Viscoelastic properties of PET filament fibers on stress relaxation were investigated in the solvents of $H_2$O, 0.05% NaOH and 50% DMF using an Instron (UTM4-100 Tensilon) with solvent chamber. The theoretical stress relaxation equation derived by applying the Ree-Eyring's hyperbolic sine law to dashpot of three element non-Newtonian model was applied to the experimental stress relaxation curves, and the model parameters $G_1,G_2$, ${\alpha}$ and ${\beta}$ were obtained. By analyzing temperature dependency of the relaxation time, the values of activation entropy, activation enthalpy and activation free energy for flow in PET filament fiber were evaluated, the activation free energy being about 25.7 kcal/mol. The self diffusion coefficient and hole distance were obtained from parameters ${\alpha}$, ${\beta}$ and crystallite size in order to study the self diffusion and the orientation of crystallites in amorphous region and the effect of solvent.

The preferential transport phenomena of neutral cation-anion moieties in neutral macrocycle-facilitated emulsion liquid membrane were described in this study. Emulsion membrane systems consisting of (1) aqueous source phase containing 0.001 M M($NO_3$)$_2(M=Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cu^{2+},\;Zn^{2+},\;Sr^{2+},\;Cd^{2+},\;and\;Pb^{2+})$ (2) a toluene membrane containing 0.01 M ligand $(DBN_3O_2$, DA18C6, DT18C6, TT18C6, HT18C6) and the surfactant span 80 (sorbitan monooleate) (3% v/v) and (3) an aqueous receiving phase containing $Na_2S_2O_3$ or $NaNO_3$ were studied with respect to the disappearence of transition metal ions from the source phase as a function of time. Cation transports for various two component or three component equimolar mixture of transition metal and $Cu^{2+}$ in a emulsion membrane system incorporating macrocyclic ligand (HT18C6) as carrier were determinded. $Cu^{2+}$ was transported higher rates than the other $M^{2+}$ in the mixture solution. Equilibrium constants for cation-source phase co-anion, cation macrocycle and cation-receiving phase reagent interaction are examined as parameters for the prediction of cation transport selectivities.

In the three-parameter ellipsometry (TPE), also known as reflectance-ellipsometry, the ellipsometric measurements, ${\Psi} and {\Delta}$, are combined with the reflectometric measurement, R, to determine the optical parameters and the thickness of a light-absorbing thin film. The constant ${\Psi}, {\Delta}$ and R surfaces are analyzed graphically to understand the nature of the TPE solutions. A sensitivityanalysis is shown to be useful not only for identifying the film properties which affect most the TPE measurements, but also for estimating errors in film properties arising from the uncertainties in measurements.

The tetraaza macrocyclic ligand 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18} ,0^{7.12}]$docosa-2,12-diene(B), that contains two cyclohexane rings, has been prepared as its dihydroperchlorate salt by the nontemplate condensation of methyl vinyl ketone with 1,2-diaminocyclohexane and perchloric acid. Reduction of B with sodium borohydride produces 3,14-dimethyl-2,6,13,17-tetraazatricyclo$[14,4,0^{1.18},0^{7.12}]$docosane(C). Square planar Ni(Ⅱ) and Cu(Ⅱ) complexes of B and C have been prepared by the reaction of the metal ions and the ligands. Synthesis, characterization, and the properties of the ligands and their metal complexes are reported.

Electrochemical studies of alkali metal cations $(Na^+, K^+, Rb^+, Cs^+)$ were performed in methanolic solutions of 18-crown-6 and tetrabutylammonium salts at dropping mercury electrodes (DME) and thin mercury film electrodes (TMFE). All the cations investigated were reduced reversibly at DME in the absence and presence of 18-crown-6, and in the latter the limiting currents were decreased and the reduction potentials shifted to the negative direction. The reduction potentials of the metal ions (0.2 mM) in the presence of the crown (10 mM) were - 2.14 $(Na^+)$, - 2.26 $(K^+)$, - 2.20 $(Rb^+) and - 2.14 $(Cs^+)$ V vs. SCE, respectively. The measured potentials were rationalized with ion recognition of the cations by the crown. Electroreduction at TMFE were highly irreversible. A new representation method of ion recognition is presented. In aqueous solutions, electroreduction of the alkali metal ions were characterized by adsorption.

The ${\beta} to {\alpha}$ phase transition in silver iodide is studied with the (N, V, E) and (N, P, T) molecular dynamics (MD) method. In experiments, the phase transition temperature is 420 K. Upon heating of ${\beta}$ form, the iodine ions undergo hcp to bcc transformation and silver ions become mobile. MD simulations for the ${\beta}$ and ${\alpha}$ phases are carried out at several temperatures and the radial distribution functions (rdf) are obtained at those temperatures in the (N, V, E) ensemble. But the phase transition is not found in our calculation. Next the phase transition is studied with the (N, P, T) MD and we find some evidences of phase transition. At 3 Kbars and 2 Kbars the phase transition temperatu re is about 300 K. For 3.55 Kbars, the phase transition is higher (420 K) than the low pressure case. The phase transition temperature is somewhat dependent on the pressure in our calculations.

The changes in the free energy and hydration free energy of N-acetyl-N'-methylalaninamide in the unhydrated and hydrated states were calculated with ECEPP/2 and the hydration shell model. The configurational entropy change of each conformation in both states were computed by a harmonic method. To understand the hydration structure of each hydrated conformation, the hydration-shell coordination numbers of functional. groups of the molecule were estimated from water-accessible volumes, and the contributions of water-accessible volume and polarization of each group to the hydration free energy were analyzed. The results show a reasonable agreement with those of recent theoretical studies and experiments.

EPR spectra of the high $T_c$ superconductor $YBa_2Cu_3O_{7-y}$ (YBCO) doped with $Pd^{2+} or Zn^{2+}$ have been measured at several temperatures and dopant concentrations. The spectral intensity of $YBa_2({Cu_{1-x}}{Pd_x})_3O_{7-y}$ is proportional to the dopant concentration. The behavior of $YBa_2(Cu_{1-x}Zn_x)_3O_{7-y}$ is quite different: the spectral intensity remains almost constant up to x=0.10 and then increases rapidly above x=0.10. The results are interpreted in terms of localized and antiferromagnetically spin-paired d holes in both CuO chain and planes. The $Pd_{2+}$ ion substitutes on the CuO chain consisting of "CuOCu dimers", and a $Cu_{2+}$ ion with an unpaired spin is gene rated for each $Pd_{2+}$ ion substituted. On the other hand, $Zn_{2+}$ substitutes on the CuO planes, and all or most of the spins in the two-dimensional plane manage to pair up in the region of low dopant concentration. When the dopant concentration exceeds a certain limit, it becomes more difficult for the spins to find partners, and the number of unpaired spins increases rapidly with increasing dopant concentration. The $Zn_{2+}$ ion is more effective than the $Pd_{2+}$ ion in suppressing the superconductivity of YBCO. This is attributed to the fact that $Zn_{2+}$ substitutes on the CuO planes which are mainly responsible for the superconductivity, while $Pd_{2+}$ substitutes on the CuO chain which is of secondary importance in the superconductivity.

S. fradiae showed very high activity of isocitrate dehydrogenase compared to other microorganisms. The activity of this enzyme was increased with the growth of the organism. But the increase might not imply its involvement in the growth. Rather its increased activity seemed to have a connection with the biosynthesis of neomycin. The enzyme showed high specificity toward $NADP^+$ and D-isocitrate with Km values of 5.75 and 6.74 uM, respectively, It was activated by $Mn^{2+}$. Its molecular weight was estimated from its gel retardation coefficient to be in the range of 61,000-63,000 daltons and its optimum pH was 8.0. The enzyme was thermally unstable.

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

The electronic behavior of a organic metal $(BEDT-TTE)_2$${Cu_5}{I_6}$ observed to be stable at low temperatures was examined by performing tight-binding band electronic structure calculations. The suppression of a metal-insulator tansition is likely to originate from its quasi-two-dimensional Fermi surface with no nesting, in agreement with experiment.

The reaction of dichlorophenylvinylsilane with tert-butyllithium in hydrocarbon solvents at room temperature or below generated the Z and E-isomers of 1-chloro-1-phenyl-2-neopentylsilene. The intermediates were trapped by cyclopentadiene, anthracene and methoxytrimethylsilane to give a consistent 90/10 ratio for the Z-silene to E-silene adduct. This result was interpreted as an evidence for stereochemical induction in the silene generation reaction.

Stainless steel 304 2B and BA are oxidized in 2.5 M $CrO_3/$ 5.0 M $H_2SO_4$ solution, and elemental composition and oxidized state of the surface region is analyzed as a function of the surface depth using X-ray photoelectron spectroscopy. It is found that Fe and Cr are preferentially oxidized and diffuse outward following the oxidation. Element Ni, the third major component of the steel is not oxidized and remains deep under the surface. It is also found that the oxidized Fe dissolves considerably into the solution thereby enriching the gas-oxide interface with Cr.

A simple route is described for the selective functionalization of calixarene at the para positions of phenyl rings. Calix[4]arene tetraacetate 2, obtained from the treatment of calix[4]arene with acetic anhydride, undergoes Fries rearrangement to yield the diametrically para substituted p-diacetylcalix[4]arene 3 in 80% yield. The crystal and molecular strucutre has been determined by X-ray diffraction method. The crystals are orthorhombic, space group Pna21, with a = 11.121 (3), b = 10.374 (3), c = 21.690 (6) $\AA$ and Z = 4. The structure was solved by direct method and refined by full-matrix least-squares methods to final R of 0.036 for 1795 observed reflections. Each hydroxyl hydrogen atom is disordered over two positions. The macrocycle exists in the cone conformation which is determined by the strong circular intramolecular flip-flop type hydrogen bonds of phenolic OH, while crystal packing effects of the diametrically para-acetyl substituents seem to be responsible for the distortion of the cone conformation.

In this paper, the question whether the curvature of the minimum energy path can affect the dynamic threshold was tested using the boundary trajectory method developed by Chesnavich and coworkers. For nonreactive system, the MO EXP model potential surface was used with modified equilibrium distance to control the curvature. The results showed that there is no relation between the curvature and the dynamic threshold. In order to study the reactive system, a generalization of the boundary trajectory method was achieved to apply on the nonsymmetric system. We have found no correspondence between the curvature and the dynamic threshold of the system. It was also shown that the fate of the trajectories strongly depends on the shape of potential surface around the turning points along the symmetric stretch line.

Electrophilic methylation reactions of five-membered heteroaromatic compounds, furan, pyrrole and thiophene, with the dimethylfluoronium ion, ${CH_3}{FCH_3}(+), have been investigated theoretically by the MNDO method. The site selectivity of ${\alpha}, {\beta}$ and heteroatom (X) is related to charge density of the site, indicating that the site selectivity is dictated by electrosatic interaction between two reaction centers. The reactivity order between the three heteroaromatics can not be determined decisively since the order differs depending on which site is compared, with relatively low activation enthalpies, ${\Delta}{H^\neq}$= 20-30 kcal/mol, in all cases. These site and substrate selectivity behaviors are consistent with the gas-phase experimental results.

Thin film being formed on the surface of cobalt in the early stage of electrochemically induced passivation was studied by the three-parameter ellipsometry. The growth of the passive film was complete in a few seconds from the onset of the passivating potential, and was followed by a slight decrease in the thickness in 4-40 seconds. The optical constants of the passive film changed gradually during the changes in the thickness. The thickness and the optical properties at the steady state of passivation depended on the potential of the electrode. From the coulometric data and the optical properties, the composition of the passive films was deduced to be close to those of CoO, ${Co_3}{O_4}$ and ${Co_2}{O_3}$ depending on the potential. Cathodic reduction in the presence of EDTA was found to be an efficient way to obtain film-free reference surface of cobalt.

Using the Huckel method, we obtain the analytical expressions for eigenvalues and eigenvectors of s.c., f.c.c. and b.c.c. clusters of rectangular parallelepiped shape, and of an arbitrary size. Our formula converage to those derived from the Bloch sum, in the limit of infinite extension. DOS and LDOS reveal that the major contribution of the states near Fermi level originates from the surface atoms, also symmetry of DOS curves disappears by the introduction of 2nd nearest neighbor interactions, in all the cubic lattices. An accumulation of the negative charges on surface of cluster is observed.

The photophysical and photochemical properties of khellin were compared with those of 8-methoxypsoralen (8-MOP). Quantum yields of fluorescence and triplet formation decreases as solvent polarity increases, which is opposite to 8-MOP, and photocycloadditivity of khellin to olefins is much lower than that of 8-MOP. Electron ejection from khellin by laser flash was not observed, but observed from 8-MOP. As models of 4',5'-monoadducts of khellin or 8-MOP with thymine base, khellin<>dimethylfumarate 4',5'-monoadduct (KDF) was also compared with 8-MOP<>thymidine 4',5'-monoadduct (F-2) in those properties to give some insight on the second-step biadduct formation resulting in cross-links of DNA duplex. KDF and F-2 were very similar to khellin and 8-MOP in photophysical properties, respectively. However, KDF did not form adducts with various olefins, and thus it is thought that 2,3-double bond of chromone moiety in khellin is hardly reactive in contrast with 3,4-double bond of coumarin moiety in 8-MOP. These results indicate that khellin is fairly photostable compound, a poor type Ⅰ photodynamic sensitizer and producer of ${O_2}^{-}$ which is some cause of phototoxic erythemal reactions and undesirable side effects. Therefore khellin is safer to use than 8-MOP in photochemotherapy of some skin diseases. Although khellin is much less reactive than 8-MOP, khellin must be also a monofunctional drug. Since khellin is, however, as effective as 8-MOP in photochemotherapy of some skin diseases, it is suggested that khellin may be different from 8-MOP in the action mechanism.

The gas-phase pyrolysis reactions of iminoethers (Ⅱ), 2-alkoxypyridines (Ⅲ), 2-N-alkylated pyridones (Ⅳ) and N-alkylated acetamides (Ⅴ) have been studied MO theoretically with the AM1 method. The decomposition of these compounds proceeds by a concerted retro-ene process through a six-membered cyclic transition state. The reactivity decreases in the order (Ⅱ) > (Ⅲ) > (Ⅳ) > (Ⅴ), with a greater reactivity for the imine series, (Ⅱ) and (Ⅲ), compared to the amide series, (Ⅳ) and (Ⅴ), and a difference in basicity between the N and O atoms. Within a given series, however, the reactivity is dictated mainly by the aromaticity in the transition state. The reactivity order with respect to side alkyl chain of a species was found to increase as the steric crowding effect increases. The AM1 reactivity in this work agree well with the experimental results.

Enantioselective synthesis of 1-substituted tetrahydroisoquinoline alkaloids (1) via asymmetric reduction of 1-substituted 3,4-dihydroisoquinolines (2) and the corresponding iminium salts (3) with the selected chiral hydride reagents, such as K glucoride (5), Itsuno's reagent (6), and Mosher's reagent (7) were examined. In these reactions, dihydroisoquinolines were not reduced by the hydride reagents, whereas the iminium salts were easily reduced under the same reaction conditions found in successful reduction of ketones. Thus, the reduction of 6,7-dimethoxy-3,4-dihydroisoquinolium iodide(3a) with 5, 6 and 7 provided the product 1a with 52.3 % ee, 18 % ee, and 66.4 % ee, respectively. For 1-benzyl derivatives (3b-3d), syntheses of 1b-1d with 0.7-6.2 % ee, 5.9-21 % ee, and 1.4-2.7 % ee were achieved with chiral reducing agents 5, 6 and 7, respectively. For 1-aryl derivatives, use of 5, 6 and 7 resulted in optical inductions in the range of 25.2-43 % ee, 13-21.1 % ee, and 6.3-16 % ee, respectively.

Methyl red diffusion in polymer solutions was studied by a transient holographic method, forced Rayleigh scattering. In semi-dilute solutions of a polystyrene, where no specific interaction with the probe exists, we found within experimental uncertainty that the retardation of diffusion rate of methyl red is independent of the solvents used. This indicates that the hydrodynamic interaction in polymer coils is not affected by the nature of solvents enough to exhibit a detectable change in the diffusion rate of the probe. On the other hand, a substantial reduction of diffusion rate was observed in poly(methyl methacrylate) solutions in toluene. Together with the similar observation reported with poly(vinyl acetate), it is confirmed that hydrogen bond between the probe and the polymer is responsible for the retarded diffusion. The decay-growth-decay profile found in this system reveals a finite difference in diffusion coefficients of cis and trans isomer of methyl red. We estimate the difference and suggest that the cis isomer interacts with the polymer more strongly than the trans isomer.

The CO molecules adsorbed on Ni(111) surface is studied in the cluster approximation employing EH method with self-consistent charge iteration. The effect of CO coverage is simulated by allowing the variation of valence state ionization potentials of each Ni atom in model cluster according to the self-consistent charge iteration method. The CO coverage dependent C-O stretching frequency shift, adsorption site conversion, and metal work function change are attributed to the charge transfer between metal surface and adsorbate. For CO/Ni(111) system, net charge transfer from Ni surface to chemisorbed CO molecules makes surface Ni atoms be more positive with increasing coverage, and lowers Ni surface valence band. This leads to a weaker interaction between metal surface valence band and Co $2{\pi}^{\ast}$ MO, less charge transfer to a single CO molecule, and the bule shift of C-O stretching frequency. Further increase of coverage induces the conversion of 3-fold site CO to lower coordination site CO as well as the blue shift of C-O stretching frequency. This whole process is accompanied by the continuous increase of metal work function.

A series of dimesogenic compounds having two identical, terminal Schiff base type mesogens and a central polymethylene spacer were prepared and their properties were compared with those of the corresponding monomesogenic compounds. The mesomorphic properties of the compounds were studied by differential scanning calorimetry and on a hot-stage of a polarizing microscope. All of the dimesogenic compounds formed mesophases enantiotropically with the exception of pentamethylene-1,5-bis(4-oxybenzylidene 4-n-butylaniline). This compound was monotropic and formed only a nematic phase on heating the solid, whereas it formed nematic as well as smectic A phases on cooling the isotropic liquid. Those compounds containing longer (octamethylene and decamethylene) spacers favored the formation of nematic phase whereas those having shorter (dimethylene and tetramethylene) spacers formed smectic phases. In general, the variety of mesophase forms exhibited by the dimesogenic compounds was significantly less than that shown by the corresponding monomesogenic compounds.