A solid state chemical approach to discover new mateials with enhanced thermoelectric properties is described. The aim is to construct three-dimensional bismuth chalcogenide framework structures which contain tonically interacting alkali or alkaline earth atoms. The alkali atoms tend to have soft "rattling" type phonon modes which result in very low thermal conductivity in these materials. Another desirable feature in this class of compounds is the low crystal symmetry and narrow band-gaps. Several promising materials such as BaBiTe3, KBi6.33S10, K2Bi8S13, β-K2Bi8Se13, K2.5Bi8.5Se14, Ba4Bi6Se13, Eu2Pb2Bi6Se13, Al1+xPb4-2xSb7+xSe15 (A=K, Rb), and CsBi4Te6 are described.

A solid state chemical approach to discover new mateials with enhanced thermoelectric properties is described. The aim is to construct three-dimensional bismuth chalcogenide framework structures which contain tonically interacting alkali or alkaline earth atoms. The alkali atoms tend to have soft "rattling" type phonon modes which result in very low thermal conductivity in these materials. Another desirable feature in this class of compounds is the low crystal symmetry and narrow band-gaps. Several promising materials such as BaBiTe3, KBi6.33S10, K2Bi8S13, β-K2Bi8Se13, K2.5Bi8.5Se14, Ba4Bi6Se13, Eu2Pb2Bi6Se13, Al1+xPb4-2xSb7+xSe15 (A=K, Rb), and CsBi4Te6 are described.

The oligo(methylsilene) (1) was treated with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalysts and with the group 6 metal carbonyl M(CO)6 (M = Cr, W) catalysts, producing the modified, cross-linked polymers. The average molecular weights and percent ceramic residue yields of modified polymers increase as the catalyst goes down from Ti to Hf and similarly as the catalyst goes down from Cr to W. An interrelationship between average molecular weights and percent ceramic residue yield is found within the respective group of catalysts, but is not observed as the catalyst goes down from Ti to W. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weights and similar percent ceramic residue yields as compared to the polymers modified with the group 6 metal carbonyl catalysts. The catalytic activities of group 4 metallocene combinations appear to be higher -100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls.

Electronic structures and properties of the organometallic precursors [Me2AlNHR]2 (R =Me, iPr, and tBu) have been calculated by the semiempirical (ASED-MO, MNDO, AM1 and PM3) methods. Optimized structures obtained from the MNDO, AM1, and PM3 calculations indicate that the N-C bond lengths are considerably affected by the change of the R groups bonded to nitrogen, but the bond lengths of the Al-N and Al-C bonds are little affected. This result is useful in explaining the experimental results for the elimination of the R groups bonded to nitrogen, and could serve as a guide in designing an optimum precursor for the AlN thin film formation.

ZnGa2O4: Mn phosphors were prepared by a new chemical process, and their photoluminescence and electron paramagnetic resonance characteristics were investigated. The chemical method showed a low temperature formation of phosphors and a rod-type shape of particles. The strong ultraviolet emission was observed in the undoped ZnGa2O4 phosphor, while strong green emission in the Mn2+-activated ZnGa2O4 phosphor. The green emission intensity of the phosphor prepared by the chemical method was much stronger than that prepared by the conventional method. This difference with preparation methods was interpreted as due to the difference in the distribution of Mn2+ in the host lattice. From EPR results, it was explained that the line intensity of the undoped ZnGa2O4 is associated with the electrical conductivity of this material and the concentration quenching of green luminescence of ZnGa2O4: Mn at higher Mn2+ concentration is attributed to the coupling by exchange interaction between Mn2+ ions.

The study of coupled relaxation for methyl spin system in 2,6-dichlorotoluene was performed on the basis of the magnetization mode formalism. Using five initial perturbing pulse sequences, eight experimntal data sets were obtained, which were fitted with theoretical expressions with nine spectral density parameters. The same experiment was carried out at both 50.3 MHz and 125.6 MHz in carbon frequency. The measured spectral densities at both fields are similar in the exception of that related with carbon random field term. Furthermore, from the dipolar spectral density, the physical values may be extracted depending on the model of molecular reorientation. For example, it was assumed that the molecular framework undergoes asymmetric diffusive rotational process and methyl group reorients by either diffusive rotation about its symmetry axis or jump among internal rotational potential minima.

Kinetic studies are carried out on the reactions of 2-chloro-2-propen-1-yl arenesulfonates with anilines and N,N-dimethylanilines in acetonitrilile at 45.0 ℃. The 2-chloro substituent is found to deactive the allyl moiety with considerable decrease in the rates. The sign and magnitude of the cross-interaction constant (ρxz 0.3) and the inverse secondary kinetic isotope effect (kH/kD 0.92) support an SN2 mechanism with a relatively tight transition state. The possibility of an SN2' mechanism can be safely precluded based on the ρxz values observed.

The charge transfer (CT) complex dyes between electron donor phenothiazine and electron acceptors namely, 2, 3-dichloro-1,4-naphtoquinone and 2,3-dichloro-5-nitro-1,4-naphtoquinone, were formed in the dichloromethane solution and electrochromic properties were studied using Bu4NC1O4 as supporting electrolyte. A 1 : 1 correspondence between the donor and acceptor molecules in the CT complex was found.

The dehydrogenation of ethylbenzene with carbon dioxide has been carried out over ZSM-5 zeolite-supported iron oxide catalyst as well as commercial catalyst (K-Fe2O3) and unsupported iron oxide (Fe3O4) for comparison. In the dehydrogenation over the ZSM-5 zeolite-supported iron oxide catalyst, ethylbenzene is predominantly converted to styrene by an oxidative pathway in the presence of excess carbon dioxide. Carbon dioxide in this reaction is found to play a role as an oxidant for promoting catalytic activity as well as coke resistance of catalyst. On the other hand, both of commercial catalyst and unsupported Fe2O4 exhibit considerable decrease in catalytic activity under the same condition. It is suggested that an active phase for the dehydrogenation with carbon dioxide over ZSM-5 zeolite-supported iron oxide catalyst would be rather a reduced and isolated magnetite (Fe3O4)-like phase having oxygen deficiency in the zeolite matrix.

The equivalent conductances for tetraethylammonium perchlorate (TEAP), tetrabutylammonium perchlorate (TBAP), tetrahexylammonium perchlorate (THAP), and tetradodecylammonium perchlorate (TDDAP) were measured in pyridine (Py) at 25 ℃. The measured data have been analyzed by Onsager conductance theory. From Kohirausch's law of independent migration of ion, the limiting ionic conductances of tetraalkylammonium ions were determined using the limiting ionic conductance of perchlorate cited from reference. Using those and viscosity of pyridine, the Stokes and hydrodynamic radii of tetraethylammonium, tetrabutylammonium, tetrahexylammonium, and tetradodechylammonium ions were calculated. And, the salvation numbers of corresponding ions were also calculated using the hydrodynamic and crystallographic radii and the volume of one pyridine molecule. From those results, the model of salvation for those ions was extracted by comparison with the model for ion salvation. And the electrostatic Gibbs free energy (ΔGel) fitted for our salvation model was calculated. Those of corresponding ions in pyridine at 25 ℃ also increased with increasing radii of tetraalkylammonium ions. This trend of ΔGel was explained by the different ion-solvent interaction between tetraalkylammonium ion and pyridine.

A simple apparatus for adding a modifying solvent to supercritical CO2 extractant was described. Small, fixed volumes (typically 100 μL) of liquid modifying solvents were delivered during the extraction process by use of an in-line high pressure loop injector and an air pump. Without disconnecting the extraction cell from the supercritical fluid extraction system, the modifying solvent was repeatedly delivered. The solvent modification device was optimized during the extraction of carbaryl and bis(acetylacetonato) copper(Ⅱ). Extraction recoveries from spiked filter paper and soil samples ranged between 22% and 109%, depending on the analyte and matrix components. The addition of polar modifying solvents were necessary to improve the extractability of the nonpolar CO2.

The treatment of 1,1-bis(phenylthio)-2,2,3,3,3-pentafluoropropylbenzene (1) with 2 equiv. of phenyllithium in THF at -78 ℃ resulted in the formation of isomeric mixture (70: 30) of trifluoromethylated 1,2-diphenylvinyl sulfide 2 in 87% yield. The further oxidation of 2 with m-chloroperbenzoic acid in methylene chloride afforded isomeric mixture (70:30) of trifluoromethylated 1,2-diphenylvinyl sulfone 3 in 87% yield. When 3 was reacted with carbon nucleophiles such as methyllithium, n-butyllithium, phenyllithium and lithium octylide, the corresponding addition-elimination adducts 4, 5, 6 and 7 were obtained in moderate to good yields. The reaction of 3 with 4 equiv. of tributyltin hydride in benzene at reflux temperature provided isomeric mixture (90 : 10) of trifluoromethylated 1,2-diphenylvinyl stannane 8 in 41% yield. The reaction of 8 with methyllithium in the presence of trimethylsilyl chloride gave isomeric mixtures (90: 10) of trifluoromethylated 1,2-diphenylvinyl silane 9 in 88% yield. Finally, the treatment of 8 with Br2 and 12 resulted in the formation of isomeric mixtures (90: 10) of trifluoromethylated 1,2-diphenylvinyl bromide 10 and iodide 11 in 72% and 90% yields, respectively.

The p-fluorobenzyl radical was generated from the p-fluorotoluene and vibronically excited in a corona excited supersonic expansion with inert buffer gases. The vibronic emission spectra of the jet cooled p-fluorobenzyl radical in the D1 → D0 transition have been observed in the visible region. The spectra exhibit several low frequency sequence bands in the vicinity of the every strong vibronic band. The characteristics of the sequence bands have been examined by varying the experimental conditions such as carrier gas and nozzle size to identify the origin of the transition in the spectra.

Mo/γ-Al2O3 catalysts were prepared by impregnation method in various conditions to identify the states of surface Mo species. TPR (Temperature-Programmed Reduction) and Raman spectroscopy were applied to analyze the surface Mo species. TPR analysis revealed that MoO3 was reduced to Mo through MoO2, the intermediate state and the increase of Mo loading enhanced the reducibility of Mo oxide till the formation of monolayer coverage. High temperature calcination induced oxygen defects in MoO3 giving their unstable states for easier reduction. Raman spectroscopy analysis showed that the increase of Mo loading induced the polymeric Mo oxide.

The (-)-polyoxamic acid 2 and its stereoisomer 3 have been prepared from D-glucono-δ-lactone which has three available stereocenters as required for 2 and 3. Key transformations included the selective cleavage of the terminal isopropylidene group.