The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

New banana-shaped achiral compounds, 1,3-phenylene bis [4-{4-(alkenyloxy) phenyliminomethyl}benzoate]s were synthesized by varying the length of alkenyl group; their ferroelectric properties are described. The smectic mesophases, including a switchable chiral smectic C $(Sm\;C^*)$ phase, were characterized by differential scanning calorimetry, polarizing optical microscopy and triangular wave method. The presence of vinyl groups at the terminals of linear side wings in the banana-shaped achiral molecules containing Schiff's base mesogen induced a decrease in melting temperature and formation of the switchable $(Sm\;C^*)$ phase in the melt. The smectic phases having the octenyloxy group such as $(CH_2)_6CH=CH_2$ showed ferroelctric switching, and their values of spontaneous polarization on reversal of an applied electric field were 120 nC/cm² (X=H) and 225 nC/ cm² (X=F), respectively. We could obtain ferroelectric phases by controlling the number of carbon atom in alkenyloxy chain of a bent-core molecule.

The One Pass Method (OPM) previously presented for the identification of single input single output systems is used to estimate the parameters of a Decentralized Control System (DCS). The OPM is a linear and therefore a simple estimation method. All of the calculations are performed in one pass, and no initial parameter guess, iteration, or powerful search methods are required. These features are of interest especially when the parameters of multi input-output model are estimated. The benefits of the OPM are revealed by comparing its results against those of two recently published methods based on pulse testing. The comparison is performed using two databases from the literature. These databases include single and multi input-output process transfer functions and relevant disturbances. The closed loop responses of these processes are roughly captured by the previous methods, whereas the OPM gives much more accurate results. If the parameters of a DCS are estimated, the OPM yields the same results in multi or single structure implementation. This is a novel feature, which indicates that the OPM is a convenient and practice method for the parameter estimation of multivariable DCSs.

An analytical method for the simultaneous determination of trace Ge, As and Se in biological samples by inductively coupled plasma/mass spectrometry has been investigated. The effects of added organic gas into the coolant argon gas on the analyte signal were studied to improve the detection limit, accuracy and precision. The addition of a small amount of methane (10 mL/min.) into the coolant gas channel improved the ionization of Ge, As and Se. The analytical sensitivity of the proposed Ar/CH₄system was superior by at least two-fold to that of the conventional Ar method. In the present method, the detection limits obtained for Ge, As and Se were 0.014, 0.012 and 0.064 ㎍/L, respectively. The analytical reliability of the proposed method was evaluated by analyzing the certified standard reference materials (SRM). Recoveries of 99.9% for Ge, 103% for As, 96.5% for Se were obtained for NIST SRM of freeze dried urine sample. The proposed method was also applied to the biological samples.

A highly interferent-resistive membrane, poly-5-amino-1-naphthol (poly-5A1N), underlied beneath enzymeembedded poly-1,3-phenylendiamine (poly-m-PD) network for miniturized continuous monitoring glucose sensors. The enzyme layer was prepared from a mixed solution of glucose oxidase (GOx) and m-PD monomer by simple electrolysis. The mass change of poly-5A1N was monitored by electrochemical quartz crystal microbalance (EQCM) in situ and the corresponding thickness was measured. Successive electropolymerization of poly-5A1N and poly-m-PD create a several tens nm-thick bilayer showing excellent selectivity for $H_2O_2$ and low activity loss of immobilized enzymes.

α,β-Unsaturated aldehydes and ketones are regioselectively reduced to the corresponding allylic alcohols with /Dowex1-x8 system in THF at room temperature. This system is also efficient for the conversion of α-diketones and acyloins to the vicinal diols in refluxing THF.

Physical properties and microstructure of new coumarin 4 doped $SiO_2$-PDMS ORMOSILs, synthesized by one-step (OS, acid-catalysis) and two-step (TS, acid-base catalysis) routes of sol-gel method with varying pH (0.6 to 7) and dye content $(5\;{times}\;10^{-4}\;to\;5{\times}\;10^{-2}\;mole)$, are reported. BET, UV-visible spectroscopy and SEM were used for characterizations. The increase in acid or base concentration increased the size of pores and aggregated silica particles. The samples with pH ≤ 2.5 were transparent and attributed to the small size of pores (~20 Å) and silica particles. The samples with pH > 2.5 were translucent or opaque due to non-uniform pore system formed by voids and large aggregated silica particles. The surface area was found a key factor controlling the interactions between the gel matrix and the dye. The OS samples with the highest dye concentration exhibited the minimal values of pore size, surface area and silica particle size, resulting in the concentration-quenching phenomenon.

Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

Vanadium oxides supported on zirconia and modified with MoO₃were prepared by adding Zr(OH)₄powder into a mixed aqueous solution of ammonium metavanadate and ammonium molybdate followed by drying and calcining at high temperatures. The characterization of prepared catalysts was performed using FTIR, Raman spectroscopy and solid-state $^{51}V$ NMR. In the case of a calcination temperature of 773 K, for samples containing low loading of $V_2O_5$, below 15 wt %, vanadium oxide was in a highly dispersed state, while for samples containing high loading of $V_2O_5$, equal to or above 15 wt %, vanadium oxide was well crystallized because the $V_2O_5$ loading exceeded the formation of a monolayer on the surface of $ZrO_2$. The $ZrV_2O_7$ compound was formed through the reaction of $V_2O_5\;and\;ZrO_2$ at 873 K and the compound decomposed into $V_2O_5\;and\;ZrO_2$ at 1073 K, which were confirmed by FTIR spectroscopy and solid-state $^{51}V$ NMR. IR spectroscopic studies of ammonia adsorbed on $V_2O_5-MoO_3/ZrO_2$ showed the presence of both Lewis and Bronsted acids.

A time-resolved probe beam deflection (PBD) technique was employed to study the energy relaxation dynamics of photofragments produced by photodissociation of $CH_3I$ at 266 nm. Under 500 torr argon environment, experimental PBD transients revealed two energy relaxation processes; a fast relaxation process occurring within an acoustic transit time (less than 0.2 ㎲ in this study) and a slow relaxation process with the relaxation time in several tens of ㎲. The fast energy relaxation of which signal intensity depended linearly on the excitation laser power was assigned to translational-to-translational energy transfer from the photofragments to the medium. As for the slow process, the signal intensity depended on square of the excitation laser power, and the relaxation time decreased as the photofragment concentration increased. Based on experimental findings and reaction rate constants reported previously, the slow process was assigned to methyl radical recombination reaction. In order to determine the rate constant for methyl radical recombination reaction, a theoretical equation of the PBD transient for a radical recombination reaction was derived and used to fit the experimental results. By comparing the experimental PBD curves with the calculated ones, the rate constant for methyl recombination is determined to be $3.3({\pm}1.0)\;{\times}\;10^6\;s^{-1}torr^{-1}$ at 295 ± 2 K in 500 torr Ar.

An analysis of the electronic structure and bonding in the ternary silicide YNiSi₃is made, using extended Huckel tight-binding calculations. The YNiSi₃structure consists of Ni-capped Si₂dimer layers and Si zigzag chains. Significant bonding interactions are present between the silicon atoms in the structure. The oxidation state formalism of $(Y^{3+})(Ni^0)(Si^3)^{3-}$ for YNiSi₃constitutes a good starting point to describe its electronic structure. Si atoms receive electrons from the most electropositive Y in YNiSi₃, and Ni 3d and Si 3p states dominate below the Fermi level. There is an interesting electron balance between the two Si and Ni sublattices. Since the ${\pi}^*$ orbitals in the Si chain and the Ni d and s block levels are almost completely occupied, the charge balance for YNiSi₃can be rewritten as $(Y^{3+})(Ni^{2-})(Si^{2-})(Si-Si)^+$, making the Si₂layers oxidized. These results suggest that the Si zigzag chain contains single bonds and the Si₂double layer possesses single bonds within a dimer with a partial double bond character. Strong Si-Si and Ni-Si bonding interactions are important for giving stability to the structure, while essentially no metal-metal bonding exists at all. The 2D metallic behavior of this compound is due to the Si-Si interaction leading to dispersion of the several Si₂π bands crossing the Fermi level in the plane perpendicular to the crystallographic b axis.

A simple synthetic method for haptens of organophosphorus (OP) pesticides with a spacer arm (aminocarboxylic acid) attached at the pesticide thiophosphate group was developed and was applied to the synthesis of haptens for the OP fungicide tolclofos-methyl. Using the haptens, a selective enzyme-linked immunosorbent assay (ELISA) for tolclofos-methyl was developed. One of the haptens was coupled to BSA to use as an immunogen. Rabbits were immunized with this conjugate to obtain polyclonal antibodies to tolclofos-methyl. The antisera were screened against another hapten coupled to ovalbumin (OVA). Using the serum with highest specificity, an antigen-coated ELISA was developed, which showed an $IC_{50}$ of 160 ng/mL with the detection limit of 20 ng/mL. The antibodies showed negligible cross-reactivity with other OP pesticides. An antibody-coated ELISA was also developed, which showed an $IC_{50}$ of 410 ng/mL with a detection limit of 130 ng/mL.

The conformation of synthetic oligosaccharide can be elucidated by employing molecular modeling and highfield proton NMR (nuclear magnetic resonance) spectroscopy. Information with respect to the composition and configuration of saccharide residues and the sequence and linkage positions of the oligosaccharide can be obtained by employing a variety of one- and two-dimensional NMR techniques and molecular modeling. These techniques are also useful in establishing the solution conformation of the oligosaccharide moiety. This study is focused on the elucidation of linkage positions of synthetic trisaccharides, Gal(β1-4)Glc(β1-3)Glc, Gal(β1-4)Glc(β1-4)Glc and Gal(β1-4)Glc(β1-6)Glc.

The quantity, process and kinetics of di-(2-ethylhexyl)phthalate (DEHP) migration in the 30/70 and 40/60 poly(vinylchloride) (PVC)/DEHP blends were investigated using gas chromatograph. A thin and flexible PVC sheet was soaked in surrounding medium (SM) of water/ethanol mixture and acetonitrile with constant stirring to release DEHP. By observed concentration of DEHP in the SM, it is found that acetonitrile is more intense in DEHP migration than water/ethanol mixture. In addition the amount of extracted DEHP is proportional to the leaching temperature and added ratio of DEHP. The behavior of DEHP migration from flexible PVC sheets was described by the Ficks's law with $2.72-10.1\;{times}\;10^{-10}$ cm²/s of the diffusion coefficients.

The mechanism of the decomposition of a bronchodilator, S-nitroso-N-acetyl-D,L-penicillamine (SNAP) by a bronchoconstrictor, aqueous sulfite, has been investigated in detail. The decomposition was studied using a conventional spectrophotometer at 336 nm over the ranges: 0.010 ≤ $[S^{IV}]_T$ ≤ 0.045 mol $dm^{-3}$, 3.96 ≤ pH ≤ 6.80 and 15.0 ≤ θ≤ 30.0 ℃, 0.60 ≤ I ≤ 1.00 mol $dm^{-3}$, and at ionic strength 1.00 mol $dm^{-3}$ (NaCl). The rate of reaction is dependent on the total sulfite concentration and pH in a complex manner, i.e., $k_{obs}\;=\;k_1K_2[S^{IV}]_T/ ([H^+]\;+\;K_2)$. At 25.0 ℃, the second order rate constant, $k_1$, was determined as $12.5\;{\pm}\;0.15\;mol^{-1}\;dm^3\;s^{-1}$. ${\Delta}H^{neq}\;=\;+32\;{\pm}\;3 kJ\;mol^{-1}\;and\;{\Delta}S^{\neq}\;=\;-138\;{\pm}\;13\;J\;mol^{-1}K^{-1}$. The N-nitrosohydroxylamine-N-sulfonate ion was detected as an intermediate before the formation of any of the by-products, namely, N-acetyl-D,L-penicillamine. The effect of concentration of aqueous copper(Ⅱ) ions on this reaction was also examined at pH 4.75, but there was no dependence on $[Cu^{2+}]$. In addition, the $pK_a$ of SNAP was determined as 3.51 ± 0.06 at 25.4 ℃ [I = 1.0 mol $dm^{-3}$ (NaCl)].

The pathway producing imide ring closure during the thermal imidization of poly(amic acid) (PAA) was investigated in detail using a new analytical method, two-dimensional (2D) Raman correlation spectroscopy. The signs of the cross peaks in synchronous spectra provided evidence of the thermal imidization of PAA into PI as the heating temperature increased. The signs of the cross peaks in asynchronous spectra suggested that the imide-related modes changed prior to the amide or carboxylic mode, which indicates that cyclization occurred before the amide proton was abstracted.

The major ionic components of precipitation collected at the 1100 Site of Mt. Halla and Jeju city have been determined. The reliability of the analytical data was verified by the comparison of ion balances, electric conductivities and acid fractions; all of their correlation coefficients were above 0.94. Ionic strengths lower than $10^{-4}$ M were found in 53% of the 1100 Site samples and 28% of the Jeju city samples. Compared with other inland areas, the wet deposition of $Na^+,\;Cl^-\;and\;Mg^{2+}$ was relatively larger, but that of $NH_4^+,\;nss-SO_4^{2-}$(non-sea salt sulfate) and $NO_3^-$ was lower. Especially the wet deposition increase of $Ca^{2+}$ in the spring season supports the possibility of the Asian Dust effect. The acidification of precipitation was caused mostly by $SO_4^{2-}\;and\;NO_3^-$ in the Jeju area, and the organic acids have contributed only about 7% to the acidity. The neutralization factors by NH₃were 0.47 and 0.48, and that of CaCO₃was 0.31 and 0.25 at the 1100 Site and Jeju city, respectively. Investigation into major influencing sources on precipitation components by factor analysis showed that the precipitation at the 1100 Site had been influenced mostly by an anthropogenic source, followed by soil and seawater sources. The precipitation at Jeju city was mainly influenced by oceanic sources, followed by anthropogenic and soil sources.

Coulson (ZINDO), Mulliken $(MP2/6-31G^*)$ and Natural $(MP2/6-31G^*)$ population analyses of several large molecules were performed by the Fragment Reassociation (FR) method. The agreement between the conventional ZINDO (or conventional MP2) and FR-ZINDO (or FR-MP2) charges of these molecules was excellent. The standard deviations of the FR-ZINDO net atomic charges from the conventional ZINDO net atomic charges were 0.0008 for $C_{10}H_{22}$ (32 atoms), 0.0012 for $NH_2-C_{16}O_2H_{28}-COOH$ (53 atoms), 0.0014 for $NH_3^+-C_{16}O_2H_{28}-COOH$ (54 atoms), 0.0017 for $NH_2-C_{16}O_2H_{28}-COO^-$ (52 atoms), 0.0019 for $NH_3^+-C_{16}O_2H_{28}-COO^-$ (53 atoms), 0.0024 for a conjugated model $(O=CH-(CH=CH)_{15}-C=O-(CH=CH)_{12}-CH=CH_2)$, 118 atoms), 0.0038 for aglycoristocetin $(C_{60}N_7O_{19}H_{52}^+$, 138 atoms), 0.0023 for a polypropylene model complexed with a zirconocene catalyst $(C_{68}H-{121}Zr^+$, 190 atoms) and 0.0013 for magainin $(C_{112}N_{29}O_{28}SH_{177}$, 347 atoms), respectively. The standard deviations of the FR-MP2 Mulliken (or Natural) partial atomic charges from the conventional ones were 0.0016 (or 0.0016) for $C_{10}H_{22}$, 0.0019 (or 0.0018) for $NH_2-C_{16}O_2H_{28}-COOH$ and 0.0033 (or 0.0023) for $NH_3^+-C_{16}O_2H_{28}-COO^-$, respectively. These errors were attributed to the shape of molecules, the choice of fragments and the degree of ionic characters of molecules as well as the choice of methods. The CPU time of aglycoristocetin, conjugated model, polypropylene model complexed with zirconocene and magainin computed by the FR-ZINDO method was respectively 2, 4, 6 and 21 times faster than that by the normal ZINDO method. The CPU time of $NH_2-C_{16}O_2H_{28}-COOH\;and\;NH_3^+-C_{16}O_2H_{28}-COO^-$ computed by the FR-MP2 method was, respectively, 6 and 20 times faster than that by the normal MP2 method. The largest molecule calculated by the FR-ZINDO method was B-DNA (766 atoms). These results will enable us to compute atomic charges of huge molecules near future.

Physicochemical properties of a series of PC monolayers with different alkyl chains (C24, C20, C16, and C8), at the air/water interface were investigated. The surface pressure is influenced mainly by the hydrophobicity of the PCs, which is confirmed by the curve shape and the on-set value of π-A isotherms at the air/water interface by increasing the number of alkyl chain. The on-set values of surface pressure were 125 Ų/molecule for DOPC(C8), 87 Ų/molecule for DPPC(C16), 75 Ų/molecule for DAPC(C20), and 55 Ų/molecule for DLPC(C24), respectively. The orientations of alkyl chains at the air/water interface are closely connected with the rigidity of the monolayers, and it was confirmed by the tendency of monolayer thickness in ellipsometry data. The temperature dependence of a series of PCs shows that the surface pressure decreases by increasing temperature, because the longer the alkyl chain length, the larger the hydrophobic interaction in surface pressure. The temperature effects and the conformational changes of unsaturated and saturated PCs were confirmed by the computer simulation study of the cis-trans transition with POPC and DPPC(C16). The cistrans conformational energy difference of POPC is 62.06 kcal/mol and that of DPPC(C16) is 6.75 kcal/mol. Due to the high conformational energy barrier of POPC, phase transition of POPC is limited in comparison with DPPC(C16).

The emission and excitation spectra of $cis-[Cr(cyclam)(NCS)_2]NCS$ (cyclam = 1,4,8,11-tetraazacyclotetradecane) taken at 77 K are reported. The infrared and visible spectra at room temperature are also measured. The vibrational intervals due to the electronic ground state are extracted from the far-infrared and emission spectra. The ten pure electronic origins due to spin-allowed and spin-forbidden transitions are assigned by analyzing the absorption and excitation spectra. Using the observed transitions, a ligand field analysis has been performed to determine the bonding properties of the coordinated ligands in the title chromium(Ⅲ) complex. According to the results, it is found that nitrogen atoms of the cyclam ligand have a strong σ-donor character, while the NCS ligand has medium σ- and π-donor properties toward chromium(Ⅲ) ion.