A series of new hydridocarbonyl osmium(Ⅱ) complexes, OsHCl(CO)(PPh3)(L-L)[L-L=Ph2P(CH2)nPPh2 (n=1 (1), 2 (2), 3 (3), cis-Ph2PCH=CHPPh2 (4), and Fe(η5-C5H4PPh2)2 (5)] has been synthesized from OsHCl(CO)(PPh3)3 and chelating diphosphines. These complexes have been characterized by IR, 1H NMR and elemental analysis. The catalytic activities of these complexes both for the transfer hydrogenation of trans-cinnamaldehyde with 2-propanol as the hydrogen donor, and for the selective hydrogenation of trans-cinnamaldehyde with H2, have been examined. Complexes (1)-(5) were shown to have higher selectivities for the transfer hydrogenation of the C=O bond of aldehyde than for the transfer hydrogenation of the C=C bond of aldehyde. The selectivities for the transfer hydrogenation with 2-propanol as well as for the hydrogenation with H2 have been found to decrease in the order 3 > 5 > 2 > 4 > 1. Complex (3) has shown to possess almost 90% of the selectivity to cinnamyl alcohol for transfer hydrogenation. It is also found that there is a correlation between the ν(CO) of each complex and the hydrogenation, of the C=O bond of trans-cinnamaldehyde. Overall, the selectivities with the complexes (1)-(5) are greater for the transfer hydrogenation with 2-propanol than for the hydrogenation with H2.

An oxidative thermal regeneration process was developed and evaluated for its potential applicability in several environmental areas. The feasibility of the process is affected strongly by the gradual carbon loss, energy consumption, physical changes of carbon, and effective destruction efficiency of adsorbed materials during the regeneration. The aim of the study is to determine the optimum conditions to maintain acceptable destruction efficiency for adsorbed organics, controlling oxidant flow rate. Prior to its applications, various preliminary tests were carried out to determine the effects of experimental parameters on the process. The tests performed were reaction temperature, carbon loss, surface area, surface structure, and adsorptive property. The results of these tests show that the parameters are dependent on oxidant flow rate, and suggest that the process is comparable and, in some ways, possibly superior to conventional regeneration techniques because the oxidative process is a single step and less energy intensive.

The chemical waste treatment, APEG (alkali/polyethylene glycol) process has been shown to be effective for the dechlorination of PCBs in transformer oil. Considerable amount of PCBs, however, still remains in the waste exceeding the 25-50 ppm limit set by regulatory agency. A new thermal regeneration technology has been developed in our laboratory for disposal of hazardous organic wastes. Due to the limited oxidation of carbon surface through the reverse movement of flame front to oxidant flow, this technology was termed counterflow oxidative system (COS). Specially, the oxidant flow in the COS process is a principal parameter which determines the optimum conditions regarding acceptable removal and destruction efficiency of adsorbed organic wastes at minimal carbon loss. The COS process, under optimum conditions, was found to be very effective and the removal and destruction efficiency of 99.99% or better was obtained for residual PCBs in the waste while bulk (≥90%) of carbon was recovered. Any toxic formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo furans (PCDFs) were not detected in the regenerated carbon and impinger traps. The results of surface area measurement showed that the adsorptive property of regenerated carbon is mostly reclaimed during the COS process.

The luminescence and photoexcitation spectra of cis-[Cr(cyclam)(NO3)2]NO3·½ H2O (cyclam=1,4,8,11-tetraazacyclotetradecane) taken at 77 K are reported. The infrared and visible spectra at room-temperature are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. With observed transitions, a ligand field analysis has been performed to determine the bonding property of nitrate group in the chromium(Ⅲ) complex. According to the results, it is found that nitrate ligand has weak σ- and π-donor properties toward chromium(Ⅲ).

Bis(ethylene)rhodium(Ⅰ) chloride dimer reacted with vinylcyclopropane to give σ,η3-allylrhodium(Ⅲ) complex 3. Complex 3 underwent C-C bond cleavage of 8-quinolinyl ethyl ketone 11, to form η3-1,3-dimethylallylrhodium(Ⅲ) complex 8, which was reductively eliminated by trimethyl phosphite to give 8-quinolinyl-1-methylbut-2-enyl ketone (10). More sterically hindered 8-quinolinyl alkyl ketones were allowed to react with complex 3 to afford corresponding alkenes as well as a mixture of complex 8 and η3-1-ethylallyl rhodium(Ⅲ) complex 19, identified as 10 and 8-quinolinyl-pent-2-enyl ketone (20) after reductive elimination. 8-Quinolinyl alkyl ketone bearing a sterically hindered alkyl group showed less reactivity for C-C bond cleavage and higher 20/10 ratio compared with those having a less sterically hindered alkyl group, such as 8-quinolinyl ethyl ketone (11).

A novel ONNO-type tetradentate ligand, 1,3-diaminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2apmp) and its cobalt(Ⅲ) complexes, [Co(apmp)X2]n+, (X=Cl-, NO2-, H2O, X2=CO32-, en, L-phenylalanine) have been synthesized. During the preparation of the dichloro cobalt(Ⅲ) complex of apmp, [Co(apmp)Cl2]-, the ligand has coordinated to the cobalt(Ⅲ) ion in a geometric selectivity to give only the uns-cis isomer and, during the substitution reaction between L-phenylalanine and [Co(apmp)Cl2]-, the L-phenylalanine has coordinated to the cobalt(Ⅲ) ion in a geometric selectivity to give only an uns-cis-meridional isomer. It is of interest that this is a rare case of the [Co(ONNO ligand)X2]n+-type complex preparations, which gives only an uns-cis isomer with geometric selectivity.

Core/shell structured composite metal oxides of Fe2O3/MgO were prepared by thermal decomposition of Fe(acac)3 adsorbed on the surface of MgO cores. The morphology of the composites conformed to that of the MgO used as the cores. Broad powder X-ray diffraction peaks shifted toward larger d, large BET surface area (∼350 m2/g), and the size of crystalline domains in nano range (4 nm), all corroborate to the nanocrystallinity of the Fe2O3/MgO composite which was prepared by using nanocrystalline MgO as the core. By use of microcrystalline MgO as the core, microcrystalline Fe2O3/MgO composite was prepared, and it had small BET surface area of less than 35 m2/g. AFM measurements on nanocrystalline Fe2O3/MgO showed a collection of spherical aggregates (∼80 nm dia) with a very rough surface. On the contrary, microcrystalline Fe2O3/MgO was a collection of plate-like flat crystallites with a smooth surface. The nitrogen adsorption-desorption behavior indicated that microcrystalline Fe2O3/MgO was nonporous, whereas nanocrystalline Fe2O3/MgO was mesoporous. Bimodal distribution of the pore size became unimodal as the layer of Fe2O3 was applied to nanocrystalline MgO. The macropores in a wide distribution which the nanocrystalline MgO had were absent in the nanocrystalline Fe2O3/MgO. The decomposition of CCl4 was largily enhanced by the overlayer of Fe2O3 on nanocrystalline MgO making the reaction between nanocrystalline Fe2O3/MgO and CCl4 be nearly stoichiometric. The reaction products were environmentally benign MgCl2 and CO2. Such an enhancement was not attainable with the microcrystalline samples. Even for the nanocrystalline MgO, the enhancement was not attained, if not with the Fe2O3 layer. Without the layer of Fe2O3, it was observed that the nanocrystalline domain of the MgO transformed into microcrystalline one as the decomposition of CCl4 proceeded on its surface. It appeared that the layer of Fe2O3 on the particles of nanocrystalline Fe2O3/MgO blocked the transformation of the nanocrystalline domain into microcrystalline one. Therefore, in order to attain stoichiometric reaction between CCl4 and Fe2O3/MgO core/shell structured composite metal oxide, the morphology of the core MgO has to be nanocrystalline, and also the nanocrystalline domains has to be sustained until the core was exhausted into MgCl2.

A simple molecular theory of mixtures is formulated based on the nonrandom two-fluid lattice-hole theory of fluids. The model is applicable to mixtures over a density range from zero to liquid density. Pure fluids can be completely characterized with only two molecular parameters and an additional binary interaction energy is required for a binary mixture. The thermodynamic properties of ternary and higher order mixtures are completely defined in terms of the pure fluid parameters and the binary interaction energies. The Quantitative prediction of vapor-liquid, and solid-vapor equilibria of various mixtures are demonstrated. The model is useful, in particular, for mixtures whose molecules differ greatly in size. For real mixtures, satisfactory agreements are resulted from experiment. Also, the equation of state (EOS) is characterized well, even the liquid-liquid equilibria behaviors of organic mixtures and polymer solutions with a temperature-dependent binary interaction energy parameter.

A series of tetradentate Schiff-base ligands; 1,3-bis(salicylideneimino) propane, 1,4-bis(salicylideneimino)butane, and 1,5-bis(salicylideneimino)pentane, and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been synthesized. The properties of ligands and complexes have been characterized by elemental analysis, IR, NMR, UV-Vis spectra, molar conductance, and thermogravimetric anaylsis. The mole ratio of Schiff base to metal at complexes was found to be 1 : 1. All complexes were four-coordinated configuration and non-ionic compound. The electrochemical redox processes of the ligands and their complexes in DMF solution containing 0.1 M TEAP as supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry at glassy carbon electrode, and by controlled potential coulometry at platinum gauze electrode. The redox process of the ligands was highly irreversible, whereas redox process of Cu(Ⅱ) and Ni(Ⅱ) complexes was observed as one electron transfer process of quasi-reversible and diffusion-controlled reaction. Also the electrochemical redox potentials of complexes were affected by chelate ring size of ligands. The diffusion coefficients of Cu(Ⅱ) and Ni(Ⅱ) complexes in DMF solution were determined to be 4.2-6.6×10-6 cm2/sec. Also the exchange rate constants were determined to be 3.6-9.7×10-2 cm/sec.

The arene epoxides from naphthalene, 1β,2α-dihydroxy-3α,4α-epoxy- (1) and 1β,2α-dihydroxy-3β,4β-epoxy-1,2,3,4-tetrahydronaphthalene (2) (anti- and syn-diol epoxide), 1,2-epoxy-1,2,3,4-tetrahydronaphthalene (3), and 1,2-epoxy-l,2-dihydronaphthalene (4), are model compounds of the ultimate carcinogenic metabolites of polycyclic aromatic hydrocarbons, ubiquitous environmental pollutants which may be causal in several human cancers. The product distribution in the hydrolysis of 1-4 have been studied by HPLC analysis of reaction mixtures. The yields of the trans product from the hydronium-ion-catalyzed and pH-independent hydrolysis in 9 : 1 (v/v) 20 mM buffer-dioxane at 25 ℃, respectively, were; 1: 98, 100; 2: 74, 87, 3: 95, 97, 4:100, 100. The results were rationalized by conformational equilibria of the epoxides and the carbocationic and zwitterionic intermediates from the epoxides.

Luminescence spectrum of Na3[Eu(ODA)3]·7H2O (ODA≡oxydiacetato) was measured at various temperatures. The characteristic band splitting within 5D0→7FJ (J = 1, 2, 3 and 4) were phenomenologically simulated by using crystal field theory. The set of crystal field parameters reproduces the emission lines in a satisfactory manner with a rms deviation of 21.4 cm-1. It leads the reliable assignment of the luminescence bands and the energy level scheme of 7FJ (J = 1, 2, 3 and 4) multiplets.

Second-order rate constants have been measured spectrophotometrically for the reactions of p-nitrophenyl phenylacetate (1) and benzoate (2) with a series of alicyclic amines in H2O containing 20 mole % DMSO at 25.0 ℃. 1 appears to be more reactive than 2 toward all the amines studied, although phenylacetic acid is a weaker acid than benzoic acid. The higher reactivity of 1 can be attributed to resonance and/or steric effect, since the ground state of 2 can be stabilized by resonance and 1 would experience less steric hindrance due to the presence of CH2 group between phenyl and C=O group. The reactivity of the amines increases with increasing their basicity. The Bronsted-type plots for aminolysis of 1 and 2 show good linearity with βnuc values of 0.81 and 0.85, respectively, indicating that the TS structures of the aminolyses of 1 and 2 are similar. Besides, the linear Bronsted plots obtained in the present system clearly suggest that there is no mechanism change for the given series of the amines and the reactions of 1 and 2 proceed in a same mechanism.

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

Various classes of phospholipids were investigated for the structural determination of fatty acyl groups by fast atom bombardment tandem mass spectrometry (FAB-MS/MS). Phospholipids were desorbed by FAB as molecules chelated with sodium ion (or ions). Collision-induced dissociation (CID) of intact sodium adduct molecular ions ([M+Na]+, [M-H+2Na]+ or [M+Na-2H]-) produced a series of homologous fragment ions via the charge-remote fragmentation along the fatty acid chains. These ions were found useful to locate the double bond positions even for the polyunsaturated fatty acid chains. The regiospecificity of the acyl chain linkages in phosphatidylcholine (PC) could also be determined based on the ratio of relative abundance of the product ions (i.e., [M+Na-85-R2COOH]+ vs [M+Na-85-R1COOH]+) in CID-MS/MS of [M+Na]+. These are generated by the loss of fatty acyl groups at sn-1 and sn-2, respectively, together with the choline group. In all the phospholipid compounds investigated, loss of the fatty acid at the sn-2 position was dominant. The present method was applied to the structural determination of molecular species of phosphatidylglycerols (PG) isolated from cyanobacterium Synechocystis sp. PCC 6803.

Ab initio calculations were carried out on the gas phase acid-catalyzed hydrolysis reactions of sulfinamide using the 3-21G* basis sets. Single point calculations were also performed at the MP2/6-31G* level. The first step in the acid-catalyzed hydrolysis of N-methylmethanesulfinamide, Ⅰ, involves protonation. The most favorable form is the O-protonated one, Ⅱ, which is then transformed into a sulfurane intermediate, Ⅲ, by addition of a water molecule. The reaction proceeds further by an intramolecular proton transfer from O to N (TS2), which is followed by N-S bond cleavage (TS3) leading to the final products. The rate determining step is the N-S bond cleavage (TS3) at the RHF/3-21G* level, whereas it becomes indeterminable at the MP2/6-31G*//3-21G* level of theory. However, the substituent effect studies with N-protonated N-arylmethanesulfinamide, ⅩⅢ, at the MP2/6-31G*//3-21G* level support the N-S bond breaking step as rate limiting.

The crystal structure and optical properties of copper nanoparticles, prepared in fused silica by ion-implantation and subsequent heat-treatment, were characterized by X-ray, TEM, linear absorption, and degenerate four-wave mixing (DFWM) technique. The X-ray data show fcc lattice structure of the nanocrystals and their size was measured as 8-20 nanometer by high resolution TEM. Using DFWM, the third-order nonlinear optical coefficient of the Cu-SiO2 thin films was measured as 0.4-1.1×10-8 esu in the surface plasmon resonance absorption region (540-570 nm).

The approximate rates and stoichiometry of the reaction of excess lithium tripiperidinoaluminum hydride (LTPDA), an alicyclic aminoaluminum hydride, with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 25°) were examined in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTPDA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(diethylamino)aluminum hydride (LTDEA), a representative aliphatic aminoaluminum hydride. In general, the reactivity of LTPDA toward organic functionalities is weaker than LTDEA and much weaker than LAH. LTPDA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and thiols evolve a quantitative amount of hydrogen rapidly. The rate of hydrogen evolution of primary, secondary and tertiary alcohols is distinctive. LTPDA reduces aldehydes, ketones, esters, acid chlorides and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. Tertiary amides and nitriles are also reduced readily to the corresponding amines. The reagent reduces nitro compounds and azobenzene to the amine stages. Disulfides are reduced to thiols, and sulfoxides and sulfones are converted to sulfides. Additionally, the reagent appears to be a good partial reducing agent to convert primary carboxamides into the corresponding aldehydes.