Theoretical investigations have been performed for the ground state ($S_0$) and the first excited state ($S_1$) of the hydrogen bonded green fluorescent protein (GFP) model. The potential energy surface (PESs) of $S_0$ was obtained by B3LYP method and that of $S_1$ was obtained by CIS method. Based on the relative stabilities of species and the energy barriers for the proton transfer, it was found that proton transfer could take place both under the ground state and the first excited state. As determined by the proton motions along the reaction coordinate, both the ground state proton transfer (GSPT) and the excited state proton transfer (ESPT) are considered as a concerted and asynchronous process.

Aim of our study is finding adsorbents suitable for pre-concentration of chemical warfare agents (CWAs). We considered Tenax, bare silica and polydimethylsiloxane (PDMS)-coated silica as adsorbents for dimethyl methylphosphonate (DMMP) and dipropylene glycol methyl ether (DPGME). Tenax showed lower thermal stability, and therefore, desorption of CWA simulants and decomposition of Tenax took place simultaneously. Silica-based adsorbents showed higher thermal stabilities than Tenax. A drawback of silica was that adsorption of CWA simulant (DMMP) was significantly reduced by pre-treatment of the adsorbents with humid air. In the case of PDMS-coated silica, influence of humidity for CWA simulant adsorption was less pronounced due to the hydrophobic nature of PDMS-coating. We propose that PDMS-coated silica can be of potential importance as adsorbent of CWAs for their pre-concentration, which can facilitate detection of these CWAs.

Microtubules play an important role in intracellular transport, mobility, and particularly mitosis. Paclitaxel (Taxol$^{TM}$) and paclitaxel-like compounds have been shown to be anti-tumor agents useful for various human tumors. Paclitaxel-like compounds operate by stabilizing microtubules through interface binding at the interface between two ${\beta}$-tubulin monomers in adjacent protofilaments. In this paper we present the elucidation of the structural features of paclitaxel and paclitaxel-like compounds (e.g., epothilones) with microtubule stabilizing activities, and relate their activities to spatial and chemical features of the molecules. CATALYST program was used to generate three-dimensional quantitative structure activity relationships (3D-QSARs) resulting in 3D pharmacophore models of epothilone- and paclitaxel-derivatives. Pharmacophore models were generated from diverse conformers of these compounds resulting in a high correlation between experimental and predicted biological activities (r = 0.83 and 0.91 for epothilone and paclitaxel derivatives, respectively). On the basis of biological activities of the training sets, five- and four-feature pharmacophore hypotheses were generated in the epothilone and paclitaxel series. The validation of generated hypotheses was achieved by using twelve epothilones and ten paclitaxels, respectively, which are not in the training sets. The clustering (grouping) and merging techniques were used in order to supplement spatial restrictions of each of hypothesis and to develop more comprehensive models. This approach may be of use in developing novel inhibitor candidates as well as contributing a better understanding of structural characters of many compounds useful as anticancer agents targeting microtubules.

A simple colorimetric and fluorescent anion sensor 1 based on salicylimine showed a high selectivity and sensitivity for detection of cyanide in aqueous solution. The receptor 1 showed high selectivity toward $CN^-$ ions in a 1:1 stoichiometric manner, which induces a fast color change from colorless to orange and a dramatic enhancement in fluorescence intensity selectively for cyanide anions over other anions. Such selectivity resulted from the nucleophilic addition of $CN^-$ to the carbon atom of an electron-deficient imine group. The sensitivity of the fluorescence-based assay (0.06 ${\mu}M$) is below the 1.9 ${\mu}M$ suggested by the World Health Organization (WHO) as the maximum allowable cyanide concentration in drinking water, capable of being a practical system for the monitoring of $CN^-$ concentrations in aqueous samples.

A novel multi-cationic borane, tri-N-methylpyridinium substituted triarylborane, $[BAr^N_3]I_3$ ($[2]I_3$) ($Ar^N=4-(4-C_5H_4N-Me)-2,6-Me_2-C_6H_2$) was prepared from the corresponding neutral tris-pyridyl borane, $BAr_3$ (2a) ($Ar=4-(4-C_5H_4N)-2,6-Me_2-C_6H_2$). The crystal structure of 2a determined by X-ray diffraction study reveals the presence of tri-coordinate boron center with peripheral pyridyl moieties. The fluoride ion affinity of the cationic borane, $[2]I_3$ was investigated by UV-vis absorption titrations and was compared with that of neutral 2a. While 2a binds fluoride with the binding constant of $1.9{\times}10^2\;M^{-1}$ in $THF/H_2O$ (9:1 v/v) mixture, $[2]I_3$ shows a very high binding constant ($K=1.0{\times}10^8\;M^{-1}$) that is greater by six orders of magnitude than that of 2a in the same medium. This result indicates that the fluorophilicity of triarylborane can be drastically enhanced by multiple pyridinium substitutions.

Layered $Li_{1.2}(Fe_{0.16}Mn_{0.32}Ni_{0.32})O_2$ was prepared by the mixed hydroxide method at various temperatures. Xray diffraction (XRD) pattern shows that this material has a ${\alpha}-NaFeO_2$ layered structure with $R{\bar{3}}m$ space group and that cation mixing is reduced with increasing synthesis temperature. Scanning electron microscopy (SEM) reveals that nano-sized $Li_{1.2}(Fe_{0.16}Mn_{0.32}Ni_{0.32})O_2$ powder has uniform particle size distribution. X-ray absorption near edge structure (XANES) analysis is used to study the local electronic structure changes around the Mn, Fe, and Ni atoms in this material. The sample prepared at $700^{\circ}C$ delivers the highest discharge capacity of 207 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ with good capacity retention of 80% after 20 cycles.

The second-order rate constants ($k_{OH^-}$) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $OH^-$ in $H_2O$ at $25.0{\pm}0.1^{\circ}C$ have been measured spectrophotometrically. Comparison of $k_{OH^-}$ with $k_{EtO^-}$ (the second-order rate constants for the corresponding reactions with $EtO^-$ in ethanol) has revealed that $EtO^-$ is less reactive than $OH^-$ although the former is ca. 3.4 $pK_a$ units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Br${\o}$nsted-type plot for the reactions of 4a-4i with $OH^-$ is linear with ${\beta}_{lg}$ = -0.36. The Hammett plot correlated with ${\sigma}^-$ constants results in a slightly better correlation than that correlated with ${\sigma}^{\circ}$ constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ${\rho}$ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with $OH^-$ have been concluded to proceed through a concerted mechanism.

Leukocyte common antigen-related phosphatase (LAR) has been considered a promising target for the development of therapeutics for neurological diseases. Here, we report the first example for a successful application of the structure-based virtual screening to identify the novel small-molecule LAR inhibitors. Five of these inhibitors revealed micromolar inhibitory activities with the associated $IC_{50}$ values ranging from 2 to 6 ${\mu}M$. Because the newly identified inhibitors were also screened for having desirable physicochemical properties as a drug candidate, they may serve as a starting point of the structure-activity relationship study to optimize the medical efficacy. Structural features relevant to the stabilization of the new inhibitors in the active site of LAR are discussed in detail.

To improve the water solubility of arylsulfonylimidazolidinone (JSH-2282), a potent anti-cancer agent, two urea derivatives, sodium (S)-2-(3-(4-(5-((S)-2-oxo-4-phenylimidazolidin-1-ylsulfonyl)indoline-1-carbonyl)-phenyl)ureido)succinate (2a) and sodium (S)-2-(3-(4-(5-((S)-2-oxo-4-phenylimidazolidin-1-ylsulfonyl)indoline-1-carbonyl)phenyl)ureido)pentanedioate (2b), were synthesized and studied for solubility and anti-cancer activity.

Ionically modified ${\beta}$-cyclodextrins, which have excellent water-solubility, have been interested in purification technology as well as drug carrier system. The present study summarizes the synthesis and characterization of cationic and anionic ${\beta}$-cyclodextrin (${\beta}$-CyD) products using by polycondensation. The oligo (${\beta}$-CyD)s are synthesized from ${\beta}$-CyD, epichlorohydrin (EP) and choline chloride (CC; for cationic polymer) or chloroacetic acid (CAA; for anionic polymer) through one step polycondenstaion process. Unlike the previous studies, we successfully purified the ionic ${\beta}$-CyD condensation products from the ${\beta}$-CyD reaction mixtures and accomplished a great level of structural analysis. The detailed structural analysis of these ionic ${\beta}$-CyD compounds is done by $^1H$ NMR, MALDI-TOF as well as GPC analysis and confirms the formation of oligomers with a few units of ${\beta}$-CyD. We found that the sequence of reactant addition also could effect on the molecular weight of the resulting product as well as the molar ratio of the reactants. Finally, we used the cationic and anionic ${\beta}$-CyD oligomers for fabricating multilayer films by layer-layer process.

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

The impact of phosphorous (P)-doping on the electrochemical performance and surface chemistry of soft carbon is investigated by means of galvanostatic cycling and ex situ X-ray photoelectron spectroscopy (XPS). P-doping plays an important role in storing more Li ions and discernibly improves reversible capacity. However, the discharge capacity retention of P-doped soft carbon electrodes deteriorated at $60^{\circ}C$ compared to non-doped soft carbon. This poor capacity retention could be improved by vinylene carbonate (VC) participating in forming a protective interfacial chemistry on soft carbon. In addition, the effect of P-doping on exothermic thermal reactions of lithiated soft carbon with electrolyte solution is discussed on the basis of differential scanning calorimetry (DSC) results.

Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.

A layered perovskite of Dion-Jacobson phase, $RbLaTa_2O_7$, was successfully exfoliated into colloidal suspension via successive ion-exchange and intercalation reaction. The pristine perovskite $RbLaTa_2O_7$ was synthesized by conventional solid-state reaction, and then, it was ion-exchanged with hydrochloric acid to obtain a protonic form of perovskite. The resulting proton-exchanged perovskite was reacted with ethylamine to increase interlayer spaces for further intercalation reaction. Finally, the ethylamine-intercalated form was exfoliated into nanosheets via an intercalation of bulky organic cations (tetrabutylammonium). According to X-ray diffraction (XRD) analysis, the TBA-intercalated form showed remarkably increased interlayer spacing (${\Delta}d$ = 1.67 nm) in comparison with that of the pristine material. Transmission electron microscopic image of exfoliated perovskite clearly revealed that the present exfoliated perovskite were composed of very thin layers. This exfoliated perovskite nanosheets could be applicable as building blocks for fabricating functional nanocomposites.

A series of poly(glycerol-succinic acid) dithiocarbamate and 1,3,4-thiadiazole dendrimers, which have potential as anti-wear oil additives, were synthesized. Their anti-wear properties in three different oils (100N, DB-51, and soybean) were evaluated using a four-ball wear tester. The results indicated that thiocarbamate dendrimers have moderate anti-wear properties in DB-51 oil, and 1,3,4-thiadiazole dendrimers exhibited good anti-wear properties in 100N and DB-51 oils. However, dithiocarbamate and 1,3,4-thiadiazole dendrimers were not effective anti-wear additives in soybean oil.

Existing theoretical calculations predict that infrared spectra of the two most fundamental reactive carbo-ions, methyl cation $CH{_3}^+$ with $D_{3h}$ symmetry and protonated methyl cation $CH{_5}^+$ with $C_s(I)$, $C_s(II)$, and $C_{2v}$ symmetries, appear together in the 7-${\mu}m$ region corresponding to the C-H bending modes. Vibrational band profiles of $CH{_3}^+$ and $CH{_5}^+$ have been compared by ab initio calculation methods that use the basis sets of MP2/aug-cc-pVTZ and CCSD(T)/cc-pVTZ. Our results indicate that the bands of rotation-vibration transitions of $CH{_3}^+$ and $CH{_5}^+$ should overlap not only in the 3-${\mu}m$ region corresponding to the C-H stretching modes but also in the 7-${\mu}m$ region corresponding to the C-H bending modes. Five band intensities of $CH{_5}^+$ among fifteen vibrational transitions between 6 and 8 ${\mu}m$ region are stronger than those of the ${\nu}_2$ and ${\nu}_4$ bands in $CH{_3}^+$. Ultimate near degeneracy of the two bending vibrations ${\nu}_2$ and ${\nu}_4$ of $CH{_3}^+$along with the stronger intensities of $CH{_5}^+$ in the three hydrogen scrambling structures may cause extreme complications in the analysis of the high-resolution carbo-ion spectra in the 7-${\mu}m$ region.

The dihydroxy naphthalene/$TiO_2$ complexes with different substitution patterns were prepared by surface modification. X-ray diffraction, UV-Vis spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy were used to characterize the prepared composite materials. The results indicated that the surface modification did not influence the crystallization of $TiO_2$. The visible-light absorbances of prepared dihydroxy naphthalene/$TiO_2$ complexes could be assigned to the ligand-to-metal charge transfer. The obtained catalyst exhibited outstanding photocatalytic activity and stability under visible light. A linear relationship existed between the percentages of hydroxynaphthalenes coordinated on $TiO_2$ surface and $H_2$ production ability. The substitution pattern of dihydroxy naphthalene and $CH_3OH$ content could also influence the photocatalytic performance remarkably. The photocatalytic $H_2$ production ability was further improved after loading with ultra low concentration of Pt, 0.02 wt %. The possible mechanism was proposed.

While many eukaryotic and some prokaryotic proteins show a phosphorylation-dependent mobility shift (PDMS) on SDS-PAGE, the molecular mechanism for this phenomenon had not been elucidated. We have recently shown that the distribution of negatively charged amino acids around the phosphorylation site is important for the PDMS of some proteins. Here, we show that replacement of the phosphorylation site with a negatively charged amino acid results in a similar degree of the mobility shift of a protein as phosphorylation, indicating that the PDMS is due to the introduction of a negative charge by phosphorylation. Compared with a protein showing no shift, one showing a retarded mobility on SDS-PAGE had a decreased capacity for SDS binding. The elucidation of the consensus sequence (${\Theta}X_{1-3}{\Theta}X_{1-3}{\Theta}$, where ${\Theta}$ corresponds to an acidic function) for a PDMS suggests a general strategy for mutagenizing a phosphorylatable protein resulting in a PDMS.

Hydrogen ($H_2$) treatment using a two-step $TiO_2$ nanotube (TONT) film was performed under various annealing temperatures from $350^{\circ}C$ to $550^{\circ}C$ and significantly influenced the extent of hydrogen treatment in the film. Compared with pure TONT films, the hydrogen-treated TONT (H:TONT) film showed substantial improvement of material features from structural, optical and electronic aspects. In particular, the extent of enhancement was remarkable with increasing annealing temperature. Light absorption by the H:TONT film extended toward the visible region, which was attributable to the formation of sub-band-gap states between the conduction and valence bands, resulting from oxygen vacancies due to the $H_2$ treatment. This increased donor concentration about 1.5 times higher and improved electrical conductivity of the TONT films. Based on these analyses and results, photoelectrochemical (PEC) performance was evaluated and showed that the H:TONT film prepared at $550^{\circ}C$ exhibited optimal PEC performance. Approximately twice higher photocurrent density of 0.967 $mA/cm^2$ at 0.32 V vs. NHE was achieved for the H:TONT film ($550^{\circ}C$) versus 0.43 $mA/cm^2$ for the pure TONT film. Moreover, the solar-to-hydrogen efficiency (STH, ${\eta}$) of the H:TONT film was 0.95%, whereas a 0.52% STH efficiency was acquired for the TONT film. These results demonstrate that hydrogen treatment of TONT film is a simple and effective tool to enhance PEC performance with modifying the properties of the original material.

In this study the effects of adding alkaline-earth (IIA) metal oxides to NiZr-loaded Zeolite Y catalysts were investigated on hydrogen rich production by ethanol steam reforming (ESR). Four kinds of alkaline-earth metal (Mg, Ca, Sr, or Ba) oxides of 3.0% by weight were loaded between the $Ni_6Zr_4O_{14}$ main catalytic species and the microporous Zeolite Y support. The characterizations of these catalysts were examined by XRD, TEM, $H_2$-TPR, $NH_3$-TPD, and XPS. Catalytic performances during ESR were found to depend on the basicity of the added alkaline-earth metal oxides and $H_2$ production and ethanol conversion were maximized to 82% and 98% respectively in 27($Ni_6Zr_4O_{14}$)3MgO/70Zeolite Y catalyst at $600^{\circ}C$. Many carbon deposits and carbon nano fibers were seen on the surface of $30Ni_6Zr_4O_{14}$/70Zeolite Y catalyst but lesser amounts were observed on alkaline-earth metal oxide-loaded 27($Ni_6Zr_4O_{14}$)3MO/70Zeolite Y catalysts in TEM photos after ESR. This study demonstrates that hydrogen yields from ESR are closely related to the acidities of catalysts and that alkaline-earth metal oxides reduce the acidities of 27($Ni_6Zr_4O_{14}$)3MO/70Zeolite Y catalysts and promote hydrogen evolution by preventing progression to hydrocarbons.

A quantitative method for determining levels of three bioactive compounds based on pattern recognition was developed and fully validated for the quality control of Alismatis Rhizoma (AR) by HPLC. Separation conditions were optimised using an Optimapak $C_{18}$ column ($250mm{\times}4.6mm$, 5 ${\mu}m$) with a mobile phase of acetonitrile and 0.1% aqueous phosphoric acid and detection wavelengths of 205 and 245 nm. Method validation yielded acceptable linearity ($r^2$ > 0.9998) and percent recovery (98.06%-101.71%). Limits of detection ranged from 0.08 to 0.15 ${\mu}g/mL$. Levels of the three bioactive compounds, alisol C acetate, alisol B, and alisol B acetate, in AR were 0.07-0.45, 0.38-10.32, and 1.13-8.59 mg/g dried weight, respectively. Pattern analyses based on these three compounds were able to differentiate Chinese and Korean samples accurately. The results demonstrate that alisol B and its acetate may be used as marker compounds for AR quality and can be regulated to no less than 0.36 and 1.29 mg/g of dried sample, respectively. The method described here is suitable for quantitative analyses and quality control of multiple components in AR.

Two new high-nitrogen energetic compounds $ZTO{\cdot}2H_2O$ and $ZTO(phen){\cdot}H_2O$ have been synthesized (where ZTO = 4,4-azo-1,2,4-triazol-5-one and phen = 1,10-phenanthroline). The crystal structure, elemental analysis and IR spectroscopy are presented. Compound 1 $ZTO{\cdot}2H_2O$ crystallizes in the orthorhombic crystal system with space group Pnna and compound 2 $ZTO(phen){\cdot}H_2O$ in the triclinic crystal system with space group P-1. In $ZTO(phen){\cdot}H_2O$, there is intermolecular hydrogen bonds between the -NH group of ZTO molecule (as donor) and N atom of phen molecule (as acceptor). Thermal decomposition process is studied by applying the differential scanning calorimetry (DSC) and thermo thermogravimetric differential analysis (TG-DTG). The DSC curve shows that there is one exothermic peak in $ZTO{\cdot}2H_2O$ and $ZTO(phen){\cdot}H_2O$, respectively. The critical temperature of thermal explosion ($T_b$) for $ZTO{\cdot}2H_2O$ and $ZTO(phen){\cdot}H_2O$ is $282.21^{\circ}C$ and $195.94^{\circ}C$, respectively.

Density functional theory (DFT) was used to determine the ground state geometries of indigo and new design dyes (IM-Dye-1 IM-Dye-2 and IM-Dye-3). The time dependant density functional theory (TDDFT) was used to calculate the excitation energies. All the calculations were performed in both gas and solvent phase. The LUMO energies of all the dyes were above the conduction band of $TiO_2$, while the HOMOs were below the redox couple (except IM-Dye-3). The HOMO-LUMO energy gaps of new design dyes were smaller as compared to indigo. All new design dyes were strongly red shifted as compared to indigo. The improved light harvesting efficiency (LHE) and free energy change of electron injection ${\Delta}G^{inject}$ of new designed sensitizers revealed that these materials would be excellent sensitizers. The broken coplanarity between the benzene near anchoring group having LUMO and the last benzene attached to TPA unit in all new design dyes consequently would hamper the recombination reaction. This theoretical designing will the pave way for experimentalists to synthesize the efficient sensitizers for solar cells.

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

Carbon-fiber-supported NiO catalytic filters for oxidation of volatile organic compounds were prepared by electroless Ni-P plating and subsequent annealing processes. Surface structure and crystallinity of NiO film on carbon fiber could be modified by post-annealing at different temperatures (500 and $650^{\circ}C$). Catalytic thermal decompositions of toluene over these catalytic filters were investigated. $500^{\circ}C$-annealed sample showed a higher catalytic reactivity toward toluene decomposition than $650^{\circ}C$-annealed one under same conditions, despite of its lower surface area and toluene adsorption capacity. X-ray diffraction and X-ray photoelectron spectroscopy studies suggest that amorphous structures of NiO on $500^{\circ}C$-annealed catalyst caused the higher reactivity for oxidation of toluene than that of $650^{\circ}C$-annealed sample with a higher crystallinity.

This paper reports substituent effects on the conformational changes in polyaniline (PAni) derivatives. PAni, poly-o-toluidine (POT), and poly-o-anisidine (POA) were formed by potentiodynamic electropolymerization in aqueous solution containing (+)-camphorsulfonic acid (CSA) as a dopant. UV-Vis spectroscopy and cyclic voltammetry measurements revealed that the methyl group showed a greater steric hindrance than the methoxy group. Further, the doping level decreased with increasing steric hindrance. The sign pattern of the circular dichroism (CD) bands for POA was opposite to that for PAni. However, no CD bands were observed in POT. The steric hindrance caused helical inversion, but at a high level of steric hindrance, the helical conformation could not be adopted, because of the reduced doping level. The reduced crystallinity was greatly affected by the decreased doping level. The steric effect influenced the polymer conformation and the doping level, thus determining the optical activity, morphology, and crystallinity of the PAni derivatives.

The binding properties and sequence selectivities of ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with $poly[d(A-T)_2]$ and $poly[d(G-C)_2]$ were investigated using conventional spectroscopic methods. When bound to $poly[d(A-T)_2]$, a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of $poly[d(A-T)_2]$. These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of $45^{\circ}$ between the molecular plane of the bridging moiety of the ${\Delta}{\Delta}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex and the local DNA helix axis calculated from reduced linear dichroism ($LD^r$) spectrum further supported the minor groove binding mode. In the case of ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex, this angle was $55^{\circ}$, suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the $poly[d(A-T)_2]$. In contrast, neither ${\Delta}{\Delta}$-nor ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex produced significant CD or $LD^r$ signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes were partially accessible to the $I^-$ quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to $poly[d(G-C)_2]$. These observations suggest that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes bind at the surface of $poly[d(G-C)_2]$, probably electrostatically to phosphate group. The results indicate that ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ are able to discriminate between AT and GC base pairs.

A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

In this work, the key intermediate, 4-amino-4'-(2-amino-4-anilino-1,3,5-triazine-6-yl)-aminostilbene-2,2'-disulfonic acid, was prepared from 4-(2-amino-4-anilino-1,3,5-triazine-6-yl)amino-4'-nitrostilbene-2,2'-disulfonate by using Tin(II) chloride as the reducing agent. Using this intermediate, nineteen new asymmetrically substituted bistriazinylstilbene fluorescent brightening agents were synthesized. Chemical structures of the obtained compounds 5a-s were analyzed by proton NMR spectrum. The physical properties of the new compounds 5a-s were characterized by fastness test and whiteness measurement test and the obtained data were compared to measurements obtained from CI 86.

Two new 3D coordination complexes [Cd(3-bpcd)(pht)] (1) and [Zn(3-bpcd)(pht)] (2) [3-bpcd = N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide, $H_2pht$ = phthalic acid] have been hydrothermally synthesized. X-ray diffraction analysis reveals that the complexes 1 and 2 represent a 4-connected diamondoid topology with a 3-fold interpenetrating feature. Moreover, the fluorescent properties of complexes 1 and 2 are studied.

Matrix assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is a very effective method for lipid mass fingerprinting. However, MALDI MS suffered from spectral complexities, differential ionization efficiencies, and poor reproducibility when analyzing complex lipid mixtures without prior separation steps. Here, we aimed to find optimal MALDI sample preparation methods which enable selective or class-wide mass fingerprinting of two totally different lipid classes. In order to achieve this, various matrices with additives were tested against the mixture of phosphatidylcholine (PC) and cerebrosides (Cers) which are abundant in animal brain tissues and also of great interests in disease biology. Our results showed that, from complex lipid mixtures, 2,4,6-trihydroxyacetophenone (THAP) with $NaNO_3$ was a useful MALDI matrix for the class-wide fingerprinting of PC and Cers. In contrast, THAP efficiently generated PC-focused profiles and graphene oxide (GO) with $NaNO_3$ provided Cer-only profiles with reduced spectral complexity.

Three push-pull organic semiconductors, TPA-$Th_3$-MMN (1), TPA-ThTT-MMN (2), and TPA-ThDTT-MMN (3), comprising a triphenylamine donor and a methylene malononitrile acceptor linked by various ${\pi}$-conjugated thiophene units were synthesized, and the effects of the ${\pi}$-conjugated bridging unit on the photovoltaic characteristics of solution-processed small-molecule organic solar cells based on these semiconductors were investigated. Planar bridging units with extended ${\pi}$-conjugation effectively facilitated intermolecular ${\pi}-{\pi}$ packing interactions in the solid state, resulting in enhanced $J_{sc}$ values of the SMOSCs fabricated with bulk heterojunction films.

Composite materials of mesoporous carbon and carbon nanotubes were synthesized using Ni, Co and Pd-loaded CMK3 via a catalytic reaction of methane and $CO_2$. The CNTs grew from the pores of the mesoporous carbon supports, and they were attached tightly to the CMK3 surface in a densely tangled shape. The CNT/CMK3 composite showed both non-graphitic mesoporous structures, and graphitic characteristics originating from the MWCNTS grown in the pores of CMK3. The electrochemical properties of the materials were characterized by their electrorheological effects and cyclic voltammetry. The CNTs/CMK3 composites showed high electrical conductivity and current density. The CNT/CMK3 or KOH-modified CNT/CMK3 particles were incorporated in a PMMA matrix to improve the thermal and electrical conductivity. Even higher thermal conductivity was achieved by the addition of KOH-modified CNT/CMK3 particles.

The tailored surface modification of electrode materials is crucial to realize the wanted electronic and electrochemical properties. In this regard, a dexterous carbon encapsulation technique can be one of the most essential preparation methods for the electrode materials for lithium rechargeable batteries. For this purpose, DL-malic acid ($C_4H_6O_5$) was here used as the carbon source enabling an amorphous carbon layer to be formed on the surface of Si nanoparticles at enough low temperature to maintain their own physical or chemical properties. Various structural characterizations proved that the bulk structure of Si doesn't undergo any discernible change except for the evolution of C-C bond attributed to the formed carbon layer on the surface of Si. The improved electrochemical performance of the carbon-encapsulated Si compared to Si can be attributed to the enhanced electrical conductivity by the surface carbon layer as well as its role as a buffering agent to absorb the volume expansion of Si during lithiation and delithiation.

A low-cost and simple recycling process of waste thermoelectric modules has been investigated using chemical reduction methods. The recycling is separated by two processes, such as dissolving and reduction. When the waste thermoelectric chips are immersed into a high concentration of $HNO_3$ aqueous solution at $100^{\circ}C$, oxide powders, e.g., $TeO_2$ and $Sb_2O_3$, are precipitated in the $Bi^{3+}$ and $HTeO{_2}^+$ ions contained solution. By employing a reduction process with the ions contained solutions, $Bi_2Te_3$ nanoparticles are successfully synthesized. Due to high reduction potential of $HTeO{_2}^+$ to Te, Te elements are initially formed and subsequently $Bi_2Te_3$ nanoparticles are formed. The average particle size of $Bi_2Te_3$ was calculated to be 25 nm with homogeneous size distribution. On the other hand, when the precipitated powders reduced by hydrazine, $Sb_2O_3$ and Te nanoparticles are synthesized because of higher reduction potentials of $TeO_2$ to Te. After the washing step, the $Sb_2O_3$ are clearly removed, results in Te nanoparticles.

The electronic structure and elastic properties of the 4d transition metal carbides MC (M = Y, Zr, Nb, Rh) were studied by means of extended H$\ddot{u}$ckel tight-binding band electronic structure calculations. As the valence electron population of M increases, the bulk modulus of the MC compounds in the rocksalt structure does not increase monotonically. The dominant covalent bonding in these compounds is found to be M-C bonding, which mainly arises from the interaction between M 4d and C 2p orbitals. The bonding characteristics between M and C atoms affecting the variation of the bulk modulus can be understood on the basis of their electronic structure. The increasing bulk modulus from YC to NbC is associated with stronger interactions between M 4d and C 2p orbitals and the successive filling of M 4d-C 2p bonding states. The decreased bulk modulus for RhC is related to the partial occupation of Rh-C antibonding states.

A novel sol-gel method was implied to prepare CuO-doped ZnO nanoparticles. XRD and SEM techniques were used to characterize the CuO-doped ZnO sample. The photocatalytic degradation of Lidocaine HCl was investigated by two methods. The degradation was studied under different conditions such as the amount of photocatalyst, pH of the system, initial concentration, presence of electron acceptor, and presence of anions. The results showed that they strongly affected the photocatalytic degradation of Lidocaine HCl. The photodegradation efficiency of drug increased with the increase of the irradiation time. After 6 h irradiation with 400-W mercury lamp, about 93% removal of Lidocaine HCl was achieved. The degree of photodegradation obtained by Taguchi method compatible with the trial-and-error method showed reliable results.