New bisaryl corands (crown ethers) bearing 1,2-dibenzyl- and 1,2-dibenzoylbenzene subunits have been synthesized: The reaction of 1,2-bis(2-hydroxybenzyl)benzene in base with mono-tetrahydropyranyl oligoethylene glycol tosylate, deprotection of the bis-condensation product to give a corresponding diol, tosylation of the free hydroxyls of the diol, and condensation of the ditosylate in base with 1,2-bis(2-hydroxybenzyl)benzene afforded a new type of bisaryl corand(Ⅰ) of 1,2-dibenzyl-benazene system. Oxidation of the benzylic positions of the corands (Ⅰ) furnished novel aromatic corands(Ⅱ) containing partly carbonyl functions.

Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.

The surface enhanced Raman scatterings of Zn(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrins were studied in silver sol. Zn(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrin was found to be adsorbed on silver surface via flat-on geometry with some inhomogeneous distribution in the orientation of pyridyl groups. Both the selective enhancement of Raman modes depending on the mode character and the theoretical arguments of SERS are utilized to support the above conclusion. The surface induced substitution reaction of Mn(Ⅲ) tetrakis (4-N-methyl pyridyl) porphyrin chloride to Ag(Ⅱ) tetrakis (4-N-methyl pyridyl) porphyrin was detected via surface enhanced Raman spectrum.

Ion-surface collision studies at low kinetic energies (1-100 eV) provide a unique opportunity for investigating reactions and collision dynamics at surfaces. A special ion optics system for generating an energy- and mass-selected ion beam of this energy is designed and constructed. An ultrahigh vacuum (UHV) reaction chamber, in which the ions generated from the beamline collide with a solid surface, is equipped with Auger electron spectroscopy (AES) and thermal desorption spectrometry (TDS) as in-situ surface analytical tools. The resulting beam from the system has the following characteristics : ion current of 5-50 nA, energy spread < 2eV, current stability within ${\pm}5%,$ and unit mass resolution below 20 amu. The performance of the instrument is illustrated with data representing the implantation behavior of $Ar^+$ into a graphite (0001) surface.

Retention of mono-substituted phenols in reversed-phase liquid chromatography has been studied based on the linear solvation energy relationships using the solvatochromic mobile phase parameters, ${\pi}_m^{\ast}, {\alpha}_m$ and ${\beta}_m$. It has been observed that retention behavior of phenols in RPLC were well represented by regression equations vs. solvatochromic mobile phase parameters even though the equations may be incomplete due to lack of an explicit cavity term. Dependence of retention of monosubstituted phenols on the mobile phase properties were varied depending on the type of the organic cosolvent in the mobile phase, e.g., ${\beta}_m$ and {\alpha}_m$ in methanol-water system, but ${\pi}_m^{\ast} and ${\beta}_m$ in THF-water system. It has been suggested that retention of phenols in methanol-water system is controlled by the solvophobicity of the mobile phase.

Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

The stereoselectivity of the reaction between methyl vinyl ketone dimer, which contains two possible sites of chelation, and zinc borohydride or diisobutylaluminum hydride has been studied in order to illuminate the factors involved in the high levels of asymmetric induction obtained in the bicyclic system. The conditions for the formation of the exo-5,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane are DIBAH reduction of MVK dimer in ether at reflux followed by acidic cyclizatioan, and for the endo isomer are $Zn(BH_4)_2$ reduction with $ZnCl_2$ at $0^{\circ}C.$.

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

Geometries for several representative quinolone carboxylate type antibacterials have been calculated by computer graphics/molecular mechanics energy minimization procedures using both MM2 and AMBER force fields. The calculated geometries were found to be in reasonable agreements with the corresponding X-ray crystal structures. It has been pointed out that notwithstanding the weaknesses associated with calculating the resonance and hydrogen bonding contributions, the employed methods are capable of generating credible ring geometries and torsional angle dispositions of N(1)-ethyl and 3-carboxylate substituents of the quinolones.

The bis(malonato)diaquochromate(III) ion, $Cr(C_3H_2O_4)_2^-$ in acidic solution hydrolyzes to give $Cr(C_3H_2O_4)^{+}.$ This reaction is catalyzed by ferric ion and the rate law for this cation catalyzed-aquation in a $HClO_4/NaClO_4$ medium, $I = 1.00 M, is-d[Cr(C_3H_2O_4)_2^-]/dt = ({\kappa}_1[Fe^{3+}] + {\kappa}_2[H^+])[Cr(C_3H_2O_4)_2^-]$ where ${\kappa}_1(25^{\circ}C) = 4.72×10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 22.5 Kcal/mol, {\Delta}S^{\neq} = - 2.58 eu) and {\kappa}_2(25^{\circ}C) = 4.75{\times}10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 21.2 Kcal/mol, {\Delta}S^{\neq} = - 7.13 eu).$ Rapid preequilibrium association of basic Cr-bound oxygen with $Fe^{3+},$ followed by rate-determining ring opening, is proposed to account for the ${\kappa}_1,$ hydrolysis pathway.

The synthesis and some biological properties of $7{\beta} $-[2-(Z)-(2-aminothiazole-4-yl)-2-(N-substitutedcar bonyl)ethoxyiminoacetamido]-3-vinyl-3-cephem-4- carboxylic acid are described. The effect of substituents on the carbamoly group in the 7-side chain were investigated in order to improve antibacterial activities. Two of these new orally active $7{\beta} $-lactam derivatives showed wide expanded antimicrobial activities against Gram-positive and Gram-negative bacteria, including Pseudomonas aeruginosa, as well as good stability to $7{\beta} $ -lactamases.

Three crystal structures of dehydrated Cd(II) and Rb(I) exchanged zeolite A, $Cd_{4.0}Rb_{4.0}-A (a = 12.204(3) {\AA}), Cd_{5.0}Rb_{2.0}-A (a = 12.202(1) {\AA}),$ and $Cd_{5.95}Rb_{0.1}-A (a = 12.250(2) {\AA}),$ have been determined by single-crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at $21(1)^{\circ}C.$ All crystals were ion exchanged in flowing streams of mixed $Cd(NO_3)_2·4H_2O$ and $RbNO_3$ aqueous solution with total concentration of 0.05 M. All crystals were dehydrated at ca. $450^{\circ}C$ and $2×10^{-6}$ Torr for 2 days. In all of these structures, $Cd^{2+}$ ions are found on threefold axes, each nearly at the center of a 6-oxygen ring. The first three $Rb^+$ ions per unit cell preferentially associate with 8-oxygen rings, and additional $Rb^+$ ions, if present, are found on threefold axes in the large cavity. The final $R_1$ and $R_2$ values for the three structures are 0.087 and 0.079, 0.059 and 0.067, and 0.079 and 0.095, respectively.

The most general algebraic Hamiltonian for vibron model of diatomic molecules is obtained by using the theorems on the Jordan Schwinger representations of Lie groups.

A series of new dimesogenic compounds whose mesogens are of aromatic ester or amide type having a trifluoromethyl $(CF_3)$ substituent at the para-position of each terminal phenolic rings were prepared and their liquid crystalline properties were studied by differential scanning calorimetry (DSC) and on a cross-polarizing microscope. The compounds have two identical mesogenic units bracketing a central decamethylene spacer. Trifluoromethyl group appears to favor the formation of smectic phases when it is attached to a phenoxy or anilide terminal. Its group efficiency for mesophase formation seems to be inferior to other common substituents. A thermodynamic analysis of the phase transitions was made and the results were explained in relation to the structures of the compounds.

$Gd_2O_3-ThO_2$ solid solutions containing 8,10 and 12 mol % $ThO_2$ were synthesized with spectroscopically pure $Gd_2O_3,$ and $ThO_2$ polycrystalline powders. X-ray diffraction revealed that all synthesized specimens have the modified fluorite structure, and the lattice parameter of $Gd_2O_3$ is nearly unchanged with increasing $ThO_2$ mol %. Both ac and dc conductivities were measured in the temperature range $500-1100^{\circ}C$ under $Po_2's$ from $10^{-6}$ to $10^{-1}$ atm. The dc conductivities are nearly independent of $Po_2,$ and agree with the ac values. This implies that the solid solutions are ionic conductors. The conductivity increases with increasing $ThO_2$ mol % with an average activation energy of 1.23 eV. An oxygen interstitial defect and ionic hopping conduction are suggested.

A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at $413_{\circ}K$ using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition 4(t-BuO·→ CH_3COCH_3 + CH_3·)$ and hydrogen abstraction reaction from trimethylsilane $(t-BuO·+ HSi(CH_3)_3 → t-BuOH + Si(CH_3)_3)·).$ The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant $({\kappa}_d)$ with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure $(P_{1/2})$ were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.

The association between psoralens and some micelles is measured by the fluorescence quenching of psoralens by methylviologen $(MV^{2+})$ and bromide ion in some ionic micellar solutions. The association constants were estimated to be ca. $10^4$ for all the psoralens studied even though they show different hydrophobicity.

New bisaryl corands (crown ethers) bearing 1,2-dibenzyl- and 1,2-dibenzoylbenzene subunits have been synthesized: The reaction of 1,2-bis(2-hydroxybenzyl)benzene in base with mono-tetrahydropyranyl oligoethylene glycol tosylate, deprotection of the bis-condensation product to give a corresponding diol, tosylation of the free hydroxyls of the diol, and condensation of the ditosylate in base with 1,2-bis(2-hydroxybenzyl)benzene afforded a new type of bisaryl corand(Ⅰ) of 1,2-dibenzyl-benazene system. Oxidation of the benzylic positions of the corands (Ⅰ) furnished novel aromatic corands(Ⅱ) containing partly carbonyl functions.

Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.