The electroless deposition of copper on the hydrogen-terminated Si(111) surface was investigated by means of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, scanning tunneling microscopy (STM), and energy-dispersive spectroscopy (EDS). The hydrogen-terminated Si(111) surface prepared was stable under air atmosphere for a day or more. It was found from ATR-FTIR that two bands centered at 2000 and 2260 $cm^{-1}$ appeared after the H-Si(111) surface was immersed in 40% $NH_4F$ solution containing 10 mM $Cu^{2+}$. On the other hand, STM image included the copper islands with a height of 5 nm and a diameter of 10-20 nm. The EDS data displayed the presence of copper, silicon and oxygen species. The results were rationalized in terms of the redox reaction of surface Si atoms and $Cu^{2+}$ ions in solutions, which are changed into $Si(OH)_x(F)_y$ containing $SiF_6^{2-}$ ions and neutral copper islands.

A highly selective membrane electrode based on1,3,5-triphenylpyrylium perchlorate (TPPP) is presented. The proposed electrode shows very good selectivity for sulfate ions over a wide variety of common inorganic and organic anions. The sensor displays a nice Nernstian slope of -29.7 mV per decade. The working concentration ranges of the electrode is 1.0{\times}10^{-1}-6.3{\times}10^{-6} $M with a detection limit of $4.0{\times}10^{-6}$ M (480 ng per mL). The response time of the sensor in whole concentration ranges is very short (< 6 s). The response of the sensor is independent on the pH range of 2.5-9.5. The best performance was obtained with a membrane composition of 32% PVC, 59% benzyl acetate, 5% TPPP and 4% hexadecyltrimethylammonium bromide. It was successfully used as an indicator electrode for titration of sulfate ions with barium ions. The electrode was also applied for determination of salbutamol sulfate and paramomycine sulfate.

A PVC membrane electrode for silver ion based on a new cone shaped calix[4]arene (CASCA) as membrane carrier was prepared. The electrode exhibits a Nernstian response for $Ag^+$ over a wide concentration range ($1.0{\times}10^{-1}-8.0{\times}10^{-6}$M) with a slope of 58.2 {\pm}$ 0.5 mV per decade. The limit of detection of the sensor is $5.0{\times}10^{-6}$M. The sensor has a very fast response time (~5 s) in the concentration range of ${\leq}=1.0{\times}10^{-3}$ M, and a useful working pH range of 4.0-9.5. The proposed sensor displays excellent discriminating ability toward $Ag^+$ ion with respect to common alkali, alkaline earth, transition and heavy metal ions. It was used as an indicator electrode in potentiometric titration of $Ag^+$ with EDTA and in direct determination of silver ion in wastewater of silver electroplating.

Fine $La_{2/3}Ca_{1/3}MnO_3$ nanocrystalline powders have been successfully prepared by modified citrate pyrolysis process. The obtained LCMO nanoscale grains have a mean particle size of about 30 nm under optimal treatment conditions. The particle size can be controlled by adjusting processing parameters, such as treatment temperature and calcination time. X-ray diffraction, SEM and magnetoresistance effect were employed to study the crystal structure, morphology and magnetic property of these nanosized powders. A novel MR effect (MR > 45% (0 K < T < 340 K)) at room temperature has been found.

Methanol dehydration to dimethyl ether (DME) has been investigated over ZSM-5 zeolites and compared with that of ${\gamma}-Al_2O_3$. Although the catalytic activity was decreased with an increase in silica/alumina ratio, the DME selectivity increased. H-ZSM-5 and NaH-ZSM-5 zeolites were more active for conversion of methanol to DME than ${\gamma}-Al_2O_3$. $Na^+$ ion-exchanged H-ZSM-5 (NaH-ZSM-5) shows higher DME selectivity than H-ZSM-5 due to the selective removal of strong acid sites.

The structures and complexation energies of penta-O-tert-butyl ester 1 of p-tert-butylcalix[5]arene toward a series of alkyl ammonium guests have been optimized by ab initio HF/6-31G method. The calculated complexation efficiencies of 1 for alkyl ammonium guests have been found to be similar to the values of previously reported debutylated-calix[5]arene 2. Calculation results show that both of the calix[5]aryl derivatives have much better complexation ability toward ammonium cation without alkyl group over other alkyl ammonium guests. The structural characteristics of the calculated complexes are discussed as a function of the nature of the alkyl substituents of the ammonium guests.

Methyl-4-[[(2E)-3,7-dimethyl-2,6-octadienyl]oxy]-3-hydroxybenzoate (5) has been identified from the New Zealand liverwort Trichocolea hatcheri (T. hatcheri) on the basis of spectroscopic evidence. This compound was tested for its growth inhibitory effects against tumor cell lines, using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. It showed growth inhibition activity against Staphylococcus epidermidis (MIC, 1,000 ${\mu}$g/mL). These results suggest that compound 5 possesses antitumoral , antimicrobial and antioxidative activities.

Hydrogen bond is an important factor in the structures of carbohydrates. Because of great strength, short range, and strong angular dependence, hydrogen bonding is an important factor stabilizing the structure of carbohydrate. In this study, conformational properties and the hydrogen bonds in GlcNAc( ${\beta}$1,3)Gal(${\beta}$)OMe in DMSO are investigated through NMR spectroscopy and molecular dynamics simulation. Lowest energy structure in the adiabatic energy map was utilized as an initial structure for the molecular dynamics simulations in DMSO. NOEs, temperature coefficients, SIMPLE NMR data, and molecular dynamics simulations proved that there is a strong intramolecular hydrogen bond between O7' and HO3' in GlcNAc( ${\beta}$1,3)Gal(${\beta}$)OMe in DMSO. In aqueous solution, water molecule makes intermolecular hydrogen bonds with the disaccharides and there was no intramolecular hydrogen bonds in water. Since DMSO molecule is too big to be inserted deep into GlcNAc(${\beta}$1,3)Gal(${\beta}$)OMe, DMSO can not make strong intermolecular hydrogen bonding with carbohydrate and increases the ability of O7' in GlcNAc(${\beta}$1,3)Gal(${\beta}$)OMe to participate in intramolecular hydrogen bonding. Molecular dynamics simulation in conjunction with NMR experiments proves to be efficient way to investigate the intramolecular hydrogen bonding existed in carbohydrate.

The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 $^{\circ}C$ have been investigated. The Bronsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at $pK_a$ ~ 5.2 ($pK_a^{\circ}$). The Bronsted plots for these nucleophilic reactions show a change in slope from a large ( ${\beta}_X{\cong}$0.78-0.87) to a small ( ${\beta}_X{\cong}$0.33-0.35) value, which can be attributed to a change in the rate-determining step from breakdown to formation of a zwitterionic tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the crossinteraction constants, ${\rho}_{XZ}$, from +0.92 to -0.23 supports the proposed mechanistic change. The breakpoint at $pK_a$ = 5.2 for R = thiophene ring in the present work is in agreement with those for the pyridinolysis of R = Me and 2-furyl, and attests to the insignificant effects of acyl group, R, on the breakpoint.

In this study, we attempted to prepare compounds with heterocyclic replacements for metabolically unstable esters of benzopyranyl indole-2-carboxylic esters, which showed good in vitro and in vivo cardioprotective efficacies possibly through the opening of mitochondrial ATP-sensitive potassium channel ($K_{ATP}$). Initially, we tried to construct indolin-2-yl-heterocycles using unprotected indoline-2-carboxylic acid, but the cyclization was proceeded with oxidation of the indoline ring to the indole, which didn't react with benzopyranyl epoxide. Thus we introduced N-Boc group to deplete the electron density of the indoline ring. We successfully prepared various indolin-2-yl-heterocycles by the cyclization of the building blocks including carboxamide, ${\beta}$-hydroxy amide, hydrazide, nitrile starting from N-Boc-indoline-2-carboxylic acid.

An indirect, sensitive and accurate method for the determination of trace amounts of hydrazine is described. The method is based on the oxidation of hydrazine by a known excess of iodate in the presence of hydrochloric acid. The unreacted iodate is used in the oxidation of hydroxylamine to nitrite. Sulfanilic acid is diazotized by the nitrite formed. The resulting diazonium ion is coupled with N-(1-naphthyl)ethylenediamine to form a stable azo dye, which shows an absorption maximum at 540 nm. Hydrazine can be determined in the range of 20-400 ng $mL^{-1}$ with a detection limit of 3.1 ng $mL^{-1}$. The relative standard deviation for 50, 200 and 400 ng $mL^{-1}$ of hydrazine is 2, 1.5 and 1.3%, respectively (n = 10). The method was applied to the determination of hydrazine in water samples.

${\beta}$-CD and CM- ${\beta}$-CD as chiral NMR shift agents were used to resolve the enantiomers of noradrenaline (NA). The stoichiometry of each complex formed between the CDs and the enantiomers of NA was found to be 1 : 1 through the continuous variation plots. The binding constants (K) of the complexes were determined from $^1H$ NMR titration curves. This result indicated that both ${\beta}$-CD and CM- ${\beta}$-CD formed the complexes with the S(+)-NA more preferentially than its R(-)-enantiomer. The K values for the complexes with ${\beta}$-CD ($K_{S(+)}$ = 537 $M^{-1}$ and $K_{R(-)}$ = 516 $M^{-1}$ was larger than those with CM- ${\beta}$-CD ($K_{S(+)}$ = 435 $M^{-1}$ and $K_{R(-)}$ = 313 $M^{-1}$), however, enantioselectivity (${\alpha}$) of S(+)- and R(-)-NA to CM- ${\beta}$-CD ( ${\alpha}$ = 1.38) was larger than that to ${\beta}$-CD ( ${\alpha}$ = 1.04), indicating that CM- ${\beta}$-CD was the better chiral NMR solvating agents for the recognition of the enantiomers of NA. Two dimensional rotating frame nuclear Overhauser enhancement spectroscopy (ROESY) experiments were also performed to explain the binding properties in terms of spatial fitting of the NA molecule into the macrocyclic cavities.

A series of 2',3'-dideoxy-3'-fluoro-D-apiosyl nucleosides 15, 16, 17 and 18 were synthesized enantiomerically with L-Gulonic- ${\gamma}$-lactone as the starting material. The reduction of butenolide 1 with DIBAL-H followed by the Luche procedure afforded the allylic alcohol 2. Ozonolysis and the reduction of compound 4 induced the cyclized lactol, which was acetylated to give the acetate 7. Condensation of the acetate 7 with silylated pyrimidine ($N^4$-benzoyl cytosine) and a purine base (6-chloropurine) under Vorbruggen conditions and deblocking afforded a series of fluorinated apiosyl nucleosides.

Ground and low-lying electronic states of Cr atoms in the gas phase were generated from photolysis of $Cr(CO)_6$ vapor in He or Ar using an unfocussed weak UV laser pulse and their reactions with $O_2$ and $N_2O$ were studied. When 0.5-1.0 Torr of $Cr(CO)_6$ /$O_2$ /He or Ar mixtures were photolyzed using 295-300 nm laser pulses, broadband chemiluminescence peaked at ~420 and ~500 nm, respectively, was observed in addition to the atomic emissions from $z^7P^{\circ}$, $z^5P^{\circ}$, and $y^7P^{\circ}$ states of Cr atoms. When $N_2O$ was used instead of $O_2$, no chemiluminescence was observed. The chemiluminescence intensities as well as the LIF intensities for those three low-lying electronic states ($a^7S_3,\;a^5S_2\;and\;a^5D_J$) showed second-order dependence on the photolysis laser power. Also, the chemiluminescence intensities were first-order in $O_2$ pressure, but the presence of excess Ar showed a strong inhibition effect on them. Based on the experimental results, the chemiluminecent species in this work is attributed to $CrO_2^*$ generated from hot ground state Cr atoms with $O_2$. The apparent radiative lifetimes of the chemiluminescent species and collisional quenching rate constants by $O_2$ and Ar also were investigated.

Total impurity analysis of a primary standard solution is one of the essential procedures to determine an accurate concentration of the standard solution by the gravimetry. Bi impurity is determined in Pb standard solutions by inductively coupled plasma mass spectrometry (ICP-MS). The direct nebulization of the Pb standard solution produces a significant amount of the Pb matrix-induced molecular ions which give rise to a serious spectral interference to the Bi determination. In order to avoid the spectral interference from the interferent $^{208}PbH^+$, the hydride generation method is employed for the matrix separation. The Bi hydride vapor is generated by reaction of the sample solution with 1% sodium borohydride solution. The vapor is then directed by argon carrier gas into the ICP after separation from the mixture solution in a liquid-gas separator made of a polytetrafluoroethylene membrane tube. The presence of 1000 ${\mu}$g/mL Pb matrix caused reduction of the bismuthine generation efficiency by about 40%. The standard addition method is used to overcome the chemical interference from the Pb matrix. Optimum conditions are investigated for the hydride-generation ICPMS. The detection limit of this method is 0.5 pg/mL for the sample solutions containing 1000 ${\mu}$g/mL Pb matrix.

Recombinant human ferritin homopolymers (rHF and rLF) were successfully produced in the Saccharomyces cerevisiae Y2805, which was transformed with human ferritin H or L-chain genes, respectively. In order to characterize the molecular properties of the recombinant ferritins in relation to mineralization, the proteins were isolated and apoferritins were prepared. The apoferritins were reconstituted with 2000 Fe atoms per protein molecule under various experimental conditions (the concentration of the protein, the buffer concentration of the MOPS buffer, the total volume of the reaction and the reconstitution method). The structure and composition of the iron cores formed in the ferritins were examined using transmission electron microscopy. The recombinant ferritins behaved in a similar manner to other mammalian ferritins in accumulating iron in the core. Proteins of rHF and rLF showed varying reconstitution yields of 37-72% depending on the reaction conditions. In general, the rHF showed higher reconstitution yield than the rLF at the protein concentrations and the reaction volumes we examined. Iron cores with a similar mean particle size were obtained in the rHF, rLF and horse spleen ferritin reconstituted at a protein concentration of 1.0 mg/mL. Electron diffraction of all the three ferritins showed 2-3 diffuse lines, with d-spacings corresponding to those of the mineral ferrihydrite with a limited crystallinity.

As diverse synthetic precursors of cyclic adenosine diphosphate ribose (cADPR), several adenosine derivatives in which azido or amino group is introduced at 2'- or 3'-position of the sugar moiety of adenosine were prepared from readily available adenosine via conventional protocols. These synthetic sequence employs very efficient reactions conditions that proceed at or below ambient temperature with actual yields of >80% for each individual step.

Cytochrome P450 (P450)/$O_2$/NADPH engender electron transfer reaction of N-benzyl-N-substituted benzylamines to yield corresponding radical cation 1 that is simultaneously converted into 2 and 3. Subsequently, expulsion of proton and hydroxylation yielding a-hydroxylamines are followed by formation of benzaldehydes and benzylamines.

Some new topological indices based on the distance matrix and Randic connectivity (as graph invariants) are proposed. The calculation of these indices is simple and they have good discriminating ability toward alkanes. Incorporating the number of carbon atoms to one of the calculated indices gives a highly correlating topological index (Sh index) which found to correlate with selected physicochemical properties of wide range of alkanes, specially, their boiling points. Most of the investigated properties are well modeled (with $r^2$> 0.99) by the Sh index. Meanwhile, the resulting regressions were compared with the results based on the well-established Randic and newly reported Xu indices and, in most cases, better results were obtained by the Sh index. Moreover, multiple linear regression analysis of the alkane properties via calculated indices gives highly correlating models with low standard errors.

In agreement with the results of previous MP2 calculations by Sauers, B3LYP, CASSCF, and CASPT2 calculations on the parent 2-carbena-1,3-dioxolane show that it fragments to ethylene plus $CO_2$ by a concerted pathway with only a small energy barrier. Not only is fragmentation via stepwise C-O bond cleavage computed to be a much higher energy pathway, but the singlet diradical that would be an intermediate along such a reaction path is not even computed to be a local minimum on the potential energy surface.

A sensitive, selective and rapid method has been developed for the determination ${\mu}$g/L level of vanadium ion based on the rapid reaction of vanadium(V) with 2-(2-quinolylazo)-5-diethylaminophenol (QADEAP) and the solid phase extraction of the colored chelate with $C_{18}$ cartridge. The QADEAP reacts with V(V) in the presence of citric acid-sodium hydroxide buffer solution (pH = 3.5) and cetyl trimethylammonium bromide (CTMAB) medium to form a violet chelate of a molar ratio 1 : 2 (V(V) to QADEAP). This chelate was enriched by solid phase extraction with $C_{18}$cartridge and the enrichment factor of 50 was obtained by elution of the chelates from the cartridge with ethanol. The molar absorptivity of the chelate is $1.28 {\times}10^5L\;mol^{-1}cm^{-1}$ at 590 nm in the measured solution. Beer's law is obeyed in the range of 0.01-0.6 ${\mu}$g/mL. The detection limit is 0.04 ${\mu}$g/L in the original samples. This method was applied to the determination of vanadium(V) in water and biological samples with good results.

The bromate-1,4-cyclohexanedione-ferroin oscillating reactions are uncovered to support two types of wave activities, in which spontaneous formation of circular waves has been achieved after the disappearance of initial waves. The induction period of the revival wave is typically above 10 hours and its dependence on the initial concentrations of reactants is qualitatively different from that of initial waves. In addition to their differences in propagating speed and wavelength, the initial waves and the revival patterns have different colors, suggesting that different reaction mechanisms are involved in the formation of these spatiotemporal behaviors. Our experiments further show that the addition of hydroquinone to the reacting system can significantly shorten the induction time of the revival wave, which implicates that hydroquinone is not only a product in the bromate-1,4-cyclohexanedione-ferroin oscillating reaction but also plays a critical role in the following reactions.

The aroma component of Hallabong peel has been characterized by GC-MS with two different extraction techniques: solid-phase trapping solvent extraction (SPTE) and headspace solid-phase microextraction (HSSPME). Aroma components emitted from Hallabong peel were compared with those of other citrus varieties: lemon, orange and grapefruit by SPTE and GC-MS. d-Limonene (96.98%) in Hallabong was the main component, and relatively higher peaks of cis- ${\beta}$-ocimene, valencene and -farnesene were observed. Other volatile aromas, such as sabinene, isothujol and ${\delta}$-elemene were observed as small peaks. Also, principal components analysis was employed to distinguish citrus aromas based on their chromatographic data. For HSSPME, the fiber efficiency was evaluated by comparing the partition coefficient ($K_{gs}$Kgs) between the HS gaseous phase and HS-SPME fiber coating, and the relative concentration factors (CF) of the five characteristic compounds of the four citrus varieties. 50/30 ${\mu}$m DVB/CAR/PDMS fiber was verified as the best choice among the four fibers evaluated for all the samples.

The optimum conditions for the most effective precipitate of surfactant complex of sodium alkylsulfate with cetylpyridinium chloride were studied in the aqueous solution. The parameters such as the alkyl chain length of anionic surfactants, molar ratio of two surfactants, temperature and the concentration of added NaCl in the aqueous solution were correlatively studied for the productivity of the precipitate formation. By the productivity, the optimum conditions to produce complex of anionic surfactant with cationic surfactant were the longer alkyl chain, equivalent molar ratio between anionic and cationic surfactants, 0 $^{\circ}C$ and 1.5 M NaCl.

A canonical transformation changes variables such as coordinates and momenta to new variables preserving either the Poisson bracket or the commutation relations depending on whether the problem is classical or quantal respectively. Classically canonical transformations are well established as a powerful tool for solving differential equations. Quantum canonical transformations have been defined and used relatively recently because of the non-commutativeness of the quantum variables. Three elementary canonical transformations and their composite transformations have quantum implementations. Quantum canonical transformations have been mostly used in time-independent Schrodinger equations and a harmonic oscillator with time-dependent angular frequency is probably the only time-dependent problem solved by these transformations. In this work, we apply quantum canonical transformations to a harmonic oscillator in which both angular frequency and equilibrium position are time-dependent.

A trisaccharide, GlcNAcp- ${\beta}-(1{\to}3)-Galp-{\alpha}-(1{\to}2)$-6-deoxy-altroHepp- ${\alpha}-(1{\to}O$-propyl, as an O-antigenic repeating unit of C. jejuni serotype O:23 and O:36 was synthesized. Coupling of the GlcNPhth-(1${\to}$3)-Gal disaccharide donor with allyl 6-deoxy-altroHep acceptor in the presence of iodonium dicollidine perchlorate (IDCP) promoter afforded the ${\alpha}$-galactosidic trisaccharide with high stereoselectivities. Subsequent deacetalation, dephthaloylation, N-acetylation, and hydrogenolytic debenzylation furnished the title compound.

The ignition of monomethylamine was studied in reflected shock waves over the temperature range of 1255- 1579 K and the pressure range of 1.04-1.51 bar. The ignition delay time was measured by the sudden increase of pressure profile and the radiation emitted by OH radicals. The relationship between the ignition delay time and the concentrations of monomethylamine and oxygen was determined in the form of mass-action expressions with an Arrhenius temperature dependence. In contrast to the behavior observed in hydrocarbons, monomethylamine acts to accelerate rather than inhibit its own ignition. And numerical modeling of the ignition of $CH_3NH_2$ has also been carried out to test the several kinetic mechanisms.

An alternative molecular porphyrin-phthalocyanine aggregate was prepared and characterized with UV-visible and X-ray absorption spectroscopies. UV-visible experiments evidence 1-dimensional porphyrin-phthalo-cyanine array formed by mixing $SnTPPCl_2 ({\lambda}_{max}=429,\;{\varepsilon}=2.4{\times10^ 5 /M{\cdot}cm)\;and\;NiPc(OBu)_8({\lambda}_{max}=744 nm,\;{\varepsilon}= 2.0{\times}10^ 5 /M{\cdot}cm)$ in solution. In the UV-visible spectrum of the porphyrin-phthalocyanine array, $(SnPNiPc)_n$, a new Q-band appeared at 844 nm with decrease of the Q-band peak of $NiPc(OBu)_8$ at 744 nm. The red-shift of Q-band evidences an alternative porphyrin-phthalocyanine array formed in solution through metal-halide interaction rather than ${\pi}-{\pi}$ facial interaction, in which nickel of $NiPc(OBu)_8$ coordinates with chloride of $SnTPPCl_2$ through self assembly. Ni K-edge XANES (X-ray absorption near edge structure) spectra also support the axial ligation of nickel to chloride. The square planar structure of $NiPc(OBu)_8$ turns to an octahedral structure in (SnPNiPcSnP) by axial ligation. A higher energy-shift (0.2 eV) of the preedge peak of (SnPNiPcSnP) indicaties partial oxidation of nickel by charge transfer from NiPc$(OBu)_8$ to SnTPPCl$_2$.