Solvatochromic effect and hydrogen bonding interaction of NPNOH, NPNO- and NPNOR were investigated. Electronic transition energies of the dyes were plotted against empirical solvent polarity parameters, Taft's π* and Reichardt's ET(30). Good correlations were observed when the excitation energies were plotted against the energy calculated by multiple linear regression method which was developed by Taft. There is an intrinsic difference between betaine for ET(30) polarity scale and the azoderivative, which is derived from the specific hydrogen bond incurred with probe molecules and solvents. The hydrogen bonding plays a very important role for stabilization of an excited state molecule by solvents especially when a solute possesses a negative charge as with NPNO-.

The resonance ionization mass spectrometry (RIMS) system with angular reflectron type time-of-flight mass spectrometer (AREF-TOFMS) has been developed and characterized. The system is applied for the ultratrace determination of Pb element. The 2-color 3-photon laser ionization scheme is adopted for the study and the mass resolution of the system is determined as T/ΔT=1680. The calibration curve for Pb is obtained in the range of 100 ppb to 0.01 ppb by using standard solutions. The minimal amount of detection for the present RIMS system is determined as less than 100 femtograms (10-13 gram).

The preconcentration and determination of trace Cd(Ⅱ), Cu(Ⅱ), Pb(Ⅱ), Mn(Ⅱ) and Zn(Ⅱ) in water samples were studied by the precipitate flotation using La(OH)3 as a coprecipitant. The analytes were quantitatively coprecipitated by adding 3.0 mL of 0.1 M La(Ⅲ) solution in a 1,000 mL water sample and adjusting the pH to 9.5 with NaOH solution. After the addition of the 1:8 mixed surfactant solution of each 0.1% sodium oleate and sodium lauryl sulfate, the solution was stirred with a magnetic stirrer for 10 minutes. The precipitates were floated to the surface by bubbling with nitrogen gas and collected in a small sampling bottle. The precipitates were dissolved in nitric acid and then the solutions were diluted to 25.00 mL with a deionized water. The analytes were determined by flame atomic absorption spectrometry. This procedure was applied to the waste water analysis. This technique was simple, convenient and especially rapid for the analysis of a large volume of sample. And also, from the recoveries of better than 92% which were obtained from real samples, this method could be judged to be applicable to the preconcentration and quantitative determination of trace elements in water samples.

Single crystals of (ZnSe)1-x(CuMSe2)x (M=Al, Ga, or In) were grown by chemical vapor transport technique. Powdered polycrystalline samples of (ZnSe)1-x(CuMSe2)x (M=Al, Ga, or In) were also prepared by the direct combination of the elements. The chemical composition of these single crystals was determined by comparing their lattice parameters with those of the standard polycrystalline samples. The IR transmission range of single crystals of (ZnSe)1-x(CuMSe2)x (M=Al, Ga, or In) is slightly narrower than that observed for pure ZnSe. However, these materials still show good transmission in the long-wavelength IR range. The addition of small amounts of CuMSe2 (M=Al, Ga, or In) considerably increases the hardness of ZnSe.

The influence of protecting groups on the β-sheet-structure-stability of protected peptides was studied in organic solvents. α-amino groups, carboxyl groups and side chain functional groups of model peptides were protected by suitable groups commonly used in peptide synthesis. The difference of the solubilities of model peptides was investigated by the solvent-titration method by using IR absorption spectra. The β-sheet structure of model peptide in CH2Cl2 was easily disrupted by increasing the amounts of DMSO. The β-sheet-structure-stabilizing potentials of each protecting group showed similar behaviors except Npys, Mts and Z2. The result exhibits that the < SPβ > values of protected peptides are almost independent of the kinds of their protecting groups.

The kinetics of the reaction between O(3P) and C2H4 was investigated by measuring time-dependent concentrations of OH resulting from the reaction by using the LIF detection. Oxygen atoms were generated by titrating microwave discharged N2/He with NO to the chemiluminescent end point. The operating pressures in the flow reactor ranged from 5 to 15 torr and the mixtures consisted of He/O(3/P)/C2H4 in the approximate ratios from 100/1/0.1 to 100/1/1. The controlled residence time prior to the detection were estimated to be 0.8-17 ms at the reactor pressure of 7 torr. Experimentally determined profiles both in shape and magnitude were compared with the computed OH density for a specified set of experimental parameters, allowing us to arrive at a complete mechanism for the reaction of O(3P) with ethylene.

A series of samples in the Sm1-xSrxCoO3-y(x=0.00, 0.25, 0.50, 0.75 and 1.00) system has been prepared at 1200 ℃ under ambient atmosphere. The X-ray diffraction patterns of the samples with x=0.00 and 0.25 are indexed with orthorhombic symmetry like GdFeO3 and x=0.50 appears to be perfectly cubic. In the tetragonal system (x=0.75), the structure is similar to that of SrCoO2.80. The composition of x=1.00, SrCoO2.52, shows the brownmillerite-type structure. The reduced lattice volume is increased with x value in this system. The chemical analysis shows the τ value (the amount of the Co4+ ions in the system) is maximized at the composition of x=0.50. Nonstoichiometric chemical formulas are determined by the x, τ and y values. The electrical conductivity has been measured in the temperature range of 78 to 1000 K. The activation energy is minimum for those of x=0.25 and x=0.50 with metallic behavior. First-order semiconductor-to-metal transition of SmCoO3 is not observed. Instead, a broad, high-order semiconductor-to-metal transition is observed. In general, the effective magnetic moment is increased with increasing τ values at low temperature. At high temperature, the magnetic moment is maximum for that of x=0.00. The 3d-electrons are collective and give ferromagnetism in x=0.50.

The relative dissociation constants of 4-substituted bicyclo[2,2,2]octane-1-carboxylic acids, 4-substituted quinuclidines, and 3-and 4-substituted pyridines were collected from a number of sources. In order to understand the actual substituent effects with a combination of inductive effect (σI) and resonance effect (σR) components. The DSP correlation has been employed statistically for each of the p-and m-series. The inductive effect from the m-position was 1.2 times more effective than that from the p-position and the requirement of σR+ for the best-fit led to the conclusion that pyridine system belongs to the σ+-class reactivity. Also compared with results from Yukawa-Tsuno's LArSR treatment and relevant treatment.

The reaction of chloro(methylthio and arylthio)methanephosphonate (1) and Pummerer-type reaction of sulfinylmethanephosphonate (2) with nucleophiles such as aromatic compounds and thiols were examined. The direct chlorination of (methylthio and arylthio)methanephosphonate with N-chlorosuccinimide (NCS) led to the formation of monochlorinated phosphonates (1) in good yield. The reaction of 1 with aromatic compounds and thiols in the presence of stannic chloride afforded a variety of aryl(methylthio)methanephosphonates (3) and thioacetals of formylphosphonates (4), respectively. Phosphonates 3 and 4 were also obtained from the reaction of Pummerer intermediate, generated from sulfinylmethanephosphonate (2), with aromatic compounds and thiols, respectively. A versatile reaction conditions to generate Pummerer intermediate were examined. The best condition was the combination of trifluoroacetic anhydride with stannic chloride. All reactions may involve an initial formation of α-phosphoryl thiocarbocation and a subsequent nucleophilic attack of aromatic compounds and thiols.

The influence of carrier solutions on particle retention was studied by varying surfactants and ionic strength in flow field-flow fractionation. Experiments were made with five different submicron polystyrene latex standards at three different types of surfactants and seven different ionic strengths. Departures in particle retention from the general theory were observed. At low ionic strength, it is shown that migrating sample zone is clearly lifted away from the ideal equilibrium height and that the repulsive interaction dominates between the particle and the channel wall. As ionic strength increases up to a certain level, particle retention becomes closer to the general theory. Further increase in ionic strength is shown to prolong the retention. An optimum regime of ionic strength is also suggested with the proper choice of surfactants.

Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

α-Linked D-altropyranosidic derivatives were obtained by configurational change at C-3 of α-D-mannopyranosides as the key step in preparation of allyl and methyl α-D-glycopyranosides of 6-deoxy-D-altro-heptose. The manno-altro conversion was effected by sequential reactions of Swern oxidation and stereoselective borohydride reduction. Allyl 4,6-O-benzylidene-2-O-p-methoxybenzyl-α-D-mannopyranoside was transformed to the corresponding altropyranoside via 3-oxo-arabino-hexopyranoside. Allyl 7-O-benzyl-6-deoxy-3,4-O-isopropylidene-α-D-altro-heptopyranoside has been prepared as a glycosyl acceptor to be coupled with β-D-GlcpNAc-(1→3)-α-D-Galp glycosyl donor for the synthesis of an O-antigen repeating unit of Campylobacter jejuni serotypes O:23 and O:36. Stereoselective borohydride reduction also succeeded in yielding methyl 2,4,7-tri-O-benzyl-6-deoxy-α-D-altro-heptopyranoside from the corresponding 3-oxo-α-D-arabino-heptopyranoside. C-6 Homologation was achieved by sequential reactions of cyanide displacement of 6-sulphonates, reduction of the resulting heptopyranosidurononitrile with diisobutylaluminum hydride, hydrolysis of the imine, and further reduction with sodium borohydride.

The cluster distributions for different concentrations of 1,4-dibromonaphthalene (DBN) in 4,4'-dibromobenzophenone (DBBP)/1,4-dibromonaphthalene (DBN) choleic acid were determined by a computer simulation in order to model the energy transfer dynamics. The results of the simulation indicate that long range interaction between molecules further apart than nearest does not occur and energy transfer efficiency is restricted by single range interaction. The results also demonstrate that the trapping is diffusion limited. The energy transfer rate is reduced by a factor of 15 in DBBP/DBN choleic acid realtive to that in DBBP/DBN doped into polystyrene due to the larger distance between molecules.

The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

The internal standard method, which is widely used in chromatographic techniques, is applied to the size exclusion chromatography for the on-line determination of dn/dc value of the sample. This method is found to provide the dn/dc value with suitable accuracy in determining the absolute molecular weight and the molecular weight distribution of the polymers when a light scattering detector is used.

Based on the collisional time correlation function (CTCF) formalism, Kim and Micha derived a simple expression which gives nascent rotational state distribution of molecules after collision with fast atoms.32 The expression is valid when the collision time is short and the collision is impulsive in nature. This expression has been applied to analyze the experimentally measured, state resolved rotational distribution of CO2 in various types of vibrational levels, i.e., (0001), (0111), (0002), and (1000/0200). The theoretical distributions obtained from this CTCF based expression can represent the experimentally measured rotational distributions remarkably well, and have been found to be much superior to those obtained from other simple theories such as Boltzmann distribution, prior distribution, breathing ellipsoid model, and phase space statistical calculation.

Solution-state structure of native F430 was determined by using NMR methods and NMR-based distance geometry (DG) computations. Structures were generated with loose NOE-derived interproton distance restraints (2.0-2.5 Å, 2.0-3.5 Å and 2.0-4.5 Å for strong, medium, and weak NOE cross-peak intensities, respectively). 2D NOESY back-calculations of structures were subsequently carried out for establishing the consistence between experimental data and DG-model structures. The back-calculated 2D NOESY spectra of resulting DG structures were well consistent with experimental 2D NOESY spectra. Superposition of 20 independent structures with macrocyclic ring atoms and all atoms of F430 afforded pairwise root mean square deviations (RMSD) of 0.025-0.125 Å and 0.64-1.3 Å, respectively. The macrocyclic rings of structures are well converged to a unique conformation with saddle-shaped deformation whereas most of side chains are not converged. The average dihedral angle (N1-N2-N3-N4, 27.78±1.50°) of 20 DG-structures exhibits that the macrocyclic ring conformation is puckered as much as 12,13-diepimeric F430 (28.75±4.07°).

A series of excitation spectra (7Fo→5Do transition) of Eu(Ⅲ) ion in aqueous solution ([Eu(Ⅲ)]=1.12 × 10-2 mol L-1; pH 1.0 to 7.0) were obtained under CO2 free atmosphere using a pulsed tunable dye laser system. The broad and low intensity spectra (peak maximum: 578.89 nm) showed that the trivalent ion (Eu3+) underwent a low degree of hydrolysis at pH below 6.0. Eu(Ⅲ) hydroxo complex formation seemed more significant at pH above 6.0, shown by the occurrence of intense new peak at 578.63 nm. The spectra of those solutions prepared in N2 atmosphere showed no signs of the presence of interfering carbonate species. The Eu(Ⅲ) hydroxo complex formation was not observed when complexation studies between Eu(Ⅲ) ion and weak organic acids (e.g. glutarate and diglycolate) were conducted at pH 6.0 or below.

Kinetic studies are carried out on the reaction of S-phenyl dithiobenzoates with benzylamines in acetonitrile at 30.0 ℃. Small magnitude of ρX (βX) as well as ρZ (βZ) obtained suggests rate-limiting nucleophilic attack of the thiocarbonyl carbon. This is supported by the unusually small magnitude of ρXY and ρYZ, albeit their signs do not agree with those expected. Moreover, the inverse secondary kinetic isotope effects (kH/kD<1.0) involving deuterated benzylamine nucleophiles are also in line with the proposed mechanism.

The surface structure of the adsorption site for the identification of active sites involved in the Ziegler-Natta catalyst was studied by surface science techniques. As an example of a real catalyst, TiCl3 single crystals were prepared in a gradient furnace designed for this study and characterized by Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED) under ultrahigh vacuum condition. The chlorine covered Ti (0001) surface was employed as a model catalyst for the study of Ziegler-Natta catalyst. The diffuse LEED (DLEED) technique for the surface structural determination was applied to this disordered chlorine adsorbed on Ti (0001) surface. The diffuse scattering intensities were measured by a TV-computer method using a low light level video camera. From an analysis of two catalyst systems, the informations for the surface structure of the model catalyst surfaces were derived.