that the complexation becomes optimal and the complex has a compact structure in this ratio. Variation of pH also supports this conclusion. This is the case of the system of st-PMAA and PVP in water as well as in DMF. Also the complexation is much enhanced when the molecular weight of PVP is high. Meanwhile, the system of st-PMAA and PEO shows a little different behavior, i.e., this system does not form the complex in DMF and does only in water. It is because the interaction st-PMAA with PEO is weaker than that with PVP.

The vibration-vibration energy exchange of $N_2(v=1)+O_2(v=0){\to}N_2(v=0)+O_2(v=1)$ has been investigated, in particular, at low temperatures. The energy exchange rate constants are calculated by use of the solution of the time-dependent Schrodinger equation with the interaction potential of the colliding molecule as a perturbation term. The predicted rate constants are significantly agree with a experimental values in the range of 295∼$90^{\circ}K$. The consideration of the VV-VT coupling decreases the predicted pure VV energy exchange value by a factor of ∼2. When the collision frequency correction is introduced, the VV-VT rate constant is consistent with the observed value in the liquid phase. The consideration of the population of the rotational energy level increases the VV-VT value significantly.