Deficiencies in wear and frost resistance as well as mechanical strength constitute the main causes of equipment failure under the harsh climatic conditions of the Earth's polar regions. To improve the properties of the materials used in this equipment, nanoparticle composites have been prepared from clays such as kaolinite, hectorite, and montmorillonite in combination with polytetrafluoroethylene (PTFE) or ultrahigh molecular weight polyethylene (UHMWPE). A number of techniques have been proposed to disperse silicate particles in PTFE or UHMWPE polymer matrices, and several successful processes have even been widely applied. Polymer nanocomposites that exhibit enhanced mechanical and thermal properties are promising materials for replacing metals and glass in the equipment intended for Arctic use. In this article, we will review PTFE- and UHMWPE-based layered silicate nanocomposites.

This study introduces a new method of combining Imaging Differential Optical Absorption Spectroscopy (Imaging-DOAS) data and plume dispersion formulas for power plant emissions to determine the three-dimensional structure of a dispersing pollution plume and the spatial distributions of trace gas volume mixing ratios (VMRs) under conditions of negligible water droplet and aerosol effects on radiative transfer within the plume. This novel remote-sensing method, applied to a power plant stack plume, was used to calculate the two-dimensional distributions of sulfur dioxide ($SO_2$) and nitrogen dioxide ($NO_2$) VMRs in stack emissions for the first time. High $SO_2$ VMRs were observed only near the emission source, whereas high $NO_2$ VMRs were observed at locations several hundreds of meters away from the initial emission. The results of this study demonstrate the capability of this new method as a tool for estimating plume dimensions and trace gas VMRs in power plant emissions.

A new method for the synthesis of 2,2-dimethyl-6-substituted 4-piperidone was developed; two equivalents of acetone were annulated with N-unsubstituted imines in-situ generated from benzyl azides using a ruthenium catalyst in the presence of $\small{L}$-proline.

A well-known carbazole-based precursor (probe 1) was used for the detection of cysteine/homocysteine and fluoride. Probe 1 shows a "turn-on" response to cysteine/homocysteine and fluoride via enhancement in emission intensity at 442 nm and 462 nm respectively, in solutions and living cells. Furthermore, probe 1 behaves as a fluorescent molecular switch between cysteine/homocysteine and fluoride as the chemical inputs, which have been used for the development of a combinatorial logic circuit and a molecular keypad lock.

We present the solution of Klein Gordon equation with new generalized Morse-like potential using SUSYQM formalism. We obtained approximately the energy eigenvalues and the corresponding wave function in a closed form for any arbitrary l state. We computed the numerical results for some selected diatomic molecules.

Detailed chemical investigation of Boscia senegalensis (Per) Lam. ex Poir. led to the isolation of one new flavonol glycoside, rhamnocitrin-3-O-${\beta}$-$\small{D}$-(6"-O-E-feruloyl)-glucopyranoside named bosenegaloside A (1), with seven known compounds, rhamnocitrin-3-O-${\beta}$-$\small{D}$-(6"-O-E-p-coumaroyl)-glucopyranoside (2), rhamnocitrin-3-O-${\beta}$-$\small{D}$-glucopyranoside (3), 3,4,5-trimethoxyphenol-${\beta}$-$\small{D}$-glucopyrinoside (4), lasianthionoside A (5), 3,7-dimethyl-1-octene-3,6,7-triol-6-O-${\beta}$-$\small{D}$-glucopyranoside (6), syringin (7), and austroside B (8). The chemical structures of these compounds were elucidated from spectroscopic data and by comparison of these data with previously published results. The inhibitory activity of the isolated compounds on soluble epoxide hydrolase (sEH) was assessed. Compounds 1-3 potently inhibited sEH activity with $IC_{50}$ values of $12.8{\pm}0.5$, $18.4{\pm}0.2$, and $11.3{\pm}0.9{\mu}M$, respectively.

An efficient and practical synthesis of natural moracins, which have diverse range of biological properties including anticancer, antioxidant, and antibacterial activities, has been achieved using $Pd(OAc)_2/P(^tBu)_3-HBF_4$ as a Sonogashira coupling reagent which solved the unreactive problems in case of higher electron density of haloaryl compounds in the reaction. Lowering electron density of halophenol with acetylation and changing Sonogashira coupling reagent from $PdCl_2(PPh_3)_2$ to $Pd(OAc)_2/P(^tBu)_3-HBF_4$ smoothly produce the benzofuran structures in the syntheses of moracins M, N and S. The electron deficient halobenzaldehyde, however, easily forms the benzofuran using original Sonogashira conditions, and utilized for the first synthesis of moracin Y.

Synthesis and structural characterization of mercury(II) halides and perchlorate complexes (1-4) of bis-$OS_2$-macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type $[Hg(L)X_2]_n$ (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer $\{[Hg_2(L)I_4]{\cdot}CHCl_3\}_n$ (3) in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer $\{[Hg_2(L)(DMF)_6](ClO_4)_4{\cdot}2DMF\}_n$ (4) instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes.

Porous silica particles are the most prevailing raw material for stationary phases of liquid chromatography. During a long period of time, various methodologies for production of porous silica particles have been proposed, such as crashing and sieving of xerogel, traditional dry or wet process preparation of conventional spherical particles, preparation of hierarchical mesoporous particles by template-mediated pore formation, repeated formation of a thin layer of porous silica upon nonporous silica core (core-shell particles), and formation of specific silica monolith followed by grinding and calcination. Recent developments and applications of useful porous silica particles will be covered in this review. Discussion on sub-$3{\mu}m$ silica particles including nonporous silica particles, carbon or metal oxide clad silica particles, and molecularly imprinted silica particles, will also be included. Next, the individual preparation methods and their feasibilities will be collectively and critically compared and evaluated, being followed by conclusive remarks and future perspectives.

This paper describes how primary contaminants in ambient air affect the performance of the cathode in fuel cell electric vehicle applications. The effect of four atmospheric pollutants ($SO_2$, $NH_3$, $NO_2$, and CO) on cathode performance was investigated by air impurity injection and recovery test under load. Electrochemical analysis via polarization and electrochemical impedance spectroscopy was performed for various concentrations of contaminants during the impurity test in order to determine the origins of performance decay. The variation in cell voltage derived empirically in this study and data reported in the literature were normalized and juxtaposed to elucidate the relationship between impurity concentration and performance. Mechanisms of cathode degradation by air impurities were discussed in light of the findings.

Matrix-induced mass bias and its effect on the accuracy of isotope ratio measurements have been examined for a quadrupole-based inductively coupled plasma-mass spectrometer (Q ICP-MS). Matrix-induced mass bias effect was directly proportional to % mass difference, and its magnitude varied for element and nebulizer flow rate. For a given element and conditions in a day, the effect was consistent. The isotope ratio of Cd106/Cd114 under $200{\mu}g\;g^{-1}$ U matrix deviated from the natural value significantly by 3.5%. When Cd 111 and Cd114 were used for the quantification of Cd with isotope dilution (ID) method, the average of differences between the calculated and measured concentrations was -0.034% for samples without matrix ($0.076{\mu}g\;g^{-1}$ to $0.21{\mu}g\;g^{-1}$ for the period of 6 months). However, the error was as large as 1.5% for samples with $200{\mu}g\;g^{-1}$ U. The error in ID caused by matrix could be larger when larger mass difference isotopes are used.

In search of new antileukopenia agents, twenty dithiolopyrrolone derivatives were synthesized and evaluated for their leukocyte-increasing activities in normal mice. Among the synthesized compounds 4-23, compounds 5 and 6 showed significant leukocyte-increasing activity ( p < 0.01), and compounds 4, 9 and 16 had a moderate effect ( p < 0.05). Compound 5 also displayed stronger leukocyte-increasing activity than that of the positive recombinant human granulocyte colony stimulating factor (rhG-CSF). Above all, compound 5 would be a potential antileukopenia agent which deserved further research.

A novel crystal, the mono-protonated metformin acetate (1), was obtained and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. It was found that one of the imino group in the metformin cation was protonated along with the proton transfer from the secondary amino group to the other imino group. Its crystal structure was then compared with the previously reported diprotonated metformin oxalate (2). The difference between them is that the mono-protonated metformin cations can be linked by hydrogen bonding to form dimers while the diprotonated metformin cations cannot. Both of them are stabilized by intermolecular hydrogen bonds to assemble a 3-D supermolecular structure. The four potential tautomer of the mono-protonated metformin cation (tautomers 1a, 1b, 1c and 1d) were optimized and their single point energies were calculated by Density Functional Theory (DFT) B3LYP method based on the Polarized Continuum Model (PCM) in water, which shows that the most likely existed tautomer in human cells is the same in the crystal structure. Based on the optimized structure, their Wiberg bond orders, Natural Population Analysis (NPA) atomic charges, molecular electrostatic potential (MEP) maps were calculated to analyze their electronic structures, which were then compared with the corresponding values of the diprotonated metformin cation (cation 2) and the neutral metformin (compound 3). Finally, the possible tautomeric mechanism of the mono-protonated metformin cation was discussed based on the observed phenomena.

The first synthetic route to 5'-norcarbocyclic C-nucleoside [7-oxa-7,9-dideazadenosine (furo[3,2-d]pyrimidine) and 9-deazaadenosine (pyrrolo[3,2-d]pyrimidine)] phosphonic acids from commercially available 1,3-dihydroxy cyclopentane was described. The key C-C bond formation from sugar to base precursor was performed using Knoevenagel-type condensation from a ketone derivative. Synthesized C-nucleoside phosphonic acids were tested for anti-HIV activity as well as anti-leukemic activity. Compound 26 showed significant anti-leukemic activity.

Phospholipase D (PLD) catalyzed the generation of phosphatidic acid (PA) from phosphatidylcholine (PC) at the outer layer of the vesicles prepared through layer by layer via a double emulsion technique. The generation induced a curvature change in the vesicles, which eventually led them to fuse each other. The ratio of two-fatty-acid-tail ethanolamine (PE) to one-fatty-acid-tail ethanolamine (PE) was found to acquire the condition where the mixed-phospholipid vesicles were stable identically with pure two-fatty-acid-tail PC. The effect of the outer-layer mixture on the PLD-induced vesicle fusion was investigated using the fluorescence intensity change. 8-Aminonaph-thalene-1,3,6-trisulfonic acid disodium salt (ANTS) and p-Xylene-bis(N-pyridinium bromide) (DPX) were encapsulated in the vesicles, respectively, for the quantification of the fusion. The fluorescence scale was calibrated with the fluorescence of a 1/1 mixture of ANTS and DPX vesicles in NaCl buffer taken as 100% fluorescence (0% fusion) and the vesicles containing both ANTS and DPX as 0% fluorescence (100% fusion), considering the leakage into the medium studied directly in a separate experiment using vesicles containing both ANTS and DPX. The fusion data for each composition were acquired with the subtraction of the leakage from the quenching. From the monitoring, the vesicle fusion caused by the PLD reaction seems dominantly to occur rather than the vesicle lysis, because the composition effect on the fusion was observed identically with that on the change in the vesicle structure. Furthermore, the diameter measurements also support the fusion dominancy.

Molecular structures of the various conformers of para-bromocalix[4]aryl derivatives 1-4 were optimized using the DFT B3LYP calculation method. The total electronic and Gibbs free energies and normal vibrational frequencies of the different structures (CONE, partial cone (PACO), 1,2-Alternate(1,2-A) and 1,3-Alternate(1,3-A)) were calculated from the four kinds of para-bromocalix[4]aryl derivatives. The B3LYP/6-31G(d,p) calculations suggested the following: 1(PACO) is the most stable among four conformers of 1; 2(CONE) is the most stable among five conformers of 2; 3(PACO) is the most stable among four conformers of 3; 4(1,3-A) is the most stable among four conformers of 4. All the most stable structures optimized by the B3LYP calculation method were in accordance with the experimental crystal structures of 1-4. The calculated IR spectra of the various conformers (CONE, PACO, 1,2-A and 1,3-A) of 1-4 were compared.

A magnetic sonophotocatalyst $Fe_3O_4@SiO_2@TiO_2$ is synthesized for the enhanced biodegradability of organophosphate pesticide. The as-prepared catalysts were characterized using different techniques, such as X-ray diffraction (XRD) and transmission electron microscopy (TEM). The radial sonophotocatalytic activity of $Fe_3O_4@SiO_2@TiO_2$ nanocomposite was investigated, in which commercial dichlorvos (DDVP) was chosen as an object. The degradation efficiency was evaluated in terms of chemical oxygen demand (COD) and enhancement of biodegradability. The effect of different factors, such as reaction time, pH, the added amount of catalyst on $COD_{Cr}$ removal efficiency were investigated. The average $COD_{Cr}$ removal efficiency reached 63.13% after 240 min in 12 L sonophotocatalytic reactor (catalyst $0.2gL^{-1}$, pH 7.3). The synergistic effect occurs in the combined sonolysis and photocatalysis which is proved by the significant improvement in $COD_{Cr}$ removal efficiency compared with that of solo photocatalysis. Under this experimental condition, the $BOD_5/COD_{Cr}$ ratio rose from 0.131 to 0.411, showing a remarkable improvement in biodegradability. These results showed that sonophotocatalysis may be applied as pre-treatment of pesticide wastewater, and then for biological treatment. The synthesized magnetic nanocomposite had good photocatalytic performance and stability, as when it was used for the fifth time, the $COD_{Cr}$ removal efficiency was still about 62.38%.

In this paper, we report thermodynamic and transport properties (diffusion coefficient, viscosity, and thermal conductivity) of diatomic gases ($H_2$, $N_2$, $O_2$, and $Cl_2$) at 273.15 K and 1.00 atm by performing molecular dynamics simulations using Lennard-Jones intermolecular potential and modified Green-Kubo formulas. The results of self-diffusion coefficients of diatomic gases obtained from velocity auto-correlation functions by Green-Kubo relation are in good agreement with those obtained from mean square displacements by Einstein relation. While the results for viscosities of diatomic gases obtained from stress auto-correlation functions underestimate the experimental results, those for thermal conductivities obtained from heat flux auto-correlation functions overestimate the experimental data except $H_2$.

In theoretical simulations of proton transfer in DNA, environmental factors nearly have not been considered. In our calculations, using QM/MM method on the basis of CP2K, proton transfer on adenine-thymine base pair is studied in water, at wide scope temperature, and under the external electric field. Our results indicate that the external electric field induces the proton transfer at room temperature, and its intensity and temperature have some effect on hole localization and proton transfer.

Bisphenol A is considered as pollutant, because it is toxic and hazardous to living organisms even at very low concentrations. Biological oxidation used for removing this organic from waste water is not suitable and consequently application of catalytic wet oxidation has been considered as one of the best options for treating bisphenol A. We have developed Fe/SBA-15, Ni/SBA-15 and Fe-Ni/SBA-15 as heterogeneous catalysts using the advanced impregnation method for oxidation of bisphenol A in water. The catalysts were characterized with physico-chemical characterization methods such as, powder X-ray diffraction (PXRD), FT-IR measurements, N2 adsorption-desorption isotherm, thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. This work illustrates activity of the catalysts for heterogeneous catalytic degradation reaction revealed with excellent conversion and recyclability. The degradation products identified were not persistent pollutants. GC-MS analysis identified the products: 2,4-hexadienedioic acid, 2,4-pentadienic acid and isopropanol or acetic acid. The leachability study indicated that the catalysts release very little metals to water. Therefore, the possibility of water contamination through metal leaching was almost negligible.

Relationship between molecular freedom of amyloidogenic protein and its self-assembly into amyloid fibrils has been evaluated with ${\alpha}$-synuclein, an intrinsically unfolded protein related to Parkinson's disease, by restricting its structural plasticity through an end-to-end disulfide bond formation between two newly introduced cysteine residues on the N- and C-termini. Although the resulting circular form of ${\alpha}$-synuclein exhibited an impaired fibrillation propensity, the restriction did not completely block the protein's interactive core since co-incubation with wild-type ${\alpha}$-synuclein dramatically facilitated the fibrillation by producing distinctive forms of amyloid fibrils. The suppressed fibrillation propensity was instantly restored as the structural restriction was unleashed with ${\beta}$-mercaptoethanol. Conformational flexibility of the accreting amyloidogenic protein to pre-existing seeds has been demonstrated to be critical for fibrillar extension process by exerting structural adjustment to a complementary structure for the assembly.

Laser Raman spectroscopy is one of the most powerful technologies for standoff detection of hazardous materials including explosives. Supported by recent development of laser and sensitive ICCD camera, the technology can identify trace amount of unknown substances in a distance. Using this concept, we built a standoff detection system, in which nanosecond pulse laser and nanosecond gating ICCD technique were delicately devised to avoid the large background noise which suppressed weak Raman signals from the target sample. In standoff detection of explosives which have large kill radius, one of the most important technical issues is the detection distance from the target. Hence, we focused to increase the detection distance up to 54 m by careful optimization of optics and laser settings. The Raman spectra of hazardous materials observed at the distance of 54 m were fully identifiable. We succeeded to detect and identify eleven hazardous materials of liquid or solid particles, which were either explosives or chemical substances used frequently in chemical plants. We also performed experiments to establish the limit of detection (LOD) of HMX at 10 m, which was estimated to be 6 mg.

The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.

Study on the unimolecular reaction for $CH_2FO$ and $CD_2FO$ is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6-311++G(3df, 3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of 500-5000 K and microcanonical system at total energy of 19.05-71.68 kcal/mol. The results indicate that the anharmonic effect and isotope effect are very small for the three channels, and the anharmonic rate constants, around $10^9-10^{11}s^{-1}$, are close to the experimental prediction reasonably.

The most stable adsorption structures and energies of four tautomers of 3-methyl-5-pyrazolone (keto-1, enol-1, keto-2, and enol-2) on Ge(100) surfaces were investigated using density functional theory (DFT) calculations. The enol-1, keto-2, and enol-2 tautomers, but not the keto-1 tautomer, were found to exhibit stable adsorption structures on the Ge(100)-$2{\times}1$ surface. Of these three adsorption structures, that of enol-2 is the most stable.

Proteasome, a multicatalytic protease complex, has been validated as a promising therapeutic target in oncology. Carfilzomib (Kyprolis$^{(R)}$), a tetrapeptide epoxyketone, irreversibly inhibits the chymotrypsin-like (CT-L) activity of the proteasome and has been recently approved for multiple myeloma treatment by FDA. A chemistry effort was initiated to discover the compounds that are reversibly inhibit the proteasome by replacing the epoxyketone moiety of carfilzomib with a variety of ketones as reversible and covalent warheads at the C-terminus. The newly synthesized compounds exhibited significant inhibitory activity against CT-L activity of the human 20S proteasome. When the compounds were tested for cancer cell viability, 14-8 was found to be most potent in inhibiting Molt-4 acute lymphoblastic leukemia cell line with a $GI_{50}$ of $4.4{\mu}M$. Cytotoxic effects of 14-8 were further evaluated by cell cycle analysis and Western blotting, demonstrating activation of apoptotic pathways.

Zeolite-templated carbons (ZTCs), which have high specific surface area, were prepared by a conventional templating method using microporous zeolite-Y for catalyst supports in direct methanol fuel cells. The ZTCs were synthesized at different temperatures to investigate the characteristics of the surface produced and their electrochemical properties. Thereafter, Pt-Ru was deposited at different carbonization temperatures by a chemical reduction method. The crystalline and structural features were investigated using X-ray diffraction and scanning electron microscopy. The textural properties of the ZTCs were investigated by analyzing $N_2$/77 K adsorption isotherms using the Brunauer-Emmett-Teller equation, while the micro- and meso-pore size distributions were analyzed using the Barrett-Joyner-Halenda and Harvarth-Kawazoe methods, respectively. The surface morphology was characterized using transmission electron microscopy and inductively coupled plasma-mass spectrometry. The electrochemical properties of the Pt-Ru/ZTCs catalysts were also analyzed by cyclic voltammetry measurements. From the results, the ZTCs carbonized at $900^{\circ}C$ show the highest specific surface areas. In addition, ZTC900-PR led to uniform dispersion of Pt-Ru on the ZTCs, which enhanced the electro-catalytic activity of the Pt-Ru catalysts. The particle size of ZTC900-PR catalyst is about 3.4 nm, also peak current density from the CV plot is $12.5mA/cm^2$. Therefore, electro-catalytic activity of the ZTC900-PR catalyst is higher than those of ZTC1000-PR catalyst.

This study evaluated a simple and useful route to the synthesis of mesoporous $TiO_2$ microcapsules with a hollow macro-core structure. A hydrophilic precursor sol containing the surfactants in the hydrophobic solvents was deposited on PMMA polymer surfaces modified by non-thermal plasma to produce mesoporous shells after calcination. The surface of the PMMA polymer spheres was coated with $NH_4F$ and CTAB to control the interfacial properties and promote the subsequent deposition of inorganic sols. These hollow type mesoporous $TiO_2$ microcapsules could be applied as an efficient substrate for the immobilization of DNA oligonucleotides.

Blue phosphorescent $(dfpypy)_2Ir(mppy)$, where dfpypy = 2',6'-difluoro-2,3'-bipyridine and mppy = 5-methyl-2-phenylpyridine, has been synthesized by newly developed effective method and its solid state structure and photoluminescent properties are investigated. The glass-transition and decomposition temperature of the compound appear at $160^{\circ}C$ and $360^{\circ}C$, respectively. In a crystal packing structure, there are two kinds of intermolecular interactions such as hydrogen bonding ($C-H{\cdots}F$) and edge-to-face $C-H{\cdots}{\pi}(py)$ interaction. This compound emits bright blue phosphorescence with ${\lambda}_{max}=472nm$ and quantum efficiencies of 0.23 and 0.32 in fluid and the solid state. The emission band of the compound is red-shifted by 40 nm relative to homoleptic congener, $Ir(dfpypy)_3$. The ancillary ligand in $(dfpypy)_2Ir(mppy)$ has been found to significantly destabilize HOMO energy, compared to $Ir(dfpypy)_3$, $(dfpypy)_2Ir(acac)$ and $(dfpypy)_2Ir(dpm)$, without significantly changing LUMO energy.

Monitoring of pH, especially under highly alkaline conditions, is necessary in various processes in the industrial, biotechnological, agricultural, and environmental fields. However, few pH indicators that can function at highly alkaline levels are available, and most of which are organic-based pH indicators. Several years ago, it was reported that gold nanoparticles prepared using trisodium citrate dihydrate were rapidly aggregated at pH values higher than ~12.7. A shift of surface plasmon resonance for such aggregated gold nanoparticles can be applied to pH indicators, allowing for the substitution of traditional organic-based pH indicators. The most important characteristic of pH indicators is the transition pH range. Herein, gold and silver nanoparticles are prepared using different reducing agents, and their transition pH ranges are examined. The results showed that all nanoparticles prepared in this study exhibit similar transition pH ranges spanning 11.9-13.0, regardless of the nanoparticle material, reducing agents, and concentration.

RGB light emitting ZnSe based nanocrystals: ZnSe (blue), ZnSe:Cu (green) and ZnSe:Mn (red) were synthesized by capping the surface of the nanocrystals with oleic acid. The obtained nanocrystal powders were characterized by using XRD, HR-TEM, ICP-AES, FT-IR, and FT-Raman spectroscopies. The optical properties were also measured by UV/Vis and photoluminescence (PL) spectroscopies. The PL spectra showed broad emission peaks at 471 nm (ZnSe), 530 nm (ZnSe:Cu) and 665 nm (ZnSe:Mn), with relative PL efficiencies in the range of 0.7% to 5.1% compared to a reference organic dye standard. The measured average particle sizes from the HR-TEM images for those three nanocrystals were 4.5 nm on average, which were also supported well by the Debye-Scherrer calculations. The elemental compositions of the ZnSe based nanocrystals were determined by ICP-AES analyses. Finally, the drawn CIE diagram showed the color coordinates of (0.15, 0.16) for ZnSe, (0.22, 0.57) for ZnSe:Cu, and (0.62, 0.35) for ZnSe:Mn respectively, which were fairly well matched to that of the RGB color standards.

A series of compounds containing both 1,3,4-oxadiazole and thiohydantoin were synthesized as a promising scaffold for application in medicinal chemistry. The key step of the synthesis is a microwave-assisted cyclization of semicarbazides possessing a thiohydantoin moiety at one of the acyl termini using $POCl_3$ as a dehydrating reagent. A wide range of semicarbazides were prepared through the substitution of hydrazides with an N-acylated thiohydantoin derived from the cyclization of the corresponding isothiocyanate with an amino acid and subsequent N-acylation of the resultant thiohydrantion. Consequently, the 58 number of 1,3,4-oxadiazole derivatives having a thiohydantoin substituent were prepared in good overall yields.

Simple and practical synthesis of natural benzofuran derivative eupomatenoid-6 via Horner-Emmons type condensation as the key step is described. The umpolung property of aldehyde derivative, ${\alpha}$-aminophosphonate was efficiently employed in this reaction. ${\alpha}$-Aminophosphonate of anisaldehyde subjected to Horner-Emmons type condensation with 5-bromo-2-methoxybenzaldehyde to yield the deoxybenzoin, which was further methylated and then underwent tandem demethylation-cyclodehydration to afford the benzofuran scaffold in excellent yield. Finally Suzuki coupling with propenyl boronic acid afforded eupomatenoid-6 with an overall yield of 56.8%.

Nuclear factor-erythroid 2-related factor 2 (Nrf2) regulates the expression of over 200 genes of antioxidant and phase II drug-metabolizing enzymes, and is highly expressed in non-small cell lung cancer (NSCLC). Nine derivatives of 4-(2-cyclohexylethoxy)aniline were designed. Our previous study demonstrated that IM3829 increases radiosensitivity of several lung cancer cells in vitro and in vivo. Here, biological effects of IM3829 derivatives (2a-2i) were evaluated. Compound 2g derivative effectively inhibits mRNA and protein expression of Nrf2 and HO-1. In addition, we observed over two fold enhancement in IR-induced cell death, from $2.90{\pm}0.22$ to $6.02{\pm}0.87$, in H1299 cancer cell-line. Among the nine derivatives, compound 2g derivative exhibited the highest enhancement of radiosensitizing effect via inhibition of Nrf2 activity.

In this study we examined two ester-containing cross-links, hex-2-enyl acetate and hex-2-enyl propionate, as new cross-linking systems for helix stabilization of short peptides. We demonstrated that these hexenyl ester cross-links can be readily installed via a ruthenium-mediated ring-closing metathesis reaction of L-aspartic acid 4-allyl ester or L-glutamic acid 5-allyl ester at position i and (S)-2-(4'-pentenyl)alanine at position i+4 using second generation Hoveyda-Grubbs catalyst at $60^{\circ}C$. Between these two cross-links, we found that the hex-2-enyl propionate significantly stabilizes the ${\alpha}$-helical conformations of short model peptides. The helix-stabilizing effects of the hex-2-enyl propionate tether appear to be as powerful as Verdine's i,i+4 all-hydrocarbon stapling system, which is one of the most widely used and the most potent helix-stabilizing cross-linking systems. Furthermore, the hex-2-enyl propionate bridge is reasonably robust against non-enzymatic hydrolytic cleavage at a physiological pH. While extended studies for probing its chemical scopes and biological applications are needed, we believe that this new helix-stabilizing system could serve as a useful chemical tool for understanding protein folding and designing conformationally-constrained peptide drugs.

In this study we designed and synthesized several heptapeptides that are enforced to form an amphipathic helix using all-hydrocarbon stapling system and evaluated their antimicrobial and hemolytic activities. The antimicrobial activity showed clear structure-activity relationships, confirming the importance of helicity and amphipathicity. Some stapled heptapeptides displayed a moderate antimicrobial activity along with a low hemolytic activity. To our best knowledge, although not highly potent, these stapled peptides represent the shortest helical amphipathic antimicrobial peptides reported to date. The preliminary data obtained in this work would serve as a good starting point for further developing short analogs of amphipathic helical antimicrobial peptides.

In this study, we analyzed the toxicity of mixtures of dimethylformamide (DMF) and methyl ethyl ketone (MEK) or DMF and toluene (TOL) and predicted their toxicity using quantitative structure-activity relationships (QSAR). A QSAR model for single substances and mixtures was analyzed using multiple linear regression (MLR) by taking into account the statistical parameters between the observed and predicted $EC_{50}$. After preprocessing, the best subsets of descriptors in the learning methods were determined using a 5-fold cross-validation method. Significant differences in physico-chemical properties such as boiling point (BP), specific gravity (SG), Reid vapor pressure (rVP), flash point (FP), low explosion limit (LEL), and octanol/water partition coefficient (Pow) were observed between the single substances and the mixtures. The $EC_{50}$ of the mixture of DMF and TOL was significantly lower than that of DMF. The mixture toxicity was directly related to the mixing ratio of TOL and MEK (MLR $EC_{50}$ equation = $1.76997-1.12249{\times}TOL+1.21045{\times}MEK$), as well as to SG, VP, and LEL (MLR equation $EC_{50}=15.44388-19.84549{\times}SG+0.05091{\times}VP+1.85846{\times}LEL$). These results show that QSAR-based models can be used to quantitatively predict the toxicity of mixtures used in manufacturing industries.