Complexation of cesium ion by p-tert-butylcalix[6]arene ethyl ester was studied by NMR spectroscopy in nonpolar $CDCl_3$ and polar acetone-$d_6$ and the results were compared with each other. Analysis of temperature dependent $^1H$ spectra and titration curves reveals that both solvents result in a 1 : 1 cone-form complex with nonpolar $CDCl_3$yielding a more tightly bound one than acetone-$d_6$. Unexpectedly, at very low temperature, we have found that two phenyl ring proton peaks of equal intensity appear both in $CDCl_3$and in acetone-$d_6$ solution which gradually collapse and eventually coalesce into a single line as temperature is raised. This observation could be interpreted in terms of the chemical exchange through direct and/or indirect interconversion between two equivalent conformations possible the complex in both solvents over the temperature range observed. And broadening of $^{133}Cs$ (I = 7/2) nmr line with increasing temperature has also been observed, indicating the exchange of $^{133}Cs$ ion between the complex and the solvent. From numerical fitting of lineshape changes for one-dimensional $^1H$ and $^{133}Cs$ spectra, the exchange rate constants and other relevant parameters for this conformational interconversion and the complex-solvent exchange were deduced.

As an pretreatment, a Fe$(NO_3)_3{\cdot}9H_2O-Al(OH)_3$mixture was ground by a high energy mill and used as a supported catalyst for the growth of carbon nanotubes by a thermal CVD. The crystal structure of the catalyst disordered by the grinding influenced significantly the synthesis of carbon nanotubes in a thermal CVD.

Optical emission studies were performed to investigate thermal and dynamical properties of a plume produced by laser ablation of a graphite target in a nitrogen atmosphere. Experimental spectra of $C_2(d^3{\Pi}_g{\to}a^3{\Pi}_u$, ${\Delta}_V$=1) and CN ($B^2{\Sigma}^+{\to}X^2{\Sigma}^+,{\Delta}_V=0)$ were simulated to obtain the vibrational and rotational temperatures of the electronically excited species at various laser fluences and distances from the target. The spectroscopic temperatures of both molecules were found to be nearly independent of the laser fluence. The temperature of CN molecules was peaked in the middle of the plume while that of $C_2$decreased with increase in the distance. At a given distance, the temperature of CN molecules was clearly higher than that of $C_2$.

Ceruloplasmin (CP), the blue oxidase present in all vertebrates, is the major copper-containing protein of plasma. It has been proposed that oxidation of L-3,4-dihydroxyphenylalanine (DOPA) may contribute to the pathogenesis of neurodegenerative disorders. The effect of the oxidized products of DOPA on the modification of human CP was investigated. When CP was incubated with the oxidized L-DOPA, the protein was induced to be aggregated and ferroxidase activity was decreased in a time-dependent manner. Radical scavengers and catalase significantly inhibited the oxidized DOPA-mediated CP aggregation. Copper chelatrors, Diethylenetriaminepenta acetic acid (DTPA) and Diethyldithiocarbamic acid (DDC), also inhibited the oxidative modification of CP. The results suggested that DOPA oxidation led to the formation of free radical and induced the CP aggregation.

A new PVC membrane electrode for $UO_2^{2+}$ ion based on 2,2'-[1,2-ethanediyl bis (nitriloethylidene)]bis(1-naphthalene) as a suitable ionophore was prepared. The electrode exhibites a Nernstian response for $UO_2^{2+}$ ion over a wide concentration range ($1.0{\times}10^{-1}-1.0{\times}10^{-7}$M) with a slope of 28.5 ${\pm}$ 0.8 mV/decade. The limit of detection is $7.0{\times}10^{-8}$M. The electrode has a response time of < 20 s and a useful working pH range of 3-4. The proposed membrane sensor shows good discriminating abilities towards $UO_2^{2+}$ ion with regard to several alkali, alkaline earth transition and heavy metal ions. It was successfully used to the recovery of uranyl ion from, tap water and, as an indicator electrode, in potentiometric titration of $UO_2^{2+}$ ion with Piroxycam.

Titanium silicalite-1 (TS-1) molecular sieve was produced by microwave heating of amorphous titanium-containing solid precursors after impregnation with aqueous TPAOH solution. $SiO_2-TiO_2$ xerogel, sub-micron sized $SiO_2-TiO_2$ prepared by thermal plasma process, and Ti-containing mesoporous silica, Ti-HMS, were tested as the solid phase substrates. Highly crystalline product was obtained within 30 min. after microwave irradiation with yields over 90% using $SiO_2-TiO_2$ xerogel, which showed essentially identical physicochemical properties to TS-1 prepared by conventional hydrothermal method. Excellent catalytic activity was also obtained for 1-hexene epoxidation using $H_2O_2.\;SiO_2-TiO_2$ particles prepared by thermal plasma and Ti-HMS were found inferior as a substrate for TS-1, probably due to difficulties in wetting the surface uniformly with TPAOH.

Metal treated activated carbons are prepared using various metals. Adsorption behaviors, morphologies, as well as antibacterial effects of metal treated samples are compared before and after solvent washing. Adsorption isotherms are used to characterize the porous structure of metal treated activated carbons before and after the solvent washing with acetone or ethyl alcohol. From these data, it is noticed that the changes in physicochemical properties of metal treated activated carbons depend on the solvents employed. Similar results are observed from BET data obtained from nitrogen adsorption isotherms. From scanning electron microscopy (SEM) studies, the changes in shape and size of metal particles are observed after the samples are washed with solvents. These changes result in different blocking effects, which, in turn, affect the adsorption behavior of metal treated activated carbons. X-ray diffraction (XRD) patterns of the samples treated with different metals are different each other. High intense sharp peaks attributed to metals are observed from silver treated samples, while the peaks are not observed from copper treated samples. To compare thermodynamic behavior of metal treated activated carbons washed with different type of solvents, differential scanning calorimetric (DSC) analysis is carried out. The analysis shows similar endothermic curves for all of the samples. Finally, antibacterial effects of metal treated activated carbon against Escherichia coli are discussed. Comparing the effects among the metals employed, highest effects are obtained from Cd, while lowest effects are obtained from Cu. Antibacterial activity becomes higher with the increase of the amount of metals treated, Optimum concentrations of metals to treat activated carbons, obtained from a shake flask test, are known to be 0.4, 0.1, and 0.6 moles for Ag, Cd, and Cu, respectively.

Partial Least Squares (PLS) calibration performance has been systematically investigated by changing spectral resolutions of near-infrared (NIR) spectra. For this purpose, synthetic samples simulating naphtha were prepared to examine the calibration performance in complex chemical matrix. These samples were composed of $C_6-C_9$ normal paraffin, iso-paraffin, naphthene, and aromatic hydrocarbons. NIR spectra with four different resolutions of 4, 8, 16, and 32$cm^{-1}$ were collected and then PLS regression was performed. For PLS calibration, five different group compositions (such as total paraffin content) and six different pure components (such as benzene concentration) were selected. The overall results showed that at least 8$cm^{-1}$ resolution was required to resolve the complex chemical matrix such as naphtha. It was found that the influence of resolution on the PLS calibration was varied by the spectral features of a component.

A new luminescent polymer, poly{1,4-phenylene-1,2-ethenediyl-2'-[2"-(4'"-octyloxyphenyl)-(5"-yl)-1",3",4"-oxadiazole]-1,4-phenylene-1,2-ethenediyl-2,5-bis-dodecyloxy-1,4-phenylene-1,2-ethenediyl} (Oxd-PPV), was synthesized by the Heck coupling reaction. Electron withdrawing pendant, conjugated 1,3,4-oxadiazole (Oxd), is on the vinylene unit. The band gap of the polymer figured out from the UV-visible spectrum was 2.23 eV and the polymer film shows bright yellow emission maximum at 552 nm. The electroluminescence (EL) maximum of double layer structured device (ITO/PEDOT:PSS/Oxd-PPV/Al) appeared at 553 nm. Relative PL quantum yield of Oxd-PPV film is 3.6 times higher than that of MEH-PPV film. The HOMO and LUMO energy levels of Oxd-PPV figured out from the cyclic voltammogram and the UV-visible spectrum are -5.32 and -3.09 eV, respectively, so that more balanced hole and electron injection efficiency can be expected compared to MEH-PPV. A double layer EL of Oxd-PPV has an maximum efficiency of 0.15 cd/A and maximum brightness of 464 cd/$m^2$.

Titanium sulfate supported on $TiO_2$was prepared by impregnation of powdered $TiO_2$with an aqueous solution of titanium sulfate followed by calcining in air at high temperature. For Ti$(SO_4)_2/TiO_2$ samples calcined at 300 $^{\circ}C$, no diffraction lines of titanium sulfate are observed at $Ti(SO_4)_2$loading up to 30 wt%, indicating good dispersion of $Ti(SO_4)_2$ on the surface of $TiO_2$. The acidity of the catalysts increased in proportion to the titanium sulfate content up to 20 wt% of $Ti(SO_4)_2$. 20 wt% $Ti(SO_4)_2/TiO_2$ calcined at 300 $^{\circ}C$ exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for these reactions, were correlated with the acidity of catalysts measured by ammonia chemisorption method.

In previous studies, charged mosaic membranes having two different fixed charges in the membrane matrix indicated unique transport behavior such as preferential material transport. In this study, the composite charged mosaic membrane endurable to mechanical pressure in practical application was investigated from the same aspect of solute and solvent transport as before. Lp and ${\omega}$ estimated by taking account of active layer thickness were satisfactorily consistent with those in mosaic membrane without reinforcement. On the other hand, the reflection coefficient s indicated the negative value that suggests preferential material transport.

This paper reports the stereoselective synthesis of a novel nucleoside, 4'-methyl branched and bicyclo [3.1.0] hexane locked-nucleoside 12, using a sequential [3,3]-sigmatropic rearrangement/carbene cycloaddition reaction/Curtius reaction strategy with a high stereoselectivity.

The tetranuclear copper(II) cluster compound $[Cu_4OCl_6(C_{14}H_{12}N_2)_4]$ has been synthesized by hydrothermal reaction and studied by X-ray diffraction. The four copper(II) atoms locate four capsheaves of a tetrahedral skeletal structure and a oxygen atom as interstitial atom occupies the center position of the same tetrahedron, and each edge of the Cu-Cu tetrahedron is bridged by one ${\mu}_2$-Cl anion. The copper atom possesses slightly distorted trigonal bipyramidal geometry with three ${\mu}_2$-Cl atoms in equatorial position and the interstitial O atom and one N atom from 3-benzyl-benzimidazole ligand occupying axial position. The Cu-Cu distances are in the range of 3.0986-3.1162 ${\AA}$. The EPR spectrum suggested that the copper(II) ground state $d_{x2-y2}$ and the coordination geometry was trigonal bipyramidal.

Complexes M($C_7H_2NO_5)3H_2O{\cdot}H_2O{\cdot}0.25MeCN$ (M=Ni, Co) were crystallized from the reactions of $Ni(CH_3COO)_2{\cdot}4H_2O\;or\;Co(CH_3COO)_2{\cdot}2H_2O$ with KSCN and 2,6-dicarboxy-4-hydroxypyridine (chelidamic acid). The structures were characterized by X-ray crystallography. The crystal structures of 1 and 2 show a distorted octahedral coordination geometry around the M(II) ions, which are chelated by one nitrogen atom and two oxygen atoms of the chelidamic acid and three water molecules. Complexes 1 and 2 display the hydrogen-bonded 3D framework. The magnetic behavior of 2 exhibits antiferromagnetic interaction.

Ti-ZSM-5 prepared by secondary synthesis, from the reaction of H-ZSM-5 with vapor phase $TiCl_4$, was characterized with several physicochemical techniques including FT-IR and UV/VIS-DRS. It was found that zeolite structure, surface area and pore volume did not change, and the framework aluminum could not be replaced by titanium atom during the secondary synthesis of Ti-ZSM-5. The incorporation of titanium into the framework might be due to reaction of $TiCl_4$with the silanol groups associated with defects or surface sites. The formation of extra-framework titanium could not be avoided, unless the samples were further treated by water vapor at 550 $^{\circ}C$ or higher temperature. High temperature steam treatment of Ti-ZSM-5 prepared by chemical vapor deposition with $TiCl_4$was efficient to prevent the formation of non-framework titanium species. Ti-ZSM-5 zeolites prepared in this work contained only framework titanium species and exhibited improved catalytic property close to TS-1 prepared by hydrothermal synthesis.

Composite membranes with a titania layer were prepared by soaking-rolling method with the titania sol of nanoparticles formed in the sol-gel process and investigated regarding the vapor permeation of various organic mixtures. The support modification was conducted by pressing $SiO_2$ xerogel of 500 nm in particle size under 10 MPa on the surface of a porous stainless steel (SUS) substrate and designed the multi-layered structure by coating the intermediate layer of ${\gamma}-Al_2O_3$. Microstructure of titania membrane was affected by heat-treatment and synthesis conditions of precursor sol, and titania formed at calcination temperature of 300$^{\circ}C$ with sol of [$H^+$]/[TIP]=0.3 possessed surface area of 210 $m^2$/g, average pore size of 1.25 nm. The titania composite membrane showed high $H_2/N_2$ selectivity and water/ethanol selectivity as 25-30 and 50-100, respectively. As a result of vapor permeation for water-alcohol and alcohol-alcohol mixture, titania composite membrane showed water-permselective and molecular-sieve permeation behavior. However, water/methanol selectivity of the membrane was very low because of chemical affinity of permeants for the membrane by similar physicochemical properties of water and methanol.

A new method for the simultaneous determination of seven transition metal ions in water and food by microcolumn high-performance liquid chromatography has been developed. The lead, cadmium, mercury, nickel, cobalt, silver and tin ions were pre-column derivatized with tetra-(4-aminophenyl)-porphyrin ($T_4$-APP) to form the colored chelates which were then enriched by solid phase extraction with $C_{18}$ cartridge. The enrichment factor of 50 was achieved by eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The chelates were separated on a ZORBAX Stable Bound microcolumn ($2.0{\times}50\;mm,\;1.8\;{\mu}m$)with methanol-tetrahydrofuran (95 : 5, v/v, containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH = 10.0) as mobile phase at a flow rate of 0.5 mL/min and detected with a photodiode array detector from 350-600 nm. The seven chelates were separated completely within 2.0 min. The detection limits of lead, cadmium, mercury, nickel, cobalt, silver and tin are 4 ng/L, 3 ng/L, 6 ng/L, 5 ng/L, 5 ng/L, 6 ng/L, 4 ng/L respectively in the original samples. This method was applied to the determination of the seven transition metal in water and food samples with good results.

Solvolyses of isopropylsulfonyl chloride (IPSC) in water, D_2O,\;CH_3OD$, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45$^{\circ}C$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of IPSC with $Y_{Cl}$ (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small slope (m < 0.30). The extended Grunwald-Winstein plots for the solvolysis of IPSC show better correlation. The kinetic solvent isotope effects determined in water and methanol are in consistent with the proposed mechanism of the general base catalyzed and/or $S_AN/S_N2$ reaction mechanism for IPSC solvolyses based on mass law and stoichiometric solvation effect studies.

A poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) (PHDP) was prepared and its luminescence in tetrahydrofuran (THF) was studied. When PHDP is excited by UV light, it produces very strong blue luminescence. The quantum yield of PHDP (Q = 36.9%) is much greater than that of the monomer, 1-hexyl-3,4-dimethylpyrrole (HDP) with Q = 0.61%. The principal luminescence of PHDP has a single decay component with ca. 1 ns, whereas the decay of HDP is complicated. The molecular structure and conformational behavior of HDP and the oligomers up to trimer have been also determined by ab initio Hartree-Fock (HF/6-31$G^{**}$), density functional theory (DFT-B3LYP/6-31$G^{**}$), and semiempirical (ZINDO) methods. According to the results of calculations, it is proposed that the enhanced quantum yield of the polymer PHDP results mostly from the ${\pi}$-conjugation between neighboring pyrrole rings.

Peroxynitrite enters erythrocytes through band 3 anion exchanger and oxidizes cytosolic proteins therein. As a protein associated with band 3, carbonic anhydrase II may suffer from peroxynitrite-induced oxidative damages. Esterase activity of carbonic anhydrase II decreased as the concentration of peroxynitrite increased. Neither hydrogen peroxide nor hypochlorite affected the enzyme activity. Inactivation of the enzyme was in parallel with the release of zinc ion, which is a component of the enzyme's active site. SDS-PAGE of peroxynitrite-treated samples showed no indication of fragmentation but non-denaturing PAGE exhibited new bands with lower positive charges. Western analysis demonstrated that nitration of tyrosine residues increased with the peroxynitrite concentration but the sites of nitration could not be determined. Instead MALDI-TOF analysis identified tryptophan-245 as a site of nitration. Such modification of tryptophan residues is responsible for the decrease in tryptophan fluorescence. These results demonstrate that peroxynitrite nitrates tyrosine and tryptophan residues of carbonic anhydrase II without causing fragmentation or dimerization. The peroxynitrite-induced inactivation of the enzyme is primarily due to the release of zinc ion in the enzyme's active site.

Amineterminated, ethylenediamine core polyamidoamine starburst dendrimers of generation 2 (G2), generation 4 (G4) and generation 6 (G6) have been successfully surface-modified via an amide coupling reaction with 4-ethyl, 4'-(3-propionic) bipyridinium cation and the electrochemical behavior of the resulting dendrimers were investigated in aqueous potassium chloride electrolyte solutions. The 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide-mediated reaction resulted in 25-39% end-group functionalization. The water-soluble 4-ethyl, 4'-(3-propylamide) bipyridinium dibromide dendrimers (G2-V2+, G4-V2+ and G6-V2+) were characterized by $^1H$ NMR and UV-Vis spectroscopic methods. The cyclic voltammetric and chronoamperometric experiments were performed to determine the diffusion coefficient and the number of electrons transferred in the process of the first reduction of the viologen-functionalized dendrimers. Adsorption of viologen-functionalized dendrimers at electrode surface was evidenced in the voltammograms. Experimentally determined diffusion coefficients were in good agreement with the values expected from the Stokes-Einstein relation, while the number of electrons transferred concurred with the extent of functionalization determined by $^1H$ NMR and UV-Vis spectra.

Acetohydroxy acid synthase (AHAS) is one of several enzymes that require thiamine diphosphate and a divalent cation as essential cofactors. The active site contains several conserved ionizable groups and all of these appear to be important as judged by the fact that mutation diminishes or abolishes catalytic activity. Recently, we have shown [Yoon, M.-Y., Hwang, J.-H., Choi, M.-K., Baek, D.-K., Kim, J., Kim, Y.-T., Choi, J.-D. FEBS Letters 555 (2003), 185-191] that the activity is pH-dependent due to changes in $V_{max}$ and V/$K_m$. Data were consistent with a mechanism in which substrate was selectively catalyzed by the enzyme with an unprotonated base having a pK 6.48, and a protonated group having a pK of 8.25 for catalysis. Here, we have in detail studied the pH dependence of the kinetic parameters of the cofactors (ThDP, FAD, $Mg^{2+}$) in order to obtain information about the chemical mechanism in the active site. The $V_{max}$ of kinetic parameters for all cofactors was pH-dependent on the basic side. The pK of ThDP, FAD and $Mg^{2+}$ was 9.5, 9.3 and 10.1, respectively. The V/$K_m$ of kinetic parameters for all cofactors was pH-dependent on the acidic and on the basic side. The pK of ThDP, FAD and $Mg^{2+}$ was 6.2-6.4 on the acidic side and 9.0-9.1 on the basic side. The well-conserved histidine mutant (H392) did not affect the pH-dependence of the kinetic parameters. The data are discussed in terms of the acid-base chemical mechanism.

In this paper, kinetics of reaction between Bromophenol blue (BPB) and $OH^-$, called fading, has been studied through a spectrophotometric method in the presence of nonionic Triton X-100 (TX-100), anionic sodium dodecyl sulfate (SDS) and cationic dodecyl trimethylammonium bromide (DTAB) surfactants. The influence of changes in the surfactant concentration on the observed rate constant was investigated. The results are treated quantitatively by pseudophase ion-exchange (PPIE) model and a new simple model called "classical model". The binding constants of BPB molecules to the micelles and free molecules of surfactants, their stoichiometric ratios and thermodynamic parameters of binding have been evaluated. It was found that SDS has nearly no effect on the fading rate up to 10 mM, whereas TX-100 and DTAB interact with BPB which reduce the reaction rate. By the use of fading reaction of BPB, the binding constants of SDS molecules to TX-100 micelles and their Langmuir and Freundlich adsorption isotherms were obtained and when mixtures of DTAB and TX-100 were used, no interaction was observed between these two surfactants.

We presents new results for transport properties of dumbbell fluids by equilibrium molecular dynamics (EMD) simulations using Green-Kubo and Einstein formulas. It is evident that the interaction between dumbbell molecules is less attractive than that between spherical molecules which leads to higher diffusion and to lower friction. The calculated viscosity, however, is almost independent on the molecular elongation within statistical error bar, which is contradicted to the Stokes' law. The calculated thermal conductivity increases and then decreases as molecular elongation increases. These results of viscosity and thermal conductivity for dumbbell molecules by EMD simulations are inconsistent with the earlier results of those by non-equilibrium molecular dynamics (NEMD) simulations. The possible limitation of the Green-Kubo and Einstein formulas with regard to the calculations of viscosity and thermal conductivity for molecular fluids such as the missing rotational degree of freedom is pointed out.