A new ternary lanthanum complex, La (Glu) (Im)6 (ClO4)3·4HClO4·4H2O (Glu: glutamic acid, Im: imidazole), was synthesized and its thermodynamic properties were studied. Heat capacities of the complex were measured with a high-precision automatic adiabatic calorimeter over a temperature range from 80 to 390 K and the thermodynamic functions (HT-H298.15) and (ST-S298.15) were derived from the heat capacity data with a temperature interval of 5 K. Glass and phase transitions of the new complex at around 216 and 246 K were observed both by adiabatic calorimetry and differential scanning calorimetry (DSC) analyses. Thermodynamic data of the phase transitions were calculated and the transition mechanism was determined to be a re-orientational process of the perchlorate ions in the complex. The thermal stability of the complex was tested by the thermogravimetric (TG) technique and a possible mechanism for its decomposition was proposed.

An anion exchange fiber containing polyamine functional group was synthesized by chemical modification using polyacrylonitrile fiber as the raw material. The adsorption behavior of Cr(VI) using the self-made fiber was studied.Within the observed temperature and concentration range, equilibriumdata for the adsorption of Cr(VI) from aqueous solutions by the fiber were obtained and correlated with Langmuir-type and Freundlich-type isotherm equations. The adsorption is shown to be a favorable type and the polyamine functional group has a strong affinity for Cr(VI). We mainly studied the adsorption kinetics of Cr(VI) onto the self-made fiber and fitted the kinetic data to the Lagergren first-order equation, the pseudo second-order equation, the modified pseudo first-order equation, and the intra-particle diffusion model. The respective characteristic rate constants were calculated and analyzed. Results show that the adsorption process is fast and that it reaches equilibrium at about 20 min. The experimental data for the adsorption systems fit well to a pseudo second-order equation and chemical adsorption is the main adsorption process. The fiber can be regenerated and repeatedly used for the adsorption of Cr(VI).

A nanoparticle reinforced Ni-based alloying layer was prepared by a duplex surface treatment on the surface of AISI 316L stainless steel. This steel contained Ni/nano-SiO2 or Ni/nano-SiC layer which was predeposited by brush plating and subsequent surface alloying with Ni-Cr-Mo-Cu by a double glow process. The microstructures of the two kinds of nanoparticles that reinforced the Ni-based alloying layers were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The corrosion behaviors of the composite layers under hydrodynamic conditions and at different rotational speeds were characterized by current responses at a potential of +0.2 V, a potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS) under a static state (3.5%(w, mass fraction) NaCl solution) and under slurry flow conditions (3.5%(w) NaCl solution+10%(w) sand particles). To assess possible erosion-corrosion mechanisms, the worn sample surfaces were observed by SEM. Electrochemical tests showed that the corrosion resistance of the composite layer with the brush plated Ni/nano-SiO2 particle interlayer was slightly lower than that of the single Ni-based alloying layer produced under static state conditions. However, under hydrodynamic conditions, the corrosion resistance of the composite layer with the brush plated Ni/nano-SiO2 particle interlayer was obviously superior to that of the single Ni-based alloying layer. The corrosion resistance of the composite layer produced with the brush plated Ni/nano-SiC particle interlayer was lower than that of the single Ni-morphologies we found that highly dispersive nano-SiO2 particles were helpful in improving the erosion-corrosion resistance of the Ni-based alloying layer whereas the carbides and silicide phases were deleterious to the Ni-based alloying layer.

The formation of solid electrolyte interphase (SEI) filmon graphite in a lithiumbis(oxalato)borate (LiBOB)-based electrolyte was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). The effects of SEI filmon the cycleabilities of graphite were examined at roomtemperature (25 ℃) and at high temperature (70 ℃). Results showed that the SEI filmwas formed at around 1.7 V and BOB- ions were reduced to oxalate, which was one of the components of the SEI film. EIS showed that the impedance of the SEI film decreased during the charge/discharge cycle and this was favorable for cycle stability. Whether it was at room temperature or at high temperature, the graphite had better cycleability in the LiBOB-based electrolyte than in the LiPF6-based electrolyte.

Carbon paper was heat-treated at different temperatures and used as an electrode for the VO2+/VO+2 redox couple. Kinetics of the VO2+/VO+2 redox couple on the carbon paper electrode was studied using cyclic voltammetry (CV), polarization curves (PC), and electrochemical impedance spectroscopy (EIS). Results obtained from CV and PC show that the reaction rate constant and the exchange current of the VO2+/VO+2 redox couple on the carbon paper electrode increase as the heat treatment temperature increases. An equivalent circuit model for the VO2+/VO+2 redox couple on the carbon paper electrode was established. Fitting the experimentally obtained electrochemical impedance spectra with established equivalent circuits shows that heat treatment increases the double-layer capacitance of the carbon paper electrode and reduces the charge transfer resistance of the VO2+/VO+2 redox couple. Similar diffusion coefficients for VO2+ and VO+2 were obtained from CV and EIS, indicating that the established equivalent circuit model is consistent with the electrode process for the VO2+/VO+2 redox couple.

Nickel-sulfur electrodes with different crystallographic structures were obtained by galvanostatic electrodeposition froma typical Watts bath containing sodiumthiosulfate as a sulfur source. The chemical composition, crystalline structures, and surface morphologies of deposited films were determined by energy dispersion spectrum (EDS), X-ray diffraction (XRD) pattern, and scanning electron microscope (SEM) analyses. The electrocatalytic activities of the electrodes for hydrogen evolution reaction were studied in detail. The XRD result shows that the Ni-S active electrodes comprise amorphous/Ni3S2 mixed phase structures and intermetallic compound phase structures (Ni3S2) as the S content in the deposited films is increased. When the S content is 33.9% (atomic fraction) the amorphous/Ni3S2 mixed phase electrodes have a higher catalytic activity for the hydrogen evolution reaction in an alkaline solution because of the strong hydrogen adsorption ability of the Ni3S2 intermetallic compound phase. The alternating current (AC) impedance analysis results indicate that hydrogen evolution from the Ni3S2 intermetallic compound belongs to a one-step electrochemical reaction process and that for the amorphous/Ni3S2 mixed phase structures involves three steps.

The effect of lithium difluoro(oxalato)borate, which was added to the propylene carbonate (PC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (mass ratio 1:1:3) mixed solvent as a lithiumsalt, on the cyclic performance of LiFePO4/graphite batteries at high temperature (60 ℃) was investigated. Linear sweep voltammetry(LSV) was used to examine the electrochemical stability of the lithium difluoro(oxalato)borate-based electrolyte. Inductively coupled plasma (ICP) and energy dispersive spectroscopy (EDS) were used to analyze the stability of the LiFePO4 cathode in the LiODFB-based electrolyte at high temperature. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) were used to analyze the thermal stability of the solid electrolyte interphase (SEI) film formed on the graphite anode. Results showed that the LiODFB-based electrolyte could restrain iron dissolution from LiFePO4 and prevent the reduction of dissolved iron ions'reducing at the anode's surface which decreased the impedance effectively. On the other hand, the SEI film formed on the graphite surface in the LiODFB-based electrolyte had better thermal stability. The cyclic performance of the LiFePO4/graphite battery at high temperatures improved dramatically.

Mesoporous MnO2 and mesoporous carbon were prepared using silica mesoporous molecular sieves (SBA-15) as a hard template. A meso-C/MnO2 asymmetrical supercapacitor was assembled and characterized in 6 mol·L-1 KOHelectrolyte. Low X-ray diffraction (LXRD), transmission electron microscopy (TEM), and nitrogen adsorption-desorption results indicated that the as-prepared samples had mesoporous structures, large specific surface areas, and a narrow pore diameter distribution range. Galvanostatic charge/discharge, cyclic voltammetry, and AC (alternating current) impedance were used to investigate the electrochemical performance. At 0.1 A·g-1 current density, different potentials were applied to obtain the optimum cell voltage of 1.8 V. Under this condition, the supercapacitor exhibited od charge/discharge capacities. Results showed that the equivalent series resistance (ESR), power density, and energy density were 1.15 Ω, 89.0 W·kg-1, and 31.3 Wh·kg-1, respectively. The initial specific capacitance was 76.7 F·g-1 and 69.5 F·g-1 was obtained after 1000 cycles.

A thermodynamic study of temperature effects on the 0.1 mol·L-1 Zn(NO3)2 systemby means of potential pH diagram, species repartition diagram, and solubility of ZnO/Zn(OH)2 was presented with the aim of guiding future electrodeposition conditions and for the prediction of the ultimate product. These thermodynamic calculations were testified by analyzing curves of the cathodic current density as a function of time and cyclic voltammetry (CV), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric-differential scanning calorimeter (TG-DSC), and ultraviolet-visible (UV-Vis) spectroscopy. Optical studies revealed that the ZnO films exhibited a high transmittance in the visible region (>80%) and a steep absorption edge. A reaction mechanism was proposed for ZnO electrodeposition in zinc nitrate aqueous solutions.

The interaction between ionic liquids (ILs) and nitrobenzene was investigated using ultraviolet spectroscopy. Compared to the ultraviolet spectrum in cyclohexane and water, a red shift of the absorption peak of the nitro group was observed in ionic liquids and no end absorption was found when the wavelength was less than 210 nm. These phenomena may be attributed to the strong interaction between ILs and nitrobenzene. The transfer coefficient (α) of the electrochemical reduction of nitrobenzene for transferring the second electron in RMimBF4 (1-alkyl-3-methylimidazolium tetrafluoroborate) was investigated by cyclic voltammetry. The effect of the dielectric nature of nitrobenzene and water on the dielectric constants of the solution and on the capacitance of the electric double layer as well as the interaction between EMimBF4 (1-ethyl-3-methylimidazolium tetrafluoroborate) and nitrobenzene and water was found to have a complicated effect on α. Increasing the concentration of nitrobenzene during the electrochemical reduction in RMimBF4, α decreased. Increasing the temperature the value of α increased while increasing the length of the imidazolium side chain had an opposite effect. At the same nitrobenzene concentration, with an increase in the water concentration α was reduced in EMimBF4-H2O system at lower water concentration and had reverse effect at higher water concentration.

Three new mixed-ligand cobalt(II) complexes [Na2Co(μ4-btec)(H2O)8]n (1), [Co2(μ2-btec)(bipy)2(H2O)6]·2H2O (2), and [Co2(μ2-btec)(phen)2(H2O)6]·2H2O (3) (H4btec = 1,2,4,5-benzenetetracarboxylic acid, bipy=2,2'-bipyridine, phen=1,10-phenanthroline) were synthesized using hydrothermal and microwave methods after which the products were characterized by single crystal X-ray diffraction. Complex (1) crystallizes in a monoclinic systemwith a C2/m space group, a=1.5690(2) nm, b=0.9550(1) nm, c=0.6102(2) nm, and β=92.78(3)°. Complex (2) belongs to a monoclinic systemand has a P21/n space group, a=1.2290(1) nm, b=0.7594(2) nm, c=1.7920(1) nm and β=100.07(2)°. Complex (3) belongs to a triclinic systemand has a P1 space group, a=0.7454(1) nm, b=1.1072(2) nm, c=1.2177(2) nm, α=108.41(3)°, β=101.94(3)°, and γ=109.03(3)°. All three complexes are bridged by the betc4- ligands to form 3 dimensional (D) (1) and binuclear (2and 3) structures. The betc4- ligands adopt μ4-η2η2η2η2, μ2-η1η1, and μ2-η1η1 coordinated modes in the three complexes, respectively. The hydrogen bonds allow complexes (2) and (3) to be further connected into 2D and 3D networks. The complexes were characterized by IR, UV-visible-near infrared (UV-Vis-NIR), and surface photovoltage spectroscopy (SPS). The SPS of the three complexes (1)-(3) indicate that they all exhibit positive surface photovoltage (SPV) responses from 300 to 600 nm. However, the intensity, position, and number of SPV responses are different, which may be attributed to the differences in their structures and coordination environment of the Co ions in the three complexes. The SPS results are consistent with associated UV-Vis-NIR spectrumresults.

Three dissymmetric quaternary ammonium Gemini surfactants (referred to as a4-6-m) were synthesized. One of the two hydrophobic chains of a4-6-m was a butyl chain terminated by an azobenzene group and the other was a conventional aliphatic chain of different length (m=12, 14, 16). The results showed that the trans-a4-6-m molecules adsorbed at the air/water interface with a vertical orientation of the two hydrophobic chains. The π-π interaction between azobenzene groups resulted in a denser arrangement of the surfactants. The azobenzene groups toward the air-side in the adsorption layer yielded a higher γcmc (surface tension value corresponding to the critical micelle concentration (cmc)) by comparison to 12-6-12. After UV-light irradiation, the trans-azobenzene groups converted into twisted cis-forms with a large dipole moment. These cis-azobenzene groups lay among the vertically oriented aliphatic chains and their relatively free location enhanced their dipole-dipole interactions, which promoted the tight packing of adsorbed molecules and slightly reduced the minimummolecular occupation area (Amin). The increase in aliphatic chain length led to a reduction of the cmc and the C20 (concentration of surfactant required to reduce 20 mN·m-1 surface tension of water), but had little effect on the γcmc.

The effect of inorganic salts on the physical-chemical properties of the commercial alkyl polyglucoside (APG) APG1214 was studied to explain how it enhanced the crude oil removal. We found that the properties of APG1214 were different from those of typical nonionic surfactants. An inorganic salt formula greatly reduced the criticalmicelle concentration (CMC) and the cloud point ofAPG1214, which was beneficial for oil removal. Properties of the APG1214 aggregates were investigated using dynamic light scattering (DLS) and transmission electron microscopy (TEM). We found that low concentrations of inorganic salts reduced the size of the APG1214 aggregates while high concentrated inorganic salts led to larger aggregates. After soil washing, the distribution of the hydrodynamic radius (Rh) narrowed and the average Rh increased. TEM images indicated that the wall of the vesicles thickened after soil washing which confirmed that solubilization was a way of oil removal by APG1214. These findings provide guidelines for the use of APG1214 in soil washing as well as in other fields.

Adsorption of arsenate on TiO2 surfaces was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculation. The adsorption process was independent of ion strength, indicating the formation of inner-sphere complexes of arsenate on TiO2 surfaces. EXAFS analysis showed that the —AsO4 tetrahedral geometry remained relatively rigid before and after adsorption with an As-O distance (R) of (0.169±0.001) nm. When —AsO4 approached TiO2 surfaces, the As—O—Ti bond formed through the O atoms in —AsO4 clusters. Furthermore, based on the combined results from EXAFS and DFT, As(V) in the “equilibrium”adsorption samples was in at least two metastable equilibrium adsorption (MEA) states: double corner (DC) linkage mode (R1=(0.321±0.002) nm, stronger adsorption) and single corner (SC) linkage mode (R2=(0.360±0.002) nm, weak adsorption). The proportion of coordination number between DC and SC MEA states (CN1/CN2) decreased from 3.3 to 1.6 as the surface coverage increased from 9.79 to 28.0 mg·g-1. This result indicated that at low surface loading arsenate was adsorbed in more stable DC MEA state, but As(V) tended to be adsorbed in SC MEA state as surface coverage increased.

A novel catalyst was prepared for the first time by supporting iridium on porous hydroxyapatite (Ir/HAP). The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy(SEM) equippedwithanenergydispersiveX-rayspectroscopy(EDS),X-rayphotoelectronspectroscopy(XPS), and Brunauer-Emmett-Teller (BET) surface area analysis. In the presence of (1S,2S)-1,2-diphenyl-1,2-ethylenediamine ((1S,2S)-DPEN), the catalytic properties of the catalyst were investigated by the asymmetric hydrogenation of aromatic ketones. Under optimum reaction conditions of temperature T=303 K, pressure p=3.0 MPa, and reaction time t=3 h, the conversion of aromatic alcohols that were produced from the hydrogenation of acetophenone and its derivatives reached 94.7%. The enantiomeric excess (ee) value for the 2'-(trifluoromethyl) phenethyl alcohol was 81.5%. Without using other ligands as stabilizers, the enantiomeric excess value was found to be higher than that reported in literature. As a catalyst carrier, hydroxyapatite is superior to SiO2 and other inorganic carriers. The catalyst is reusable with no sign of Ir leaching.

We prepared novel monolithic microfiber-structured Nafion/SiO2 solid acid catalysts with 60%-75% (φ, volume fraction) void volume by coating Nafion/SiO2 sol-gel onto a sinter-locked stainless steel (SS-316L) microfibrous network. We characterized the microstructured Nafion/SiO2 catalysts using Fourier transform-infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and NH3-chemisorption. Results show that the sol-gel technology results in highly dispersed Nafion particles which significantly increase the number of accessible acid sites. The Nafion/SiO2 catalyst coating layer is made up of 200-400 nmparticles and looks porous. The catalytic performance of the microstructured Nafion/SiO2 catalysts was tested using the nitration of benzene in a continuous-flow microreactor that integrated heat-exchange, mixture, and catalytic reactions. The best catalyst had a loading capacity of 36.3% (w, mass fraction) for the Nafion/SiO2 composite in which the Nafion content was 20% (w). At a reaction temperature of 75 ℃, this optimized microstructured solid acid catalyst resulted in a benzene conversion of 44.7% with a nitrobenzene selectivity of 99.9%. At an equivalent conversion level, the activity per acid site of the microstructured Nafion/SiO2 catalyst is nearly 600 times as that of liquid sulfuric acid.

A novel nanoporous poly(N-acetylaniline) (np-PAANI) film with a network structure modified with Pt nanoparticles (C/np-PAANI/Pt) was fabricated using chemical oxidation polymerization and a reduction method. The morphology and composition of the final products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The electrocatalytic activity of C/np-PAANI/Pt towards the oxidation of methanol was investigated using cyclic voltammetry and chronoamperometric methods in 0.5 mol·L-1 CH3OH+0.5 mol·L-1 H2SO4 mixture solution. Results indicated that C/np-PAANI/Pt catalysts exhibited improved electrocatalytic activity, anti-poisoning ability, and od stability towards methanol oxidation by comparison to C/PAANI/Pt or C/Pt.

The catalytic performance of a ZSM-5/ZSM-57 composite zeolite catalyst for the conversion of mixed C4 hydrocarbons was investigated. The acidic properties of the ZSM-5/ZSM-57 composite zeolite catalyst were characterized by means of ammonia temperature-programmed desorption (NH3-TPD) and pyridine adsorption Fourier transform infrared (FT-IR) spectroscopy. Results indicated that compared with ZSM-5 zeolite, the ZSM-5/ZSM-57 composite zeolite with lower ZSM-5 content showed higher catalytic activity and higher selectivity for ethylene and propylene because of its enhanced acidic strength and increased acid amount. ZSM-57 has small pores in the composite zeolite and this is beneficial in the shape-selective reaction of ethylene and propylene. On the contrary, the ZSM-5/ZSM-57 composite zeolite with higher ZSM-5 content exhibited higher selectivity for benzene and toluene. This probably results from the pore structure and the structure matching property of the ZSM-5/ZSM-57 composite zeolite, which favors the aromatization of mixed C4 hydrocarbons.

We report on a direct electron transfer and bioelectrocatalysis of horseradish peroxidase (HRP) immobilized in mesoporous silica FDU-12 with three-dimensional (3D) large cages and entrances. UV-Vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and impedance spectroscopy were used to prove the interaction between HRP and FDU-12. Results from cyclic voltammetry show that immobilized HRP can under a direct quasi-reversible electrochemical reaction. Its formal potential, E0', is -0.325 V in a phosphate buffer solution (PBS, pH 6.9) and this is almost independent of the scan rate from 40 to 300 mV·s -1. The experimental results also demonstrate that the immobilized HRP retains its bioelectrocatalytic activity for the reduction of H2O2. Furthermore, the electrode can be stored at 4 °C for several weeks without any loss of enzyme activity. Thus, FDU-12 is a novel matrix for realizing a direct electron transfer of various proteins and enzymes and the preparation of electrodes for the third biosensors.

We investigated the electroluminescence (EL) characteristics of a novel yellow emitting material: (E)-2-(2-(9-(4-methoxyphenyl)-9H-carbazol-3-yl)quinolato-zinc (MoBCzHQZn). The results demonstrated the MoBCzHQZn with strong yellow emitting and hole-transporting ability. Based on these performances, a series of un-doping white and doping yelloworganic light-emitting devices (OLEDs) were fabricated. The white device was fabricated as follows: ITO/2T-NATA(20 nm)/MoBCzHQZn(25 nm)/NPBX(13 nm)/BCP(8nm)/Alq3(34 nm)/LiF(0.5 nm)/Al, white OLEDs were obtained with Commission International de L'Eclairage coordinates of (0.3719, 0.3275), the maximum luminance was 3414 cd·m-2 at an applied voltage of 15 V and the maximum luminous efficiency was 1.69 cd·A-1 at an applied voltage of 14 V. The yellow device was fabricated as follows: ITO/2T-NATA(20 nm)/CBP:6% Ir(ppy)3:10% MoBCzHQZn(25 nm)/TPBi:6% Ir(ppy)3(47 nm)/LiF (0.5 nm)/Al, yellow OLEDs were obtained with Commission International de L'Eclairage coordinates of (0.3590, 0.5787), the maximumluminance was 11073 cd·m-2 at an applied voltage of 15 V and the maximumluminous efficiency was 2.51 cd·A-1 at an applied voltage of 9 V.

All 20 standard polycrystalline α-amino acids were examined using terahertz time-domain spectroscopy (THz-TDS) at room temperature. They are strikingly sensitive to the THz pulse and yield a complete set of THz fingerprint spectra between 0.2 and 3.0 THz. These spectra were compared to those from previous reports in terms of spectral shape and frequencies of absorption peaks. We validated the characteristic absorption peaks and provided supplementary data. For the first time, correlations between THz spectral peaks and the molecular structures of amino acids are revealed and a classification of amino acids based on both molecular structures and THz spectra was established. These correlations can help identify amino acids, trace some functional groups, and examine if the THz spectra are dominated by internal or intermolecular vibrations. These correlations can thus promote the application of THz spectroscopy in the study of biological and medicinal materials in the biomedical fields.

The inflammatory effects, pharmacodynamical basis, and multi-targeting properties of Xuebijing, a traditional Chinese medicine (TCM) prescription, were investigated on molecular level. Using computer aided drug design (CADD) consisting of homology modeling, molecular docking, pharmacophore construction, and virtual screening was carried out to search for the molecules included in Xuebijing that inhibit the three inflammatory related targets: 5-lipoxygenase (5-LOX), cyclooxygenase-2 (COX-2), and IKK-2. An aggregate analysis was then performed to evaluate the chemical compositions of Xuebijing molecules. There were 30, 36, and 8 molecules that showed od interaction with the inflammatory targets: 5-LOX, COX-2, and IKK-2, respectively. There were 16 molecules that inhibited two or three targets among which 15 molecules inhibited both 5-LOX and COX-2, rosmarinic acid inhibits all targets. This investigation shows that there are many multi-targeting molecules in Xuebijing. Our research gives a molecular description of the multi-target effect and a pharmacodynamical material basis of the inflammatory effect. On the other hand, as multi-target could be a new trend in the field of drug design, our research points the way to discovering new anti-inflammation entities.

Properties of four indoline dyes were studied by means of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) with the al of finding an excellent photosensitizer for use in dye-sensitized solar cells. Theoretical results showed that the frontier molecular orbital structures of indoline dyes are suitable for electron injection from the excited states of indoline dyes to a TiO2 electrode. Calculated UV-visible absorption spectra of indoline dyes in vacuum match well with solar radiation spectra. The calculated energy levels of these dye molecules demonstrate that indoline dyes can be used as photosensitizers for TiO2 nanocrystalline solar cells together with the I-/I-3 electrolyte. The lowest unoccupied molecular orbital (LUMO) energy levels of indoline dyes are higher than the conduction band edge of the TiO2 crystal, which ensures a high efficiency of electron transfer from indoline dyes to TiO2 electrodes. As the highest occupied molecular orbital (HOMO) energy levels of indoline dyes are lower than those of I-/I-3, molecules that donated electrons can receive electrons from the electrolyte. By comparison with the experimental data, the transfer efficiency of dye-sensitized solar cells may be determined mainly by the LUMO energy levels. The working lifetime of a dye-sensitized solar cell depends mainly on the stability of the dye molecule. From an analysis of the bond length of chemical bonds, we find that the stability of the four indoline dye molecules is basically the same. We further show that indoline dye 1 (ID1) has the highest LUMO energy level and the highest molecular stability. Its absorption spectra match solar radiation spectra well in an ethanol solution, therefore, it is the best photosensitizer among the analyzed dyes for application in dye-sensitized solar cells.

A molecular dynamics simulation was performed to examine the formation properties of clusters during the solidification of liquid Ca7Mg3 alloy. Pair distribution functions, Honeycutt-Andersen (HA) bond-type index method, cluster-type index method, and genetic tracking were used to analyze the formation and evolution of cluster structures during rapid solidification processes. Results show that amorphous structures are mainly formed with the 1551, 1541, and 1431 bond-types at a cooling rate of 1×1012 K·s-1. The basic cluster (12 0 12 0) plays a key role in the formation of amorphous structures during rapid solidification processes. The stability of a cluster is related to the type of basic clusters and also the type of central atoms as well as the bonding modes between all central atoms. Bonding among the basic clusters (12 0 12 0) allows the formation of larger clusters because of the lower energy and the better genetic characteristic of the basic cluster (12 0 12 0). These bigger clusters are obviously different from those obtained by gaseous deposition and ionic spray methods.

A mechanism for the intramolecular O-arylation reaction of N-(ortho-chlorophenyl)benzamide catalyzed by CuX(X=I, Br) was studied using the density functional theory at B3LYP/6-31+G* level. We optimized the geometric configurations of reactants, intermediates, transition states, and products. A vibrational analysis and an energy calculation proved the authenticities of the intermediates and the transition states. Nature bond orbital (NBO) and atoms in molecules (AIM) theories were used to discuss the bond nature and orbital interactions at the same levels. At the same time, we compared the influence of two different copper catalysts on the catalytic activity. Computation results indicate that they have the same reaction path and that the activation energy with CuBr catalysis is smaller than the activation energy with CuI catalysis. CuBr, therefore, promotes the higher catalytic activity, which is in od agreement with experimental results.

A novel and reliable docking model based on the protein structure of cyclin dependent kinase 7 (CDK7) for CDK7 inhibitors was developed using LigandFit module within Discovery Studio 2.1 package. Receiver operating characteristic curves (ROC) were applied as a method of validation to evaluate the accuracy of the established model. LigScore2 was selected as the best score function. The area under curve (AUC) of the ROC curve was 0.95. Compounds designed by our group were docked with CDK7 to study the binding mode between the target molecules and the receptor protein CDK7. Two compounds, namely 16 and 17, with favorable scores from the docking studies were selected for synthesis and required a thirteen-step route but they were obtained in moderate to od yields. The two synthesized compounds were then evaluated for their in vitro cytotoxic activities against five human cancer cell lines including human acute promyelocytic leukemia cells (HL60), human nasopharynx carcinoma cells (KB), human hepatoma cells (SMMC-7721), human colon adenocarcinoma cells (HCT-116), and human lung cancer cells (A549). Both tested compounds showed potent cytotoxic activities with IC50 values ranging from 0.84 to 19.70 μmol·L-1 . Compound 16 showed the most potent antitumor activity against HL60 human cancer cell lines with IC50 value of 0.84 μmol·L-1.

A reasonable interpretation of multi-color luminescence mechanisms for molecular materials can be obtained from theoretical research into molecular excited states. Molecular structures and photophysical properties of the restricted (T1a) and relaxed (T1b) lowest triplet excited states of four two-coordinated Au(I) complexes, Ph3PAuCl, Ph3PAuBr, Ph3AsAuCl, and Ph3AsAuBr, were investigated using the single-excitation configuration interaction (CIS) method. Because of a remarkable distortion of the θ(PAuX)/θ(AsAuX) from 180°to about 120°, the T1b state was found to be considerably reduced in energy, e.g. 0.805-1.124 eV using CIS, 0.820-0.947 eV using density functional theory (DFT). An analysis of the natural bond orbital (NBO) electronic spin density indicates that two single electrons mostly populate on one of the three phenyls for the T1a state and on the PAuX/AsAuX fragment for the T1b state. Finally, a higher-energy phosphorescence was observed in the crystals and was assigned to one inter-phenyl 3π*→1πtransition of the T1a state, whereas a lower-energy phosphorescence was mostly due to a 3σ*→1σtransition in the T1b state with a sp2 hybridized Au(I).

Methyl 3-nitrosalicylate (3-MNS) and methyl 5-nitrosalicylate (5-MNS) were synthesized by a nitration reaction between methyl salicylate (MS) and iron (III) nitrate under reflux. 3-MNS and 5-MNS were characterized by infrared spectra (IR), proton nuclear magnetic resonance spectra (1H-NMR), electronic absorption spectra (UV-Vis), and photoluminescence (PL). The structures of 3-MNS and 5-MNS were fully optimized at the B3LYP/6-31G** level. The optimized results and nature bond orbital (NBO) analysis results were used to illustrate the red-shift of the O—H and C=O stretching vibrations in the IR, the lower field shift of the phenol hydroxyl proton chemical shift in 1H-NMR, and the bathochromic shift in the UV-Vis spectra of 3-MNS. Potential energy surfaces for the intramolecular proton transfer of ground (GSIPT) and excited (ESIPT) states of MS and 3-MNS were obtained and the Stokes-shift values for MS and 3-MNS were computed to be 8.4 ×103 and 8.9×103 cm -1 using CIS/6-31G**, respectively. All these results demonstrate that differences in intramolecular hydrogen bonding in MS, 3-MNS, and 5-MNS give rise to large differences in their spectral properties.

NH3 adsorption in Mordenties H-[M']MOR, Cu-[M']MOR, and Ag-[M']MOR (M'=B, Al, Ga, Fe) was investigated using density functional theory (DFT) with the generalized gradient approximation (GGA) and the Becke exchange plus Lee-Yang-Parr correlation (BLYP) method as well as the DND basis set in the Dmol3 module. Equilibrium configurations and adsorption energies of NH3 in H-[M']MOR, Cu-[M']MOR, and Ag'[M']MOR were obtained and discussed. NH3 was adsorbed in H-[M']MOR by the interaction between the lone electron pair of nitrogen and the proton acidic site. NH3 was adsorbed in H-[Al]MOR, H-[Ga]MOR, and H-[Fe]MOR by chemical adsorption and in H-[B]MOR by physical adsorption which agreed well with results from the literature. NH3 was adsorbed in Cu-[M']MOR (or Ag-[M']MOR) through the chemical adsorption between the lone electron pair of nitrogen and the s empty orbital of the Cu+ (or Ag+) cation. Calculated adsorption energies showed that the acidities of H-[A1]MOR, Cu-[A1]MOR and Ag-[A1]MOR were the strongest among all the H-[M']MOR, Cu-[M']MOR and Ag-[M']MOR, respectively. The acidity decreased as follows: Cu-[M']MOR>Ag-[M']MOR>H-[M']MOR for the same atom substitution. In addition, Mulliken populations of counterpoise ions (H+, Cu+, and Ag+) and the NH3 molecule were also investigated and analyzed before and after adsorption.

Brownian dynamics method was used to simulate the influence of hydrodynamic interaction on the suspension particle coagulation process in a dilute solution. In the simulation, the possibility of one particle colliding simultaneously with more than two particles was ignored and results from previous studies concerned with the hydrodynamic interaction between two particles were used. Our simulations confirm that the hydrodynamic interaction slows the coagulation process down greatly and this is an important reason for the experimental values of the coagulation rate being significantly less than those predicted by Smoluchowski theory. In addition, the particle coagulation process was simulated under varying conditions of combined two factors: gravity and hydrodynamic interactions. Results of how each factor affecting the particle coagulation process were obtained when the two factors were coupled. The mechanism responsible for these effects is discussed froma dynamics point of view.

The relationship between the energy level position, energy splitting of the s1p1 configuration of selected cations and a host was studied. Results indicated that the position of the A, B, and C bands of Sn2+ and the A and B bands of In+ and Tl+ decreased linearly with an increase in the environment factor (he) of the host. A corresponding empirical formula was determined. Calculated values for the A and B bands of the free-ions In+ and Tl+ were in od agreement with experimental results. The largest error was from the B band of Tl+ and the deviation ratio was only -7.34%. Spacings for the energy levels A, B, and C become smaller because high energy level energies drop faster as he increases. By comparison, we found that the sensitivities of the A and B band energies of Sn2+, In+, and Tl+ to the host were different. The greatest change was observed for the Sn2+ ion and the In+ ion energy change was the smallest. More importantly, we found that the A, B, and C band energies splitting tendency for Sn2+, In+, and Tl+ also decreased as he increased even without splitting.

The Davidson's method originally developed for eigenvalue problems was extended to solve large-scale linear equations. It can be used for symmetrical and nonsymmetrical matrices. Numerical results presented in this study demonstrate that the present scheme is much more effective than conjugate gradient method and biconjugate gradient method for symmetrical and nonsymmetrical problems, respectively.

The binding of itraconazole (ITZ), a potential antifungal, to human serumalbumin (HSA) and bovine serum albumin (BSA) were studied at the physiological acidity (pH=7.4±0.1) by fluorescence and UV-Vis spectroscopies. A decrease in the quenching constant was observed with an increase in temperature. From the fluorescence spectrum and the fluorescence intensity, we observed that ITZ strongly quenches the intrinsic fluorescence of both BSA and HSA by static quenching. Thermodynamic parameters, such as △G, △H and △S, were calculated at different temperatures, showing that electrostatic and hydrophobic interactions were mostly responsible for the binding of ITZ to serum albumin. The distance d between the donor (HAS or BSA ) and acceptor (ITZ) was obtained according to fluorescence resonance energy transfer theory (FRET). Synchronous fluorescence and UV-Vis spectroscopy clearly revealed that the microenvironment and the conformation of serumalbumins changed during the binding reaction.

C-Al2O3 nanocomposites were synthesized via the sol-gel tri-constituent co-assembly process using an amphiphilic triblock copolymer F127 (PEO106PPO70PEO106, MW=12600) as a template, aluminum iso-propoxide as an inorganic source, and resol as an organic precursor. X-ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen adsorption/desorption were used to characterize the structures and properties. The results showed that the nanocomposite MC5A5 has ordered mesoporous structures with a high specific surface area of 175 m2·g-1 and a pore volume of 0.22 cm3·g-1. Low infrared emissivity coatings were obtained using the ethylene-propylene-diene monomer (EPDM) as an adhesive and the ordered mesoporous C-Al2O3 nanocomposites as a filling. As the mass percentage of Al2O3 was increased from 30% to 70%, the infrared emissivity decreased from 0.575 to 0.456. Al2O3 can effectively reduce the infrared emissivities of nanocomposites. Ordered mesoporous C-Al2O3 nanocomposites are thus promising for application in martial equipment.

A proton exchange membrane of poly(vinylidene fluoride) (PVDF) grafted onto polystyrene sulfonated acid (PVDF-g-PSSA)was prepared as follows. Styrene was first added to N-methyl pyrrolidone (NMP) solution containing PVDF that was modified with plain sodiumsilicate. Benzoyl peroxide (BPO) was then added as an evocating agent and polystyrene was directly grafted onto the PVDF that was modified with plain sodium silicate. Lastly, the formed membrane was sulfonated. The microstructures, morphologies, and mechanical properties of the membranes and the distributions of sulfur and silicon were investigated using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and a multifunctional material experiment machine. The influence of styrene content on the proton conductivity and methanol permeability of these membranes was studied using an impedance analyzer and a gas chromatograph. Results showed that, depending on the content of styrene, styrene was easily grafted onto the PVDF that was modified by plain sodium silicate. A sulfonation reaction was also found to occur in the membranes and the mechanical properties had improved. As the styrene content increased, the proton conductivity of the PVDF-g-PSSA membranes also increased. The degree of PVDF-g-PSSA swelling was 20.4% at 20% (w, mass fraction) styrene content and 8% Na4SiO4 and at 25 ℃. The membranes possess a methanol permeability of around 10-7 cm2·s-1, which is about ten times as few as that of Nafion115. These composite membranes have high selectivity and are promising for use in direct methanol fuel cells.

FeNi3 alloy nanostructures were synthesized by hydrothermal methods in the surfactant/n-octane/n-hexanol/water quaternary reverse microemulsion systems. The size and shape of the products could be controlled by changing the type and dosage of the surfactant. Spherical particles with a diameter of ca 75 nmwere prepared when polyethylene glycol 4000 (PEG4000) was used as the surfactant. Sea-urchin-like particle was obtained when cetyltrimethylammonium bromide (CTAB) was used as the surfactant. The single sea-urchin-like particles were composed of many nanorods with diameters of ca 42 nm and lengths of 0.4-1.2 μm. The as-synthesized products were characterized by powder X-ray diffraction (XRD), Mossbauer spectroscopy, scanning electronic microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and multi-purpose magnetic variable field translation balance (MM VFTB). Both the spherical and sea-urchin-like FeNi3 samples exhibited typical ferromagnetic behavior at roomtemperature. Their saturation magnetization values (Ms) were 114.4 and 97.4 emu·g-1, respectively, while their coercivity values (Hc) were 94.0 and 329.0 Oe, respectively.