Using an atom superposition and electron delocalization molecular orbital (ASED-MO) method, we have compared adsorption properties of adsorbates on the Pt(Ill) surface with the Pt(lll)/γ-Al203 surface in the ethylene hydrogenation reaction. In two-layer thick model systems, the calculated activation energy of the hydrogenation by the surface platinum hydride is equal to the energy by the hydride over supported platinum/γ-alumina. The transition structure on platinum is very close to the structure on the supported platinum/γ-alumina surface. Hydrogenation by the surface hydride on platinum can take place easily because the activation energy is about 0.5 eV less than hydrogenation by ethylidene. On supported platinum/,y-alumina the activation energy of the hydride mechanism is about 0.61 eV less than that of ethylidene mechanism. In one-layer thick model systems, the activation energy of hydrogenation by ethylidene is about 0.13 eV less than the activation energy of hydride reaction. The calculated activation energy by the hydride over the supported platinum y-alumina is 0. 24 eV higher than the platinum surface. We have found from this result that the catalytic properties of one-layer thick model systems have been influenced by the support but the two-layer thick model systems have not been influenced by the support.

A new polyamide was prepared from 4,4'-(hexafluoroisopropylidene)di-aniline and 4-[NN-bis(2-carboxyethyl)] amino-4'-nitrostilbene. This polymer was cast into thin films by spin coating cyclohexanone solution. After being poled, the electro-optic coefficients of electrode poled polymer films were measured by the reflection measurement technique using an incident laser beam of 1.3 Jim. The film poled at the field strength of 1.2 V/μm exhibited the electro-optic coefficient (r33) of 5.9 pm/V. The relaxation behavior of the poled polymer film was compared with other reported polymers bearing the same NLO chromophores. Due to stiff and highly polar nature of the backbone and also due to formation of interchain hydrogen bonds, this polymer reveals a slower relaxation characteristics. The polymer is amorphous and soluble in various organic solvents.

The Belousov-Zhabotinskii (BZ) reaction, which is composed of a bromate-organic acid-metal catalyst and an acidic solution is a commonly employed chemical oscillating reaction system. Cyclohexanedione (CHD) has been used as an initial organic substrate in oscillation systems. We studied each system of 1,4-CHD/BrO3-/Ce4/H+ and 1,3-CHD/BrO3-/Ce4+/H+ oscillating reactions, and studied the control of oscillating characters in a CHD/BrO3-/Ce4+/H+ batch system using a mixed substrate of 1,4-CHD and 1,3-CHD under a fixed total CHD concentration. In the mixed reactions, 1,4-CHD was used as a main substrate and small amounts of 1,3-CHD were used in order to vary the oscillatory behaviours by changing the mixing amount ratio of two substrates.

The phoisomerization process of symmetric carbocyanine dyes such as 3,3'-diethyloxadicarbocyanine iodide (DODCI), 3,3'-diethylthiadicarbocyanine iodide (DfDCI), 1,1'-diethyl-2,2'-dicarbocyanine iodide (DDI), 1,1'-diethyl-2,2'-carbocyanine iodide (DCI), and cryptocyanine (1,1'-diethyl-4,4'-carbocyanine) iodide (CCI) have been studied by measuring the steady state and time resolved fluorescence spectra and the ground-state recovery profiles. The steady-state fluorescence spectrum of photoisomer as a function of concentration and excitation wavelength provides the evidence that the fluorescence of photoisomer is formed by the radiative energy transfer from the normal form and the quantum yield for the formation of photoisomer is increased by decreasing the excitation wavelength. The fluorescence decay profiles have been measured by using the time correlated single photon counting (TCSPC) technique, showing a strong dependence on the concentration and the detection wavelength, which is due to the formation of excited photoisomers produced either by the radiative energy transfer from the non-nal form or by absorbing the 590 nm laser pulse. We first report the fluorescence decay time of photoisomers for these cyanine dyes. The experimental results are explained by introducing the semiempirical calculations. The ground state recovery profiles of DTDCI, DDI, and CCI normal forms have been measured, showing that the recovery time from the singlet excited state is similar with the fluorescence decay time.

It was found that the adsorption of a cobalt(III) complex with a macrocyclic ligand, C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc), was induced on a glassy carbon electrode by heavily oxidizing the electrode surface. Adsorption properties are discussed. The glassy carbon electrode with the adsorbed complex was employed to see the catalytic activities for the electro-reduction of O2. In the presence of oxygen, reduction of (hmc)Co3+ showed two cathodic waves in cyclic voltammetry. Compared to the edge plane graphite electrode at which two cathodic waves were also observed in a previous study, catalytic reduction of O2 occurred in the potential region of the first wave while it happened in the second wave region with the other electrode. A rotating disk electrode after the same treatment was employed to study the mechanism of the O2 reduction and two-electron reduction of O2 was observed. The difference from the previous results was explained by the different reactivity of the (hmc)CoOOH2+ intermediate, which is produced after the two electron reduction of (hmc)Co3+ in the presence of O2.

Fluorination of alkenyllithium reagents can be accomplished in acceptable yield under conditions which give rise to low competitive alkene formation. These reactions are abetted by the use of the low temperature soluble, mild fluorinating agent N-fluoro-N-tert-butylbenzenesulfonamide; "simpler" fluorinating reagents such as F2, XeF2 or FClO3 failed to give acceptable amounts of the fluoroolefin with these alkenyllithiums.

On-line preconcentration by direct precipitation with hydroxide has been developed and applied for the analysis of Cd in Inductively Coupled Plasma Atomic Emission Spectrometry. Cadmium is continuously precipitated with hydroxide and dissolved by nitric acid in on-line mode. Currently, the enrichment factor is more than 90 times for 20.0 mL of sample and could be further increased very easily. For a large sample throughput, 1.0 mL of sample loop is used and the enrichment factor is 4.5 with the sampling speed of 15/hr. The method has been applied to the analysis of NIST reference sample and has yielded good results with the certified value.

Several ABCH type chiral calix[4]arenes were prepared from monoalkyl calix[4]arenes by treating with various acyl halide, followed by reacting with benzoyl chloride in pyridine. These asymmetrically substituted ABCH type calix[4]arenes are obtained as racemates mixture which are confirmed by the chiral shift reagent in 1H NMR spectra. The molecular and crystal structure of 5-nitro-26-allyloxy-25-benzoyloxy-28-isobutyryloxy-27-hydroxycalix[4]arene 8a has been determined by the X-ray diffraction method. Two independent enantiomeric molecules are crystallized in a 1: 1 racemate mixture. They are in the partial cone conformation in which the benzoyloxy phenyl group is down. There is a bifurcated intramolecular hydrogen bonding involving three functional groups in each molecule.

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.