Thermodynamic and electrical functions of aminophenol and anthranilic acid complexes with Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) were determined. ΔG°, ΔH° and ΔS° were calculated with the help of stability constant values at different temperatures. It was found that the complexing processes have an exothermic nature. The studied complexes behave like semiconductors. The conduction takes place according to hopping mechanism. To show the composition of complexes conductometric and photometric titrations, IR spectra, thermal analysis and X-ray diffraction techniques were employed.

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

Porous silica-pillared montmorillonites were prepared by simultaneous intercalation of dodecylamine-TEOS [tetraethylorthosilicate, Si(OC2H5)4] into the H-montmorillonite and intragallery amine-catalyzed hydrolysis of TEOS. Mixtures of the H-montmorillonite, dodecylamine and TEOS at molar ratios of 1 : 2 : 15-30 and 1 : 2-6 : 20 resulted to swollen and viscous gel once at room temperature, allowing intercalation compounds which dodecylamine and TEOS were simultaneously intercalated into interlayer of H-montmorillonite. The hydrolysis of the gallery TEOS was conducted in water solution for 40 min at room temperature, affording siloxane-pillared H-montmorillonite. Calcination of samples at 500 $^{\circ}C$ in air resulted in silica-pillared montmorillonite with large specific surface areas between 403 and 577 m2 /g, depending on the reaction stoichiometry. The reaction at H-montmorillonite : dodecylamine : TEOS reaction stoichiometries of 1 : 2 : 15 and 1 : 4 : 20 resulted in high specific surface areas and mesopores with a narrow pore size distribution. Result indicates that the intragallery-amine catalyze the hydrolysis of gallery-TEOS and simultaneously have a role of gallery-templated micellar assemblies.

A gas chromatography/mass spectrometric assay method has been developed for the simultaneous determination of benzidine (BZ), N-acetyl benzidine (ABZ) and N,N-diacetyl benzidine (DABZ) in rat urine. BZ, ABZ and DABZ were extracted from urine at pH 8 with ethyl ether. Conjugated urinary metabolites were extracted at pH 8 after hydrolysis with 1 M HCl for 30 min at 100 $^{\circ}C.$ The dried extract was dissolved in 100 ${\mu}{\ell}$ of ethylacetate and then injected in gas chromatography-mass spectrometric (GC-MS) system without further purification or modification. BZ, ABZ and DABZ have good chromatographic properties and offer very sensitive response for the EI-MS (SIM) without any derivatization. The recoveries for BZ, ABZ and DABZ were about 98.0, 81.8 and 71.4%, respectively, at pH 8.0 and the concentration of 5.0 ng/mL. The coefficients of variation of BZ and ABZ were less than 9.5% from 0.1 to 100 ng/mL and that of DABZ was less than 13% in the same concentration range. The detection limits of the assay were 0.01 ng/mL for both BZ and ABZ, and 0.05 ng/mL for DABZ in urine or plasma 1.0 mL.

An imprinting technique with labile covalent interactions has been developed in the design of new polymer catalysts. The template monomer 2 was prepared and copolymerized with DVB or EDMA to provide the polymer with a cavity having the shape of th e transition state of the reaction as well as binding sites for the substrate and catalytic functionalities. The rate of hydrolysis of diphenyl carbonate (1) in the presence of the imprinted polymer IP-DVB-THF was found to be 120 times faster than the background uncatalyzed reaction. A Km of 32 mM and a kcat of 1.8 ${\times}$ 10-3min-1 were observed from Michaelis-Menten kinetics with the imprinted polymer IP-DVB-THF.

Ab initio density functional calculations on the structural isomers, the hydration energies, and the hydrogen bond many-body interactions for gauche-, trans-protonated ethylenediamine-(water)3 complexes (g-enH+(H2O)3, t-enH+(H2O)3) have been performed. The structures and relative stabilities of three representative isomers (cyclic, tripod, open) between g-enH+(H2O)3 and t-enH+(H2O)3 are predicted to be quite different due to the strong interference between intramolecular hydrogen bonding and water hydrogen bond networks in g-enH+(H2O)3. Many-body analyses revealed that the combined repulsive relaxation energy and repulsive nonadditive interactions for the mono-cyclic tripod isomer, not the hydrogen bond cooperativity, are mainly responsible for the greater stability of the bi-cyclic isomer.

A series of cleft-type ionophores having two convergent hydroxamic acid functions are prepared and their selective ionophoric properties toward heavy metal and transition metal ions have been investigated. Hydroxamic acids 3 exhibited a prominent selectivity toward heavy metal ions of Hg2+ and Pb2+, and transition metal ions of Cu2+ over other transition metal and alkaline earth metal ions from slightly acidic source phase (pH 6) to an acidic receiving phase (pH 1). Selective ionophoric properties toward Pb2+ and Cu2+ ions over other surveyed metal ions are also confirmed by the FAB-MS measurements.

K2NiF4-type organic-based perovskites of the (C4H9NH3)2FexPb1-xCl4 (x=0.00, 0.25, 0.50, and 0.75) system have been synthesized using a low-temperatu re solution method under a flowing argon gas. When stoichiometric butylamine, iron chloride, and lead chloride are mixed, a yellow solution are obtained from slow cooling of 90 to -10 $^{\circ}C.$ The final product is a plate-like yellow crystal. The X-ray crystallographic analysis has been carried out using XRD in the range of $5^{\circ}{\leq}$ 2${\theta}$ ${\leq}80^{\circ}.$ The local symmetry around the absorbing Pb atom of the samples has been determined by the EXAFS spectroscopic study. The crystals assign to orthorhombic system by the XRD analysis. The FT-IR spectra are analyzed in the range of 600 to 3300 cm-1 . DSC and TGA are measured to detect thermal stability between 30 and 300 $^{\circ}C.$ Two endothermic peaks are detected in all samples. The electrical conductivity has been measured using the four-probes technique for the (C4H9NH3)2FexPb1-xCl4 system in 300-460 K. Photoluminescence phenomenon was also investigated at room-temperature.

We have been studied photosensitization mechanism's additive effect, of perylene 3,4,9,10-tetracarboxyl-diimide and X-phthalocyanine (charge generation materials), using the photochemical and photoelectrochemical approach. It was found that the photoreceptor on the excited state reacts with metal oxide, which creates the charge transfer on the interface of SnO2/electrolyte. In the electrode (X5P1) made of five X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, the cathodic photocurrent of X-phthalocyanine in the 400-600 nm region was increased by the addition of perylene 3,4,9,10-tetracarboxyldiimide. The maximum wavelength of fluorescence of perylene 3,4,9,10-tetracarboxyldiimide showed no dependence on the temperature. The addition of 4-dibenzylamino-2-methylbenzaldehyde diphenylhydrazone known as charge transport material was represented as decreasing photocurrent for X-phthalocyanine and perylene 3,4,9,10-tetracarboxyldiimide, respectively. In the electrode (X1P1) made of single X-phthalocyanine and single perylene 3,4,9,10-tetracarboxyldiimide layers, an anodic photocurrent of about 10.5 nA was generated by addition of hydroquinone at 550 nm. And the characteristic of photoinduced discharge was shown to decrease by a factor of 5 and the speed of dark decay was increased by a factor of 1.2.

To test the metal ion effect, hydrolysis experiments for two cellobiohydrolases (CBHⅠ and CBH Ⅱ) from Trichoderma reesei have been carried out in the presence of 10 mM metal ions, such as Cu++, Mn++, Ca++, Hg++, Ba++, Pb++, and Cd++. The addition of Mn++, Ba++, and Ca++(10 mM) during the hydrolysis of Avicel PH 101 caused an increase in the total reducing sugar (TRS) for CBH Ⅰ by 142, 135, and 114 percent, respectively. Those for CBH Ⅱ increased by 177, 175, and 115 percent, respectively. The Mn++ was the most stimulatory metal ion, whereas Hg++ was the most inhibitory metal ion. The adsorption experiments were performed to investigate how the influence of Mn++ and Hg++ on the hydrolysis is related to the adsorption of cellobiohydrolases on cellulose. The increase in TRS during hydrolysis by adding Mn++ caused an increase in adsorption affinity (Kad) and tightness (ΔHa). While, the decrease of TRS during hydrolysis by adding Hg++ caused a decrease in the adsorption affinity (Kad) and tightness (ΔHa). These results indicate the changes in the tightness and affinity of adsorption by adding metal ions play a crucial role in the degradation of the microcrystalline cellulose.

The vibrational transition probability expressions for the forced Morse oscillator have been derived using the commutation relations of the anharmonic Boson operators. The formulation is based on the collinear collision model with the exponential repulsive potential in the framework of semiclassical collision dynamics. The sample calculation results for H2+ He collision system, where the anharmonicity is large, are in excellent agreement with those from an exact, numerical quantum mechanical study by Clark and Dickinson, using the reactance matrix. Our results, however, are markedly different from those of Ree, Kim and Shin's in which they approximate the commutation operator I。 as unity, the harmonic oscillator limit. We have concluded that the quantum number dependence in I。 must be retained to get accurate vibrational transition probabilities for the Morse oscillator.

Conjugated-non-conjugated alternating block copolymers containing distyrylarylene units were synthesized via Wittig reaction for chemiluminescent fluorophores. The polymers were differentiated from others by the presence of aromatic unit in the chromophoric block. When UV-VIS, photoluminescence and chemiluminescence spectra of these materials were compared with copolymers, a strong bathochromic effect was observed. A more pronounced red shift and higher chemiluminscence efficiency were observed in the polymer with anthracene ring. Sodium salicylate-catalyzed reaction of bis(2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate with hydrogen peroxide produced a strong chemiluminescence from blue to yellow-green light emission with wavelength of 450-537 nm in the presence of the fluorophore. The chemiluminescent intensity decayed exponentially. The glow of chemiluminescence maintained more than l2 hr and was visible with the naked eye.

The cross second-derivative of the activation energy,${\theta}$G${\neq}$ , with respect to the two component thermodynamic barriers, ${\theta}$G˚X and ${\theta}$G$^{\circ}C$Y, can be given in terms of a cross-interaction constant (CIC), $\betaXY(\rhoXY)$, and also in terms of the intrinsic barrier,${\theta}$G${\neq}$ , with a simple relationship between the two: $\betaXY$ = $-1}(6${\theta}$G${\neq}$).$ This equation shows that the distance between the two reactants in the adduct (TS, intermediate, or product) is inversely related to the intrinsic barrier. An important corollary is that the Ritchie N+ equation holds (for which $\betaXY$ = 0) for the reactions with high intrinsic barrier. Various experimental and theoretical examples are presented to show the validity of the relationship, and the mechanistic implications are discussed.

Reactions of [Cp*Ir(η3-CH2CHCHPh)(NCMe)]OTf (1) with HC≡CR (R = H, CH2OH) in the presence of bases, B (B=NEt3, PPh3, AsPh3) produce stable Cp*Ir-η3-allyl-alkenyl compounds [Cp*Ir(η3-CH2CHCHPh)(-CH=CH-+B)]OTf (2) and [Cp*Ir(η3-CH2CHCHPh)(-C(CH2OH)=CH- +PPh3)]OTf (3), respectively in high yields. Cp*Ir-η3-allyl-alkynyl compounds Cp*Ir(η3-CH2CHCHPh(-C≡C-R') (4) and Cp*(η3-CH2CHCHPh)Ir-C≡C-p-C6H4-C≡C-Ir(η3-CH2CHCHPh)Cp* (5) have been prepared from reactions of 1 with HC≡CR'(R' = C6H5, p-C6H4CH3, C3H5, C6H9) and HC≡C-p-C6H4-C≡CH in the presence of NEt3.

New azomethine metal complexes were synthesized systematically and characterized. Beryllium, magnesium, or zinc ions were used as a central metal cation and aromatic azomethines (L1-L4) were employed as a chelating anionic ligand. Emission peaks o f the complexes in both solution and solid states were observed mostly at the region of 400-500 nm in the luminescence spectra, where blue light was emitted. Three of them (BeL1 (Ⅰ), ZnL2 (Ⅱ), and ZnL3 (Ⅲ)) were sublimable and thus were applied to the organic light-emitting devices (OLED) as an emitting layer, respectively. The device including the emitting layer of Ⅰ exhibited white emission with the broad luminescence spectral range. The device with the emitting layer of Ⅱ showed blue luminescence with the maximum emission peak at 460 nm. Their ionization potentials, electron affinities, and electrochemical band gaps were investigated with cyclic voltammetry. The electrochemical gaps of 2.98 for I, 2.70 for Ⅱ, and 2.63 eV for Ⅲ were found to be consistent with their respective optical band gaps of 3.01, 2.95 and 2.61 eV within an experimental error. The structure of OLED manufactured in this study reveals that these complexes can work as electron transporting materials as well.

Alkanethiols (CH3(CH2)n-1SH) based self-assembled monolayers (SAMs) on the clean copper surfaces have been examined for n = 4, 8, and 16. Using X-ray photoelectron spectroscopy (XPS) and contact angle analysis, it is found that alkanethiolate monolayers similar to those on gold are formed on clean copper surfaces. The monolayers are stable in air up to about 140 $^{\circ}C.$ Above 160 $^{\circ}C$ the monolayers begin to desorb through the oxidation reaction of the thiolate to sulfonate, with the alkyl chains remaining intact. Following this desorption step, the copper surface has begun to oxidize to CuO at about 180 $^{\circ}C$.

1-(2'2'3'-Tricyano-3-carbomethoxycyclopropyl)-34-di-(2'-hydroxyethoxy)benzene, (4) was prepared by the reaction of bromomalononitrile with methyl 3,4-di-(2'-hydroxyethoxy)benzylidenecyanoacetate (3). Diol 4 was condensed with tolylene-2,4-diisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, and 1,6-hexamethylenediisocyanate to yield polyurethanes 5, 6, and 7 containing tricyanocyclopropane functionalities in the pendant group. The resulting polymers 5-7 were soluble in common organic solvents and the inherent viscosities were in the range of 0.25-0.30 dL/g. Polyurethanes 5-7 showed a thermal stability up to 300 $^{\circ}C$ in TGA thermograms. Solution-cast films showed Tg values in the range of 100-125 $^{\circ}C$ and piezoelectric coeffcients (d31) of the poled polymer films were 1.3-2.0 pC/N, which are acceptable for piezoelectric device applications.