Oxidative dimerization of methane to C2-hydrocarbons was performed over lead aluminate spinel catalysts. These spinel catalysts were prepared by co-precipitation, aerogel, and sol-gel methods. The active phase of lead aluminate oxides was found to be PbAl2O4 spinel. The activities of the catalysts were strongly dependent on the preparation method as well as the composition of PbAl2O4 phase. The proper oxygen mobility of PbAl2O4 spinel oxides appeared to be important to get high catalytic activity and selectivity for C2-hydrocarbon formation.

The conformational details of β-lactose are investigated through molecular dynamics simulations in conjunction with the adiabatic potential energy map. The adiabatic energy map generated in vacuo contains five local minima. The lowest energy structure on the map does not correspond to the structure determined experimentally by NMR and the X-ray crystallography. When aqueous solvent effect is incorporated into the energy map calculation by increasing the dielectric constant, one of the local minima in the vacuum energy map becomes the global minimum in the resultant energy map. The lowest energy structure of the energy map generated in aquo is consistent with the one experimentally determined. Molecular dynamics simulations starting from those fivelocal minima on the vacuum energy map reveal that conformational transitions can take place among various conformations. Molecular dynamics simulations of the lactose and ricin B chain complex system in a stochastic boundary indicate that the most stable conformation in solution phase is bound to the binding site and that there are conformational changes in the exocyclic region of the lactose molecule upon binding.

The structures of dehydrated Ca4Na4-A (a=12.243(1) Å) and of its bromine sorption complex (a=12.214(1) Å) have been determined by single crystal x-ray diffraction techniques in the cubic space groupPm&bar{3}m at 21(1) ℃. Both crystals were dehydrated at 360 ℃ and 2 X 10-3 Torr for 2 days and one crystal was treated with 180 Torr of bromine vapor at 24 ℃ for 1 h. The structures were refined to final error indices, R1=0.066 and R2=0.078 with 192 reflections and R1=0.109 and R2=0.093 with 100 reflections, respectively, for which I>3σ(I). In these structures, four Ca2+ and four Na+ ions are located on two different threefold axes associated with 6-ring oxygens, respectively. In Ca4Na4-A·6Br2, four Ca2+ ions are recessed 0.28(1) Å into the large cavity and four Na+ ions extend 0.63(1) Å into the sodalite unit. A total of six dibromine molecules are sorbed per unit cell. Each Br2 molecule approaches a framework oxide ion axially with O(1)-Br(1)=3.27(2) Å Br(1)-Br(2)=2.66(6) Å and O(1)-Br(1)-Br(2)=172(1)°, indicating a charge-transfer interaction.

A coverage of about 1 μm-sized pores of a membrane filter by four monolayers of maleic acids copolymers and poly(allylamine) (PAA) was attained by Langmuir-Blodgett (LB) technique through a covalent cross-linking followed a polyion complexation at the air-water interface. The copolymers were prepared to have side chains of hydrocarbon tail, carboxyl, and/or oligoether in the repeat unit. The surface pressure-area isotherms showed that the monolayers on an aqueous PAA have more expanded area than on pure water. The monolayers were transferable on a calcium fluoride substrate and a fluorocarbon membrane filter as Y deposition type, and the resulting LB films were characterized by FT-IR spectroscopy and scanning electron microscopy. A polymer network produced through interchain amide formation was confirmed in as-deposited films. The films were heat-treated in order to complete the cross-linking. SEM observation of the heat-treated film on a porous membrane filter showed that the four layer film was sufficiently stable to cover the filter pore of about 1 μm. Immersion of the film in water or in chloroform did not cause any change in its appearance on SEM and in FT-IR spectra.

The explicit results of the degrees of circularity for various kinds of completely polarized light in a nonpolar fluid composed of chiral molecules are obtained with the aid of the Ornstein-Zernike form for the correlation function of density fluctuations. Then, the results are in detail discussed in two limiting cases of critical region and compared with circular intensity differences.

1H NMR spectra of pyridine, α-, β-, and γ-picoline coordinated to the paramagnetic heteropolyanion [Ni3(PW9O34)2]12- (P2Ni3) are reported. NMR lines are assigned to [Ni3(ptl)n(PW9O34)2]12- (n=1, 2 or 3; ptl=pyridine-type ligand) on the basis of their [P2Ni3]/[ptl] dependence. The formation constants for γ-picoline complexes at 25 ℃ are K1=80, K2=610, and K3=190 L mol-1. The monopicoline complex has greater affinity for γ-picoline than P2Ni3. A degradation product, [Ni2(WO2)(PW9O34)2]12-, was also identified at low pH by measuring the NMR spectrum of pyridine coordinated to it. The isotropic NMR shifts come mainly from the contact interaction due to σ-electron delocalization.

The precursors of Ba1-xSrxTiO3(x=0.0-0.3) were prepared by the rapid addition of aqueous solution of titanyl oxalate to the mixed aqueous solution of barium and strontium at room temperature. The optimum pH was theoretically calculated from the equilibrium constants and solubility products. The chemical formula of the precursors obtained corresponded to Ba1-xSrxTiO(C2O4)2·4H2O(x=0.0-0.3) as determined by thermal gravimetric analysis. The precursors were converted to stoichiometric Ba1-xSrxTiO3(x=0.0-0.3) with a particle size of 0.01-0.04 μm. As increasing the amount of strontium substituted to barium sites, the structure of crystal changed from the tetragonal phase to the cubic and the unit cell volume was decreased.

The rapid quenching dynamics of F center excitation by OH- defects in KCl crystals are investigated by monitoring ground state absorption bleach recovery, using a picosecond streak camera absorption spectrometer. F center absorption bleach in OH--doped crystals shows three distinguishable recovery components with the current temporal resolution, designated as slow, medium and fast components. The slow one is due to the normal relaxation process of F* centers as found in OH--free crystals. The others are consequent on energy transfer from electronically excited F centers to OH--vibrational levels. The fast component is a minor energy transfer process and resulting from the relaxation of somewhat distant, not the closest, associated pairs of F* and OH- defects. The energy transfer between widely separated F* and OH- defects opens up a recovery process via the medium component which is assisted by OH- librations, lattice vibrations and OH- dipole reorientations. The quenching behaviors of F* luminescence and photoionization by OH- are explained well by the relaxation process of the medium component.

The comparative molecular field analysis (CoMFA) method has been employed to correlate the apparent lipophilicity (logkw) and global lipophilicity (logP) for orthopramide derivatives. This study demonstrated that CoMFA is an excellent method in predicting the complex properties of molecules such as apparent lipophilicity (logkw) or lipophilicity (logP). The better predictability of lipophilicity by introducing logkw as an independent descriptor suggests that the HPLC capacity factor measured in a buffer of pH 7.5 (logkw) can be effectively utilized in the prediction of global lipophilicity.

In this work, we focused on the setup of the tools for the analysis of the final rotational state distribution of photofragments in vibrational predissociations of triatomic van der Waals molecules A-B2. We found that reflection principle used for the direct photodissociation processes can also be applied to find out the final rotational state distributions for indirect photodissociation processes. The quantity which represents the strength of rovibrational coupling between the quasi-bound state and the final state is reflected into the mirror of the classical angular momentum function, instead of the initial state before light absorption used in the reflection principle of direct processes. The sign change in the first derivative of the interaction potential with respect to the bond distance of B2 is found to be the source of the binodal structures in the final rotational distributions of photofragments in the model system studied in this work. In MQDT analysis, short range eigenchannel basis functions were found to be localized in angle, in the previous work [Lee, C.W. Bull. Korean Chem. Soc. 1995, 16, 957.] and may be called angle functions. Angle functions enjoy simple geometrical structures which have simple functional relations with the final state distributions of photofragments. Two processes take place along the angle functions which resemble the quasi-bound state and dominate over other processes. Two such angle functions are found to be not only localized angularly but also localized either one of ends of B2 in motions along the bond of B2. These dominating photodissociation processes, however, cancel each other. This cancellation causes photodissociation to depend sensitively on the interaction potential at other angles than the dominant one. Part of potential surface where much larger torque exists can now play an important role in photodissociation. MQDT also enables us to see which processes play important roles after cancellation. This is done by examining the amounts of time delayed by asymptotic eigenchannels.

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

A 86:14 isomeric mixture of 3,4-[3'-(dichlorosilyl)isopropyl]benzo-1,1-dichloro-1-silacyclopentene and 3,4-[2'-(dichlorosilyl)isopropyl]benzo-1,1-dichloro-1-silacyclopentene was prepared by the regioselective Friedel-Crafts reaction of allyldichlorosilane with 3,4-benzo-1,1-dichloro-1-silacyclopentene catalyzed by Lewis acid AlCl3. The structure of the products was confirmed by methylation with methylmagnesium bromide and by methoxylation with trimethylorthoformate.

An efficient synthesis of 6,8-dioxa-1,4-diazacyclopenta[b]phenanthren-5-one (Pyrazinopsoralen) (4) has been carried out by the Suzuki coupling reaction as a key step starting from 5-bromo-6-methoxybenzofuran (6) and methyl 2-iodo-3-pyrazinecarboxylate (8).

The pKa values of benzyltetrahydrothiophenium halides 1a-f in water have been estimated by measuring the absorbances of the solution in aqueous hydroxide ion solution. Assuming that the ratios of the activity coefficients remains close to unity, the absorbance of the solution can be expressed as A/[SH]o=(εSH+εS-K[OH-])/(1+K[OH-]), where A, [SH]o, K, εSH, and εS- are the absorbance of solution, the initial concentration of 1a-f, the equilibrium constant, and the extinction coefficients for SH and S-, respectively. The εS- and K values that best fit with this equation were calculated by a nonlinear regression analysis with a large number of absorbance data determined at different [OH-] and [SH]o. The pKa values of the SH were then calculated with the relationship Ka=-log K+14. The validity of this method has been demonstrated by the excellent agreements between the experimental and literature pKa values of three organic acids. The pKa values of 1a-f estimated by this method are in the range of 12.5-15.3 and correlate well with the Hammett equation. The large negative deviation for the pKa values of 1e and 1f from the Hammett plot has been attributed to the extra hydrogen bonding between the phenyl group and water molecules attracted by the hydrophilic substituents.