Non-doped red-emitting electrofluorescent single-layer organic light-emitting devices based on an ambipolar small molecule, 4,9-bis(4-(2,2-diphenylvinyl)phenyl)naphtho[2,3-c][1,2,5] thiadiazole (BDPNTD), were studied. A WO3 or MoO3 buffer layer with an optimized thickness of 1 nm was used and the single-layer device has a low turn-on voltage (2.4 V) and a high luminance (4950 cd·m-2). The maximum emission wavelength was at about 636 nm and the CIE coordinates are at about (0.65, 0.35). We confirmed that the WO3 or MoO3 buffer layer can improve hole injection at the ITO/ BDPNTD interface and it creates a hole-electron balance in these devices.

Novel branched acrylamide-based copolymers (PAE) were synthesized by an aqueous free radical copolymerization technique using acrylamide (AM), sodium 2-acrylamido-2-methylpropane sulphonate (NaAMPS) and p-vinylbenzyl-terminated octylphenoxy poly(ethylene oxide) (VE, polymerization number: 18) to improve the poor salt resistance of the oil-flooding polymer at high salt concentrations. The PAE polymer was characterized with Fourier transform infrared (FT-IR) spectroscopy and proton nuclear magnetic resonance (1H-NMR). The PAE brine solutions exhibited salt-thickening twice and heat-thickening twice over the ranges of NaCl concentration and temperature. For 2.0 g·L-1 PAE containing 0.93%(molar fraction) VE, the apparent viscosities of 5.0 and 90.0 g·L-1 NaCl solutions were 1167.0 and 338.0 mPa·s at 30 ℃, respectively. This showed the excellent thickening property and salt resistance of the polymer. The apparent viscosity of the 5.0 g·L-1 NaCl solution was still up to 685 mPa·s at 85 ℃, which exhibited od heat resistance of the polymer. Moreover, the polymer showed od surfactant and interfacial activities. The scanning electron microscope (SEM) morphologies showed that unique associated structures were formed for PAE in water and continuous network structures were still formed in the brine solution of PAE. Results indicated that the extense polymer chains in water were still able to expand comparatively in the brine solution.

Magnetic field (MF) and the mass ratio of a co-surfactant and a surfactant (Km=mn-butanol/mSDBS) on effects the phase behavior, conductivity, and micro-emulsification of the microemulsion system during aniline polymerization were investigated by a pseudo-ternary phase diagram of sodium dodecyl benzene sulfonate (SDBS)/n-butanol/aniline/H2O. Our results show that with an increase in alcohol content, the area of the microemulsion region increased initially and then decreased. This area reached a maximumat a Kmof 1.0 and increased under the influence of a MF. Characterization of the pseudo-ternary phase diagram was undertaken by an analysis of the solution conductivity as the water content varied in the presence of a MF. Transmission electron microscopy (TEM) indicated the particle-size of the polyaniline (PAn), which polymerized in the presence of the MF, was much smaller than that of the PAn polymerized in the absence of the MF.

The fast thermolysis of 3,4-dinitrofurazanfuroxan (DNTF) at 0.1-0.4MPa was investigated by temperature-jump Fourier transform infrared (T-jump/FTIR) spectroscopy. All tests were carried out using a heating rate of 1000 ℃·s-1 at 800 and 1000 ℃. Structures and concentrations of the gaseous products were obtained in situ and in real time by fast scanning FTIR. Results showed that the relative molar concentrations c*of the main gaseous products (CO, CO2, NO and NO2) that were released by the thermolysis of DNTF were related to pressure and temperature. The relative molar concentration ratios of c*NO /c*NO2 changes as the temperature and pressure change. These results reveal that the two competitive reactions of C—NO2 homolysis (to form NO2) and isomerization (to form NO) may occur during the fast thermolysis of DNTF. NO formation from the cracking of furazan or furoxan rings may be limited by pressure. Heterogeneous gas/condensed phase and homogeneous gas phase reactions may occur in the secondary and tertiary class reactions of the fast thermolysis of DNTF because the relative molar concentrations of c*CO and c*CO2 increase and the relative molar concentration ratios of c*CO /c*CO2 decrease with increasing pressure.

Comparison study between Mg2+ and Ca2+ adsorption kinetics, as influenced by different particle surface potentials, was investigated by the miscible displacement technique. In this study, important new features of ion adsorption were discovered. (1) The initial stage of experiment the adsorption process had zero-order kinetics because of strong adsorption. First-order kinetics then resulted because of weak adsorption and the transition point from zero-order to first-order kinetics was very sharp for each system. (2) At equivalent supporting electrolyte concentrations, the adsorption rate of Ca2+ is obviously faster than that of Mg2+，and the equilibrium adsorption capacity of Ca2+ is more than that of Mg2+. The coverage of Ca2+ on the solid soil particle's surface is also higher than that of Mg2+. (3) The differences between the relative effective charge coefficient and the surface electrochemical properties are the reason why the Ca2+, Mg2+ adsorption kinetics are different. (4) We also determined some important properties of the adsorbed ions such as the rate coefficients, the adsorption quantities, the surface coverage of the adsorbed ions and the distributed space in the fixed liquid film of the adsorbed ions. These parameters allow a future quantitative evaluation of the effects of different colloid surface potentials on the ion diffusion/adsorption kinetics.

A ternary Sn-Co-Zn alloy film was successfully prepared by electrodepositi on copper foil. Electrochemical deposition of the Sn-Co-Zn alloy was studied by cyclic voltammetry (CV) and chronoamperometry (CA). The structure and electrochemical performance of the electroplated Sn-Co-Zn alloy electrodes were also investigated in detail. The CV and CA results revealed that the initial deposition kinetics of the Sn-Co-Zn alloy corresponds to a model that includes a three-dimensional progressive nucleation and diffusion controlled growth. XRD results showed that the electrodeposited Sn-Co-Zn alloy consists of CoSn3, Co3Sn2, and Zn phase. Electrochemical tests indicated that at the first cycle, the discharge capacity (desertion) and columbic efficiency are measured 751 mAh·g-1 and 88%, respectively, at the 30th cycle, the Sn-Co-Zn alloy electrodes still delivered a discharge capacity of 510 mAh·g-1. The od lithium storage performance of the Sn-Co-Zn electrode is ascribed to multi-phase structure of the electrode.

The layerd cathode materials LiNi1/3Co2/3-xAlxO2 (x=1/12, 1/6, 1/3, 1/2, 7/12) for lithiumion battery has been successfully synthesized using eutectic lithium salts of 0.38LiOH·H2O-0.62LiNO3 mixed with Ni1/3Co1/3Al1/3(OH)2 as a precursor. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical performance tests. Results show that the LiNi1/3Co2/3 -xAlxO2 can be maintained as a well-layered α-NaFeO2 structure in the range of 1/12≤x≤1/3. At x>1/3, a miscellaneous phase is present. The LiNi1/3Co1/3Al1/3O2 products have the highest crystallinity, the least cation mixing effect and the most uniform particle size with a tap-density of 2.88 g·cm-3. Additionally, the initial discharge capacity of the product was 151.5 mAh·g -1 and after 50 cycles, 91.4%of the initial discharge capacity was maintained. The reversible capacities of the products are 133.7 and 120.9 mAh·g-1 at 1C and 2C discharge rates, respectively.

A novel lithium-ion battery cathode material, nano-LiVOPO4, was synthesized by a new rheological phase method. The microstructure, surface morphology, and electrochemical properties were characterized by various electrochemicalmethods in combination withX-ray diffraction (XRD) and scanning electron microscopy (SEM). Results show that the orthorhombic LiVOPO4, obtained by this rheological phase method, is made up of 10-60 nm particles. The first discharge capacity, charge capacity, and columbic efficiency of LiVOPO4 were found to be 135.7 mAh·g-1, 145.8 mAh·g-1, and 93.0%, respectively. After 60 cycles, the discharge capacity remained 134.2 mAh·g-1, at 98.9% of the first discharge capacity, and the capacity loss per cycle was only 0.018%at 0.1C (1C=160 mA·g-1).More than 96.5% and 91.6% of the discharge capacity at 0.1C were maintained at 1.0C and 2.0C, respectively. The charge transfer resistance increased with the increase of the cycle number and the diffusion coefficient of lithium ion in the nano-LiVOPO4 was in the order of 10-11 cm2·s-1. Experimental results suggest that the rheological phase method is a od route for the synthesis of LiVOPO4 cathode material of high capacity, od cycling performance, and od current rate capability for lithiumion batteries.

We prepared 3-methyl benzothiazoliumiodide (MBTI) and 2,3-dimethyl benzothiazoliumiodide (DMBTI) by a quaternization reaction of benzothiazole/2-methyl benzothiazole and iodomethane using Teflon-lined, stainless steel autoclaves. The influence of the 2-position methyl group of the benzothiazolium heterocycle on the thermal stability and melting point of benzothiazolium iodides was studied by thermogravimetric analysis and differential scanning colorimetry. The relationship between I-3/I- redox behavior in solution and the Pt counter electrode/solution interface with the benzothiazolium structure was investigated by cyclic voltammetry using a Pt disk ultramicroelectrode and electrochemical impedance spectroscopy (EIS). Dye sensitized solar cells (DSCs) with MBTI and DMBTI were then assembled. The preparation of the benzothiazolium iodides is simple with short reaction time, easy purification, and high yields. Compared with MBTI, DMBTI has a higher melting point and excellent thermal stability. DSCs with an electrolyte solution composed of 0.1 mol·L-1 I2, 0.1 mol·L-1 LiI, 0.6 mol·L-1 1-methyl-3-propylimidazolium iodide (MPII), and 0.3 mol·L-1 DMBTI in γ-butyrolactone gave a short circuit photocurrent density of 16.91 mA·cm-2, an open circuit voltage of 0.65 V and a fill factor of 0.57. This corresponds to a photoelectric conversion efficiency of 6.28% at the illumination (air mass 1.5, 100 mW·cm-2).

Highly porous yttria stabilized zirconia (YSZ) supported dense (ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 (10ScSZ-1CeO2) bilayers were fabricated by removing NiO with a reduction-acid leaching method using NiO-YSZ/10ScSZ-1CeO2 half cells that were prepared by dry-pressing. By allowing Ce and Cu nitrate solutions to infiltrate the porous YSZ matrix, single cells of Cu-CeO2-YSZ/10ScSZ-1CeO2/LSCF (LSCF: La0.6Sr0.4Co0.2Fe0.8O3-δ) were fabricated. The cell's structure was characterized by X-ray diffractometry (XRD) and field-emission scanning electron microscopy (FESEM). Results showed that the porous YSZ matrix of the YSZ/10ScSZ-1CeO2 bilayers prepared by the reduction-acid leaching method was of high porosity (more than 64%) and it was highly connected, which was beneficial for the introduction of Ce and Cu nitrate by infiltration. The 10ScSZ-1CeO2 electrolyte filmwith a thickness of 30 μm was dense and pinhole-free. A single cell composed of Cu-CeO2-YSZ/10ScSZ-1CeO2/LSCF showed excellent generation performance with maximum power densities of 0.29 and 0.09 W·cm-2 at 650 ℃, as well as 0.48 and 0.21 W·cm-2 at 700 ℃using moist hydrogen and methane as fuel, respectively. This excellent performance is attributed to the electrolyte's small ohmic resistance, small cathode polarization resistance, and favorable anode microstructure.

Fe-triethonolamine (Fe-TEA) complexes as mediator are well suitable for the indirect reduction of indi . In our work, the reduction of indi was investigated in a Fe-TEA systemby cyclic voltammetry (CV). The electrocatalytic performance of four kinds of cathode materials (graphite, silver, nickel, and stainless steel) for the reduction of Fe(III)-TEA was compared. Further experiments were carried out to compare the effects of operating parameters including temperature, current, concentrations of NaOH and Fe(III)-TEA. Experimental results showed that this new route was feasible for the production of water-soluble indi . A high current efficiency (44.7%) was achieved using optimized conditions and the concentration of the Fe(III)-TEA mediator was found to be the main influence. A new indi radical mediator was formed during electrolysis and under certain condition, the effect of this indi radical on the current efficiency was larger than that of Fe(III)-TEA.

316L stainless steels are the most promising materials for use as bipolar plates in proton exchange membrane fuel cells (PEMFC) because of their low cost, light weight, convenience of machining, ease of shaping into thin sheets, excellent electrical conductivity, and their heat exchange properties. However, the interfacial contact resistance (ICR) between carbon paper and stainless steel was found to increase because of passive film formation in a PEMFC cathodic environment. Additionally, the catalyst was poisoned by the corrosion products of the bipolar plate in the PEMFC anodic environment and the output power of the cell decreased. We added a conductive graphite coating onto the surface of 316L stainless steel and found the ICR of the sample reached 80.6 mΩ·cm2. The ICR was only 19.8 mΩ·cm2 when a thin layer of silver was present between the 316L stainless steel and the graphite layer. Various electrochemical tests, such as Tafel curves and oxidation curves using steady potential, were used to study the corrosion behavior of the three samples (316L stainless steel, silver-plated 316L stainless steel, silver-plated and graphite-coated 316L stainless steel) in PEMFC environments. Results showed that compared to 316L stainless steel, the corrosion potential of the silver-plated and graphite-coated 316L stainless steel increased by 0.49 and 0.35 V, respectively and the corrosion current density decreased to 10 -6-10 -7 A·cm-2. The silver-plated sample was easily damaged as small holes in the silver-layer allowed parts of the stainless steel substrate to be exposed.

We electropolymerized polypyrrole (PPy) films doped with para-toluene sulfonate (pTS-) and dodecyl sulfonate (DS-) by a galvanostatic method. The influence of potential and overpotential process on the electrochemical properties of the PPy films in NaCl aqueous solution were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In addition, the influence of insertion with or without ions on the PPy films was also studied by the EIS of PPy inserted with or without Na+ or Cl- ions in specially prepared aqueous solutions. Results showed that the ionic conductivity and the capacitance of the PPy films increased after the first CV and the electronic conductivity of the PPy/pTS increased after the insertion of Cl- ions. However, PPy films inserted with or without Na+ ion showed little difference in the EIS of the PPy films. Furthermore, the ion conductivity was affected by a change in the microstructure of the PPy films with or without ions which was also apparent in the EIS.

A novel zinc (II) coordination polymer {[Zn(C10H6O6S2)(C3H4N2)2(H2O)]·2H2O}n was synthesized by reacting ZnO, 1,5-naphthalenedisulfonic acid, and imidazole in H2O/MeOH solution. It was characterized by elemental analysis, infrared (IR) spectroscopy, 1H nuclear magnetic resonance (1H NMR) spectroscopy, and thermogravimetric analysis (TGA). The crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system with a P1 space group, and the crystallographic characteristics of the compound are: a=0.85313(19) nm, b=1.0253(2) nm, c=1.3357(3) nm, α=100.653(2)°, β=100.135(3)°, γ=108.859(2)°, V=1.0511(4) nm3, Dc=1.712 g·cm-3, Mr=541.85, Z=2, F(000)=556, μ=1.425 mm-1. The zinc ions are bridged by naphthalene-1,5-disulfonate anions, which forms a neutral two-dimensional (2D) coordination polymer. Hydrogen bonds that are generated by water molecules between the layers connect the layers to form a three -dimensional (3D) supramolecular structure. A theoretical investigation of the title complex as a structural unit was carried out using Gaussian 03W. The distribution of charges and the composition of the frontier molecular orbitals provided confirmation about the coordination
geometry of the crystal structure.

The preparation of avermyctin emulsions in water was achieved by mixing the surfactants polyoxyethylene (10) octylphenyl ether (OP10), polyoxyethylene styrenated phenol ether (602), and polyoxyethylene (40) castor oil ether (EL-40) with polyoxyethylene (20) castor oil ether (EL-20), separatively. Emulsion stability was investigated by analyzing the hydrophile-lipophile balance (HLB), critical micelle concentration (cmc), and surface tension. Then, the surfactants of polyoxyethylene polyoxypropylene styrenated phenol ether (1601), block copolymer (L64), and octyl phenyl polyoxyethylene phosphonate (A) were added to the emulsion made by blending EL-40 and EL-20, separatively. The stability of the emulsions was investigated further and discussed in terms of droplet size, surface tension, and zeta potential. Results showed that the blend of EL-40 and EL-20 resulted in a relatively stable emulsion because of its lower surface tension. The addition of 1601 and L64 improved the stability of the emulsion to some extent, while A greatly enhanced the stability because it markedly decreased the droplet size and the surface tension while increased the zeta potential.

In this paper, the interaction between a dendrimer, composed of G1 (generation 1.0) poly(amidoamine) (PAMAM) and branched with poly(propylene oxide) (PPO)-poly(ethylene oxide) (PEO), and sodium dodecyl sulfate (SDS) was investigated by turbidity titration, dynamic light scattering (DLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Interestingly, at low concentrations of added SDS far from the critical micelle concentration (cmc), the system with the dendrimer at 1%(mass fraction) exhibited higher turbidity, indicating that the aggregates grew larger and this was confirmed by DLS, TEM, and AFM. It is mainly due to the strong interaction between the dendrimer and the SDS molecules, as well as the formation of a dendrimer-SDS complex. With a SDS concentration of more than 0.1 mmol·L-1 (about 1%of the cmc), the variation of turbidity value was not obvious mainly because the aggregate size tended to be constant observed from DLS, TEM, and AFM. As the concentration increased further (0.25 and 0.5 mol·L-1), self-aggregation of the SDS molecules or aggregation of the monomolecular dendrimer that interacted with the multimolecular SDS occurred in the system.

The dilational rheological properties of five types of surfactants: sodium 3,4-dihexylbenzene sulfonate (66), sodium 3,4-diheptylbenzene sulfonate (77), sodium 2-ethyl-4,5-dihexylbenzene sulfonate (266), sodium 2-propyl-4,5-dihexylbenzene sulfonate (366), and sodium 2-butyl-4,5-dihexylbenzene sulfonate (466) at the air-water and decane-water interfaces were investigated by a drop shape analysis method. The influence of hydrophobic chains located at different positions on the benzene ring on the interfacial molecular behavior was investigated. Experimental results showed that the hydrophobic chains that were located at different positions affected the dilational elasticity and dilational viscosity differently. The dilational elasticity appeared to increase with an increase in the length of the hydrophobic group and the dilational viscosity behaved differently. The short alkyl chain (2-4) ortho to the sulfonate group had little influence on the dilational viscosity, while an increase in the long meta alkyl group played an important role in the surface relaxation process, which resulted in higher surface dilational viscosity. The insertion of decane molecules from the oil phase weakened the strong interactions between the meta-alkyl chains and therefore the interfacial dilational parameters were obviously lower than those of the surface. We also found that the interfacial dilational viscosities of a pair of structural isomers, 77 and 266, were approximately equal.

We used a surface tension method to investigate the thermodynamic properties of micellization in aqueous solution for several alkyl aryl sulfonates that were synthesized in our laboratory. The influence of temperature and molecular structure on the micellization is discussed. Results show that the micellization of alkyl aryl sulfonates in aqueous solutions is spontaneous and entropy-driven. As the temperature rises, the micellization is easy initially but then becomes more difficult. The contribution of entropy change to the change in Gibbs free energy tends to decrease but the contribution of enthalpy change to the change in Gibbs free energy tends to increase. The micellization is enthalpy-entropy compensated. The compensation temperature (Tc) is found to be (306±2) K, which is independent of the molecular structure of the alkyl aryl sulfonates. The formation ability and the stability of the micelles increase when the carbon atoms of the short or long alkyl chains on the aromatic rings increase, but decrease as the aromatic rings shift fromthe edge to the middle of the long carbonic chains.

Polymer/inorganic hybrid materials were prepared by supercritical carbon dioxide (scCO2) impregnation. Tetraethyl orthosilicate (TEOS) was infused into polypropylene (PP) strips in scCO2 using ethanol as the co-solvent. The effect of this co-solvent on mass uptake was investigated. We found that the mass uptake of TEOS into PP strips increased to a maximum and then decreased after the addition of more co-solvent. The effects of other impregnation conditions on the mass uptake were also investigated with using ethanol. Moreover, the depth profile of the infused elements inside the polymer/inorganic hybrid material was obtained by Rutherford backscattering spectrometry (RBS). The RBS spectrum demonstrated that the concentration of Si in the PP strips was not uniform and decreased with infusion depth.

Chitosan films were prepared by wet casting followed by natural withering (NW), vacuum drying (VD), and infrared drying (ID). Atomic force microscope (AFM) was used to study the effects of these three drying methods on the microstructural and micromechanical properties of the chitosan films. Results showed that VD and ID effectively enhanced the planeness and evenness of the chitosan films. The average roughness of the VD films ((5.47±1.34) nm) and the ID films ((2.79±0.93) nm) were lower than that of the NWfilms ((30.67±8.06) nm). The adhesion force of the ID films ((2595.0±68.5) pN) was larger than that of the NWfilms ((982.6±149.3) pN) and the VD films ((1817.9±279.2) pN). The Youngs modulus of the ID films ((158.8±15.2) MPa) was less than that of the NW films ((204.3±22.7) MPa) and the VD films ((195.8±14.6) MPa).

TiO2-graphite oxide (TiO2- ) composites were successfully prepared at low temperature (80 ℃) using graphite oxide ( ) and titanium sulfate (Ti(SO4)2) as initial reactants. The photocatalytic properties of TiO2- under UV light irradiation were also studied. Results show that the degradation rate of methyl orange is 1.17 mg·min-1·g-1 (referring to the efficiency of the initial 15 min). Compared with Degussa P25 powders, this intercalation composite is far more efficiently. In addition, the crystalline structure, interface status and microscopic structure of TiO2- were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FESEM). Result showed that the TiO2 crystallites in the intercalated structure were composed of anatase and rutile phase with the former phase being enriched. The functional groups present in such as carboxyl (C=O) were mostly reduced in the intercalation composite. On the other hand, the synthesis mechanism and the main reasons responsible for the superior photocatalytic properties of TiO2- are also discussed.

TiO2/ZnO and N-doped TiO2/ZnO composite nanotube arrays were synthesized by the sol-gel method using ZnOnanorod arrays as a template. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance UV-Vis spectroscopy (UV-Vis) were used to characterize the samples. The nanotubes had a uniform hexa nal shape. The diameter and wall thickness of the nanotubes were about 100 nm and 20 nm, respectively. Some N dopants were substitutionally doped into the TiO2 lattice, while the N-Ox, N-C, and N-N were chemically absorbed onto the surface of the TiO2/ZnO composite nanotubes. Dopant-induced narrowing of the bandgap resulted from the doping of N ions into the TiO2 lattices. The surface N species enhanced the visible-light response and promoted the separation of photogenerated carriers. Compared with the TiO2/ZnO composite nanotube arrays, the N-TiO2/ZnO composite nanotube arrays exhibited higher photocatalytic activity.

Ball milling was used with ethanol as a milling aid agent to shorten the carbon nanotubes (SCNT) from 5-15 μmto ca 200 nm. We prepared a platinum catalyst Pt/SCNT and a platinum ruthenium alloy catalyst PtRu/SCNT using the shortened nanotubes as supports by a colloidal method. We found that Pt/SCNT showed much higher activity than Pt/CNT during the anodic oxidation of methanol. The peak current density for Pt/SCNT was 1.4 times as high as that of Pt/CNT and it was also much higher than that of the commercial Pt/C catalyst. Furthermore, we found that PtRu/SCNT showed higher activity than that of Pt/SCNT and PtRu/C catalysts. The results of X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), and the specific surface area (BET) method. revealed that the crystal structure of the nanotubes did not change before or after shortening whereas the special surface area and the electrochemical activity increased significantly.

A ruthenium phosphine diamine complex RuCl2[(S)-P-Phos]-[(S)-DAIPEN] [P-Phos: 2,2',6,6'-tetramethoxy-4,4'-bis(diphenylphosphino)-3,3'-bipyridine, DAIPEN: 1,1'-di(4-anisyl)-2-iopropyl-1,2-ethylenediamine] for the asymmetric hydrogenation of aromatic ketones has been studied. The influences of different bases , (CH3)3COK concentration, organic solvent, and molar ratio of substrate to catalyst on activity and enantioselectivity were investigated. Under the following optimum conditions: n(ketone):n(KOH):n(catalyst)=1000:20:1, pH2=2 MPa and T=30 ℃, the conversion of acetophenone and the enantioselectivity (ee) of S-1-phenylethanol was 100% and 88.5%, respectively. Additionally, the ee value of 2'-bromophenyl ethanol was 97.1%.

Supported niobium pentoxide materials are effective catalysts for a variety of reactions. Nb2O5/γ-Al2O3 catalysts with different Nb2O5 loadings were prepared by aqueous solution impregnation using niobium oxalate as a precursor on γ-Al2O3. The samples were characterized with respect to the dispersion state of the niobium oxide species on γ-Al2O3 by X-ray power diffraction (XRD) and laser Raman spectroscopy (LRS). The nature of the surface acidity was investigated using Fourier-transform infrared spectroscopy of pyridine adsorption (Py-IR). The catalytic activity of the as-prepared catalysts was evaluated by the condensation reaction of iso-butene (IB) and iso-butyraldehyde (IBA) to form 2,5-dimethyl-2,4-hexadiene (DMHD). Results reveal that the dispersion capacity (ΓNb) of Nb on γ-Al2O3 is about 7.6 μmol·m-2. This value is almost identical to the density of the octahedral vacant sites of the preferentially exposed (110) plane (7.5 μmol·m-2) on the surface of the γ-Al2O3 support. Additionally, the“incorporated model”suggests that Nb5+ cations are located on the vacant sites of the (110) plane on γ-Al2O3. These results suggest that isolated niobia (NbOx) species are present and are bound to the surface of the γ-Al2O3 support through Nb—O—Al bonds at a loading well below that corresponding to monolayer dispersion. This is consistent with the result from LRS. The formation of isolated NbOx species, which binds to the surface of the support through Nb—O—Al bonds, causes a decrease in the amount of surface Lewis acid sites (LAS) on the Nb2O5/γ-Al2O3 catalysts. With an increase in Nb2O5 loading, polymeric NbOx species are formed by the Nb—O—Nb bridging of neighboring isolated NbOx species and Bronsted acid sites (BAS) are generated. We found that the catalytic activity towards the condensation reaction of IB and IBA to form DMHD increased because the amount and strength of the Bronsted acid sites increased as the number of polymeric niobia species increased. When the loading exceeds the monolayer dispersion capacity, the catalytic activity (turnover frequency (TOF) of DMHD) decreased because of the formation of the three-dimensional NbOx species. Additionally, the selectivity of DMHD decreased because of an increase in the strength of the Bronsted acid sites. We suggest that the strength of the Bronsted acid sites are related to the state of NbOx on the surface of the Nb2O5/γ-Al2O3 catalysts.

β-BaB2O4 (β-BBO) nanorods, rare earth ion Er3+ doped (β-BBO:Er3+) and Er3+, Ce3+/Ce4+ co-doped (β-BBO:Er3+/Ce3+/Ce4+) nanorods were synthesized by the cetyltrimethylammoniumbromide (CTAB) assisted hydrothermal method using Ba(NO3)2, NaBH4, Er2O3, and CeO2 as raw materials. The as-prepared products were studied by X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and photoluminescence (PL) spectroscopy. Results indicate that the structure of the β-BBO nanorods doped with Er3+, Ce3+/Ce4+ was unchanged. The obtained nanorods have uniformdiameters of 10-20 nmand lengths of 200-500 nm. Upon excitation with 400 nm light, the doped β-BBO nanorods exhibit a strong green light emission. PL spectra indicate that the emission bands at 515 and 542 nm correspond to the 2H11/2→4I15/2 and 4S3/2→4I15/2 transitions of Er3+, respectively. In the samples, the cerium dopant exists as Ce3+ and Ce4+. Ce3+ sensitizes Er3+ and enhances the luminescence intensity of the doped nanorods remarkably and energy transfer fromCe3+→Er3+ was observed.

High quality zinc blende CdSe nanocrystals were successfully synthesized using an environmental friendly method. Pre-synthesized cadmium decanoate was used as the Cd precursor and selenium powder dissolved in octadecene was used as the Se precursor. The use of expensive and toxic tributylphosphine or trioctylphosphine was thus avoided. The properties and structures of the as-synthesized CdSe nanocrystals were characterized by absorption spectroscopy, photoluminescence (PL) spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The PL emission peak of the as-synthesized CdSe nanocrystals could be easily tuned from470 to 630 nm using different reaction times. The quality of the crystals was high and this was confirmed by their high quantum yields (exceeding 60%at 535 nm) and their narrow size-distributions with full width at half maximum values between 24 and 30 nm.

The precursor was prepared in two steps: the soybean lecithin latex containing Eu3+ ions was prepared first using a EuCl3 solution. The vesicles formed spontaneously in the soybean lecithin aqueous solution and were used as a template. The precursor was then obtained by precipitating Eu3+ ions with NH4F in the vesicle system that was formed by soybean lecithin. EuF3 nanowires with diameters of about 10-20 nm were obtained from the precursor that was annealed at 600 ℃. The formation of the EuF3 nanowires is discussed considering a comparative analysis by fluorescence spectra, Fourier transforminfrared (FTIR) spectra, thermal gravimetric analysis-differential thermal analysis (TGA-DTA), and transmission electron microscopy (TEM) of the products from each stage. Results show that the Eu—O—P bond is formed by the coordination of Eu3+ ions and the nanowires are multi-crystalline phase EuF3.

A novel porphyrin (1) and its zinc, copper complexes (2, 3) were synthesized and characterized by proton nuclear magnetic resonance (1H NMR), ultraviolet-visible (UV-Vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, electron spray ionization mass spectrometry (ESI-MS), and elemental analysis. The circumfluent effect of the porphyrin was exerted on the imidazole, which resulted in the chemical shifts of three hydrogen atoms moving upfield. The Soret band in the UV-Vis spectrum of the porphyrin was split because of this effect. The lowest energy conformation of the porphyrin obtained by simulated annealing coincided with the analysis of the spectrum where the imidazole was above the porphyrin. We also studied the third-order nonlinear optical properties of the porphyrin and its zinc, copper complexes using Z-scan techniques. We found that the porphyrin and its zinc, copper complexes all gave rise to a strong reverse saturable absorption and that the nonlinear optical property of the copper complex was stronger than that of the zinc complex.

The nonlinear optical properties and the excited state dynamics of a new blue-light emitting polymer poly[5-(diphenylamino)-1,3-phenylenevinylene] (Yu1) and its starting material 5-(N,N-diphenylamino)benzene-1,3-dicarbaldehyde (Yu0) were studied. In contrast to the monomer Yu0, the two-photon absorption (TPA) properties of Yu1 were found to be significantly enhanced upon polymerization. The TPA cross section of Yu1 (per repeating unit) increased about tenfold compared to Yu0. Femtosecond pump-probe experiments were carried out to study the excited state dynamics of the two materials. An investigation of the ultrafast dynamics demonstrated that different relaxation processes occurred in the Yu0 and Yu1 samples. Apparent optical anisotropy was observed from a one-color pump-probe experiment of the polymer Yu1 at 400 nm. The fast component observed in the parallel configuration of Yu1 disappeared when the perpendicular polarization configuration was used because of the high orientation of exciton migration. The nonlinear optical study and the ultrafast dynamics results indicated that the onlinear optical properties were enhanced because of monomer polymerization.

The radial distributions of ar n as a solvent as well as the vibrational relaxation dynamics of the solute I2 confined in a single-walled carbon nanotube (SWCT) were investigated by mixed quantum-classical molecular dynamics simulations. Functions of the vibrational frequency shift and the vibrational relaxation time of I2 with varying radii were presented. Using the frequency shift of I2 as a spectral probe, an analysis of the instantaneous interactions of I2 with the surroundings was determined by breaking down the shift into the contributions of the nanotube and the solvent atoms. Detailed mechanistic information related to the shift was investigated at the atomic and molecular level. In addition, by analysis of the sensitivity of the spectral probe and the dependence of the frequency shift on the vibrational relaxation time of the probe molecule, we conclude that the frequency shift is a od spectral probe to investigate the interactions in confined condensed phases.

The molecular structure and thermal decomposition of nitromethane confined inside armchair (CNT(5,5), CNT(6,6), CNT(8,8)) and zigzag (CNT(9,0), CNT(10,0), CNT(11,0)) single-walled carbon nanotubes (CNTs) with different diameters were investigated using the ONIOM (B3LYP/6-311++G**:UFF) method. Results showed that the Cs symmetry of nitromethane confined inside CNT(5,5) and CNT(9,0) was destroyed and that the C—N bond was compressed slightly. Confinement in CNT(6,6), CNT(8,8), CNT(10,0), and CNT(11,0) had no evident influence on the molecular structure of nitromethane. By analyzing the potential energy surface along the C—N bond, we found that a transition state existed during the thermal decomposition of nitromethane confined inside CNT(5,5) and CNT(9,0). This was very different from the behavior of the nitromethane monomer as no transition state existed during C—N bond dissociation. The activation energy barriers of the thermal decomposition for nitromethane confined inside CNT(5,5) and CNT(9,0) were found to be lower by about 71 and 58 kJ·mol-1, respectively, compared with the bond dissociation energy of the nitromethane monomer. Confinement in CNT(6,6) and CNT(8,8) resulted in a slight decrease in the activation energy. Confinement in CNT(8,8) and CNT(11,0) did not affect the thermal decomposition of nitromethane. We concluded that the activation energy of nitromethane decomposition was significantly reduced by confinement in a carbon nanotube with a small diameter. Additionally, the activation energy was not influenced by the chirality of the carbon nanotube.

To investigate the influence of surfactant molecular structure on micellization in solution, we used molecular dynamics to simulate the molecular structure and interaction of three alkyl aryl sulfonates in vacuum and in solution. The solvation free energy was calculated from the free energy perturbation (FEP) method and the obtained result was consistent with that obtained using the surface tension method. Research has shown that the micellization of alkyl aryl sulfonates in an aqueous solution is a spontaneous process as the aromatic ring shifts from the edge to the center of long carbonic chains, which results in a decrease in the ability of micelles to form and a decrease in their stability. Changes in the “iceberg structure”around the hydrophobic groups and the water molecules may affect the stability of the micelles and we studied the “iceberg structure”by considering the lifetime of the hydrogen bonds. Additionally, we find that the number of hydrogen bonds between the hydrophilic groups of the alkyl aryl sulfonates and the water molecules can affect the decomposition and stability of the micelles.

Theoretical calculations on a series of N—H…O=C hydrogen bond trimers were carried out using the MP2 method. We investigated the effect of substituents in hydrogen bond donor molecules on their hydrogen bond strength. The calculated results show that electron donating groups shorten the H…O distance and strengthen the N—H…O=C hydrogen bond whereas electron withdrawing groups lengthen the H…O distance and weaken the N—H…O=C hydrogen bond. Natural bond orbital (NBO) analysis further indicates that a stronger hydrogen bond in N—H…O=C results in a larger positive charge for the H atomand a larger negative charge for the O atomin the N—H…O=C bond. Natural bond orbital analysis also indicates that a stronger hydrogen bond in N—H…O=C results in a more charge transfer between the hydrogen bond donor and acceptor molecules, and results in a stronger second-order interaction energy between the oxygen lone pair and the N—H antibonding orbital. Hydrogen bonds in the N—H…O=C molecules closer to the substituent will be affected more.

Potential energy curves (PECs) for the ground electronic state (X4∑) and the three lowest excited electronic states (a2Π, b2∑, A4Π) of NaCmolecule were calculated using the multi-configuration reference single and double excited configuration interactionmethod, including Davidson's corrections for quadruple excitations (MRCI+Q). The equilibrium bond length Re and the vertical excited energy Te were determined directly and the PECs were fitted to an analytical Murrell-Sorbie (MS) potential function to determine the spectroscopic parameters, which were the rotation coupling constant ωe, dissociation energy De, the anharmonic constant ωe Χe, the equilibrium rotation constant Be and Drot, and the vibration-rotation coupling constant αe. These values were also compared and were in agreement with other theoretical and experimental results currently available. It is evident that the X4∑, a2Π, and b2∑ states are bound. We found that in the ground state X4∑, Re was 0.2259 nm, ωe was 431 cm-1, and De was 1.92 eV, while in the excited states a2Πand b2∑, Re and ωe were 0.2447, 0.2369 nm and 329, 335 cm-1, respectively. Te was found to be 1.58 and 1.75 eV and De was 0.71 and 0.42 eV. A4Πis a repulsive excited state when Te is 2.48 eV relative to the ground state. By solving the radial Schrodinger equation of nuclear motion the vibration levels and inertial rotation constant at rotational quantum number J=0 are reported for the X4∑, a2Π, and b2∑ states.

Reaction mechanisms for the reaction between CpRu(PPh3)2SH (Cp=cyclopentadienyl) and RNCS (R = Ph, 1-naphthyl) were investigated by density functional theory using the model reaction between CpRu(PH3)2SH and HNCS. Two possible mechanisms are proposed. First, one PH3 ligand dissociates from CpRu(PH3)2SH to give a 16e intermediate upon which hydrogen migration occurs giving the product. Second, hydrogen migration occurs before the dissociation of a PH3 ligand, giving the product. Based on our calculations, the second mechanism is more favorable. From the potential energy curves for the two possible mechanisms, the rate-determining step for the reaction is hydrogen migration. The overall reaction activation energy for the first mechanism is markedly higher than that for the second mechanism. Therefore, we predict that this reaction tends to experience hydrogen migration before the dissociation of PPh3 from the metal center. In the second mechanism, the product is eventually obtained because of an increase in entropy but the product is thermally less stable than the intermediate that directly connects to the product.

The effect of In and Sc p-type doping on the structural stability, electronic structure, and optical properties of SrTiO3 was investigated by first-principles calculations of plane wave ultra-soft pseudo-potential based on density functional theory (DFT). The calculated results revealed that the structural stability of SrTiO3 was weakened after In and Sc doping and that the partial substitution of In for Ti (or Sc for Ti) merely resulted in local structural changes around the dopant sites. The doped SrIn0.125Ti0.875O3 and SrSc0.125Ti0.875O3 systems are p-type degenerate semiconductors. The optical bandgap was broadened by about 0.35 eV for SrIn0.125Ti0.875O3 and 0.30 eV for SrSc0.125Ti0.875O3. In addition, a noticeable blue-shift of the absorption spectral edge was observed in the two p-type doping systems and a new absorption appeared at around 1.25 to 2.00 eV because of the Drude-type behavior of the free-carrier excitation. The optical transmittance of SrIn0.125Ti0.875O3 and SrSc0.125Ti0.875O3 improved significantly after doping and the transmittances were higher than 85% from 350 to 625 nm. The wide bandgap, small transition probability, and weak absorption because of the low partial density of states of impurities in the Fermi level result in SrIn0.125Ti0.875O3 and SrSc0.125Ti0.875O3 being optically transparent.

A theoretical study on Sb-doped SnO2 was carried out using a plane wave pesudopotential schene density functional theory (DFT) at the generalized gradient approximation (GGA) level. Stability and conductivity analyses were performed based on the formation energy of doping and the electronic structures. Results show that the SnO2 lattice constants expand into a distorted rutile structure as the antimony content increases. The formation energy of doping shows little change as the doping ratio changes and it has a minimum value of 5.08 eV at a doping ratio of 0.083. This suggests that the Sn0.917Sb0.083O2 solid solution has the highest stability. Density of state (DOS) calculations showed that a Sb 5s distribution of electronic states exists from the Fermi level to the lowest conduction band after doping with antimony. In addition, 19 electrons were present in the lowest conduction band after doping compared to 4 electrons before doping. This results in the increased conductivity of the solid solution. At a doping ratio of 0.063, the Sn0.937Sb0.063O2 solid solution had the strongest conductivity. These results provide a theoretical basis for the development and application of Sn1-xSbxO2 solid solution electrodes.

Based on density functional theory, the geometric structures of SnO2 and transition metal (M) V-, Cr-, and Mn-doped SnO2 were studied by an ultrasoft pseudopotential implemented in the plane wave method. The geometrical parameters, density of states, and magnetic properties were calculated. By comparing two kinds of dopants with concentrations of 6.25% or 12.5%, no significant changes were observed for the electronic and magnetic properties of these systems. The O atom tended to be attracted by the M and the bond distance between O and the metal was shortened. After doping with M, spin polarization appeared near the Fermi surface and the SnO2 doped with V and Cr had a half-metal nature, but the system containing Mn did not show such behavior. The impurity concentration had little effect on the spin and magnetic moment. The magnetic moment of the Mdoped SnO2 mainly originated from the 3d spin polarization and was also related to the electron configuration. The total magnetic moments of the SnO2 doped with V, Cr, and Mn were 0.94μB, 2.02μB, and 3.00μB, respectively. These magnetic moments mainly originate from the 3d spin polarization as some negative moments exist for O and the Sn atomcontributes little to the magnetic moment.

Based on a non-collinear magnetic structure calculation, the magnetism, energy gap, and electronic structures of the triangular lattice antiferromagnetic delafossite CuFeO2 were investigated by density functional theory (DFT) within the generalized gradient approximation (GGA) approach. By producing three types of magnetic configurations including ferromagnetic (FM), frustrated triangular non-collinear antiferromagnetic (FAFM), and up-up-down-down collinear antiferromagnetic (↑↑↓↓AFM) ordering, a full optimization of the lattice parameters and internal coordinates was performed for the low temperature hexa nal structure. The calculations show that the up-up-down-down spin arrangement plays an important role in the formation of the band gap, the decrease in total energy and the increase in magnetic moment. Since a small difference exists between the total energy of the FAFMand ↑↑↓↓AFM phase, the ↑↑↓↓AFMeasily under es a phase transition to the FAFMstate when an external magnetic field is applied. Additionally, the electronic densities of states (DOS) in the ↑↑↓↓AFMphase qualitatively agrees with the results of X-ray emission spectra, that is, the Fe ion is in a high-spin state with the spectral weight of the Fe 3d spin-up band centered slightly below the Cu 3d but above the O 2p bands. Analysis with ligand field theory also indicates that the empty orbital of the Fe 3d spin-down provides a chemical environment favorable for ferroelectric polarization.

The pharmacological mechanism of 514 compounds contained in a Chinese medicine, Jingzhi Tougu Xiaotong Granule (JZTGXTG) was studied by computational pharmacological methods including analysis of molecular similarity, chemical space, molecular docking, network technology, and the predictions of absorption, distribution, metabolism, excretion and toxicity (ADME/T). Results show that compounds in JZTGXTG have the diverse structural properties and most of these compounds have od drug-like properties in their chemical spaces. The possible action mechanism is illuminated and potential active-molecules of JZTGXTG are found by studying the interactions between 514 compounds of JZTGXTG and 35 drug targets related to osteoarthritis disease and the distribution of 514 compounds in drug-target space. By analyzing network parameters of JZTGXTG compound-target interaction network and drug-target interaction network including network heterogeneity and characteristic path length, the results reveal the molecular mechanism of multi-drugs, multi-targets, and multi-pathways in JZTGXTG. The results are helpful for understanding the complicated mechanismof JZTGXTG.

Iron oxide magnetic nanoparticles with a narrow size distribution were prepared by thermal decomposition of iron (III) acetylacetonate using benzyl alcohol as the only solvent. The structure and morphology of the as-prepared nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS). Fourier transforminfrared (FT-IR) spectroscopy and thermal gravimetric analysis (TGA) were used to study the surface chemistry of the particles, and it was found that the nanoparticles were stabilized by benzoic acid molecules with less than 20% monolayer coverage. At room temperature, the surface ligands can easily exchange for other molecules. This method will facilitate the functionalization and application of iron oxide magnetic nanoparticles.

We propose a convenient method to synthesize surface amino-coated magnetic nanoparticles. Fe3O4 nanoparticles with a grain diameter of about 10 nm were synthesized by the chemical co-precipitation of ferrous chloride and ferric chloride. The obtained superparamagnetic nanoparticles were surface-modified with alendronate to introduce an amino group onto their surfaces. The particles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), vibrating sample magnetometry (VSM), dynamic light scattering (DLS), thermogra-vimetric analysis (TGA), Fourier transforminfrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The data showed that alendronate was successfully linked to the SPM nanoparticles. These particles are stable for more than 4 weeks without precipitation at pH= 6.3.

Present study provides an approach to produce porous crystal material of C12A7-Cl- (Ca12Al14O32Cl2) by sol-gel method. Reactants for the gel were Ca(NO3)2·4H2O, Al(NO3)3·9H2O, CaCl2, urea, and ethylene glycol. The mixture solution was stirred for 2-3 h to form the sol, after thermal treatment at 350 ℃, the formed gel was then sintered under flowing ar n at 1000 ℃. The prepared porous crystal material was investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), electron paramagnetic resonance (EPR), and ion chromatography (IC). Results indicated that the C12A7-Cl-material was successfully prepared via sol-gel method and the Cl- anions were the dominant anions stored in the bulk of the material. The emission of Clanions from the C12A7-Cl- surface was detected by time-of-flight mass spectrometry (TOF-MS). Our results show that the sol-gel method can be potentially useful in the development of C12A7-Cl- materials.