Alternating multilayer films of a cationic bipolar amphiphile and an anionic polyelectrolyte were prepared by a self-assembly method based on electrostatic attraction between opposite charges. The bipolar amphiphile contains an azobenzene unit in order to allow for a trans-cis photoisomerization to take place. Optical birefringence or dichroism was induced in the self-assembled film upon linearly polarized light irradiation. This dichroism could be reversibly written and erased by irradiation with light of an appropriate wavelength.

The catalytic transformation of sterically bulky tertiary stannane n-Bu3SnH by the Cp2MCl2/Red-Al (M=Ti, Zr, Hf) and M(CO)6 (M=Cr, Mo, W) catalysts yielded two kinds of catenated products: one is a cross-linked polystannane as minor product, and the other is hexabutyldistannane (n-Bu3Sn)2 as major product. The distannane was produced by simple dehydrocoupling of n-Bu3SnH, whereas the cross-linked polystannane could be obtained via redistribution/dehydrocoupling combination process of n-Bu3SnH. The redistribution/dehydrocoupling combination process may initially produce a low-molecular-weight oligostannane with partial backbone Sn-H bonds which could then undergo an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane.

2-Tetrahydropyranyl methacrylate with a self-crosslinkable moiety was copolymerized with methyl methacrylate and 4-[(2-methacryloxyethyl)methylamino]-4'-nitrostilbene or 4-[(2-methacryloxyethyl)ethylamino]-4'nitroazobenzene to provide second-order nonlinear optical property. Glass transition temperatures (Tg of the copolymers are around 140 ℃. The copolymers were soluble in common organic solvents such as tetrahydrofuran (THF), cyclohexanone, and N,N-dimethylformamide (DMF). Poling was carried out at 140 ℃ for 20 min and identified with UV-Vis spectroscopy. Electro-optic coefficient (r33) of copolymer was 62 pm/V for polymer 2 at 633 nm, and relaxation did not remarkably occur due to the formation of a crosslinked network at 200 ℃ for 15 min.

Two kinds of second-order nonlinear optical copolymers were prepared by the copolymerization of the vinyl monomers containing NLO chromophore, methacrylic acid, and methyl methacrylate or butyl methacrylate. Glass transition temperatures (Tg of copolymers were around 130 ℃. The copolymers were soluble in common organic solvents such as tetrahydrofuran (THF), cyclohexanone, and N,N-dimethylformamide (DMF). The crosslinked copolymer was obtained by thermal treatment using pentaerythritol tetrakis(2-mercaptoacetate) as a crosslinker and became insoluble in tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). Poling was carried out at 120 ℃ for 20 min and identified with UV-Vis spectroscopy. Electro-optic coefficient (r33) measurement showed a value of 35 pm/V for polymer 2 at 633 nm. Temporal stability of copolymers was improved owing to the crosslinked network, which was successfully obtained at 170 ℃ for 30 min after poling.

Spatial(radial and height) distributions of excited argon species are measured for an inductively coupled plasma under five operating conditions: 1) no carrier gas, 2) carrier gas without aerosol, 3) carrier gas with desolvated aerosol, 4) carrier gas with aerosol, 5) carrier gas with aerosol and excess lithium. A complete RF power mapping of argon excited states is obtained. The excited states of argon for a typical analytical torch rapidly diffuse towards the center in the higher region of the plasma. The presence of excess lithium makes no significant change in the excited states of argon. The increase in the RF power increases the intensity of argon excited states uniformly across the radial coordinate.

The aerobic reaction of 2-(acetylpyridine)-S-methyldithiocarbazate (acpy-mdtcH) and 2-(acetylpyridine)-N-phenylthiosemicarbazate(acpy-phTscH) with manganese(Ⅱ) acetate affords Mn(acpy-mdtc)2 and Mn(acpyphTsc)2, respectively. The spectroscopic data and X-ray structure of Mn(acpy-mdtc)2 are reported. Crystal data for Mn(acpy-mdtc)2; C18H20N6S4Mn, mol wt 503.58, monoclinic crystal system(P21/c) a=12.240(5) Å, b= 10.918(l) Å, c=17.651(3) Å, β=105.93(2), and V=2268(l) Å3, Z=4, 5071 data collected with 0°< 2θ < 52.64°, 2995 data with I > 3σ(I), R= 0.046, Rw= 0.065. The ligands act as tridentate NNS donors. The two Mn-S distances are not equal, and respectively 2.512(2) Å and 2.541(2) Å. The average Mn-N (azomethine) length, 2.242(5) Å, is slightly shorter than the average Mn-N (pyridyl) length, 2.262(5) Å. The coordination environment about MN(Ⅱ) center deviates considerably from octahedral geometry. The manganese(Ⅱ)-manganese(Ⅰ) and manganese(Ⅰ)-manganese(0) reduction potentials of Mn(acpy-mdtc)2 are ∼-l.71 and ∼-l.98 V while those of Mn(acpy-phTsc)2 are ∼-l.87 and ∼-2.11 V vs. Ag/Ag+ in dimethyl sulfoxide, respectively.

Mesogenic and azo monomers were synthesized and copolymerized to obtain two copolymers composed of methacrylate and itaconate backbone. Glass transition temperatures of the copolymers were found to be slightly higher than ambient temperature. Both the copolymers showed liquid crystalline properties. Trans-cis isomerization in film state was observed under UV-irradiation with a light of 365 nm. Regarding the photochemical phase transition behavior, the transition rate of nematic-to-isotropic state was slightly faster in the methacrylate copolymer during irradiation at 365 nm and the rate of the reverse transition was much faster in itaconate copolymer under thermal effect.

Layered nanocomposite, SiO2/TiO2 sol pillared clay, has been prepared by the ion exchange reaction of Na' ion in montmorillonite with positively charged mixed SiO2/TiO2 sol. The nanosized sol particles were synthesized by mixing SiO2 sol solution with TiO2 one, which is obtained by acidic hydrolysis of TEOS and TiCl4, respectively. From powder XRD, the basal spacing (d001) of the sample calcined at 400 ℃ was found to be ca. 60 Å, due to the multistacking of nanosized SiO2 and TiO2 sol particles, which was confirmed by the pore size analysis from 129Xe NMR and micropore analysis calculated from nitrogen adsorption. The BET specific surface area shows the value of 684 m2g-1 (Langmuir 1115 m2g-1), which is the highest among various pillared clays ever reported previously, and the total porosity is found to be 0.51 mlg-1, and the pores are mainly composed of micropore with a size of ca. 11.8 Å. This result agrees with the adsorption capacity obtained from water adsorption. According to diffuse reflectance ultraviolet-visible spectroscopy, it is found that the TiO2 particles stabilized in the interlayer space of montmorillonite are quantum-sized of ca. 20 Å.

The determination of total paraffin, naphthene, and aromatic (PNA) contents in naphtha samples, which were directly obtained from actual refining process, has been studied using near-infrared (NIR) spectroscopy. Each of the total PNA concentrations in naphtha has been successfully analyzed using NIR spectroscopy. Partial least squares (PLS) regression method has been utilized to quantify the total PNA contents in naphtha from the NIR spectral bands. The NIR calibration results showed an excellent correlation with those of conventional gas chromatography (GC). Due to its rapidity and accuracy, NIR spectroscopy is appeared as a new analytical technique which can be substituted for the conventional GC method for the quantitative analysis of petrochemical products including naphtha.

The density and the viscosity of aqueous PEO solutions are observed with the several concentrations of PEO at 20 ℃. The effects of urea on them are also observed. The apparent and the partial specific volumes of PEO are calculated from the density data, which result that the polymer-polymer interaction is dominating in the binary aqueous PEO solutions, while the polymer-solvent interaction is dominating in the ternary aqueous urea-PEO solutions. It is explained by the urea induced breakage of the structured water originated from the hydrophobic interactions and the binding of the urea to the PEO chain. The concentration dependence of relative viscosity and the density dependence of fluidity is also discussed with the concept of the polymersolvent and the polymer-polymer interactions of aqueous urea-PEO solutions.

Aminolysis of aryl thiol-2-furoates and thiol-2-thiophenates with benzylainines are investigated in acetonitrile at 50.0 ℃. Relatively large selectivity parameters, ρx(βx), ρz(βx) and ρxz (> 0) together with the valid reactivity-selectivity principle are consistent with a stepwise acyl transfer mechanism with rate-limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T±. The first-order kinetics with respect to the benzylamine concentration and the relatively large secondary kinetic isotope effect involving deuterated benzylamine nucleophiles suggest a four-center type transition state in which concurrent leaving group departure and proton transfer are involved.

We have explored the impact of altering the Ras-cAMP pathway on cell survival upon oxidative exposures. A hyperactivated Ras mutant of Saccharomyces cerevisiae, intrinsically more sensitive to heat shock than the wild type, was investigated with regard to oxidative stress. In this paper we report that the response of iral, ira2-deleted mutant (IR2.53) to an oxidant, such as hydrogen peroxide (H2O2) or menadione is more sensitive than that of the wild type. IR2.53 showed a dramatic decrease in survival rate when challenged with 0.1 mM H2O2 for 30 min. The greater sensitivity of IR2.53 was also noticed with treatment of 0.01 mM menadione. Prior to oxidative stresses by these oxidants, both the wild type and the mutant were preconditioned with a mild heat shock (37 ℃, 30 min), resulting in improved survivals against oxidative stresses. Rescue of IR2.53 from menadione stress by heat pretreatment was more clearly demonstrated than that from H2O2 treatment. On the other hand, no significant difference was observed between the wild type and the IR2.53 mutant in their survival rates upon paraquat treatments. These findings imply that the mechanism by which H2O2 and menadione put forth their oxidative effects may be closely associated with the cAMP-Ras pathway whereas that of paraquat is independent of the Ras pathway. Finally, the level of glutathione (GSH) was measured enzymatically as an indicator of antioxidation and compared with the survival rate. Taken all these together, this study provides an insight into a mechanism of the Ras pathway regulated by several oxidants and suggests that the Ras pathway plays a crucial role in protection of cell damage following oxidative stress.

The diamagnetic six-coordinate ruthenium polypyridyl complexes have been prepared and assigned. 1H NMR spectral studies were used to unravel the ligand field strength and the basicity on the chemical shift to the particular proton of ligand L in [(tpy)(L)RuⅡ(X)]+/2+ (L=bpy, bqi, dmbpy, phen; X=Cl, CN, N3, NCCD3, NO2, SCN) complexes.

Bis(diethyldithiocarbamato)ioxomolybdenum(VI), cis-MoO2(S2CNEt2)2, 1, reacted with chlorotrimethylsilane (Me33SiCl) to give a seven-coordinate, pentagonal bipyramidal complex MoOC12(S2CN]Et2)2, 3, in which the oxo ligand is trans to the chloride ligand and the two chloride ligands are mutually cis. The monooxo molybdenum complex bis(diethyidithiocarbamato)oxomolybdenum(IV), MoO(S2CNEt2)2, 2, reacted with phenyl isocyanate (PhNCO) to give an Mo dimer MO2{μ-N(CONPh)Ph}(μ-NPh)(NPh)2(S2CNEt2)2, 4, which contains an Mo-Mo bond, two diethyldithiocarbamato ligands, two terminal imido (NPh) ligands, and two bridging hnido (NPh) ligands. One of the two bridging NPh ligands seemed to have been attacked by the electrophilic phenyl isocyanate carbon, which suggests that the bridging imido NPh ligand is more nucleophilic than the terminal one. Crystallographic data for 3: monoclinic space group P21/c, a=8.908(l) Å, b=17.509(3) Å, c=12.683(2) Å, β=110.15(1)°, Z=4, R(wR2)=0.0611(0.1385). Crystallographic data for 4-THF: orthorhombic space group P212121, a=17.932(4) Å, b=22.715(5) Å, c=11.802(3) Å, Z=4, R(wR2)=0.0585(0.1286).

We present results of molecular dynamic (MD) simulations for the segmental motion of liquid n-heptadecane in order to investigate conformational transitions from one rotational isomeric state to another. The behavior of the hazard plots for n-heptadecane obtained from our MD simulations are compared with that for polymer of Brownian dynamics (BD) study. The transition rate at the ending dihedrals of the n-heptadecane chain is much higher than that at the central dihedrals. In the study of correlation between transitions of neighboring dihedrals, the large value of c2 implies that some 30% of the transitions of the second neighbors can be regarded as following transitions two bonds away in a correlated fashion. Finally the analysis of multiple transitions and the number of times occurred in the initial 0.005 ns are discussed.

The crystal structure of a benzene sorption complex of fully dehydrated Cd2+-exchanged zeolite X, Cd46Si100Al92O384·43C6H6 (a=24.880(6) Å), has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 ℃. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Cd(NO3)2 for 3 d, followed by dehydration at 400 ℃ and 2 x 10-6 Torr for 2 d, followed by exposure to about 92 Torr of benzene vapor at 22 ℃. The structure was determined in this atmosphere and refined to the final error indices R1=0.054 and Rw=0.066 with 561 reflections for which I > 3σ(I). In this structure, Cd2+ ions are found at four crystallographic sites: eleven Cd2+ ions are at site 1, at the centers of the double six-oxygen rings; six Cd2+ ions lie at site I', in the sodalite cavity opposite to the double six-oxygen rings; and the remaining 29 Cd2+ ions are found at two nonequivalent threefold axes of unit cell, sites Ⅱ' (in the sodalite cavity ) and site Ⅱ (in the supercage) with occupancies of 2 and 27 ions, respectively. Each of these Cd2+ ions coordinates to three framework oxylkens, either at 2.173(13) or 2.224(10) Å, respectively, and extends 0.37 Å into the sodalite unit or 0.60 Å into the supercage from the plane of the three oxygens to which it is bound. The benzene molecules are found at two distinct sites within the supercages. Twenty-seven benzenes lie on threefold axes in the large cavities where they interact facially with the latter 27 site-Ⅱ Cd2+ ions (Cd2+-benzene center=2.72 Å; occupancy=27 molecules/32 sites). The remaining sixteen benzene molecules are found in 12ring planes; occupancy=16 molecules/16 sites. Each hydrogen of these sixteen benzenes is ca. 2.8/3.0 Å from three 12-ring oxygens where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.

The frequency response on the tip-sample distance in scanning electrochemical microscopy (SECM) that is combined with an electrochemical quartz crystal microbalance (EQCM) is described. The oscillation frequency of the EQCM increases rapidly when the SECM tip is very close to the substrate electrode surface. This frequency increase is reproducible regardless of the current feedback in SECM, which is attributed to the stress caused by the tip pressing the quartz crystal. It is useful to calibrate the tip-sample distance with respect to the frequency change when a combined system of SECM and EQCM (SECM-EQCM) is used. This method could be applied to several cases such as rigid metal electrode and non-conducting or partially conducting polymer coating prepared on the quartz crystal regardless of the feedback current.

Transglycosylation reactions among methyl 2,3,4,6-tetra-O-methyl-D-glycopyranosides and isomeric butyl alcohols or cyclohexanol took place in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) in dichloromethane. The extent of the reaction after 1 h and 24 h from mixing was determined by gas chromatography (GC). Anomerization of the substrate took place during the course of transglycosylation, which favors α anomer regardless of the anomeric configurations of the starting glycosides. Transglycosylation also favors the a anomer regardless of the steric bulkiness of the alcohol. tert-Butyl alcohol did not give any transglycosylation, suggesting the steric hindrance of approaching the bulky alcohol to the oxonium intermediate. A mechanism for the transglycosylation have been proposed.

Derivatives of ethylthio α-D-mannopyranoside as glycosyl donors are compared in coupling efficiency and stercoselectivity with varying thiophilic promoters from methyl triflate (MeOTf), dimethyl(methylthio)sulfonium triflate (DMTST) to iodonium dicollidine perchlorate (IDCP), solvents and glycosyl acceptors. IDCP was the most efficient promoter in coupling of perbenzylated ethylthio-α-D-mannopyranosides (1 and 2), giving α-Dmannosyl disaccharides preferentially, whereas inactive in coupling of 4,6-O-benzylidene derivatives 3 and 4. MeOTf and DMTST promoted coupling of 4,6-O-benzylidene derivatives 3 and 4, but P-D-mannopyranosyl disaccharides were formed preferentially. Coupling reaction was retarded as solvent polarity decreased.

Ozonolysis reactions of cyclic olefins 1a-c and norbomene In in the presence of trifluoroactophenone 6 provided the corresponding cross-ozonides 7a-c and 7n. Further reactions of ozonides 7a-c and 7n with the independently prepared carbonyl oxide 11 gave diozonides of structure l0a-c and 10n. The ozonolysis of 1methylcyclopentene 12a and 1-methylcyclohexene 12b in the presence of trifluoroactophenone 6 provided exclusively ozonide 15 and 16 derived from capture of carbonyl oxide 13. All of the new ozonides have been isolated as pure substances and characterized by their 1H NMR and 13C NMR spectra.