A novel tetrathiafulvalene (TTF)-based main-chain polymer (6TTF-polymer) was successfully synthesized via a condensation polymerization between a newly synthesized dihydroxy TTF derivative and a malonyl chloride, and its chemical structure was characterized by spectroscopic techniques. Molecular weight of the 6TTF-polymer (9,030 g/mol by gel permeation chromatography) was large enough to form the ductile film. The electrochemical and optical properties of the 6TTF-polymer were further estimated by cyclic voltammetry, ultraviolet and photoluminescence spectroscopes. The highest occupied molecular orbital level ($E_{HOMO}$=-4.79 eV) and band-gap energy ($E_g$=1.91 eV) of the 6TTF-polymer suggested that TTF-based polymer could act as a good electron donating material for the optoelectronic applications.

An ecofriendly catalytic route for selective synthesis of $N$-substituted azacyclopentanes, nitrogen-containing heterocyclic intermediates for many bioactive compounds, was established by carrying out $N$-heterocyclization (di $N$-alkylation) of primary amines with 1,4-dichloro butane (as dialkylating agent) using catalytic amount of hydrotalcite as solid base catalyst. The hydrotalcite was found to be efficient solid base catalyst for di $N$-alkylation of different primary amines (aniline, benzyl amine, cyclohexyl amine and n-butyl amine) giving 82 to 96% conversion (at optimized reaction condition) of 1,4-dichloro butane and > 99% selectivity of respective $N$-substituted azacyclopentanes within 30 min. under solvent free condition. The reaction parameters significantly influence the conversion of 1,4-dichloro butane to $N$-substituted azacyclopentanes. The nature of substituent present on amino group affects the reactivity of amine substrates for di $N$-alkylation reaction with 1,4-dichloro butane. The 1,4-dichloro butane was found to be highly reactive alkylating agent for di $N$-alkylation of amines as compared to 1,4-dihydroxy butane. The reusability of the catalyst and its chemical stability in the reaction was demonstrated.

For given electrolytes, different behaviors of anodic aluminum oxide (AAO) and anodic titanium oxide (ATO) during electrochemical thinning are explained by ionic and electronic current modes. Branched structures are unavoidably created in AAO since the switch of ionic to electronic current is slow, whereas the barrier oxide in ATO is thinned without formation of the branched structures. In addition, pore opening can be possible in ATO if chemical etching is performed after the thinning process. The thinning was optimized for complete pore opening in ATO and potential-current behavior is interpreted in terms of ionic current-electronic current switching.

The pharmacokinetics of prunasin after oral administration of amygdalin or a decoction of peach seeds was determined and compared in rats. A $C_{18}$ column was used for separation at a column temperature of $25^{\circ}C$. The mobile phase consisted of 20% aqueous acetonitrile, and the flow rate was 0.5 mL/min. After oral administration of a decoction of peach seeds, prunasin was absorbed rapidly, reaching a maximum plasma concentration ($C_{max}$) of 62.1 mg/L within 45 min. After oral administration of amygdalin, the absorption of prunasin was delayed. The $C_{max}$ of prunasin was 42.9 mg/L and was reached at 60 min. Values for the pharmacokinetic parameters of prunasin, including $T_{max}$, $C_{max}$, AUC, $T_{1/2}$, CL/F, and V1/F, were significantly different for the oral administration of amygdalin compared with that of a decoction of peach seeds.

Human peroxisome proliferator-activated receptor gamma ($hPPAR{\gamma}$) has been implicated in numerous pathologies, including obesity, diabetes, and cancer. In this study, we verified that amentoflavone is an agonist of $hPPAR{\gamma}$ and probed the molecular basis of its action. It was demonstrated that amentoflavone bound $hPPAR{\gamma}$ with high (picomolar) affinity and increased the binding between $hPPAR{\gamma}$ and steroid receptor coactivator-1 (SRC-1) by approximately 4-fold. Based on a docking study, for the first time, we propose a model of amentoflavone and $hPPAR{\gamma}$ binding in which amentoflavone forms three hydrogen bonds with the side chains of His323, Tyr327, and Arg280 in $hPPAR{\gamma}$ and participates in two hydrophobic interactions.

We report a series of novel imidazolium iodides based ionic liquids (NMIPHI, NAIPHI, and NBIPHI) with different functional groups for the development of a quasi-solid type electrolyte for dye-sensitized solar cells (DSSCs). The diffusion coefficients of redox ions ($I^-$ and $I_3{^-}$) are dependent on the molecular weight and it was higher for lighter salts. Among the three ionic liquids, NMIPHI showed highest efficiency of 4.18% when it was used in a liquid electrolyte of a DSSC with $ca$. 6 ${\mu}m$ thick $TiO_2$ mesoporous film. Even though the efficiency was $ca$. 19% lower than that obtained from a liquid electrolyte composed of PMII. When NMIPHI was mixed with PMII with a molar ratio of 1:1 in a solvent free electrolyte, the efficiency of the DSSCs was enhanced compared to that based on pristine PMII.

An electrochemical immunoassay based on osmium-hippuric acid (HA) conjugate films onto the electrode is presented for the detection of urinary HA. This is the first report on the use of the oxidative electropolymerization of 5-amino-1,10-phenanthroline (5-$NH_2$-phen) for immobilizing an antigen, osmium-conjugated HA. As a redox mediator, [Os(5-amino-1,10-phenanthroline)$_2$(4-aminomethylpyridine-HA)Cl]$^{+/2+}$ (Os-phen-HA) was successfully synthesized and electropolymerized onto the screen-printed carbon electrodes (SPCEs). The interaction between osmium-HA conjugate films and antibody-HA ($anti$-HA) was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The electrical signals were linearly proportional to urinary HA in the range of 0.1-5.0 mg/mL, which is sufficient for use as an immunosensor using a cutoff concentration of 2.0 mg/mL in urine samples. The proposed electrochemical immunoassay method can be extended to various applications for detecting a wide range of different small antigens in the health care area.

InP quantum dot (QD)-organosilicon nanocomposites were synthesized and their photoluminescence quenching was mainly investigated because of their applicability to white LEDs (light emitting diodes). The as-synthesized InP QDs are capped with myristic acid (MA), which are incompatible with typical silicone encapsulants. We have introduced a new ligand, 3-aminopropyldimethylsilane (APDMS), which enables embedding the QDs into vinyl-functionalized silicones through direct chemical bonding. The exchange of ligand from MA to APDMS does not significantly affect the UV absorbance of the InP QDs, but quenches the PL to about 10% of its original value with the relative increase in surface related emission intensities, which is explained by stronger coordination of the APDMS ligands to the surface indium atoms. InP QD-organosilicon nanocomposites were synthesized by connecting the QDs using a short cross-linker such as 1,4-divinyltetramethylsilylethane (DVMSE) by the hydrosilylation reaction. The formation and changes in the optical properties of the InP QD-organosilicon nanocomposite were monitored by ultraviolet visible (UV-vis) absorbance and steady state photoluminescence (PL) spectroscopies. As the hydrosilylation reaction proceeds, the QD-organosilicon nanocomposite is formed and grows in size, causing an increase in the UV-vis absorbance due to the scattering effect. At the same time, the PL spectrum is red-shifted and, very interestingly, the PL is quenched gradually. Three PL quenching mechanisms are regarded as strong candidates for the PL quenching of the QD nanocomposites, namely the scattering effect, F$\ddot{o}$rster resonance energy transfer (FRET) and cross-linker tension preventing the QD's surface relaxation.

Protein tyrosine phosphatase 1B (PTP1B) is a key factor in negative regulation of the insulin pathway, and is a promising target for the treatment of type-II diabetes, obesity and cancer. Herein, compound ($\mathbf{4}$) was first observed to have moderate inhibitory activity against PTP1B with an $IC_{50}$ value of $13.72{\pm}1.53{\mu}M$. To obtain more potent PTP1B inhibitors, we synthesized a series of chalcone derivatives using compound ($\mathbf{4}$) as the lead compound. Compound $\mathbf{4l}$ ($IC_{50}=3.12{\pm}0.18{\mu}M$) was 4.4-fold more potent than the lead compound $\mathbf{4}$ ($IC_{50}=13.72{\pm}1.53{\mu}M$), and more potent than the positive control, ursolic acid ($IC_{50}=3.40{\pm}0.21{\mu}M$). These results may help to provide suitable drug-like lead compounds for the design of inhibitors of PTP1B as well as other PTPs.

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixarene in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of $p-tert-calix$[4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized including the calixarene scaffold $\mathbf{3}$ (4 wt %) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100 mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98-99%.

Anion effects on structures of $Cd^{II}$ complexes containing 2,2'-bipyridine (2,2'-bpy) ligands have been studied, and compared with $Zn^{II}$-(2,2'-bpy) complexes. For each anion, different structures have been obtained in both $Zn^{II}$-(2,2'-bpy) and $Cd^{II}$-(2,2'-bpy). Polymeric structures of $Cd^{II}$-2,2'-bpy complexes can be produced by hydrogen bonding interactions as shown in $Zn^{II}$-2,2'-bpy complexes. In addition, the bigger size of a $Cd^{II}$ ion gives higher coordination numbers forming variety of structures, and it makes that chlorides can act as bridging ligands to form a one-dimensional structure. The compound $\mathbf{5}$ catalyzed efficiently the transesterification of a variety of esters with methanol, while the rest of the compounds have displayed very slow conversions. In addition, the emission bands of complexes $\mathbf{1}$, $\mathbf{2}$, $\mathbf{4}$, and $\mathbf{6}$ are blue-shifted compared to the corresponding ligand 2,2'-bpy, whereas $\mathbf{3}$ and $\mathbf{5}$ showed the similar emission observed for the ligand.

In this work, we prepared activated multi-walled carbon nanotubes/polyacrylonitrile (A-MWCNTs/C) composites by film casting and activation method. Electrochemical properties of the composites were investigated in terms of serving as MWCNTs-based electrode materials for electric double layer capacitors (EDLCs). As a result, the A-MWCNTs/C composites had much higher BET specific surface area, and pore volume, and lower volume ratio of micropores than those of pristine MWCNTs/PAN ones. Furthermore, some functional groups were added on the surface of the A-MWCNTs/C composites. The specific capacitance of the A-MWCNTs/C composites was more than 4.5 times that of the pristine ones at 0.1 V discharging voltage owing to the changes of the structure and surface characteristics of the MWCNTs by activation process.

Selection of the most informative molecular descriptors from the original data set is a key step for development of quantitative structure activity/property relationship models. Recently, mutual information (MI) has gained increasing attention in feature selection problems. This paper presents an effective mutual information-based feature selection approach, named mutual information maximization by replacing collinear variables (MIMRCV), for nonlinear quantitative structure-property relationship models. The proposed variable selection method was applied to three different QSPR datasets, soil degradation half-life of 47 organophosphorus pesticides, GC-MS retention times of 85 volatile organic compounds, and water-to-micellar cetyltrimethylammonium bromide partition coefficients of 62 organic compounds.The obtained results revealed that using MIMRCV as feature selection method improves the predictive quality of the developed models compared to conventional MI based variable selection algorithms.

Chicken primordial germ cells (cPGCs) are founder germ cells in embryonic stage of development that eventually give rise to sperms or oocytes. Currently cPGCs are only known cells enabling germline transmission in chicken and their cultivation protocols were recently established. Although genome modifications of chickens are now theoretically possible using cPGCs, there are still several hurdles to overcome to practically use cPGCs as mediators for chicken transgenesis. First, efficiency of gene delivery into cPGCs remains low with current methods. Second, there aregene silencing mechanisms against the expression of foreign genes in cPGCs. In this study, we successfully increased the efficiency of gene delivery in cPGCs by taking advantage of the TTAA-specific $piggybac$ transposon system. Moreover, a pipette-type electroporator significantly enhanced transfection efficiency up to 5-fold compared withcuvette-type methods. Taken together, the technological advances in our study will provide practical benefits for the application to fulfill genetic modifications of chicken genome.

The early stages of bismuth (Bi) electrodeposition on glass carbon electrode from alkaline electrolyte were studied by cyclic voltammetry, chronoamperometry, scanning electron microscopy, atomic force microscopy and X-ray diffraction. The CV analysis showed that the electrodeposition of Bi was determined to be quasireversible process with diffusion controlled. The current transients for Bi electrodeposition were analyzed according to the Scharifker-Hills model and the Heerman-Tarallo model. It can be concluded that the nucleation and growth mechanism was carried out under a 3D instantaneous nucleation, which was confirmed by SEM analysis. The kinetic growth parameters were obtained through a nonlinear fitting. In addition, the Bi film obtaining at -0.86 V for 1 hour was of compact and uniform surface with good smoothness, small roughness and a very high purity. The Bi film were indexed to rhombohedral crystal structure with preferred orientation of (0 1 2) planes to growth.

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{3}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{3}$ with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Substrate $\mathbf{4}$ is much less reactive than $\mathbf{3}$ and the steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been attributed to its decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{3}$ and $\mathbf{4}$ are linear with ${\beta}_{nuc}=0.57$ and 0.45, respectively. Thus, the reactions have been concluded to proceed through a concerted mechanism, although the current reactions were expected to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$. It has been proposed that the rate of leaving-group expulsion is accelerated by the intramolecular H-bonding interaction in $T^{\pm}$ and the "push" provided by the RO group through the resonance interaction. Thus, the enhanced nucleofugality forces the reactions to proceed through a concerted mechanism. The reactivity-selectivity principle (RSP) is not applicable to the current reaction systems, since the reaction of the less reactive $\mathbf{4}$ results in a smaller ${\beta}_{nuc}$ than that of the more reactive $\mathbf{3}$. Steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been suggested to be responsible for the failure of the RSP.

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{7}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{8}$ with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. Substrate $\mathbf{8}$ is less reactive than $\mathbf{7}$. Steric hindrance exerted by the bulky $t$-Bu group of $\mathbf{8}$ has been suggested to be responsible for the decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{7}$ and $\mathbf{8}$ are linear with ${\beta}_{nuc}=0.49$ and 0.44, respectively, which is typical for reactions reported previously to proceed through a concerted mechanism. Aminolyses of $\mathbf{7}$ and $\mathbf{8}$ were expected to proceed through a zwitterionic tetrahedral intermediate $T^{\pm}$, which would be stabilized through an intramolecular H-bonding interaction. However, the kinetic results suggest that the reactions proceed through a concerted mechanism. The H-bonding interaction in $T^{\pm}$ has been suggested to accelerate the rate of leaving-group expulsion from $T^{\pm}$. Another factor that might accelerate expulsion of the leaving group is the "push" provided by the RO group in $T^{\pm}$ through resonance interactions. Thus, it has been concluded that the enhanced nucleofugality through the H-bonding interaction and the "push" provided by the RO group forces the reactions to proceed through a concerted mechanism.

A simple highly versatile and efficient method has been developed for the three-component coupling of aldehydes, amines and alkynes to prepare propargylamines, in the presence of a catalytic amount of $BiCl_3$. The advantages of methods are high yield, mild reaction conditions, no environmental pollution and easy work up procedure.

The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the $NH_2$ group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [$NH_3{^+}-CHCH_3-COO{\bullet}$], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol.

The combined use of indium and polysorbate 20 (Tween 20) was considered as a new inhibition technique for zinc corrosion. Zn and Zn-In alloy coatings were prepared by electrodeposition and their morphology and composition were characterized by scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The corrosion inhibition effect of indium and Tween 20 on zinc was investigated by polarization curves and electrochemical impedance spectroscopy (EIS). The corrosion inhibition efficiencies obtained from Tafel and EIS analyses are well in agreement. Zinc corrosion can be inhibited to some extent by the individual use of indium and Tween 20 and higher corrosion inhibition efficiency can be obtained by the combined use of indium and Tween 20.

A diarylurea compound 1 possessing pyrrolo[3,2-$c$]pyridine nucleus was designed and synthesized with structure similarity to Sorafenib. Compound 1 was tested over 60-cancer cell line panel at a single dose concentration of 10 ${\mu}M$ and showed high activity. It was further tested in a five-dose mode to determine its $IC_{50}$, TGI, and $LC_{50}$ values over the 60 cell lines. Compound 1 showed high potency and good efficacy, and was accordingly tested at a single dose concentration of 10 ${\mu}M$ over a panel of 40 kinases. At this concentration, it completely inhibited the enzymatic activities of a number of oncogenic kinases, including ABL, ALK, c-RAF, FLT3, KDR, and TrkB. The target compound was subsequently tested over these 6 kinases in 10-dose testing mode in order to determine its $IC_{50}$ values.

The orientational and dynamic behavior of liquid crystal molecules on the alignment layer surfaces of liquid crystal display (LCD) devices is crucial to their performance, but there are only a few methods of experimentally elucidating the interactions between the liquid crystals and the alignment layers. Inspired by the natural and technical similarities between membrane proteins in lipid bilayers and liquid crystals in LCDs, we employed solid-state NMR methodologies originally developed for the study of membrane proteins in lipid bilayers for the in-situ analysis of liquid crystal display panels. In this article, we present a home-built 500 MHz narrowbore (NB) The orientational and dynamic behavior of liquid crystal molecules on the alignment layer surfaces of liquid crystal display (LCD) devices is crucial to their performance, but there are only a few methods of experimentally elucidating the interactions between the liquid crystals and the alignment layers. Inspired by the natural and technical similarities between membrane proteins in lipid bilayers and liquid crystals in LCDs, we employed solid-state NMR methodologies originally developed for the study of membrane proteins in lipid bilayers for the in-situ analysis of liquid crystal display panels. In this article, we present a home-built 500 MHz narrowbore (NB) $^{19}F-^{13}C$ double resonance solid-state NMR probe with a flat-square coil and the first application of this probe for the in-situ analysis of LCD panel samples. double resonance solid-state NMR probe with a flat-square coil and the first application of this probe for the in-situ analysis of LCD panel samples.

Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.

A series of Novel Mannich bases has been synthesized and evaluated $in$ $vitro$ cytotoxic activity against the human hepatocellular carcinoma (HepG2), human lung carcinoma (SK-LU-1), and human breast cancer (MCF-7). Compound $\mathbf{9f}$ was found to be most potent against three cell lines with $IC_{50}$ values of 1.57, 1.16 and 1.21 ${\mu}g$/mL, respectively. In addition, compounds $\mathbf{9g}$, $\mathbf{10f}$ exhibited very significant activity against MCF-7 cell line with $IC_{50}$ values of 2.0 ${\mu}g$/mL.

A new enzyme immobilization method based on hydrophobic interaction between supporting material and enzyme has been successfully developed. The efficacy of the new technique has been investigated by loading a horse radish peroxidase (HRP) enzyme on the surface of conducting polymer-silica composites and by measuring the enzyme activity and leaching property of HRP loaded within polymer-silica composites. The immobilized HRP enzyme showed activity profiles similar to that of free HRP in phosphate buffer (pH 6). Above all, HRP adsorbed on the polymer-silica composites has showed excellent stability over 10 days, compared to HRP adsorbed on the pristine silica. It is thought that with appropriate optimization works, the present method would be used as a cost-effective and facile route for the immobilization of biomolecules.

In this study, we determined the 3D-structure of Arabidopsis thaliana KAPAS by homology modeling. We then investigated the binding mode of compounds obtained from in-house library using computational docking methods. From the flexible docking study, we achieved high dock scores for the active compounds denoted in this study as compound $\mathbf{3}$ and compound $\mathbf{4}$. Thus, we highlight the flexibility of specific residues, Lys 312 and Phe 172, when used in active sites.

The effects of plating process on the surface coverage of the accelerator were investigated in terms of Cu superfilling for device metallization. When a substrate having 500 nm-wide trench patterns on it was immersed in an electrolyte containing poly (ethylene glycol) (PEG)-chloride ion ($Cl^-$)-bis(3-sulfopropyl) disulfide (SPS) additives without applying deposition potential for such a time of about 100s, voids were generated inside of the electrodeposit. In time-evolved electrochemical analyses, it was observed that the process (immersion without applying potential) in the electrolyte led to the build-up of high initial coverage of SPS-Cl on the surface, resulting in the fast saturation of the coverage. Repeated experiments suggested that the fast saturation of SPS-Cl failed in superfilling while a gradual increase in the SPS-Cl coverage through competition with initially adsorbed PEG-Cl enabled it. Consequently, superfilling was achievable only in the case of applying the plating potential as soon as the substrate is dipped in an electrolyte to prevent rapid accumulation of SPS-Cl on the surface.

Singlet oxygen ($^1O_2$) is an important species for oxidation in biological processes. $^1O_2$ is implicated in the genotoxic effect, and plays an important role in the cell-signaling cascade and in the induction of gene expression. However, the rapid detection of $^1O_2$ in biological environments with sufficient specificity and sensitivity is hampered by its extremely low emission probability. Here, a layer-by-layer (LbL) film of CdTe quantum dots (QDs), polymers, and ascorbate have been designed as a rapid, highly selective, and sensitive fluorescence probe for $^1O_2$ detection. Upon reaction with $^1O_2$, the probe exhibits a strong photoluminescence (PL) response even at trace levels. This remarkable PL change should enable the probe to be used for $^1O_2$ detection in many chemical and biological systems and as an environmental sensor.

Ni nanoparticles-$TiO_2$ nanotube arrays (Ni/$TiO_2NTs$) composites were prepared by pulsed electrodeposition method and subsequently characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). The FESEM results showed that highly dispersed Ni nanoparticles were not only loaded on the top of the $TiO_2NTs$ but also within the tubular structure, and the particle size of Ni prepared at different current amplitude (100, 200 and 300 $mA{\cdot}cm^{-2}$) was in the range of 15 to 70 nm. The electrochemical studies indicated that Ni nanoparticles loaded on the highly ordered $TiO_2NTs$ are readily accessible for electrochemical reactions, which improve the efficiency of the Ni nanoparticles and $TiO_2NTs$. A maximum specific capacitance (27.3 $mF.cm^{-2}$) was obtained on the Ni/$TiO_2NTs$ composite electrode that prepared at a current of 200 $mA.cm^{-2}$, and the electrode also exhibited excellent electrochemical stability.

The titanate nanotube (TNT) was hydrothermally synthesized in 10 M NaOH aqueous solution at $150^{\circ}C$ for 72 h. Titanate nanotube with high surface area (292 $m^2$/g) is a good candidate as a support for catalytic reaction or organic synthesis. Palladium nanoparticles with an average size of $ca$. 3 nm were well dispersed onto the surface of TNT nanotubes. Palladium loaded catalyst with high surface area shows a highly efficient ${\alpha}$ alkylation of ketones with primary alcohols.

An efficient synthetic method of various 5-hydroxy-3-pyrrolin-2-one derivatives has been developed starting from the MBH adducts. In addition, some synthetic applicability of the prepared 5-hydroxy-3-pyrrolin-2-ones was demonstrated including the synthesis of lactam-fused tetrahydroisoquinolines.

The coupling reaction between 5-bromo-3-phenylbenzo[c]isoxazole and diphenylamine followed by further condensation with a mono-, di- or ter-acetyl aromatic compound in the presence of diphenyl phosphate at $145^{\circ}C$ gave a novel asymmetric diarylquinolines, oligoquinolines with diphenylamine endgroups, and a first generation quinoline dendrimer in 41-82% isolated yield. The electrochemical and photophysical properties of the oligoquinolines were characterized by cyclic voltammograms (CVs) and spectroscopy. All the quinolines emit bright sky blue light due to charge transfer from quinoline group to diphenly amine with very high quantum efficiency (> 90%). Organic light-emitting diodes (OLEDs) were fabricated using these quinolines as emitting materials. Among different device architectures explored, OLEDs with a structure of ITO/PEDOT (40 nm)/TAPC (15 nm)/D-A quinoline (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al using TAPC as an electron blocking layer and TPBI as a hole blocking layer gave the best performance. A high external quantum efficiency in the range of 1.2-2.3% were achieved in all the quinolines with the best performance in BBQA(5). Our results indicate diarylamino-substituted oligoquinoline and dendrimer are promising materials for OLEDs applications.

A series of poly (lactic acid) (PLA) and poly (ethylene glycol) (PEG) tri and multiblock copolymers with relatively high molecular weights were synthesized through the coupling reaction between the bis(acyl chloride) of carboxylated PLA and mono or dihydroxy PEG. The coupling reaction and the copolymer structures were monitored by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The melting temperature (Tm) of PEG blocks decreased with the presence of PLA sequences attaching to PEG blocks. The CMC values were determined to be 10-145 mg/L depending on the length of PLA and PEG blocks and the structure of the block copolymers.

Three Ni-based catalysts with different clay as support were prepared and tested in the hydrogenation of maleic anhydride, among which Ni/clay1 showed best activity and selectivity. Over Ni/clay1 catalyst prepared by impregnation method, 97.14% conversion of maleic anhydride and 99.55% selectivity to succinic anhydride were obtained at $180^{\circ}C$ under a pressure of 1 MPa. Catalytic activity was greatly influenced by the temperature and weighted hourly space velocity. Catalyst deactivation studies showed that this catalyst have a long life time, the yield of MA still higher than 90% even after a reaction time of 60 h. X-ray diffraction (XRD) and $H_2$ temperature programmed reduction (TPR) were use to investigate the properties of the catalyst. XRD and TPR studies showed that Ni was present as $Ni^{2+}$ on the support, which indicated that there was no elemental nickel ($Ni^0$) and $Ni_2O_3$ in the unreduced samples. The formation of Ni was strong impact on catalytic activity.

With the objective to design and synthesis of Schiff's base symmetrical liquid crystal dimmers and to study the effect of molecular structure variation ($o-ortho$, $m-meta$, $p-para$) and change in alkoxy terminal chain length on mesomorphic properties of liquid crystals, We have synthesized Schiff base dimers from dialdehyde derivative containing 2-hydroxy-1,3-dioxypropylene as short spacer with aniline derivatives having different lengths of terminal alkoxy chains ($n$ = 5, 7, 9). The chemical structure of the final products was characterized by proton nuclear magnetic resonance ($^1H$ NMR) spectroscopy and fourier transform infrared (FT-IR) spectroscopy. The mesomorphic properties and optical textures of the resultant dimers were characterized by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The existence of smectic A phase transition was confirmed by the observation of batonnets and fan shaped textures in optical microscopy when compound were heated from crystalline phase. All of the dimers of this series, with the exception of $\mathbf{2S_5}$ -ortho, -meta, -para, were thermotropic liquid crystal. The compound $\mathbf{2S_9}$ -meta was monotropic, while the rest were enantiotropic. It was found that the change in terminal alkoxy chain length has pronounced effect on the mesomorphic properties. The temperature range of smectic A phase window widens with increasing alkoxy chain length.

A new anthracene-containing conjugated molecule was synthesized through the Sonogashira coupling and reduction reactions. 1-Ethynyl-4-hexylbenzene was coupled to 2,6-bis((4-hexylphenyl) ethynyl)anthracene-9,10-dione through a reduction reaction to generate 2,6,9,10-tetrakis((4-hexylphenyl)ethynyl) anthracene. The semiconducting properties were evaluated in an organic thin film transistor (OTFT) and a single-crystal field-effect transistor (SC-FET). The OTFT showed a mobility of around 0.13 $cm^2\;V^{-1}\;s^{-1}$ ($I_{ON}/I_{OFF}$ > $10^6$), whereas the SC-FET showed a mobility of 1.00-1.35 $cm^2\;V^{-1}\;s^{-1}$, which is much higher than that of the OTFT. Owing to the high photoluminescence quantum yield of 2,6,9,10-tetrakis((4-hexylphenyl)ethynyl) anthracene, we could observe a significant increase in drain current under irradiation with visible light (${\lambda}$ = 538 nm, 12.5 ${\mu}W/cm^2$).

New semiconducting polymer, poly[1,4-bis(($E$)-2-(5-bromo-3-dodecylthiophen-2-yl)vinyl)benzene], was designed, synthesized and characterized. The structure of polymer was confirmed by $^1H$-NMR, IR and elemental analysis. The polymer was soluble in specific organic solvent. The weight-average molecular weights (MW) of polymer was found to be 11,000 with polydispersity of 1.82. UV-Visible absorption spectrum showed the maximum absorption at 428 nm (in solution) and 438 nm (in film). The highest occupied molecular orbital (HOMO) energy of the polymer is -5.36 eV by measuring cyclic voltammetry (CV). A solutionprocessed polymer thin film transistor device shows a mobility of $8.59{\pm}10^{-4}\;cm^2\;V^{-1}\;s^{-1}$, an on/off current ratio of $2.0{\times}10^4$.

In this study, we have expanded the applicability of the pre-established generalized preparation protocol to MIPs with a neutral template. The ($4S,5R$hyl-5-phenyl-2-oxazolidinone MIP layer was formed inside a pretreated and silanized fused silica capillary, and its chiral separation performance was examined. Optimization of chiral separation was also carried out. This is the very first report of somewhat successful application of the generalized preparation protocol to a MIP with a genuine neutral template.

A novel superabsorbent composite was prepared by intercalation polymerization of acrylic acid (AA) and 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) in the presence of montmorillonite (MMT), using ammonium persulfate (APS) as an initiator and $N,N'$-methylenebisacrylamide (MBA) as a cross linker. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Maximum absorbency of the composite in distilled water and 0.9% sodium chloride solution was 722 and 108 g/g, respectively. The composite was used for removal of heavy metal ions from aqueous solutions. Maximum amount of adsorption for $Ni^{2+}$, $Cu^{2+}$ and $Pb^{2+}$ was 211.0, 159.6 and 1646.0 mg/g, respectively, and the adsorption was in accordance with both Langmuir and Freundlich model. The composite could be regenerated and reused in wastewater treatment.

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

A sensitive liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed to determine valproic acid in human red blood cell (RBC). It is important to measure the drug concentration of the RBC as well as that of the plasma because of drug partitioning for pharmacokinetic and pharmacodynamic study. The method was linear over the dynamic range of 1-100 ${\mu}g$/mL with a correlation coefficient $r$ = 0.9997. The linearity of this method was established from 1 to 100 ${\mu}g$/mL for valproic acid in red blood cell with accuracy and precision within 15% at all concentrations. The intra-run and inter-run assay accuracy and coefficient of variations are all within 15% for all QC samples prepared in plasma and red blood human samples. Then, valproic acid amount by protein precipitation in plasma was quantified by LC-MS/MS mass spectrometry. The distribution ratio of VPA in RBC and plasma was analyzed by clinical samples. Based on measurement of the valproic acid in human red blood cell, this method has been applied to clinical research for study of distribution ratio of valproic acid in blood.

Densities (${\rho}$), Viscosities (${\eta}$) and ultrasonic speeds (u) of pure acetophenone (AP), propiophenone (PP), $p$-methyl acetophenone ($p$-MeAP), $p$-chloroacetophenone ($p$-ClAP) and those of their binary mixtures with $N$-ethyl aniline ($N$-EA) as a common component, were measured at 303.15 K over the entire composition range. These experimental data were used to calculate the excess volume $V^E$, deviation in ultrasonic speeds ${\Delta}u$, isentropic compressibility $K_s$, intermolecular free length $L_f$, acoustic impedance Z, deviations in isentropic compressibility ${\Delta}K_s$, deviation in viscosity ${\Delta}{\eta}$ and excess Gibbs free energy of activation of viscous flow ($G^{*E}$) at all mole fractions of $N$-ethyl aniline. These parameters, especially excess functions, are found to be quite sensitive towards the intermolecular interactions between component molecules. Theoretical values of viscosity of the binary mixtures were calculated using different empirical relations and theories. The relative merits of these relations and theories were discussed. The experimental results were correlated by using the polynomial proposed by Redlich-Kister equation.

A headspace gas chromatographic mass spectrometric (GC-MS) assay method was developed for the simultaneous determination of methyl tertiary butyl ether (MTBE), $tert$-butyl alcohol (TBA) and benzene, toluene, ethyl benzene and xylene (BTEX) in soil contaminated with gasoline. 2 g of soil sample were placed in a 10 mL headspace vial filled with 5 mL of phosphoric acid solution (pH 3) saturated with NaCl, and the solution was spiked with fluorobenzene as an internal standard and sealed with a cap. The vial was heated in a heating block for 40 min at $80^{\circ}C$. The detection limits of the assay were 0.08-0.12 ${\mu}g$/kg for the analytes. For five independent determinations at 10 and 50 ${\mu}g$/kg, the relative standard deviations were less than 10%. The method was used to analyze fifty six soil samples collected from various regions contaminated with gasoline in Korea. The developed method may be valuable for the monitoring of the analytes in soil.

$TiO_2$ nanostructures with various morphologies like cubes, spheres, hexahedral pillars and spherical tubes were synthesized by microwave-assisted hydrothermal process. Each structure was obtained by changing the relative concentrations of titanium tetraisoproxide (TTIP), tetrabutylammonium hydroxide (TBAH) and ethanol. Scanning electron microscopy (SEM), transmission electoron microscopy (TEM), X-ray diffraction and Brunauer-Emmett-Teller (BET) surface area analysis were used to characterize the synthesized $TiO_2$ nanostructures. From these results, it has been proved that $TiO_2$ structure could be controlled to have specific morphology, size, surface area, pore volume and pore size distribution.

Rice blast is the most serious disease of rice due to its harmfulness and its world wide distribution. $Magnaporthe$ $grisea$ is the cause of rice blast disease and destroys rice enough to feed several tens of millions of people each year. Fungicides are commonly used to control rice blast. But $M.$ $grisea$ acquires resistance to chemical treatments by genetic mutations. 2-Phenylimino-1,3-thiazolines were proposed as a novel class of fungicides against $M.$ $grisea$ in the previous study. To develop compounds with a higher biological activity, a new series of 2-phenylimino-1,3-thiazolines was synthesized and its fungicidal activity was determined against $M.$ $grisea$. The QSAR analysis was carried out on a series of 2-phenylimino-1,3-thiazolines. The QSAR results showed the dependence of fungicidal activity on the structural and physicochemical features of 2-phenylimino-1,3-thiazolines. Our results could be used as guidelines for the study of the mode of action and further design of optimal fungicides.

Grb2 is an adapter protein involved in the signal transduction and cell communication. The Grb2 is responsible for initiation of kinase signaling by Ras activation which leads to the modification in transcription. Ligand based pharmacophore approach was applied to built the suitable pharmacophore model for Grb2. The best pharmacophore model was selected based on the statistical values and then validated by Fischer's randomization method and test set. Hypo1 was selected as a best pharmacophore model based on its statistical values like high cost difference (182.22), lowest RMSD (1.273), and total cost (80.68). It contains four chemical features, one hydrogen bond acceptor (HBA), two hydrophobic (HY), and one ring aromatic (RA). Fischer's randomization results also shows that Hypo1 have a 95% significant level. The correlation coefficient of test set was 0.97 which was close to the training set value (0.94). Thus Hypo1 was used for virtual screening to find the potent inhibitors from various chemical databases. The screened compounds were filtered by Lipinski's rule of five, ADMET and subjected to molecular docking studies. Totally, 11 compounds were selected as a best potent leads from docking studies based on the consensus scoring function and critical interactions with the amino acids in Grb2 active site.

2-Hydroxy-6-(1-(3-phenylurylphenyl)ethoxy)-benzaldehyde ($\mathbf{2}$) has been synthesized in racemic form from 1,3-Dihydroxybenzene via formylation and reaction with 3-phenyluryl-methylbenzylbromide. The optically pure form of $\mathbf{2}$ was separated by normal silica column chromatography from the imine diastreomer which was obtained by the reaction of racemic mixture of $\mathbf{2}$ with optically pure leucinol. The absolute configuration of the separated enantiomer of $\mathbf{2}$ was decided from the energy calculation of the corresponding imine diastereomers. The activity of $\mathbf{2}$ as a chirality conversion reagent (CCR) for amino acids was determined by $^1H$ NMR analysis. The efficiency of $\mathbf{2}$ is not better than the previous CCRs based on binaththol. Compound $\mathbf{2}$, however, has lower molecular weight compared to other CCRs. This work demonstrates that asymmetric carbon can control the selectivity of amino acids.

We have investigated the $H_2$ adsorption structures and binding energies of the metal (M)-doped (M = Li, Na, K, Mg, and Al) silicon complexes, $M-Si_{19}H_{11}$ and $M-Si_{24}H_{12}$, using density functional calculations. Alkali metals are preferred as doping elements because the Mg-Si and Al-$H_2$ interactions are weak. The maximum numbers of $H_2$ molecules that can be adsorbed are four and five for M=Li and K, respectively. We propose that the K-decorated silicon material might be an effective hydrogen storage material with high hydrogen capacity and high reversibility.

During the analyzing processes of the compounds, some researchers are puzzled by the analytical signals for some TSNAs (with or without splitting peaks at various pHs and temperatures). In this work, a detailed theoretical study of structural and thermal properties of the $E/Z$ isomers of TSNAs and the corresponding protonated structures was performed using DFT methods. The calculations showed that the $E$ isomers are almost stable than $Z$ isomers, while the $Z$ isomers would be more stable when in protonation. The calculated results predicted the possibility of separation of their $E$ and $Z$ isomer forms and also showed that protonation affects the dipole moment of molecules significantly (0.1-0.5 to 0.7-2.1 Debye). The calculations agreed well with the experiments that the split-up of the HPLC signal for TSNAs into two peaks are very sensitive to the pH and temperature of the mobile-phase.

The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate ($Cl_3CCH_2OCOCl$, $\mathbf{3}$) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $1.28{\pm}0.06$ and $0.46{\pm}0.03$ for $l$ and $m$, respectively. The activation enthalpies (${\Delta}H^{\neq}$) are 10.1 to 12.8 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) are -27.8 to -36.8 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect ($k_{MeOH}/k_{MeOD}$) of 2.39 is also in accord with $S_N2$ mechanism probably assisted by general-base catalysis.

Voltammetric characterization of hydrophilic anion transfer processes across a 66 microhole array interface between the water and polyvinylchloride-2-nitrophenyloctylether gel layer is demonstrated. Since the transfer of hydrophilic anions including $Br^-$, $NO_3{^-}$, $I^-$, $SCN^-$ and $ClO_4{^-}$ across the liquid/gel interface usually sets the potential window within a negative potential region, a highly hydrophobic organic electrolyte, tetraoctylammonium tetrakis(pentafluorophenyl)borate, providing a wider potential window was incorporated into the gel phase. The transfer reaction of perchlorate anions across the microhole-water/gel interface was first studied using cyclic voltammetry and differential pulse voltammetry. The full voltammetric response of perchlorate anion transfer was then used as a reference for evaluating the half-wave transfer potentials, the formal transfer potentials and the formal Gibbs transfer energies of more hydrophilic anions such as $Br^-$, $NO_3{^-}$, $I^-$, and $SCN^-$. The current response associated with the perchlorate anion transfer across the micro-water/gel interface versus the perchlorate concentration was also demonstrated for sensing applications.

Water-dispersible ZnS:Mn nanocrystals were synthesized by capping the surface of the nanocrystals with conventional aminoacids ligands: serine and threonine. The aminoacids capped ZnS:Mn nanocrystal powders were characterized by XRD, HR-TEM, EDXS, ICP-AES and FT-IR spectroscopy. The optical properties were also measured by UV/Vis and solution photoluminescence (PL) spectroscopies in aqueous solvents. The solution PL spectra showed broad emission peaks around 600 nm with PL efficiencies of 9.7% (ZnS:Mn-Ser) and 15.4% (ZnS:Mn-Thr) respectively. The measured particle sizes for the aminoacid capped ZnS:Mn nanocrystals by HR-TEM images were about 3.0-4.0 nm, which were also supported by Debye-Scherrer calculations. In addition, cytotoxic effects of four aminoacids capped ZnS:Mn nanocrsystals over the growth of wild type E. coli were investigated. Although toxicity in the form of growth inhibition was observed with all the aminoacids capped ZnS:Mn nanocrystals at higher dose (1 mg/mL), ZnS:Mn-Met and ZnS:Mn-Thr appeared non-toxic at doses less than 100 ${\mu}g$/mL. Low biological toxicities were seen at doses less than 10 ${\mu}g$/ mL for all nanocrystals.

We carried out the tip-enhanced Raman scattering (TERS) with a tip that is functionalized with a Aunanoparticle (AuNP, with a diameter of 250 nm). The AuNP tip is fabricated by a direct mechanical pickup of a AuNP from a flat substrate, and the TERS signal from the AuNP tip - organic monolayer - Au thin film (thickness of 10 nm) is recorded. We find that such a AuNP-tip interacting with a thin film routinely yields signal enhancement larger than ${\sim}10^4$, which is sufficient not only for local (with detection area of ~200 $nm^2$) Raman spectroscopy, but also the nanometric imaging of organic monolayers within a reasonable acquisition time (~20 minutes/image).

A novel, efficient and controlled protocol for the synthesis and enhanced photocatalytic activity of $Au@TiO_2$ nanocomposite is developed. $TiO_2$ (P25) was pretreated by employing UV light (${\lambda}$ = 254 nm) and the pretreated $TiO_2$ was uniformly decorated by gold nanoparticles (AuNPs) in presence of sodium citrate and UV light. UV pretreatment makes the $TiO_2$ activated, as electrons were accumulated within the $TiO_2$ in the conduction band. These accumulated electrons facilitate the formation of AuNPs which were of very small size (2-5 nm), similar morphology and uniformly deposited at $TiO_2$ surface. It leads to formation of stable and crystalline $Au@TiO_2$ nanocomposites. The rapidity (13 hours), monodispersity, smaller nanocomposites and easy separation make this protocol highly significant in the area of nanocomposites syntheses. As-synthesized nanocomposites were characterized by TEM, HRTEM, TEM-EDX, SAED, XRD, UV-visible spectrophotometer and zeta potential. Dye degradation experiments of methyl orange show that type I ($Au@TiO_2$ nanocomposites in which $TiO_2$ was pretreated with UV light) has enhanced photocatalytic activity in comparison to type II ($Au@TiO_2$ nanocomposites in which $TiO_2$ was not pretreated with UV light) and $TiO_2$ (P25). This shows that pretreatment of $TiO_2$ provides type I a better catalytic activity.