In this study, we have developed QSAR models for a series of 38 piperidine-4-carboxamide CCR5 antagonists using CoMFA, CoMSIA and HQSAR methods. Developed models showed good statistics in terms of $q^2$ and $r^2$ values. Best predictions obtained with standard CoMFA model ($r^2$ = 0.888, $q^2$ = 0.651) and combined CoMSIA model ($r^2$ = 0.892, $q^2$ = 0.665) with electrostatics and H-bond acceptor parameter. The validity of developed models was assessed by test set of 9 compounds, which showed good predictive correlation coefficient for CoMFA (0.804) and CoMSIA (0.844). Bootstrapped analysis showed statistically significant and robust CoMFA (0.968) and CoMSIA (0.936) models. Best HQSAR model was obtained with a $q^2$ of 0.662 and $r^2$ of 0.936 using atom, connection, hydrogen, donor and acceptor as parameters and fragment size (7-10) with optimum number of 6 components. Predictive power of developed HQSAR model was proved by test set and it was found to be 0.728.

We present a rapid biogenic method for the production of nanoscale gold particles using pear extract. The formation and stability of pear-derived gold nanoparticles (Pear-AuNPs) were monitored by ultraviolet-visible spectroscopy. Their morphology, elemental composition and crystalline phase were determined by transmission electron microscopy, energy-dispersive X-ray spectroscopy and selected area electron diffraction. The average core size of crystalline Pear-AuNPs was in the range of $10{\pm}5\;nm$ and the observed morphology was spherical. The X-ray photoelectron spectrum showed a strong peak for the pure 'Au' phase. The circular dichroism spectrum indicated the natural capping ability of the pear extract, which generated peptide-gold nanoparticles. These nanoparticles were stable in aqueous solution for two months. A cell viability assay of Pear-AuNPs showed biocompatibility with human embryonic kidney 293 cells. Accordingly, this eco-friendly process for the bio-mimetic production of Pear-AuNPs is nontoxic in nature; consequently, it will find potential application in nano-biotechnology.

Newly developed Horner-Wadsworth-Emmons (HWE) reagents 5 having triphenylphosphorane ylide subunits readily condensed with various carbonyl compounds under mild reaction conditions to afford $\beta,\gamma$-unsaturated $\alpha$-keto triphenylphorane ylides in good to excellent yields, which were hydrogenated over Pd-C (10%)/$H_2$ (1 atm) to give the corresponding $\alpha$-keto triphenylphorane ylides in quasi-quantitative yields. These triphenyphosphorane ylides have been utilized as the precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units in Wasserman's synthetic protocols, and have previously been prepared only from carboxylic acids/acid chlorides. Our new approaches provide excellent alternatives for the synthesis of triphenylphosphorane ylide precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units directly from carbonyl compounds in good to excellent yields.

Searching for new molecular radicals which are believed to play an important role as reaction intermediates in aromatic chain reactions, we have applied the technique of corona excited supersonic expansion employing a pinhole-type glass nozzle to obtain the vibronic spectrum from the corona discharge of precursor 3,5-difluorotoluene with a large amount of inert carrier gas helium. An analysis of the observed spectrum revealed that many vibronic bands are from other isomeric difluorobenzyl radicals generated in the jet by migration of the fluorine atom or methylene group to the adjacent position in the 3,5-difluorobenzyl radical. A possible mechanism was proposed for the formation of other isomers by using a bridged cyclic intermediate structure.

Three new oleanane-type triterpene saponins (1, 2 and 3) were isolated from aerial parts of Gladiolus gandavensis, along with two known compounds (4 and 5). Their structures were elucidated as 29-O-($\beta$-D-glucopyranosyl)-$2{\beta}$,$3{\beta}$-dihydroxyolean-12-en-28-oicacid(1), 3-O-($\beta$-D-xylopyranosyl)-29-O-($\beta$-D-glucopyranosyl)-12-en-28-oic acid (2), and $2{\beta}$,$3{\beta}$,29-trihydroxyolean-12-en-28-oic acid 28-O-[$\beta$-D-glucopyranosyl($1{\rightarrow}2$)-($\alpha$-L-rhamnopyranosyl($1{\rightarrow}6$))-$\beta$-D-glucopyranosyl] ester (3), by spectroscopic methods, and by comparison with known analogues. These oleanane-type triterpene saponins glycosidated at C-29 were not obtained frequently.

In the present study, we constructed a membrane inlet assembly for selective permeation of volatile airborne organic compounds for subsequent analysis by time-of-flight mass spectrometry. The time-dependent diffusion of analytes through a $75\;{\mu}m$ thick polydimethylsiloxane membrane was measured by monitoring the ion signal after a step change in the sample concentration. The results fit well to a non-steady-state permeation equation. The diffusion coefficient, response time, and sensitivity were determined experimentally for a range of polar (halogenated) and nonpolar (aromatic) compounds. We found that the response times for several volatile organic compounds were greatly influenced by the alkyl chain length as well as the size of the substituted halogen atoms. The detection limits for benzene, ethylbenzene, and 2-propanol were 0.2 ppm, 0.1 ppm, and 3.0 ppm by volume, respectively, with a linear dynamic range greater than three orders of magnitude. These results indicate that the membrane inlet/time-of-flight mass spectrometry technique will be useful for a wide range of applications, particularly for in situ environmental monitoring.

For the purpose of developing advanced new absorbents for carbon dioxide, ionic liquids (ILs) are considered as alternative materials due to their superior properties to conventional organic solvents. Since low $CO_2$ solubility in ionic liquids is a major concern for their application as absorbents, it is essential to focus on improving $CO_2$ absorbing capability of ILs. In this paper, strongly basic ionic liquids, namely [$C_n$-mim]OPh (n = 2, 4, 6), have been synthesized and studied over a wide range of temperature and pressure changes. [$C_n$-mim]OPh can be easily synthesized from corresponding [$C_n$-mim]Cl and sodium phenoxide and has been found to be good $CO_2$ absorbents.

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

The structure of 3-aminophenol $(CO_2)_1$ cluster was computationally studied both in the ground and the lowest singlet excited electronic states. The ground state structure and binding energy of the cluster was investigated using the second-order M$\ddoot{o}$ller-Plesset perturbation theory (MP2) at the complete basis set (CBS) limit. The excited state geometry of the cluster was obtained at the second-order approximate coupled cluster (CC2) level with cc-pVDZ basis set, and the $S_0-S_1$ absorption spectrum was simulated by calculating Franck-Condon overlap integral. The ground state geometry of the global minimum with a very high binding energy of 4.3 kcal/mol was found for the cluster, due to the interaction between amino group and $CO_2$ in addition to the strong $\pi-\pi$ interaction between the aromatic ring and $CO_2$. The excited state geometry shows a very big shift in the position of $CO_2$ compared to the ground state geometry, which results in low intensity and broad envelope in the Franck-Condon simulation.

The Chemical Doping of epitaxial graphene (EG) due to p-tert-butylcalix[4]arene was investigated using high resolution photoemission spectroscopy (HRPES). The measured work function changes verified that increased adsorption of the p-tert-butylcalix[4]arene on EG showed p-type doping characteristics due to charge transfer from the graphene to the p-tert-butylcalix[4]arene through the hydroxyl group. A single oxygen bonding feature associated with the O 1s peak was clearly observed in the core-level spectra, indicating the presence of one equivalent adsorption state.

A novel method was developed for the speciation of chromium in natural water samples based on homogeneous liquid-liquid extraction and determination by flame atomic absorption spectrometry (FAAS). In this method, Cr(III) reacts with a new Schiff's base ligand to form the hydrophobic complex, which is subsequently entrapped in the sediment phase, whereas Cr(VI) remained in aqueous phase. The Cr(VI) assay is based on its reduction to Cr(III) by the addition of sodium sulfite to the sample solution. Thus, separation of Cr(III) and Cr(VI) could be realized. Homogeneous liquid-liquid extraction based on the pH-independent phase-separation process was investigated using a ternary solvent system (water-tetrabutylammonium ion ($TBA^+$)-chloroform) for the preconcentration of chromium. The phase separation phenomenon occurred by an ion-pair formation of TBA and perchlorate ion. Then sedimented phase was separated using a $100\;{\mu}L$ micro-syringe and diluted to 1.0 mL with ethanol. The sample was introduced into the flame by conventional aspiration. After the optimization of complexation and extraction conditions such as pH = 9.5, [ligand] = $1.0{\times}10^{-4}\;M$, [$TBA^+$] = $2.0{\times}10^{-2}\;M$, [$CHCl_3$] = $100.0\;{\mu}L$ and [$ClO_4$] = $2.0{\times}10{-2}\;M$, a preconcentration factor (Va/Vs) of 100 was obtained for only 10 mL of the sample. The relative standard deviation was 2.8% (n = 10). The limit of detection was sufficiently low and lie at ppb level. The proposed method was applied for the extraction and determination of chromium in natural water samples with satisfactory results.

Forest of single-walled carbon nanotubes (SWNTs) was grown at $450^{\circ}C$ by water-plasma chemical vapor deposition using ultrathin iron on alumina supporting film. The growth rate of the SWNT forest is ${\sim}0.9\;{\mu}m/min$, and the diameters of nanotubes are mainly in a range of 3.0 ~ 3.5 nm. The low intensity ratio of D- to G-band ($I_D/I_G$ ~ 0.098) in Raman spectra indicates that our SWNT forest grown at $450^{\circ}C$ is fairly pure and crystalline. This low temperature growth of SWNT forest may enable variable applications requiring the vertically-aligned nanotubes to obtain large surface area.

We investigated the solvent effects on the relative free energies of binding of $Na^+$ and $Li^+$ ions to 12-crown-4 and ${\Delta}log\;K_s$ (the difference of stability constant of binding) by a Monte Carlo simulation of statistical perturbation theory (SPT) in several solvents. Comparing the relative free energies of binding of $Na^+$ and $Li^+$ ions to 12-crown-4, in $CH_3OH$ of this study with experimental works, there is a good agreement among the studies. We have reported the quantitative free energy polarity (of solvent) relationships (QFPR) of the relationship between the relative free energies and solvent polarity studied on the solvent effects on the relative free energies of binding of $Na^+$ and $Li^+$ ions to 12-crown-4.

The degradation efficiencies of phenol in aqueous solution were studied by semi-continuous experiments in the processes of ozone alone, ozone/bulky $Co_3O_4$ and ozone/$Co_3O_4$ nanoparticles. Catalyst samples (bulky $Co_3O_4$ and $Co_3O_4$ nanoparticles) were characterized by X-ray diffraction and transmission electron microscopy. The Brunauer-Emmett-Teller surface area, $pH_{pzc}$ and the density of surface hydroxyl groups of the two catalyst samples were also measured. The catalytic activity of $Co_3O_4$ nanoparticles was investigated for the removal of phenol in aqueous solutions under different reaction temperatures. Tert-butyl alcohol had little effect on the catalytic ozonation processes. Based on these results, the possible catalytic ozonation mechanism of phenol by $Co_3O_4$ nanoparticles was proposed as a reaction process between ozone molecules and pollutants.

A series of $MoO_3/CeO_2-ZrO_2$ catalysts with different Mo content (8 - 20 wt %) were prepared by simple co-precipitation followed by impregnation method and were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy dispersive spectroscopic (EDS) techniques. The prepared materials were tested for catalytic activity by the synthesis of benzimidazole derivatives using condensation of aromatic aldehydes and o-phenylenediamine by conventional and microwave method. Obtained results reveal that the catalytic activity increases with increase in Mo wt % loading. The best catalytic activity was obtained with 20 wt % $MoO_3/CeO_2-ZrO_2$. The particle size or crystallite size was estimated using Debye-Scherrer equation. After completion of reaction, the catalyst can be recovered efficiently and reused with consistent activity.

Quasiclassical trajectory (QCT) method has been used to investigate stereodynamics information of the reaction $O(^1D)+H_2{\rightarrow}\;OH$+H on the DK (Dobbyn and Knowles) potential energy surface (PES) at a collision energy of 23.06 kcal/mol, with the initial quantum state of reactant $H_2$ being set for v = 0 (vibration quantum number) and j = 0-5 (rotation quantum number). The PDDCSs (polarization dependent differential cross sections) and the distributions of P($\theta_r$), P($\phi_r$), P($\theta_r$, $\phi_r$) have been presented in this work. The results demonstrate that the products are both forward and backward scattered. As j increases, the backward scattering becomes weaker while the forward scattering becomes slightly stronger. The distribution of P($\theta_r$) indicates that the product rotational angular momentum j' tends to align along the direction perpendicular to the reagent relative velocity vector k, but this kind of product alignment is found to be rather insensitive to j. Furthermore, the distribution of P($\phi_r$) indicates that the rotational angular momentum vector of the OH product is preferentially oriented along the positive direction of y-axis, and such product orientation becomes stronger with increasing j.

A method to improve the photocatalytic activity of titanium dioxide by modification with a sensitizer and a metal oxide is proposed. To achieve this goal, we used metal oxides as dopants. In particular, $CaWO_4$ and $Gd_2O_2S$:Tb were used because their 2.6 eV and 2.2 eV band gap energy and optical properties have a large positive effect on photocatalysis. The improvement in the photocatalytic activity of $TiO_2$ modified with $Gd_2O_2S$:Tb under ultraviolet light irradiation is described in a previous study. The present work focuses on the sensitization of metal oxide-modified $TiO_2$. Having observed the ultraviolet-visible absorption spectra of 3,4,9,10-Perylenetetracarboxylic diimide in the wide visible-light region from 400 nm to 650 nm and the broad peaks in its photoluminescence spectra at 695 nm and 717 nm, we decided to use this perylene dye to sensitize modified $TiO_2$ to enhance its activity as a visible-light harvesting photocatalyst. We also explored the positive effects thin-film surface changes stemming from ultraviolet pre-treatment have on photocatalytic activity. Finally, we subjected several metal oxide-modified $TiO_2$ products sensitized by the perylene dye to ultraviolet pre-treatment, obtaining the most active photocatalysts.

Synthesis of a new series of pyrimidinyl-imidazo[2,1-b]thiazole derivatives is described. Their antiproliferative activity against A375 human melanoma cell line was tested and the effect of substituents on the pyrimidinyl ring side chain was investigated. The biological results indicated that most of the newly synthesized compounds showed moderate activity against A375, compared with Sorafenib. Among all of these derivatives, the cyclic sulfamide derivatives IIIa, IIIb, and IIIe showed the most potent antiproliferative activity against A375 human melanoma cell line. The IC50 values of compounds IIIa,b were in nanomolar scale. In addition, compound IIIe ($IC_{50}=1.9\;{\mu}M$) also demonstrated more potent antiproliferative activity compared with Sorafenib ($IC_{50}=5.6\;{\mu}M$).

We studied effects of the 11-Mercaptoundecylphosphoric-acid layer formation on gold surfaces that have the interactions with the titanium dioxide surface for design of gold- titanium dioxide distribution. The atomic force microscope (AFM) was used to measure forces between the surfaces as a function of the salt concentration and pH value. The forces were analyzed with the DLVO (Derjaguin-Landau-Verwey-Overbeek) theory, to evaluate the potential and charge density of the surfaces quantitatively for each salt concentration and each pH value. The interpretation for the evaluation was performed with the law of mass action and the ionizable groups on the surface.

Two new energetic organic alkali metal salts, 1,1-diamino-2,2-dinitroethylene rubidium salt [Rb(FOX-7)${\cdot}H_2O$] and 1,1-diamino-2,2-dinitroethylene cesium salt [Cs(FOX-7)${\cdot}H_2O$], were synthesized by reacting of 1,1-diamino-2,2-dinitroethylene (FOX-7) and rubidium chloride or cesium chloride in alkali methanol aqueous solution, respectively. The thermal behaviors of Rb(FOX-7)${\cdot}H_2O$ and Cs(FOX-7)${\cdot}H_2O$ were studied with DSC and TG methods. The critical temperatures of thermal explosion of the two compounds are 216.22 and $223.73^{\circ}C$, respectively. Specific heat capacities of the two compounds were determined with a micro-DSC method, and the molar heat capacities are 217.46 and $199.47\;J\;mol^{-1}\;K^{-1}$ at 298.15 K, respectively. The adiabatic times-to-explosion were also calculated to be a certain value of 5.81 - 6.36 s for Rb(FOX-7)${\cdot}H_2O$, and 9.92 - 10.54 s for Cs(FOX-7)${\cdot}H_2O$. After FOX-7 becoming alkali metal salts, thermal decomposition temperatures of the compounds heighten with the rise of element period, but thermal decomposition processes become intense.

Excess free iron generates oxidative stress that may contribute to the pathogenesis of various causes of neurodegenerative diseases. Previous studies have shown that one of the primary causes of increased brain iron may be the release of excess iron from intracellular iron storage molecules. In this study, we attempted to characterize the oxidative damage of DNA induced by the reaction of ferritin with $H_2O_2$. When DNA was incubated with ferritin and $H_2O_2$, DNA strand breakage increased in a time-dependent manner. Hydroxyl radical scavengers strongly inhibited the ferritin/$H_2O_2$ system-induced DNA cleavage. We investigated the generation of hydroxyl radical in the reaction of ferritin with $H_2O_2$ using a chromogen, 2,2'-azinobis-(2-ethylbenzthiazoline-6-sulfonate) (ABTS), which reacted with ${\cdot}OH$ to form $ABTS^{+\cdot}$. The initial rate of $ABTS^{+\cdot}$ formation increased as a function of incubation time. These results suggest that DNA strand breakage is mediated in the reaction of ferritin with $H_2O_2$ via the generation of hydroxyl radicals. The iron-specific chelator, deferoxamine, also inhibited DNA cleavage. Spectrophotometric study using a color reagent showed that the release of iron from $H_2O_2$-treated ferritin increased in a time-dependent manner. Ferritin enhanced mutation of the lacZ' gene in the presence of $H_2O_2$ when measured as a loss of $\alpha$-complementation. These results indicate that ferritin/$H_2O_2$ system-mediated DNA cleavage and mutation may be attributable to hydroxyl radical generation via a Fenton-like reaction of free iron ions released from oxidatively damaged ferritin.

The folding kinetics of $WT^*$ ubiquitin variant with valine to alanine mutation at sequence position 26 (HubWA) was studied by stopped-flow fluorescence spectroscopy. While unfolding kinetics showed a single exponential phase, refolding reaction showed three exponential phases. The semi-logarithmic plot of urea concentration vs. rate constant for the first phase showed v-shape pattern while the second phase showed v-shape with roll-over effect at low urea concentration. The rate constant and the amplitude of the third phase were constant throughout the urea concentrations, suggesting that this phase represents parallel process due to the configurational isomerization. Interestingly, the first and second phases appeared to be coupled since the amplitude of the second phase increased at the expense of the amplitude of the first phase in increasing urea concentrations. This observation together with the roll-over effect in the second folding phase indicates the presence of intermediate state during the folding reaction of HubWA. Quantitative analysis of Hub-WA folding kinetics indicated that this intermediate state is on the folding pathway. Folding kinetics measurement of a mutant HubWA with hydrophobic core residue mutation, Val to Ala at residue position 17, suggested that the intermediate state has significant amount of native interactions, supporting the interpretation that the intermediate is on the folding pathway. It is considered that HubWA is a useful model protein to study the contribution of residues to protein folding process using folding kinetics measurements in conjunction with protein engineering.

Two red fluorescent DCJTB derivatives (Red 1 and 2) based on modified pyrans were synthesized and their electroluminescent properties were investigated. Multilayered OLEDs were fabricated with the device structure of ITO/NPB (40 nm)/Red 1, 2 or DCJTB (0.5 or 1%): $Alq_3$ (20 nm)/$Alq_3$ (40 nm)/Liq (2 nm)/Al. All devices exhibited efficient red emissions. In particular, a device containing emitter Red 2 as a dopant in the emitting layer, the maximum luminance was $8737\;cd/m^2$ at 12.0 V, the luminous and power efficiencies were 2.31 cd/A and 1.25 lm/W at $20\;mA/cm^2$, respectively. The peak wavelength of the electroluminescence was 638 nm with the CIE (x,y) coordinates of (0.63, 0.36) at 7.0 V.

The objective of this study was to validate performance characteristics of the Access 2 (Beckman coulter) system for hCG assays for use as a confirmation test for doping control. The Access 2 assay was linear up to 500 IU/L. The correlation coefficient was higher than 0.999, and the sensitivity of the linearity was 0.82. There were no false positive or false negative cases. LOD was 0.59 IU/L. The method was robust when performed by different people. Repeatability and reproducibility were below 7%. We compared reproducibility and recoveries of Access 2 and Elecsys 2010. Access 2 demonstrated higher reproducibility than Elecsys 2010. Recoveries (accuracy) of Access 2 were between 85 and 105%. Recoveries for Elecsys 2010 were between 91 and 104%.

In this study, the optimal preparation conditions in the polymerization process of poly(ethylene terephthalate) (PET) were studied in detail. As a result, the dispersibility of $TiO_2$ was significantly improved by the addition of dispersant and steric hinderance additives into $TiO_2$/ethylene glycol (EG) slurry during the esterification step. The addition sequence of $TiO_2$/EG slurry and stirring also affected the dispersibility of $TiO_2$. The SEM results showed that some $TiO_2$ particles were agglomerated in the PET matrix. The full dull (FD) PET chip and fiber were prepared according to the optimal preparation conditions. The FD PET fiber exhibited a better dispersibility than that of the FD PET chip.

Seven fully optimized geometries of 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) dimers have been obtained with density functional theory (DFT) method at the B3LYP/$6-311++G^{**}$ level. The intermolecular interaction energy was calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction energy of the dimers is $-23.69\;kJ{\cdot}mol^{-1}$. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. Based on the vibrational analysis, the changes of thermodynamic properties from the monomers to dimer with the temperature ranging from 200.0 K to 800.0 K have been obtained using the statistical thermodynamic method. It was found that the hydrogen bonds dominantly contribute to the dimers, while the binding energies are not only determined by hydrogen bonding. The dimerization process can not occur spontaneously at given temperatures.

Protein S-nitrosation is common in cells under nitrosative stress. In order to model proteins with S-nitrosocysteine (CysSNO) residues, we first developed an Amber force field for S-nitrosoethanethiol (EtSNO) and then transferred it to CysSNO. Partial atomic charges for EtSNO and CysSNO were obtained by a restrained electrostatic potential approach to be compatible with the Amber-99 force field. The force field parameters for bonds and angles in EtSNO were obtained from a generalized Amber force field (GAFF) by running the Antechamber module of the Amber software package. The GAFF parameters for the CC-SN and CS-NO dihedrals were not accurate and thus determined anew. The CC-SN and CS-NO torsional energy profiles of EtSNO were calculated quantum mechanically at the level of B3LYP/cc-pVTZ//HF/6-$31G^*$. Torsional force constants were obtained by fitting the theoretical torsional energies with those obtained from molecular mechanics energy minimization. These parameters for EtSNO reproduced, to a reasonable accuracy, the corresponding torsional energy profiles of the capped tripeptide ACE-CysSNO-NME as well as their structures obtained from quantum mechanical geometry optimization. A molecular dynamics simulation of myoglobin with a CysSNO residue produced a well-behaved trajectory demonstrating that the parameters may be used in modeling other S-nitrosated proteins.

Hydrogenated microcrystalline silicon (${\mu}c$-Si:H) thin film for solar cells is prepared by plasma-enhanced chemical vapor deposition and physical properties of the ${\mu}c$-Si:H p-layer has been investigated. With respect to stable efficiency, this film is expected to surpass the performance of conventional amorphous silicon based solar cells and very soon be a close competitor to other thin film photovoltaic materials. Silicon in various structural forms has a direct effect on the efficiency of solar cell devices with different electron mobility and photon conversion. A Raman microscope is adopted to study the degree of crystallinity of Si film by analyzing the integrated intensity peaks at 480, 510 and $520\;cm^{-1}$, which corresponds to the amorphous phase (a-Si:H), microcrystalline (${\mu}c$-Si:H) and large crystals (c-Si), respectively. The crystal volume fraction is calculated from the ratio of the crystalline and the amorphous phase. The results are compared with high-resolution transmission electron microscopy (HR-TEM) for the determination of crystallinity factor. Optical properties such as refractive index, extinction coefficient, and band gap are studied with reflectance spectra.

When rubber dissolved in toluene was used as a binding material of graphite powder, the mechanical robustness of the carbon paste was guaranteed by the fast volatility of the solvent immediately after electrode construction. This characteristic of the rubber solution met qualifications for practical use of carbon paste electrodes and enabled the design of a new enzyme electrode bound with EPDM. In order to confirm whether the electrode shows quantitative electrochemical behaviors or not, its kinetic parameters, e. g. the symmetry factor (0.2), the exchange current density ($3.66\;{\mu}A/cm^2$), the capacity of the double layer ($2.0{\times}10^{-5}\;F$), the Michaelis constant ($4.39{\times}10^{-3}\;M$), the diffusion coefficient of substrate ($2.58{\times}10^{-12}\;cm^2/sec$), the time constant (0.018 sec) and other factors were investigated.

We demonstrate a facile route to synthesize silver chloride nanocubes and derivative nanomaterials. For the synthesis of silver chloride nanocubes, silver nitrate and hydrochloric acid were used as precursors in ethylene glycol, and poly (vinyl pyrrolidone) as a surfactant. Molar ratio of the two precursors greatly influenced the morphology and composition of the final products. As-synthesized silver chloride nanocubes showed size-dependent optical properties in the visible region of light, which is likely due to a small amount of silver clusters formed on the surface of silver chloride nanocubes. Moreover, we show for the first time that simple reduction of silver chloride nanocubes with different reducing reagents leads to the formation of delicate nanostructures such as cube-shaped silver-nanoparticle aggregates, and silver chloride nanocubes with truncated corners and with silver-nanograin decorated corners. Additionally, we quantitatively investigated for the first time the evolution of silver chloride nanocubes to silver chloride nanocubes decorated with silver nanoparticles upon exposure to e-beam. Our novel and facile synthesis of silver chloride related nanoparticles with delicately controlled morphologies could be an important basis for fabricating efficient photocatalysts and antibacterial materials.

This study examined the synthesis of the crystal structure of bis(2,2'-bipyridine)nitrato zinc (II) nitrate, $[Zn(bipy)_2(NO_3)]^+NO_3^-$ using a microwave treatment at 300 W and 60 Hz for the application to dye-sensitized solar cells. The simulated complex structure of the complex was optimized with the density functional theory calculations for the UV-vis spectrum of the ground state using Gaussian 03 at the B3LYP/LANL2DZ level. The structure of the acquired complex was expected a penta-coordination with four nitrogen atoms of bipyridine and the oxygen bond of the $NO_3^-$ ion. The reflectance UV-vis absorption spectra exhibited two absorptions (L-L transfers) that were assigned to the transfers from the ligand ($\sigma$, $\pi$) of $NO_3$ to the ligand ($\sigma^*$, $\pi^*$) of pyridine at around 200 - 350 nm, and from the non-bonding orbital (n) of O in $NO_3$ to the p-orbital of pyridine at around 450 - 550 nm, respectively. The photoelectric efficiency was approximately 0.397% in the dye-sensitized solar cells with the nanometer-sized $TiO_2$ at an open-circuit voltage (Voc) of 0.39 V, a short-circuit current density (Jsc) of $1.79\;mA/cm^2$, and an incident light intensity of $100\;mW/cm^2$.

Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

Some open tubular (OT) molecule imprinted polymer (MIP) silica capillary columns with templates of camphor derivatives such as 10-camphorsulfonic acid (10-CSA), 10-camphorsulfonamide (10-CS) and camphor-p-tosyl hydrazone (CTH) have been successfully prepared by the prior generalized preparation protocol. The three MIP thin layers of different templates showed quite different morphologies. The chiral selectivity of each MIP column for the template enantiomers was optimized by changing eluent composition and pH. The optimization conditions were found to be different for the three MIPs. This work suggests prospective successful extension of the generalized preparation protocol for OT-MIP silica capillary columns toward templates of a variety of chemical groups.

A new high-temperature pH sensor has been successfully developed by reforming the internal reference systems of the pH sensors based on oxygen-ion conducting ceramic membrane. The conventional internal reference system, a mixture of Ni and NiO, has been replaced with partially oxidized Ni powders, where Ni and NiO coexist on the surface of particles, in order to avoid the cumbersome mixing step of Ni and NiO particles. The partially oxidized Ni particles were made by oxidizing Ni under air atmosphere at $600^{\circ}C$ and characterized by X-ray diffraction (XRD) and FTIR spectroscopy. The viability of the pH sensor developed was assessed in boric acid (1000 ppm-B)/ lithium hydroxide (1 to 3 ppm-Li) buffer solutions at $280^{\circ}C$. The pH sensor showed excellent accuracy with a small error less than ${\pm}0.2$ pH units.

Silica monolith powders were prepared by a new procedure where ground powders of proper size distribution were obtained without sieving. An initiator was attached to this ground monolith and polystyrene was bound by reversible addition-fragmentation chain transfer polymerization to give a new stationary phase. The separation efficiency of this phase was found better than that of the polystyrene bound phase based on conventional silica particles and that of the C18 bound silica monolith powders.

Ionic liquid-functionalized ordered mesoporous silica SBA-15 modified carbon paste electrode (CISPE) was fabricated and its electrochemical performance was investigated by cyclic voltammetry, electrochemical impedance spectra. The electrochemical behavior of $Cd^{2+}$, $Pb^{2+}$, $Cu^{2+}$ and $Hg^{2+}$ at CISPE was studied by differential pulse anodic stripping voltammetry (DPASV). Compared with carbon paste electrode, the stripping peak currents had a significant increase at CISPE. Under the optimized conditions, the detection limits were $8.0{\times}10^{-8}\;M$ ($Cd^{2+}$), $4.0{\times}10^{-8}\;M$ ($Pb^{2+}$), $6.0{\times}10^{-8}\;M$ ($Cu^{2+}$), $1.0{\times}10^{-8}\;M$ ($Hg^{2+}$), respectively. Furthermore, the present method was applied to the determination of $Cd^{2+}$, $Pb^{2+}$, $Cu^{2+}$ and $Hg^{2+}$ in water samples and people hair sample.

Spiro-type orange phosphorescent host materials, 9-diphenylphosphine oxide-spiro[fluorene-7,9'-benzofluorene] (OPH-1P) and 5-diphenylphosphine oxide-spiro[fluorene-7,9'-benzofluorene] (OPH-2P) were successfully prepared by a lithiation reaction followed by a phosphination reaction with diphenylphosphinic chloride. The EL characteristics of OPH-1P and OPH-2P as orange host materials doped with iridium(III) bis(2-phenylquinoline)acetylacetonate ($Ir(pq)_2acac$) were evaluated. The electroluminescence spectra of the ITO (150 nm)/DNTPD (60 nm)/NPB (30 nm)/OPH-1P or OPH-2P: $Ir(pq)_2acac$ (30 nm)/BCP (5 nm)/$Alq_3$ (20 nm)/LiF (1 nm)/Al (200 nm) devices show a narrow emission band with a full width at half maximum of 75 nm and $\lambda_{max}$ = 596 nm. The device obtained from OPH-1P doped with 3% $Ir(pq)_2acac$ showed an orange color purity of (0.580, 0.385) and an efficiency of (14 cd/A at 7.0 V). The ability of the OPH-P series to combine a high triple energy with a low operating voltage is attributed to the inductive effect of the P=O moieties and subsequent energy lowering of the LUMO, resulting in the enhancement of both the electron injection and transport in the device. The overall result is a device with an EQE > 8% at high brightness, but operating voltage of less than 6.4 V, as compared to the literature voltages of ~10 V.

Reduction of carbonyl compounds such as aldehydes, ketones, $\alpha,\beta$-unsaturated enals and enones, $\alpha$-diketones and acyloins was carried out readily with $NaBH_3CN$ in the presence of wet $SiO_2$ as a neutral media. The reactions were performed at solvent-free conditions in oil bath (70 - $80^{\circ}C$) or under microwave irradiation (240 W) to give the product alcohols in high to excellent yields. Regioselective 1,2-reduction of conjugated carbonyl compounds took place in a perfect selectivity without any side product formation.

Poly-N-vinylcarbazole/polyaniline (PVK-PANI) composites are synthesized by varying target loading concentrations of aniline (0.025 - 0.1 M). The surface morphology of the composites is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The temperature-dependent DC conductivity of PVK-PANI composite films was studied at the temperature range of 300 - 500 K. The data suggest that the conductivity increase with an increase in aniline concentration in the composite with an increase in temperature. Further based on the conductivity behavior we can suggest that the PVK-PANI composites show a semiconducting behavior with a positive temperature coefficient of resistivity (TCR). The enhanced conductivity and the positive TCR of the PVK-PANI composite films may be due to the strong interaction between PANI and PVK in the composite films.

The newly synthesized homogeneous chiral Co(III) salen complexes were anchored non-covalently on the acidic sites of mesoporous Al-SBA-15. The Bronsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. XRD, BET, TEM, FT-IR and ESCA (XPS) analyses were performed to characterize the property of support, and the structure of new homogeneous and heterogeneous chiral Co salen catalyst. The homogeneous and heterogeneous catalysts could be applied in asymmetric ring opening of epichlorohydrine (ECH) by water. They showed very high enantioselectivity and a good yield up to 99% in the catalytic synthesis of optically active products.

A new poly (vinyl chloride) (PVC) membrane electrode that is highly selective to $Mn^{+2}$ ions was prepared using N,N'-bis(2'-pyridinecarboxamide)-1,2-ethane ($bpenH_2$) as a suitable neutral carrier. This concentration range ($1.0{\times}10^{-5}$ to $1.0{\times}10^{-1}\;M$) with Nernstian slope of $29.3{\pm}0.5\;mV$ per decade. The detection limit and the response time of electrode were $8.0{\times}10^{-6}\;M$ and (${\leq}15\;s$) respectively. The membrane can be used for more than two months without observing any divergence. The electrodes exhibited excellent selectivity for $Mn^{+2}$ ion over other mono-, di- and trivalent cations. Selectivity coefficients were determined by the matched potential method (MPM). The electrode can be used in the pH range from 4.0 - 9.0. The isothermal coefficient of this electrode amounted to 0.00023 V/$^{\circ}C$. The stability constant (log $K_s$) of the $Mn^{+2}$ - $bpenH_2$ complex was determined at $25^{\circ}C$ by potentiometric titration in mixed aqueous solution. The proposed electrode was applied to the determination of $Mn^{+2}$ ions in real samples.