The structures of modified Ti$(OPr^i)_4$ with chelating ligands (L) such as ethylacetoacetate (Etac), acetylacetone (Acac) and methylacetoacetate (Mtac) were identified by using IR, ¹H NMR and $^13C$ NMR spectroscopies, and the octahedral structure was confirmed after modification. The pre-edge peaks of XANES spectra of modified metal alkoxides also denoted the mixture of five-fold and six-fold structures. The EXAFS fitting results showed the local structure around Ti atom after alkoxide modification. The hydrolysis-condensation rates of modified Ti alkoxide with organic additives were investigated by ¹H NMR spectroscopy. The Ti$(OPr^i)_4$ modified by Acac was less reactive toward hydrolysis-condensation reaction than those modified by the other alkoxides, which can be attributed to the stable ligand structure between Ti$(OPr^i)_4$ and Acac. The small particle size of modified Ti$(OPr^i)_4$ sol was obtained when Acac was employed.

Geometrical structures for the dimerization of (NO)₂ from (NO + NO) have been calculated using ab initio Har-tree-Fock (SCF), second-order Møller-Plesset perturbation (MP2), and coupled cluster with the single, double, and triple substitution [CCSD(T)] methods with a triple zeta plus polarization (TZP) basis set including diffuse Rydberg basis functions. The structure of (NO)₂ can be described by two interactions (N…N, N…O). One is the ONNO structure with an (N…N) interaction. In this structure, acyclic cis-ONNO with $C_{2v}$-symmetry, acyclic trans-ONNO with $C_{2h}$, and cyclic ONNO with trapezoidal structure ($C_{2v}$) are optimized at the MP2 level. The other structure is the ONON structure with an (N…O) interaction. In the structure, acyclic cis-ONON with Cs$^{-symmetry}$ and cyclic ONON of the rectangular ($C_{2h}$), square $(D_{2h})$, rhombic $(D_{2h})$, and parallelogramic $(D_{2h})$ geometries are also optimized. It is found that acyclic cis-ONNO (¹A₁) is the most stable structure and cyclic ONNO (³A₁) is the least stable. Acyclic trans-ONNO (³A₁) with an (N…N) interaction, acyclic trans-ONON and bicyclic ONON $(C_{2v})$ with (N…O) interaction, and acyclic cis- and trans-NOON with an (O…O) interaction can not be optimized at the MP2 level. Particularly, acyclic trans-ONNO with $C_{2h}$-symmetry can not be optimized at the CCSD(T) level. Meanwhile, acyclic NNOO (¹A₁, $C_s)$ and trianglic NNOO (¹A₁,$C_{2v})$ formed by the (O…N) interaction between O₂ and N₂ are optimized at the MP2 level. The binding energies and the relative energy gaps among the isomers are found to be relatively small./sec. Spiral CT scans during the arterial phase were obtained 35 seconds after the injection of contrast medium. CT findings of 78 lesions less than 4cm in diameter were correlated with angiographic findings. Results : The attenuation of lesions was high(n = 69), iso(n = 5), and low(n = 4) compared with liver parenchyma during the arterial phase of spiral CT. In lesions with high-, iso-, and low-attenuation during the arterial phase of spiral CT, hypervascularity on angiograms was found in 63 of 69(91.3%), three of five(60%), and three of four lesions(75%), respectively. Six lesions with high-attenuation on the arterial phase of spiral CT were not seen on angiography. Two iso-attenuated and one low-attenuated lesion were hypovascular on angiograms. Conclusion : The results of this study suggest that with some exceptions there was good correlation between the arterial phase of spiral CT and angiography.

The spectrophotometric determination method of scandium with eriochrome cyanine R (ECR) and the composition ratio of the complex were investigated in the presence of surfactants. A volume of 5 mL of 1.0×$10^{-3}$ M ECR and 10 mL of 2.0×$10^{-4}$ M CTMAB are necessary for the determination of 1.0×$10 ^{-7}$ ~ 3.0×$10^{-6}$ M Sc(III) at pH 6.5. The apparent molar absorption coefficient of the Sc(III)-ECR-CTMAB, ternary complex at 610 nm is 5.6×$10^5$ $mol^{-1}cm{-1}$L and its detection limit is 1.0×$10^{-7}$ M. Separation studies were conducted by the column method. The effect of pH, elution solution and the influence of rare earth elements as interferents was discussed. Their separation was carried out in 0.1 M HCl-50% methanol solution and 1.0 M HCl media. The method was applied for the determination of Sc(III) in monazite.

Chemical poisoning of Ni/MgO catalyst was induced by hot alkali carbonate vapor in molten carbonate fuel cell (MCFC), and the poisoned (or contaminated) catalyst was characterized by TPR/TPO, FTIR, and XRD analysis. Carbonate electrolytes such as K and Li were transferred to the catalyst during DIR-MCFC operation at 650 ℃. The deposition of alkali species on the catalyst consequently led to physical blocking on catalytic active sites and structural deformation by chemical poisoning. TPR/TPO analysis indicated that K species enhanced the reducibility of NiO thin film over Ni as co-catalyst, and Li species lessened the reducibility of metallic Ni by chemical reaction with MgO. FTIR analysis of the poisoned catalyst did not exhibit the characteristic ${\vector}_1$$(D_{3h})$ peaks (1055 $cm^{-1},\;1085\;cm{-1})$ for pure crystalline carbonates, instead a new peak (1120 $cm^{-1})$ was observed proportionally with deformed alkali carbonates. From XRD analysis, the oxidation of metallic Ni into $Ni_xMg_{1-x}O$ was confirmed by the peak shift of MgO with shrinking of Ni particles. Conclusively, hot alkali species induced both chemical poisoning and physical deposition on Ni/MgO catalyst in DIR-MCFC at 650 ℃.

Kinetics and mechanism of the aminolysis of Z-thiophenyl acetates with X-benzylamines are investigated in acetonitrile at 45.0 ℃. The magnitudes of Bronsted coefficients β$_x$ (=1.3~-1.6) and β$_z$ (= -2.1~-2.4) are all large and cross-interaction constant ρxz is relatively large and positive (0.90). These trends are consistent with the rate-limiting breakdown of a tetrahedral intermediate, $T^±$. The proposed mechanism is also supported by adherence of the rate data to the reactivity-selectivity principle (RSP). The kinetic isotope effects, $k_H/k_D$, are greater than unity (1.3-1.4) suggesting a possibility of hydrogen-bonded four-centered transition state. The activation parameters, ΔH$^≠$ and ΔS$^≠$, are consistent with this transition-state structure.

4-Hydroxy-4'-methoxyazobenzene and 4-hydroxy-4'-cyanoazobenzene were synthesized from phenol with p-anisidine and p-aminobenzonitrile through a diazotization reaction, respectively. They were reacted with 2-chloroethanol, 2-(2-chloroethoxy)ethanol, or 2-[2-(2-chloroethoxy)ethoxy]ethanol to produce six kinds of new mesogenic alcohols having an azobenzene group that is sensitive to the ultraviolet. Twelve kinds of new photoresponsive monomers with two symmetrical mesogens were prepared by the reaction of the mesogenic alcohols with fumaric acid or maleic acid through a Mitsunobu reaction. The resulting monomers have different length of flexible ethyleneoxy spacer tethered to azobenzene group. The length of the spacer affected their thermal stability, solubility, and phase transition temperature. Structures of the monomers were identified by FT-IR and ¹H-NMR spectra. Their phase transition temperatures and thermal stability were also investigated by a differential scanning calorimetry (DSC) and a thermogravimetric analysis (TGA). From an optical polarizing microscopy, all the prepared monomers except fumarate-1 and maleate-1 were found to show enantiotropic liquid crystallinity with a smectic texture like focal-conic, fan-shaped, and batonnet textures.

[Fe$^{II}$(BLPA)DBCH]BPh₄ (1), a new functional model for the extradiol-cleaving catechol dioxygenases, has been synthesized, where BLPA is bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine and DBCH is 3,5-di-tert-butylcatecholate monoanion. ¹H NMR and EPR studies confirm that 1 has a high-spin Fe(II) (S = 2) center. The electronic spectrum of 1 exhibits one absorption band at 386 nm, showing the yellow color of the typical [Fe$^{II}$(BLPA)] complex. Upon exposure to O₂, 1 is converted to an intense blue species within a minute. This blue species exhibits two intense bands at 586 and 960 nm and EPR signals at g = 5.5 and 8.0 corresponding to the high-spin Fe(III) complex (S = 5/2, E/D = 0.11). This blue complex further reacts with O₂ to be converted to (μ-oxo)Fe$^{III}_2$ complex within a few hours. Interestingly, 1 affords intradiol cleavage (65%) and extradiol cleavage (20%) products after the oxygenation. It can be suggested that 1 undergoes two different oxygenation pathways. The one takes the substrate activation mechanism proposed for the intradiol cleavage products after the oxidation of the $Fe^II\;to\;Fe^{III}$. The other involves the direct attack of O₂ to $Fe^{II}$ center, forming the $Fe^{III}$-superoxo intermediate which can give rise to the extradiol cleavage products. 1 is the first functional Fe(II) complex for extradiol-cleaving dioxygenases giving extradiol cleavage products.

The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

Ozonolysis reactions of indene 5 in the presence of carbonyl compounds 6 provided the corresponding indenemonoozonide 9 and cross-ozonides 10a-c and 11a-c. Further reactions of ozonides 10 and 11 with the independently prepared carbonyl oxide 13 gave diozonides of structure 14a-c and 15a-c.

Laser-induced fluorescence (LIF) spectroscopy has been applied to study the supersonic jet of radicals of nitric oxide (NO) and atomic iodine produced in the flash pyrolysis of precursors n-butylnitrite (CH₃(CH₂)₃ONO) and allyl iodide (C₃$H_5$I), respectively. The systematic population analysis with spectral simulations demonstrates that the precursors are efficiently pyrolyzed and that radical beams show a substantial supersonic cooling. In addition, absence of local equilibrium was observed in the distributions of two electronic spin-orbit states ²Π$_{1/2}$ and ²Π$_{3/2}$ of NO products and can be rationalized in terms of the efficiency of collision-induced energy transfer rates.

Countercurrent oxygen reaction (COR) was developed and evaluated for regeneration of exhausted activated carbon. Whether the regeneration technique is feasible or not is affected strongly by gradual loss and physical changes of activated carbon, energy consumption, and effective removal of adsorbed materials during the process. Various parameters such as reaction temperature, the loss of activated carbon, surface area, pore volume, surface structure, adsorptive property, etc. were examined to determine the effectiveness of COR. The results of these tests showed that the parameters were strongly dependent on oxidant flow rate, and suggest that the newly developed COR is comparable and, in some ways, possibly superior to conventional regeneration techniques because the overall process runs in a single step and is less energy intensive, and also because the adsorptive capacity of exhausted activated carbon was completely recovered.

Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

Structure and their redox property of the vanadium oxides prepared by decomposing NH₄VO₃ at various temperatures were studied by XRD, SEM, XPS, and temperature programmed reduction/temperature programmed oxidation (TPR/TPO) experiment. All TPR profiles have two sharp peaks in the temperature range 650-750℃, and the area ratio of the two sharp peaks changed from sample to sample. There were three redox steps in TPR/TPO profiles. The oxidation proceeded in the reverse order of the reduction process, and both the reactions proceeded via quite a stable intermediates. The changes of the morphological factor $(I_{(101)}/I_{(010)})$, the ratio of $O_{1S}$ peak area (O$_{1S}$( α)/O$_{1S}$( β)) in the XPS results, and the ratio of hydrogen consumption in TPR profiles with various vanadium oxides showed the distinct relationship between the structural property and their redox property of vanadium oxides. The change of the specific yield of phthalic anhydride with various vanadium oxides showed a very similar trend to those of the peak area ratio in TPR profiles, which meant that the first reduction step related to the partial oxidation of o-xylene on the vanadium oxide catalyst.

Non-activated indolinobenzospiropyrans, 6-(p-substituted phenylazo)-1',3',3'-trimethylspiroindolinobenzopyrans(1-4) have been synthesized by the reaction of commercially available Fischer's base with 2-hydroxy-5-arylazobenzaldehyde (S1-S4). The arylazosalicylaldehydes were obtained from the diazocoupling reaction of substituted anilines with salicylaldehyde. The rate of spiro-ring formation from the open form of these nonactivated spiropyran derivatives at room temperature has been investigated utilizing the stopped-flow method de-veloped earlier. Half life times $(t_{1/2})$ of the ring-closure reaction in ethanol are about 0.3-14 seconds for the nonactivated spiropyrans examined. UV-Visible absorption spectral data of the open merocyanine form of nonactivated spiropyrans, which showed no chromotropism at room temperature, have also been obtained.

New platinum(II) complexes with asymmetrically substituted chiral diamine ligands A₂PtX₂, (A₂ = NH₂CH(CH₃)CH₂NH($c-C_5H_9)$ (apcpa), NH₂CH(CH₃)CH₂NH($c-C_6H_11)$ (apcha); X₂ = 2Cl, isopropylidenmalonate (IPM), 1,1'-cyclobutandicarboxylate (CBDCA)) have been synthesized and characterized by means of elemental analyses, infrared and NMR spectroscopies, and X-ray crystallography. The crystal structures of (S-apcha)Pt[CBDCA] ·3H₂O (orthorhombic, P2₁2₁2(No. 18), a = 6.926(3), b = 15.243(3), c = 19.319(4)Å, V = 2039.5(10) ų, Z = 4, R = 0.072) and (S-apcha)Pt[IPM] ·2.5 H₂O (monoclinic, P2/C(No. 13), a = 9.882(1), b =18.502(1), c = 22.056(1)Å, V = 4032.8(5)ų, Z = 8, R=0.093) exhibit that the platinum atoms achieve a typical square planar arrangement with two nitrogen atoms in cis position and with the chiral center retained. The spectroscopic data disclose that these platinum complexes are stable and their molecular structures are retained in aqueous solution. Among these platinum complexes, the asymmetric diamine-Pt(II) complexes with chloride leaving group exhibit high in vivo activity comparable to cisplatin against leukemia L1210 cell line.

Ligand field calculations have been performed based on the data from the absorption and low temperature sharp-line excitation spectra of fac-Cr(gly)₃, fac-Cr(L-serine)₃ · 2H₂O and fac-Cr(L-leucine)₃·2H₂O. The optimized ligand field parameters for all complexes show that the carboxylate and the amino groups are moderate σ-donor. The values of $e_{{\pi}O}$ are typical of other complexes with carboxylate ligands. However, the π-interaction of carboxylic oxygen to the chromium in serinato complex is much weaker than that of other complexes. The inclusion of π-anisotropy is necessary to adequately explain the large doublet splittings.

We have studied the behavior of interdiffusion between partially miscible polymer pair from a theoretical viewpoint by applying the reptation model for collective interdiffusion and spinodal decomposition in polymer mixtures with different molecular weights. We find that our predictions agree well with the experiments of Klein and co-workers, where the exponent α of the initial increase of interfacial width with time in $t^{\alpha}$ is significantly lower than 0.5 for free diffusion.

The contents of pentachlorophenol (PCP) and 2,3,5,6-tetrachlorophenol (TeCP) in textile products are regulated for safety. Since an organic solvent such as 2-methoxyethanol is needed to extract chlorinated phenols from textile samples, nonaqueous capillary electrophoresis has been applied to achieve the separation of PCP and isomers of TeCP. The run buffer was 100 mM Tris/acetate in methanol whose pH was adjusted to 8.0. All of the analytes were negatively charged at pH 8.0 and their electrophoretic velocities were higher than the electroosmotic flow of the methanol buffer. A reverse voltage of -20 kV was applied along a 27-cm fused silica capillary with ID of 50 μm, and PCP and 3 TeCP isomers were separated based on the difference in $pK_a$ values in less than 4 min. The limits of detection (S/N = 3) were about 0.02 μM. By varying pH of the methanol run buffer, $pK_a$ values of the 4 chlorinated phenols were also estimated.

The kinetics of oxidation of substituted styryl 4-biphenyl ketones and of substituted styryl 2-fluorenyl ketones by pyridinium chlorochromate (PCC) have been studied in 90% acetic acid- 10% water (v/v) containing perchloric acid and NaClO₄ at $10^0,\;20^0,\;30^0$ and 40℃. The reactions are first order in styryl ketones and PCC. The second order rate constants are well correlated only with σ$^+$ constants implying development of positive charge adjacent to benzene ring in the transition state. The effects of varying [HClO₄] and the percentage of acetic acid on the reactions have also been analysed. A mechanism involving nucleophilic attack of PCC leading to an unsymmetric intermediate from which epoxides are formed is proposed.

The electronic transitions from the ground state to low-lying excited states of CF₃OH have been investigated using high level ab initio quantum mechanical techniques. Also the possible photodissociation procedures of CF₃OH have been considered. The highest level employed in this study is TZP CCSD(T) level of theory. The possible four low-lying excited states can result by the excitation of the lone pair electron (n) in oxygen to σ$^*$ molecular orbital in C-O or O-H bond. The vertical transition (n → σ$^*$) energy is predicted to be 220.5 kcal/mol (130 nm) at TZ2P CISD level to theory. The bond dissociation energies of CF₃OH to CF₃O +H and CF₃+OH have been predicted to be 119.5 kcal/mol and 114.1 kcal/mol, respectively, at TZP CCSD level of theory. In addition, the transition state for the unimolecular decomposition of CF₃OH into CF₂O + HF has been examined. The activation energy and energy separation for this decomposition have been computed to be 43.6kcal/mol and 5.0 kcal/mol including zero-point vibrational energy corrections at TZP CCSD(T) level of theory.ed phenols were also estimated.

Expansion dynamics of C$^{+}$ ions ejected from 355-nm laser ablation of graphite target in vacuum has been investigated by pulsed-field time-of-flight (TOF) mass spectrometry. A strong nonlinear dependence of the amount of desorbed C$^{+}$ ions on laser fluence is interpreted by the mechanism that C$^{+}$ ions are produced directly from the graphite via conversion of the multiphoton energy into thermal energy. The temporal evolution of C$^{+}$ ions was measured by varying the delay time of the ion repelling pulse with respect to the laser irradiation, which provides significant information on the ablated plume characterization. The TOF distributions of ablated ions showed a bimodal shape and could be fitted by shifted Maxwell-Boltzmann distributions. The velocity of the fast component increases with the delay time, whereas the slow component (< 500 m/s) exhibits a constant velocity. Also studied were the effects of the laser fluence on the energetics of C$^{+}$ ions.