We report the organization of polymer-dispersed liquid crystals (PDLCs) into ordered concentric rings over large areas by drying a drop of bound PDLC toluene solution (i.e., confined between a spherical lens and an indium tin oxide (ITO)-coated glass substrate; sphere-on-ITOgeometry). The formation of regular ring-like deposits was a direct consequence of controlled "stick-slip" cycles of three-phase contact line during the course of solvent evaporation, which was effectively regulated through the use of the sphere-on-ITO geometry. This simple approach based on controlled evaporative organization may provide a new means of processing polymer/LC mixture to produce ordered surface patterns in one step, where microscopic LCs are dispersed within the polymer matrix.

The inhibition of steel corrosion in hydrochloric acid solutions by limonene, which was extracted from citrus and orange fruit, was studied using measurements of mass loss, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) methods. Naturally, the substance reduced the rate of corrosion. The linearity of the cathodic curves for all concentrations indicated that the law of Tafel was followed. The effectiveness of inhibition increased with the increase in concentration of limonene and this exceeded 72% at 0.220 g·L-1. The inhibition efficiency is temperature independent in the temperature range of 298-328 K. Adsorption of the substance on the surface of steel obeys the Frumkin isothermmodel.

Three-dimensional structure model of M1 receptor was built through homology modeling. Mreceptor full a nist acetylcholine (ACh) and M1 receptor selective a nist xanomeline were docked into the model protein to form receptor-ligand complexes. Those complexes together with a receptor protein were put into a phospholipid bilayer for a 10 ns molecular dynamics (MD) simulation. Numbers of known active molecules were scattered into randomly selected databases, and the ACh compounds were docked with a model protein and ranked by their docking scores. The best model protein with the highest enrichment factor (EF) was chosen. The EF of the top5% of the active molecules for the chosen M1 protein receptor-xanomeline docking complex, the receptor-acetylcholine complex, and the non-complex were 8.0, 6.5, and 1.5, respectively. These results indicate that optimization of structures by MD simulation of M1 selective ligand-receptor is reasonable for virtual screening. The optimized M1 receptor protein structure can be used for virtual screening and for novel design to discover more potent compounds.

It has been found that the mechanical properties of solid propellants and plastic bonded explosives (PBX) depend heavily on the compatibility of the polymer binder and plasticizer used in their formulation. Two systems, one miscible and the other immiscible, were simulated by molecular dynamics (MD) simulations to test the usefulness of this molecular simulation technique. Density, cohesive energy density, and solubility parameters of hydroxyl-terminated polybutadiene (HTPB), dioctyl sebacate(DOS), nitroglycerine (NG), HTPB/DOS blend and HTPB/NG blend were calculated by MD simulations with the COMPASS force field for the prediction of polymer binder and plasticizer compatibility. Results show that HTPB/DOS is a miscible system but HTPB/NG is not miscible by comparing the difference in the solubility parameter value (△δ), pair correlation function and the change of density. The predictions agreed well with experimental observations. By calculating the pair correlation function the HTPB/plasticizer interaction was clarified. Therefore, the method used in this work is a useful tool to provide information on miscibility and other properties of a given polymer/plasticizer blend. In addition, it is a promising technique to help to design formulations for screening solid propellants and PBX before experimental tests.

Host-guest interactions of β-cyclodextrin (β-CD) with enantiomers of ethyl α-chloropropionates ((R/S)-ECPA) were simulated using the quantum mechanics PM3 method. The chiral recognition mechanism of (R/S)-ECPA enantiomers on β-CD was investigated. Modeling results showed that the stabilization of complexes formed by (R/S)-ECPA enantiomers and β-CD were different. (R)-ECPA was located on the cavity wide mouth end of β-CD to form an associated molecule, but (S)-ECPAinserted into the β-CDcavity to forman inclusion molecule. The stabilization energy of the (S)-ECPA and β-CD complex was lower than that of the (R)-ECPA and β-CD complex. The chiral carbon in the ECPA of (R/S)-ECPA and β-CD complexes was close to the C2 and C3 in the glucose unit. The chiral recognition mechanism was thus closely related to the chiral environment provided by C2 and C3 in the glucose unit and the degree of (R/S)-ECPA and β-CD inclusion.

A spinel lithium manganese oxide doped with nickel (LiNi0.05Mn1.95O4) was prepared by a sol-gel method using acetic lithium, nickel and manganese as rawmaterials. The lithiumion-sieve (denoted as LiNiMn-H) was obtained by acidification of the obtained LiNi0.05Mn1.95O4 with 0.5 mol·L-1 (NH4)2S2O8. After testing, we found that the dissolution ratio of Mn2+ fromLiNi0.05Mn1.95O4 during the acid-modification process was only 0.31% (w, mass fraction) and the saturation ion-exchange capacity of LiNiMn-Hfor Li+ was 5.29 mmol (36.72 mg) Li+/g ion-sieve. The exchange isothermal curves of LiNiMn-H in the H+-Li+ system were measured at 15, 25, 35 and 45 ℃ and the average activity coefficients of the electrolyte were calculated using Pitzer electrolyte solution theory. Other thermodynamic constants, such as the equilibrium constants Ka, △Gm, △Hm, and △Sm, were calculated during the exchange process. We conclude that the equilibrium constants reduce with the increase in temperature and that the selectivity of LiNiMn-H for Li+ is higher than the original ionH+. The exchange process is exothermic and the adsorption process occurs spontaneously (△Gm<0).

We hope to improve the biological activity and the osteo-conductivity of a porous polymer scaffold by the deposition of a hydroxyapatite (HA) coating.We used an alternate soaking deposition method to prepare HAcoating. A massive chitosan (Cs) porous scaffold was used as a deposition template and immersed alternately in calciumchloride and disodium hydrogen phosphate solutions. Finally, a hydroxyapatite coating was deposited in/on the massive chitosan porous scaffold. The compositions, micromorphology, porosity, inorganic deposition amount and compressive strength were characterized by XRD, FT-IR, SEM, porosity measurements, calcination and a compression experiment. Results indicated that the deposition mineral was a low crystallinity carbonate hydroxyapatite with c axis preferential growth and was similar to hydroxyapatite in natural bone. SEMresults showed that the sedimentary hydroxyapatite had a gradient distribution in the scaffold. More deposition was observed on the outer pore wall surface than the inner pore wall surface. The exterior pores of the scaffold were partially blocked but the inner pore structure of the scaffold was still interconnected. The porosity of the deposited scaffold was 94.0% and the deposited hydroxyapatite was 13.5% of the total mass after 6 alternate soaking cycles. The compressive strength of the scaffold increased from 0.055 MPa to 0.109 MPa.

Rhodopsin is a membrane protein and its retinal (RET) active binding sites are related to the process of vision and the pathology of some ophthalmic ailments. Based on the bovine rhodopsin crystal structure (PDB code: 1U19), computations were performed using density functional theory to explore the interaction and binding energies between the RET-Lys296 residue and each of the 30 amino acid residues arranged in a sphere with 0.6 nm radius around a RET molecule. Results show that Glu113, Glu181 and Glu122 residues are the active binding sites for the protonated RET-Lys296 residue and that their binding energies are -333.38, -205.67 and -194.56 kJ·mol-1, respectively. They each have one negative charge to interact with the protonated RET-Lys296 residue through a strong electrostatic interaction. Other residues Ala292, Cys187, Phe293, Pro291 and Trp265 have smaller binding energies with the protonated RET-Lys296 residue at the 1U19 protein. When the RET-Lys296 residue is deprotonated, the interactions mentioned above disappear therefore to promote the dissociation of retinal from rhodopsin. Our results demonstrate that two crystal H2O molecules that form hydrogen bonds to Glu113 and Glu181 residues also play an important role in stabilizing the RET-Lys296 residue.

The micellization behavior of the nonionic surfactant Triton X-100 (TX100) and the cationic cetyltrime-thylammonium bromide (CTAB) binary mixtures was investigated in ethylene glycol (EG) and water mixtures using a tensiometric technique. We show that synergistic effects exist for surface tension reduction and mixed micelle formation. When the molar fraction of CTAB in the mixture is about 0.3, the synergistic effect is at its optimum. The critical micelle concentration of the mixture increases as the content of EG in the mixed solvents increases. The established theories of Rubingh and Maeda were applied to determine the molar fraction of the different components, the interaction parameters and several thermodynamic properties of the micellar phase. We found that the micelle composition and the interaction parameters fromRubingh's model and Maeda's model were in agreement.

After TiO2 nanoparticles were surface modified by the coupling agent anilinomethyltriethoxysilane (AMTES-TiO2), polyaniline (PANI) was grafted onto the surface of the AMTES-TiO2 nanoparticles by in situ chemically oxidative polymerization resulting in a PANI/AMTES-TiO2 nanocomposite photocatalyst. PANI and TiO2 are linkaged by chemical bonds. The nanocomposites were characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), UV-Visible diffuse reflectance spectrum (UV-Vis-DRS) and photoluminescence (PL). The photocatalytic activity was evaluated by the degradation of methylene blue (MB) in aqueous solution under UV and solar light irradiation. Results show that the sensitizing effect of PANI can improve the light response of TiO2 and enhance the separation efficiency of electron and hole pairs which in turn promotes the photocatalytic ability of the nanocomposites. The mass ratio (w) of aniline to AMTES-TiO2 has a significant effect on the photocatalytic activity of nanocomposites and the optimal activity is obtained when the w is 0.025.

Shenfu Dongsheng (SD) coal liquefaction is a critical part for the energy diversification strategy in China. However, because of the unique behavior of Chinese western coal macerals during the liquefaction process, no theory exists that explains the difference between Shenfu Dongsheng inertinite (SDI) and vitrinite (SDV) and Chinese eastern coal macerals. The different thermochemistry of inertinite and vitrinite cannot be explained by only considering the structure of these coals. To investigate the unique behavior of SDI and SDV in the liquefaction process a qualitative analysis of the characteristics and transformation of covalent bonds during pyrolysis of the‘average’molecular structure of a SD coal was performed using quantum chemistry, molecular mechanics and molecular dynamics. The formation of residual coal, pyrolyzed gases and tar during pyrolysis was simulated. Results showed that the activity of SDI was higher than that of SDV during cracking and initially CO2 was released without destroying the macromolecular structure. From a statistical analysis of bond order in the molecular model, the amount of broken covalent bonds in SDV was found to be far more than that found in SDI after pyrolysis. When SDI cracked further during pyrolysis, the extent of inertinite decomposition eventually reached the same level as that for vitrinite. There was a difference in pyrolysates from SDI and SDV and there were mainly aliphatic hydrocarbons and single-ring aromatic hydrocarbons for SDV while dual-ring aromatic hydrocarbons were dominant after SDI pyrolysis. Molecular fragments obtained from quantum chemical calculations were compared to thermal gravimetric analyzer-mass spectrometry (TG-MS) data and found to agree well.

We discuss the synthesis and characterization of 3',4'-bis(p-benzoylphenylmethoxy)yl-4-nitrostilbene (C1). Ultraviolet and fluorescence spectroscopy was used to investigate its behavior in various solvents. Results showed that the visible absorption of C1 could be assigned to the chromophore and that the attached benzophenone made major contribution to the ultraviolet absorption of C1. This compound exhibited strong fluorescence in modest polar solvents.Acomprehensive investigation of the two-photon properties and electrochemistry of C1 and 2',4'-bis(p-benzoylphenylmethoxy)yl-4-nitrostilbene (C2) was undertaken. Results suggested that at 800 nm femtosecond laser excitation, C1 and C2 showed strong two-photon induced upconversion fluorescence. The two-photon absorption cross-section of the compound was shown to be related to the substitution position of benzophenone. Molecular geometry optimization and electrochemistry suggested that the energies of the frontier orbitals and electron densities of C1 and C2 could be correlated to the position of benzophenone substitution as well.

By constructing a mesoscopic stochastic model for intracellular calcium oscillations in coupled cell system, we investigated the influence of internal noise on the detection of weak stimulation using the chemical Langevin equation (CLE). We found that an optimal cell size V existed for a coupled cell chain length N and an optimal value of N existed for a given cell size V. At these values, the collective calcium oscillations showed the best performance, indicating the occurrence of“system size resonance (SSR)”or“internal noise stochastic resonance (INSR)”. And such a phenomenon was robust to the coupling strength. Living cells may have learned to exploit the internal noise to detect weak stimulation via the mechanism of INSR, and then encode information to specifically regulate distinct cellular functions. It is interesting to note that the optimal cell size is always present at V抑103 μm3, which is close to the real living cell size in vivo. Since the internal noise in living systems can not be ignored and the systems may often encounter weak stimulations, our findings might have significance for stimulation detecting processes in living systems.

Electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the adsorption and corrosion inhibition of sodium dodecylbenzenesulfonate (SDBS) on AZ31 magnesium alloy in 3.5% (w, mass fraction) NaCl corrosive medium. Results showed that SDBS strongly inhibited the corrosion of AZ31 magnesium alloy in NaCl medium. The inhibition efficiency of 0.008 mol·L-1 SDBS was more than 90%. Increasing temperature did not increase the inhibition efficiency. Physical adsorption of SDBS at the AZ31 magnesium alloy surface mainly occurred. The adsorption process was spontaneous and exothermic and the entropy increased, which obeyed the Langmuir isotherm. SDBS is a mixed-type inhibitor and mainly inhibits the anodic dissolution reaction of AZ31 magnesium alloy.

A copper(core)-nickel(shell) nanostructure was synthesized by porous anodic aluminum oxide template (AAO) combined with electrochemical deposition according to a new two-step method, i.e., the copper nanowire core was prepared first and then the AAO pore was widened and followed by the growth of the nickel shell in the interspace between the wall of the pore and the copper nanowire. The structure and morphology were characterized and analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission election microscopy (TEM). The results verified that this method for the fabrication of the core-shell structure was effective. Adenine was used as a probe molecule to investigate the surface-enhanced Raman scattering (SERS) effect of this type of core-shell nanowire and the results revealed that the controllable one-dimensional core-shell nanomaterial is a potential SERS active substrate, which may exploit the use of transition metals for SERS.

The interaction between zidovudine (ZDV) and bovine serum albumin (BSA) was investigated by fluorescence spectroscopy and ultraviolet-visible spectroscopy in aqueous solution (Tris-HCl buffer, pH 7.1). The effect of metal ions (Cu2+, Mg2+, Zn2+) on the interaction was also investigated. Results showed that the fluorescence intensity of BSA at 346 nm was quenched when zidovudine or metal ions were added. The quenching mechanism was a static quenching mechanism. A strong interaction exists between zidovudine and BSA. The thermodynamic parameters △H and △S were -10.2 kJ·mol-1 and 77.5 J·mol-1·K-1 at 298 K, respectively, indicating that electro-static forces played a major role. The binding constant, the number of binding site and the binding distance were 6.92×105 L·mol-1, 1.18, and 2.28 nm at 298 K, respectively. The binding constant and the number of binding sites decreased with the increase in temperature. The metal ions, Cu2+, Mg2+ and Zn2+, all decreased the binding constant and increased the binding distance for binding between ZDV and BSA.

TiO2/MCM-41 composites with various titania content were prepared by loading titania into the mesopores of MCM-41 molecular sieves via the sol-gel method. TiO2/MCM-41 composites were characterized by X-ray diffraction(XRD), N2 adsorption, ultraviolet-visible (UV-Vis) absorption spectroscopy and transmission electron microscopy (TEM) techniques. The titania crystalline phase was anatase. The BET surface area and pore volume of the composites decreased with the increase of titania loading (mass ratio of TiO2 to MCM-41 in the composite). The average crystal size of these titania particles increased as the titania loading increased. The photocatalytic activities of TiO2/MCM-41 composites were evaluated by the photocatalytic degradation of Rhodamine B. The degradation of Rhodamine B followed first-order reaction kinetics. The composites showed higher photocatalytic activities than P-25 commercial pure titania nanoparticles. The photocatalytic activities of the composites depended on their adsorption abilities and the activity of titania loaded into the MCM-41 molecular sieves.

The adsorption of formate (HCOO) on Cu(110), Ag(110), and Au(110) surfaces has been studied by the density functional theory (DFT) and generalized gradient approximation (GGA) with slab model. To find the most stable adsorption site of HCOOon M(110) (M=Cu, Ag, Au), we investigated several adsorption forms like bidentate and monodentate adsorption sites. The calculated results show that the most stable adsorption site is short-bridge bidentate form for all the three metals, which is independence of the metallic lattice constants. The calculated atomic geometries agree well with the experimental results and the previous calculation results. Adsorption energy of formate follows the order of Cu(110) (-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), in agreement with decomposition temperature of formate measured by experiments. The order of the adsorption energy can be explained by Pauli repulsion between molecular orbitals of formate with d-band of metal, i.e., the more occupied population of formate, the larger Pauli repulsion, which results in the weaker adsorption of formate. In addition, the activation energy of formate synthesis from CO2 and H2 was predicated using the adsorption energy of formate and the decomposition temperature of formate, which follows the order of Au(110)>Ag(110)>Cu(110).

The micelle shape transformation of tert-octylpheny phenol polyethylene glycol ether (TX-100), sodium dodecyl benzene sulfonate (SDBS) and tetradecyl trimethyl ammonium bromide (TTAB) in heavy water solutions was studied by 1H nuclear magnetic resonance (NMR) spectroscopy, including an NMR self-diffusion experiment. These experiments showed that the surfactants formed several shapes of micelles (spherical, ellipsoidal, and rodlike) at the respective concentrationswhich were far above their criticalmicelle concentration (cmc). At ambient temperature, normal pressure and when the concentration of the surfactant was above the cmc without other additives, spherical micelles were formed. At higher surfactant concentrations, 1H NMR spectra and self-diffusion experiments showed that abrupt changes occurred in their chemical shifts (δ) and in their self-diffusion coefficients (D). This indicated that spherical micelles transformed into larger micelles. By careful examination of every proton resonance peak in the 1H NMR spectra, we found that the protons near the head group experienced larger chemical shift changes than protons near the hydrophobic group. This suggests that the shape of surfactant micelles most likely transforms from spherical to ellipsoidal or rodlike.

Structures of the mononuclear complex Ir(CO)Cl(Ph2Ppy)2(1), binuclear complexes Ir(CO)(Cl)2(Ph2Ppy)2·HgCl (2), Ir (CO)Cl (Ph2Ppy)2HgCl2 (3), and Ir (CO) (Cl)2 (HgCl2) (Ph2Ppy)2HgCl (4) were optimized using the density functional theory (DFT) PBE0 method with SDD basis sets for Ir and Hg, 6-31G* basis sets for H, C, O, and N atoms and 6-311G* basis sets for P and Cl atoms. Based on the optimized geometries of complexes 1-4, a counterpoise correction was carried out for the basis-set superposition error (BSSE) of the interaction energies. Nature bond orbital (NBO) and frontier orbital analyses were also performed for all the complexes to study the Ir-Hg interactions and the nature of the redox reactions. Our conclusions are as follows: products of the redox reactions (complexes 2 and 4) are more stable than that of the nonredox reaction (complex 3). The strength of the Ir-Hg interaction increases as follows: 3<4<2. As the strength of the Ir-Hg interaction increases, the difference between the Ir and the Hg contribution to the HOMO gradually decreases. Ir-Hg σbonding and antibonding orbitals all exist in complexes 2 and 4, and can be described as 0.5985sd0.06Hg+0.8012sd2.48Ir for complex 2 and 0.5794sd0.05Hg+0.8151sd2.48Ir for complex 4. However, in complex 3, the Ir-Hg interaction results from nIr→nHg, σIr—P(1)→nHg, and σIr—C(1)→nHg charge transfer interactions.

Melamine is an important precursor of induced stones in the human kidney. Using density functional theory (DFT), conceptual DFT and time-dependent (TD) DFT, the structure, spectroscopy and reactivity properties of melamine (L) and its metal complexes ML2(OH)2 (M=Ca, Mg, Fe, Cu, Zn, Ni) were systematically investigated in this work.We found that ML2(OH)2 complexes were structurally and spectroscopically different fromtheir precursors (L) and more reactive in electrophilic and nucleophilic reactions. A few quantitative linear relationships were discovered between bonding interactions, charge distributions, and DFT chemical reactivity indices with R2=0.889-0.997, respectively. Results from frontier molecular orbital and electrostatic potential analyses show that ML2(OH)2 systems fromtransition metal cations such as FeL2(OH)2, CuL2(OH)2 and NiL2(OH)2 tend to be more covalently bound and they possess larger molecular twists and more electrophilic regions on the molecular contour surface. These results are believed to be implicative in our better understanding of the melamine stone production mechanism in the human body.

Grand canonical Monte Carlo and molecular dynamics simulations were used to study the adsorption and diffusion of oxygen in polypropylene (PP). It is found that at roomtemperature, the loading of oxygen in PP increases and the diffusion coefficient of oxygen in PP decreases as the polymerization degree of PP increases. The loading and diffusion coefficient reach platform values when the polymerization degree of PP is relatively high. The loading of oxygen decreases and the diffusion coefficient of oxygen in PP increases as the temperature increases. The oxygen diffusion mechanism in PP is also discussed according to free volume theory. Oxygen molecules firstly oscillate inside one cavity of PP and then jump from this cavity to another one through a channel formed by the thermal motion of PP chains. In general, simulation results indicate that polymer materials with a high degree of polymerization used at room or low temperatures should be preferred in food reservation technology. This work provides some guidance and basis for developments in food packing materials.

We used molecular docking software LD to investigate the binding mode of corydaline, a type of cordalis alkaloid, with acetylcholinesterase and to screen a series of open ring derivatives with different carbon linkages and different substituent groups. The best result was obtained when corydaline was bound to the enzyme catalytic site in an open conformation. The conformation model indicates that phenyl ring A interacts with the phenyl group of Tyr334 via a classic parallel π-π accumulation and that the positively charged nitrogen atom interacts with the phenyl group of Phe330 in the hydrophobic site by the cation-π effect. Both dimethoxy radicals of phenyl D that penetrate to the bottom of the active pocket interact at the catalytic position. Virtual screening showed that the scores of most derivatives were higher than that of corydaline and that the 15 open ring substances with the highest scores were mainly derived from those substituted by phenoxy groups and those with 2 to 7 carbon linkages. Based on these virtual screening results, compound 7 was synthesized and a pharmacological study showed that its inhibition activity was three times as high as galanthamine.

Antimony doped tin dioxide coated electrodes (Ti/SnO2-Sb2O5) on Ti substrates were prepared by the brush coating thermal decomposition method. Preparation conditions, structure, electrochemical characterization and service life of Ti/SnO2-Sb2O5 electrodes were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry (CV) and accelerated life test methods. Results show that Ti/SnO2-Sb2O5 electrodes have a dry cracked-mud coating structure. A Ti/SnO2-Sb2O5 electrode coating prepared at an annealing temperature of 550 ℃ and with a molar ratio of nSn:nSb=9:1 for the precursor solution has a flat and compact surface, few cracks, low porosity, and od stability.

An experimental procedure is presented for the synthesis of crouching hedgehog-like and core/shell AlOOH microspheres by a one-step hydrothermal process in an aqueous solution of trisodium citrate at 200 ℃. The structure, morphology, purity and size of the products were characterized by several techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption/desorption measurement and photoluminescent (PL) analysis. The reaction time and concentrations of trisodium citrate influenced the final structures and shapes of the AlOOHmicrospheres. Brunauer-Emmett-Teller (BET) analyses revealed high values (171.5 and 178.6 m2·g-1) of the specific surface areas for the crouching hedgehog-like and core/shell AlOOH microspheres. A possible formation mechanism of core/shell AlOOH microspheres is proposed and discussed based on the reaction dynamics process and the assisted growth process. The photoluminescent spectra of these nanostructures showed different emission bands and this difference might be because of their distinct sizes and morphologies.

Three CeO2 materials were prepared with precipitation (A), hydrothermal route (B) and citrate sol-gel (C) methods, and then used as the support of CuO/CeO2 catalysts, which were prepared by a deposition-precipitation method and examined with respect to their catalytic activities for the water-gas shift (WGS) reaction. The effect of the CeO2 support prepared with different methods on the structural properties, redox properties, catalytic activities and stabilities of the CuO/CeO2 catalysts for the WGS reaction was studied in detail using N2 physics adsorption (Brunauer-Emmett-Teller, BET), powder X-ray diffraction (PXRD), in situ PXRD, H2-temperature programmed reduction (H2-TPR) and cyclic voltammetry (CV). Results indicate that both the catalytic activities and stabilities of the as-synthesized CuO/CeO2 catalysts are CuO/CeO2-A>CuO/CeO2-B>CuO/CeO2-C. Characterization results show that catalytic activities of the CuO/CeO2 catalysts are closely related to the crystal size of CuO particles, the microstrain value for CuO, and the amount of moderate size copper oxides (crystalline) that interacted with ceria. These factors depend greatly on the thermal stabilities of the CeO2 supports. CV results suggest that the peak area of Cu2+←→Cu0 redox reaction decreased from the first to the second cycle, indicating that the electrode reaction is irreversible and this might be a reason for the observed deactivation of CuO/CeO2 catalysts after the temperature cycle.

We developed a low temperature solvothermal approach to synthesize single crystal silver nanoplates with edge lengths of 1-4 μm, thicknesses of 50-100 nm and aspect ratios ≥10 in a large-scale. In this solvothermal approach, N,N-dimethyllformamide (DMF) was used as a main reducing agent and as a solvent, polyvinylpyrrolidone (PVP) was used as a supplementary reducing agent and capping agent, and silver nitrates were used as precursors. The as-obtained silver products of high-purity were characterized by powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). We investigated the impact of different solvents on the morphologies of these silver nanostructures and proposed a possible growth mechanism for the as-synthesized silver nanoplates with large edge lengths and high aspect ratios. The current work provides a new reliable kinetic approach to tune the edge lengths and aspect ratios of silver nanoplates. The as-obtained silver nanoplates with large edge lengths and high aspect ratios have potential important application in polymer-based conductive composites and electromagnetic shielding materials.

The dielectric relaxation behavior of the sodiumdodecyl benzene sulfonate (SDBS) surfactant was investigated in a concentration range from0.1 to 80 mmol·L-1 by dielectric relaxation spectroscopy (DRS) method. Near the critical micelle concentration (CMC) of SDBS, significant relaxation phenomena of SDBS solutions around the frequency 107 Hz were observed. The dielectric data of the overall concentration were fitted by using the Cole-Cole equation, which revealed information about the relationship between dielectric parameters and concentration. Although the relaxation increment (△ε) increased with the concentration of SDBS (cs), this change exhibited two kinds of linear relationship, which intersected at an inflexion near 36 mmol·L-1. On the other hand, the curve of relaxation time (τ0) and concentration reached the lowest point at 45 mmol·L -1. Based on the spherical micelle model, the dielectric phenomena are due to the amount of bound Na+ counter-ions and the change in micellar volume.

(Ce0.9Nd0.1)1-xMoxO2-δ(x=0.00, 0.02, 0.05, 0.10) were prepared by a modified sol-gel method. Sample structures were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The ionic conductivity was systematically studied over a temperature range from 350 to 800 ℃ in air using impedance spectroscopy. Results showed that the materials were single phase with a cubic fluorite structure. A higher relative density was obtained for (Ce0.9Nd0.1)0.98Mo0.02O2-δsintered at 1200 ℃ for 24 h compared to the relative density of Ce0.9Nd0.1O2-δ. Impedance spectroscopy showed a sharp increase in conductivity for the ceria system that contained a small amount of MoO3. The solution (Ce0.9Nd0.1)0.98Mo0.02O2-δ was shown to be the best conducting phase as it had the highest conductivity (total conductivity (σt) is 2.42 S·m-1, grain boundary conductivity (σGB) is 3.96 S·m-1 at 700 ℃) compared to a sample that was not doped with Mo (σt=0.05 S·m-1, σGB=0.19 S·m-1 at 700 ℃).

The oxidation behavior of iodide ion on platinumelectrode in sulfuric acid media was investigated by the technique of cyclic voltammetry. The electrochemical performance showed that the electrochemical reaction of 2I--2e→I2 occurred when the potential scanning range lowered than 0.6 V(vs Hg/Hg2SO4). The obtained cyclic voltammograms were affected by the formation of iodine film and triiodide species. The whole reaction performance is consistent with electrochemical-chemical (E-C)model. Iodine filmcan be formed during electrochemical oxidation process and dissolved by chemical reaction of I2+I-=I-3 . When the electrode was polarized to over 0.6 V(vs Hg/Hg2SO4), high-valent iodine-containing compounds could be formed by I-+3H2O→IO-3+6H++6e, not by iodine which was the product of anodic oxidation. Two reduction peaks occurred during reverse cathodic potential scanning and they could be assigned to the reduction of iodine film and triiodide ion in the solution, respectively. The anodic oxidation of iodide ion is controlled by the liquid-phase diffusion process of iodide ion when there is no iodine film formed on the electrode. However, when iodine film is formed on the electrode, solid-phase diffusion process of iodide ion through the iodine film would become the rate determining step. In addition, the acidity of the solution would affect the process of anodic oxidation of iodide ion seriously. The onset potential and peak potential corresponding to the anodic current in linear sweep voltammetry are shifted to lower direction with the increase of acid concentration.

Using 13C solid-state nuclear magnetic resonance(NMR) we studied the structures of two spidroin-like polymers which were synthesized by the polymerization of polyalanine ((Ala)5) with oli mers of polystyrene(PS, MW=2000) and polyisoprene(PI, MW=2210). 13C CP/MAS (cross polarization/magic angle spinning) NMR spectra and spin-lattice relaxation time in the rotating frame (T1ρ(13C)) results of the polymers indicated that the chemical shifts of (Ala)5 in both polymers of polystyrene-co-polyalanine (PS-co-PAL) and polyisoprene-co-polyalanine (PI-co-PAL) were almost the same. This means that (Ala)5 peptide segments in the two polymers have similar chemical environments and secondary structures. The similar T1ρ(13C) values for (Ala)5 in the two polymers indicate that (Ala)5 peptide segments also have similar aggregate structures. The mechanical properties of the two spidroin-like polymers are quite different: PS-co-PAL is granular and tough while PI-co-PAL is rubber-like and tensible at roomtemperature. This indicates that the mechanical performances of spidroin-like polymers are strongly linked to the properties of the chosen polymers. The T1ρ(13C) values of the skeletons —CH2CH— in PI-co-PAL and PS-co-PAL were (5.3±0.4) and (47.0±5.5) ms, respectively, which indicates that PI segments are softer than PS segments in the polymers. In addition, the density functimal theory (DFT) based chemical shift calculation showed that (Ala)5 peptide segments in the polymers of PS-co-PAL and PI-co-PAL had dihedral angles of (-131°, 142°), which correspond to a β-sheet conformation.

A nano-TiO2 film electrode loaded with Pt nanoparticles (Ti/nanoTiO2-Pt) was prepared by a sol-gel method and electrochemical deposition technique. The formation of an anatase phase of TiO2 was confirmed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) images showed that cluster scattered state Pt particles were distributed on the surface of the multi-nanoporous TiO2 film and the average particle size of Pt particles was about 25 nm. The electrocatalytic oxidation of glyoxal on the Ti/nanoTiO2-Pt modified electrode was investigated by cyclic voltammetry (CV) and chronoamperometry. The results showed that the Ti/nanoTiO2-Pt modified electrode exhibited significant electrocatalytic activity for the oxidation of glyoxal. The oxidation peak potentials were 0.60 and 1.23 V (vs SCE (saturated calomel electrode)). Current densities were 16 and 42 mA·cm-2, respectively, and they were about 2 and 1.5 times as high as those of a pure Pt electrode. The reaction process was controlled by concentration diffusion.

We found an alternative method for the derivation of transition state structure energy in chemical reactions which would be less dependent on the starting geometry of reactants by combining a mathematical tool and artificial neural networks (ANN) with conventional transition state optimization al rithms. When two reactants approach each other, every geometric structure corresponds to a system energy value. The purpose of this investigation was to collect as many energy values on the reaction energy surface as possible. By simulating the energy surface using the geometric parameters as independent variables, the first order saddle point in the energy surface corresponding to the transition state structure was derived. The nucleophilic attack step of a classical Aldol reaction was studied using acetaldehyde anion and formaldehyde as reactants. The intrinsic reaction coordinate (IRC) path calculation started with 3 different sets of starting reactant geometries and 96 points on the reaction energy surface were derived. The energy surface was simulated using ANN. Cross-validation was applied to evaluate the result and avoided a possible overfitting of the ANN.

α-Al2O3 nanoflakes with od dispersion and uniform size were controllably synthesized using a self-burning method under similar conditions and with aluminum nitrate and glycin as raw materials. Product structure was studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, etc. Thermodynamic properties of the precursor were studied using thermogravimetry-differential thermal analysis (TG-DTA). The effects of different morphologies and sizes of α-Al2O3 nanomaterials on their polishing property were investigated for the first time. Results of the polishing study indicate that the small size nanoflakes with a high purity quotient have the best polishing property compared to other α-Al2O3 materials. This study is expected to have potential value for the industrial production and practical application of these α-Al2O3 nanomaterials in the polishing field.

Equilibria between square planar and pseudo octahedral species of the mixed diamine/β-diketonate Ni(II) complex ([Ni(II)(Me4en)(acac)]ClO4) in four kinds of alcoholic solvents were investigated by means of Vis-spectra. Equilibriumconstants and thermodynamic parameters, which included enthalpy changes (△H) and entropy changes (△S), were evaluated from peak fitting the thermo-solvatochromic Vis-spectra of this complex in the alcoholic solutions. Spectra of the involved square planar and the pseudo octahedral species were also derived from the same analysis. △H data showed that the formation of the pseudo octahedral species was exothermic and the △H values reflect the coordination ability of alcoholic solvents with the central Ni(II) ion. Absolute values of △S relate to the number of liberated alcohol molecules or those coordinated to the central Ni(II) ion. The calculation results are helpful to thoroughly understand the thermochromic behavior of the mixed diamine/β-diketonate ligand Ni(II) complex.

A carbon nanofiber (CNF) covered alumina composite of tri-lobular shape was synthesized by catalytic chemical vapor deposition using Ni as catalyst and ethylene as carbon source. Its morphology and microstructure, textural and mechanical properties, and crystallinity were investigated using N2 physisorption, scanning electron microscopy, particle crushing strength measurement and X-ray diffraction. It was shown that the CNFs grown on the surface of the tri-lobular granule alumina had a high degree of graphitization, and the alumina substrate and the CNF layer were combined into a composite, which had a mesoporous structure and a surface area larger than 187 m2·g-1. The pore volume of the composite was larger than 0.24 cm3·g-1 and more than 85% of the pore volume corresponded to a pore size range between 3 and 10 nm. The side crushing strength of the composite satisfied the requirements for industrial catalyst supports. Therefore, the composite is very promising for industrial application.

The H6P2W18O62/TiO2 (Brij-76) composite was prepared by a combination of the nonionic surfactant polyethylene glycol octadecyl ether polyoxyethulene 10 stearyl ether (C18H37(OCH2CH2)10OH)(Brij-76) as the template and a single-step sol-gel-hydrothermal method. The as-synthesized composite was characterized by Fourier transform infrared (FT-IR) spectrum, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), N2 adsorption-desorption and NH3-temperature programmed desorption (NH3-TPD). Results showed that the average pore diameter of the composite H6P2W18O62/TiO2(Brij-76) was ca 3.31 nm, and it had a large surface area of 99.78 m2·g-1. Additionally, the aggregation of particles was effectively inhibited and the surface acidity increased substantially. The photocatalytic elimination of monochlorobenzene was used as a model reaction to evaluate the microwave enhanced photocatalytic activity of the composite, and the results showed that the composite H6P2W18O62/TiO2 (Brij-76) could effectively degradate monochlorobenzene and had high catalytic activity under microwave irradiation.

Without anyorganic additives andmetal ions, hollowhydroxyapatite (HAp)microsphereswere successfully synthesized using hollow CaCO3 microspheres and Na2HPO4 as reactants. The hollow microspheres were characterized by scanning electron microscopy (SEM), field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). The results showed that the as-prepared HAp was hollow microspheres with diameter of 2-4 μm and were composed of many needle-like particles of 40-60 nm in diameter and 80-200 nm in length. The effects of synthesis conditions, such as reaction temperature, were studied. Furthermore, the reaction temperature has an important influence on the morphology of the hollow HAp microspheres. Based on this result, the formation mechanism of hollow HAp microspheres was discussed preliminarily.

Electron transfer through organic molecules is affected by several factors. The influence of electrodes, the interface between the organic molecule and electrodes, the environment and the molecular structure should be considered. In this paper, we reviewed theoretical and experimental studies of molecular electron transfer, such as the molecular dynamics simulations on the formation of the metallic electrodes, quantum chemistry studies on molecular conformation and conductance, and experimental studies of electron transfer in molecular junction using scanning probe microscopy and electrochemistry. Among the experimental methods, microscopic techniques such as scanning probe microscopy have been developed to study molecular electron transfer. Alternatively, macroscopic measurements have also been instructive to obtain the microscopic structural information.