The preparation and characterization of semiconductive electrodes of MgO doped $Fe_2O_3$ were investigated. Pellets of MgO doped $Fe_2O_3$ were sintered at high temperatures between 1300$^{\circ}$C and 1400$^{\circ}$C and quenched rapidly in distilled water. The surfaces were analyzed by X-ray diffraction and scanning Auger electron spectroscopy. The surfaces of pellets contained both corundum structure ($Fe_2O_3$) and spinel structure ($Mg_xFe_{3-x}O_4$). Electrodes made of this material gave comparable anodic and cathodic photocurrents under illumination. The cathodic and anodic photocurrent on these photoelectrodes were verified high at 5-10 wt. percent that is critical doping amounts.

Fourier transform infrared spectroscopy has been applied to the characterization of titania supported molybdena. The equilibrium adsorption method seemed to produce molybdena species homogeneously dispersed on the support. Even under an oxidizing environment, molybdena species appeared to be able to possess coordinatively unsaturated $Mo^{5+}$ ions owing to the natures of TiO$_2$, i.e. oxygen deficiency and permeability toward oxygen diffusion. At the initial stage of reduction, the terminal double bond oxygen ( Mo=O ) seemed to be removed, generating presumably $Mo^{4+}$. The carbonyl bands at 2198 and 2190 $cm^{-1}$ observed after CO exposure were attributed to the $Mo^{5+}{\cdots}CO\;and\;Mo^{4+}\;{\cdots}CO$ complexes, respectively, while the band pair at 2136 and 2076 $cm^{-1}$ to $Mo^{4+}(CO)_2$.

Potential energy surfaces for the proton transfer in a formamide dimer have been obtained by ab initio SCF calculations with STO-3G, 3-21G, and 4-31G basis sets and several features have been discussed. Energy minima for a formamide dimer and its tautomer are varied with basis sets. But the general features of the potential energy surfaces are similar among them.

Facile and efficient syntheses of terpenic perfumeries cis-jasmone, dihydrojasmone, and tetrahydrojasmone have been investigated. Cis-jasmone was synthesized by successive metallation followed by alkylation of acetone N,N-dimethylhydrazone with (Z)-2-penten-1-yl tosylate (or 2-pentyn-1-yl tosylate) and propylene oxide in one flask to give a ketonic alcohol, which was oxidized to the corresponding diketone, followed by base-catalyzed intramolecular aldol condensation to give a regioselective cyclization product. Dihydrojasmone and tetrahydrojasmone could be conveniently obtained from 2-octanone. The dimethylhydrazone of the ketone was lithiated with butyllithium and reacted with propylene oxide to give a ketonic alcohol, which was oxidized to a diketone, followed by base-catalyzed intramolecular cyclization to afford dihydrojasmone. Tetrahydrojasmone was prepared by converting the ketonic alcohol into corresponding iodoketone, followed by base-catalyzed intramolecular cycloalkylation to furnish an odoriferous product.

Three isomers of damascenone, odorous terpenic ketones, have been synthesized conveniently from a same starting material, ethyl 2,6,6-trimethyl-4-oxo-2-cyclohexene-1-carboxylate(1), which was easily available by the acid-catalyzed condensation of mesityl oxide or acetone with ethyl acetoacetate. ${\alpha}$-Damascenone(7) was prepared by converting the enone ester 1 into the corresponding tosylhydrazone(4), followed by treating with 4 molar equiv of allyllithium. ${\beta}$-Damascenone(12) was synthesized by chemoselective reduction of 1 with sodium borohydride/cerium chloride to give corresponding allylic alcohol 8, conversion of 8 into acetate 9, and thermal decomposition of 9 with DBU to afford ethyl ${\beta}$-safranate(10), followed by reaction with an excess amount of allyllithium. ${\gamma}$-Damascenone(15) was obtained by dehydration of 8 with boric acid to furnish ${\gamma}$-safranate(13), followed by treatment with 2 molar equiv of allyllithium.

The catalytic activity of $Nd_{1-x}Sr_xCoO_{3-y}$, $0{\leq}x{\leq}0.75$ and $0.001{\leq}y{\leq}0.103$, on the oxidation of carbon monoxide has been investigated from the structure analyses of the catalysts by X-ray diffraction and infrared spectroscopy and the measurements of the oxidation and adsorption rates of carbon monoxide. The catalytic activity is found to be correlated with Sr substitution (x) and nonstoichiometry (y). The oxidation power of carbon monoxide increases continuously with increasing Sr substitution without oxygen, but increases with Sr substitution up to x = 0.25 and then is almost constant at larger x values up to x = 0.75 with oxygen. This change of catalytic activity is explained by the oxidation-reduction properties of the catalyst due to the variation of nonstoichiometry.

A cluster made of $N_A,\;N_B\;and\;N_C$ atoms in the x, y and z directions respectively, is treated with Huckel method. We obtain the approximate expressions for the eigenvalues and eigenvectors of f.c.c., b.c.c. and h.c.p. clusters in closed forms. The maximum and minimum values of the band so obtained converge to those derived from the Bloch sum in the limit of infinite extension. For a small cluster (of $9{\times}9{\times}5$ atoms, for instance), LDOS from the analytical (approximate) solution manifests better agreement at the surface, than inside the bulk.

Spin-lattice relaxation of methyl protons in 2,6-dichlorotoluene and N-methyl phthalimide, each dissolved in CDCl$_3$, has been studied at 34$^{\circ}$C and the contribution from spin-rotation interaction to the relaxation process has been separated from that due to dipole-dipole interactions among methyl protons. The results show that the spin-rotational contributions to the initial rate of relaxation in 2,6-dichlorotoluene and N-methyl phthalimide amount to 18 and 31%, respectively, of the total relaxation rate at 34$^{\circ}$C. The method of separating the spin-rotational contribution from that of dipolar interactions adopted in this paper is based on the well known fact that in an A$_3$ spin system such as methyl protons in liquid phase dipolar relaxation mechanism gives non-exponential decay of the z-component of total magnetization of protons while the random field fluctuation such as spin-rotational mechanism causes exponential decay.

To find optimum conditions necessary in converting physical properties of any resin into those of others, eleven kinds of HIPS (High-Impact Polystyrene) resins were prepared. First physical properties of eleven samples divided into three groups are analyzed by a torque rheometer (named Plasti-Corder, Model No.: PLD 651) and GPC (Gel Permeation Chromatography), and then optimum conditions on conversion among samples are obtained by calculation from computer simulation so that any sample subjected to each group can show physical properties of other samples in its group. Even though the kind of plasticizer of any sample is different with others in its group, once optimum conditions on conversion among samples are met, it is found that physical properties of any sample are identical or similar to those of others in each group.

Benzosilacyclobutenes were prepared from the reactions of 1,1-dichlorobenzosilacyclobutene with Grignard reagents or t-butyllithium. In the thermal reactions with alcohols, benzosilacyclobutenes underwent both benzyl-silicon and aryl-silicon bond rupture to yield (dialkyl)alkoxy-o-tolylsilanes and (dialkyl)alkoxybenzylsilanes, respectively. The photochemical reactions, however, produced only the former products via o-silaquinone methides.

Conformational free energy calculations using an empirical potential function and the hydration shell model (a program CONBIO) were carried out on the neutral L-ascorbic acid (AA) in the unhydrated and hydrated states. The conformational energy was minimized from starting conformations which included possible conformations of six torsion angles in the molecule. The conformational entropy of each low energy conformation in both states was computed using a harmonic approximation. From the analysis of conformational free energies for AA in both states, intramolecular hydrogen bonds (HBs) are proved to be an essential factor in stabilizing the overall conformations, and cause the conformations in both states to be quite different from those in crystal. In the case of hydrated AA, there is a competition between HBs and hydration, and the hydration around the two hydroxyl groups attached to the acyclic side chain forces the molecule to form less stable HBs. The hydration affects strongly the conformational energy surfaces of AA. Several feasible conformations obtained in this work indicate that there exists an ensemble of several conformations in aqueous solution. The calculated probable conformations for the rotation about the C5-C6 bond of the acyclic side chain are trans and gauche +, which are in good agreement with results of NMR experiment.

A hexagonal hexamer of water cluster is optimized by ab initio method using the 4-31G basis set. At this geometry the nonadditive many-body interactions are calculated. The ab initio calculation with large basis set [T. H. Dunning, J. Chem. Phys., 53, 2823 (1970); 54, 3958 (1971)] shows that a pentagonal unit is rather stable among several kinds of clustering units of water molecules.

Facile methods are reported for the synthesis of optically pure derivatives of (2S,3R)-3-amino-2-hydroxy-4-(4'-hydroxyphenyl)b utanoic acid. To avoid troublesome synthesis of O-benzyl-N-Boc-D-tyrosine, without the protection of phenolic OH group of tyrosine N-Boc-D-tyrosine methyl ester was reduced with DiBAL to the aldehyde. The aldehyde was converted via the cyanohydrin to (2S,3R)-3-amino-2-hydroxy-4-(4'-hydroxyphenyl)butanoic acid (AHpHBA). The mixture of diastereomers was converted to the corresponding Boc-AHpHBA methyl ester derivatives and separated by chromatography over silica gel. Optically active (2S,3R)-AHpHBA was used to synthesize aminopeptidase inhibitors.

A series of compounds, N-(2-substituted-1-carboxy)vinylazetidinones were successfully synthesized in order to test the hypothesis that biological activities of ${\beta}$-lactam antibiotics could be attributed to the smooth flow of electrons after a nucleophilic attack at the carbonyl carbon in the ${\beta}$-lactam ring. After introduction of aminothiazolylacetamido group at 3-position of the azetidinones, their biological activities were evaluated. Their low activities led to the conclusion that the smooth electron flow in ${\beta}$-lactams in not the sufficient source for the biological activities.

Laser Raman spectroscopy has been used to study the tungsta catalyst supported on titania. The surface tungsten species which forms on titania after calcination appeared to possess a structure that is independent of the initial impregnation condition. The surface polytungstate seemed to be stable only at the interfacial region since the crystalline WO$_3$ phase was observed as long as the tungsta loading was in excess of monolayer coverage. The close intact and strong interaction between the polytungstate and the titania could be evidenced from the inhibition of the phase transition of TiO$_2$ from anatase to rutile.

Poly[(tri-O-acetyl-D-glucal)-alt-(maleic anhydride)] was synthesized by free radical copolymerizations of the relevant comonomers. The alternating sequence of the copolymer was confirmed by $^1$H-NMR, elemental analysis, and titration of anhydride groups incorporated into the copolymer. Hydrolysis of the copolymer under different conditions resulted in poly[(2-acetoxymethyl-3,4-diacetoxytetrahydropyran-5,6-diyl) (1,2-dicarboxyethylene)] and poly[(2-hydroxymethyl-3,4-dihydroxytetrahydropyran-5,6-diyl) (1,2-dicarboxyethylene)]. The cytotoxicities of these polymers measured against normal and tumor cells (3LL, B16) in vitro were found to be higher than that of DIVEMA, a prototype polymer having a high antitumor activity.

A dual capillary column system is described for the simultaneous measurement of retention index (RI) and area ratio (AR) values of each peak on two capillary columns of different polarity, DB-5 & DB-1701. Both capillary columns were connected to a common splitless injector via a deactivated fused-silica capillary tubing of 1 m length and a 'Y' splitter, the dead volume effect of which was found to be negligible. RI and AR were measured with high reproducibility(${\leq}$0.05% RSD) and with high accuracy (<10% RE), respectively. When applied to the test samples of the organic acid mixture, each acid was positively identified by the combined computer RI library search-AR comparison.

Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.

Gas-phase pyrolyses of carbonate esters, ${\alpha}$- and ${\beta}$-hydroxy esters and ${\beta}$-hydroxy ketones have been studied theoretically by the AM1 MO method. Carbonate esters were found to decompose by two types of processes; in the reaction pathway involving an intermediate, the decomposition of the intermediate was rate-limiting, but direct pyrolyses were also possible via a six-membered cyclic transition state in which the methoxy oxygen attacks a hydrogen atom on the ${\beta}$-carbon. The hydroxy esters and ketones were found to decompose in a concerted process involving a six-membered cyclic transition state. Successive methylation on the ${\alpha}$- and ${\gamma}$-carbon led to an increase in the reactivity in agreement with experiments.

The kinetic isotope effects (KIE) are determined for the reactions of benzyl benzenesulfonates (BBS), ethyl benzenesulfonates (EBS) and phenacyl benzensulfonates (PAB) with deuterated benzylamine nucleophiles. The inverse secondary ${\alpha}$-deuterium KIE observed were somewhat smaller than those for the corresponding reactions with aniline nucleophiles. The primary $KIE_s$ obtained with PAB were slightly greater than those for the corresponding reactions with anilines, which suggested that the inverse secondary KIE is decreased due to a relatively earlier transition state for bond-making with little change in the hydrogen bonding strength to the carbonyl oxygen.