In order to find out the relationship between electronic structures of metal oxychlorides (MOCl) and their physicochemical properties, we have carried out the tight-binding band electronic structure calculations with Extended Huckel (EH) method for TiOCl, VOCl and FeOCl. The relative contribution of metal atom to DOS at Fermi level increases in the order of Ti, V and Fe, which is parallel to the reactivities of MOCl toward guest species. The M2+ ion plays a crucial role in the electric conductivity of MOCl and its intercalation compounds. Hopping conduction theory is applied to explain the increase of conductivity after intercalation.

The enantiomeric separation of several amino acid derivatives by reversed-phase liquid chromatography using two (R)-and (S)-naphthylethylcarbamate-β-cyclodextrin(NEC-β-CD) bonded stationary phases was studied to illustrate the chiral recognition model of the enantiomeric separation. The retention and enantioselectivity of the chiral separations with (R)-and (S)-NEC-β-CD bonded phases were compared with similar separations with the native β-CD stationary phases. Especially, the enantioselectivity and elution orders between the derivatized amino acid enantiomers are carefully examined. These results can be illustrated by the chiral recognition models involving inclusion complexation, π-π interaction, and/or hydrophobic interaction. Inclusion complexation and hydrophobic interaction of the naphthyl group of the NEC moiety seem to be major chiral recognition components in the enantiomeric separation of 2,4-dinitrophenyl amino acids and dabsyl amino acids on (R)-and (S)-NEC-β-CD columns. For dansyl amino acids, only the inclusion complexation is the dominant factor. Three different chiral recognition models containing π-π interaction, inclusion complexation and hydrogen bonding were proposed for the separation of the 3,5-dinitrobenzoyl amino acid enantiomers, depending on the size and shape of amino acids.

The heterobimetallic anion, (OC)5CrMn(CO)5-M+ (M+=Na+, PPN+), which has a donor-acceptor metal-metal bond1, was reacted with allyl bromide to yield BrCr(CO)5- and Mn(CO)5(CH2CHCH2). The reaction mechanism has been proposed in terms of the consecutive reaction pathway in which Cr(CO)5(THF) is an important intermediate leading to the corresponding product. Counterion effect on this reaction was also evaluated and the results were compared with those of the corresponding reaction of the mononuclear carbonyl anion, Mn(CO)5-.

The incorporation of metal ion into the Langmuir-Blodgett (LB) film of an itaconate copolymer was investigated. The polymer was prepared via radical copolymerization of monooctadecyl itaconate with triethyleneglycol methyl vinyl ether. The metal ions employed were Na+, Cs+, Mg2+, Fe2+, Al3+, and Fe3+. The surface pressure-area isotherms indicated that all the monolayers studied on subphases with metal ions showed more expanded areas than that observed on pure water. The monolayers showed an irreversible collapse behavior. The collapse pressure of the monolayers was low on subphases containing trivalent metal ions. From the FT-IR spectra by reflection and transmission modes, the formation of carboxylate salts and the uprisen orientation of the pendant against substrate surface in the polymer LB film were determined. It was estimated by XPS measurement that ca. 13.1 repeat units of the polymer contain one Na+ ion, while one Mg2+ ion corresponds to 5.9 carboxyls.

Adsorption mechanisms of diisobutyl dithiophosphinate (DIBDTPI) and diisobutyl monothiophosphinate (DIBMTPI) on gold and gold-silver alloys (80:20 and 50:50) have been studied. The adsorption mechanisms on gold-silver alloys can be explained by the EC mechanism involving an electron transfer step and a chemical reaction step. Thus, the adsorption should be controlled by the E of the electrochemical oxidation of the electrode involved and the pK of the metal collector complex. Both di- and mono- thiophosphinate adsorb on 50:50 Au-Ag alloy at lower potential than on 80:20 Au-Ag alloy surface. There are no significant differences between the reactivities of DIBDTPI and DIBMTPI with precious metals except that the dithio- compound can be oxidized to dimer on gold at high potentials, while the monothio- homologue cannot. In this regard, DIBDTPI may be a better surface active reagent for pure gold than DIBMTPI.

Poly(enaryloxynitriles) containing Schiff bases were prepared from p-bis(1-chloro-2,2-dicyanovinyl)benzene (2) and various aromatic diols having Schiff base moiety by interfacial polymerization. The chemical structure of the polymers was confirmed through synthesis of their corresponding model compounds. All the polymers were soluble in polar aprotic solvents and their brittle films were cast from DMF solution. They showed a large exotherm around 340 ℃ attributable to the chemical change of dicyanovinyl group. Especially, curing of azomethine group was observed to occur at 390 ℃ by differential scanning calorimetry. According to the thermogravimetric analyses, they exhibited excellent thermal stability with 60-90% residual weight at 500 ℃ in nitrogen.

The macroscopic and microscopic redox potentials of tetrahemoprotein, cytochrome c3 from Desulfovibrio vulgaris(Hildenborough) (DvH) were estimated from 1H NMR and differential pulse polarography(DPP). Five sets of NMR resonances were confirmed by a redox titration. They represent cytochrome c3 molecules in five macroscopic redox states. The electron transfer in cytochrome c3 involves four consecutive one-electron steps. The saturation transfer method was used to determine the chemical shifts of eight heme methyl resonances in five different oxidation states. Thirty two microscopic redox potentials were estimated. The results showed the presence of a strong positive interaction between a pair of particular hemes. Comparing the results with those of Desulfovibrio vulgaris Miyazaki F (DvMF), it was observed that the two proteins resemble each other in overall redox pattern, but there is small difference in the relative redox potentials of four hemes.

3',5'-Dimethoxy-4'-(2-vinyloxyethoxy)-4-nitrostilbene 2 and 3',5'-dimethoxy-4'-(2-vinyloxyethoxy)-2,4-dinitrostilbene 5 were prepared by the reactions of 2-iodoethyl vinyl ether with 3',5'-dimethoxy-4'-hydroxy-4-dinitrostilbene 1 and 3',5'-dimethoxy-4'-hydroxy-2,4-dinitrostilbene 4, respectively. Monomers 2 and 5 were polymerized with cationic initiators to obtain polymers with 3',5'-dimethoxy-4'-oxy-4-nitrostilbene and 3',5'-dimethoxy-4'-oxy-2,4-nitrostilbene, which are presumably effective chromophores for second-order nonlinear optical application in the side chain. The resulting polymers 3 and 6 were soluble in DMSO and DMF. The inherent viscosities of the polymers were in the range of 0.28-0.33 dL/g in DMSO. Polymers 3 and 6 showed a thermal stability up to 250 ℃ in TGA thermogram, and the Tg values obtained from DSC thermograms were in the range of 81-87°.

Laser-induced fluorescence (LIF) excitation spectra were measured for fluorene (FR) cooled in pulsed supersonic expansions of He in the range 283.7-296.7 nm. Ab initio studies of FR have also been carried out for determining the electronic and vibrational structures by using the standard 3-21G basis sets. In the LIF excitation spectra of FR, highly resolved vibronic bands are observed having the band origin of 33,791 cm-1. The vibrational bands above the electronic origin were assigned on the basis of the well-characterized electronic vibrational bands reported previously and of normal modes of vibrations derived by our HF/3-21G calculations.

As an effort to elucidate the chiral recognition mechanisms exerted by the (S)-naproxen-derived CSP bearing both π-acidic and π-basic sites, a homologues series of π-basic N-acyl-α-(1-naphthyl)alkylamines and π-acidic N-(3,5-dinitrobenzoyl)-α-amino esters were prepared and resolved. Based on the chromatographic resolution trends of the homologues series of analytes on the (S)-naproxen-derived chiral stationary phase, we proposed chiral recognition mechanisms which demonstrate that the intercalation of the substituent in the analyte molecule between the strands of bonded phase does significantly influence the enantioselectivity for resolving N-acyl-α-(1-naphthyl)alkylamines but the intercalation process is not involved in resolving N-(3,5-dinitrobenzoyl)-α-amino esters.

Bromo-and chlorotrimethylsilane react with selenium dioxide in halocarbon solvents and generate selenium oxybromide and oxychloride, respectively. These in-situ generated oxyhalides turned out to be very efficient for selective bromination and chlorination of aldehydes and ketones. Under carefully controlled reaction conditions, second and third introduction of halogens into carbonyl compounds can be greatly suppressed, and high yields of monohalo compounds were obtained. The product ratios of this halogenation reactions can be best explained if the reactions are assumed to involve intermediate β-ketoselenenyl chlorides.

The reaction of 5-aryl-2-phenylisoxazolidine-3-thiones with more than 3 equivalents of anhydrous aluminum chloride in benzene at reflux gave N-(p-biphenylyl)-3-aryl-3-phenylpropanothioamides in good yields. It is conceived that the propanothioamides are formed via the formation of the corresponding N-phenyl-3-aryl-3-phenylpropanothiohydroxamic acids.

The photopolymerization of methyl methacrylate(MMA) with phenylsilane wasperformed. The molecular weights of the poly(MMA) containing SiH moieties were increased with augment of molar ratio of PhSiH3 over MMA by cross-linking via hydrosilation at the expense of isolated yield. Phenylsilane apparently influenced on the photopolymerization as a chain transfer agent and solvent.

Hydroiminoacylations of allyl and homoallyl alcohol and their derivatives with benzaldimine by Wilkinson's complex have been studied. All these terminal alkene derivatives except allyl alcohol were hydroacylated according to anti-Markownikoff's rule to give the corresponding linear alkyl compounds without showing oxygen directing effect, even though hydroiminoacylation of 3-acetoxy-1,5-hexadiene showed strong allyloxy directing effect over homoallyloxy directing effect in a 92:8 ratio. Solvolysis of 4-acetoxy-1-phenylbutan-1-one, previously prepared by hydroiminoacylation, in ethanol led to etherification giving 4-ethoxy-1-phenylbutan-1-one through neighbouring group participation, while that of 5-acetoxy-1-phenylpentan-1-one led to common transesterification giving 5-hydroxy-1-phenylpentan-1-one. Application of branched alkanols such as isopropanol and t-butanolin solvolysis of 4-acetoxy-1-phenylbutan-1-one underwent competition between etherification and transesterification.