Recent progress in the filed of transition-metal mediated C-H bond activation has had a great influence on organic synthesis. Among such transition-metal catalyzed reactions, ortho-functionalization via the chelationassisted strategy has been paid great attentions as one of the powerful methodologies for converting aromatic compounds into ones that are more functionalized at the exclusively ortho-position. In this context, various transition metal-catalyzed ortho-functionalizations such as alkylation, alkenylation, silylation and carbonylation are described briefly and their prospects are suggested.

Copper(II) ion-selective PVC membrane electrode based on 2-mercaptobenzoxazole as a new ionophore and o-nitrophenyl octyl ether (o-NPOE) as plasticizer is proposed. This electrode revealed good selectivity for $Cu^{2+}$ over a wide variety of other metal ions. Effects of experimental parameters such as membrane composition, nature and amount of plasticizer, and concentration of internal solution on the potential response of $Cu^{2+}$ sensor were investigated. The electrode exhibits good response for $Cu^{2+}$ in a wide linear range of 5.0 ${\times}$ 10−.6-1.6 ${\times}$ $10^{-2}$ mol/L with a slope of 29.2 ${\pm}$ 2.0 mV/decade. The response time of the sensor is less than 10 s, and the detection limit is 2.0 ${\times}$ $10^{-6}$ mol/L. The electrode response was stable in pH range of 4-6. The lifetime of the electrode was about 2 months. The electrode revealed comparatively good selectivities with respect to many alkali, alkaline earth, and transition metal ions.

Novel nickel catalyst deposited on nanoporous carbon was found to be an efficient catalyst for the epoxidation of simple alkenes with $O_2$ and isobutyraldehyde under mild conditions. Alkenes exhibited different reactivities towards Ni-catalyst and epoxidation with stilbene proceeds stereospecifically. This may be rationalized with the mechanism involving coordinated acylperoxy radical intermediate. Nickel contents depend on the preparative methods and the KNI-3 catalyst, which was synthesized by wet impregnation of $Ni(NO_3)_2$ into nanoporous carbon, shows the highest activity. The activity of the catalyst is well correlated with contents of nickel. Recycled catalysts suffer considerable loss of activity due to leaching of catalytic active species, nickel.

A long, bis(monodentate), linking Schiff-base ligand L (py-CH=N-$C_6H_4$-N=CH-py) was prepared from 1,4-phenylenediamine and 3-pyridinecarboxaldehyde by the Schiff-base condensation. Ligand L has two terminal pyridyl groups capable of coordinating to metals through their nitrogen atoms. In contrast, the same reaction between 1,2-phenylenediamine and 3-pyridinecarboxaldehyde produced a mixture of imidazol isomers (2-pyridin-3-yl-1H-benzoimidazole), which are connected to one another by the N-H…N hydrogen bonding to form a tetramer. From Zn($NO_3)_2{\cdot}6H_2O$ and ligand L under various conditions, one discrete molecule, trans- [Zn($H_2O)_4L_2]{\cdot}(NO_3)_2{\cdot}(MeOH)_2$, and two 1-D zinc polymers, [Zn$(NO_3)(H_2O)_2(L)]{\cdot}(NO_3){\cdot}(H_2O)_2$ and [Zn(L) (OBC)($H_2O$)], were prepared. In ligand L, the N$\ldots$N separation between the terminal pyridyl groups is 13.994 $\AA$, with their nitrogen atoms at the meta positions (3,3’) in a trans manner. The corresponding N$\ldots$N separations in its compounds range from 13.853 to 14.754 $\AA$.

Indirect electrochemical oxidation of phenol by $Ce^{4+}$ was investigated in sulfuric acid solutions. It was found that electrode fouling during oxidation of phenol can be controlled by adjusting the time interval (TI) of double potential steps (DPSs). While the electroactivity was greatly decreased after several DPSs of a relatively long TI, repeated DPSs with a short potential pulse showed substantial amounts of electroactivity after a few hundreds or thousands DPS, suggesting that the formation of an insulating layer can be controlled by adjusting a potential program. Effectiveness of the consecutive application of DPSs for phenol decomposition was confirmed by GC-MS.

The sharp-line absorption and emission spectra of $(H_{13}O_6)${$trans-[Cr(Me_2tn)_2Br_2]$}$_2Br_2(ClO_4)\;(Me_2$tn = 2,2-dimethyl-1,3-diaminopropane) have been measured between 13000 $cm^{-1}$ and 16000 $cm^{-1}$ at 5 K. The 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex ion. The zero-phonon line in the sharp-line absorption spectrum splits into two components by 286 $cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the Me2tn ligand have a strong $\sigma$-donor character, but the bromide has weak $\sigma$- and $\pi$-donor properties toward chromium(III) ion.

Calculations are presented for the structures of various conformers of the bare proline and proline –($H_2O$) cluster. The effects of hydrogen bonding with a water molecule on the relative stability of the low energy conformers of proline are examined. Microsolvation by a water molecule is predicted to affect the relative stability, structures and the infrared frequencies of the conformers to a large degree.

The three new lignans 1-3 were isolated from the methanol extracts of the flower buds of Magnolia fargesii. They were elucidated as (7S,8R)-1-(3,4-dimethoxyphenyl)-2-O-(2-methoxy-4-omegahydroxypropylphenyl) propane-1,3-diol, (7S,8S)-1-(4-hydroxy-3-methoxyphenyl)-2-O-(6-hydroxy-2-methoxy-4-omegahydroxypropylphenyl) propane-1,3-diol, and [tetrahydro-4-hydroxy-2-(3,4,5-trimethoxyphenyl)furan-3-yl]methyl 3,4-dimethoxy benzoate by spectral analysis.

Acetohydroxy acid synthase catalyzes the first common step in the biosynthesis of branched chain amino acids. AHAS plays two distinct metabolic roles, and is designated as anabolic AHAS and catabolic AHAS, depending on its function. Anabolic AHAS is FAD-dependent, while its catabolic counterpart is not. In this work, a conserved motif was identified in the $\beta$-domain of anabolic AHASs, but not in catabolic AHAS ($_{372}RFDDR_{376}$). In order to determine the functions of this motif, we replaced the motif with the corresponding sequence in FAD-independent AHAS, SPVEY. None of these three mutants (SPV, SPVE, and SPVEY) was detected with bound FAD. However, two of these mutants (SPVE and SPVEY) were active at a low level of specific activity. Although they exhibited pyruvate- and ThDP- dependent characteristics, the activity of the two active mutants appears to be FAD-independent. The SPVEY mutant was completely insensitive to the three tested herbicides, even at extremely high concentrations and is also somewhat more thermolabile than the wild type enzyme. The data provided in this work suggest that the RFDDR motif is a possible determinant of the FAD-dependent and herbicide-resistant properties of tobacco AHAS. The SPVEY mutant appears to exhibit catabolic AHAS-like activity.

It is known that metallothionein (MT) plays a role in the scavenging of free radicals, which is produced under various stress conditions. MT may function as an antioxidant that protects against oxidative damage of DNA, protein, and lipid induced by superoxide anion, hydrogen peroxide, hydroxyl radical, nitric oxide, and peroxynitrite. This study was undertaken to test the hypothesis that MT also protects from RNA damage induced by peroxynitrite, an important reactive nitrogen species that causes a diversity of pathological processes. A cell-free system was used. RNA damage was detected by the mobility of $tRNA^{Phe}$ in electrophoresis. Cleavages on tRNA were not induced by 3-morpholinosydnomine, which produces peroxynitrite directly. MT induced tRNA damage which was site specific.

Some new metal(II) complexes, $M^{II}L_2$ [M = Mn (1), Co (2), Ni (3), Cu (4), and Zn (5)] of 2-acetylpyridine benzoylhydrazone ligand (HL) containing trifunctional NNO-donor system have been synthesized and crystallographically characterized for the complex 1 and 5. The complexes consist of two ligands to give sixcoordinate, which are bonded to the metal atom on a meridional plane through acetylpyridine ring nitrogen, azomethine nitrogen, and benzoyl oxygen atoms, respectively. The coordination geometry for other complexes was identified on the basis of the physicochemical data by elemental analyses, FAB -MS, IR, $^1H$ NMR, and electronic spectral measurements. The resulting data indicated that the complexes are accordance with the above formulation.

A chloroform membrane system containing a given mixture of benzylaza-12-crown-4 and oleic acid is introduced for the selective and efficient transport of $Pb^{2+}$ ion. The transport was capable of moving metal ions ‘up-hill’. In the presence of ${S_2O_3}^{2-}$ion as a suitable metal ion acceptor in the receiving phase, the amount of lead ion transport across the liquid membrane after 150 minutes is (95.0 ${\pm}$ 1.7)%. The selectivity and efficiency of lead transport from aqueous solution containing $Tl^+,\;Ag^+,\;Mg^{2+},\;Ca^{2+},\;Co^{2+},$ $Ni^{2+},\;Cu^{2+},\;Zn^{2+},\;Hg^{2+}$ and $Cd^{2+}$were investigated. In the presence of thiosulfate as a suitable masking agent in the source phase, the interfering effects of $Ag^+\;and\;Cu^{2+}$ were diminished drastically.

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

For the detection of cyanobacterial toxin, an Enzyme-linked immunosorbent assay (ELISA) was integrated into a PDMS microchip. The conjugates of microcystin-LR (MCLR) and keyhole limpet hemocyanin (KLH) were adsorbed on the surface of polystyrene beads and these MCLR-KLH polystyrene beads were introduced into a microchamber. MCLR on the surface of polystyrene beads reacted with horseradish peroxides (HRP) conjugated anti-MCLR monoclonal antibody (mAb) which had a competitive reaction with MCLR in water sample. After the enzyme substrate 3,3,5,5-tetramethyl benzidine (TMB) was injected into the chamber and catalyzed by HRP, the color change was detected with a liquid-cord waveguide. This integration shortened the conventional ELISA analysis time from several hours to about 30 min with only 4.2 $\mu$L MCLR sample consuming which was useful for the environmental analysis. More over, troublesome operations required for ELISA could be replaced by simple operations. The microchip based detection system showed a good sensitivity of 0.05 $\mu$g/L and maintained good reliability through its quantitative range with low coefficients of variation (2.5-10.5%).

An effective spectrophotometric determination of palladium with 4-(2-pyridylazo)-resorcinol (PAR) using molten naphthalene as a diluent has been studied. A red complex of palladium with PAR is formed at 90 ${^{\circ}C}$. In the range of pH 9.0-11.0, the complex is quantitatively extracted into molten naphthalene. The organic phase is anhydrously dissolved in $CHCl_3$ to be determined spectrophotometrically at 520 nm against the reagent blank. Beer’s law is obeyed over the concentration range of 0.1-2 ${\mu}g{\cdot}mL^{-1}$. The molar absorptivity and Sandell’s sensitivity are 8.0 ${\times}\;10^5\;L{\cdot}mol^{-1}{\cdot}cm^{-}1\;and\;0.49\;{\mu}g{\cdot}cm^{-2}$ respectively. From the results of tolerance limits, it was found that there was no interferences were observed for most of the ions examined and those somewhat high interferences by Co(II), Fe(II) and Bi(III) could be effectively masked by EDTA.

Rotating compensator multichannel spectroscopic ellipsometry has been employed to determine the optical functions of various liquids used in chemistry. We attempted three different measurement configurations: (1) air-liquid interface, (2) prism-liquid interface, and (3) liquid-sample interface. In prism-liquid interface, we found that the prism surface had roughness and it should be considered in analysis for accurate results. In liquidsample interface, we had much higher reflection, better sensitivity, and less limitation compared to the other two configurations when crystalline silicon was used as reference sample. We discuss the merit of each configuration and present the optical functions of various liquids. Also we demonstrate Bruggeman effective medium theory to determine the optical properties of mixed liquid.

Angiotensin-converting enzyme (ACE) is known to be primarily responsible for hypertension. Threedimensional quantitative structure-activity relationship (3D-QSAR) models have been constructed using the comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) for a series of 28 ACE inhibitors. The availability of ACE crystal structure (1UZF) provided the plausible biological orientation of inhibitors to ACE active site (C-domain). Alignment for CoMFA obtained by docking ligands to 1UZF protein using FlexX program showed better statistical model as compared to superposition of corresponding atoms. The statistical parameters indicate reasonable models for both CoMFA ($q^2$ = 0.530, $r^2$ = 0.998) and CoMSIA ($q^2$ = 0.518, $r^2$ = 0.990). The 3D-QSAR analyses provide valuable information for the design of ACE inhibitors with potent activity towards C-domain of ACE. The group substitutions involving the phenyl ring and carbon chain at the propionyl and sulfonyl moieties of captopril are essential for better activity against ACE.

Investigation of structure-activity relationships of novel quinazolines has identified 7,8-dihydro-[1,4]dioxino-[2,3-g]quinazolines as a potent inhibitor of EGFR. These compounds have a benzodioxane framwork, which was prepared by regioselective O-alkylation of ethyl 3,4-dihydroxy benzoate by epoxide ring opening. Compounds 3f and 3k were more potent than ZD-1839 in EGF enzyme and EGFR autophosporylation inhibition assays.

To measure the thickness of liquid films from 10 to 60 ${\mu}m$, we used photochromic dye activation. And we used silicone oil with 10 centi-Stokes and commercial photochromic dyes. To make films with exact and known thicknesses, we used two glass wafers. A film formed between two wafers after placing a drop of liquid of known volume on one wafer and covering the other. The film thickness could be estimated from the diameter of wafer and the dropped liquid volume. To quantitatively evaluate the result, captured the images using digital camera then analyzed the images using the image tool. The gray scale intensity using the captured images of activated dye with these thicknesses showed the repeatability below ${\pm}$ 1.0% when measured with a silicone oil solution containing 0.1% SO and SO-ANTH dyes. And we showed that photochromic dye activation method could be used to measure our liquid film thickness ranges.

Dynamic kinetic resolution of $\alpha$-bromo carboxylic acid derivatives in nucleophilic substitution with chiral $\alpha$-amino ester nucleophiles in the presence of TBAI and DIEA has been investigated for stereoselective syntheses of 1,1'-iminodicarboxylic acid derivatives. Nucleophilic substitutions with various chiral $\alpha$-amino esters gave iminodiacetates 2-8 with stereoselectivities up to 87 : 13 dr. Also, the reactions of N-($\alpha$-bromo-$\alpha$-phenylacetyl)-L-alanine methyl ester with L-alanine, D-alanine and glycine methyl ester nucleophiles afforded N-carboxyalkyl dipeptide analogues 10-12 up to 90 : 10 dr.