A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

The present work reports on the investigations based on the interaction of sodium hydroxide with catechol derivatives. The first derivative spectra allowed the simultaneous determination of levodopa and carbidopa. The calibration graph was constructed from the first derivative signals by measuring $^1D$ at 350 nm for standard samples containing between 3 and 30 mg $L^{-1}$ of levodopa and at 305 nm for standard samples containing between 3 and 80 mg $L^{-1}$ of carbidopa. This method offers the advantages of simplicity, rapidity, selectivity and higher sensitivity than most of the existing spectophotometric methods.

Jun/Fos, a crucial factor in transmitting the tumor-promoting signal from the extracellular environment to the nuclear transcription machinery, has a dimerization interface possessing several coiled structural properties. Jun and Fos can interact with the DNA regulatory region, AP-1 (Activator Protein-1), which is composed of 5'-TGAC/GTCA-3'.$^1$ Curcumin is a well-known anticancer and anti-inflammatory compound.$^{2,3}$ It also acts as an inhibitor of the Jun-Fos function. c-Fos and c-Jun with a bZIP region are overexpressed in BL21 E. coli and purified with an $Ni^{2+}$ affinity column. The inhibitors of Fos-Jun-AP-1 complex formation were searched through the EMSA (electrophoresis mobility shift assay) experiment, and new curcuminoids were synthesized and investigated as to their inhibitory effect on the same system. Two curcuminoids showed a stronger inhibitory effect than curcumin. This inhibitory activity was quantified with EMSA. 1,7-bis(4-methyl)-1,6-heptadiene-3,5-dione (BJC003) and 1,7-bis(4-hydroxy-5-methoxy-3-nitrophenyl)-1,6-heptadiene-3,5-dione (BJC005) showed remarkably high inhibitory activities. $IC_{50}$ of 1,7-bis(4-methyl)-1,6-heptadiene-3,5-dione (BJC003) and 1,7-bis(4-hydroxy-5-methoxy-3-nitrophenyl)-1,6-heptadiene-3,5-dione (BJC005) are 8.98 ${\mu}M$ and 5.40 ${\mu}M$, respectively. However, 1,7-bis(4-methyl-3-nitrophenyl)-1,6-heptadiene-3,5-dione (BJC004) did not show inhibitory activity.

The branch-like, feather-like $BaCrO_4$ nano-superstructures were synthesized with bioactive eggshell membrane as directing and assembly template. Studies on the two products revealed that they formed through the self-assembly of nanoparticles, and that the optical properties of the products were different from $BaCrO_4$ bulk materials.

In the present study, we carried out comparative research on the anthraquinones Raman spectrum and on the anthraquinones derivative 1,4-diamino-anthraquinone focusing on change in its intermediate in terms of pH and change in the substituent. WE use the SERS method and employ a silver sol prepared by Creighton et al.'s method. From the analysis of the UV spectrum of the mixture solution of 1,4-diamino-anthraquinone and silver sol, we could see that the 1,4-diamino-anthraquinone physically adsorbs silver sol. In terms of the adsorbing orientation, the adsorption of the nitrogen atom in the amino group is perpendicular to the surface of silver sol according to the surface selection rule. From the structure of the 1,4-diamino-anthraquinone intermediate according to the change of pH, we could see that the C=O bond is strengthened in the acidic state and weakened in the neutral and the alkaline state because of the resonance effect of the amines.

A series of 2-(3-chlorophenyl)-2-hydroxyethylamine derivatives containing a tetrahydrocarbazole linker were prepared and evaluated for their ${\beta}_3$-adrenoceptor agonistic activity. Several compounds showed potency comparable to CL-316243.

Angiotensin I, a model decapeptide, was glycosylated and partially hydrolyzed with HCl (6 N, 80 $^{\circ}C$, 4 h), aminopeptidase, and carboxypeptidase Y. A single peptide mass map obtained from truncated peptides in the partial acid hydrolysate of angiotensin and its glycosylation product mixture by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry enabled sequencing of angiotensin by a combinatorial procedure. MALDI-TOF and electrospray ionization (ESI) tandem mass spectrometric results indicate that both the N-terminal amino group of aspartic acid and the guanidinium group of the second residue arginine are glycosylated.

Ligand-based quantitative structure-activity relationship (QSAR) studies were performed on indolinones derivatives as a potential inhibitor of the protein tyrosine kinase of fibroblast growth factor receptor (FGFR) by comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) implemented in the SYBYL packages. The initial X-ray structure of docked ligand (Su5402) to FGFR was used to minimize the 27 training set molecules using TRIPOS force field. Seven models were generated using CoMFA and CoMSIA with grid spacing 2 ${\AA}$. After the PLS analysis the best predicted CoMSIA model with hydrophobicity, hydrogen bond donor and acceptor property showed that a leave-one out(LOO) cross validated value $({r^2}_{cv})^$ and non-cross validated conventional value $({r^2}_{ncv})^$ are 0.543 and 0.938, respectively.

Supercritical fluid chromatography (SFC) was considered for separating racemic ibuprofen. The chromatographic column (3.9 ${\times}$ 150 mm) was packed with Kromasil$^{\circledR}$ CHI-TBB, and the mobile phase was supercritical carbon dioxide with modifier of IPA. The experimental variables were the content of IPA, and temperature and pressure of supercritical mobile phase. To determine the separation condition, the empirical equation of retention factor and resolution was proposed. In the case of retention factor, the empirical equation was in the form, $k\;=\;a{\rho}\;+b/F\;+\;c\;({\rho}/F)\;+\;d$. The empirical equation for resolution was proposed as a linear form, $R\;=\;a{\rho}\;+\;bF\;+\;c$.

The stereoselective synthesis 4′,6′-dually branched carbocyclic nucleosides was accomplished in this study. The introduction of a methyl group in the 6′$({\alpha})$-position was accomplished by Felkin-Anh controlled alkylation. The construction of the required 4′$({\alpha})$-quaternary carbon was carried out using a [3,3]-sigmatropic rearrangement. Bis-vinyl 6 was successfully cyclized using a Grubbs' catalyst II. The natural bases (adenine, cytosine) were efficiently coupled using a Pd(0) catalyst. When the synthesized compounds were examined for their activity against several viruses such as the HIV-1, HSV-1, HSV-2 and HCMV, the cytosine analogue 13 exhibited good antiviral activity against the HCMV.

Fourier transform Raman spectra of methyl red adsorbed on untreated and pretreated ${\gamma}$-alumina and silicaalumina calcined at 900 $^{\circ}C$ under 1 atm steam flowing were recorded. Spectral analysis shows that the active species adsorbed on ${\gamma}$-alumina was to be deprotonated methyl red, and on silica-alumina to be di-protonated. This indicates that ${\gamma}$-alumina adapted in this work holds Bronsted basicity, and silica-alumina Bronsted acidity. Raman intensities of methyl red on pretreated ${\gamma}$-alumina are about three times stronger than on untreated ${\gamma}$-alumina, while spectral features are unchanged. For silica-alumina, spectral features show modified vibrational characteristics upon surface hydroxylations generated from pretreatment. Consequently, the acidity loss for silica-alumina and the basicity gain for ${\gamma}$-alumina were observed by increasing the surface hydroxyl groups on the catalysts through pretreatment of the steam calcination.

Electrochemical, in situ electrochemical scanning tunneling microscope (EC-STM), and attenuated total reflectance-FTIR (ATR-FTIR) spectroscopic methods were employed to investigate the preparation of atomically flat Si(111)-H surface in ammonium fluoride solutions. Electrochemical properties of atomically flat Si(111)-H surface were characterized by anodic oxidation and cathodic hydrogen evolution with the open circuit potential (OCP) of ca. -0.4 V in concentrated ammonium fluoride solutions. As soon as the natural oxide-covered Si(111) electrode was immersed in fluoride solutions, OCP quickly shifted to near -1 V, which was more negative than the flat band potential of silicon surface, indicating that the surface silicon oxide had to be dissolved into the solution. OCP changed to become less negative as the oxide layer was being removed from the silicon surface. In situ EC-STM data showed that the surface was changed from the initial oxidecovered silicon to atomically rough hydrogen-terminated surface and then to atomically flat hydrogenterminated surface as the OCP moved toward less negative potentials. The atomically flat Si(111)-H structure was confirmed by in situ EC-STM and ATR-FTIR data. The dependence of atomically flat Si(111)-H terrace on mis-cut angle was investigated by STM, and the results agreed with those anticipated by calculation. Further, the stability of Si(111)-H was checked by STM in ambient laboratory conditions.

We have developed a new femtosecond probe technique by using stimulated Raman spectroscopy. The cross phase modulation in femtosecond time scale associated with off-resonant interaction was shown to be eliminated by integrating the transient gain/loss signal over the time delay between the Raman pump pulse and the continuum pulse. The stimulated Raman gain of neat cyclohexane was obtained to demonstrate the feasibility of the technique. Spectral and temporal widths of stimulated Raman spectra were controlled by using a narrow band pass filter. Femtosecond stimulated Raman spectroscopy was proposed as a highly useful probe in time-resolved vibrational spectroscopy.

Recently mass spectrometry and separation methods such as liquid chromatography have become major tools in the field of proteomics. In this report, we describe in detail our efforts to develop ultra-high pressure capillary reverse-phase liquid chromatography (cRPLC) and its online coupling to a mass spectrometer by a nanoelectrospray (nanoESI) interface. The RPLC system is constructed in house to deliver LC solvents at the pressure up to 20,000 psig, which is four times higher than conventional RPLC systems. The high operation pressure allows the efficient use of packed micro-capillary columns (50, 75 and 150 ${\mu}$m i.d., up to 1.5 m long). We will discuss the effect of column diameter on the sensitivity of cRPLC/MS/MS experiments and the utility of the developed technique for proteome analysis by its application in the analysis of proteome samples having different levels of complexity.

The mass spectra of benzophenones, 2-benzoylthiophenes, 2-benzoylpyrroles, and 2-benzoylfurans which have substituents at the m- and p-positions of the benzoyl ring were analyzed to find correlations against the Hammett substituent parameter ${\sigma}\;and\;{\sigma}^+$. The slopes of the plots of the intensities of the fragments from the heterocycles against those of the benzene gave sets of meaningful values for the indices of aromaticity of the heterocycles: benzene 1.00; thiophene 0.94, pyrrole 0.82, and furan 0.74.

Apolipoprotein B-100 (Apo-B100) is a major protein component for low density lipoproteins (LDL). A number of mimetic peptides of Apo-B100 were screened from the phase-displayed random peptide library by utilizing monoclonal antibody (B9). Mimetic peptide for B9 epitope against apo B-100 was CRNVPPIFNDVYWIAF (pB1). From the BLAST search, the mimetic peptide pB1 had 40% homology with apo B-100. As a result of the structural determination of this mimotope using homo/hetero nuclear 2D-NMR techniques and NMR-based distance geometry (DG)/molecular dynamic (MD) computations, DG structure had low penalty value of 0.3-0.6 ${\AA}^2$ and the total RMSD was 0.5-1.5 ${\AA}. Moreover, pB1 structure included a weak $3_{10}$-helix from $Ile^7$,/TEX> to $Trp^{13}$.

Recently a fullerene isoxazoline was reported as an example for nanoscale connectors in molecular electronic devices. The construction of nanoscale devices is a potentially important area of technology. By using the semiempirical PM3 calculation, we optimized the structures for two fullerene isoxazoline derivatives and thirteen regioisomers of the second addition of a nitride oxide to a fullerene isoxazoline derivative. Our results suggest that fullerene isoxazoline derivatives could be used as nanoscale connectors with the possibility of attaching of spacer units in a specific angle arrangement.

Molecular geometries for the cationic and neutral species of OXO (X=Cl, Br, and I) are optimized using the Hartree-Fock (HF) theory, the second order Moller-Plesset perturbation theory (MP2), the density functional theory with the B3LYP hybrid functional (B3LYP), and the coupled cluster theory using single and double excitation with a perturbational treatment of triplet excitation (CCSD[T]) methods, with two basis sets of triple zeta plus polarization quality. The single point calculations for these species are performed at the CCSD(T,Full) level. The harmonic vibrational frequencies for these species are calculated at the HF, MP2, B3LYP and CCSD(T) levels. The adiabatic ionization potential for OIO is calculated to be 936.7 kJ/mol at the CCSD(T,Full) level and the correct value is estimated to be around 945.4 kJ/mol.

Europium doped yttrium vanadate ($YVO_4$:Eu) phosphor thin films were grown using a pulsed laser deposition (PLD) technique on silicon substrate. The structural characterization carried out on a series of ($YVO_4$:Eu films at post annealing temperature in the range of 550 $^{\circ}C$-1150 $^{\circ}C$ indicating that films were preferentially (200) oriented at post annealing temperature above 950 $^{\circ}C.$ Photoluminescence of thin film increased with the increase of post annealing temperature and ambient oxygen pressure though the thin film has the powder-like surface morphology at oxygen pressure above 200 mTorr. Photoluminescence decay from $^5D_1$ level of $Eu^{3+}$ show the great concentration dependency, which can be used as a good parameter to control the composition of ($YVO_4$:Eu thin film.

Kringle 5 (K5), located outside of angiostain (K1-4) in human plasminogen, displays more potent antiangiogenic activity on endothelial cell proliferation than angiostatin itself. Using a yeast two-hybrid system in vivo, we have recently identified Rgl2 (guanine nucleotide dissociation stimulator (RalGDS)-like factor 2) as a binding protein of human K5. In order to confirm in vitro protein interaction between K5 and Rgl2, we developed bacterial recombinant expression systems for them. K5 and Rgl2 proteins were expressed in high yields and purified into pure forms with His tags and GST fusion, respectively. GST-pull down experiments clearly demonstrated that K5 interacts specifically with Rgl2 in vitro. These results indicate that Rgl2 functions as a receptor protein for K5 in vitro as well as in vivo, leading to anti-angiogenesis through regulating Ras signaling pathways.

trans-Dihydroxo[5,10,15,20-tetrakis(n-pyridyl)porphyrinato]tin(IV) (n = 3 and 4) complexes have been synthesized and fully characterized. X-ray structural analysis of trans-dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]tin(IV) reveals that the supramolecular hydrogen bondings between the hydroxotin(IV) porphyrins and lattice water molecules form a hydrogen-bonded two-dimensional network. The hydrogen bonding mode between the tin(IV) porphyrins and the water molecules closely resembles that of the hydrogenbonded outer-sphere intermediate in the acidolysis of dihydroxotin(IV) porphyrins.

Quantitative structure activity relationship has been probed for spirosuccinimide-fused tetrahydropyrrolo[1,2-a]pyrazine-1,3-dione derivatives acting as aldose reductase inhibitors. While the spirosuccinimide compounds contain a chiral center, the aldose reductase inhibition assay was performed with racemic mixtures in the published work. As the physicochemical descriptors of the QSAR analysis must be evaluated for a definite molecular structure, we devise a new 'racemic' descriptor as the arithmetic mean of the (R)-enantiomer descriptor and the (S)-enantiomer descriptor. The resultant QSAR model derived from the racemic descriptors outperforms the original QSAR models, closely reproducing the observed activity of optically pure enantiomers as well as racemic mixtures.

The simple and convenient determination of trace Hg(II) with its 2-mercaptobenzothiazole (MBT) complex in cetyltrimethylammonium bromide (CTAB) media has been studied. The UV-visible spectrum of Hg(II)-MBT complex in CTAB media had a good sensitivity and reproducibility. The Hg(II)-MBT complex in CTAB solution was very stable at pH 10.0 and could be quantitatively complexed if MBT were added to the sample solution more than 10 equivalent of Hg(II). The optimum concentration of CTAB was 0.001%. The calibration curve of Hg(II)-MBT complex with good linearity ($R^2$ = 0.9985) was obtained at the concentration range between $1.0{\times}10^-7$ and $1.0{\times}10^-5$ M in 0.001% CTAB media. The detection limit was $3.1{\times}10^-8$ M (6.2 ng m$L^{-1}$). Hg(II) in the synthetic samples and in the wastewater of the university's wastewater tank and the industrial wastewater tank could also be determined. Based on the experimental results, this proposed technique could be applied to the simple and convenient determination of trace Hg(II) in real samples.

A series of $NiO-TiO_2$/$WO_3$ catalysts was prepared by drying powdered $Ni(OH)_2-Ti(OH)_4$ with ammonium metatungstate aqueous solution, followed by calcining in air at high temperature. Characterization of prepared catalysts was performed by using FTIR, Raman, XPS, XRD, and DSC and by measuring surface area. Upon the addition of tungsten oxide to titania up to 25 wt%, the specific surface area and acidity of catalysts increased in proportion to the tungsten oxide content due to the interaction between tungsten oxide and titania. Since the -$TiO_2$/stabilizes the tungsten oxide species, for the samples equal to or less than 25 wt%, tungsten oxide was well dispersed on the surface of titania, but for the samples containing above 25 wt%, the triclinic phase of $WO_3$ was observed at calcination temperature above 400 $^{\circ}C$. The catalytic activities of 10-NiO-$TiO_2$/$WO_3$ for 2-propanol dehydration and cumene dealkylation were correlated with the acidity of catalysts measured by ammonia chemisorption method. NiO may attract reactants and enhance the local concentration of reactants near the acid sites, consequently showing the increased catalytic activities.

The peroxidase activity of cytochrome c was studied by using a chromogen, 2,2'-azinobis-(2-ethylbenzthiazoline-6-sulfonate) (ABTS). Initial rate of ABTS oxidation formation was linear with respect to the concentration of cytochrome c between 2.5-10 ${\mu}$M and $H_2O_2$ between 0.1-0.5 mM. The optimal pH for the peroxidase activity of cytochrome c was 7.0-8.5. The peroxidase activity retained about 40% of the maximum activity when exposed at 60 $^{\circ}C$. for 10 min. The peroxidase activity showed a typical Michaelis-Menten kinetics for $H_2O_2$ which Km value was 29.6 mM. Radical scavengers inhibited the peroxidase activity of cytochrome c. The peroxidase activity was significantly inhibited by the low concentration of iron chelator, deferoxamine. The results suggested that the peroxidase activity was associated with iron in the heme of cytochrome c.

Hydrodynamic simulations of mesoscopic solvent have been performed by multi-particle collision algorithm in a real dimensional system without and with the random shifting of the grid. A systematic conversion of the dimensionless units to a real dimensional system was confirmed by jump rates of solvent particles. Speed distributions of solvent particles obtained from the simulations agreed very well with the Maxwell-Boltzmann distributions. Solvent viscosities obtained from the simulations and from the conversion of units are exactly the same which confirmed the correct conversion of the units once again. The calculation of the friction coefficient of a massive Brownian particle in a mesoscopic solvent as a function of Brownian particle diameter was examined as an example.

Nonclassical quinazolinone analogs I, II, and III, in which the glutamic acid moiety of the classical antifolates is substituted by phenylglycine, phenylalanine or aminobenzoic acid and their methyl esters, were synthesized and evaluated as lipophilic inhibitors of thymidylate synthase (TS). The target compounds were generally potent inhibitors of L. casei and human TS with $IC_{50}$ values within the narrow range of 0.2-10 ${\mu}$M and 0.003-0.03 ${\mu}$M, respectively. Further, most of the target compounds showed cytotoxicity against tumor cell lines of murine and human origin with $IC_{50}$ values of as low as 0.050 ${\mu}$M. Substitution of another hydroxyl or carboxylic acid/ester group at the phenyl ring further increased the potency of TS inhibition and cell growth inhibition. Most effective were compounds If and Ic in which extra carboxylic acid/ester was present at the phenyl ring with nanomolar $IC_{50}$ values of 0.0044 and 0.0093 ${\mu}$M against human TS and submicromolar cytotoxic growth inhibition against all four tumor cell lines.

Generation of hydroxyl radical, one of their major active species in ozonation of water was directly observed with spin-trapping/electron spin resonance (ESR) technique using 5,5-dimethyl-pyrrolidine-1-oxyl (DMPO) as a spin-trapping reagent. Hydroxyl radical was trapped with DMPO as a stable radical, DMPO-OH. 80 mM of ozone produced $1.08{\times}10^{-6}$M of DMPO-OH, indicating that 1.4% of ${\cdot}$OH is trapped with DMPO if ${\cdot}$OH is produced stoichiometrically from ozone. Humic acid suppressed DMPO-OH generation in a dose-dependent manner. Generation rate of DMPO-OH was determined with ESR/stopped-flow measurement. Phenol derivatives increased the amount and generation rate of DMPO-OH, indicating that phenol derivatives enhance·OH generation during ozonation of water.

The conformational preference of tetrahomodioxacalix[4]arenes with three different para substituents on the phenolic ring has been investigated by using ab initio molecular orbital theory (RHF/6-31$G^{\ast}$) and density functional theory (B3LYP/6-31$G^{\ast}$). The stability order is predicted to be cone > C-1,2-alternate > partial cone > 1,3-alternate > COC-1,2-alternate. The distorted cone conformation is found to be most stable in a gas phase and the calculated results are in agreement with the reported $^1$H NMR and X-ray experimental observations. The substitution of methylene with dimethyleneoxa bridges increases the size of the annulus of the molecule, its conformational mobility, and the number of hydrogen bonding patterns. The thermodynamic stability and the conformational characteristics of tetrahomodioxacalix[4]arenes are discussed in regards of the number of phenolic hydrogen bonding patterns and the polarity of a molecule. The substituent effects on the para position of the phenolic ring are also introduced.

Although the proteolytic activity of the Cu(II) complex of cyclen (Cyc) is greatly enhanced upon attachment to a cross-linked polystyrene (PS), the Cu(II)Cyc-containing PS derivatives reported previously hydrolyzed only a very limited number of proteins. The PS-based artificial metalloproteases can overcome thermal, mechanical, and chemical instabilities of natural proteases, but the narrow substrate selectivity of the artificial metalloproteases limits their industrial application. In the present study, artificial metalloproteases exhibiting broad substrate selectivity were synthesized by attaching Cu(II)Cyc to a PS derivative using linkers with various structures in an attempt to facilitate the interaction of various protein substrates with the PS surface. The new artificial metalloproteases hydrolyzed all of the four protein substrates (albumin, myoglobin, ${\gamma}$-globulin, and lysozyme) examined, manifesting $k_{cat}/K_m$ values of 28-1500 $h_{-1}M_{-1}$ at 50 $^{\circ}C$. The improvement in substrate selectivity is attributed to steric and/or polar interaction between the bound protein and the PS surface as well as the hydrophobicity of the microenvironment of the catalytic centers.

Allylations of N-benzyl and N-methyl cyclic imides were accomplished successfully under mild Barbier type conditions using zinc metal, allyl bromide and catalytic amount of $PbBr_2$. Subsequent coupling reactions with some carbon nucleophiles afforded 1,2- and 1,4-addition products in moderate to high yields.