The conformational analysis has been done for catecholamines (dopamine, norepinephrine, and epinephrine) in the cationic and di-anionic states. The species responsible for adsorption on silver metal surface is anionic deprotonated at hydroxyl groups of catechol moiety, i.e., di-anionic states of catecholamines. This was deduced from Fourier-transform Raman spectra of sodium salts of catecholamines. High resolution proton NMR (400 MHz) spectra of catecholamines in basic and neutral $D_2O$ solution show that the conformations of norepinephrine and epinephrine in the di-anionic states are preferred in gauche, but not for dopamine in the di-anionic state. However the energy difference between trans and gauche of catecholamines in the protonated cationic states is small enough to rotate freely through C-C bond in ethylamine moiety. The conformational calculations using an empirical potential function and the hydration shell model (a program CONBIO) show consistent with above experimental results. The calculations suggest that the species of catecholamines adsorbed on silver metal surface would be in favor of the gauche conformations.

The paramagnetic complex of $(CO)_4ReL_2[L_2=$ 2,3-Bis(diphenylphosphino)maleic anhydride] was prepared both by the photochemically induced homolytic splitting of $Re_2(CO)_10withL_2and$ by the chemical reduction of $[(CO)_4ReL_2]SO_3CF_3.$ The $(CO)_4ReL_2$ compound was characterized by ESR spectrum. The spectrum exhibits three group of sextets arising from one $^{185.187}Re$ nucleus (Ⅰ= 5/2) and two equivalent $^31P$ nuclei (Ⅰ= 1/2). Infrared, ESR, and cyclic voltammetric data are reported for all of the complexes prepared in this study.

The effect of the addition of sodium dodecyl sulfate (SDS) to a buffered mobile phase (pH 3.4) on the retention of nucleotides, nucleosides and bases was investigated with a polyvinyl alcohol (PVA) column. Depending on the concentration of SDS, two different trends in the retention of nucleosides and bases containing an $NH_2$ group were observed. If the concentration of SDS was less than 5.5 mM, the retention of compounds containing an $NH_2$ group increased as the concentration of SDS in the mobile phase increased. In contrast, if the concentration was greater than 5.5 mM, the retention of compounds containing an $NH_2$ group decreased. Thus, the SDS acted as an ion-pairing reagent at lower concentration but formed micelles at higher concentrations. The retention behavior of the nucleosides and bases in the presence of a micellar concentration of SDS in the mobile phase on the PVA column was compared to the retention behavior on other types of columns.

Polyethylene oxide (PEO) surfaces are recognized as having an effective steric stabilization character. A theoretical scaling analysis involves the osmotic and elastic coefficients of the polymer as a function of molecular weight, in a good solvent. The calculated results show that PEO in water may exhibit the greatest flexibility among water soluble polymers, probably due to its lowest elastic contribution.

$ZrO_2-dopedYb_2O_3solid$ solutions containing 1, 3, 5, 7 and 9 mol% $ZrO_2were$ synthesized from spectroscopically pure $Yb_2O_3$ and $ZrO_2$ powders and found to be rare earth C-type structure by XRD technique. Electrical conductivities were measured as a function of temperatures from 700 to $1050^{\circ}C$ and oxygen partial pressures from 1${\times}$$10^-5$ to 2${\times}$ $10^-1$atm. The electrical conductivities depend simply on temperature and the activation energies are determined to be 1.56-1.68 $_eV$. The oxygen partial pressure dependence of the electrical conductivity shows that the conductivity increases with increasing oxygen partial pressure, indicating p-type semiconductor. The $PO_2$ dependence of the system is nearly power of 1/4. It is suggested from the linearity of the temperature dependence of electrical conductivity and only one value of 1/n that the solid solutions of the system have single conduction mechanism. From these results, it is concluded that the main defects of the system are negatively doubly charged oxygen interstitial in low. $ZrO_2doping$ level and negatively triply charged cation vacancy in high doping level and the electrical conduction is due to the electronic hole formed by the defect structure.

Preparative methods for and catalytic activities of monoaza-18-crown-6 or monoaza-15-crown-5 in the reaction of 1-bromooctane with aqueous KI or NaI were investigated. Monoazacrown ethers were prepared by debenzylation of N-benzylmonoazacrown ethers, obtained from the reaction of N-benzyldiethanolamine and oligoethylene glycol ditosylate. The phase-transfer catalytic activity of N-benzylmonoazacrown ethers was higher than that of the corresponding monoazacrown ethers.

The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

Cyclic voltammetric behavior of symmetric (dimethyl, diheptyl, dioctyl, dibenzyl) and asymmetric (methyloctyl, methyldodecyl, methylbenzyl) viologens was investigated in homogeneous aqueous solution and sodium dodecyl sulfate (SDS) micellar media. In SDS-free 0.1 M NaCl solutions, the reduction potential is less negative as the chain length of alkyl substituent is longer. This is due to the stabilization of the reduced cationic radical and neutral form of viologen by adsorption on electrode surface. The adsorbed species show the "aging-effect". With the exceptions of methyldodecyl viologen and methylbenzyl viologen, the viologens show strong tendency of conproportionation reaction between viologen dications and neutral forms. In cases of methyldodecyl viologen and methylbenzyl viologen, the conproportionation reaction is kinetically disfavored, though it is thermodynamically favorable. SDS micelles dissolve the adsorbed species and the viologens exhibit two reversible redox processes in SDS micellar solutions. The reduction potentials of viologens in SDS micellar solutions depend little on the length of alkyl chain. Benzyl-substituted viologens are more easily reduced than the alkyl substituted viologens, presumably due to electron-withdrawing character of benzyl group.

Ruthenium(III) unsymmetrical Schiff base complexes, $[Ru(CHBPH-TP)Cl_2]$ and $K[Ru(CHBPH-HB)Cl_2]$ were synthesized, where CHBPH-TP and CHBPH-HB are 5-chloro-2-hydroxybenzophenonethiophencarba aldehydephenylenediimine and 5-chloro-2-hydroxybenzophenonehydroxybenzophe nonephenylenediimine. These Schiff bases were obtained from the reactions of 5-chloro-2-hydroxybenzophenone (CHB) and 2-thiophenecarbaldehyde (TP) or hyroxybenzophenone (HB) and 1,2-diaminobenzene. Elemental analysis, conductivity and infrared studies of the complexes suggest an octahedral geometry around ruthenium. Magnetic moments of the complexes indicate a single unpaired electron in alow spin $d^5$ configuration. The complexes are capable of catalyzing the oxidation of styrene with sodium hypochlorite in the presence of phase transfer agent. Oxidative cleavage of C=C bond is the major reaction pathway to form benzaldehyde for styrene oxidation.

An attempt to improve the second harmonic generation (SHG) efficiency of MAP (methyl (2,4-dinitrophenyl)aminopropanoate) by modifying the substituents on the amino group of MAP is described. Several MAP analogues have been prepared using optically active amino acids alanine, phenylalanine and serine, and their SHG efficiencies measured. None of the MAP analogues exhibited SHG efficiencies as high as that of MAP. X-ray crystal structures of three MAP analogues have been determined. In the crystal structures of two of them, which were the derivatives of phenylalanine, two crystallographically-independent molecules existing in the asymmetric unit are aligned almost antiparallel. These structures are consistent with the very low SHG efficiencies of these compounds. On the other hand, the crystal structure of a serine derivative reveals substantial alignment of the dinitroaniline chromophore along the polar axis. However, the angle of 86.2° between the molecular charge tranfer axis and the polar axis of the crystal is still far away from the optimum value of 54.74° for the phase-matchable SHG. The structure is consistent with the SHG efficiency of this compound which is much higher than those of the phenylalanine derivatives but still lower than that of MAP. This study demonstrates the importance of the orientation of molecules in the crystal lattice in determining secod-order nonlinear optical properties of crystalline materials.

Immobilization method of lariat azacrown ethers, containing hydroxyl group in the side arm of crown ring, on the polymer matrix and the phase-transfer catalytic activity of thus obtained immobilized lariat azacrown ethers were studied. Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of crosslinked polystyrene resins containing epoxy groups with monoaza-15-crown-5 or monoaza-18-crown-6. Microporous crosslinked polystyrene resins containing epoxy group for the syntheses of these immobilized lariat crown catalysts were prepared by suspension polymerization of styrene, divinylbenzene (DVB 2%) and vinylbenzylglycidyl ether. The immobilized lariat catalysts with 10-20% ring substitution exhibited maximal activity for the halogen exchange reactions of 1-bromooctane with aqueous KI or NaI under triphase heterogeneous conditions. Immobilized catalyst exhibited higher activity than corresponding catalyst without the hydroxyl group and this result was suggested that the active site have a structure in which the $K^+$ ion was bound by the cooperative coordination of the crown ring donors and the hydroxyl group in the side arm.

Enantiomeric separation of free amino acids has been achieved by a reversed phase liquid chromatography with addition of a Cu(Ⅱ) complex of N-alkyl-L-proline (alkyl: propyl, pentyl or octyl) to the mobile phase. The amino acids eluted were detected by a postcolumn OPA system. N-alkyl-L-proline was prepared and used as a chiral ligand of Cu(Ⅱ) chelate for the enantiomeric separation. The concentration of the Cu(Ⅱ) chelate, the organic modifier and pH affect the enantiomeric separation of free amino acids. The retention behaviour, varied with change in pH and the concentration of the Cu(Ⅱ) chelate, was different compared with those of the derivatized amino acids. The elution orders between D- and L-forms were consistent except histidine showing that L-forms elute earlier than D-forms. The retention mechanism for the enantiomeric separation can be illustrated by the stereospecificity of the ligand exchange reaction and the hydrophobic interaction between the substituent of amino acids and reversed phase, $C_18$.

Enantiomeric separation of underivatized amino acids using N-alkyl-L-proline (octyl, dodecyl or hexadecyl) coated HPLC has been accomplished. The anchoring N-alkyl groups of L-proline provides a permanent adsorption of there solving chiral agent on the hydrophobic interface layer of a reversed phase. The factors controlling retention and enantioselectivity such as the Cu(II) concentration, pH of the eluent, the type and concentration of organic modifier in the hydroorganic eluent, and extent of coating were examined. The elution orders between D- and L-amino acids were consistent, L-forms eluting first, except histidine and asparagine. The extremely high enantioselectivity $(\alpha$ upto 13 for proline) is observed. The retention mechanism for the chiral separation can be illustrated by a complexation and hydrophobic interaction.

Four plausible precursors (21, 22, 24, and 25), just prior to formation of the oxathiazepine ring in eudistomin, were synthesized by the Pictet-Spengler condensation of N-hydroxytryptamine (15) or N-hydroxytryptophan ester (19) with cysteinal derivatives (5 and 10). In the case of the parent compound (21), one of these four precursors, treatment with dihalomethane in the presence of a phase transfer catalyst gave an eudistomin analogue (26) having the oxathiazepine ring in 35-50% yield.

$^{13}C$ spin-lattice relaxation times were measured for n-alkanes of moderate chain length, ranging from n-octane to n-dodecane, under the condition of proton broad-band decoupling within the temperature range of 248-318 K in order to gain some insight into basic features of segmental motions occurring in long chain ploymeric molecules. The NOE data showed that except for methyl carbon-13 dipole-dipole interactions between $^{13}C$ and directly bonded $^1H$ provide the major relaxation pathway, and we have analyzed the observed $T_1data$ on the basis of the internal rotational diffusion theory by Wallach and the conformational jump theory by London and Avitabile. The results show that the internal rotational diffusion constants about C-C bonds in the alkane backbone are all within the range of $10^9\;-10^10\;sec^{-1}$ in magnitude while the mean lifetimes for rotational isomers are all of the order of $10^{-11}\;-10^{-10}$ sec. Analysis by the L-A theory predicts that activation energies for conformational interconversion between gauche and trans form gradually increase as we move from the chain end toward the central C-C bond and they are within the range of 2-4 kcal/mol for all the compounds investigated.

The stable structures of pure ethylene and mixed ethylene-ammonia cluster ions are studied using an electron impact ionization time-of-flight mass spectrometer. Investigations on the relative cluster ion distributions of $(C_2H_4)_n(NH_3)_m^+$ under various experimental conditions suggest that $(C_2H_4)_2(NH_3)_3^+$ and $(C_2H_4)_3(NH_3)_2^+$ ions have the enhanced structural stabilities, which give insight into the feasible structure of solvated ions. For the stable configurations of these ionic species, we report an experimental evidence that both $(C_2H4)_2^+(C_2H_4)_3^+$ clusters as the central cations provide three and two hydrogen-bonding sites, respectively, for the surrounding $NH_3$ molecules. This interpretation is based on the structural stability for ethylene clusters and the intracluster ion-molecular rearrangement of the complex ion under the presence of ammonia solvent molecules.

A new monocyclic ${\beta}-lactam$ analogue, sodium (3R,4S)-3-[2-(2-aminothiazol-4-yl)-(Z)-2-methoxyi minoacetamido]-4-methoxymethyl-2-azetidinone-1- sulfonate (3) was synthesized from L-aspartic acid. Starting from L-aspartic acid, (S)-1-benzyl-4-benzyloxycarbonyl-2-azetidinone (7) was synthesized in four steps by following the established procedures and converted into (3R,4S)-3-amino-1-t-butyldimethylsilyl-4-methoxym ethyl-2-azetidinone (13) in six steps. Acylation of the amino group of 13 with $2-amino-{\alpha}$ -(methoxyimino)-4-thiazoleacetic acid, desilylation, and sulfonation with sulfur trioxide-pyridine complex followed by ion exchange afforded sodium (3R,4S)-3-[2-(2-aminothiazol-4-yl)-(Z)-2-methoxyi minoacetamido]-4-methoxymethyl-2-azetidinone-1- sulfonate (3). Antibacterial activities of this ${\beta}$ -lactam compound 3 were, however, found to be quite low compared to cefotaxime.

Sodium (3S,4R)-3-[2-(2-aminothiazol-4-yl)-(Z)-2-methoxyi minoacetamido]-4-methoxymethyl-2-azetidinone-1- sulfonate (2) was synthesized in fourteen steps from D-aspartic acid. Starting from D-aspartic acid, (3S,4R)-3-amino-1-t-butyldimethylsilyl-4-methoxym ethyl-2-azetidinone (12) was synthesized in ten steps. Acylation of the amino group of 12 with $2-amino-{\alpha}-(methoxyimino)-4-thiazoleacetic$ acid, desilylation, sulfonation, and ion exchange afforded sodium (3S,4R)-3-[2-(2-aminothiazol-4-yl)-(Z)-2-methoxyi minoacetamido]-4-methoxymethyl-2-azetidinone-1- sulfonate (2). This new ${\beta}-lactam$ compound 2 showed low antibacterial activities.

Structure and dynamics of $Na^+$ ions are investigated by molecular dynamics simulations of rigid dehydrated zeolite-A at several temperatures using a simple Lennard-Jones potential plus Coulomb potential. A best-fitted set of electrostatic charges is chosen from the results of simulation at 298.15 K and Ewald summation technique is used for the long-ranged character of Coulomb interaction. The calculated x, y, and z coordinates of $Na^+$ ions are in good agreement with the positions determined by X-ray crystallography within statistical errors, their random movings in different types of closed cages are well described by time-correlation functions, and $Na_Ⅰ$ type ions are found to be less diffusive than $Na_Ⅱ$ and $Na_{III}$. At 600.0 K, the unstable $Na_{III}$ type ion pushes down one of nearest $Na_{I}$ ions into the $\beta-cage$ and sits on the stable site Ⅰ, and the captured ion in the $\beta-cage$ wanders over and attacks one of 8 $Na_{I}$ type ions.

By using the general theoretical framework proposed recently for treating the fluorescence quenching kinetics, we investigate the effect of light pulse intensity on the decay of fluorescence which follows excitation of fluorophors by the light pulse of very short but finite duration. It is seen that conventional theory breaks down when the exciting light pulse has a pulse width comparable to the fluorescent lifetime and its intensity is very high. We also find that even when the light intensity is not too high, conventional theory may fail in either of the following cases: (i) when the quencher concentration is high, (ii) when there is an attractive potential of mean force between the fluorophor and quencher, or (iii) when the energy transfer from the fluorophor to the quencher may also occur at a distance, e.g., via dipole-dipole interaction. The validity of the predictions of the present theory may thus be tested by fluorescence quenching experiments performed under such situations.

An accurate method of density measurement is proposed. The method makes use of a gravimetric adsorption apparatus and is quite suitable for powdery and porous solid samples. The sample volume is determined by measuring its buoyancy with microbalance and the mass is measured in vacuum in the absence of buoyancy effect. Densities of inorganic compounds, such as alumina and perovskite, and some organic compounds are determined with the proposed method, and the results are compared with the values either determined with conventional methods or obtained from literatures.

Through two different techniques TGA and DSC the thermal decomposition processes of salicyaldehyde G-P complexes having the general formula: $$[MCl_2(L)_2]^{2+}$2Cl^-$; where L = salicyaldehyde carbohydrazone pyridinum cation, and M= Fe(III), Co(II), Cu(II) and Zn(II), have been studied. From the obtained thermogravimetric curves the following parameters n, $E_{\alpha}$, A, ${\Delta}S^{\neq}$, ${\Delta}H^{\neq}$ and ${\Delta}G^{\neq}$ were evaluated. The effect of the nature of the metal ions present in the complexes studied upon the calculated thermodynamic parameters was reported. A suitable mechanism for the thermal decomposition process was suggested.