Partial oxidation of methane has been conducted over $CeO_2$and it has been found that $CeO_2$has an extraordinary catalytic activity in the reaction. Its activity was strongly dependent on the $CH_4/CO_2$ ratio. Total combustion was dominant with stoichiometric feed ratio$(CH_4/O_2=$ 2.0) but partial oxidation was achieved between the $CH_4/O_2$ ration of 3.8 4.3 and the period depended upon the feed composition. The proposed raaction mechanism it that oxygen vacancies in raduced deria are supplied with oxygen molecules from the reactant, and then activate adsorbed oxygen, followed by releasing activated axygen species reacting with methane to produce $H_2$ and CO.

The conversion of dimethyl ether(DME) has been carried out over $\gamma-alumina$, silica-alumina, and modified $\gamma-aluminal$ catalysts. Especially, the water effect has been investigated on purpose to develop a suitable catalyst for one-step synthesis of DME from $CO_2$ hydrgenation, The $\gamma-Al_2O_3$ modified with 1 wt% silica is more active and less deactivated by water than unmodified one. $CO_2has$ no effect on catalytic dehydration of methanol to DME.

We present a hypothetical quantum scattering model to propose a novel electroluminescence device. Adoping with features of solid state semiconductor LED and exciplex laser, the cathode (electrol incoming potential) and anode(electron outgoing potential) are made to correspond to two 1-dimensional resonance supporting potentials, and the light emitting part to an interaction potential in the intermediate region. When an external voltage is applied, the electron flows into the cathode having small work function. Subsequently in flows via LUMO of the " electron incoming potential" loses kinetic energy emitting a photon, then continues to flow via LUMO of the "electron outgoing potential" unlike the conventional LUMO to HOMO transitions occurring in solid state semiconductor LED. In this model, the photon frequency can be controlled by adijusting the applied voltage. The model hopefully could be realized as partially conjugated hydrocarbon chains.

Gibbs ensemble Monte Carlo simulations were performed to calculate the vapor-liquid coexistence properties for the binary mixtures $CO_2/CH_3OH$, $CO_2/C_2H_5OH$, and $CO_2/CH_3CH_2CH_2OH.$ The configurational bias Monte Carlo method was used in the simulation of alcohol. Density of the mixture, composition of the mixture, the pressure-composition diagram, and the radial distribution function were calculated at vapor-liquid equilibrium. The composition and the density of both vapor and liquid from simulation agree considerably well with the experimental values over a wide range of pressures. The radial distribution functions in the liquid mixtures show that $CO_2$ molecules interact more stogly with methyl group than methylene group of $C_2H_5OH$ and $CH_3CH_2CH_2OH$ due to the steric effects of the alcohol molecules.

Granular activated carbon(GAC) is highly effective in removing organic compounds which are resistant to biological disintegration in wastewater treatment. However, GAC has reached its full adsorptive capacity, GAC needs to be regenerated before it can be used for a further adsorption cycle. Countercurrent oxidative reaction (COR) technique has been developed and evaluated for the regeneration of spent GAC. Various parameters such as flame temperature, the loss of carbon, destruction and removal efficiency (DRE) of organic compounds, surface area, surface structure, adsorptive capacity, etc. were examined to determine the performance of COR. The results of these tests showed that adosorptive capacity of regenerated GAC was completely recovered, the loss of carbon was controllable, flame temperature was high enough to insure complete destruction and removal $(\geq99.9999%)$ of specific organics of interest, polychlorinated biphenyls (PCBs), that are thermally stable, and on formation of toxic byproducts such as polychlorinated dibenzo-p-dioxins (PCDDs) or polychlorinated dibenzofurans (PCDFs) were detected during the regeneration process. The COR technique is environmentally benign, easy to use and less copital intensive than other available regeneration technologies.

New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

Recently it was reported that cycloaddition of 6,6-disubstituted cyclohexa-2,4-dienone, 1 with cyclopentadiene gave solely the adduct of type 1.while its reaction with 1,3-cyclohexadiene gave both Ⅱ and Ⅲ. Semiempirical MO calculations were done to elucidate the origin of the selectivity difference between the two dienes. Cycloaddition of 1 with cyclopentadiene is controlled thermodynamically to give only 1-diene adduct by ΔGvalues of 10.6-20.3 kcal/mol, while its reaction with 1,3-cyclohexadiene does not show 1-diene/1-dienophile selectivity due to similar stabilities of the two adducts. Thermodynamic parameters also show that 두애 adducts are more fabourably fromed in the cycloadditions of 1 with both cyclopentadiene and 1,3-cyclohexadiene, which coincides with experimental observations. Cope rearrangements of endo adducts are another avenue to convert between 1-diene and 1-dienophile.

Based on ab initio calculations at the MP2(FULL)/6-31+G**//RHF/6-31G** level, we compare the energetic and mechanistic features of a model reaction for catalytic action of Δ?-3-ketosteroid isomerase (KSL,E.C.5.3,3.1) with those of a corresponding nonenzymatic reaction in aqueous solution. The results show that the two catalytic acid residues,Tyr14 and Asp99, can lower the free energy of activation by 8.6kcal/mol, which is in good agreement with the experimentally predicted~9 kcal/mol,contribution of electrophilic catalyses to the whole enzymatic rate enhancement. The dienolate intermediate formed by proton transfer from the substrate carbon acid to the catalytic base residue (Asp38) ins predicted to be stabilized by 12.0 kcal/mol in the enzymatic reaction, making its formation thermodynamically favorable. It has been argued that enzymes catalyzing the reactions of carbon acids should resolve the thermodynamic problem of stabilizing the enolate intermediate as well as the kinetic porblem of lowering the free energy of activation for porton abstraction. We find that KSI can successfully overcome the thermodynamic difficulty ingerent in the nonenzymatic reaction through the electrophilic catalyses of the two acid residues. Owing to the stabilization of dienolate intermediate, the reketonization step could influence the overall reaction rate more significantly in the KSI- catalyzed reaction than in the nonenzymatic reaction, further supporting the previous experimental findings. However, the electrophilic catalyses alone cannot account for the whole catalygic capability (12-13 kcal/mol), confiming the earlier experimental implications for the invement of additional catalytic components. The present computational study indicates clearly how catalytic residues of KSI resolve the fundamental problems associated with the entropic penalty for forming the rate-limiting transition state and its destabilization in the bulk solvation environment.

The synthesis of the intramolecular donor - stabilized silyl and germyl complexes of the type ($Cab^c.p) MMe_2X$ (2a:M=Si, X=Cl;2b;M= Ge, X=Cl;2e;M=Si,X=H) was achieved by the reaction of $LiCab^c,p$ (1) with $Me_2SiClX$ and $Me_2GeCl_2$ respectively. The intramolecular M←P interacion in 2a-2c is provided by $^1H$, $13^C.$, $31^P$ and $29^Si$ NMR spectroscopy. The salt elimination reactions of dichlorotetramethyldisilane and -digermane with 1 afforded the $bis(\sigma-carboranylphosphino)disilane$ and disgermane [$(Cab^C.P)MMe_2]_2(4a;M$ = Si;4b: M=Ge). The oxidative addition reaction of 4a-4b with $pd_2(dba)_3CHCl_3afforded$ the bis(silyl)-and bis(germyl)-palladium complexes. The chloro-bridged dipalladium complexes were obtained by the reaction of 2a-2b with $pd_2(dba)_3CHCl_3$ The crystal structures of 5a and 7b were determined by X-ray structural studies.

The Reaction of S-methyl-S-cysteine(L-Smc) with racemic $s-cis-[Co(demba)Cl_2]-1$ (Hydmedba = $NN'-dimethylethylenediamine-NN'-di-\alpha-butyric$, acid) yields ${\Delta}$-s-cis-[Co(dmedba)(L-Smc)] 2 with N, O-chelation. Oxidation of sulfur of 2 with $H_2O_2$ in a 1 : 1 mole ratio gives ${\Delta}$-s-cis[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Sm with $H_2O_2in$ a 1: 1 mole ratio produces S-methyl-L-cysteinesulfenate (L-S(O)me) 5. Direct reaction of 1 with 5 in basic medium gives an N.O-chelated ${\Delta}$s-cis[Co(dmedba)(L-S(O)mc)-N.O], which turmed out be same as obtained by oxidation of 2, while an N, S-chelated ${\Delta}$-s-cis-[Co(dmedba)(S-S(O)mc)-N,O] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare $[$Co^{III}$(N_2O_2-type$ ligand)(amino acid)] type complex preparations, where the reaction conditions determine which mode of N, O and N, S caelation modes is favored.

The general reducing charagteristics of a newly synthesized reducing agent, lithium(2.3-dimethyl-2-butyl)-${\iota}$-butoxyborohydride (Li $Thx'BuOB_2$, 1), in tetrahydrofuran (THF) toward selected organic compounds containing representative fundtional groups under practical has been examined. The reagent revealed an interesting and unique reducing characteristics. Especially, the stereoselectivity in the reduction of cyclic ketones was extraordinary. Thus, the introduction of bulky alkyl and alkoxy groups into the parent borohydride affonds a high stereoselectivity. In general, the reducing power of the reagent is somewhere between the dialiylborohydride and the parent borohydride. This permits the reagent to be a reagent of choice for selecitive reduction of organic compounds with an improved selectivity.

A sensitive method for the determination of trace copper(II) after the preconcentration by adsorbing its cupferron complex onto microcrystalline benzophenone was developed.Several experimental conditions such as the pH of sample solution,concentration of cupferron, amount of benzophenone and atirring time were optimized. Trace compper(II) in 100mL solution was chelated with $3.0\;{\times}\;10^3$ M cupferron at pH 5.0. After 0.20g benzophenone, The benzophenone adsorbing Cu-cupferron complex was filtered and then Cu-cupferron complex was desorbed in 10 mL ethanol. Copper was determined by a flame atomic absorption spectrophotomethry. The interfering effects of diverse concomitant ions were investigated. Fe(III) interfered seriously with, but the interference by Fe(III) was completely eliminated by adjusting the concentration of copferron to $5.0\;{\times}\;10^3$ M. The detection limit of this method was 8.6${\times}$10 M(5.5 ngmL$^1$). Recoveries of 97% and 96% were obtained for Cu(II) in a stream water and a brass sample, respectively. Based on the results from the experiment. this proposed technique could be applied to the determination of copper(II) in real samples.

A systematic way of determining the equilibrium orientation of carbon monoxide (CO) in heme proteins using time-resolved polarized mid-IR spectroscopy is presented. The polarization anisotropy at pump-probe delay time of zero in the limit of zero photolysis and the angular distrbution function of CO are required to obtain the equilibrium orientation of CO. An approach is developed for determining the polarization anisotropy in the zero-photolysis limit from the anisotropy measured under finite photolysis conditions in an optically thick sample where the fraction of molecules photolyzed decreased as the pump pulse passes through and is absorbed by the sample. This approach is verified by measuring the polarization anisotropy of CO of carbonmonoxy myoglobin at various levels of photolysis. This method can be readily applied to other photoselection experiments determining precise angle between transition dipoles.

One of the improtant characteristics of core-shell type nanoparticles is the long-term storage and reuse as an aqueous injection solution when required. For this reason, reconstruction of lyophilized core-shell type nanoparticles is considered to be essential . BAB type triblock copolymers differ from AB type diblock copolymers, which contain the A block as a hydrophilic part and the B block as a hydrophobic part. by not being easily redistributed into phosphate-buffered saline (PBS, pH 7.4, 0.1 M). Therefore, lyophilized core-shell type nanoparticles of CEC triblock copolymer were reconstituted using a somication process with a bar-type sonicator in combination with a freezing-thawing process. Soncation for 30s only resuspended CEC nanoparticles in PBS; their particle size distribution showed a monomodal pattern with narrow size distribution. The bimodal size distribution pattern and the aggregates were reduced by further sonication for 120 s but these nanoparticles showed a wide size distribution. The initial burst of drug release was increased by reconstitution process. The reconstitution of CEC core-shell type nanoparticles by freezing-thawing resulted in trimodal distribution pattern and formed aggregates, although freezing-thawing process was easier than sonication . Drug release form CEC nanoparticles prepared by freezing-thawing was slower than from the original dialysis solution. Although core-shell typenanoparticles of CEC triblock copolymers were not easily performed. Cytotoxicity testing of core-shell type nanoparticles of CEC-2 triblock copolymers containing clonazepam (CNZ) was performed using L929 cells. Cytotoxicity of CNZ was decreased by incorporation into nanoparticles.

A series of novel 1,3-alternate calix[4]-mono-thiacrown and -bis-thiacrowns were synhesized within good yields. The three dimensional 1,3-alternate conformation was confimed by X-ray crystal structure. From the results of two phase extraction and NMR studies on the ligand-metal complex, one can conclude that the calix[4]thiacrown ethers showed the very high selectivity for silver ion over other metal ions by an electrostatic interaction between sulfur atom and silver ion and by a $\pi-metal$ complexation.

An inorganic-organic hybrid system, silica-poly(ethylene glycol) songel is reported. This system was prepared via sol-gel method by varying varous processing variables. e.g. ultrasonic radiation time, gelling temperanture, PEG content and its molecular weight. Various experimental techniques wee employed to analyze the morphological, mechanical and optical properties of the system. The results were discussed in the light of existing theories. The sonogel system exhibited the common features of inorganic-organic hybrids. $SiO_2-10$ wt% PEG sonogel exhibited the morphological and optical properties superior to those reported earlier for the classic gels and found suitable for device applications.

The structures and energies of p-tert-butylcalix[4]crown-6-ether(1) in various conformers and their alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. We have tried to obtain the relative affinity of partial-cone and 1,3-alternate conformers of 1 for alkyl ammonium guests by comparison with its cone-shaped analogue. We have also calculated the relative complexation efficiency of these host-guest complexes focusing on the binding sites of $crown-\sigma-enther$ moiety or benzene-rings pocket of the host molecule 1. These calculations revealed that the crown moiey has better complexation efficiency than upper rim part of calyx[4]arene that is in similar trend to the cone-shaped complexes.