Despite increasing importance of in vitro cell-based assays for the assessment of nanoparticles (NPs) cytotoxicity, their suitability for the assessment of NPs toxicity is still in doubt. Here, limitations of widely used cell viability assay protocol (i.e., MTT asssay) for the cytotoxicity assessment of P25 $TiO_2$ NPs were carefully examined and an alternative toxicity assessment method to overcome these limitations was proposed, where the artifacts caused by extracellularly formed formazan and light scattered by agglomerated NPs were minimized by measuring only the intracellular formazan via image cytometric methods.

Solid dispersion (SD) system of everolimus (EVR) with Gelucire 50/13 (Stearoyl polyoxyl-32 glycerides) was prepared using melt granulation technique with the aim of improving the physicochemical properties and dissolution rate. The solid state characterization using scanning electron microscopy and X-ray powder diffraction, indicated that the drug was homogeneously distributed in the surfactant carrier in a stable amorphous form. The dissolution rate of EVR from the optimized SD composed of the drug, Gelucire 50/13 and microcrystalline cellulose in a weight ratio of 1:5:10, was markedly rapid and higher than that from the drug powder and the market product (Afinitor$^{(R)}$, Novartis Pharmaceuticals) in all dissolution mediums tested from pH 3.0 to pH 6.8. The results of this study suggest that formulation of SD with Gelucire 50/13 using melt granulation procedure may be a simple and promising approach for improving the dissolution rate and oral absorption of the anti-cancer agent without the need for using an organic solvent.

Employment of a time consuming, sophisticated calculation using the all-atom force field and generalized-Born implicit solvent model (GBIS) for refinement of NMR structures has become practical through advances in computational methods and capacities. GBIS refinement improves the qualities of the resulting NMR structures with reduced computational times. However, the contribution of GBIS to NMR structures has not been sufficiently studied in a quantitative way. In this paper, we report the effects of GBIS on the refined NMR structures of ubiquitin (UBQ) and GB1 with subsets of distance restraints derived from experimental data. Random omission prepared a series of distance restraints 0.05, 0.1, 0.3, 0.5, and 0.7 times smaller. For each number, we produced five different restraints for statistical analysis. We then recalculated the NMR structures using CYANA software, followed by GBIS refinements using the AMBER package. GBIS improved both the precision and accuracy of all the structures, but to varied levels. The degrees of improvement were significant when the input restraints were insufficient. In particular, GBIS enabled GB1 to form an accurate structure even with distance restraints of 5%, revealing that the root-mean-square deviation was less than 1 ${\AA}$ from the X-ray backbone structure. We also showed that the efficiency of searching the conformational space was more important for finding accurate structures with the calculation of UBQ with 5% distance restraints than the number of conformations generated. Our data will provide a meaningful guideline to judge and compare the structural improvements by GBIS.

Catalytic pyrolysis of Geodae-Uksae 1, a kind of miscanthus found in Korea, was carried out over mesoporous MCM-48 catalysts. For rapid product analysis and catalyst evaluation, pyrolysis-gas chromatography/mass spectrometry was used. X-ray diffraction, nitrogen sorption, pyridine adsorbed Fourier transform infrared, and NH3 temperature programmed desorption were utilized to analyze the properties of the catalysts. Compared to non-catalytic reaction, catalytic upgrading over mesoporous Al-MCM-48 catalysts produced a higher-quality bio-oil with a high stability and low oxygen content. Al-MCM-48 exhibited higher deoxygenation ability than Si-MCM-48 due to its higher acidity.

To provide the scientific corroboration of the traditional uses of Akebia quinata (Thunb.) Decne., a detailed analytical examination of A. quinata stems was carried out using a reversed-phase high performance liquid chromatography (RP-HPLC) method coupled to photodiode array detector (PDA) for the simultaneous determination of four phenolic substances; cuneataside D (1), 2-(3,4-dihydroxyphenyl)ethyl-O-${\beta}$-D-glucopyranoside (2), 3-caffeoylquinic acid (3) and calceolarioside B (4). Particular attention was focused on the main compound, 3-caffeoylquinic acid (3), which has a range of biological functions. In addition, 2-(3,4-dihydroxyphenyl)ethyl-O-${\beta}$-D-glucopyranoside (2) was considered as a discernible marker of A. quinata from its easy confuse plants. The contents of compounds 2 and 3 ranged from 0.72 to 2.68 mg/g and from 1.66 to 5.64 mg/g, respectively. The validation data indicated that this HPLC/PDA assay was used successfully to quantify the four phenolic compounds in A. quinata from different locations using relatively simple conditions and procedures. The pattern-recognition analysis data from 53 samples classified them into two groups, allowing discrimination between A. quinata and comparable herbs. The results suggest that the established HPLC/PDA method is suitable for quantitation and pattern-recognition analyses for a quality evaluation of this medicinal herb.

A new tetranuclear Mn(III) complex $[Mn^{III}{_4}(sae)_4({\mu}_3-O)({\mu}_{1,1}-N_3)(OH)(H_2O)_2]{\cdot}H_2O$ (1) ($H_2sae$ = 2-salicylideneamino-1-ethanol) has been synthesized by the reaction of $MnCl_2{\cdot}4H_2O$, $H_2sae$ and sodium azide in the mixed solvent of methanol, acetonitrile and water. The X-ray diffraction analysis shows that the four Mn(III) ions in complex 1 have a unique adamantine arrangement, whereas the coordination environment of each Mn(III) ions is different. Magnetic studies indicate that complex 1 manifests antiferromagnetic behaviors. The magnetic susceptibilities of complex 1 have been fitted by two magnetic models based on the suitable analysis of its magnetic structural topology.

A facile and efficient synthesis of dronedarone hydrochloride starting from commercially available 4-nitrophenol is described. This approach features a tandem-type synthesis of 3-carbonylated benzofuran involving cyclization of 2-ethynylphenol followed by $CO_2$ fixation at the 3-position of the benzofuran ring mediated by potassium carbonate without the addition of any transition metal catalyst.

Here, we present a facile method to synthesize Pt nanoparticles (NPs) and graphene composite materials (Pt/G) via vacuum filtration. Anodic aluminum oxide (AAO) templates were used to separate Pt/G composite and liquid phase. This method can be used to easily tune the mass ratio of Pt NPs and graphene. Pt NPs, graphene, and carbon nanotubes (CNTs) as building blocks were characterized by a variety of techniques such as scanning electron microscopy, UV-Vis spectroscopy, and Raman spectroscopy. We compared the electrocatalytic activities of Pt/G with Pt NP and CNT films (Pt/CNT) by cyclic voltammetry (CV), CO oxidation, and methanol oxidation. Pt/G was much more stable than pure Pt films. Also, Pt/G had better electrochemical activity, CO tolerance and methanol oxidation than Pt/CNT loaded with the same amount of Pt NPs due to the better dispersion of Pt NPs on graphene flakes without aggregation. We further synthesized Au@Pt disk/G and Pt nanorods/G to determine if our synthetic method can be applied to other NP shapes such as nanodisks and nanorods, for further electrocatalysis studies.

We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in $H_2$ and $O_2$ gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

$Cu_2ZnSnSe_4$ (CZTSe) thin films were synthesized on transparent conducting oxide glass substrates via a simple, non-toxic, and low-cost process using a precursor solution paste. A three-step heating process (oxidation, sulfurization, and selenization) was employed to synthesize a CZTSe thin film as an absorber layer for use in thin-film solar cells. In particular, we focused on the effects of sulfurization conditions on CZTSe film formation. We found that sulfurization at $400^{\circ}C$ involves the formation of secondary phases such as $CuSe_2$ and $Cu_2SnSe_3$, but they gradually disappeared when the temperature was increased. The formed CZTSe thin films showed homogenous and good crystallinity with grain sizes of approximately 600 nm. A solar cell device was tentatively fabricated and showed a power conversion efficiency of 2.2% on an active area of 0.44 $cm^2$ with an open circuit voltage of 365 mV, a short current density of 20.6 $mA/cm^2$, and a fill factor of 28.7%.

The small library of new enantiomerically pure (S,S)-diamino alcohols 1 and their hydroxyldiamide precursors 2 were conveniently synthesized on a gram scale from inexpensive and commercially chiral pool amino acids. The catalytic and induced asymmetric effects of the chiral ligands 1 in the asymmetric allylic oxidation of cycloolefins were investigated.

Licochalcone C was synthesized from commercially available 2,4-dihydroxybenzaldehde by using regioselective $Al_2O_3$-mediated C-prenylation followed by conventional Claisen-Schmidt condensation in basic condition.

Indium tin oxide ($In_2Sn_{1-x}O_{5-y}$) nanoparticles were synthesized by hydrothermal method from stable indium tin acetylacetone complexes and postannealing at $600^{\circ}C$. The absence of chlorine ions shortened the synthesis process, decreased the particle agglomeration and improved the particle purity. The introduced complexing ligand acetylacetone decreased the obtained nanoparticle size. The improved powder properties accelerated the sintering of the $In_2Sn_{1-x}O_{5-y}$ nanoparticles and reached a relative density of 96.4% when pressureless sintered at $1400^{\circ}C$.

This paper reports the facile synthesis methods of zinc oxide (ZnO) nanoparticles, Z1-Z10, using diethylene glycol (DEG) and polyethylene glycol (PEG400). The particle size and morphology were correlated with the PEG concentration and reaction time. With 0.75 mL of PEG400 in 150 mL of DEG and a 20 h reaction time, the ZnO nanoparticles began to disperse from a collective spherical grain shape. The ZnO nanoparticles were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and a $N_2$ adsorption-desorption studies. The Brunauer-Emmett-Teller (BET) surface areas of Z4, Z5 and Z10 were 157.083, 141.559 and 233.249 $m^2/g$, respectively. The observed pore diameters of Z4, Z5 and Z10 were 63.4, 42.0 and 134.0 ${\AA}$, respectively. The pore volumes of Z4, Z5 and Z10 were 0.249, 0.148 and 0.781 $cm^3/g$, respectively. The photocatalytic activity of the synthesized ZnO nanoparticles was evaluated by methylene blue (MB) degradation, and the activity showed a good correlation with the $N_2$ adsorption-desorption data.

An anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), was introduced during the ultrasonication process for exfoliation of graphene. The surfactant plays the roles of exfoliator and stabilizer by binding to the graphene surface. The obtained modified graphene was characterized by Fourier-transform infrared spectroscopy (FT-IR) and solid state $^{13}C$ CP/MAS NMR to analyze the binding between molecules, and by X-ray diffraction (XRD) to characterize the bulk structure. The resulting graphene exhibited good dispersion stability in both water and organic solvents.

The adsorption and decomposition of trimethylene oxide ($C_3H_6O$) molecule on the Al(111) surface were investigated by the generalized gradient approximation (GGA) of density functional theory (DFT). The calculations employed a supercell ($6{\times}6{\times}3$) slab model and three-dimensional periodic boundary conditions. The strong attractive forces between $C_3H_6O$ molecule and Al atoms induce the C-O bond breaking of the ring $C_3H_6O$ molecule. Subsequently, the dissociated radical fragments of $C_3H_6O$ molecule oxidize the Al surface. The largest adsorption energy is about -260.0 kJ/mol in V3, V4 and P2, resulting a ring break at the C-O bond. We also investigated the decomposition mechanism of $C_3H_6O$ molecules on the Al(111) surface. The activation energies ($E_a$) for the dissociations V3, V4 and P2 are 133.3, 166.8 and 174.0 kJ/mol, respectively. The hcp site is the most reactive position for $C_3H_6O$ decomposing.

NiCu alloys have been suggested as potential candidates for catalysts in glucose oxidation. In this study, NiCu alloys with different compositions were prepared on a glassy carbon substrate by changing the electrodeposition potential to examine the effect of Ni/Cu ratios in alloys on catalytic activity toward glucose oxidation. Cyclic voltammetry and chronoamperometry showed that NiCu alloys had higher catalytic activity than pure Ni and Cu catalysts. Especially, Ni59Cu41 had superior catalytic activity, which was about twice that of Ni at a given oxidation potential. X-ray analyses showed that the oxidation state of Ni in NiCu alloys was increased with the content of Cu by lattice expansion. Ni components in alloys with higher oxidation state were more effective in the oxidation of glucose.

Anion receptor 1 based on acylhydrazone has been designed and synthesized. UV-vis and $^1H$ NMR titration showed that receptor 1 is selective receptor for dihydrogen phosphate ($H_2PO_4{^-}$). Dihydrogen phosphate was complexed by the receptor 1 via at least 4 hydrogen bonding interactions, contributing from two amide N-Hs and two imine C-Hs. In addition, nitrogen in the aromatic ring could make 2 additional hydrogen bondings with OH groups in the dihydrogen phosphate. However, the receptor 1 could make only 4 hydrogen bonds with halides. Therefore, receptor 1 could bind anions through hydrogen bonds with a selectivity in the order of $H_2PO_4{^-}$ > $Br^-$ > $Cl^-$ in highly polar solvent such as DMSO.

Magnetically nano-$CoFe_2O_4$ efficiently catalyzes oxidation of primary and secondary benzylic and aliphatic alcohols to give the corresponding carbonyl products in good yields. The reactions were carried out in an aqueous medium at room temperature in the presence of oxone (potassium hydrogen monopersulfate) as an oxidant. In addition, the catalysts could be reused up to 6 runs without significant loss of activities. Catalyst was characterized by SEM, XRD and IR.

A reaction mixture was developed for formation of soft organic monolith that was easily smashed, rinsed, refluxed, filtered, and dried to give monolith particles having high pore volume of macropores. This phase was almost without mesopores. The reaction mixture was composed of methacrylic acid, ethylene glycol dimethacrylate, polyethylene glycol (porogen), and an initiator in a mixed solvent of toluene and isooctane. The selection of porogen and its amount was carefully carried out to obtain the optimized separation efficiency of the resultant phase. The median macropore size was 1.6 ${\mu}m$, and the total pore volume was 3.0-3.4 mL/g. The median particle size (volume based) was 15 ${\mu}m$, and the range of particle size distribution was very broad. Nevertheless the column (1 ${\times}$ 300 mm) packed with this phase showed good separation efficiency (N~10,000-16,000) comparable to that of a commercial column packed with 5 ${\mu}m$ C18 silica particles.

4-(tert-Octyl)phenol derivatives bearing the D-mannitol substructure (6a, 6b, 7) were prepared from $\small{D}$-mannitol and evaluated their anticancer activity against human lung (A549) and prostate (Lncap, Du145, PC3) cancer cell lines. Among derivatives tested, the bis(tert-octyl)phenoxy compound 7 exhibited strongest proliferation inhibitory activities against human cancer cell lines tested, especially high sensitivity to human Du145 prostate cancer cells ($IC_{50}=7.3{\mu}M$).

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

A simple method for exfoliating pristine graphite to yield mono-, bi-, and multi-layers of graphene sheets as a highly concentrated (5.25 mg/mL) and yielded solution in an organic solvent was developed. Pre-thermal treatment of pristine graphite at $900^{\circ}C$ in a sealed stainless steel bath under high pressures, followed by sonication in 1-methyl-2-pyrrolidinone solvent at elevated temperatures, produced a homogeneous, well-dispersed, and non-oxidized graphene solution with a low defect density. The electrical conductivities of the graphene sheets were very high, up to 848 S/cm. These graphene sheets were used to fabricate graphene-polyimide nanocomposites, which displayed a higher electrical conductivity (1.37 S/m) with an improved tensile strength (95 MPa). The synthesized graphene sheets and nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy.

Thermochemical sulfate reduction (TSR) was conducted in autoclave on the system of crude oil and $MgSO_4$ at different temperatures. Gas chromatography pulsed flame photometric detector (GC-PFPD) was used to detected the composition of organic sulfur compounds in oil phase products. The results of the analysis indicate that with increased temperature, the contents of organic sulfur compounds with high molecular weight and thermal stability, such as benzothiophenes and dibenzothiophenes, gradually became dominated. In order to gain greater insight into the formation and distribution of organic sulphur compounds from TSR, positive ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used in detecting the detailed elemental composition and distribution of them. The mass spectra showed that the mass range of sulfur compounds was 200-550 Da. Four sulfur class species, $S_1$, $N_1S_1$, $O_1S_1$ and $O_2S_1$, were assigned in the positive-ion spectrum. Among the identified sulfur compounds, the $S_1$ class species was dominant. The most abundant $S_1$ class species increase associated with the DBE value and carbon number increasing which also indicates the evolution of organic sulfur compounds in TSR is from the labile series to the stable one. In pure blank pyrolysis experiments with crude oil cracking without TSR, different composition and distribution of organic sulfur compounds in oil phase products were seen from mass spectra in order to evaluate their pyrolysis behaviors without $MgSO_4$. FT-IR and XRD were used in analyzing the products of solid phases. Two distinct crystallographic phases MgO and $MgSO_4$ are found to coexist in the products which demonstrated the transformation of inorganic sulfur compounds into organosulfur compounds exist in TSR.

${\beta}$-Secretase (beta-amyloid converting enzyme 1 [BACE1]) is involved in the first and rate-limiting step of ${\beta}$-amyloid ($A{\beta}$) peptides production, which leads to the pathogenesis of Alzheimer's disease(AD). Therefore, inhibition of BACE1 activity has become an efficient approach for the treatment of AD. Ligand-based and docking-based 3D-quantitative structure-activity relationship (3D-QSAR) studies of acyl guanidine analogues were performed with comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) to obtain insights for designing novel potent BACE1 inhibitors. We obtained highly reliable and predictive CoMSIA models with a cross-validated $q^2$ value of 0.725 and a predictive coefficient $r{^2}_{pred}$ value of 0.956. CoMSIA contour maps showed the structural requirements for potent activity. 3D-QSAR analysis suggested that an acyl guanidine and an amide group in the $R_6$ substituent would be important moieties for potent activity. Moreover, the introduction of small hydrophobic groups in the phenyl ring and hydrogen bond donor groups in 3,5-dichlorophenyl ring could increase biological activity.

Sub-micrometer size gold particles were electrodeposited on a transparent fluorine-doped tin oxide (FTO) from acetonitrile solution containing $AuCl_4{^-}$ and tetramethylammonium tetraflouroborate (TMATFB) for detecting $NO_2{^-}$. A series of two-electron ($2e^-$) and one-electron ($1e^-$) reductions of the $AuCl_4{^-}-AuCl_2{^-}-Au$ redox systems were observed at FTO and a highly stable and homogeneous distribution of Au on FTO (Au/FTO) was obtained by stepping the potential from 0 to -0.55 V (vs. Ag/$Ag^+$). The Au/FTO electrode exhibited sufficiently high catalytic activity toward the oxidation of $NO_2{^-}$ with a detection limit (S/N = 3) and sensitivity of 2.95 ${\mu}M$ and 223.4 ${\mu}A{\cdot}cm^{-2}{\cdot}mM^{-1}$, respectively, under optimal conditions. It exhibited an interference-free signal for $NO_2{^-}$ detection with excellent recoveries from real samples.

Cobalt-immobilized SBA-15 6a-c was synthesized from alkyne-attached SBA 5a-c by the reaction with $Co_2(CO)_8$ in toluene. Alkyne group was introduced into amino SBA-15 (4) by imine-linkage or substitution with propargyl bromide to afford iminoalkyne 5a and aminoalkyne 5b, respectively. Meanwhile, alkyne 5c was prepared in one-step by reacting triethoxysilyl hexyne with SBA-15. Dicobalt-complexes 6a-c were characterized by means of FT-IR, solid-state NMR and elemental analysis.

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

Two novel coordination compounds $[Cu_2(pypya)_3(H_2O)_2]{\cdot}Cl{\cdot}(H_2O)_5$ (1) and $\{[Cd(pypya)(ta)_{1/2}]{\cdot}H_2O\}_n$ (2) (Hpypya=2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid, $H_2ta$=terephthalic acid) were synthesized and characterized by single X-ray diffraction. Structure determination reveals that complex 1 and complex 2 crystallize in the triclinic system, with the P-1 space group. The asymmetric unit of 1 contains two Cu(II) ions, and their coordination modes are different. These units of complex 1 are linked together via hydrogen bonds and ${\pi}-{\pi}$ interactions, and the 3D structure of complex 1 was formed. Complex 2, a mononuclear Cd(II) coordination compound, has a 2D structure which was constructed via coordination bonds. TGA and fluorescence spectra analysis of complex 1 and complex 2 have also been studied. In addition, the geometry parameters of complex 1 have been optimized with the B3LYP method of density functional theory (DFT) to explain its coordination behavior. The electronic properties of the complex 1 and ligand Hpypya have been investigated based on the nature bond orbital (NBO) analysis at the B3LYP level of theory. The result verifies that the synergistic effect have occurred in the compound.

2H-azirine, a less known acetonitrile isomer, is observed in matrix IR spectra from the precursor exposed to radiation from laser ablation of transition-metals. Its vibrational characteristics confirm the previous results, and those for the deuterated and $^{13}C$ substituted isotopomers are also newly reported. The weak absorptions are traced to the low production yield due to its high energy and low extinction constants. IRC computations reveal smooth inter-conversion between 2H-azirine and $CH_2NCH$, providing a rationale for the observed variation of their relative contents during photolysis.

Chemical feature based quantitative pharmacophore models were generated using the HypoGen module implemented in DS2.5. The best hypothesis, Hypo1, which was characterized by the highest correlation coefficient (0.96), the highest cost difference (61.60) and the lowest RMSD (0.74), consisted of one hydrogen bond acceptor, one hydrogen bond donor, one hydrophobic and one ring aromatic. The reliability of Hypo1 was validated on the basis of cost analysis, test set, Fischer's randomization method and GH test method. The validated Hypo1 was used as a 3D search query to identify novel inhibitors. The screened molecules were further refined by employing ADMET, docking studies and visual inspection. Three compounds with novel scaffolds were selected as the most promising candidates for the designing of Mcl-1 antagonists. Finally, a 10 ns molecular dynamics simulation was carried out on the complex of receptor and the retrieved ligand to demonstrate that the binding mode was stable during the MD simulation.

Solvent extraction of Fe(III) from chloride solution by using a mixture of D2EHPA (Di-(2-ethylhexyl)-phosphoric acid) and TBP (Tri-butyl phosphate) and the reductive stripping of Fe(III) from the loaded organic were investigated. Quantitative extraction of Fe(III) from the solution (Fe concentration = 90 g/L) was accomplished in two cross-current extraction stages by using the mixture of D2EHPA and TBP. In order to facilitate the stripping efficiency, a reductive stripping method was employed by using $H_2SO_3$ or $Na_2SO_3$ as a reducing agent. The addition of $H_2SO_4$ into reducing agents led to improvement in the stripping efficiency while high concentration acid would suppress it. Both of the mixtures of $H_2SO_4+H_2SO_3$ and $H_2SO_4+Na_2SO_3$ showed good efficiency for the stripping of Fe(III), while the latter was recommended as the stripping solution based on the economics and experimental condition.

The association of silybin with ${\beta}$-cyclodextrin and its influence on silybin's binding with bovine serum albumin are reported. The stoichiometry, binding constant, and the structure of silybin-${\beta}$-cyclodextrin inclusion complex are reported. The titrations of silybin with bovine serum albumin in the absence and presence of ${\beta}$-cyclodextrin are carried out and the differences in binding strengths are discussed. Molecular modeling is used to optimize the sites and mode of binding of silybin with bovine serum albumin. F$\ddot{o}$rster resonance energy transfer is calculated and the proximity of interacting molecules is reported in the presence and absence of ${\beta}$-cyclodextrin.

Pim kinases are promising targets in the treatment of hematopoietic and solid cancers. Meridianin C was chosen as a starting point to discover novel pim kinase inhibitors. Using known pim kinase's structural information, aminopyrimidine was introduced to provide the hydrogen-bonding interactions with the conserved lysine residue in the ATP binding pocket of all three Pim kinases. Synthesized 3,5-bis(aminopyrimidinyl)indole derivatives showed pan-pim inhibitory activity. Aminoalkyl substituent was attached on the aminopyrimidine to further enhance the potency and physicochemical properties of compound. The research reveals a significative way of designing compounds with high potency and kinase selectivity for pan-pim kinases.

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

A one-pot, facile and ecofriendly approach to the fabrication of covalently fluorinated graphene using mild reaction conditions is reported. This straightforward and efficient strategy allows fluorine groups to be covalently and stably anchored onto graphene to produce single-layer functionalized graphene sheets from a graphene oxide precursor.

Ketene-forming elimination from 2-X-4-nitrophenyl furylacetates (1a-d) promoted by $R_2NH-R_2NH_2{^+}$ in 70 mol % MeCN(aq) has been studied kinetically. When X = Cl and $NO_2$, the reactions exhibited second-order kinetics as well as Br$\ddot{o}$nsted ${\beta}$ = 0.37-0.54 and $|{\beta}_{lg}|$ = 0.31-0.45. The Br$\ddot{o}$nsted ${\beta}$ decreased with a poorer leaving group and $|{\beta}_{lg}|$ increased with a weaker base. The results are consistent with an E2 mechanism. When the leaving group was changed to a poorer one [X= H (1a) and $OCH_3$ (1b)], the reaction mechanism changed to the competing E2 and E1cb mechanisms. A further change to the E1cb mechanism was realized for the reaction of 1a with $i-Pr_2NH/i-Pr_2NH_2{^+}$ in 70 mol % MeCN-30 mol % $D_2O$. By comparing the kinetic results in this study with the existing data for $ArCH_2C(O)OC_6H_3-2-X-4-NO_2$, the effect of the ${\beta}$-aryl group on the ketene-forming elimination was assessed.