A complete potential profile of an electrical double layer is calculated from a distribution function of charged particles based upon a model where the effect of a charged electrode and the finite size of ion are explicitly included. Electrons which are distributed on the electrode surface are assumed not to penetrate the electrode/electrolyte boundary. Formation of the constant density regions and their effects on potential and the electrical double layer capacitances are studied in great detail. The distribution of surface electrons as well as the constant density regions are found to be essential in characterizing the electrical double layer. The introduction of the ion size into the prior electrical double layer model of an ideally polarizable electrode/point charged electrolyte system, shows a great improvement in its characteristics mostly at negative potential region.

Catalytic effects of tertiary amines on N-sulfinylation of p-toluenesulfonamide, p-toluidine, and p-toluamide have been investigated by proton NMR studies. Though the catalytic effects were dependent on the substrates, 4-dimethylaminopyridine, pyridine and triethylamine exerted stronger catalytic effects than imidazole and N,N-dimethylaniline. Among the substrates employed, p-toluenesulfonamide turned out to be catalyzed greater than p-toluidine and p-toluamide.

The function exp$(x^2)$erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with a prior chemical equilibrium (i.e., a CE type process). Various parameters that characterize the peak asymmetry (such as ratios of peak-heights, ratios of half-peak-widths, and separations in peak-potentials) are analyzed to find how kinetic and thermodynamic parameters influence shapes of the derivatives. The results from the CE process is compared with those from an EC process in which a reversible electron transfer is coupled with a follow-up homogeneous chemical reaction. The two processes exibit quite contrasting differences for values of the parameters.

The electrochemical reduction and electrogenerated chemiluminescence (ECL) of $Ru(bpy)_3^{2+}-S_2O_8^{2-}\;in\;CH_3CN-H_2O$ solution were studied in the presence of sodium dodecyl sulfate (SDS) as an anionic surfactant. SDS enhanced the ECL and the fluorescence intensities and lengthened the duration of ECL due to the solubilization of reactants and possibly to the stabilization of ECL intermediates in the SDS micellar environment.

The simple binary mixtures of pure phospholipids such as DPPC:DSPC and DPPC:DPPA were investigated with differential scanning calorimeter. The thermotropic properties of DPPC and DSPC mixtures did not deviate much from the ideal curves that was obtained on varying either the temperature or the relative proportions of phospholipids. This means that the two phospholipids are completely miscible in the liquid and solid phase. But the thermotropic properties of DPPC and DPPA mixture deviated much from the ideal phase diagram. It resulted from the repulsion between the head groups of acidic phospholipids. Heat capacity suggested by Harden McConell was calculated. The larger $C_p$ was, the sharper the endothermic peak became.

Ab initio calculations with MP3 and CISD method were performed for the FCO and $FCO^+$. The equilibrium geometry of FCO shows the reasonable agreement with experimental values. $FCO^+$ has a linear geometry with $R_{CF}=1.213\;and\;R_{CO}=1.118{\AA}$. The quadratic force constants of $FCO^+$ are 23.21 md ${\AA}^{-1}$ for CO stretch and 12.38 md ${\AA}^{-1}$ for CF stretch. The cubic force constants and the other molecular constants are also calculated.

The product distribution obtained by the addition of hydride of $-CR_2CN$ (R = H and Me) to (disubstituted benzene)-$FeCp^+$ is studied. The formation of the substituted arene from ${\eta}^5$-cyclohexadienyl-${\eta}^5$-cyclopentadienyliron is described.

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

The effects of the concentration and the pressure of reactants on laser output were reported in the previous study. The present study is made of the following main parameters on laser characteristics; the initial temperature of the reaction mixture, inert gas (He) added in the reaction mixture, and the level of initiation as a function of time. As the initial temperature of reaction mixture decreases, both the output energy and the duration time increase. Especially, the output energy is linearly proportional to the inverse of the initial temperature. In order to obtain a proper lasing for a given condition, a sufficient amount of He must be added: The optimum ratio of [He] to $[D_2\;+\;F_2\;+\;CO_2]$ is found to be greater than 2. In addition, the time dependence of level of initiation (TDLI) shows no significant difference in total output energy from that of the premixed model, but only the power profile.

The reaction of $Os_3(CO)_{10}(NCMe)_2$ with a tungsten alkylidyne $Cp(CO)_2W{\equiv}CTol(Cp={\eta}^5-C_5H_5,\;Tol=p-C_6H_4Me)$ produces the compound, $CpWOs_3(CO)_{11}({\mu}_3-CTol)$(1). The structure of compound 1 can be viewed as one in which the metalla-alkyne, $Cp(CO)_2W{\equiv}CTol$, is ${\mu}_3-{\eta}^2-{\bot}$ (perpendicular) bound to an $Os_3(CO)_9$ fragment. Variable-temperature $^{13}C$ NMR spectra of 1 show no evidence for the analogous rotation of the metalla-alkyne molecule as shown alkyne rotation in $Os_3(CO)_9(C_2Tol_2)$ compound. This lack of the metalla-alkyne fluxionality supports the apparent saturated nature of compound 1.

Glucagon was found to interact with DMPC vesicles electrostatically and hydrophobically. It appears that glucagon bound irreversibly to the vesicles through hydrophobic interaction was partially protected from the proteolysis by trypsin. Out of three possible sites, only the peptide bond preceded by Arg-18 was cleaved by a prolonged trypsin treatment. ${\alpha}$-chymotrysin did not affect the vesicle-bound glucagon. Based on these observations, possible structure of irreversibly bound glucagon on the vesicle surface is discussed.

New aminothiazolyl cephalosporins with alkoxyiminomethyl(2-aminothiazol-4-yl)acetyl substituents at 7-position of cephems were synthesized starting from (2-aminothiazol-4-yl)acetate via one carbon homologation followed by acylation with 7-aminoceph-3-em-4-carboxylic acid derivatives. These new aminothiazolyl cephalosporins exhibit promising in vitro activities against various strains including Gram positive bacteria.

N- vs. S-Substitution reactions of 1-substituted tetrazoline-5-thiones with various allyl or benzyl halides were studied in order to find effective conditions for N-substitution reactions. When allyl or benzyl halides were reacted with 1-substituted tetrazoline-5-thiones in the presence of TMSI or $BF_3{\cdot}OEt_2$ (or other Lewis acids), N-substitution at 4-position in addition to S-substitution occurred. Reactions were performed either with or without a solvent such as dioxane or propionitrile in the presence of potassium iodide.

Enthalpies of solution of aniline, pyridine and benzylamine in iso-dielectric mixtures of methanol with acetonitrile (AN), nitrobenzene (NB) and nitromethane (NM) have been measured calorimetrically. The solute-solvent interaction was analyzed using a model developed by Waghorne et al. and found that the relatively weak base, aniline, tended to behave anomalously, especially in the NB and NM binary systems by forming bidentate hydrogen bonds between the two-$NH_2$ hydrogens and the two-$NO_2$ oxygens. Pyridine and benzylamine were found to be preferentially solvated by methanol in all the binary mixtures.

Luminescence quenching reactions of photoexcited tris(2,2'-bipyridine)ruthenium (Ⅱ) complex cation, $Ru(bpy)_3\;^{2+}$, by dialkylviologens (dimethyl, dioctyl, dibenzyl, methyloctyl, methyldodecyl, and methylbenzyl) were studied in sodium dodecylsulfate (SDS), poly(styrenesulfonate) (PSS), and poly(vinylsulfonate) (PVS) solutions. The relative quenching rate varies widely with the microheterogeneous media employed: the highest quenching rate is observed for methyldodecylviologen in homogeneous aqueous medium, dibenzylviologen in SDS and PVS solutions, and dimethylviologen in PSS solution; the lowest rate is found for dimethylviologen in homogeneous medium and SDS solution, methyldodecylviologen in PSS and PVS solutions. These results were interpreted in terms of reduction potential of viologens, affinity of $Ru(bpy)_3\;^{2+}$ and viologens to the microparticles, and the structures of the viologen-colloid complexes.

The transition from one stable steady state branch to another stable steady state branch in a simple metabolic system with positive feedback is discussed with the aid of the bimodal Gaussian probability distribution method. Fluctuations lead to transitions from one stable steady state branch to the other, so that the bimodal Gaussian evolves to a new distribution. We also obtain the fractional occupancies in the two stable steady states in terms of a parameter characterizing conditions of the system.

A.c. susceptibility for $Bi_{1.4}Pb_{0.6}Sr_2Ca_2Cu_{3.6}O_x$ superconductor is measured as a function of temperature at different value of a.c. magnetic field amplitude. Two transition steps are attributed to the intergranular and intragranular properties. Based on Bean's critical state model, intergranular critical current density, $J_c^{gb}$ (11 $A/cm^2$ at 77 K) and intragranular critical current density, $J_c^g (7{\times}10^3\;A/cm^2$ at 100 K) are estimated. The low values of $J_c^{gb}$and $J_c^g$ reflect a poor nature of coupling between grains and the low pinning force density of intragrain in $Bi_{1.4}Pb_{0.6}Sr_2Ca_2Cu_{3.6}O_x$ superconductor.

A lithiated compound $Li_{0.1}Pr^{3+}Ba_2Cu_3O_y$ has been successfully prepared by electrochemical method, which is achieved with a two electrode cell of the type: Metal(Li)/($Li^+\;,\;ClO_4^-$) + propylene carbonate/$PrBa_2Cu_3O_y$. All Pr ions in the lithiated compound are stabilized with a trivalent state as the other rare earths (Ⅲ) substituted in the 90K superconductor lattice ($Y_{1-x}Ln_x^-Ba_2Cu_3O_{7-{\delta}}$). Powder X-ray diffraction analysis shows that both compounds, $PrBa_2Cu_3O_y$ and $Li_{0.1}PrBa_2Cu_3O_y$ are isostructural with the 90 K superconductor, ($YBa_2Cu_3O_{7-{\delta}}$), nevertheless both of them are non-metallic and also non-superconducting down to 10 K. Magnetic susceptibility ${\chi}$ vs. temperature data indicate that Curie contribution from the magnetic ions (Pr and Cu) is weakened on the one hand, but on the other hand temperature-independent part of susceptibility ${\chi}_o$ increases depending upon the rate of lithium intercalation in $PrBa_2Cu_3O_y$ lattice.