Abstract:In order to make the xanthine oxidase (XOD) to be recoverable and durable, a new kind of immobilized XOD was prepared. The silica microspheres were chosen as the supporter and the carbon nanotubes (CNTs) were coated on the surface of microspheres by covalent bonding. Then, free XOD were immobilized on the surface of XOD@CNTs@SiO2. The morphology and chemical group on the new XOD@CNTs@SiO2 were characterized by TEM and FTIR, respectively. Uric acid, the reaction product, was used as the evaluation indicator of the relative activity. The loading of XOD was calculated by Bradford method. It was shown that, the loading and relative activities of XOD@CNTs@SiO2 were increased 2 and 2.6 times than XOD@SiO2. The relative activity could keep 80% after saving for 400 min under 60oC. The XOD@CNTs@SiO2 were kept under 4 oC and away from light, and the relative activity could still keep 60%-70% until the 11th day. Under the normal temperature, the relative activity could keep 66.1% after 9 times continuous reactions.

Abstract:Polyaniline/sodium alginate(PANI/SA) was successfully synthesized by oxidative polymerization of aniline using sodium alginate (SA) as soft template. The structure and morphology of the products were characterized by Fourier transform infrared spectrum (FTIR) and scanning electron microscopy (SEM). The electrochemical properties of the as-prepared PANI/SA were investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (CD) test and electrochemical impedance spectroscopy (EIS) in 1 mol/L H2SO4 aqueous electrolyte. The results showed that the specific capacitance of the prepared PANI/SA increased firstly but decreased then with the increasing of the concentration of SA. The PANI/SA appeared as a network morphology intertwined with the nanofibers and showed a higher specific capacitance of 459.7 F/g with the SA mass fraction of 0.01%, which was an improvement over that of pure PANI(20.8%).

Abstract:Vanadium oxides were synthesized by hydrothermal synthesis with vanadium pentoxide(V2O5) and sodium sulfite anhydrous(Na2SO3). The effects of preparation factors including pH, fullness, reaction temperature, the amount of sodium sulfite anhydrous were systematically studied. The valence, phase and morphology of vanadium oxides were analyzed by chemical titration, X–rays diffraction(XRD), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC). The results showed that the content of vanadium oxides could reach 98.5% under the optimal conditions of pH of 3, fullness of 0.7, reaction temperature of 250℃, n(V2O-5):n(Na2SO3) of 1:1.2 after purification. The total yield is 85.4%. The product is high purity needle-like VO2 powder with uniform morphology and fine crystalline. The product's diameter is about 80～100nm, the length is about 3μm, and the product is changed from B phase to M phase at 69.0℃after calcined at 800℃for two hours.

Abstract:Two kinds of adsorbents, Cu/AC-HN and Ag/AC-HN, were prepared by using an incipient wetness impregnation method using copper nitrate and silver nitrate as the raw materials and activated carbon treated by nitric acid（AC-HN）as the support. The effects of impregnants, calcination temperature, calcination time and amount of loaded on the adsorption capacity of low concentration of carbonyl sulfide(COS) at ambient temperature were investigated. The adsorbents were characterized by employing N2-physical adsorption, FE-SEM, TG-DTG, XRD and FTIR. Dynamic adsorption experiments results showed that the adsorption capacities of the adsorbents were significantly improved after modified. Silver ions were reduced to Ag0 in the surface of AC. The adsorbent Cu/AC-HN showed a better adsorption capacity and the active sites were existed in the form of Cu2O. The specific surface areas of the adsorbents were getting down and the functional groups of AC had no change after modified by Cu(NO3)2. The active sites phase of Cu/AC-HN showed high dependent on the calcination temperature in the preparation process. Copper nitrates were decomposed into CuO, then reduced to Cu2O by AC with the calcination temperature increased and the amount of Cu2O achieved maximun at 350℃. Above 350℃, Cu2O were reduced to Cu0 and the active sites were lowered. The adsorption capacity of AC was 7.5mg/g for removal carbonyl sulfide(COS), while the adsorption capacity of Cu/AC-HN reached 14.8mg/g. The optimal preparation conditions were as follows: the calcination temperature and time were 350℃ and 1.5h respectively, and the copper loading amount was 5%.

Abstract:The kaolin was modified by ball-milling method, using poly (methyl hydrosiloxane) (PMHS) as a hydrophobic modifier. Subsequently, immobilization of emamectin benzoate onto the modified kaolin particles was carried out by freeze-drying technology, and then the drug-loaded clays were encapsulated in Alginate matrix to form modified kaolin-calcium alginate composite microgel beads (MKL-CA-CMBs). The structure, morphology and property of the modified kaolin were characterized by laser particle size and zeta potential analyzer, FTIR, SEM, XRD, Specific surface area and pore size analyzer. Simultaneously, the drug-loaded property and release performance of MKL-CA-CMBs were also investigated. Experimental results showed that PMHS was absorbed onto the surface of kaolin via physical adsorption or chemical adsorption under the mechanical action of ball-mill. After the modification of kaolin, its size decreased, specific surface area and hydrophobicity increased, beneficial to the load of hydrophobic organic pesticide, making the drug loading rate (DLR) and encapsulation efficiency (EE) of kaolin-calcium alginate composite microgel beads (KL-CA-CMBs) upgrade from 6.5% and 53.1% to 9.7% and 72.5%, respectively. The slow-release performance of MKL-CA-CMBs was mainly based on the affinity of MKL to hydrophobic organic pesticide, and the release model of the formulation belonged to the Non-fickian diffusion model.

Abstract:Siloxane-modified two-component waterborne polyurethane (Si-2KWPU) was synthesized by the reaction between siloxane-modified hydroxyl-functional polyurethane aqueous dispersion（Si-HPUA）,which were prepared by prepolymer process,with isophorone diisocyanate(IPDI), polypropylene glycol (PPG), dimethylol propionic acid (DMPA) and trimethylolpropane (TMP) as main raw materials, dihydroxybutyl terminated polydimethylsiloxane (DHPDMS) as modifier, and the hydrophilic-modified polyisocyanate. The polymer structure and properties was characterized respectively by FTIR、1HNMR and XRD、TGA,and studied the effect of silicone content on the performance of hydroxyl-functional polyurethane aqueous dispersion and the 2K-WPU film. The results showed that the particle size of the dispersion increased,the viscosity decreased,the water absorption rate and tensile strength of membrane decreased,the water contact angle and elongation at break increased,with the increase of conent of silicone.When the mass fraction of silicone was 5%,the membrane had the best comprehensive performance.Water absorption rate and the contact angle were respectively 6.2%, 94.96°;The decomposition temperature of 5% mass loss was 272℃.

Abstract:In order to study the behaviors of waste cotton fiber under hydrothermal conditions, the carbonization process and physicochemical characteristics of waste cotton fiber were explored with microcrystalline cellulose and glucose as models. The structures and properties of different hydrothermally carbonized products were investigated with SEM, XRD, FTIR, XPS and EA while liquid products were characterized by HPLC. The results showed that cotton fiber could form carbon microspheres under hydrothermal conditions. Although the products of cotton fiber had similar crystal structures and oxygen functional groups with the carbonized products of microcrystalline cellulose and glucose, the morphology and properties were worse. Glucose was the key intermediate during the process of carbon microspheres formation from cotton fiber. As cotton fiber had low yield of glucose, only part of that could hydrolysis to simple sugars. These induce two different carbon paths. The main morphology of products is irregular particle. Decreasing the pH of reaction system may promote the cotton fiber carbonized into microspheres.

Abstract:Polyacrylate/nano-SiO2 was prepared by Pickering emulsion polymerization using modified nano-SiO2 powders as stabilizer of acrylic monomers. Taking monomer conversion rate and gel rate as examining index, the most optimization condition of the emulsion polymerization was established by the experiments. Morphology of Pickering emulsion was observed by optical microscope. The polyacrylate/nano-SiO2 latex and film was characterized by Dynamic Light Scattering (DLS), Transmission Electron Microscope (TEM), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope（SEM）. The results indicated that the emulsion was best when the mass ratio of SiO2 to triethoxyvinylsilane (A-151) at 5 to 1 and the mass ratio of MMA to BA at 1 to 4. FTIR result showed that the nano-SiO2 was successfully introduced. The results of DLS and TEM indicated that the latex particles had uniform size, and the size was roughly 790nm. SEM result showed that the nano-SiO2 was dispersed into the composite latex film. The polyacrylate/nano-SiO2 emulsion was applied in leather finishing process. The results show that compared with polyacrylate emulsion coating leather sample, permeability, water vapor permeability and dry wet rub resistance of leather samples coated by polyacrylate/nano-SiO2 composite emulsion were improved.

Abstract:To better understand N-nitrosodimethylamine (NDMA) formation when the ammonia nitrogen was coexist with organic nitrogen compounds, 50mg/L ammonia nitrogen was reacted with dimethylamine (DMA) during the disinfection process. Different reaction conditions such as reaction time, chloramines concentration, pH value and chlorine-nitrogen ratio (free chlorine to ammonia mass ratio) were researched. Furthermore, 3 kinds of representative organic nitrogen compounds (urea, glycine, phenylalanine) in waste water were investigated. The influences of organic nitrogen compounds on chloramines formation and NDMA formation were studied. It was suggested that the pH value and chlorine-nitrogen ratio were significant to NDMA formation. The peak point of monochloramine concentration which was generated by disinfection process moved to a higher chlorine-nitrogen ratio as the addition of the three organic nitrogen compounds. And the NDMA formation at the same chlorine-nitrogen ratio decreased as the addition of three organic nitrogen compounds.

Abstract:Horseradish Peroxidase (HRP) was immobilized on layered hydrogen peroxide, which was synthesized by hydrothermal method. Catalytic degradation characteristics of phenol wastewater by immobilized enzyme was studied under the conditions of microwave and ultrasonic combined treatment. Immobilized enzyme catalytic activity was investigated by means of UV analysis and kinetic constants of HRP immobilization were determined by Lineweaver-Burk double-reciprocal plot method. A comparison to phenol degradation efficiency and storage stability of immobilized enzyme under different conditions was conducted with liquid chromatography method. The results showed that the degradation efficiency of the immobilized enzyme was 74.4% under microwave-ultrasonic irradiation conditions, which was increased by 43.6% when phenol concentration was 60 mmol/L. Microwave–ultrasonic irradiation enhances enzyme activity, and hence the catalytic efficiency, by accelerating the decomposition of the said inhibitors. It was also found that the acceleration effect strengthens with an increased phenol concentration.After continuous use seven times, the degradation efficiency of irradiation group is still 5.06 times of that of the control group.

Abstract:By employing the H3PMo12O40 to assemble metal-organic framework((Cu3(BTC)2, BTC=1,3,5-benzenetricarboxylate), a metal organic frameworks composites, namely {H3PMo12O40@Cu3(BTC)2}?xG (G＝guest). Through X-ray powder diffraction pattern (XRD), Fourier transform infrared spectrum (FT-IR), scanning electron micrographs (SEM), thermogravimetric (TG), brunaue Emmett teller (BET) H3PMo12O40@Cu3(BTC)2 the composition, structure, morphology, stability and toleration of H3PMo12O40@Cu3(BTC)2 have been fully characterized. The adsorption of methylene blue onto H3PMo12O40@Cu3(BTC)2 in aqueous solution was studied. The effects of the experimental parameters, including sample solution initial pH, temperature and initial concentration have been investigated. The results showed that the lower temperature and lower initial pH value were beneficial to the dye adsorption. The experiment data could be well described by the Langmuir equations and pseudo-second-order kinetic model. Thermodynamic parameters ΔG<0，ΔΗ<0 and ΔS>0 indicated that the MB adsorption onto H3PMo12O40@Cu3(BTC)2 was spontaneous and endothermic, The adsorption towards methyl violet, rhodamine B, malachite green and basic fuchsine cationic dyes also showed good adsorption properties.

Abstract:The MLPB modified acrylate latex pressure sensitive adhesive(PSA) was synthesized via seed semicontinuous emulsion polymerization, using Maletic Anhydride grafted liquid Polybutadiene (MLPB) as crosslinking modification additives. The reaction mechanism of polymerization system, the influences of the MLPB content on the water resistance , thermal stability and adhesive properties of latex film were respectively investigated. The modified acrylate latex were then characterized. The results show that the latex with ω(MLPB)=5% make the latex film possess the best adhesive performance and water resistance, which the water absorption of latex film was 2.86%; The result of fourier transform infrared spectra(FTIR) indicates that it appears the copolymerization crosslinking reaction during the process of latex modification; The result of Contact Angle meter(CA) shows that the contact angle of latex film with ω(MLPB)=5% reaches to the maximum which is 108? The result of differential scanning calorimetry(DSC) reveals that the compatibility of the modified polymer system is well and the Tg of the latex film is gradually raised as the increase of MLPB content; The result of thermogravimetric analysis (TGA) demonstrates that the modified latex film own better thermal stability.

Abstract:The hemoglobin site-specifically modified with ferulic acid (FA-Hb) has been synthesized in order to analyze the autoxidation of FA-Hb. The effect on the characteristic absorption and the oxygen saturation curve of FA-Hb was investigated by UV spectro-photometry and oxygen analyzer. Furthermore, the autoxidation rate of Hb and FA-Hb was discussed, with or without nitrogen sodium, xanthine- xanthine oxidase mediated in the system. The results showed that the heme structure of FA-Hb is the same as the hemoglobin. It also demonstrated that the oxygen carrying activity of them is same. But, the autoxidation rate of FA-Hb is much lower than Hb in different systems.

Abstract:Effects of the silica source, the Si/Al ratio, and the content of template agent and H2O on the synthesis of ZSM-12 zeolite were studied. The optimal conditions for synthesis of pure ZSM-12 were determined as n(Si)/n(Al)=45～70, n (TEAOH)/(SiO2) =0.14 and n (H2O)/n (SiO2) =13 under conditions in this investigation. The physical properties of the products were characterized by means of X-ray diffraction, field emission scanning electron microscopy, N2 adsorption, and NH3-temperature programmed desorption. The results showed that colloidal silica was the best silica source and the Si/Al ratio had major effects on the crystalline phase of the product and the crystalline dynamics under the conditions studied. More specifically, the MFI-type and BEA-type zeolites appeared in product with low Si/Al ratio, and the dynamic crystallization was more effective than the static crystallization in the synthesis with high Si/Al ratio. The ratio of both TEAOH/SiO2 and H2O/SiO2 had strong effect on the phase and morphology of the as-synthesized products.

Abstract:Yttrium oxide, lanthanum oxide and cerium oxide modified SAPO-34 (M-SAPO-34，where M= Y 、La、Ce) were prepared by hydrothermal method, respectively. The samples were characterized by the methods of XRD, SEM, FT-IR, BET, NH3-TPD and TG. The results show that rare earths were added into SAPO-34 framework. They have higher specific surface area and smaller particles size, as well as the changes in the pore diameter and acidity. Bifunctional catalysts of CuO-ZnO-ZrO2/M-SAPO-34 were prepared by mechanically mixing M-SAPO-34 with CuO-ZnO-ZrO2 in the weight ratio of 1:1. Its catalytic activity for carbon dioxide hydrogenation to light olefins was investigated. Under the conditions of reaction temperature at 400℃, pressure at 3.0 MPa，space velocity (SV) of 1800 mL/(gcat •h)，CO2/H2 (molar ratio) of 1:3，bifunctional catalyst mass of 1.0g, CuO-ZnO-ZrO2/La-SAPO-34 exhibited better catalytic activity, the conversion of CO2 could reach to 49.7% with a light olefins selectivity and yield of 54.5% and 27.1%, respectively.

Abstract:The application of graphene in catalytic field is getting more and more attention. In present paper, the system of naphthalene - tert-butyl hydroperoxide (TBHP) - graphene oxide was constructed and the effect of graphene oxide (GO) on the oxidation process of naphthalene was studied in detail. The effects of graphene oxide species, types of solvent, oxidant content, the amount of graphene oxide, reaction temperature and reaction time on the oxidation of naphthalene were investigated. The results showed that graphene oxide can improve the conversion of naphthalene and the yield of 1,4-naphthoquinone. Optimum results were achieved when the amount of naphthalene was 100 mg, oxidant (TBHP) 2.4 mL, graphene oxide RGO (10 wt%) 20 mg, reaction solvent acetic acid (1.2 mL), the reaction temperature 100 ℃, reaction time 22 h . On the basis of results obtained, the mechanism of oxidation process of naphthalene in the presence of GO was discussed.

Abstract:A series of phosphotung-based catalysts was synthesized by a impregnation method using silicone ball as the support．The supported catalysts were characterized by XRD，FT-IR，UV-Vis DRS．The catalytic behaviors of these catalysts in the oxidative reaction of maleic acid to DL-tartaric acid have also been investigated．The results indicated that tungsten could more effectively dispersed in the surface of the carrier after adding phosphate．The surface properties and oxidation catalyst performance were effectively adjusted by controlling charge number of PW. The supported catalyst had better catalytic reactivity when molar ratio of W/P was 1:2，Charge number was 30%，activation temperature was 400℃and activation time was 4h．The conversion rate of maleic acid was 96.5% and yield of DL-tartaric acid was up to 91% when the mass fraction of catalyst in mixed solution was 2.5%，reaction temperature was 70℃，reaction time was 3h，hydrolysis temperature was 105℃ and hydrolysis time was 3h．

Abstract:Catalytic performances of copper complexes, which consisted of Cu(OAc)2 as a copper source and 2,2'-biimidazole (H2biim), 1,1′-dimethylene-2,2′-Biimidazole (DMe-H2biim) or l,l'-ο-Xylylene-2,2'-biimidazole (Oxy-H2biim) as a ligand, were investigated in oxidative carbonylation of methanol to dimethyl carbonate (DMC), and Cu(DMe-H2biim)(OAc)2 was characterized by infrared spectroscopy, thermogravimetric analysis and CO temperature-programmed reduction. It was found that DMe-H2biim exhibited the higher performance for DMC synthesis than H2biim and Oxy-H2biim due to the electron-donating effect of the methylene group, and the catalytic activity of Cu(DMe-H2biim)(OAc)2 was higher than that of the equimolar mixture of Cu(OAc)2 and DMe-H2biim. The turnover number and the selectivity of DMC reached 20.4 molDMC/molCu and 95.8% under the conditions of Cu(DMe-H2biim)(OAc)2 as the catalyst, reaction time 4 h, reaction temperature 110 癈 and the concentration of the catalyst 0.011 mol/L.

Abstract:To explore a new route for the synthesis of efinaconazole, intermediate 4-[(R)-2-hydroxypropiony]morpholine（Ⅱ）was prepared from starting materials R-methyl lactate by amination with morpholine, (2R)-2’,4’-difluoro-2-(3,4,5,6-tetrahydro-2H-pyran-2- lyoxy)propiophenone（Ⅳ） was synthesized by reacting with 2,4-difluorophenyl magnesium bromide after hydroxy group was protected. Precursor (2R,3R) -2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazol-1-yl)- 2,3-butanediol（Ⅶ） was obtained via Corey-Chaykovsky epoxidation, trizole alkylation and deprotection in one pot reation. After reacting with methanesulfonyl chloride , epoxidation and subsequent alkylation with 4-methylenepiperidine, the product efinaconazole（Ⅰ） was acquired. The total yield of efinaconazole（Ⅰ） was increased from 17% to 24% with purity of more than 99% determined by HPLC. The stucture of product was characterized by means of 1HNMR, ESI-MS and polarimetry.

Abstract:In order to explore the new synthetic route of quinoxaline，1, 2, 3, 4-Tetrahydro-6H-indolo [2,3-b]quinoxaline was synthesized from Ortho-diaminocyclohexane and isatins by air oxidation.12 compounds were synthesized and their structures were confirmed by IR, 1HNMR and MS. Compound 9-fluoro-1,4-dihydro-1H-indolo[2,3-b]quinoxaline (Ⅰl ) and 9-methyl-1,4-dihydro-1H-indolo[2,3-b] quinoxaline (Ⅰm ) use X-ray diffraction analysis. The results showed that the target structures products were obtained.