Abstract:Decarboxylation of amino acids is considered to be a significant pathway of renewable resource transformation, and could convert to primary amine, diamine and their derivatives. Various methods of amino acids decarboxylation were reviewed, including the way of using biocatalysts, chemical catalysts, thermal decomposition and photoelectrochemistry. China has become a country with the big amount of amino acids production and consumption. The development of food and feed industry of amino acids industry is on the way to maturity, however the industry realization of the downstream products is still lack of technology and experiences. Therefore, developing new high efficient catalysts and more efficient routing seems important to break the monopoly of the core technology of amino acids industry.

Abstract:The metal porphyrin frameworks (MPFs) is a new type of periodic mesh structure material constructed from porphyrin or metal porphyrin as a structural unit, which not only has the unique advantage that porphyrin can expand the spectral response range and reduce the photosynthetic electron-hole compound rate, but also has the advantage of the porosity , pore size adjustability and large specific surface area of MOFs. So the MPFs have become a new type of photocatalyst with good photoelectric properties at present. In recent years, many scientists have been committed to the development and application of MPFs, and many gratifying results have been achieved. This paper mainly describes the latest applications of porphyrin/metal porphyrin MOFs in the fields of carbon dioxide reduction, photocatalytic hydrogen production, photodegradation organic dyes, etc. and looks forward to the future development of MPFs in the field of photocatalysis.

Abstract:A series of humic acid modified waterborne polyurethane emulsions (HAWPU) were successfully synthesized with poly-caprolactonediol (PCL), isophoronediisocyanate (IPDI), dimethylolpropionic acid (DMPA), trimethylolpropane (TMP) as the basic raw material and humic acid (HA) as the modifier. The structural characterization and performance tests of HAWPU were carried out by FTIR, DLS, TGA, SEM and mechanical analysis. The effects of HA addition on the appearance, particle size and Water absorption rate, thermal stability and mechanical properties of HAWPU emulsion were investigated. The results showed that HAWPU emulsions had good particle size distribution and storage stability. When the HA mass fraction is 0.3% (accounting for the total mass of the emulsion system), the average particle size of the HAWPU emulsion is only 47.60 nm. The tensile strength of the film can reach 52.54MPa, which is 55.8% higher than WPU. The thermal stability is also significantly improved, and the temperature at which the mass fraction is lost by 50% (the mass before the film is pyrolyzed) is 334 ℃, which is higher than that of the WPU film (322 ℃).

Abstract:Palygorskite was firstly modified by phosphate through the surface hydroxyl groups, then dodecylamine was grafted to phosphate by acid-base reaction to produce the phosphorus and nitrogen-containing PGS@P-N flame retardant. The structure and morphology of PGS@ZB-N were characterized by FTIR, XRD and SEM methods. The flame retartancy and burning behavior of EVA/PGS@P-N/EG (EG = expandable graphite) composites were studied through TGA, LOI (limiting oxygen index), UL-94 (vertical burning test) and CCT (cone calorimeter test) characterizations. It showed that the prepared EVA/PGS@ZB-N/EG composites obtained a LOI value of 36.3% with the addition of 30 wt% of PGS@P-N/EG flame retardant. PGS@ZB-N can improve simultaneously the interfacial interaction and the mechanical properties of EVA.

Abstract:Thermo-associative cationic cellulose(TACC) was synthesized by regulating hydrophilic-lipophilic balance of cellulose derivatives. Hydroxyethyl cellulose reacted with hydrophobic reagent-butyl glycidyl ether(BGE) to prepare hydrophobic cellulose, and further reacted with cationic reagent-2, 3-epoxypropyl trimethyl ammonium chloride(GTA) to prepare thermo-associative cationic cellulose(TACC). The obtained product was characterized by FTIR, 1 H-NMR and Elemental Analyses. These prove that BGE and GTA were successfully grafted onto the TACC. The influences of the degree of GTA, concentrations of TACC aqueous solution and concentrations of NaCl on the thermothickening properties of TACC were investigated. The results showed that: When the degree of GTA increased from 0.12 to 0.32, the maximum viscosity(ηmax) value of 15g/L TACC aqueous solution increased from 13 mPa•s to 54 mPa•s, the ratio of maximum and minimum viscosity(ηmax/ηmin) increased from 1.5 to 7.0, and the temperature(Tmax) corresponding to the maximum viscosity value increased from 25 °C to 40 °C; The increase of the concentration of TACC aqueous solution improved its viscosity and thermothickening properties, but the Tmax didn’t change; On the contrary, the increase of NaCl concentration reduced the viscosity and thermothickening properties, and the Tmax also reduced.

Abstract:The amphiphilic water-soluble polymer was prepared from acrylamide, acrylic acid and styrene via self-emulsification microemulsion method. It can avoid back treatment of an excess of low-molecular weight emulsifier in comparison with the conventional microemulsion polymerization. In addition, the mechanism of self-emulsified microemulsion polymerization was explored. FTIR, 1HNMR results showed that the copolymerization of acrylamide (AM) with acrylic acid (AA) and styrene (St) was carried out. The DSC result showed that the copolymer had a block structure. The surface tension tester and numerical viscosity test results showed that when the monomer ratio of m(AM):m(AA):m(St) is 87.5:10:2.5, the surface activity and viscosity of the copolymer solution were 26.113 mN/m and 1260 mPa·s, respectively. Furthermore, the aggregation state of molecular chains in the copolymer solution was explained in the presence of different levels of hydrophobic monomers.

Abstract:Poly(butyl fumarate) (PBF) was successfully synthesized by two-step reaction with diethyl fumarate and 1,4-butanediol as basic raw material. The polymers were characterized by FTIR, 1HNMR, GPC, TG and DSC. The effects of reaction parameters on the yield of PBF were studied. Based on the polymerization mechanisms, the reaction time, temperature and doses of alcohol were investigated to achieve maximum polymer yield. The results suggested that the appropriate molecular weight (Mn=2773) and higher yield (61.94%) of PBF are obtained when the molar ratio of diethyl fumarate and 1,4-butanediol is 1:3, the reaction temperature is 130 ℃ and the reaction time is 8 h. PBF/N-Vinyl-2-pyrrolidone (NVP) composite was prepared by UV-curing and thermo-curing respectively. And the effects of initiator dosage on crosslinking and curing degree of the composite were also investigated. The results showed that crosslinking and curing effect of the composite were better, when the dosage of photoinitiator and thermal initiator were 2.5% phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide (BAPO) and 3% benzoyl peroxide (BPO) [0.2% N,N-Dimethyl-p-toluidine (DMT)], respectively.

Abstract:The conditions of coagulation process and of tiny-polluted raw water in China were taken as a background, the preliminary degradation of Poly(dimethyldiallylammonium) chloride（PDMDAAC）reacting with mono-chloramine, finally to form disinfection by product NDMA was taken as the research object, the reaction kinetics of mono-chloramine and PDMDAAC were studied by means of initial reactant concentration and isolation independently within a range of temperature 15~35℃in this paper. The results showed that the general reaction order was conformed to be more than 1.99, closed to 2; the reaction order for mono-chloramine and PDMDAAC were all more than 0.9971, and coefficient of correlation R2 was more than 0.9971. The reaction rate constant was 1.23×10-5L/(mol•h) at 25℃.And the reactive activation energy Ea was 44.22kJ/mol, approximately. Thus, the kinetics research on the starting stage of PDMDAAC reacting with mono-chloramine to form NDMA was completed.

Abstract:Adsorption behaviors and mechanism of Cu2 in solution by Pomelo peel powder composite superabsorbent (PP-SA) were studied. The influences of intial CuSO4 concentration and adsorption time on Cu2 adsorption capacity of PP-SA were investigated. The thermodynamic adsorption isotherms and adsorption kinetics models were adopted to fit the data. PP-SA saturated with Cu2 was characterized by X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TG) and the adsorption mechanisms were proposed. The results showed that the adsorption capacity of Cu2 for PP-SA in 2000 mg/L CuSO4 solution was the highest, reaching to 199.3 mg/g in about 4 h. The Cu2 adsorption process followed the pseudo-second-order kinetic model and the data were fitted to the Langmuir isotherms. The Cu2 adsorption on PP-SA can be achieved by ion exchange adsorption, chelation and electrostatic attraction. The copper species absorbed in PP-SA exist as Cu2 , a small part of which is CuSO4.

Abstract:A solid phase extraction material with specificity extracting clobetasol propionate of molecular capture was prepared by surface imprinting technique in combination with based on solid phase extraction column sieve plate coated with graphene oxide. The molecular capture(MC) was prepared by using clobetasol propionate as template molecule, 3-Aminopropyltriethoxysilane as monomer and ethyl silicate as cross-linker, respectively. The morphology and structure of the molecular-catcher was characterized by FTIR, FESEM, EDS and TGA. The molecular capture was studied by the re-binding experiments, such as adsorption kinetics, adsorption isotherm, molecular identification, applied to the separation and enrichment of clobetasol propionate in cosmetic. The results showed that the molecular capture has a fast adsorption equilibrium, highly improved imprinting capacity and significant selectivity; the detection limit was 0.04 mg/L (S/N=3). The durability test showed that the MC could be reused more than 4 times by re-binding experiments.

Abstract:With complex of p-nitrobenzyl alcohol (p-NBA) and nickel nitrate hexahydrate as template molecule, acrylamide (AM) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent, the Ni nanoparticle molecularly imprinted polymer (Ni-MIP) was prepared by bulk polymerization. The prepared Ni-MIP was characterized by FTIR, UV-Vis, SEM and TEM. Using non-molecularly imprinted polymers of Ni-NIP and NIP as comparison samples, the catalytic activity and selectivity of Ni-MIP for p-NBA were investigated. The results show that in the oxidation reaction of p-NBA with water as solvent and H2O2 as oxidant, the conversion of p-NBA reaches 72% after 1 h with Ni-MIP as catalyst. The conversion rate of p-NBA is 64% with Ni-NIP as catalyst, and NIP has no catalytic effect. The catalytic efficiency of Ni-MIP is 24% for p-NBA structural analogue of o-nitrobenzyl alcohol (o-NBA), which is much lower than that of Ni-NIP. It is indicates that the Ni-MIP catalyst has imprinted cavity matching the substrate molecule p-NBA, which can realize specific recognition catalysis.

Abstract:Sr2Ni0.4Co1.6O6 double perovskite oxide was prepared by sol-gel method, and thin layer graphene was pre-pared by modified Hummers reduction method. They were synthesized as catalysts for bifunctional cata-lysts, and used to test its oxygen catalytic performance. The analysis results (XRD, EDS, SEM, IR etc) in-dicate that Sr2Ni0.4Co1.6O6 is homogeneously dispersed on the surface of graphene layers. Electrochemical performance tests show that the maximum current densities of single Sr2Ni0.4Co1.6O6 and thin layer gra-phene oxygen reduction reaction (ORR) are 183.0 mA/cm2 and 151.6 mA/cm2 (-0.6 V vs Hg/HgO), respec-tively, and the maximum current densities of the oxygen evolution reaction (OER) are 267.7 mA/cm2 and 117.4 mA/cm2(1 V vs Hg/HgO). When the amount of thin layer graphene add is 10 % of the mass of the composite catalyst, the composite catalyst has the best oxygen catalytic performance, the maximum cur-rent density of ORR is 290.1 mA/cm2(-0.6 V vs Hg/HgO), and the maximum current density of OER is 390.5 mA/cm2(1 V vs Hg/HgO). It shows that the composite has excellent oxygen catalytic performance than the single catalyst.

Abstract:A series of sodium lauryl polyoxypropylene ether sulfates (SLPpS, p = 3, 6 and 9) were synthesized from natural lauryl alcohol by propoxylation and sulfuric acid esterification followed by neutraliza-tion. The structures of the products were confirmed by FTIR and 1HNMR. Their interfacial and micellar solution properties, such as surface tension, foamability, emulsifying power, wettability, detergency and calcium tolerance were investigated. Compared with two traditional surfactants, sodium dodecyl sulfate (SDS) and sodium lauryl ether sulfate (SLE3S), the effect of polyoxypropylene (PPO) chain on the properties of extended surfactant was discussed. It was found that the PPO chains not only provided lipophilic contribution to the SLPpS molecules, which resulted in the surface tension of SLPpS being as low as 32.1 mN/m and their critical micelle concentrations reaching the order of magnitude of 10-4 mol/L. These SLPpS surfactants exhibited better emulsifying power, wettability and detergency than SDS and SLE3S. The PPO chains but also provided a weak polar contribution to the surfactants, the critical micelle temperature was lower than 0℃ and calcium tolerance was 30 times stronger than that of SDS. Therefore, SLPpS can be used in personal care and household cleaning products.

Abstract:The fatty alkyl trimethyl ammonium oxalate was synthesized with Oxalic acid andalkyltrimethylammonium methylcarbonate, which was prepared by the reaction of alkyl tertiary amine and dimethyl carbonate (DMC). Take tetradecyltrimethylammonium oxalate as an example, the influences of reaction regents, reaction temperature, reaction time, the concentration of alkyl tertiary amine were investigated. And the optimized conditions were reaction at 150 ℃ in DMC for 3 h, the concentration ofalkyl tertiary amine 0.05 g/mL. Under the optimized conditions, the productivity could reach 85%. The structure of the products were characterized by means of 1HNMR, and the results showed that fatty alkyl trimethyl ammonium oxalates were synthesized successfully.

Abstract:3,4-Dihydropyrimidin-2(1H)-ones were synthesized via α-chymotrypsin-catalyzed Biginelli reaction between aromatic aldehyde, urea and ethyl acetoacetate. Through optimization, the optimal reaction conditions were obtained as follows: the reaction medium was ethanol, the molar ratio of aromatic aldehyde to ethyl acetoacetate and urea was 1:1.5:1, the amount of α-chymotrypsin was 20 mg, the reaction temperature was 60℃ and the reaction time was 96 h. Under this optimum reaction conditions, a series of 3,4-dihydropyrimidin-2(1H)-ones derivatives having a yield of 55% to 63% were obtained. The method has the advantages of mild reaction conditions, simple operation and broad application range of the substrates.

Abstract:With the amount of hypericin extracted as the response value, response surface methodology was used to study and optimize the effect of hypericin in hypericum attenuatum. The optimal extraction process was obtained. The cytopathogenic effect (CPE) method was used to detect the anti-infectious bronchitis virus (IBV) effects of hypericum attenuatum. The results showed that a mathematical model for ultrasonic extraction of hypericin from hypericum attenuatum was established，and the optimum conditions for extracting hypericin by ultrasound were as follows: extraction temperature 40.5?C, acetone concentration 69.5%, extraction time 43.5 min, ratio of liquid to material 15.3, and the extraction rate of hypericin was 4.70mg/. g, consistent with the theoretical value. The main effect relationship was extraction time > acetone concentration > extraction temperature > liquid to material ratio. The extract of hypericum attenuatum extract before, after and at the same time when cells were infected with IBV significantly inhibited the effects of CPE. It showed that the ultrasonic extraction process of hypericum attenuatum choisy was reliable, and the extractive amount of hypericin was much higher than that of routine extraction method. Hypericum attenuatum choisy had a good anti-IBV effect.

Abstract:The total flavonoids in eucalyptus citriodira were extracted and purified by solvent extraction, and the antioxidant activity and purification of crude extract(A) were studied. Total flavonoids in resin were qualitatively identified by hydrochloric acid-zinc powder, concentrated sulfuric acid, ferric chloride and aluminum nitrate. Total flavonoids content（based on the quality of eucalyptus citriodira resin solid powder） was 4.64% by quantitating analysis with rutin as standard substance. B、C、Dpurifications of different purity were obtained by chloroform-butyl acetate, chloroform-dimethyl formamide, dimethyl formamide-chloroform ultrasonic extractions. The total flavonoid mass fraction of B, C, D were 10.39%, 18.03% and 44.15%.The scavenging activities of 2, 2-diphenyl-1-bitter hydrazine (DPPH·), total antioxidant capacity and reduction capacity of A, B, C, Dwere investigated. The scavenging activities of DPPH· were 91.75%, 74.22%, 88.44%, 91.56%; Total antioxidiant activities were 19.99, 1.75, 4.39, 3.79μmol rutin equivalent(RE)/g. The reducing abilities were 1.16,0.36,0.39,0.45μmol RE/g.

Abstract:Esterification of acetic acid with isobutene to tert-butyl acetate catalyzed by zirconium composite oxide and macroporous strong acid cation exchange resin has been investigated. Acid strength and the number of acid site of catalysts were measured by potentiometric titration with n-butylamine. The results show that the conversion of isobu-tene increases with the amount of acid increasing, but the selectivity of tert-butyl acetate decreases with the acid strength increasing. A maximum selectivity for TBA and conversion of isobutene could be achieved at 95.98% and 80% respectively, while hydrocarbon mixture which contains 10% isobutene as feedstock for esterification catalyzed by cation exchange resin.

Abstract:To use sugar beet pulp as a high-effective catalyst for the degradation of dye wastewater, de–pectinated sugar beet pulp(DSBP) was modified using citric acid to introduce the carboxyl groups, citric acid-esterification sugar beet pulp fiber (CDSBP) was coordinated with Fe3+ ions to produce carboxylic fiber Fe(CDSBP-Fe). The surface morphology and chemical structure were characterized by FTIR, XRD, and SEM. Then, the catalytic performance of CDSBP-Fe was evaluated as heterogeneous light Fenton catalysts for oxidative degradation of reactive red 195. The results show that the carboxyl groups have been introduced into surface structure of fiber by ester linkage with citric acid and coordinated with Fe3+ ions to prepare carboxylic fiber Fe. The degradation of azo dye was significantly accelerated by the presence of CDSBP-Fe under visible irradiation, and the degradation rate was up to 95.6% after 25 min; CDSBP-Fe showed good degradation performance in the pH range of 3~9. Additionally, no significant catalyst deactivation was noted after five succesive runs.

Abstract:A kind of chitosan-derived solid acid (CASA) material with chitosan as a precursor was successfully synthesized via in situ partially hydrothermal carbonization and sulfonation method. Thereafter, the CASA material was used for catalytic fructose dehydration to 5-hydroxymethylfurural (5-HMF) under solvent-free conditions. The effects of catalyst amount, reaction temperature, reaction time and catalyst recyclability on the dehydration were studied in detail. Meanwhile, comparison of catalytic activities with the chitin-derived solid acid (CISA) material was further investigated. Besides, the obtained CASA material was characterized by various techniques, such as X-ray diffraction, scanning electron microsco-py and infrared spectra of pyridine adsorption etc. The structure-performance relationship was built by elucidating the structural and acidic properties of the material. According to the results, it was suggested that adequate strong Brӧnsted surface acid sites were grafted onto the CASA material, indicating the su-perior catalytic performance for 5-HMF production to the CISA material. The 5-HMF yield was obtained up to 63.2% at 120 ℃ within 5 h when the mass ratio of fructose to CASA material was 6:1. It was no-ticeable that the CASA catalyst could be recycled up to 4 times without any obvious deactivation.

Abstract:On the basis of single factor experiments, the effects of acid type, acid concentration, ultrasonic time, solid-liquid ratio, ultrasonic power and temperature on the extraction of alkaloid salts from lotus leaves were studied by response surface analysis and optimization of extraction methods. At the same time, the purification effect of D101 macroporous resin on the extract was explored. The results showed that the optimum technological conditions of lotus leaf alkaloid salts were as follows: heating temperature 60 C, ultrasonic power 500 W, concentration of hydrochloric acid 0.3%, ultrasonic time 41 min, liquid-solid ratio 27:1, and the yield of lotus leaf alkaloid was 4.12±0.05 mg/g. 70% ethanol was determined as elution concentration. The purity of purified alkaloid salts reached 40.81%.

Abstract:The composition of hesperidin hydrolysate is complicated, including saccharides, hesperetin and hesperetin-7-O-glucoside（HMG）. HMG from hesperidin hydrolysate was separated and purified by six macroporous adsorption resins and high performance semi-preparative liquid chromatography. The structure of the product was characterized by IR, UV-Vis and XRD analysis. And the antioxidant activities of HMG, hesperidin and hesperetin were compared by hydroxyl radical scavenging test. The results showed that HPD300 macroporous resin was the most suitable resin for the purification of HMG from enzymatic hydrolysis solution. The static and dynamic total adsorption amounts of HPD300 resin to the main components of enzymatic hydrolysis solution were 48.35 mg/g and 35.82 mg/g, respectively，which were mainly used for separation of sugar impurities. The purity of HMG in the eluent was increased from 80.37% to 97.83% by using 10BV, 45% ethanol as eluent with the flow rate of 1.2 mL/min. The final purity of monomer HMG, was 98.21% after further separation and purification by semi-prepared liquid phase. The product was verified as HMG by UV-Vis, IR and XRD spectra. And the hydroxyl radical scavenging capacity of HMG was slightly higher than those of hesperetin, much higher than that of hesperidin.

Abstract:A series of Cu-ZnO-ZrO2 catalysts were prepared by sol-gel method using nitrate and citric acid as raw materials by adding ammonia water to adjust the pH value of the solution. XRD, thermal analysis (TG-DSC), N2 adsorption desorption (BET), H2 temperature programmed reduction (H2-TPR), CO2 temperature programmed desorption (CO2 -TPD), SEM,TEM and Fourier transform infrared (FTIR) spectroscopy were used to characterize the catalysts. The catalyst activity was evaluated in a high temperature and high pressure fixed bed reactor. The effect of pH of solution on the structure of dry gel and the performance of catalyst was discussed. The results showed that there was an uncoordinated free carboxylic acid in the dried gel prepared at pH 0.5, and some carboxylic acids were coordinated with metal ions through the carboxyl group. The free carboxylic acid was not present in the dried gel prepared at pH 4, 6, 8, and 10. The carboxylic acid was coordinated to the metal ion through the carboxyl group. The change of pH regulated the coordination ability between Cu2+, Zn2+, Zr4+ and citric acid. The catalyst prepared at pH 6 had a large specific surface area and copper dispersion, with a specific surface area of 92.5 m2/g and a copper dispersion of 18.63%, which exhibited better methanol synthesis by CO2 hydrogenation performance,Xco2=24.7%,SCH3OH=42.3%.

Abstract:L-menthol was synthesized by using d-citronellal as raw material.The optimal reaction conditions were selected by investigating the reaction temperature, reaction time, catalyst dosage and catalyst steric hindrance. The results showed that the optimal reaction conditions were that toluene as solvent, d-citronellal as starting material, aluminum atom as the center, triphenylphenol as ligand, the amount of catalyst was 1% (mole fraction), reaction temperature was 0 ℃，the reaction time was 3 h, and an intermediate product was obtained by distillation under reduced pressure, followed by hydrogenation reduction to obtain 1-menthol, the total yield was 76%, and the GC purity was above 99%.

Abstract:5-Aminosalicylic acid is either an important clinical drug or an intermediate in the synthesis of drugs, which can significantly inhibit the inflammation of the intestinal mucosa. Therefore, the research on its synthetic process is of great significance. Here it is reported that the synthetic process of 5-aminosalicylic acid is mainly improved by the “one-pot” strategy. Starting from 2-chlorobenzoic acid, the nitration reaction was carried out by the mixed acids of n (mass fraction 98% sulfuric acid): n (mass fraction of 65% nitric acid) = 6:1, and then nucleophilic substitution reaction with 15% sodium hydroxide obtained the intermediate 5-nitrosalicylic acid, and finally reduction by the reducing agent, iron powder/zinc powder and concentrated hydrochloric acid, gave the final product 5-aminosalicylic acid. The total yield of this synthetic process is 61%, and the structures of intermediate and product were characterized by IR, 1HNMR and MS.

Abstract:Ultra performance liquid chromatography tandem mass spectrum/ mass spectrum (UPLC-MS/MS) was used to detect chlorpromazine residue in porcine muscle, liver, chicken and fish. Three sample preparation methods, including QuECHERS, MCX solid-phase extraction, and direct extraction by tert-butyl methyl ether, were compared. The results showed that the limit of detection (LOD) of the three methods for chlorpromazine was 0.2 μg/kg, and the limit of quantitation (LOQ) was 0.5 μg/kg. The recovery and relative standard deviation (RSD) of the three sample preparation methods at different addition levels were 75.5%~108.1% and 2.1%~7.5%, respectively. The detection limit, recovery, and RSD meet the methodological requirements. The purifying effect of MCX solid-phase extraction was better than the other sample preparation methods. The order of recovery was as follows: MCX solid-phase extraction, QuECHERS, and direct extraction by tert-butyl methyl ether. The recoveries of all the three methods for porcine muscle were lower than that for liver, chicken and fish.

Abstract:Microwave-assisted extraction (MAE) of total anthocyanins (TA) and phenolics (TP) from raspberry pomace was optimized using Box-Behnken design method in response surface methodology. Raspberry pomace anthocyanins components were identified by liquid chromatography-mass spectrometry, and SEM was employed to observe the microstructure of samples after microwave assisted extraction and conventional solvent extraction (CSE). The results showed that the optimum extracting parameters to achieve the highest TA extraction rate of 4.20 mg C3G/g and TP extraction rate of 16.05 mg GAE/g from raspberry pomace was obtained under an extraction temperature of 61 ℃, liquid-solid ratio of 30:1 mL/g and extraction time of 5 min. The cell structure of the sample was seriously damaged after microwave extraction, but the cell structure of the sample was well preserved after traditional solvent extraction. The yields of TA and TP obtained through MAE method were higher than those using a CSE method. Six major kinds of anthocyanins were identified from raspberry pomace in terms of delphinidin-3-glucoside, cyanidin-3-rutinoside, petunidin-3-glucoside, peonidin-3,5-two hexoside, peonidin-3-(6-malon)-glucoside and pelargonidin-3-(6-malon)-glucoside. The results of study can provide an effective method for the extraction of active components from the residue of food industry.

Abstract:The potassium tin sulfied (KSnS) was prepared by hydrothermal method using potassium carbonate, tin powder and sulfur powder as raw materials. The morphology and structure of KSnS were performed by SEM, XPS and XRD. The effects of contact time, pH, coexisting ions, initial cobalt concentration on the adsorption of Co2 by KSnS were investigated via batch experiments. The results show that cobalt sorption of KSnS can reach equilibrium time after about 25 min, and the saturated adsorption capacities is 149 mg/g. When initial concentration of cobalt is 5mg/L and V/m=2500mL/g, the distribution coefficient of KSnS to Co2 can reach 6.3?105mL/g and the removal rate is 99.84%. When the solution is neutral, KSnS has the best adsorption performance. KSnS has high selectivity to Co2 , and high concentration of coexisting ions (K , Na , Ca2 , Mg2 ) has little effect on the removal rate of Co2 . The sorption kinetics of KSnS for Co2 can be described by pseudo-second-order kinetic equations, and the adsorption process is mainly chemical adsorption. According to Weber-Morris model and Boyd model, the liquid film diffusion process dominates the adsorption rate.

Abstract:In this work, nano-titanium dioxide (T-NTO) was prepared by hydrothermal synthesis using tannins as template. The structure and morphology of T-NTO were characterized by FT-IR, XRD, BET, SEM, TEM, and its adsorption performances for uranium were investigated. The results show that the specific surface area of T-NTO was significantly increased，and the adsorption capacity of the T-NTO exhibits obvious different varying with different tannins as template. It was found that the nano-titaniumdioxide (BT-NTO) prepared using bayberry tannin as template has the smallest particle size and its specific surface area is up to 96.61 m2／g. Furthermore, the adsorption process of uranium by T-NTO can be described by the Langmuir isothermal model and pseudo-second-order kinetic equation, and the adsorption capacity of BT-NTO to uranium is attained to 0.7054 mmol／g at 318K. In addition, the coexisting ions, including Zn2+, Mg2+, Pb2+, Cu2+, Mn2+, Na+, Cl-, SO42- and CO32- have little effect on the adsorption capacity of uranium by BT-NTO. However, the effect of F- is very significantly, but this effect can be greatly reduced by introducing Al3+. It should be noted that the BT-NTO can be regenerated with 0.1 mol／L HNO3 solution, and can be reused many times without obvious decreased of adsorption capacity.

Abstract:The core-shell magnetic nano-composite Mn3O4@SiO2 was prepared by oxidation and hydrolysis of tetraethyl orthosilicate (TEOS), and the adsorption performance of Mn3O4@SiO2 nanocomposite was explored for the adsorption of Mo (VI) ions from aqueous solutions. The core-shell magnetic nano-composite Mn3O4@SiO2 was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy and magnetmeter (VSM) et al various methods. The effects of solution initial pH, Mo (VI) ion initial concentration and temperature on the amount of Mo (VI) adsorbed were studied. The results showed that the maximum adsorption capacity of the Mn3O4@SiO2 composite for Mo (VI) is 145.35 mg/g at 298 K. The adsorption process of Mn3O4@SiO2 composite is agreed well with Langmuir adsorption isotherm models and pseudo second-order kinetics. The thermodynamic analysis revealed that the adsorption process of Mn3O4@SiO2 composite for Mo (VI) was spontaneous and endothermic.

Abstract:A flame retardant named as ethyl neopentyl phosphate was synthesized with neopentyl glycol, phosphorus ox-ychloride and ethanol as raw materials. The chemical structure of ethyl neopentyl phosphate was identified by means of FTIR, 1HNMR, 13CNMR, 31PNMR and ESI-MS. The effects of material ratio, reaction time and reaction temperature on the reaction were studied. The results show that the optimum conditions are (neopentyl glycol chlorophosphate):n (ethanol) = 1.0:5.0, the reaction temperature is 50℃, the reaction time is 8 h and the yield of the obtained product can reach 80.8%. Ethyl neopentyl phosphate was then applied in rigid polyurethane foams (RPUF), and the flame retardancy of the resulting composite material was determined by limiting oxygen index (LOI) measurements and vertical (UL-94) tests. Meanwhile, the thermal stability of flame retardant and RPUF was characterized by thermogravimetric analysis (TGA). The results indicated that the addition of ethyl neopentyl phosphate reduced the thermal stability to a certain extent, but improved the flame retardancy of RPUF. the composite containing 30% ethyl neopentyl phosphate could achieve UL-94 V-2 rating with a LOI value of 22.5. %, higher than that of pure RPUF(17.1%), and the residual mass increased from 15.8% ( for pure RPUF) to 18.9%.

Abstract:Aiming at the characteristics of low-permeability high-temperature and high-salt in Jilin Oilfield, a temperature- and salt-tolerant foaming agent-YUDP suitable for this type of reservoir was developed. The effects of foaming agent concentration, solution mineralization degree, temperature, pH, total content of calcium and magnesium ions, residual oil saturation on the foaming ability of foaming agent, foam stability and oil-water interfacial tension were investigated. The results showed that YUDP was resistant to temperature. 75℃, salt tolerance of 31037.9mg / L, alkali resistance pH = 10, calcium and magnesium ions up to 60mg / L, resistant to residual oil up to 15% crude oil content. Experiments show that YUDP can maintain the oil-water interfacial tension in the order of ?10-2mN/m in the high temperature and high salt environment, achieving the requirement of low interfacial tension flooding. When the mass concentration of YUDP is 0.4%, the foaming volume is up to 250mL, the half-life is 25.7min, the foam strength is 4187.75mL.min, and the oil-water interfacial tension is 0.0261 mN/m to meet the requirements of low interfacial tension foam flooding in Jilin Oilfield.

Abstract:Allyl poly (ethylene glycol) block copolymer(PEG-PGA-PAGE)was synthesized by cationic ring opening polymerization using polyethylene glycol (PEG) as initiator, BF3•Et2O complex as catalyst, glycidyl ether (GA) and allyl glycidyl ether (AGE) as monomers. The product structure was characterized by FTIR and 1H NMR. The mechanical properties and thermal properties of the two elastomers (peg-pga-page-1 and peg-pga-page-2) prepared by curing binders prepared by adding GA and AGE separately and simultaneously with terephthalobisnitrile oxide were investigated. Results show that the binder can be cured at room temperature, the cured elastomer peg-pga-page-1 prepared by subsection addition of GA and AGE has better mechanical properties and thermal properties, the tensile strength of 0.948 MPa, the elongation at break of 89.32%, shaw hardness of 23.8 Ha, the storage modulus of 361.05 MPa, Tg is - 41.85 ℃, the contact angle is 74 ℃. Room temperature curing improves the mechanical properties and thermal stability of elastomers and is expected to be used in composite solid propellants.

Abstract:A series of (p-vinylbenzyl)polystyrene macromonomers were synthesized by living anionic polymerization. The graft SIS with ordered polystyrene side chains was prepared by anionic copolymerization, using n-BuLi as initiator, THF as modifier, cyclohexane as solvent, polystyrene macromonomer and isoprene as monomers. The polystyrene macromonomers and graft SIS were characterized by proton nuclear magnetic resonance spectroscopy and gel permeation chromatography, and the rheological properties of graft SIS were characterized by rotational rheometer . The results showed that polystyrene macromonomers which molecular weight were between 3000～5000 could be synthesized by above method. The graft SIS synthesized by polystyrene macromonomers with characteristics of controlled, narrowed molecular weight distribution and ordered side chains. And the apparent viscosity of graft SIS synthesized by polystyrene macromonomers were low than that of linear SIS which has the similar molecular weight and the content of bounded styrene.

Abstract:The synthesis of 3-aminofurazan-4-carboxylic acid was improved, and it was synthesized via substitution, annulation-salt forming reaction and hydrolysis, using cyanoacetate as raw materials. The structure of the product is charactered by IR, NMR and MS. The effects of substrates ratio, reaction temperature, reaction time and solvent on the annulation-salt forming reaction was investigated. And the reaction time and solvent and pH on the hydrolysis was also investigated. It is suggested that the increase of KOH, the increase of reaction temperature can improve the yield of the product. The best annulation-salt forming reaction condition is the mole ratio of hydroxylamine hydrochloride : KOH : methyl-2-cyano-2-(hydroxyimino)acetate =1:4:1, the condensation temperature is 25℃, the reaction time is 2h, the cyclization temperature is 80℃, the reaction time is 2h, the solvent water is 50mL. The best acidification reaction condition is the reaction temperature is 5℃, the solvent water is 30mL, pH＜1. The total yield of annulation-salt forming reaction and hydrolysis was 79.7%, which is higher than the yield of 64% in the reported article.

Abstract:CrO3 did a favorable performance in catalyzing oxidation reaction of 3-carene and oxygen. CrO3-Al2O3 with a loading rate of 39.21% was prepared from CrO3 and neutral Al2O3 by impregnation, which not only performed as well as CrO3, but also benefited in reducing the residual quantity of Cr in the reaction solution. Allylic oxidization dominated the reaction and hardly any epoxidation was happened, so three different α,β-unsaturated ketones were produced as main products, that were car-3-ene-2-one, car-2-ene-4-one and car-3-ene-5-one respectively. Many reaction factors were investigated for their effects on the reaction, including catalyst amount, temperature, time and oxygen flux. After a series of condition experiments, the optimum oxidation process was established as that catalyst amount was 3% of the mass of 3-carene, temperature was 25℃, time was 10h and oxygen flux was 25mL/min. By the optimum process a result was obtained with a conversion of 58.72% for raw material and a selectivity of 86.07% for the total α,β-unsaturated ketones, while 19.83% for car-3-ene-2-one, 4.61% for car-2-ene-4-one and 61.63% for car-3-ene-5-one respectively. During the separation of the oxidation product by vacuum rectification, car-3-ene-5-one was found to be very easily isomerized and converted, as which preparation and separation of 3,6,6-trimethylcyclohepta-2,4-dienone could be accomplished in one step. However, similar isomerization reactions were not happened for car-3-ene-2-one and car-2-ene-4-one in this process. Results showed that reduced pressure was a necessary condition for isomerization, and the lower the pressure, the easier the reaction would occur, and the higher the effect would be. A conversion of 99.62% for car-3-ene-5-one and a selectivity of 98.15% for 3,6,6-trimethylcyclohepta-2,4-dienone could be obtained while the pressure was 0.5kPa, temperature was 120℃ and time was 4h, which indicated that a pressure of 0.5 kPa completely satisfied the reaction requirement.

Abstract:Hexadecyl 3-amino-4-chlorobenzoate was synthesized by the esterification of 3-amino-4-chlorobenzoic and n-hexadecanol in the presence of p-toluenesulfonic acid as catalyst and xylene. as solvent. The products were characterized by FTIR, 1HNMR. The effects of molar ratio of acid to alcohol, the amount of catalyst, reacants' mass fraction on esterification rates were investigated. The optimal conditions were as followed: the molar ratio alkyd of achol to acid was 1.2:1,the catalyst was 5% of the total mass, the reacants' mass fraction was 65%, the esterification rate was 96.20%, and the one through yield was 73.91%. In addition, the best system route for product purification was estalished to improve one through yield and the filtrate recovery and reuse after removal of catalyst. The one through yield increased to 78.90%, the total yield was 82.62%, and the purity of the product was higher than 98.00%.

Abstract:Polyethylene glycol 1500 was used as raw material to synthesize bisazide polyethylene glycol (N3-PEG-N3) intermediate by two-step functional group transformation. One side of the N3-PEG-N3 was reduced by organic phase and terminated by aqueous phase to achieve unilateral reduction of azide. Reaction selectivity was evaluated by liquid chromatography-mass spectrometry (LC-MS) and the content of excimer ion peaks of each component. The reduction rate of azide group on one side reached 97%. The optimum liquid-liquid two phase reaction conditions of amino azide polyethylene glycol (NH2-PEG1500-N3) were determined by single factor experiments: the molar ratio of bisazide polyethylene glycol to tri-phenylphosphine oxide was 1:1.1, the organic phase was toluene and dichloromethane as mixed solvent (3:2), aqueous phase was 2 mol/L hydrochloric acid solution, and the ratio of the two phases was 1:1, reaction at 35 oC for 12 hours, and then NH2-PEG-N3 was purified by column separation, yield is 72%. The results show that this method is simple and high purity. The products were characterized via 1H-NMR and HRMS. Finally, the hetero-polyethylene glycol was used to synthesize azide-terminated functional phos-pholipids.

Abstract:2-Hydroxy-3-tert-butyl-5-methylbenzyl alcohol has been synthesized using 2-tert-butyl-para-cresol and paraformaldehyde as raw materials with ethylene glycol dimethyl ether and xylene as mixed solvent. The optimum synthesis conditions of 2-hydroxy-3-tert-butyl-5-methylbenzyl alcohol were obtained: the reaction temperature was 150℃, the reaction time was 20h, The molar ratio of 2-tert-butyl-para-cresol to paraformaldehyde was 1:20 and the ratio of 2-tert-butyl-para-cresol to ethylene glycol dimethyl ether was 1:1.5. The synthetic product was characterized by melting point test, FTIR, 1HNMR, 13CNMR, HRMS and X-ray diffraction analysis. The purity the synthesized product was analyzed by HPLC. The thermal stability was also investigated by using thermogravimetric analysis (TGA). The antioxidant properties of the synthesized 2-hydroxy-3-tert-butyl-5-methylbenzyl alcohol were tested. The results showed that the product had good scavenging ability to superoxide O3-· anion, ·OH and DPPH· radical.