Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in $HClO_4$ medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both $[CAB]_o$, and $[substrate]_o$, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt=$k[BAT][CTZH]^{0.80}[H^+]^{-0.48}$ in acid medium and -d[BAT]/dt=$k[BAT][CTZH]^{0.48}[OH^-]^{0.52}[PTS]^{-0.40}$ in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using $D_2O$. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out.

1,5-Diacetyl-3,7-dinitro-l,3,5,7-tetraazacyclooctane (DADN) is a key intermediate in the preparation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), one of the most powerful high-melting explosives. The present investigation focuses on nitrolysis of DADN to HMX by developing a new nitrolysis process involving the use of nitric acid catalyzed by Silica Sulfuric Acid (SSA). In order to optimize the process parameters for synthesis of HMX to obtain higher yield and purity, a study was carried out with variation of some parametric conditions like time, mole ratio of SSA and nitric. This method gave us green and mild conditions for nitration reaction.

A new highly stereoselective synthesis of pyrrolidine azasugar 1,4-dideoxy-1,4-imino-D-galacitol is being reported herein. The synthesis was achieved in a linear sequence and inexpensive chiral source (+)-diethyl tartarate was used as the starting material. The key step involved during the synthesis was Pd catalysed amino cyclization of alkenylamine, Bose modified Mitsunobu reaction and Sharpless asymmetric dihydroxylation.

An efficient one-pot synthesis of ${\beta}$-acetamido ketones was accomplished by AgOTf-catalyzed multicomponent reactions of substituted acetophenones with aromatic aldehydes and acid chloride in acetonitrile in high yields. The methods offer several significant advantages of easy handling, mild reaction conditions, and use of effective and non-toxic catalyst.

Until now, few groups reported the antifreeze activity of cyclic glycopeptides; however, the tedious synthetic procedure is not amenable to study the intensive structure activity relationship. A series of N-linked cyclic glycopeptoids and glycopeptide have been prepared to evaluate antifreeze activity as a function of peptide backbone cyclization and methyl stereochemical effect on the rigid Thr position. This study has combined the cyclization protocol with solid phase peptide synthesis and obtained significant quantities of homogeneous cyclic glycopeptide and glycopeptoids. Analysis of antifreeze activity revealed that our cyclic peptide demonstrated RI activity while cyclic glycopeptoids showed no RI activity. These results suggest that the subtle changes in conformation and Thr orientation dramatically influence RI activity of N-linked glycopeptoids.

A number of novel small molecules, safrole oxide derivatives 4a-c, 6a-c, 9a-h, were synthesized by the reaction of safrole oxide with anilines 3 and 5, or its alkyl allyl ether derivative 7 with alkyl bromide 8 in moderate yields. The antiproliferative effects of all the target molecules on A549 cell growth were investigated and it was found that the 14 novel compounds could suppress A549 lung cancer cell growth. Among them, compound 6b was the most effective compound in inhibiting the proliferation of A549 cells.

Larva-like GaS nanostructures synthesized by the thermal evaporation of Ga metals and S powders were coated with $SiO_2$ by the sputtering technique. Transmission electron microscopy and X-ray diffraction analyses revealed that the cores and shells of the GaS-core/$SiO_2$-shell larva-like nanostructures were single crystal wurtzite-type hexagonal structured-GaS and amorphous $SiO_2$, respectively. Photoluminescence (PL) measurements at room temperature showed that the passivation of the larva-like GaS nanostructures was successfully achieved with $SiO_2$ without nearly harming the major emission from the wires. However, subsequent thermal annealing treatment was found to be undesirable owing to the degradation of their emission in intensity.

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity.

Carbon composite bipolar plates with various carbon black contents were prepared by a compression molding method. The electrical conductivity and electrochemical stability of the bipolar plates have been evaluated. It is found that the electrical conductivity increases with increasing carbon black contents up to 15 wt %. When the carbon black contents are greater than 15 wt %, the electrical conductivity decreases because of a poor compatibility between epoxy resin and carbon black, and a weakening of compaction in the carbon composite bipolar plate. Based on the results, it could be concluded that there are optimum carbon black contents when preparing the carbon composite bipolar plate. Corrosion tests show that the carbon composite bipolar plate with 15 wt % carbon black exhibits better electrochemical stability than a graphite bipolar plate under a highly acidic condition. When the optimized carbon composite bipolar plate is applied to vanadium redox flow cells, the performance of flow cells with the carbon composite bipolar plate is comparable to that of flow cells with the graphite bipolar plate.

The water-soluble conjugated polymer with fluorescence quenching as a result of electrostatic interaction and aggregation was synthesized through Suzuki polymerization. The absorption and emission of anionic polymer (a-PFP) is blue shifted as compared with cationic polymer (c-PFP) although getting same backbone, and the absolute PL quantum efficiency of a-PFP in water is over 90% due to good solubility in aqueous solution. We anticipate that the fluorescence quenching of anionic and cationic polymers, with same conjugated backbone, could be shown in aqueous solution.

Thrombin binding aptamter (TBA-15) is a 15-mer guanine-rich oligonucleotide. This DNA apamer specifically binds to the thrombin protein involved in blood coagulation. Using extensive umbrella sampling molecular dynamics simulation method at all atom level, we investigated the potential of mean force (PMF) upon pulling the DNA aptamer from the binding mode of aptamer/thrombin complex. From this calculation, the free energy cost for a full dissociation of this aptamer/protein complex is 17 kcal/mol, indicating a substantial binding affinity of TBA-15. Interestingly, this PMF reveals noticeable plateau regions along the pulling coordinate. Possible structural changes of this complex in the plateau were investigated in details.

Structural properties of a small hexapeptide molecule modeled after metal-binding siderochrome immersed in a room-temperature ionic liquid (RTIL) are studied via molecular dynamics simulations. We consider two different RTILs, each of which is made up of the same cationic species, 1-butyl-3-methylimidazolium ($BMI^+$), but different anions, hexafluorophosphate ($PF_6{^-}$) and chloride ($Cl^-$). We investigate how anionic properties such as hydrophobicity/hydrophilicity or hydrogen bonding capability affect the stabilization of the peptide in RTILs. To examine the effect of peptide-RTIL electrostatic interactions on solvation, we also consider a hypothetical solvent $BMI^0Cl^0$, a non-ionic counter-part of $BMI^+Cl^-$. For reference, we investigate solvation structures in common polar solvents, water and dimethylsulfoxide (DMSO). Comparison of $BMI^+Cl^-$ and $BMI^0Cl^0$ shows that electrostatic interactions of the peptide and RTIL play a significant role in the conformational fluctuation of the peptide. For example, strong electrostatic interactions between the two favor an extended conformation of the peptide by reducing its structural fluctuations. The hydrophobicity/hydrophilicity of RTIL anions also exerts a notable influence; specifically, structural fluctuations of the peptide become reduced in more hydrophilic $BMI^+Cl^-$, compared with those in more hydrophobic $BMI^+PF_6{^-}$. This is ascribed to the good hydrogen-bond accepting power of chloride anions, which enables them to bind strongly to hydroxyl groups of the peptide and to stabilize its structure. Transport properties of the peptide are examined briefly. Translations of the peptide significantly slow down in highly viscous RTILs.

In this paper, the study of various ortho- and meta-substituted Magnolol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET-PT and SPLET for substituted Magnolols have been calculated using DFT/B3LYP method in gas-phase and water. Calculated results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP) and oxidation/reduction enthalpy (O/RE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA). In ortho- position, substituents show larger effect on reaction enthalpies than in meta-position. In comparison to gas-phase, water attenuates the substituent effect on all reaction enthalpies. In gas-phase, BDEs are lower than PAs and IPs, i.e. HAT represents the thermodynamically preferred pathway. On the other hand, SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be successfully correlated with Hammett constants (${\sigma}_m$) of the substituted Magnolols. Furthermore, calculated IP and PA values for substituted Magnolols show linear dependence on the energy of the highest occupied molecular orbital ($E_{HOMO}$).

Photodissociation dynamics of propiolic acid ($HC{\equiv}C-COOH$) at 212 nm in the gas phase was investigated by measuring rotationally resolved laser-induced fluorescence spectra of OH ($^2{\Pi}$) radicals exclusively produced in the ground electronic state. From the spectra, internal energies of OH and total translational energy of products were determined. The electronic transition at 212 nm responsible for OH dissociation was assigned as the ${\pi}_{C{\equiv}C}{\rightarrow}{\pi}^*{_{C=O}}$ transition by time-dependent density functional theory calculations. Potential energy surfaces of both the ground and electronically excited states were obtained employing quantum chemical calculations. It was suggested that the dissociation of OH from propiolic acid excited at 212 nm should take place along the $S_1/T_1$ potential energy surfaces after internal conversion and/or intersystem crossing from the initially populated $S_2$ state based upon the potential energy calculations and model calculations for energy partitioning of the available energy among products.

Fluorescent organic molecules that respond to changes in the $Fe^{2+}$ concentration with selectivity to other abundant di-valent metal ions will offer the ability to understand the dynamic fluctuations of the $Fe^{2+}$ ion in interesting media. The use of 6-Br-ppmbi, derived from 2-pyridin-2-yl-benzimidazole, for metal ion-selective fluorescence recognition was investigated. Screening of the main group and transition metal ions showed exclusive selectivity for $Fe^{2+}$ ions even in the presence of competing metal ions. In addition, the requirement for low concentrations of probe molecules to detect certain amounts of $Fe^{2+}$ ions make this sensor unique compared to previously reported $Fe^{2+}$ ion sensors.

A series of new 4-(pyridin-4-yl)-(3-methoxy-5-methylphenyl)-1H-pyrazoles (6a-k & 7a-l) has been rationally designed based on the structure of the lead compound KIST301080, a selective ROS receptor tyrosine kinase inhibitor, in order to study the activity of ROS of this new class of inhibitors. The compounds were synthesized and screened against ROS kinase, where compound 6h showed moderate inhibitory activity with an $IC_{50}$ value of $6.25{\mu}M$. The study emphasized the importance of the acetonitrile group at the pyrazole ring and also the importance of having a hydrogen bond donor on the distal phenyl ring linked to the pyridine moiety.

A series of new diarylureas possessing aminoisoquinoline scaffold was synthesized, and their in vitro antiproliferative activity against A375P human melanoma cell line was tested. Compounds 1d, 1l, 1n, 1p, 1q, and 1t showed superior potency against A375P to Sorafenib. The highest potency was shown by compound 1p possessing 3,5-bis(trifluoromethyl)phenyl terminal ring with $IC_{50}$ value of $0.41{\mu}M$.

An efficient synthetic method for direct Henry reaction catalyzed by a biguanide; namely metformin, as an organosuper-base, between a variety of aromatic and aliphatic aldehydes and nitromethane under neat conditions has been developed. Convenient procedure for removal of the catalyst, chemoselective acquiring of ${\beta}$-nitroalcohols as predominant products, as far as possible short reaction time with excellent conversions are advantages of the developed protocol.

Two new blue emitting cationic iridium(III) complexes with two substituted 2-phenlypyridine ligands as main ligands and one 2,2'-biimidazole as an ancillary ligand, $[(L1)_2Ir(biim)]Cl$ (1) and $[(L2)_2Ir(biim)]Cl$ (2), where L1 = 2-(2',4'-difluorophenyl)-4-methylpyridine, L2 = 2-(2',4'-difluoro-3'-trifluoromethylphenyl)-4-methylpyridine and biim = 2,2'-biimidazole, were synthesized for applications in phosphorescent organic light-emitting diodes (PhOLEDs). Their photophysical, electrochemical and electroluminescent (EL) device performances were examined. The photoluminescent (PL) spectra revealed blue phosphorescence in the 450 to 485 nm range with a quantum yield of more than 10%. The iridium(III) compounds studied showed good solubility in organic solvents with no solvatochromism dependent on the solvent polarity. The solution-processed OLEDs were prepared with the configuration, ITO/PEDOT:PSS (40 nm)/mCP:Ir(III) (70 nm)/OXD-7 (20 nm)/LiF (1 nm)/Al (100 nm), by spin coating the emitting layer containing the mCP host doped with the iridium phosphors. The best performance of the fabricated OLEDs based on compound 1 showed an external quantum efficiency of 4.5%, luminance efficiency of 8.52 cd $A^{-1}$ and blue emission with the CIE coordinates (x,y) of (0.16, 0.33).

The size-segregated atmospheric aerosols have been collected at 1100 m site of Mt. Halla in Jeju, a background area in Korea, using 8-stage cascade impact air sampler during Asian dust and non-Asian dust storm periods. Their ionic and elemental species were analyzed, in order to examine the pollution characteristics and composition change between Asian dust and non-Asian dust periods. The major ionic species such as nss-$SO_4{^{2-}}$, $NH_4{^+}$, and $K^+$ were predominantly distributed in the fine particles (below $2.1{\mu}m$ diameter), and besides the $NO_3{^-}$ was distributed more in coarse particle fraction than fine particle. On the other hand, the typical soil and marine species i.e., nss-$Ca^{2+}$, $Na^+$, $Cl^-$, and $Mg^{2+}$, were mostly existed in the coarse particles (over $2.1{\mu}m$ diameter). As well in the elemental analysis of aerosols, the major soil-originated Al, Fe, Ca, and others showed prominently high concentrations in the coarse particle fraction, whereas the anthropogenic S and Pb were relatively high in the fine particle fraction. From the comparison of aerosol compositions between Asian dust and non-Asian dust periods, the concentrations of the soil-originated species such as nss-$Ca^{2+}$, Al, Ca, Fe, Ti, Mn, Ba, Sr have increased as 2.7-4.2 times during the Asian dust periods. Meanwhile the concentrations of nss-$SO_4{^{2-}}$ and $NO_3{^-}$ have increased as 1.4 and 2.0 times, and on the contrary $NH_4{^+}$ concentrations have a little bit decreased during the Asian dust periods. Especially the concentrations of both soil-originated ionic and elemental species increased noticeably in the coarse particle mode during the dust storm periods.

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.

Metal-p-$NH_2$-Bn-DOTA (paraammionobenzyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid: ABDOTA) complex was synthesized and purified for bio-tagging to quantify biological target materials using laser ablation (LA)-ICP-MS. Since the preparation of a pure and stable tagging complex is the key procedure for quantification, magnetic particles were used to purify the synthesized metal-ABDOTA complex. The magnetic particles immobilized with the complex attracted to a permanent magnet, resulting in fast separation from free un-reacted metal ions in solution. Gd ions formed the metal-complex with a higher yield of 64.3% (${\pm}3.9%$ relative standard deviation (RSD)) than Y ions, 52.3% (${\pm}2.5%$ RSD), in the pH range 4-7. The complex bound to the magnetic particles was released by treatment with a strong base, of which the recovery was 81.7%. As a reference, a solid phase extraction (SPE) column packed with Chelex-100 resin was employed for separation under similar conditions and produced comparable results. The tagging technique complemented polydimethylsiloxane (PDMS) microarray chip sampling in LA-ICP-MS, allowing determination of small sample volumes at high throughputs. For application, immunoglobulin G (IgG) was immobilized on the pillars of PDMS microarray chips and then tagged with the prepared Gd complex. IgG could then be determined through measurement of Gd by LA-ICP-MS. A detection limit of 1.61 ng/mL (${\pm}0.75%$ RSD) for Gd was obtained.

${\beta}$-Amyloid accumulation in the brain is a pathological hallmark of Alzheimer's disease (AD). Since early detection of ${\beta}$-amyloid may facilitate more successful and timely therapeutic interventions, many investigators have focused on developing AD diagnostic reagents that can penetrate the blood-brain barrier (BBB). Oleanolic acid (OA) is a substance found in a variety of plants that has been reported to prevent the progression of AD in mice. In this study, we synthesized and evaluated a new radioligand in which OA was conjugated to lactoferrin (Lf, an iron-binding glycoprotein that crosses the BBB) for the diagnosis of AD. In an in vitro study in which OA-Lf was incubated with ${\beta}$-amyloid (1-42) aggregates for 24 h, we found that OA-Lf effectively inhibited ${\beta}$-amyloid aggregation and fibril formation. In vivo studies demonstrated that $^{123}I$-OA-Lf brain uptake was higher than$^{123}I$-Lf uptake. Therefore, radiolabeled OA-Lf may have diagnostic potential for ${\beta}$-amyloid imaging.

An Epstein-Barr virus (EBV)-based plasmid contains the EBV nuclear antigen 1 (EBNA1) gene and EBV replication origin (oriP) sequence. Since EBNA1 (the only EBV-encoded protein) is combined with oriP, it is replicated simultaneously with chromosomal DNA in human, primate, and canine cells and is faithfully segregated at a stable copy number upon cell division. Consequently, it can be used to stably express gene inserts over a prolonged time in target cells. We have previously shown that the polyamidoamine (PAMAM) dendrimer can be surface-modified with L-arginine. Arginine is present at a high frequency in the transactivator of transcription (Tat) sequences of human immunodeficiency virus (HIV). It presents high membrane permeability and permits effective transfer of DNA inside the cells. In this study, we constructed two kinds of recombinant DNA by inserting the luciferase gene and enhanced green fluorescence protein (eGFP) gene as reporter genes into the pCEP4 plasmid vector. We measured dynamic light scattering (DLS) and zeta potential after preparing PAMAM-based cationic polymer/EBV-based plasmid complexes. We performed transfection of HEK 293 cell lines with the polyplexes, and monitored luciferase activity and green fluorescence protein (GFP) expression. Our results show that PAMAM-based cationic polymer/EBV plasmid complexes provide enhanced and sustained gene expression.

We developed a simple and effective method for the SERS-based detection of protein-small molecule complexes and label-free proteins using avidin-induced silver aggregation. Upon excitation with light of the appropriate wavelength (633 and 532 nm), the aggregated silver nanoparticles generate a strong electric field that couples with the resonance of the molecules (atto610 and cytochrome c), increasing the characteristic signals of these molecules and resulting in sensitive detection. The detection limit of biotin with the proposed method is as low as 48 ng/mL. The most important aspect of this method is the induction of silver aggregation by a protein (avidin), which makes the silver more biocompatible. This technique is very useful for the detection of protein-small molecule complexes.

Photochemical degradation of dimethyl phthalate (DMP) in Fe(III)/tartrate/$H_2O_2$ system was investigated utilizing fluorescent lamps as the primary light source. Effects of initial pH, light source, and initial concentration of each reactant on DMP photodegradation was examined. The results show that the system was able to effectively photodegrade DMP utilizing visible light. Fluorescent lamp, halide lamp, UV lamp and sunlight could all be used as the light sources. The optimal pH ranged among 3.0-4.0 for the system. Increases of the initial concentrations of Fe(III) and $H_2O_2$ accelerated the photodegradation of DMP, whereas excessively high initial tartrate concentration resulted in the decrease of photodegradation efficiency and rate of DMP.

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations resulte in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

The colorimetric and fluorescent cyanide recognition properties of 2-[(9-ethyl-9H-carbazol-3-yl)methylene]-propanedinitrile (1) in $CH_3CN-H_2O$ (2/1, v/v, HEPES 10 mM, pH = 7.0) solution were evaluated. The optical recognition process of probe 1 exhibited high sensitivity and selectivity to cyanide ion with the detection limit of $2.04{\times}10^{-6}$ M and barely interfered by other coexisting anions. The sensing mechanism of probe 1 is speculated to undergo a nucleophilic addition of cyanide to dicyanovinyl group present in compound 1. The colorimetric and fluorescent dual-modal response to cyanide makes probe 1 has a potential utility in cyanide detection.

A simple method has been developed for four-component synthesis of disubstituted 1,3,4-oxadiazoles using (N-isocyanimino)triphenylphosphorane, a primary amine, a carboxylic acid and biacetyl in $CH_2Cl_2$ by the Ugi-4CR/aza-Wittig sequence at room temperature in excellent yields.

A novel silicon-containing arylacetylene resin (MSAR) modified by dipropargyl ether of bisphenol A (DPBPA) and dipropargyl ether of perfluorobisphenol A (DPPFBPA) was prepared separately. The curing behaviors of modified resins, DPBPA/MSAR and DPPFBPA/MSAR, were characterized with differential scanning calorimeter (DSC). The kinetic parameters of modified resins were obtained by the Kissinger and Ozawa methods. The results of dynamic mechanical analysis (DMA) revealed that the glass transition temperature ($T_g$) of the cured DPBPA/MSAR reached $486^{\circ}C$. According to the thermogravimetric analysis (TGA), the decomposition temperature ($T_{d5}$) of the cured resins and char yield ($Y_c$, $800^{\circ}C$) decreased as the dipropargyl ether loadings increased, especially in air. With the same weight loading, thermal stability of DPBPA/MSAR was better than that of DPPFBPA/MSAR. The carbon fiber (T300) reinforced composites exhibited excellent flexural properties at room temperature with a high property retention at $300^{\circ}C$.

Here, we report a chain-length dependent morphology and pore structure tailing of mesoporous silica templated from organogels, which is formed by primary alkylamine and ethylene glycol at room temperature. As the chain length of alkylamine changes from 12 to 18, the resulted materials exhibit a morphology change from layers to spheres and platelets, respectively. SEM and TEM observation revealed that these shapes appear to be inherited from their parent organogels. Further pore structure characterization by nitrogen sorption analysis demonstrates that all the resulted silicas exhibit typical IV isotherms indicative of uniform mesopores, and their pore sizes are dependent on the chain length of alkylamine used.

Formation of Z-DNA, a left-handed double helix, from B-DNA, the canonical right-handed double helix, occurs during important biological processes such as gene expression and DNA transcription. Such B-Z transitions can also be induced by high salt concentration in vitro, but the changes in the relative stability of B-DNA and Z-DNA with salt concentration have not been fully explained despite numerous attempts. For example, electrostatic effects alone could not account for salt-induced B-Z transitions in previous studies. In this paper, we propose that the B-Z transition can be explained if counterion entropy is considered along with the electrostatic interactions. This can be achieved by conducting all-atom, explicit-solvent MD simulations followed by MM-PBSA and molecular DFT calculations. Our MD simulations show that counterions tend to bind at specific sites in B-DNA and Z-DNA, and that more ions cluster near Z-DNA than near B-DNA. Moreover, the difference in counterion ordering near B-DNA and Z-DNA is larger at a low salt concentration than at a high concentration. The results imply that the exclusion of counterions by Z-DNA-binding proteins may facilitate Z-DNA formation under physiological conditions.

An analytical method has been developed for the rapid determination of perfluorinated compounds (PFCs) in human serum samples. The extraction and purification of PFCs from human serum were performed by the modified method of previous report. Ten PFCs were rapidly separated within 3.3 min by C18-monolithic column liquid chromatography (LC) and detected by electrospray ionization (ESI) tandem mass spectrometry (MS/MS) in negative ion mode. The runtime of PFCs on monolithic column LC was up to 4-fold faster than that on conventional column LC. The effect of triethylamine (TEA) to the mobile phase has investigated on the overall MS detection sensitivity of PFCs in ESI ionization. Quantification was performed by LC-MS/MS in multiple-ion reaction monitoring (MRM) mode, using $^{13}C$-labeled internal standards. Method validation was performed to determine recovery, linearity, precision, and limits of quantification, followed by, the analysis of a standard reference material (SRM 1957 from NIST). The overall recoveries ranged between 81.5 and 106.3% with RSDs of 3.4 to 16.2% for the entire procedure. The calibration range extended from 0.33 to 50 $ng\;mL^{-1}$, with a correlation coefficient ($R^2$) greater than 0.995 and the limits of quantification with 0.08 to 0.46 $ng\;mL^{-1}$. This approach can be used for rapid and sensitive quantitative analysis of 10 PFCs in human serum with high performance and accuracy.

We have developed magnetically controllable gold nanoparticles by synthesizing superparamagnetic $Fe_3O_4$ core/gold shell nanoparticles. The core/shell particles have the capability of forming gold 1D chains in the presence of an external magnetic field. Here we demonstrate dynamic and reversible self-assembly of the gold 1D chain structures in an aqueous solution without any templates or physical or chemical attachment. The spatial configuration of gold chains can be arbitrarily manipulated by controlling the direction of a magnetic field. This technique can provide arbitrary manipulation of gold 1D chains for fabrication purpose. To demonstrate this capability, we present a technique for immobilization of the gold particle chains on a glass substrate.

We synthesized three different derivatives of bis-spiropyran using simple organic reactions with high yields. BSP1, a derivative of bis-spiropyran having a connection at the position 6' and BSP2, a derivative of bis-spiropyran having a connection at the position 5 and BSP3, a derivative of bis-spiropyran containing a dithienylethene group between two spiropyran moieties were synthesized. The optical properties of BSPs were characterized. UV-Vis spectra showed that BSPs exhibit reversible photo-isomerization and the efficiency of photo-isomerization is highly dependent on the position of nitro group. BSPs having nitro group at para position of hydroxy group showed the higher efficiency of photo-isomerization that the one having nitro group at ortho position. The optical microscope images obtained under ultraviolet or visible light exposure demonstrated that the formation of nanorods can be reversibly controlled by optical signal.

This study presents a rapid and simple ${\alpha}$ source preparation method for a radioactive waste sample. The recovery of $^{239}Pu$, $^{232}U$ and $^{243}Am$ using a micro-coprecipitation method was over 95%. The ${\alpha}$-peak resolution of Pu and Am isotopes through the micro-coprecipitation method is enough to discriminate the Pu and Am isotopes from other Pu and Am isotopes. The determination of the Pu and Am isotopes using the micro-coprecipitation method was applied to the radioactive waste sample, so that the activity concentrations of the Pu and Am isotopes using the micro-coprecipitation method in the radioactive waste sample were similar to those using the electrodeposition method.

Nanoporous carbons with a high specific surface area were prepared directly from thermoplastic acrylic resin as carbon precursor and MgO powder as template by carbonization over the temperature range, $500-1000^{\circ}C$. The effect of the carbonization temperature on the pore structure and $CO_2$ adsorption capacity of the obtained porous carbon was examined. The textural properties and morphology of the porous carbon materials were analyzed by $N_2/-196^{\circ}C$ and $CO_2/0^{\circ}C$ adsorption/desorption isotherms, SEM and TEM. The $CO_2$ adsorption capacity of the prepared porous carbon was measured at $25^{\circ}C$ and 1 bar and 30 bar. The specific surface area increased from 237 to $1251m^2/g$, and the total pore volumes increased from 0.242 to $0.763cm^3/g$ with increasing the carbonization temperature. The carbonization temperature acts mainly by generating large narrow micropores and mesopores with an average pore size dependent on the level of carbonization of the MgO-templated nanoporous carbons. The results showed that the MgO-templated nanoporous carbons at $900^{\circ}C$ exhibited the best $CO_2$ adsorption value of 194 mg/g at 1 bar.

Single crystals of lithium potassium phthalate (LiKP) were successfully grown from aqueous solution by solvent evaporation technique. The grown crystals were characterized by single crystal X-ray diffraction. The lithium potassium phthalate $C_{16}\;H_{12}\;K\;Li_3\;O_{11}$ belongs to triclinic system with the following unit-cell dimensions at 298(2) K;$a=7.405(5){\AA}$;$b=9.878(5){\AA}$;$c=13.396(5){\AA}$;${\alpha}=71.778(5)^{\circ}$;${\beta}=87.300(5)^{\circ}$;${\gamma}=85.405(5)^{\circ}$; having a space group P1. Mass spectrometric analysis provides the molecular weight of the compound and possible ways of fragmentations occurs in the compound. Thermal stability of the crystal was also studied by both simultaneous TGA/DTA analyses. The UV-Vis-NIR spectrum shows a good transparency in the whole of Visible and as well as in the near IR range. Third order nonlinear optical studies have also been studied by Z-scan technique. Nonlinear absorption and nonlinear refractive index were found out and the third order bulk susceptibility of compound was also estimated. The results have been discussed in detail.

$Ag_2Se$-Graphene/$TiO_2$ composite was synthesized by a facile sonochemical method. The as-prepared products were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectrophotometer. During the reaction, both of the reduction of graphene oxide and loading of $Ag_2Se$ and $TiO_2$ particles were achieved. The as-prepared $Ag_2Se$-Graphene/$TiO_2$ composites possessed great adsorptivity of dyes, extended light absorption range, and efficient charge separation properties simultaneously. Hence, in the photodegradation of rhodamine B (Rh.B), a significant enhancement in the reaction rate was observed with $Ag_2Se$-Graphene/$TiO_2$ composites, compared to the pure $TiO_2$. The high activity can be attributed to the synergetic effects of high charge mobility, and red shift in absorption edge of $Ag_2Se$-Graphene/$TiO_2$ composites.

In this study, we investigate the potential use of $TiO_2@SiO_2$ and $ZnO@SiO_2$ core/shell nanoparticles (NPs) as effective UV shielding agent. In the typical synthesis, $SiO_2$ was coated over different types of $TiO_2$ (anatase and rutile) and ZnO by sol-gel method. The synthesized $TiO_2@SiO_2$ and $ZnO@SiO_2$ NPs were characterized by UV-Vis, XRD, SEM and TEM. The UV-vis absorbance and transmittance spectra of core@shell NPs showed an efficient blocking effect in the UV region and more than 90% transmittance in the visible region. XRD and SAED studies confirmed the formation of amorphous $SiO_2$ coated over the $TiO_2$ and ZnO NPs. The FESEM and TEM images shows that coating of $SiO_2$ over the surface of anatase, rutile $TiO_2$ and ZnO NPs resulted in the increase in particle size by ~30 nm. In order to study the UV light shielding capability of the samples, photocatalytic degradation of methylene blue dye on $TiO_2@SiO_2$ and $ZnO@SiO_2$ NPs was performed. Photocatalytic activity for both types of $TiO_2$ NPs was partially suppressed. In comparison, the photocatalytic activity of ZnO almost vanished after the $SiO_2$ coating.

Mitogen-activated protein kinase phosphatase 4 (MKP4) has proved to be a promising target for the development of therapeutics for the treatment of diabetes and the other metabolic diseases. Here, we report an example for a successful application of the structure-based virtual screening to identify three novel inhibitors of MKP4. These inhibitors have desirable physicochemical properties as a drug candidate and reveal a moderate potency with $IC_{50}$ values ranging from 4.9 to $32.3{\mu}M$. Therefore, they deserve consideration for further development by structure-activity relationship studies to optimize the inhibitory and antidiabetic activities. Structural features relevant to the stabilization of the newly identified inhibitors in the active site of MKP4 are discussed in detail.

Three kinds of 3D isomorphous and isostructural coordination polymers, namely, $\{[Ln_2(PDA)_3(H_2O)_3]{\cdot}0.25H_2O\}_{\infty}$ (Ln = La(1), Sm(2), and Gd(3)) ($PDA^{2-}$ = pyridine-2,6-dicarboxylate anion) have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. In these MOFs, Ln(III) centers adopt eight-coordinated and nine-coordinated with the $N_1O_7$ and $N_2O_7$ donor sets to construct distorted trianglar dodecahedron geometry and tricapped trigonal prism configurations, respectively. Based on the building block of tetranuclear homometallic $Ln_4C_4O_8$ unit (16-membered ring), 1-3 are connected into highly ordered 2D sheets via O-C-O linkers and further constructed into 3D architectures through hydrogen bonds. Crystallographic parameters suggest that the lanthanide contraction effect exist in these coordination polymers. Luminescent properties of the lanthanide-based MOFs (metal-organic frameworks) have been measured at room temperature, which reveal that they presenting ionselective characters toward certain metals, such as $Mg^{2+}$, $Cd^{2+}$ and $Pb^{2+}$ ions.

Spherical-shape melanin nanoparticles with good water-dispersibility were successfully synthesized by a simple oxidation polymerization of 3,4-dihydroxy-phenylalanin (DOPA) with $KMnO_4$. Similar features to those known from natural and synthetic melanin polymers were observed from prepared melanin nanoparticles by FT-IR, UV-Vis., and ESR spectroscopic methods. Their binding ability with several heavy metal ions from aqueous solution was quantitatively investigated, and the maximum binding capacities with melanin nanoparticles to lead, copper, and cadmium ions were obtained as 2.45, 2.17 and 1.88 mmol/g, respectively, which are much larger values than those reported from natural and synthetic melanin polymers. The large binding capacity and fast binding rate of melanin nanoparticles to metal ions can make them an excellent candidate for the remediation of contaminated water.

A novel 3D compound $\{[Cu(L)(H_2O)_4][Cu_2(SIP)_2(L)_2]\}{\cdot}2H_2O$ (1) (L = N,N-bis(4-pyridinecarboxamide)-1,4-butane, SIP = 5-sulfoisophthalate) is hydrothermally synthesized. X-ray diffraction analysis reveals that compound 1 is composed of 2D anionic $[Cu_2(SIP)_2(L)_2]_n{^{2n-}}$ double-layers and discrete 1D cationic $[CuL(H_2O)_4]_n{^{2n+}}$ polymeric chains, which represents a rare 3D polypseudo-rotaxane MOF from intercalation of 1D and 2D framework. In addition, the luminescent property and electrochemical behavior of compound 1 have been investigated.

We present calculations for valine (Val) - $(H_2O)_n$ (n = 0-5) to examine the effects of microsolvating water on the relative stability of the zwitterionic vs. canonical forms of Val. We calculate the structures, energies and Gibbs free energies of the conformers at B3LYP/6-311++G(d,p), wB97XD/6-311++G(d,p) and MP2/aug-cc-pvdz level of theory. We find that five water molecules are needed to stabilize the zwitterionic form of Val. By calculating the barriers of the canonical ${\leftrightarrow}$ zwitterionic pathways of Val - $(H_2O)_5$ conformers, we suggest that both forms of Val - $(H_2O)_5$ may be observed in low temperature gas phase.

Results for molecular dynamics simulation method of small liquid drops of argon (N = 1200-14400 molecules) at 94.4 K through a Lennard-Jones intermolecular potential are presented in this paper as a preliminary study of drop systems. We have calculated the density profiles ${\rho}(r)$, and from which the liquid and gas densities ${\rho}_l$ and ${\rho}_g$, the position of the Gibbs' dividing surface $R_o$, the thickness of the interface d, and the radius of equimolar surface $R_e$ can be obtained. Next we have calculated the normal and transverse pressure tensor ${\rho}_N(r)$ and ${\rho}_T(r)$ using Irving-Kirkwood method, and from which the liquid and gas pressures ${\rho}_l$ and ${\rho}_g$, the surface tension ${\gamma}_s$, the surface of tension $R_s$, and Tolman's length ${\delta}$ can be obtained. The variation of these properties with N is applied for the validity of Laplace's equation for the pressure change and Tolman's equation for the effect of curvature on surface tension through two routes, thermodynamic and mechanical.

Here we report our recent result of a new semiconductor material, which has an asymmetric structure. The synthesized molecules consist of anthracene and thiophene connected by bridged ethylene and substituted with hexyl or dodecyl groups as pendants. The semiconductors were synthesized using a McMurry coupling reaction between anthracene-2-carbaldehyde and corresponding 5-hexyl(or dodecyl)thiophene-2-carbaldehyde. A first investigation of synthesized asymmetry AVHT (9a) and AVDT (9b) for the physical properties showed that they have high oxidation potential and thermal stability. The devices prepared by using AVHT (9a) and AVDT (9b) showed the mobility of $2.6{\times}10^{-2}cm^2/Vs$ and $4.4{\times}10^{-3}cm^2/Vs$, respectively, in solution processed OTFTs.

Various alkenylphosphonates were prepared via the palladium-catalyzed oxidative arylation of cinnamylphosphonates with arenes. The regioselectivity during the ${\beta}$-H elimination of the corresponding alkylpalladium intermediate was governed most likely by steric factors.