The carbon nanofibers (CNFs) used in this study were synthesized with an iron catalyst and ethylene as a carbon source. A concentration of 30 wt % iron(III) acetylacetonate was dissolved in resol type phenol resin and polyurethane foam was put into the solution. The sample was calendered after being cured at $80^{\circ}C$ in air for 24 h. Stabilization and carbonization of the resol type phenol resin and reduction of the $Fe^{3+}$ were completed in a high-temperature furnace by the following steps: 1) heating to $600^{\circ}C$ at a rate of $10^{\circ}C/min$ with a mixture of $H_2/N_2$ for 4 h to reduce the $Fe^{3+}$ to Fe; 2) heating to $1000^{\circ}C$ in $N_2$ at a rate $10^{\circ}C/min$ for 30 minutes for pyrolysis; 3) synthesizing CNFs in a mixture of 20.1% ethylene and $H_2/N_2$ at $700^{\circ}C$ for 2 h using a CVD process. Finally, the structural characterization of the CNFs was performed by scanning electron microscopy and a synthesis analysis was carried out using energy dispersive spectroscopy and X-ray photoelectron spectroscopy. Specific surface area analysis of the CNFs was also performed by $N_2$-sorption.

Color impurity in industrial effluents pose a significant risk to human health and the environment, so much effort has been expended to degrade them using various methods, including the use of clay minerals as adsorbent. The purpose of this study was to advance understanding of the mechanisms for the removal of methylene blue (MB) from aqueous solutions onto montmorillonite as an adsorbent. Preliminary experiments showed that montmorillonite was effective for this purpose and adsorption equilibrium could be reached in about 24 h. Adsorption capacity of the clay decreased with increase in temperature and ionic strength, and increased with in pH. The fitness of equilibrium data to common isotherm equations such as the Langmuir, Freundlich, Elovich, Temkin and Dubinin-Radushkevich were tested. The Langmuir equation fitted to equilibrium data better than all tested isotherm models. Thermodynamic activation parameters such as ${\Delta}G^0$, ${\Delta}S^0$ and ${\Delta}H^0$ were also calculated and results were evaluated. As result montmorillonite clay was found as effective low cost adsorbent for removal of cationic dyes from waste waters.

New silver nanoparticle (AgNP)-loaded amino acid based hydrogels were synthesized successfully from poly (vinyl alcohol) (PVA) and poly(acryl amide-co-acryloyl phenyl alanine) (PAA) by redox polymerization. The formation of AgNP in hydrogels was confirmed by using a UV-Vis spectrophotometer and XRD. The structure and morphology of silver nanocomposite hydrogels were studied by using a scanning electron microscopy (SEM), which demonstrated scattered nanoparticles, ca. 10-20 nm. Thermogravimetric analysis revealed large differences of weight loss (i.e., 48%) between the prestine hydrogel and silver nanocomposite. The antibacterial studies of AgNP-loaded PAA (Ag-PAA) hydrogels was evaluated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) bacteria. These Ag-PAA hydrogels showed significant activities against all the test bacteria. Newly developed hydrogels could be used for medical applications, such as artificial burn dressings.

Post-synthesis is used to synthesize organic hybrid inorganic mesoporous sieves. In this method, the activity and structure of the base sieve are crucial to obtain the definable hybrid materials. The chemical and physical properties of the base can be largely changed either by the final step of its synthesizing processes, by template removal which is accomplished with the oxidative thermal decomposition (burning) method or by solvent extraction method. In this paper we compared two methods for the post-synthesis of organic hybrid MCM-48. When the template was extracted with HCl/alcohol mixture, the final product showed larger pore size, larger pore volume and better crystallinity compared to the case of the thermal decomposition. The reactivity of the surface silanol group of template free MCM-48 was also checked with an alkylsilylation reagent $CH_2=CHSi(OC_2H_5)_3$. Raman and $^{29}Si$ NMR spectra of MCM-48 in the test reaction indicated that more of the organic group was grafted to the surface of the sample after the template was removed with the solvent extraction method. Direct synthesis of vinyl-MCM-48 was also investigated and its characteristics were compared with the case of post-synthesis. From the results, it was suggested that the structure and chemical reactivity can be maintained in the solvent extraction method and that organic grafting after the solvent extraction can be a good candidate to synthesize a definable hybrid porous material.

The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

Controlled drug delivery systems employing microparticles offer lots of advantages over conventional drug dosage formulations. Microencapsulation technique have been conducted with biodegradable polymers such as poly(lactic-co-glycolic acid) (PLGA) and poly(lactic acid) (PLA) for its adjustable biodegradability and biocompatibility. In this study, we evaluated two techniques, oil-in-water (o/w) emulsion solvent evaporation and spray drying, for preparation of polymeric microparticles encapsulating a newly synthesized drug, SS-AG20, for the long-term drug delivery of this low-molecular-weight drug with a very short half-life. Drug-loaded microparticles prepared by the solvent evaporation method showed a smoother morphology; however, relatively poor encapsulation efficiency and drastic initial burst were discovered as drawbacks. Spray-dried drug-loaded microparticles had an imperfect surface with pores and distorted portions so that its initial burst was critical (70.05-87.16%) when the preparation was carried out with a 5% polymeric solution. By increasing the concentration of the polymer, the morphology was refined and undesirable initial burst was circumvented (burst was reduced to 35.93-74.85%) while retaining high encapsulation efficiency. Moreover, by encapsulating the drug with various biodegradable polymers using the spray drying method, gradual and sustained drug release, for up to 2 weeks, was achieved.

Reactive adsorption desulfurization (RADS) experiments were conducted over a series of commercial metal oxide supports ($Al_2O_{3-}$, $SiO_{2-}$, $TiO_{2-}$ and $ZrO_{2-}$) supported Ni/ZnO adsorbents. The adsorbents were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), and Fourier transform infrared spectroscopy (FTIR) in order to find out the influence of specific types of surface chemistry and structural characteristics on the sulfur adsorptive capacity. The desulfurization performance of all the studied adsorbents decreased in the following order: Ni/ZnO-$TiO_2$ > Ni/ZnO-$ZrO_2$ > Ni/ZnO-$SiO_2$ > Ni/ZnO-$Al_2O_3$. Ni/ZnO-$TiO_2$ shows the best performance and the three hour sulfur capacity can achieve 12.34 mg S/g adsorbent with a WHSV of $4h^{-1}$. Various characterization techniques suggest that weak interaction between active component and support component, high dispersion of NiO and ZnO, high reducibility and large total Lewis acidity of the adsorbents are important factors in achieving better RADS performance.

Uniform and well dispersed metal sulfide semiconductor nanoparticles incorporated into matrices of alginate biopolymer are prepared by using a facile in situ method. The reaction was accomplished by impregnation of alginate with divalent metal ions followed by reaction with thioacetamide. XRD analysis showed that the nanoparticles incorporated in the polymer matrix were of cubic structure with the average particle diameter of 1.8 to 4.8 nm. Field emission scanning electron microscopy and high resolution transmission electron microscopy images indicated that the particles were well dispersed and distributed uniformly in the matrices of alginate polymer. FT-IR spectra confirmed the presence of alginate in the nanocomposite. The crystalline nature and thermal stability of the alginate polymer was found to be influenced by the nature of the divalent metal ions used for the synthesis. The proposed method is considered to be a simple and greener approach for large scale synthesis of uniform sized nanoparticles.

The purposes of this research were to synthesize amoxicillin-carrying magnetic nanoparticles. Magnetic nanoparticles were prepared by a chemical precipitation of ferric and ferrous chloride salts in the presence of a strong basic solution. PLGA and PLGA-PEG copolymers were prepared by ring opening polymerization of lactide (LA) and glycolide (GA) (mole ratio of LA: GA 3:1) with or without polyethylene glycol (PEG). Amoxicillin loaded magnetic PLGA and PLGA-PEG nanoparticles were prepared by an emulsion-evaporation process (o/w). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) photomicrographs showed that the magnetic nanoparticles have the mean diameter within the range of 65-260 nm also they were almost spherical in shape. Magnetic nanoparticles prepared with PLGA showed more efficient entrapment (90%) as compared with PLGA-PEG (48-52%) nanoparticles. In-vitro release of amoxicillin from magnetic PLGA nanoparticles showed that 78% of drug was released over 24 hours. The amount of amoxicillin released from PLGA-PEG s was higher than PLGA.

We demonstrated the combined applications of online protein digestion using trypsin immobilized enzyme reactor (IMER) and dual tandem mass spectrometry with collisionally activated dissociation (CAD) and electron transfer dissociation (ETD) for tryptic peptides eluted through the trypsin-IMER. For the trypsin-IMER, the organic and inorganic hybrid monolithic material was used. By employing the trypsin-IMER, the long digestion time could be saved with little or no sacrifice of the digestion efficiency, which was demonstrated for standard protein samples. For three model proteins (cytochrome c, carbonic anhydrase, and bovine serum albumin), the tryptic peptides digested by the IMER were analyzed using LC-MS/MS with the dual application of CAD and ETD. As previously shown by others, the dual application of CAD and ETD increased the sequence coverage in comparison with CAD application only. In particular, ETD was very useful for the analysis of highly-protontated peptide cations, e.g., ${\geq}3+$. The combination approach provided the advantages of both trypsin-IMER and CAD/ETD dual tandem mass spectrometry applications, which are rapid digestion (i.e., 10 min), good digestion efficiency, online coupling of trypsin-IMER and liquid chromatography, and high sequence coverage.

Ionic liquids (ILs) have been extensively investigated as promising alternatives to conventional organic solvents such as sulfolane and N,N-dimethylformamide for the selective extraction of aromatic hydrocarbons from the $C_6-C_{10}$ hydrocarbon mixtures produced from the cracking processes of naphtha and light oils. The most important advantage of ILs over conventional organic solvents is that they are immiscible with aliphatic hydrocarbons, and thus the back extraction of ILs from the raffinate phases and top hydrocarbon-rich layers is not necessary. In this paper, a brief review on the state of the art in the utilization of ILs for aromatics separation is presented.

Vibrio extracellular metalloprotease (vEP), secreted from Vibrio vulnificus, shows various proteolytic function such as prothrombin activation and fibrinolytic activities. Premature form of vEP has an N-terminal (nPP) and a C-terminal (C-ter100) region. The nPP and C-ter100 regions are autocleaved for the matured metalloprotease activity. It has been proposed that two regions play a key role in regulating enzymatic activity of vEP. Especially, C-ter100 has a regulatory function on proteolytic activity of vEP. C-ter100 domain has been cloned into the E. coli expression vectors, pET32a and pGEX 4T-1 with TEV protease cleavage site and purified using gel-filtration chromatography followed by affinity chromatography. To understand how C-ter100 modulates proteolytic activity of vEP, structural studies were performed by heteronuclar multi-dimensional NMR spectroscopy. Backbone $^1H$, $^{15}N$ and $^{13}C$ resonances were assigned by data from standard triple resonance and HCCH-TOCSY experiments. The secondary structures of vEP C-ter100 were determined by TALOS+ and CSI software based on hydrogen/deuterium exchange. NMR data show that C-ter100 of vEP forms a ${\beta}$-barrel structure consisting of eight ${\beta}$-strands.

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

Aluminum oxide ($Al_2O_3$) nanofibers were treated thermally under an ammonia ($NH_3$) gas stream balanced by nitrogen to form a thin aluminum nitride (AlN) layer on the nanofibers, resulting in the enhancement of thermal conductivity of $Al_2O_3$/epoxy nanocomposites. The micro-structural and morphological properties of the $NH_3$-assisted thermally-treated $Al_2O_3$ nanofibers were characterized by X-ray diffraction (XRD) and atomic force microscopy (AEM), respectively. The surface characteristics and pore structures were observed by X-ray photoelectron spectroscopy (XPS), Zeta-potential and $N_2$/77 K isothermal adsorptions. From the results, the formation of AlN on $Al_2O_3$ nanofibers was confirmed by XRD and XPS. The thermal conductivity (TC) of the modified $Al_2O_3$ nanofibers/epoxy composites increased with increasing treated temperatures. On the other hand, the severely treated $Al_2O_3$/epoxy composites showed a decrease in TC, resulting from a decrease in the probability of heat-transfer networks between the filler and matrix in this system due to the aggregation of nanofiber fillers.

Nanoparticles (NPs) are increasingly used in consumer products, which have aroused many concerns and debates regarding their fate in biological systems from a point of their safety/toxicity. Although a number of studies on the biological effects of NPs have been published, these are often complicated by the possible toxicity of conventional NPs, caused by contamination with chemical precursors or additives during their synthesis and/or purification procedures. To explicitly understand the toxicity basis of NPs, it is necessary to directly address a main problem related to their intrinsic/inherent toxicity and/or incompatibility with biological objects. The present study is designed to take advantage of a novel laser-assisted method called laser ablation to generate Ag, Au, Co, and Cu NPs in biocompatible aqueous solution, and to evaluate the toxicity of the resulting ultra-pure NPs. Our results show that the ultra-pure NPs with nascent surfaces possess moderate cytotoxicity to human cells in a cell-dependent manner.

In this study, we report a new method for the high contrast imaging of biomolecular interactions at roller printed protein surfaces using thermotropic liquid crystals (LCs). Avidin was roller printed and covalently immobilized onto the obliquely deposited gold surface that was decorated with carboxylic acid-terminated self-assembled monolayers (SAMs). The optical response of LCs on the roller printed film of avidin contrasted sharply with that on the obliquely deposited gold surface. The binding of biotin-peroxidase to the roller printed avidin was then investigated on the obliquely deposited gold substrate. LCs exhibited a non-uniform and random orientation on the roller printed area decorated with the complex of avidin and biotin-peroxidase, while LCs displayed a uniform and planar orientation on the area without roller printed proteins. The orientational transition of LCs from uniform to non-uniform state was triggered by the erasion of nanometer-scale topographies on the roller printed surface after the binding of biotin-peroxidase to the surface-immobilized avidin. The specific binding events of protein-receptor interactions were also confirmed by atomic force microscopy and ellipsometry. These results demonstrate that the roller printing of proteins on obliquely deposited gold substrates could provide a high contrast signal for imaging biomolecular interactions using LC-based sensors.

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

Poly(benzimidazole-co-benzoxazole)s (PBI-co-PBO) are synthesized by polycondensation reaction with 3,3'-diaminobenzidine, terephthalic acid and 3,3'-dihydroxybenzidine or 4,6-diaminoresorcinol in polyphosphoric acid (PPA). All polymer membranes are prepared by the direct casting method (in-situ fabrication). The introduction of benzoxazole units (BO units) into a polymer backbone lowers the basic property and $H_3PO_4$ doping level of the copolymer membranes, resulting in the improvement of mechanical strength. The proton conductivity of $H_3PO_4$ doped PBI-co-PBO membranes decrease as a result of adding amounts of BO units. The maximum tensile strength reaches 4.1 MPa with a 10% molar ratio of BO units in the copolymer. As a result, the $H_3PO_4$ doped PBI-co-PBO membranes could be utilized as alternative proton exchange membranes in high temperature polymer electrolyte fuel cells.

The interaction of thiazole drug with (6,0) zigzag single-walled boron nitride nanotube of finite length in gas and solvent phases was studied by means of density functional theory (DFT) calculations. In both phases, the binding energy is negative and presenting characterizes an exothermic process. Also, the binding energy in solvent phase is more than that the gas phase. Binding energy corresponding to adsorption of thiazole on the BNNT model in the gas and solvent phases was calculated to be -0.34 and -0.56 eV, and about 0.04 and 0.06 electrons is transferred from the thiazole to the nanotube in the phases. The significantly changes in binding energies and energy gap values by the thiazole adsorption, shows the high sensitivity of the electronic properties of BNNT towards the adsorption of the thiazole molecule. Frontier molecular orbital theory (FMO) and structural analyses show that the low energy level of LUMO, electron density, and length of the surrounding bonds of adsorbing atoms help to the thiazole adsorption on the nanotube. Decrease in global hardness, energy gap and ionization potential is due to the adsorption of the thiazole, and consequently, in the both phases, stability of the thiazole-attached (6,0) BNNT model is decreased and its reactivity increased. Presence of polar solvent increases the electron donor of the thiazole and the electrophilicity of the complex. This study may provide new insight to the development of functionalized boron nitride nanotubes as drug delivery systems for virtual applications.

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-$NO_2(C_4H_2O)$-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of $1.20{\pm}0.05$ and $0.37{\pm}0.02$ for l and m, respectively. The activation enthalpies (${\Delta}H^{\neq}$) were 5.63 to $13.0kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -25.9 to $-43.4cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.65 was also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.

Although offline enrichment of phosphorylated peptides is widely used, enrichment for phosphopeptides using $TiO_2$ is often performed manually, which is labor-intensive and can lead to irreproducible results. To address the problems associated with offline enrichment and to improve the effectiveness of phosphopeptide detection, we developed an automated online enrichment system for phosphopeptide analysis. A standard protein mixture comprising BSA, fetuin, crystalline, ${\alpha}$-casein and ${\beta}$-casein, and ovalbumin was assessed using our new system. Our multidimensional system has four main parts: a sample pump, a 20-mm $TiO_2$-based column, a weak anion-exchange, and a strong cation-exchange (2:1 WAX:SCX) separation column with LC/MS. Phosphorylated peptides were successfully detected using the $TiO_2$-based online system with little interference from nonphosphorylated peptides. Our results confirmed that our online enrichment system is a simple and efficient method for detecting phosphorylated peptides.

Two single crystals of fully dehydrated partially $Li^+$-exchanged zeolite X were prepared by the exchange of Na-X, $Na_{92}Si_{100}Al_{92}O_{384}$ (Si/Al = 1.09), with $Li^+$ using aqueous 0.1 M $LiNO_3$ at 293 (crystal 1) and 333 K(crystal 2), followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. Their structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd{\overline{3}}$ at 100(1) K. Their structures were refined using all intensities to the final error indices (using the 1281 and 883 reflections for which ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2$ = 0.075/0.244 and 0.074/0.223 for crystals 1 and 2, respectively. Their compositions are seen to be ${\mid}Li_{86}Na_6{\mid}[Si_{100}Al_{92}O_{384}]$-FAU and ${\mid}Li_{87}Na_5{\mid}[Si_{100}Al_{92}O_{384}]$-FAU, respectively. In crystal 1, 17 $Li^+$ ions per unit cell are at site I', 15 another site I', 30 at site II, and the remaining 16 at site III; 2 $Na^+$ ions are at site II and the remaining 4 at site III'. In crystal 2, 32 and 30 $Li^+$ ions per unit cell fill sites I' and II, respectively, and the remaining 25 at site III'; 2 and 3 $Na^+$ ions are found at sites II and III', respectively. The extent of $Li^+$ exchange increases slightly with increasing ion exchange temperature from 93% to 95%.

In this paper, a layered-carbon-$Fe_3O_4$ (LC-$Fe_3O_4$) hybrid material was synthesized through a facile one-pot solvothermal method and used as the adsorbent for the preconcentration of some phthalate esters (dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate and benzyl butyl phthalate) in water samples. The effects of the adsorbent dosage, extraction time, the solution pH and salinity on the adsorption of the phthalate esters (PAEs) were investigated. The magnetic nanocomposite adsorbent could remove and enrich the PAEs from water samples efficiently. After the adsorption, the analytes were desorbed and then determined by high performance liquid chromatography-ultraviolet detection. Under the optimum conditions, the enrichment factors of the method for the analytes were in the range from 161 to 180. A linear response with peak area as the quantification signal was observed in the concentration range from 0.5 to $100ng\;mL^{-1}$. The limits of detection (S/N = 3) of the method were between 0.08 and $0.1ng\;mL^{-1}$. The method was suitable for the determination of trace phthalate esters in environmental water samples.

A novel energetic compound, bifurazano[3,4-b:3',4'-f]furoxano[3'',4''-d] oxacyclohetpatriene (BFFO), was synthesized through special etherification and its structure was determined by single crystal X-ray diffraction. The crystal of $BFFO{\cdot}H_2O$ is monoclinic, space group P2(1)/c with crystal parameters of a = $9.324(4){\AA}$, b = $9.727(4){\AA}$, c = $10.391(4){\AA}$, ${\beta}=106.305(6)^{\circ}$, V = $904.5(6){\AA}^3$, Z = 4, ${\mu}=0.17mm^{-1}$, F(000) = 512 and $D_c=1.866g\;cm^{-3}$. Spectroscopic properties and thermal behaviors of BFFO were studied. BFFO presents good detonation properties.

The complexation characteristics of mixed [2 + 2'] calix[4]aryl derivatives (3 and 4) with alkali metal cations were investigated by the mPW1PW91 (hybrid HF-DF) calculation method. The total electronic and Gibbs free energies of the various complexes (cone, partial-cone, 1,2-alternate, and 1,3-alternate) of sodium and potassium cations with 3 and 4 were analyzed and compared. The structures of the endo- or exo-complexes of the alkali metal cation with the host 3 were optimized using the mPW1PW91/6-31G(d) method, followed by mPW1PW91/6-311+G(d) calculations. The structures of the endo- or exo-complexes of the alkali metal cation with the host 4 were optimized using the mPW1PW91/6-31G(d,p) method. The mPW1PW91 calculated relative energies of the various conformations of the free hosts (3 and 4) suggest that the cone conformers of 3 and 4 are the most stable. The mPW1PW91calculations also suggest that the complexation efficiencies of the sodium ion with hosts 3 and 4 are about 24 and 27 kcal/mol better than those of the potassium ion, respectively. These trends are in good agreement with the experimental results. The exo-complexation efficiencies of the sodium ion toward the conformers of hosts 3 and 4 are roughly 14 and 17 kcal/mol better than those for the endo-$Na^+$-complexes of 3 and 4, respectively. The exo-complexation of the cone isomer of 3 with cation could be confirmed by the differences of the diagnostic C=O bands in the free host and its complex's IR spectra.

Ru-modified Pt nanoparticles of various sizes on platelet carbon nanofiber toward methanol oxidation were investigated in terms of particle size effect. The sizes of Pt nanoparticles, prepared by polyol method, were in the range of 1.5-7.5 nm and Ru was spontaneously deposited by contacting Pt nanoparticles with the Ru precursor solutions of 2 and 5 mM. The Ru-modified Pt nanoparticles were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The methanol oxidation activities of Ru-modified Pt nanoparticles, measured using cyclic voltammetry and chronoamperometry, revealed that when the Pt particle size was less than 4.3 nm, the mass specific activity was fairly constant with an enhancement factor of more than 2 at 0.4 V. However, the surface area specific activity was maximized on Pt nanoparticles of 4.3 nm modified with 5 mM Ru precursor solution. The observations were discussed in terms of the enhancement of poison oxidation by Ru and the population variation of Pt atoms at vertices and edges of Pt nanoparticles due to selective deposition of Ru on the facets of (111) and (100).

Covalent functionalization of a $B_{12}N_{12}$ nano-cage with $CO_2$ molecule has been investigated using density functional theory in terms of energetic, geometric, and electronic property analyses. Results show that besides two physisorption configurations, $CO_2$ preferably tends to perform [2+2] addition on B-N bonds of the cluster which are shared between six-membered and four-membered rings, releasing energy of 14.99 kcal/mol for adsorption of the first $CO_2$ and of 15.45 kcal/mol for the second one (per each molecule). On the basis of calculated density of states, we have found that the electronic properties of the physisorbed $B_{12}N_{12}$ by $CO_2$ have not changed, while slight changes have been predicted in the functionalized cases. Present results might be helpful to provide an effective way to modify the $B_{12}N_{12}$ properties for further purifications and applications.

The possible ways for increasing the antioxidant properties of vitamin E have been investigated with density function theory. The effect of replacing three methyl groups of vitamin E with various substituents such as electron donating and electron withdrawing groups on the antioxidant properties of vitamin E were investigated. Also the effects of the reducing the number of atoms in the heterocyclic ring and replacing the oxygen heteroatom with other heteroatoms on the antioxidant properties of vitamin E were investigated. The novel structures that obtained from replacing methyl groups with substituents such as $NH_2$, OH, COOH and NHMe have greater antioxidant activity than vitamin E. Obtained results reveal that novel structure that obtained with replacing O with NH hetroatom would be a better antioxidant than vitamin E. The results reveal that reducing the number of atoms in the heterocyclic ring is a better way to synthesize novel antioxidants.

Understanding exoelectrogenic reactions of the bioanode is limited due to its complexity and the absence of analytics. Impedance and thermodynamics of bioanode, abiotic anode, and riboflavin-amended anode were evaluated. Activation overpotential of the bioanode was negligible compared with that of the abiotic anode. Impedance spectroscopy shows that the bioanode had much lower charge transfer resistance and higher capacitance than the abiotic anode in low frequency reaction. In high frequency reaction, the impedance parameters, however, were relatively similar between the bioanode and the abiotic anode. At open-circuit impedance spectroscopy, a high frequency arc was not detected in the abiotic anode in Nyquist plot. Addition of riboflavin induced a phase angle shift and created curvature in high-frequency arc of the abiotic anode, and it also drastically changed impedance spectra of the bioanode.

To promote the photoelectric conversion efficiency of dye-sensitized solar cells (DSSCs), graphene is introduced as a working electrode with $TiO_2$ in this study, because it has great transparency and very good conductivity. XRD patterns indicate the presence of graphene and $TiO_2$ particles in graphene-linked $TiO_2$ samples. Moreover, TEM pictures also show that the nano-sized $TiO_2$ particles are highly dispersed and well-linked onto the thin layered graphene. On the basis of the UV-visible spectra, the band gaps of $TiO_2$, 1.0 wt % graphene-$TiO_2$, 5.0 wt % graphene-$TiO_2$, and 10.0 wt % graphene-$TiO_2$ are 3.16, 2.94, 2.25, and 2.11 eV, respectively. Compared to pure $TiO_2$, the energy conversion efficiency was enhanced considerably by the application of graphene-linked $TiO_2$ anode films in the DSSCs to approximately 6.05% for 0.1 wt % graphene-$TiO_2$ with N719 dye (10.0 mm film thickness and $5.0mm{\times}5.0mm$ cell area) under $100mW/cm^2$ of simulated sunlight. The quantum efficiency was the highest when 1.0 wt % of graphene was used. In impedance curves, the resistance was smallest for 1.0 wt % graphene-$TiO_2$-DSSC.

Two novel Eu(III) complexes with notable properties have been successfully prepared with hydrazone Schiff base ligands, (E)-2-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3a) and (E)-4-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3b). DFT, FMO energy and Mulliken charge distribution studies of the ligands allowed us to hypothesize that their HC=N, > C=O and -OH (naphthyl) groups were involved in coordinating with the $Eu^{3+}$ ion. The eight coordination sites of the $Eu^{3+}$ ion were occupied by the three functional groups of the two ligands (3a or 3b) mentioned above and two water molecules. Similar UV, IR and fluorescence spectra indicated the presence of comparable coordination environments for the $Eu^{3+}$ ion in both complexes. Both the ligands and their complexes exhibited moderate DPPH radical scavenging activity. Moreover, it was found that the Eu(III) complexes exhibited fluorescence properties.

The $Bi_2O_3$ nanowires are highly sensitive to low concentrations of $NO_2$ in ambient air and are almost insensitive to most other common gases. However, it still remains a challenge to enhance their sensing performance and detection limit. This study examined the influence of the encapsulation of ${\beta}-Bi_2O_3$ nanorods with $In_2O_3$ on the $NO_2$ gas sensing properties. ${\beta}-Bi_2O_3-core/In_2O_3-shell$ nanorods were fabricated by a two-step process comprising the thermal evaporation of $Bi_2O_3$ powders and sputter-deposition of $In_2O_3$. Multiple networked ${\beta}-Bi_2O_3-core/In_2O_3-shell$ nanorod sensors showed the responses of 12-156% at 1-5 ppm $NO_2$ at $300^{\circ}C$. These response values were 1.3-2.7 times larger than those of bare ${\beta}-Bi_2O_3$ nanorod sensors at 1-5 ppm $NO_2$. The enhancement in the response of ${\beta}-Bi_2O_3$ nanorods to $NO_2$ gas by the encapsulation by $In_2O_3$ can be accounted for based on the space-charge model.

A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methyl-imidazolium hydrosulfate acidic ionic liquid (PS-$[SO_3H-PMIM][HSO_4]$) catalysts were prepared and tested for mononitration of simple aromatics compounds with nitric acid. It was found that the reactivity of the catalysts increased with increasing $[SO_3H-PMIM][HSO_4]$ content. The para-selectivity was not only related to the $[SO_3H-PMIM][HSO_4]$ content but also the substituent groups in aromatics. A reaction mechanism of nitration over this new catalyst was proposed. The catalytic activity of this catalyst decreased slightly after fifth runs in the synthesis of nitrotoluene.

A superhydrophobic surface with a water contact angle > $150^{\circ}$ has attracted great interest from both fundamental and practical aspects. In this study, we demonstrated that hydrophobicity of a silica nanotube (SNT) array can be easily controlled by the SNT aspect ratio. In addition, the adhesive and anti-adhesive properties were controlled without modifying the hydrophobic surface. Various silica structures on a polydimethylsiloxane substrate were prepared using the desired alumina template. Bundle-arrayed and bowl-arrayed silica surfaces exhibited extraordinary superhydrophobicity due to the large frontal surface area and hierarchical micro/nanostructure. As the strategy used in this study is biocompatible and a wide range of hydrophobicities are capable of being controlled by the SNT aspect ratio, a hydrophobic surface composed of an SNT array could be an attractive candidate for bioapplications, such as cell and protein chips.

SnS thin films were deposited on glasses through metal organic chemical vapor deposition (MOCVD) method at relatively mild conditions, using bis(3-mercapto-1-propanethiolato) tin(II) precursor without toxic $H_2S$ gas. The MOCVD process was carried out in the temperature range of $300-400^{\circ}C$ and the average grain size in fabricated SnS films was about 500 nm. The optical band gap of the SnS film was about 1.3 eV which is in optimal range for harvesting solar radiation energy. The precursor and SnS films were characterized through infrared spectroscopy, nuclear magnetic resonance spectroscopy, DIP-EI mass spectroscopy, elemental analyses, thermal analysis, X-ray diffraction, and field emission scanning electron microscopic analyses.

In this research work the potentialities of microemulsion bulk liquid membrane for the selective transport of L-tryptophan (L-Trp) and L-tyrosine (L-Tyr) are investigated at 298.15 K. Reversed micelle formed by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in dichloroethane, was used as mobile carrier to transport amino acids between a source and a receiving aqueous phase. The effects of pH, surfactant concentration and initial amino acid concentration on the extraction efficiency and transfer rate of the amino acids were studied. It is verified that for a mixture of two amino acids, L-Trp can be extracted selectively by using this type of the bulk liquid membrane with optimized condition.

Two-dimensional infrared (2D-IR) spectroscopy can probe the fast structural evolution of molecules under thermal equilibrium. Vibrational frequency fluctuation caused by structural evolution produced the time-dependent line shape change in 2D-IR spectrum. A variety of methods has been used to connect the evolution of 2D-IR spectrum with Frequency-Frequency Correlation Function (FFCF), which connects the experimental observables to a molecular level description. Here, a new method to extract FFCF from 2D-IR spectra is described. The experimental observable is the time-dependent frequency shift of maximum peak position in the slice spectrum of 2D-IR, which is taken along the excitation frequency axis. The direct relation between the 2D-IR peak shift and FFCF is proved analytically. Observing the 2D-IR peak shift does not need the full 2D-IR spectrum which covers 0-1 and 1-2 bands. Thus data collection time to determine FFCF can be reduced significantly, which helps the detection of transient species.

Three types of spherulitic morphologies have been investigated in dual substrate mode of Belousov-Zhabotinsky (BZ) type reaction system. Prior to growth of spherulites, three distinct patterning behaviors have been observed sequentially during the reaction process. Initial and the early-phase of reaction showed the emergence of concentric ring-like wave patterns. A colloidal-state of reaction consists of numerous fine solid particles, which forms primarily some nucleation centers of dendritic characters. The nucleation centers were found to grow in sizes and shapes with the progress of reaction. It leads to growth of dendritic-like spherulitic crystal patterns. The resultant spherulites showed transitions in their morphologies, including sea-weeds and rhythmic spherulitic crystal patterns, by the effects substituted organic substrate and in the higher concentration of bromate-initiator respectively. The branching mechanism and crystal ordering of spherulitic textures were studied with help of optical microscope (OPM) and scanning electron microscope (SEM). Characteristics of crystal phases were also evaluated using X-ray diffraction (XRD) and differential thermal analysis (DTA). Results indicated that the compositions of reactants and crystal orderings were interrelated with morphological transitions of spherulites as illustrated and described.

The Ti incorporation at Fe-site in the double perovskite lattice of $Sr_2FeNbO_6$ (SFNO) system is studied. The Ti concentration optimization yielded an efficient photocatalyst. At an optimum composition of Ti as x = 0.07 in $Sr_2Fe_{1-x}Ti_xNbO_6$, the photocatalyst exhibited 2 times the quantum yield for photolysis of $H_2O$ in presence of $CH_3OH$, than its undoped counterpart under visible light (${\lambda}{\geq}420nm$). Heavily Ti-doped $Sr_2Fe_{1-x}Ti_xNbO_6$ lattice exhibited poor photochemical properties due to the existence of constituent impurity phases as observed in the structural characterization, as well as deteriorated optical absorption. The higher electron-density acquired by n-type doping seem to be responsible for the more efficient charge separation in $Sr_2Fe_{1-x}Ti_xNbO_6$ (0.05 < x < 0.4) and thus consequently displays higher photocatalytic activity. The Ti incorporated structure also found to yield stable photocatalyst.

Phenol-free resin was synthesized and its printing ink properties were investigated. The phenol-free resin was produced by esterification of poly phthalate and Diels-Alder adduct of rosin anhydride. Compared to rosin modified phenolic resin, eco-friendly phenol-free resin showed better vehicle properties in terms of gloss, yellowing, runability, and storage stability. The results suggest the utility of phenol-free resin instead of conventional rosin modified phenolic resin.

A new method for the construction of 3-aminoindole nucleosides of 2-acetamido-2-deoxy-D-glucose based is presented. Nitration and acetylation of the indole nucleosides by acetic anhydride-nitric acid mixture followed by reduction using silver catalyst (SNSM) impregnated on silica gel, afforded the corresponding amino indole nucleosides. The nucleosides were tested for antiviral activity against hepatitis B virus (HBV) to show different degrees of antiviral activities or inhibitory actions.

Dielectric measurement on binary mixtures of Allyl chloride (ALC) with 2-Pentanone (2-PE) and 2-Hexanone (2-HE) has been carried out over the entire concentration range using Time Domain Reflectometry (TDR) technique at various temperatures in microwave frequency range of 10 MHz to 10 GHz. The static dielectric constant, excess static dielectric constant (${\varepsilon}^E_S$), effective Kirkwood correlation factor ($g^{eff}$) of binary mixtures over entire concentration range were determined to study the effect of increasing alkyl group of ketones on hetero molecular interaction. It was found that magnitude of excess static dielectric constant of mixtures increases with increase of alky group of ketones. The study reveals that the dipole moment of Allyl chloride in mixture have antiparallelism tendency where as 2-pentanone and 2-hexanone have parallelism tendency. Excess static dielectric constant is also fitted to Redlich-Kister equation to get information about rates of multimers formation.