The synergistic extraction of palladium(Ⅱ) was studied with 1,2-dichloroethane containing thenoyltrifluoroacetone (TTA; HA) and tri-n-octylphosphine oxide (TOPO; S). The main composition of synergistic adduct extracted into 1,2-dichloroethane phase was found to be PdA2S2. The equilibrium constants of the synergistic reaction were calculated. The application of this method to synthetic mixture for the separation of Pd from Pt was developed.

The synthesis of new bismuth-barium containing members of layered cuprates with 2201 type structure was reported. By solution calorimetry the formation enthalpies for Bi2MLaCuO6.5 (M=Ba, Ba0.5Sr0.5, Sr) were obtained. Crucial influence of partial oxygen pressure and size of lanthanoid on stability of layered cuprates was shown. Electronic states of variable valence atoms were studied by voltammetry of solids.

A new synthetic route to chiral liquid crystal dopant, 4-[2-(7S-methylnonanyl)oxy-5-pyrimidinyl]phenyl(2S,3S)-2-chloro-3-methylpentanoate (1), starting from 4-nitrophenylacetic acid is described. The key intermediate methylthiopyrimidine compound (8) has been synthesized from 4-nitrophenylacetic acid by Vilsmyer-Haack reaction followed by the formation of pyrimidine ring, and then converted to chiral ester (1) by the replacement of nitro group by (2S,3S)-2-chloro-3-methylpentanoic acid 2 through the formation of diazonium salt.

Ultrathin networks of itaconic acid copolymers and poly(allylamine) were produced by a Langmuir-Blodgett (LB) technique employing a double-chain amine as a monolayer template which was subsequently removed by extraction after thermal crosslinking. Itaconic acid copolymers used were copoly (itaconic acid-ethyl vinyl ether) and copoly (itaconic acid-n-butyl vinyl ether). The polyion-complexed monolayers of three components consisting of template amine, itaconic acid copolymer and poly (allylamine) were formed at the air-water interface. The Langmuir film properties have been studied by the surface pressure-area isotherm and fluorescence microscopy. The monolayers were transferred on solid substrates and were characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy (SEM). Two-dimensional polymer networks were formed through imide or amide linkages by heat treatment under vacuum. The heat-treated films were extracted with chloroform after immersion in aq. sodium chloride to remove the template amines. SEM observation of a LB film on a porous fluorocarbon membrane filter with pore diameter of 0.1 μm showed covering of the pores by six layers in the polyion complex state.

The adsorption behaviors of two major components purified, endo Ⅱ and exo Ⅱ, from Trichoderma viride were investigated using microcrystalline cellulose with different specific surface area as substrates. Adsorption was found to apparently obey the Langmuir isotherm and the thermodynamic parameters, ΔH, ΔS, and ΔG, were calculated from adsorption equilibrium constant,K. The adsorption process was found to be endothermic and an adsorption entropy-controlled reaction. The amount of adsorption of cellulase components increased with specific surface area and decreased with temperature and varied with a change in composition of the cellulase components. The maximum synergistic degradation occurred at the specific weight ratio of the cellulase components at which the maximum affinity of cellulase components obtains. The adsorption entropy and enthalpy for respective enzyme system increased with specific surface area increase. The adsorption entropy was shown to have a larger value with enzyme mixture.

The reaction of Co2(CO)8 with 3,6-di-tert-butyl-1,2-benzoquinone in the presence of the respective 4,4'-chalcogenobispyridine results in the coordination polymers of [CoⅢ(4,4'-X(Py)2)(DBSQ)(DBCat)]n (X=S, Se, Te; Py=pyridine; DBSQ=3,6-di-tert-butylsemiquinone; DBCat=3,6-di-tert-butylcatechol). The title compounds undergo an intramolecular Cat → Co electron transfer, and thus change toward the [CoⅡ(4,4'-X(Py)2)(DBSQ)2]n at elevated temperature. The temperature-switching properties of the compounds directly depend upon the electronegativity of the chalcogen atom of the 4,4'-chalcogenobispyridine coligands. The spectroscopic data disclose that the properties of [CoⅢ(4,4'-S(Py)2)(DBSQ)(DBCat)]n and [CoⅢ(4,4'-Se(Py)2)(DBSQ)(DBCat)]n are similar each other in contrast to those of [CoⅢ(4,4'-Te(Py)2)(DBSQ)(DBCat)]n.

Catalytic chlorination of chlorobenzene was studied in vapor phase using various solid-acid catalysts such as silica-alumina, alumina, zeolite and a modified clay prepared by impregnating bentonite with ferric chloride. The conversions of both chlorine gas and chlorobenzene showed high over silica-alumina, alumina and modified clay catalysts. However relatively large amounts of polychlorinated benzene derivatives were also observed. The active species of catalytic activity in chlorination of chlorobenzene in vapor phase were proved to be as Lewis acid sites by in-situ IR experiments. The strength of Lewis acid sites which were effective for the vapor-phase chlorination seemed to be having Hammett acidity Ho >-3.0. The selectivity to dichlorobenzenes was proved to be high over the zeolite catalyst due to their shape-selective properties. p-Dichlorobenzene or dichlorobenzene selectivities were improved more or less by changing the reaction conditions.

Since much studies have been performed concerning the electrochemical behaviors and the practical applications of PB based devices, little has yet reported to investigate the best condition for the preparation for PB thin films. As considered some factors(peak shape, peak current, and peak separation) from the i-V curves, the optimal condition in the film growth were investigated under various immersion solutions. An electron-transfer processes of Fe2+/Fe3+ and Fe(CN)63-/4- redox couples were considered by measuring the observed currents as a function of the rotation velocity. The standard heterogeneous electron-transfer rates for these films and bare Au disc electrode in 10-3 M Fe2+/Fe3+ solution, applied at +0.65 V vs. SCE, were 6.14 × 10-3 and 7.78 × 10-3 cm/s, respectively, obtained using a rotating disc electrode. In case of the addition of potassium ion, the rate constants for these Fe2+/Fe3+ system on thin films of PB and bare electrode were given a little high values. The electron transfer rate for 10-3 M Fe(CN)63-/4- were 4.55 × 10-3 and 6.84 × 10-3 cm/s, respectively. The conductivity as directly determined during obtained the voltammogram, was 2.2 × 10-7 (Ω·cm)-1. This value is similar magnitude to that calculated from bulk sample.

YSe1.83 was synthesized by vapor transport technique and its crystal structure was determined. The structure was isostructure of LaTe2-x, which was layered structure consisting of two-atom thick layers of YSe with distorted NaCl-type structure and one-atom thick layer of Se. The substructure of YSe1.83 was tetragonal with space group of P4/nmm and a=4.011(2) and c=8.261(3) Å with final R/Rw=6.4/6.9 %. The superstructure with asuper=2a, bsuper=6b and csuper=2c was found. The measurements of electronic and magnetic properties of this compound indicate that it is an electronic insulator and diamagnet.

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

Metallic iridium and rhodium powders prepared from the reactions of [M(COD)(PhCN)2]ClO4 (M=Ir(1), Rh(2); COD=1,5-cyclooctadiene) with hydrogen at room temperature in methylene chloride show catalytic activities for hydrogenation of arenes at room temperature under atmospheric pressure of hydrogen. Most substituents (CH3, COOH, NO2, CH2OH, CHO, OPh, OCH3, C=C, halogens and CH2Cl) on aromatic ring suppress the rate of the hydrogenation of the aromatic ring while the aromatic ring hydrogenation of phenol and 1,4-dihydroxobenzene is faster than that of benzene over these metallic powders. Hydrogenation of benzoic acid occurs only at the aromatic ring leaving the COOH group intact over iridium metal powders while benzoic acid is not hydrogenated at all over rhodium metal powders. Carbonyl, nitro, acetylenic and olefinic groups on an aromatic ring are hydrogenated prior to the aromatic ring hydrogenation. Hydrogenolysis of OH groups of phenol, benzyl alcohol and 1,4-dihydroxobenzene, and hydrodehalogenation of halobenzenes, benzyl halides and cinnamyl chloride also occur along with the hydrogenation of aromatic ring.

The crystal structure of K92-X (K92Al92Si100O384), a=25.128(1) Å, dehydrated at 360 ℃ and 2X 10-6 Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd&bar{3} at 21(1) ℃. The structure was refined to the final error indices R1=0.044 and Rw=0.039 with 242 reflections for which I<3σ(I). In this structure, ninety-two K+ ions are located at the five different crystallographic sites. Sixteen K+ ions are located at the centers of the double six rings (site I; K(1)-O(3)=2.65(2) Å and O(3)-K(1)-O(3)=92.0(6)°). About twelve K+ ions lie at site I' in the sodalite cavity opposite double six rings (D6R's) and these K+ ions are recessed ca. 1.62 Å into the sodalite cavity from their O(3) plane (K(2)-O(3)=2.74(2) Å, O(3)-K(2)-O(3)=88.5(8)°). About thirty-two K+ ions are located at the site II in the supercage and these K+ ions are recessed ca. 1.20 Å into the supercage from their O(2) plane (K(3)-O(2)=2.64(2) Å, and O(2)-K(3)-O(2)=101(1)°). About twenty-two K+ ions lie at the site III in the supercage opposite 4-ring ladder and the remaining ten K+ ions lie at the site III' near the 4-ring ladder in the supercage (K(4)-O(4)=2.88(3) Å, O(4)-K(4)-O(4)=79.8(9)°, K(5)-O(4)=2.8(2) Å, and O(4)-K(5)-O(4)=68(5)°).

The reaction between CH3 radicals and H2 was investigated behind incident shock waves at temperatures between 1308 and 1825 K by following the consumption of CH3 using a time resolved UV absorption method at 213.9 nm. The rate coefficient expression 1.10 X 1013 exp(-7370 K/T) cm3mol-1s-1 for the reaction of CH3 with H2 was derived.

As an extension to the Kramers' restricted Hartree-Fock (KRHF) method [J. Comp. Chem., 13, 595 (1992)], we have implemented the Kramers' restricted configuration interaction (KRCI) program in order to calculate excited states as well as the ground state of polyatomic molecules containing heavy atoms. This KRCI is based on determinants composed of the two-component molecular spinors which are generated from KRHF calculations. The Hamiltonian employed in the KRHF and KRCI methods contains most of all the important relativistic effects including spin-orbit terms through the use of relativistic effective core potentials (REP). The present program which is limited to a small configuration space has been tested for a few atoms and molecules. Excitation energies of the group 14 and 16 elements calculated using the present KRCI program are in good accordance with the spectroscopic data. Calculated excitation energies for many Rydberg states of K and Cs indicate that spin-orbit terms in the REP, which are derived for the ground state, are also reliable for the description of highly excited states. The electronic states of the polyatomic molecule CH3I are probed from the molecular region to the dissociation limit. Test calculations demonstrate that the present KRCI is a useful method for the description of potential energy surface of polyatomic molecules containing heavy atoms.