Abstract:A series of anionic stable waterborne polyurethanes(WPUs) based on hydroxyl-terminated poly(butadiene acrylonitrile) (HTBN) as the soft segments were synthesized ，and the effect of different content of HTBN on the properties of WPU were discussed. Fourier transform infrared (FT-IR) was used to characterize the structure of the HTBN and WPU; Particle size, DSC, XRD, stretching and TG tests showed that with the increasing of the content of HTBN, the average particle size of WPUs increased gradually, the tensile strength increased first but decreased then，the heat resistance significantly improved. When the content of HTBN was 40%, the tensile strength was the highest, catching 20.2 MPa, the elongation at break was 521%.

Abstract:The modified two-step seeded swelling polymerization was used to prepare monodisperse, high cross-linked and porous poly(glycidyl mthacrylate-co-ethylene dimethacrylate) (PGMA-EDMA) microspheres with polystyrene beads as the seeds, which were prepared by dispersion polymerization. Several factors including various stabilizer, ratio of activator and seeds, swelling multiples and different porogens were investigated to further enhance the characteristics of microspheres. Electron microscope, scanning electron microscope (SEM), and infrared spectroscopy (IR) and high performance liquid chromatography (HPLC) were used to test the properties of the microspheres. The results indicated that the monodisperse PGMA-EDMA microspheres with 5 um and 10 um could be obtained satisfactorily when the PS seeds were 2 um and 4 um, the ratio of activator and seeds was four times, the swelling multiples was 20-40 times, the volume ratio of cyclohexanol and toluene as porogens was 6/4, 0.2% hypromellose was the stabilizer.

Abstract:Ten fluorinated thieno[2,3-d]pyrimidine derivatives containing 1,3,4-thiadiazole were synthesized in the yields of 64 ~ 75% by SNAr reaction of 2-amino-5-(substituted benzylthio)- 1,3,4-thiadiazoles with 4-chloro-2-trifluoromethylthieno[2,3-d]pyrimidine, which were efficiently prepared from 2-aminothiophene-3-carbonitrile, trifluoroacetic acid and phosphorus oxychloride by one-pot procedure in 60% yield. The structures of the products were confirmed by IR, 1H NMR, MS and elemental analysis. The in vitro antitumor activity of these compounds against HepG2 and BGC-823 cell lines was evaluated by MTT assay. The results showed that compounds IVc and IVf possess higher antitumor activity than the positive control gefitinib.

Abstract:The solubility and surface activity of the collector, octadecylamine (ODA), in water, saturated KCl and saturated KCl-MgCl2, respectively, were measured at 5、15 and 25 °C. The experimental results showed that critical assemble concentrations (cac) of ODA was 4.65×10-4 mol/L at 25 °C without added salt, which was 2.19×10-5 mol/L in saturated KCl and 8.63×10-6 mol/L in saturated KCl-MgCl2. Under the same temperature, solubility and surface activity of ODA both reduced in saturated salt solution compared with those in water. In addition, the surface tension and turbidity increased with the temperature decreased, with decrease of solubility and surface activity , resulting in the reduction of the saturation surface excess concentration and the increasing of minimum area. However, the effect of temperature on cac was much less obvious.

Abstract:O - methyl acryloyl - oxygen ethyl dimethyl epoxypropyl ammonium chloride (ODEAC), an active intermediate, was synthesized with 2-dimethylamino ethyl methacrylate (DM) and epichlorohydrin (ECH) as the main raw material. The influence of the solvents, reaction temperature, material ratio and reaction time on product conversion and the epoxy value were respectively discussed using single factor experiment, to discusses the optimum synthetic process conditions: the reaction temperature 60 ℃, using isopropanol as the solvent, n (ECH) : n (DM) = 1:1.6, reaction time is 4 h, the target product conversion is 91.67%. And the structure of the product was characterized by FTIR and 1HNMR.

Abstract:The rheological properties of functional Gemini surfactant propanediyl-1,3-bis(dihydroxylethyldodecylammonium bromide) (12(2OH)-3-12(2OH)2Br) in the presence of small amount of traditional carboxylate surfactant, Sodium Laurate (SL), Sodium Myristate (SM) and Sodium Palmitate (SP), respectively, were investigated by steady state and dynamic rheological measurements at 25 oC. It was found that the addition of small amount of anionic surfactants has an obvious effect on the viscoelasticity of 12(2OH)-3-12(2OH)2Br solutions. The molar ratio (β) of anionic surfactant to cationic surfactant in mixed solution was 0.3, the zero shear viscosity got a maximum, 12.35 Pas and the G΄∞ was 31.88 Pa. When β=0.4, G΄∞ was 14.67 Pa. The sequence of solution viscoelasticity was SL/12(2OH)-3-12(2OH)2Br >SM/12(2OH)-3-12(2OH)2Br >SP/12(2OH)-3-12(2OH)2Br. When the concentration of 12(2OH)-3-12(2OH)2Br was 60 mmol/L, the zero shear viscosity was 33.92 Pas and G΄∞ was 46.41 Pa in the mixtures of SL/12(2OH)-3-12(2OH)2Br where β was 0.3, respectively.

Abstract:For understanding effects of molecular structure on properties of surfactants an asymmetric double long-chain alkyl betaine, stearylhexylmethyl carboxyl betaine (C18+6B), was synthesized using stearic acid and hexanoic acid as starting materials and its surface active properties were measured and compared with that of didodecyl methyl carboxyl betaine(diC12B), a symmetric double long-chain betaine with equal total carbon number. The results show that C18+6B has a surface activity similar to that of diC12B in general, but displays an aqueous solubility much better than that of diC12B. As a surfactant for surfactant-polymer flooding free of alkali, C18+6B seems to be slightly less hydrophobic against Daqing crude oil, which solely can reduce the Daqing crude oil/connate water interfacial tension (IFT) to 10-2 mN/ m magnitude and gives a saturated adsorption 30% lower than that of diC12B at Daqing sandstone/water interface at 45 C. C18+6B solely can reduce C7-C9 n-alkanes/connate water IFT to 10-3 mN/m magnitude at 45 C, and can reduce the daqing crude oil/connate water IFT to 10-3 mN/m magnitude at 45 C by mixing with the more hydrophobic surfactant diC12B and other hydrophilic betaine surfactant, where the aqueous solubility of the formulation is greatly improved by the presence of C18+6B.

Abstract:Aspartate-β-decarboxylase is an enzyme that catalyzes the decarboxylation of L-aspartate to produce L-alanine. The gene coding and expressing this enzyme was cloned from Alcaligenes faecalis. In this study, the vector pETDuet-1 was used to recombinant express the aspartate-β-decarboxylase in Escherichia coli BL21(DE3). Several influencing factors of the enzyme reaction, such as pH, pH stability, temperature, thermal stability, concentration of substrate, were all investigated. The results indicated that the recombinant aspartate-β-decarboxylase was successfully expressed and the reaction was optimal at pH 6.0 and 45癈. The Km and Vmax values of aspartate-β-decarboxylase were 0.72 mmol/L and 10.52 mol/(L?min?g). 10 ml of 0.2 mol/L phosphate buffer included 0.1 g wet cells, 0.2 mmol/L 5'-pyridoxal phosphate, and 0.2 g L-aspartate, after 15 hours, the mole conversion rate of L-aspartate was up to 99%.

Abstract:Extraction of rhizoma coptidis alkaloids using aqueous two-phase system of polyethylene glycol (PEG) and ammonium sulfate ((NH4)2SO4). Through the change of the aqueous two-phase system, researched the distribution behavior of four major alkaloids in rhizoma coptidis: berberine, coptisine, palmatine and jatrorrhizin in aqueous two-phase system, and combined with ultraviolet spectrophotometry to detect out the best extraction craft of rhizoma coptidis alkaloids. The best extraction process parameters: pH = 6, T = 20 ℃, PEG1000 mass fraction 20%, ((NH4)2SO4) mass fraction 16%, the highest extraction of berberine, coptisine, palmatine and jatrorrhizin are 99.79%, 98.04%, 99.96%,99.39%, respectively. Aqueous two-phase extraction of rhizoma coptidis alkaloid efficient environmental protection is feasible.

Abstract:TiO2-Mn-SBA-15 were prepared by improved after grafting method,using manganese acetate as manganese source,tetra-n-butyl titanate as the titanium source.The catalyst samples were characterized using XRD,low temperature N2 adsorption-desorption.The catalyst was applied to oxidize phenol into hydroquinone under the conditions that the solvent of the reaction is water and under the irradiation of the ultraviolet lamp LED.Ti,Mn loading of the TiO2-Mn-SBA-15,the dosage of the catalyst,reaction temperature and reaction time were investigated to study the effects on the reaction.The results indicated that the conversion of phenol and selectivity of dihydroxybenzene reached 22.7% and 84.7%,respectively,under the optimal reaction conditions(Ti,Mn loading 3%、reaction temperature 30 ℃、reaction time1.5 h、catalyst dosage0.15 g).

Abstract:Nb2O5 nanowires were synthesized by thermal oxidation process on Nb foils. The phase, morphology and microstructure of the products were characterized by using XRD, SEM and TEM. The optical absorption and photocatalytic dye degradation properties of the nanowires were also investigated. The results show that the sample is composed of pure Nb2O5 with tetragonal structure. The diameter of the nanowires is 20 to 60 nm. When the oxygen flow rate is 25 sccm, the nanowires with high aspect ratio are densely distributed into the network structure. The quantity and density of the nanowires are decreased when the oxygen flow rate is increased. The UV-Vis absorption spectrums show that the Nb2O5 nanowires are direct-band-gap semiconductor with the band gap of ~ 3.42 eV. Under the illumination of UV light with the wavelength of 365 nm, the nanowires exhibit obvious photocatalytic property to methylene blue, methyl orange and rhodamine B, for which the photocatalytic efficiency factor is -0.025, -0.021 and -0.008 min-1, respectively.

Abstract:Fe modified Cu/Zn/MgO catalyst prepared by co-precipitation- impregnation method is studied for the synthesis of mixed alcohol from syngas, and characterized by BET,H2-TPR,CO-TPD and XRD for assessment of the impact of Fe on the catalyst's structure and morphology. Evaluation results show that MgFe2O4 phase is formed, which promote the dispersion of both the Fe and Mg species when Fe is added. Optimal Fe amount promotes adsorption intensity of CO and facilitates the synthesis of C2 alcohols. The mass ratio of C2 alcohols in total alcohol and space time yield of C2 alcohols increased from 19.6% to 59.7% and 23.3 g/kgcat?h to 45.3 g/kgcat?h respectively, compared with catalyst without Fe when the amount of Fe is n(Fe)/n(Cu)=0.15.

Abstract:Several SO3H-functionalized acidic ionic liquids were synthesized by two-step method, using 1, 3-propane sultone and 1, 4-Butanesultone as raw materials, respectively. Esterification of 1-butanol with adipic acid was carried out by using these different Br謓sted acidic ionic liquids as catalysts without removal of water. The relationship between the Br謓sted acidity-catalytic activity and the relative acidity were studied. Moreover, the reaction conditions of reaction temperature, molar ratio of reactants, reaction time and ionic liquid amount were optimized. The results indicated that, [MimN(CH2)4SO3H][HSO4] acidic ionic liquid was the best catalyst, and under the optimized reaction conditions of 110 ℃, n(1-butanol): n(adipic acid)=6:1, m(cat): m(adipic acid)=1.5 %, 3 h, the yield of dibutyl adipate was 90 %.

Abstract:Two apigenin derivatives Ⅰ[8-(N,N-diethyl)-methylene-amino-4',5,7,-trihydroxy flavone] and Ⅱ[8-(N,N-diethyl)-methylene-amino-4',5,7,-trihydroxy flavone-3'-sulfonic acid] were synthesized via Mannich and sulfonation reaction, and characterized by ESI-MS, 1H-NMR and 13C-NMR Then fluorescence quenching spectra, synchronous fluorescence spectroscopy, ultraviolet spectroscopy combined with correction of inner filter effect, along with molecular docking studies were used to investigate their interaction mechanism with human serum albumin (HSA) at 298 K, 303 K, 308 K. Spectroscopy results indicated that the intrinsic fluorescence of HSA was quenched by forming a complex with the drug. It was due to the static quenching and non-radiation energy transfer, and the binding site was near the subdomain IIA of HSA. Thermodynamic analysis showed that there was only one binding site while the interaction occurred. What’s more, ΔH > 0 and ΔS > 0 indicated that the hydrophobic force played a major role in the interaction. Docking results implied that both of the derivatives bound to the hydrophobic cavity of HSA by hydrophobic force and hydrogen bonding, wherein the hydrophobic force was the main force, which was consistent with the thermodynamic results.

Abstract:Emulsion liquid membrane system containing mobile carrier is widely applied in separation and preconcentration of trace substances in wastewater. The polyamine surfactants such as polyisobutylene-bis-succinimide (T-154) have attracted considerable interest due to good emulsifying and dispersing properties. In the paper, the surfactant was used as double effects of emulsifier and mobile carrier in the emulsion liquid system for the first time. The enrichment performance for phenol was investigated by the emulsion liquid membrane. Established stable conditions of the emulsion liquid membrane are as follows: the volume ratio of T-154 to liquid paraffin to kerosene is 4:2:30, the mass concentration of sodium hydroxide (NaOH) solution used as the internal phase is 3%, the ratio of oil phase to internal phase is 1:2. The separation conditions involved the pH value of feed phase (pH=6), the ratio of emulsion to external phase (1:4), and enrichment time (15min) were founded. The phenol in the wastewater was separated and enriched with the prepared emulsion. The satisfactory results show that the recovery of standard addition is between 96% and 98%, the relative standard deviation is between 3.7% and 4.8%. The established method has the advantages of simple operation, low capital and operating costs and high efficiency, which can be used to remove phenol from aqueous media such as wastewater.

Abstract:P(AM-NaAA-NIDA) was synthesized by using acrylamide(AM), sodium acrylate (NaAA) and 1-(2-N-acryloylaminoethyl)-2-oleic acid imidazole (NIDA) via redox free-radical copolymerization in the presence of (NH4)2S2O8-NaHSO3 as initiator system. The structure of synthesized copolymer was characterized by FTIR, 1H NMR analysis and intrinsic viscosity measurements. As a consequence, the rheology behavior and salt tolerant of the copolymer was substantially improved compared to partially hydrolyzed polyacrylamide (HPAM). Results showed that the thermal resistance of copolymer could be up to 21.18% at 120 oC compared to that at 30 oC. Core flooding experiments revealed the EOR of P(AM-NaAA-NIDA) could increase up to 17.68%. All the results demonstrated that obtained polymer has prominent performance for potential application in enhance oil recovery.

Abstract:Aromatic Polyester-based Polyurethane dispersions (PUDs) with about 50% solid content were synthesized using polyether diol containing sulfonate (SPPG), poly1,6-hexanediol phthalic anhydride(PHPA), hexamethylene diisocyanate(HDI) and ethylene diamine (EDA) by the acetone method. The surface tension of PUD were in the range of 34~45mN?m-1,which displayed good wettability. The average particle sizes of PUD were mostly in the range of 100 nm~250 nm and the particle size distributions of PUD were mostly in the range of 50 nm~200nm, which displayed excellent stabilization. The average particle sizes, viscosity, particle size distributions and surface tension changed regularly with hydrophilic group content (HGC), R value(NCO/OH molar ratio) and chain extension. TEM analysis showed spherical shapes of the particles with different sizes and bimodal distribution. PUDs were pseudoplastic fluid. Adhesive strength test showed good results for various materials, such as different kinds of PVC and wood.

Abstract:Bio-based polyols (P-OA-ESBO) from epoxidized soybean oil (ESBO) and oleic acid (OA) were developed using an environmentally friendly, solvent-free/catalyst-free method. The structure of P-OA-ESBO was characterized by FT-IR and 1H-NMR. Subsequently, environmental wrapping polyurethane adhesive was mainly prepared from P-OA-ESBO, isophorone diisocyanate (IPDI) and glycerin without catalysts. The polyurethane adhesives film were synthesised by different NCO/OH ratio (R value) were studied by TGA, DSC, tensile mechanical properties test, PE/OPP composite membrane peel strength test and shear strength test. Tensile mechanical properties test and shear strength test show that the more suitable NCO/OH ratio (R value) was 1.3-1.5. And when the R value was 1.7, the polyurethane adhesives from P-OA-ESBO have the best stripping resistance. Moreover, the synthetic route facilitate a more environmentally friendly and economical process than conventional soybean-based polyols used for polyurethane.

Abstract:Abstract: A 2-(2-Butoxyethoxy) ethanol acrylate (MBDEGAA) was prepared by esterification of 2-(2-Butoxyethoxy) ethanol (MBDEG) and acrylic acid (AA). The effects of n(AA)∶n(MBDEG), esterification temperature, esterification time, dosages of catalyst and polymerization inhibitor on the esterification ratio were studied. The MBDEGAA structure was identified by means of FT-IR and 1H-NMR. The results show that the highest esterification ratio between MBDEG and AA is 91.20% in the mole ratio of AA to MBDEG as 3.0∶1, esterification temperature as 130 ℃, esterification time as 4.5 h, w(PTSA) as 3.0%, and w(hydroquinone) as 2.0%.

Abstract:Ten kinds of 2-[(indol-3-yl)-arylmethyl]-malononitrile derivatives (β-indole derivatives) were synthesized through one pot three-component reactions of indole with aromatic aldehydes and malononitrile in the presence of the deep eutectic solvent (DES) choline chloride/urea. The yields ranged from 66%～94% under mild conditions. Furthermore, the relationship between reaction speed and substituent groups was described, the catalytic mechanism for the reaction catalyzed by choline chloride/urea was proposed. The catalyst could be recovered five times conveniently and reused efficiently. All the compounds synthesized were confirmed by 1H NMR、13C NMR analysis.

Abstract:The catalyst was prepared with HZSM-5 as support and ammonium sulfate as modifying agent by impregnation, filtration, desiccation and calcinations. The ethylene glycol monoethyl ether and ethylene glycol diethyl ether were synthesized from ethylene glycol and ethanol by using prepared catalysts. The results showed that modified H-ZSM-5 was the better catalyst. The conversation of ethylene glycol was 69.1% and the selectivity of ethylene glycol monoethyl ether was 72.9% and selectivity of ethylene glycol diethyl ether was 25.3%. However, the catalytic performance dropped after be used. And so the catalyst samples were characterized by X-ray diffraction (XRD), temperature-programmed desorption of NH3 (NH3-TPD), scanning electron microscopy (SEM) with the energy dispersive spectroscopy (EDS), Brunner-Emmit-Teller (BET) and thermogravimetry (TG) to investigate the deactivation of the catalyst. The results showed that the catalyst deactivation did not result from the change of the crystal structure. The main reason for catalyst deactivation is the reduced of sulfur and strong acid sites because of the absorption of organic molecules on the surface or in the pore of the catalyst.

Abstract:Anhydrous sodium silicate (Na2SiO3) was prepared by the simple calcination of Na2SiO3?9H2O and used as solid base catalyst for the synthesis of dimethyl carbonate (DMC) by transesterification of ethylene carbonate (EC) with CH3OH. Anhydrous Na2SiO3 were characterized by TG-DTA, XRD and Hammett indicator method. Results showed calcination temperature has no significant effect on the basic strength, total basicity and catalytic activity of anhydrous Na2SiO3. When the calcination temperature was 200oC, the basic strength (Ho) of catalyst (Na2SiO3-200) was in the range of 12.2?15.0, and its total basicity was about 10.9 mmol/g. Effects of raw material ratio, temperature and reaction time on the synthesis of DMC were also investigated using Na2SiO3-200 as catalyst. The optimal molar ratio of CH3OH to EC was 10: 1, and the conversion of EC could reach to 89% with 88% DMC yield at 65oC within 2 h. Na2SiO3-200 could effectively promote the reaction even at room temperature. In addition, the catalytic activity of Na2SiO3-200 has no remarkable decrease after 4 runs.

Abstract:Due to the low region-selectivity, the alkylation of 5-amino-4-cyano-pyrazole always bring forth the mixture of two substitution products. Based on the alkylation method, We start from the raw material of 3-amino-1H-pyrazole-4-carbonitrile, and compare the effect of solvents and deacid reagents on the region-selectivity and yield. Although the overall conversion yield doesn’t change so much among DMSO, DMF and CH3CN, the solvent of DMSO can distinctly improve the region-selectivity. The pure product of 5-amino-1-benzyl-4-cyano-pyrazole can be conveniently recrystallized from 95% ethanol with a separation yield of 62% when using DMSO and CsCO3 as reaction solvent and deacid reagent, respectively. Its chemical structure is characterized with 1H NMR and single crystal X Ray diffraction, which belongs to monoclinic space group P2(1)c with a = 1.4333 (3) nm, b = 0.6187(14) nm, c = 2.2389 (5) nm, α = 90°, β = 93.773(4)°, γ = 90°, V = 1.981.1(8) nm3, Z = 8, Dc = 1.329 g cm-3, λ = 0.71073 nm, μ (Mo Kα) = 0.085 mm-1, F (000) = 832.