The physicochemical properties of ionic liquids (ILs) at 298.15 K could be estimated and predicted in terms of empirical and semi-empirical equations as well as by interstice model theory. In this paper, the molecular volume, density, standard molar entropy, lattice energy, surface tension, parachor, molar enthalpy of vaporization, interstice volume, interstice fraction, and thermal expansion coefficient are discussed. These properties were first estimated by experimentally determining the density and surface tension for 1-ethyl-3-methylimidazolium ethylsulfate ([C2mim][EtSO4]), 1-butyl-3-methylimidazolium octylsulfate ([C4mim][OcSO4]), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]). The molecular volume and parachor of the three homologues of the imidazolium-based ILs [Cnmim][EtSO4], [Cnmim][OcSO4], and [Cnmim][NTf2] (n=1-6) were predicted and their densities and surface tensions were obtained. Other properties were also calculated using the obtained density and surface tension values. The predicted density was compared to the experimental values for [C4mim][NTf2] and [C2mim][OcSO4], which shows that the deviation between experimental and predicted data are within experimental error. Finally, we compared the values for the molar enthalpy of vaporization estimated by Kabo's empirical equation with those predicted by Verevkin's simple rule for [C2mim][EtSO4], [C4mim][OcSO4], [C2mim][NTf2], [C4mim][NTf2], N-butyltrimethylammoniumbis (trifluoromethylsulfonyl)imide [N4111][NTf2], N-methyltrioctylammoniumbis(trifluoromethylsulfonyl)imide ([N8881][NTf2]), and N-octyl-3-methylpyridinium tetrafluoroborate ([m3opy][BF4]) and found that the values obtained by these two equations were in od agreement with each other. Therefore, we suggest that the molar enthalpy of vaporization of ILs can be predicted by Verevkin's simple rule when experimental data for density and surface tension are not available.

The thermal stability, equilibrium vapor pressure, and standard enthalpy of vaporization of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) ion liquid were investigated using both non-isothermal and isothermal thermogravimetric analysis (TGA) under high purity nitrogen as a carrier gas. The non-isothermal thermogravimetric (TG) curve showed that the onset and peak decomposition temperatures were 697 and 734 K, respectively. However, long-term isothermal TGA studies revealed that the highest application temperature for [bmim][BF4] was 513 K. Moreover, the temperature dependence of the equilibrium vapor pressure and the standard enthalpy of vaporization of [bmim][BF4] were also investigated by TG-based transpiration. In the temperature range of 503-543 K, the relationship between the equilibrium vapor pressure (pe) of [bmim][BF4] and temperature was lgpe=(16±1)+(-6.85±0.25)×103/T. The standard enthalpy of vaporization (△vapHΘ) of [bmim][BF4] was found to be (131±5) kJ·mol-1.

The decomposition of type I ethane hydrate and type II propane hydrate stimulated by 2.45 GHz microwave (MW) were experimentally investigated. The decomposition characteristics of the hydrates under MW heating were analyzed based on the two-step dissociation mechanism accompanied by heat and mass transfer at the crystal surface. Results show that the decomposition behavior of the gas hydrate during MW heating is coupled with the real-time electromagnetic field. Volumetric heating enhances the heat and mass transfer process at the surface layer of the hydrate particles. The time-accumulated thermal effect of MWheating promotes the destruction of the clathrate host lattice. The average decomposition rates of ethane hydrate and propane hydrate obtained in this work range from 0.109 to 0.400 mol·min-1·L-1 and from 0.090 to 0.222 mol·min-1·L-1, respectively, under incident MW power that ranges from 120 to 540 W. We conclude that the average decomposition rates of ethane hydrate and propane hydrate are faster as the MW power increases within a certain range. The decomposition rates of ethane hydrate are mainly controlled by the MWpower. In contrast, the decomposition rates of propane hydrate are controlled by both the MW power and the kinetic mechanismunder relatively higher power.

A numerical study was carried out to determine the effects of CO addition on the laminar burning velocity, NOx emission, and extinction strain rate in a premixed CH4/CO/air flame under the lean condition (equivalence ratio of fuel to air φ=0.60-0.80). When more CO was added to the fuel, the laminar burning velocity decreased, which is different from that observed for H2 addition. To explain this, we studied the strong correlation between laminar burning velocity and H+OHpeak concentrations. Results showed that the H+OHpeak concentrations decreased linearly with an increase in CO content. This tendency is in od agreement with that of the laminar burning velocity. For NOx, we observed that increments in CO addition led to a remarkable reduction in the NOx emission. In addition, we investigated the NO formation mechanism and determined the relevant reactions for NO production using a sensitive analysis. The NO concentrations decreased significantly with enrichment by CO and the NO production rate also clearly decreased. We calculated the radial strain rate Srad and discussed the influence of strain rate on lean flame stability with regards to the addition of different CO mole fractions to the fuel. The extinction strain rates indicated that the lean flammability limits were extended by CO addition in some way.

An electrodeposition approach was developed for the formation of Pt50Ru50 alloy electrodes on a Au-coated Si prismas the infrared window in 1 mmol·L-1 H2PtCl6+1 mmol·L-1 RuCl3+0.1 mol·L-1 H2SO4 solution. The as-prepared Pt50Ru50 alloy electrodes consisted of 100-200 nm nanostructured particles, as determined by atomic force microscope (AFM) image. The significant alloy character of the film and its catalytic activity for CO and CH3OH electrooxidation were demonstrated by conventional electrochemical methods. CO molecules adsorbed on both the Pt and Ru sites of the Pt50Ru50 alloy electrodes could be easily identified using in situ attenuation total reflection (ATR) surface-enhanced infrared (IR) absorption spectroscopy (ATR-SEIRAS). ATR-SEIRAS also revealed that Pt50Ru50 alloy electrodes underwent a bimetallic synergetic effect in catalytic oxidation to CO and CH3OH.

An in situ electrochemistry-electron spin resonance (ESR) method was established to study the generation reaction and the variation regularity of hydroxyl radicals (·OH) on a boron doped diamond (BDD) film electrode in aqueous solution. Results indicate that, above the oxygen evolution potential of BDD filmelectrode (2.4 V in 0.5 mol·L-1 H2SO4 solution), the generation rate of·OH increases as the applied potential or current density increases. However, there was no·OH ESR response when the applied potential was below 2.4 V. Compared to H-terminated surface, the O-terminated surface has a higher·OH generation efficiency because it is hydrophilic and this favors the water splitting reaction. The degradation processes for organic pollutants are always operated under high potential or current density, which allow the BDD film electrode surface to maintain its O-terminated condition. These conditions favor the·OH generation reaction and the reaction takes place with high activity. The pH value of the solution also influenced the·OH generation reaction. BDD filmelectrode has a stronger·OH generation ability in an acidic medium than in a neutral or alkaline medium. We also found that O-·3 can be produced on the surface of BDD film electrode. This article provides new insights into the mechanism of·OH generation on the surface of BDD film electrode and evidence of a highly efficient electrochemical oxidation process during the treatment of organic pollutants.

Variations in the impedance spectra of the commercially available spinel LiMn2O4 electrode from -20 to 20 ℃ were investigated by electrochemical impedance spectroscopy (EIS) in 1 mol·L-1 LiPF6-EC (ethylene carbonate)|DEC (diethyl carbonate)|DMC (dimethyl carbonate), 1 mol·L-1 LiPF6-EC|DEC|EMC (ethyl methyl carbonate) and 1 mol·L -1 LiPF6-EC |DMC electrolyte solutions. We found that the impedance spectral characteristics of the spinel LiMn2O4 electrode was strongly influenced by temperature and only slightly influenced by the electrolyte composition. However, the electronic resistance and the resistance of the SEI filmas well as the charge transfer reaction resistance of the spinel LiMn2O4 electrode were strongly influenced by the electrolyte composition. In 1 mol·L-1 LiPF6-EC|DEC|DMC, 1 mol·L-1 LiPF6-EC|DEC|EMC and 1 mol·L-1 LiPF6-EC|DMC electrolyte solutions, the energy barriers for the ion jump relating to the migration of lithium ions through the solid electrolyte interphase (SEI) film of the spinel LiMn2O4 electrode were determined to be 7.60, 16.40, and 18.40 kJ·mol-1. The thermal active energies of the electronic conductivities were 44.77, 35.47, and 68.06 kJ·mol-1 and the intercalation-deintercalation reaction active energies were 52.19, 46.19, and 69.86 kJ·mol-1, respectively.

A series of cathode materials LiNi1/3Mn1/3Co1/3O2 for lithium-ion batteries were successfully synthesized using succinic acid as a chelating agent by a wet-chemical method. We varied the succinic acid to metal-ion molar ratios (R) and investigated the effect of this parameter on the physical and electrochemical properties of the prepared LiNi1/3Mn1/3Co1/3O2. The reaction mechanism, structural, morphological, and magnetic properties of the powders were characterized in detail by thermogravimetry (TG), X-ray diffraction (XRD), Rietveld refinement, scanning electron microscopy (SEM), and superconducting quantuminterface device (SQUID).We determine that the optimumconditions for the synthesis of LiNi1/3Mn1/3Co1/3O2 assisted with succinic acid is R=1, at the lowest amount of cation mixing. In addition, measurement of the magnetic properties revealed a concentration of Ni on the 3b Wyckoff site of the lithium-ions in od agreement with the results from the Rietveld refinement on the XRD spectra. For LiNi1/3Mn1/3Co1/3O2 (R=1), the Rietveld refinement showed that cation mixing in this sample was 1.85%, which is in quantitative agreement with that fromthe SQUIDresult (1.80%). It delivered an initial discharge capacity of 161 mAh·g-1 at a current rate of 0.2C (1C=160 mA·g-1) and at a cut-off voltage of 3.0-4.3 V with a coulombic efficiency of 93.1% and its capacity retention was 91.3% after 50 cycles.

With mesoporous carbon (CMK-3) serving as a support, we prepared a novel nanocomposite of polypyrrole/mesoporous carbon (PPy-CMK-3) by an in situ chemical polymerization method. An electrochemical hybrid capacitor was successfully designed using a PPy-CMK-3 composite and CMK-3 as positive and negative electrodes, respectively. The electrochemical capacitance performance of this kind of hybrid capacitor was investigated in 1.0 mol·L-1 NaNO3 electrolyte solution. The discharge capacity of the hybrid capacitor reached 57 F·g-1 under a current density of 5.0 mA·cm-2 and cell voltage of 1.4 V. The energy density of the hybrid capacitor reached 17 Wh·kg-1 with a power density of 2.5×102 W·kg-1. When the current density was increased from 5.0 to 50 mA·cm-2, the capacity of the hybrid capacitor remained at about 80% and it showed excellent high rate charge-discharge performance. Furthermore, the PPy-CMK-3/CMK-3 hybrid capacitor containing this PPy-CMK-3 nanocomposite could be active easily and it possessed a high charge-discharge efficiency and od cycle performance.

Novel carbonmaterials containing heteroatoms (nitrogen and oxygen)were prepared by carbonizingH2SO4-doped polyaniline at different temperatures. The morphology, elemental composition, surface chemical composition, and surface area of the as-preparedsampleswere investigatedbyscanningelectronmicroscopy(SEM), elemental analyzer, X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) measurements. Electrochemical properties were studied by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). The results show that the carbon prepared by carbonizing polyaniline at 800 ℃has od electrochemical performance and its specific capacitance value is as high as 153 F·g-1 under a current density of 0.5 A·g-1, although it has a low specific surface area (325 m2·g-1). The high specific capacitance of this carbon is believed to be due to its proper proportion of heteroatoms (nitrogen and oxygen), which provide a large amount of pseudo-capacitance. This kind of carbon material can thus be used as a promising electrode material in supercapacitors.

Surface analysis, mass loss and electrochemical mesurements were used to investigate the corrosion behavior of steel A3 under the effect of Bacillus. Scanning electron microscopy (SEM) indicated that the presence of Bacillus resulted in a compact biofilm after 7 days of exposure, which effectively protected the coupon from being corroded by the solution. Electrochemical impedance spectroscopy (EIS) showed that the number of time constants changed from 2 to 3 and returned to 2 in the Bacillus system. The mass loss and polarization curve results showed that the activity of the bacteria determined the effectiveness of the biofilm. The protective ability of the biofilm decreased when the activity of the bacteria decreased.

A ytterbium(III) complex (C84H82Yb2N4O24) [Yb2(DMPA)6(phen)2] (phen=1,10-phenanthroline; HDMPA=3,4-dimethoxyphenylacetic acid (C12H12O4)) (CCDC: 757541) was synthesized and characterized by elemental analysis, infrared (IR) spectroscopy and thermogravimetry-derivative thermogravimetry (TG-DTG). Its crystal structure was determined by single crystal X-ray diffraction. The complex, C84H82Yb2N4O24, crystallizes in the monoclinic system in space group P1 with cell parameters of a=1.22877(14) nm, b=1.23235(16) nm, c=1.45234(19) nm, α=91.726(7)°, β=103.321(7)°, γ=113.885(6)°, cell volume: V=1.9379(4) nm3, number of molecules inside the cell: Z=1, relative molecular weight: Mr=1877.62, number of electrons: F(000)=946, density calculated: Dc=1.609 g·cm-3, absorptive parameter: μ(Mo Kα)=2.481 mm-1. The emission spectra of complexes doped with Eu or Tb (2.5%, 5.0%, 10.0%, molar fraction) instead of Yb were also investigated. The results showed that no luminescence emission peak was observed from emission spectrum of free ligand, and the luminescence behavior of complexes results from metal-centered emission. It is indicated that ligand can transfer the energy to the central metal efficiently and can sensitize the central metal.

We investigated the causes of distortions and the influence of hydrogen bonding on these distortions in kaolinite. We used CLAYFF supplemented with fluorine potential parameters for the energy minimization modeling of different molar fractions of fluorine substitution for interlayer hydroxyls. Results show that the reasons for tetrahedral basal oxygen corrugation are Al—O (connected oxygen) bond stretching because of the misfit between tetrahedral and octahedral sheets and the requirement of the tetrahedron to maintain its shape. The reason for tetrahedral rotation is similar to Newnham's explanation. The counter-rotation of the upper and lower triads in the octahedron results from: (1) the misfit between tetrahedral and octahedral sheets, specifically the increase in the O—Al—O angle (θ1) and the Al—O—Al angle (θ2) between connected oxygens/inner hydroxyl oxygens and Al, the O—Al—O angle (θ4) and the Al—O—Al angle (θ5) between the interlayer hydroxyl oxygens and Al, and a decrease in the octahedral co-edge O—Al—Oangle(θ3); (2) the decrease in θ1, θ2 and the increase in θ3 because of the repulsion between Al and Si; (3) restructuring caused by the bond angles in (1) and (2); (4) the special network structure of kaolinite. In addition, the shortening of the octahedral O-O co-edge and the approach of Al to the interlayer hydroxyl oxygen also result from effects (1)-(4). Octahedral flattening results from an increase in θ1, θ2, θ4 and θ5 and from a decrease in θ3. The interlayer hydrogen bonds inhibit tetrahedral basal oxygen corrugation, octahedral flattening and the counter-rotation of the upper and lower triads in the octahedron, but it has an opposite role during tetrahedral rotation. Furthermore, when the fluorine content is low (xF=0-0.7), an increase in the interlayer distance is not obvious with an increase in fluorine content and this confirms that ammoniumfluoride may not be necessarily involved in the hydration of kaolinite.

In the SDS/Tween60/hexanol/cyclohexane/water system, a conductivity maximum was observed in the conductivity (κ) and molar ratio of water to surfactants (W0) curves for mixed reverse micelles. The W0,max moved to a bigger W0 value as the xSDS (molar fraction of anionic surfactant) value increased. At xSDS≤0.5, the conductivity values that correspond with W0,max increased as xSDS increased; and at xSDS≥0.5, the conductivity values decreased. In the AOT/Tween60/cyclohexane/water system, the observed phenomenon was similar to the SDS/Tween60/hexanol/cyclohexane/water system. However, conductivity values that correspond with W0,max increased with increasing xAOT and there was no maximum value. The difference is mainly due to cosurfactant effects, which was confirmed by the SDS/TritionX-100/hexanol/cyclohexane/water system.

Cyclic aromatic oli amides are a new class of recently discovered shape-persistent macrocycles. These molecules are prepared in high yields based on a one-step macrocyclization strategy that relies on hydrogen bond-enforced folding of the corresponding uncyclized oli meric precursors. Macrocycle 1 is a member of a series of six-residue macrocycles dubbed cyclo[6]aramides and bears polar side chains derived fromtri(ethylene glycol) monomethyl ether. We investigated its self-assembly using multiple techniques including UV-Vis spectrum, dynamic light-scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM)，and atomic force microscopy (AFM). Results from these experiments demonstrated that 1 aggregates in apolar solvents such as 1,2-dichloroethane. As temperature increases, the supramolecular aggregates gradually disintegrate into molecularly dissolved species. For example, at 70 ℃, compound 1 exists mainly in its molecularly dissolved form. In mixed solvents consisting of od (dichloromethane) and poor (aromatic hydrocarbons) components, compound 1 aggregates into spherical assemblies. These self-assembling spheres were shown by studies on thermal stability and by TEM imaging to be solid balls instead of hollow vesicles. The formation of the microspheres was found to be dependent on the properties of the poor solvents as their formation was promoted in aromatic hydrocarbons and obliteratedin aliphatic and polar solvents. In aliphatic and polar solvents, macrocycle 1 was found to assemble into films.

The mixed micelle formation of binary cationic 14-s-14 gemini with conventional single chain surfactants was studied by conductivity measurements. The critical micelle concentration (cmc) and the degree of counterion binding values (g) of the binary systems were determined. The results were analyzed by applying regular solution theory (RST) to calculate micellar compositions (X), activity coefficients (f1, f2), and the interaction parameters (β). The synergistic interactions of all the investigated cationic gemini+conventional surfactant combinations were found to be dependent upon the length of hydrophobic spacer of the gemini surfactant. The excess Gibbs free energy of mixing was evaluated, and it indicated relatively more stable mixed micelles for the binary combinations.

Graphite oxide ( ) was prepared from graphite powder by Hummers'liquid oxidation method. The graphene nanosheets supporting Pd catalysts were prepared by a one-step chemical reduction method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements were used to characterize the particle size and crystallinity of the catalysts. The Pd nanoparticles were well dispersed on the surface of the graphene nanosheets with particle sizes of 3-5 nm. The electrocatalytic oxidation of ethanol was studied by electrochemically active surface area (EASA), cyclic voltammetry(CV), chronoamperometry(CA), and chronopotentiometry(CP) measurements. It was found that the Pd/graphene composites had better catalytic activity than the Pd/Vulcan XC-72 catalysts toward ethanol oxidation in alkaline media.

A series of Co1-xNixB alloy catalysts were synthesized in ethanol by chemical reduction in an ice-water bath. The catalytic hydrolysis of an alkaline NaBH4 solution was studied by changing the Ni content in the Co1-xNixB catalyst. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy revealed that the as-prepared Co1-xNixB alloys were ultrafine nanoparticles in amorphous form. Hydrogen generation measurements showed that the as-prepared Co1-xNixB alloys exhibited excellent catalytic activity. The hydrogen generation rate firstly increased as the Ni content increased in the Co1-xNixB catalyst, and it reached the highest at x=0.15, then decreased as x increased. The highest hydrogen generation rate at 298 K was 4228 mL·min-1·g-1 for Co0.85Ni0.15B during the catalytic hydrolysis of the alkaline sodium borohydride solution. The activation energies of the Co0.85Ni0.15B alloy and CoB were 31.87 and 34.25 kJ·mol-1, respectively. This showed that the Co1-xNixB alloys synthesized in ethanol had high activity.

Modified Ag/α-Al2O3 catalysts were prepared for the gas phase epoxidation of propylene by molecular oxygen. We used temperature-programmed desorption of oxygen (O2-TPD) to study the desorption behavior of oxygen from the catalyst's surface. Results showed that over the Ag/α-Al2O3 catalyst propylene was completely oxidized to CO2 and H2O. When the catalyst was modified with K2O, a small amount of propylene oxide (PO) was obtained. When the catalyst was modified with Y2O3, a very small amount of propanal and acetone was obtained. Adding 0.1% (w) Y2O3 to the Ag-K2O/α-Al2O3 catalyst significantly improved its catalytic performance for the gas phase epoxidation of propylene. Under reaction conditions of 0.1 MPa, 245 ℃, a feed gas of 20%C3H6/8%O2/72%N2 and gas hourly space velocity (GHSV) of 2000 h-1, the conversion of propylene was 4.0%and the selectivity to PO was 46.8%over the 20% (w)Ag-0.1%Y2O3-0.1%K2O/α-Al2O3 catalyst. O2-TPD showed that when the 20%Ag/α-Al2O3 catalyst was modified with Y2O3, K2O or Y2O3-K2O, the amount of adsorbed oxygen in the higher temperature region for the total oxidation of propylene decreased and the amount of adsorbed oxygen in the lower temperature region for the gas phase epoxidation of propylene was unchanged, which improves the selectivity to PO.

Microporous-mesoporous hybrid Ti-MCM-41(H) was successfully synthesized by the nano-cluster assembling method. ld nano-particles were prepared by the deposition-precipitation method. The samples were characterized by powder X-ray diffraction (XRD), nitrogen isothermal adsorption-desorption, Fourier transforminfrared (FT-IR) spectroscopy, diffuse reflectance UV-Vis (DR UV-Vis) spectroscopy, transmission electron microscopy (TEM) and inductively coupled plasma emission spectrometry (ICP-AES). The catalytic performance of the ld nano-particles was evaluated by the direct gas phase epoxidation of propylene using hydrogen and oxygen. Results revealed that the Ti-MCM-41(H) had a typical mesoporous MCM-41 structure. The results also suggested that isolated Ti(IV) was introduced into the siliceous framework of the support material. Superior catalytic performance was obtained with the ld catalyst supported on Ti-MCM-41(H) in which the Ti/Si molar ratio was 1%. Propylene conversion reached 5.4% at the initial 30 min with 74.2% propylene oxide (PO) selectivity and produced rate 73.1 g·h-1·kg-1. The conversion and PO selectivity were 4.9%and 67.3%after running 330 min on streamat 423 K.

Fe/CMK-5 composites were synthesized by chemical vapor deposition (CVD) using ferrocene as carbon precursor and SBA-15 as silica template. The composites were characterized by powder X-ray diffraction (XRD), N2 adsorption, thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). We found that the carbon in the composites existed as CMK-5, while the metallic Fe nanoparticles were homogenously embedded in the framework of mesoporous carbon. The textural parameters of the Fe/CMK-5 composites could be adjusted in a facile manner by changing the CVD duration time. The obtained Fe/CMK-5 composites were applied as adsorbents for the adsorption of lysozymes (Lzs) in the buffer solution at a pHof 11. The stabilities of the Lzs confined in the mesopores of the Fe/CMK-5 composites were investigated and the Lz leakage from the Fe/CMK-5 composite was also measured in buffer solutions with different pH values.

A detailed density functional theory (DFT) investigation revealed three possible mechanisms (redox mechanism, carboxyl mechanism, and formate intermediate mechanism) for the water-gas shift reaction on Au(111) surface. All the pertinent species (H2O, CO, OH, O, H, CO2, COOH, HCOO) were calculated. We obtained their preferred adsorption sites. We characterized the reaction pathway containing 14 elementary steps and calculated the reaction potential energy surfaces. The calculation results show that the carboxyl mechanism and the redox mechanism are feasible while the formate intermediate mechanism is unlikely because of its high formation barrier. Our calculations also show that the carboxyl mechanism is more probable compared with the redox mechanism and the most feasible reaction pathway is H2O→-H OH→+COCOOH→+OHCO2.

The effects of silver nanoparticles on the fluorescence properties of a [Ru(bpy)3]2+ complex bound to the surface of silver nanoparticles and an electrolyte effect were studied in this paper. Chain-like nanoparticle aggregates were formed due to bridging of [Ru(bpy)3]2+ on the surface of the silver nanoparticles. The fluorescence intensity of the [Ru(bpy)3]2+ complex was quenched and the larger size silver nanoparticles were found to be more efficient quenchers. The electrolyte ions allow the formation of large silver nanoparticles and aggregates in solution. The effect of electrolytes on the aggregates of silver nanoparticles decreases in the order: CaCl2>MgCl2>Ca(NO3)2>KCl>KNO3. As the electrolyte content increases, the fluorescence intensity initially decreases and then increases until it reaches a constant value. These results indicate that the electrolytes decrease the quenching effect. The effect of electrolytes on the fluorescence intensity of the [Ru(bpy)3]2+-Ag solution decreases as follows: Ca(NO3)2>CaCl2>MgCl2>KCl>KNO3. The effects of these electrolytes on the microstructure and fluorescence properties of the [Ru(bpy)3]2+ solution containing silver nanoparticles are discussed in terms of the interaction among the electrolytes and the energy transfer is investigated by transmission electron microscopy, UV-visible spectroscopy, and spectrofluorophotometry.

TiO2/ITO, TiO2-Zn/ITO and TiO2/ZnO/ITO films were prepared by ion-beamsputtering, and then further surface-sensitized with the Ru(phen)2(PIBH) complex (Rup2P) of Rup2P/TiO2/ITO, Rup2P/TiO2-Zn/ITO, and Rup2P/TiO2/ZnO/ITOby the spin-coating method. Surface photovoltage spectra (SPS) of the films revealed that SPS responses were present at 400-600 nm after surface-sensitization and the SPS intensity ratios between the peaks at 400-600 nm and 350 nm were different because of the different energy band structures in the TiO2-based films. The physical parameters and energy band structures of TiO2-based and Rup2P modified TiO2-based films were determined by electric field induced surface photovoltage spectroscopy (EFISPS). We found that the 400-600 nm SPS peaks of the Rup2P modified films came from the Ru 4d to phen π*1 and PIBH π*2 electron transitions. The Zn2+ doping level in TiO2-Zn benefits the injection of photogenerated electrons from the ligand levels to the conduction band. The TiO2/ZnO heterostructure favors electron transfer to the surface of ITO, which can enhance the SPS response in the visible light region (400-600 nm) as well as the photoelectron transformation efficiency.

Pyrimorph and its phenyl analog were prepared by chemical synthesis and their fungicidal activities were tested against P. infestans and P. capsici.We analyzed the structure of pyrimorph by X-ray diffraction method. Furthermore, the structure of pyrimorph and its phenyl analog were optimized by density functional theory using the 6-31G(2df, 2pd) basis set. Based on the calculated frontier molecular orbitals, Mulliken charges, natural bond orbital (NBO) analysis and surface electrostatic potential, the structure-activity relationships (SARs) of pyrimorph and its phenyl analog were discussed. The results show that when the phenyl ring is replaced by pyridine, hydrogen bond formation with a receptor molecule is favored due to the negative charge center of N in the pyridine ring. In addition, pyridine makes the electron-deficient aryl ring a better electron acceptor for π-πstacking. Considering the two above-mentioned factors, pyrimorph was found to bind more easily with the receptor and possessed better activity than its phenyl analog.

Self-consistent field theory is proposed to investigate equilibrium polymers adsorbed between two parallel plates. According to numerical results, the adsorption behavior of the equilibrium polymers can be classified into two regimes, viz. weak adsorption and strong adsorption. For strong adsorption, the apparent adsorption layers of the equilibrium polymers are observed from density profiles. Within this regime, the average chain length increases rapidly as the adsorption strength rising but the chain length distribution remains exponential. Compared with short chain equilibrium polymers, long chain equilibrium polymers are closer to the plates in the case of strong adsorption and are more concentrated in the middle of the gap in the case of weak adsorption. Given that the adsorption strength is weak, the forces applied to the plates are always repulsive for all separation distances. Widening the gap gives rise to a transition of the forces from repulsion to attraction if the adsorption is strong. Furthermore, the density profiles of the equilibrium polymers suggest competition among solubility, adsorption, and depletion. Higher solubility not only makes the density profiles more homogeneous but also decreases the pressures applied by the polymeric chains.

The adsorption and separation of a binary mixture of N2 and HFC-134a (1,1,1,2-tetrafluoroethane) on activated carbon fibers (ACFs) was investigated by experiment and the grand canonical Monte Carlo (GCMC) method. The effects of pore size, pressure and temperature on the selectivity of HFC-134a over N2 on ACF were investigated. Results show that the selectivity of HFC-134a decreases with an increase in pore size, pressure and temperature. The selectivity of HFC-134a on ACF with a pore size distribution reaches 62 at room temperature, indicating that our sample is an excellent candidate for the removal of HFC-134a from air. In particular, the selectivity of HFC-134a over nitrogen on ACF with pores of 0.75 nm in size can reach 230 at 0.41×105 Pa and room temperature. Therefore, carbon materials with small pores are recommended to adsorb HFC-134a efficiently.

The molecular mechanism of the conformational transition of amyloid peptide 42(Aβ42) inhibited by trehalose was studied using molecular dynamics simulation. It is confirmed that the conformational transition of Aβ42 is prevented by trehalose in a dose-dependent manner. In water and low-concentration trehalose (0.18 mol·L-1) solutions, Aβ42 transforms from its initial α-helix to a β-sheet. In 0.37 mol·L-1 trehalose, however, the conformational transition of Aβ42 is prevented. It is obvious that there is a hydration shell within about 0.2 nm from the closest atoms of Aβ42 on the peptide surface, which is caused by the preferential exclusion of trehalose. Trehalose molecules cluster around the peptide at a distance of 0.4 nm. In addition, the intra-peptide hydrophobic interactions are weakened and the number of long range contacts of Aβ42 is decreased by trehalose. Therefore, the hydrophobic collapse of the peptide is alleviated and the conformational transition is inhibited. These findings are important for the rational design of a highly efficient inhibitor for Alzheimer's disease.

In this paper, we introduced charge transfer of Si and O atoms for molecular dynamics simulation of SiO2. The effect of atomic charge transfer on vitreous silica simulation was investigated by Morse potential. Results show that atomic charge transfer not only affects the density of vitreous silica models, but also affects the interatomic nearest distance directly. The result comparison between the NPT and NVT ensembles indicates that the interatomic nearest-distances in the two ensembles are similar with the same atomic charge transfer but larger voids are found in the NVT model, which can account for the void structure in real glass. We clarify why simulations overestimate densities compared to experimental data. We also describe a better method of molecular dynamics modeling for vitreous silica. This method resolves the conflict between maintaining the interatomic nearest distance and keeping the model density as the atomic charge transfer changes. It also describes the long-range disordered structure of density non-uniformity and larger voids well. Furthermore, the result of atomic self-diffusion coefficient shows the significance of a larger void structure in the study of diffusion properties in vitreous silica.

A systematic equilibriummolecular dynamics study was performed to investigate the diffusion rates of gas molecules as a function of the pressure in metal-organic frameworks (MOFs) with different structures. Methane was chosen as the probe molecule. The self-diffusion coefficients in eight typical MOFs were calculated at roomtemperature. Combined self-diffusion coefficients with the contour plots of the center of mass (COM) probability densities of methane, the relationship between the diffusion rates of gas molecules and the structure of the pores in the MOFs is discussed. Results show that methane tends to adsorb in pockets in MOFs with pocket and channel pores (P-C materials) at low pressure. With an increase in pressure, the gas molecules move to the channel and the self-diffusion coefficient increases. However, the diffusion coefficient of methane changes a little in the low and middle pressure range in the IRMOFs (isoreticularMOFs) with only one kind of pore.With a further increase in pressure, the self-diffusion coefficient of methane decreases in all the studied MOFs. Therefore, the difference in diffusion rates of methane in different MOFs may be mainly attributed to the pore structures of the materials. In addition, diffusion rates of the gas molecules in the P-C materials could be controlled in a wide range by varying the pressure, providing useful information for the application of MOFs in gas storage and separation.

The phase transition of TiO2 from the rutile structure to the fluorite structure under pressure was investigated by the first principles plane-wave pseudopotential density functional theory method. The thermodynamic properties of the rutile and fluorite structures for TiO2 were obtained by the quasi-harmonic Debye model. The results obtained are in od agreement with the experimental data and other theoretical results. We found that the rutile-to-fluorite transition of TiO2 occurred at 47.74 GPa from the Gibbs energy calculations. Moreover, the dependence of the relative volume (V/V0 ), the Debye temperature (Θ) and the heat capacity (CV) on the pressure (p)as well as the heat capacity (CV) on the temperature (T) were also successfully obtained.

Density functional theory (DFT) with the B3LYP method and the SDDbasis set was selected to investigate small PbmTen (m+n≤6) clusters. The geometrical structures, average binding energy per atom (Eb), dissociation energy (△Ed), and the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were analyzed. An analysis of the average binding energy per atom and the dissociation energies indicate that the Pbn and Pb-rich clusters are respectively more stable than the Ten and Te-rich clusters. The HOMO-LUMO gaps of the studied PbmTen clusters are evidently moderate and within 1.87-3.55 eV, suggesting semiconductor-like behavior. PbTe clusters are more stable than the other mixed clusters.

Histone deacetylases (HDACs) have emerged as important anti-tumor targets in recent years. As HDACs comprise multiple isoforms and there are different physiological functions among various isoforms, the development of selective HDAC inhibitors has attracted a great deal of attention. This study focused on the discovery of selective HDAC1, HDAC8 inhibitors and specifically a homology model for HDAC1 was generated. A comparison was made between the HDAC1 homology model and the crystal structure of HDAC8, which showed that some active site residues were different from each other and these residues played important roles in the selectivity between HDAC1 and HDAC8. Two linear regression models were established based on the inhibitory activities against HDAC1, HDAC8 and the docking scores of 52 compounds. The developed linear regression models for HDAC1 and HDAC8 have non-cross validated correlation coefficients R2 of 0.82 and 0.80, respectively, which indicates that the results are statistically significant. These models were used to predict the activities of the synthesized compounds and these prediction results can provide further insights into the selectivity of HDAC1, HDAC8.

The interactions of myoglobin (Mb) and its mutant Mb(D60K) with two surfactants were studied using stopped-flowfluorescence spectroscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy, fluorescence spectroscopy, and circular dichroism(CD) spectroscopy. The Mb external asparagine 60 into lysine, stopped-flow fluorescence results showed that the interactions of different concentrations of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) with Mb and Mb(D60K) were all quasi-first order reactions. Although Mb(D60K) was simply altered, the remarkable differences observed indicated that amino acid 60 influences the protein function greatly. Furthermore, results fromUV-Vis spectroscopy, fluorescence spectroscopy and CD spectroscopy all indicated that the configurations and functions ofMb andMb (D60K) were changed by the surfactants. The data indicates that Mb and its mutant exhibit different adaptabilities and stabilities in the surfactant solutions. From a comprehensive and comparative data analysis, we determined that the mutant D60K has more stable and adaptable functional and structural properties.

The effects of various concentrations of toad bufanolide diene (BD) on the growth of Tetrahymena thermophila BF5 were investigated by means of a thermal activity monitor (TAM) system. The extent and duration of toxic effects on metabolismwere evaluated by studying the growth rate constant (k), maximumheat-output power (Pmax) and half inhibitory concentration (IC50). Experimental results showed that the values of k and Pmax decreased as the concentrations of BDincreased. Furthermore, the growth rate constant (k) was linked to the concentration of BD: rcinobufagin=0.9910 (IC50=119.2 μg·mL-1); rbufalin=0.9923 (IC50=106.14 μg·mL-1); rbufotalin=0.9977 (IC50=73.80 μg·mL-1); rgamabufotalin=0.9923 (IC50=54.75 μg·mL-1). The sequence of toxicity for the four BDs was: gamabufotalin>bufotalin>bufalin>cinobufagin. The α-hydroxy group at C11, β-hydroxy group at C14, β-acetoxy at C16 and the non-dehydrolysis between C14 and C15 can possibly improve the toxicity of BD towards Tetrahymena thermophila BF5.

FeCl3 and NaOH were used as raw material and precipitator respectively to prepare a spherical Fe(OH)3 intermediate by chemical precipitation. FeCl2 and other precipitators (Na2CO3, NH3·H2O and NaOH) were also used to prepare shape-controlled intermediates via co-precipitation. The intermediates were then covered with a citric acid and Sr complex by the citrate acid method. Spherical, spindly and rod-like nano-SrFe12O19 particles were obtained after calcination of the covered precursors. The shape-controlled nano-SrFe12O19 particles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and the magnetic properties of the samples were studied using a vibrating sample magnetometer (VSM). Results showed that the type of ferric salt and the alkalinity of the precipitator greatly influenced the phase of the intermediate and the morphology of the SrFe12O19 particles. Spherical nano-SrFe12O19 particles were obtained when Fe3 + was used as a raw material, and shape-controlled nano-SrFe12O19 particles were obtained when Fe2+ was used as a raw material together with precipitators of different alkalinity. The slenderness ratio and shape-anisotropy of the samples increase as the alkalinity of the precipitator increases. The coercivity (Hc) of SrFe12O19 is mainly dependent on the anisotropy of the particle. The coercivity and the saturation magnetization (Ms) of SrFe12O19 increase as the anisotropy of the samples increases. The coercivity and the Ms of the rod-like SrFe12O19 particles obtained using FeCl2 and NaOH were optimal 458.2 kA·m-1 and 64.2 A·m2·kg-1, respectively.

We used thermal diffusion to load SnO2 into ZSM-5 crystals as it is regarded as a od host material for semiconductor guest encapsulation. The experiments were carried out at 750 and 850 ℃in air. A series of tests were conducted to investigate the basic physical chemistry properties such as chemical composition, crystal images, crystal phase and photoluminescence. An intense porosity analysis based on density functional theory was used to investigate the pore texture of the SnO2-loaded samples. We demonstrate that the SnO2 clusters are located within ZSM-5 instead of on the surface of the crystals. The SnO2 content increases as the thermal diffusion temperature rises. The SnO2 clusters are mainly distributed within the ZSM-5 channels. The sample with a low SnO2 content at 750 ℃ possesses od visible light transmittance and displays od photoluminescence behavior, which makes it a promising material for functionalization and for device-based applications.

Amino-functionalizedH2N-Zr-Ce-SBA-15 (H2N-ZCS)mesoporousmaterialswith unique hexa nal platelet morphologies and short channels were synthesized by a post-grafting method using [1-(2-amino-ethyl)-3-aminopropyl] trimethoxysilane (AAPTS) and tetraethyl orthosilicate (TEOS) as a silica source, zirconyl chloride and cerous nitrate as precursors, and pluronic P123 triblock copolymer as a structure directing agent. The as-synthesized materials were characterized by low-angle X-ray diffraction (LXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TG), and N2 adsorption/desorption isotherms. Characterization revealed that the functionalized H2N-ZCS mesoporous materials have unique hexa nal platelet morphologies with short channels and they possess a highly ordered two-dimensional hexa nal mesoporous structure similar to conventional SBA-15. The uptake of anionic dye onto the organic functionalized H2N-ZCS and H2N-SBA-15 were compared. The results demonstrate that H2N-ZCS materials have higher adsorption rates and adsorption capacities compared with H2N-SBA-15. The resultant H2N-ZCS materials with short channels are superior to conventional SBA-15 in terms of fiber morphology facilitating molecular diffusion when used in adsorption, separation, and catalytic processes.

Low-density alumina aerogel/silica fiber composites were prepared by sol-gel technology and an atmospheric pressure drying method with N,N'-dimethylformamide (DMF) as a drying control chemical additive. The variation of pore structure and specific surface area were compared with alumina aerogel without adding silica fiber based on the nitrogen adsorption-desorption method. The changes in phase structure during the heating process were characterized by X-ray diffraction. The micro-morphology of the alumina aerogel and its composites were studied in detail by scanning electron microscopy and transmission electron microscopy. The influence of DMF on the aerogel matrix is discussed. We found that the fabricated bulk composites are a close combination between alumina aerogel and silica fiber. The silica fiber improves the phase transition temperature of the alumina aerogel. An appropriate amount of DMF is helpful for the formation of a uniformgel network, thus decreasing the drying shrinkage pressure.

Polypropylene (PP) microporous membranes were successfully prepared by swift heavy ion irradiation and track-etching. Polypropylene foils were irradiated with 197Au ions of kinetic energy 11.4 MeV·u-1 (total energy of 2245.8 MeV) and fluence 1×108 ions·cm-2 at normal incidence. The damaged regions produced by the ld ions along the trajectories were etched in H2SO4 and K2Cr2O7 solutions leading to the formation of cylindrical pores in the membranes. The pore diameters of the PP microporous membranes increased from 380 to 1610 nm as the etching time increased from 5 to 30 min. The surface and cross-section morphologies of the porous membranes were characterized by scanning electron microscopy (SEM). The micropores in the membranes were found to be cylindrical in shape, homogeneous in distribution, and equal in size. Some mathematical relations of the porosity of the PP microporous membranes were established by analytic derivation. The microporous membranes were used in lithium-ion batteries to measure their properties as separators. The electrical conductivity of the porous membrane immersed in liquid electrolyte was found to be comparable to that of commercial separators by electrochemical impedance spectroscopy (EIS). The results showed that the porosity and electrical conductivity were dependent on the ion fluence and etching time. By adjusting these two factors, microporous membranes with od porosity and electrical conductivity were made that met the requirements for commercial use.